Document 8VykvaxQbbYZZy9Nn5Vv6M7pa

f GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 GLP10-01-02; Interim Report 22 - Analysis of PFBS, PFHS. and PFOS in Groundwater Samples Collected from Decatur. AL. 3rd Quarter 2011 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan Wolf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 St. Paul, MN 55144 Project Identification GLP10-01-02-22 Total Number of Pages 99 The testing reported herein m eet the requirements of ANSI/ ISO/IEC 17025:2005 "General Requirem ents fo r the Com petence o f Testing and Calibration Laboratories", in accordance with the A2LA Testing Certificate # 2052.01. Testing that complies with this International Standard also meets principles of ISO 9001:2000. Testing Cert #2052.01 Page 1 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 This page has been reserved for specific country requirements. Page 2 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 G LP Compliance Statement Report Title: Interim Report 22 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected from Decatur, AL, 3rd Quarter 2011 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system. The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determined under GLPs. Jaisimha Kesari, P.E., DEE, Study Director Date Page 3 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Q uality A ssurance Statement Report Title: Interim Report 22 - Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected from Decatur, AL, 3rd Quarter 2011 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. 1. This analytical phase was audited by the 3M Envirorimental 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 11/10/11-11/11/11 Phase Data / Interim Report Date Reported to Testing Facility Management Study Director 11/30/11 11/30/11 QAU Representative Date Page 4 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater , 3rd Quarter Sampling - 2011 Table of C ontents GLP Compliance Statement.......................... Quality Assurance Statement........................ Table of Contents.......................................... List of Tables................................................. 1 Study Information................................... 2 Summary................................................ 3 Introduction............................................. 4 Test & Control Substances .................... 5 Reference Substances.......................... 6 Test System .......................................... 7 Method Sum m ary.................................. ' 7.1 7.2 M ethods................................. Sample Collection.................. 7.3 Sample Preparation................ 7.4 Analysis.................................. 8 Analytical Results................................... 8.1 Calibration.............................. 8.2 System Suitability.................. 8.3 Limit of Quantitation (LO Q ).... 8.4 Continuing Calibration............ 8.5 Blanks..................................... 8.6 Lab Control Spikes (LCSs) ..... 8.7 Analytical Method Uncertainty 8.8 Field Matrix Spikes (FMS)...... ,.3 ..4 .5 ..6 ..8 ..9 11 11 12 13 14 14 14 14 14 16 16 17 17 17 18 18 21 21 Page 5 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 9 Data Summary and Discussion.............................................................................................. .... 22 10 Conclusion..................... ..............................................................................................................34 11 Data/Sample Retention........................................................................................ :.............. :...... 34 12 Attachm ents............................................................... ............................... ................................. 34 13 Signatures...........................................:...... .... ............................................................................35 List of Ta b les Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur G roundw ater-Q 3 2011)...10 Table 2. Sample Description Key Code..................................................................................... 13 Table 3. Instrument Parameters............................... ................................................................. 15 Table 4. Liquid Chromatography Conditions..............................................................................15 Table 5. Mass Transitions.............. :.............. ....... ......... ,............... ;......................................... 16 Table 6. Limit of Quantitation (LOQ).......................... ............ ................................................... 17 Table 7. Laboratory Control Spike Recovery............................................................................. 18 Table 8. Analytical Uncertainty............................ ....................................... ...............................21 Table 9. Field Matrix Spikes....................................................................................................... 21 Table 10. DAL GW 203L 110930 ...............................................................................................23 Table 11. DAL GW 220R 110930................... ............... ................................................. ......... 23 Table 12. DAL GW 220L110930...................................................... ..... !.............. .................. 24 Table 13. DAL GW 222R 110930..................................... .....24 Table 14. DAL GW 227R 110922................. 25 Table 15. DAL GW 227L 110922........................................... 25 Table 16. DAL GW 31OR 110928............................................ '................................................ 26 Table 17. DAL GW 312R 110929............. ,............................. .................................................. 26 Table 18. DAL GW 317 L 110928.............................................................................................21 Table 19. DAL GW 324L 110923.............................. ,.............................................................. 27 Table 20. DAL GW 327R 110928..............................................................................................28 Page 6 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 21. DAL GW 328R 110927................................................. ............................................ 28 Table 22. DAL GW 328L110928............................................................................................. 29 Table 23. DAL GW 330R 110928 .............................................................................................. 29 Table 24. DAL GW 330L110928............................................................................................. 30 Table 25. DAL GW 331S 110929..............................................................................................30 Table 26. DAL GW 335R 110927.............................................................................................. 31 Table 27. DAL GW GRS04 110930......................................................................................... 32 Table28. T rip B la n k l........................................................................................................... .....32 Table 29. Trip Blank 2..................................................................... .......... ................................ 33 Table 30. Equipment Rinseate Blanks............................. :......................................... :............. 33 Page 7 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 1 Study Information Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. W estchester, PA 19380 Phone:(610)701-3761 Fax:(610)701-7401 j.kesari@ westonsolutions.com Study Location Testing Facility ' 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 St. Paul, MN 55144 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanqe@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow; analyst Kelly Ukes; analyst Jonathan Steege; analyst Study Dates Study Initiation: March 8,2010 Interim 22 Experimental Termination: October 25, 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 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located in Decatur, AL, representing eighteen (18) different sampling locations collected September 22 - 30, 2011. A total of eighty-two sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS). For each sampling location, four sample bottles were collected; sample, sample duplicate, low field matrix spike, and high field matrix spike. Two trip blanks containing Milli-QTM water and appropriate trip blank spikes were analyzed with the groundwater samples. In addition, two equipment rinseate blank samples were collected. 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 GLP10-01-02-22. The groundwater samples, trip and equipment rinseate blanks for GLP10-01-02-22 were received from Weston personnel on October 6, 2011. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0. Many of the groundwater samples required dilution to obtain PFBS, PFHS, and/or PFOS concentrations within the range of the curve, in some instances up to a 500-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 groundwater locations ranged from <0.0400 ng/mL to 3070 ng/mL. The PFHS concentration results for all groundwater locations ranged from 0.0984 ng/mL to 6060 ng/mL. The PFOS concentration results for the reported groundwater locations ranged from 0.205 ng/mL to 3350 ng/mL. The analytical uncertainties associated with the reported results are as follows: PFBS 100% 14%, PFHS 100% 18%, and PFOS 100% 26%. Page 9 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Table 1. Summarized PFBS, PFHS, and PFOS Results (Decatur Groundwater - Q3 2011). Sampling Location DAL GW 203L 110930 DAL GW 220R 110930 DAL GW 220L 110930 DAL GW 222R 110930 DAL GW 227R 110922 DAL GW 227L 110922 DAL GW 31OR 110928 DAL GW 312R 110929 DAL GW 317L 110928 DAL GW 324L 110923 DAL GW 327R 110928 DAL GW 328R 110927 DAL GW 328L 110928 DAL GW 330R 110928 DAL GW 330L 110928 DAL GW 331S 110929 DAL GW 335R 110927 DAL GW GRS04 110930 Trip Blank (Milli-QTM Water) - 2 sets Equipment Blank s - 2 rinseate blanks PFBS Avg. Cone. (ng/mL) %RPD 23.2 9.9% 4.76 2.9% 7.87 1.0% 62.5 0.16% 13.4 4.5% 256 1.6% 730 3.7% 1140 1.8% <0.0400 70.0 0.0% 51.6 0.58% 27.9 1.4% 40.3 0.0% 3070 0.48% 530 5.5% <1) 525 3.8% <1) 1080 3.7% <1) 1690 3.6% <0.0400 <0.0400 PFHS Avg. Cone. (ng/mL) %RPD 142 9.2% 17.9 2.2% 37.6 1.1% 429 0.93% (1) 61.7 4.5% 68.5 0.58% 320 1.3% 831 0.48% 0.0984 9.3% 82.5 0.97% 126 1.6% 57.9 2.2% 18.4 1.1% 196 1.5% 434 1.4% 331 3.0% 1420 2.1% 6060 5.5% <0.0250 <0.0250 PFOS Avg. Cone. (ng/mL) %RPD 478 3.1% 27.4 7.3% (1) 49.2 10% <1) 511 0.39%(1) 578 2.1% 474 3.6% 611 3.4% 1440 8.3% 0.205 8.8% 211 0.95% 397 1.3% 178 0.28% 1.29 3.9% 593 2.4% 169 1.4% 506 4.5% 3350 3.3% (2) 1330 1.5%(1) <0.183 <0.232 The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 14%, PFHS 100% 18%, and PFOS 100% 2 6 % . (1) The analytical uncertainty has been expanded for the following samples based on FMS recovery: DAL G W 220R (PFOS 38%), DAL G W 220L (PFOS 38%), DAL G W 222R (PFOS 43%; PFHS 35%), DAL G W 330L (PFBS 34%), DAL GW 331S (PFBS 32%), DAL G W 335R (PFBS 31%), and DAL G W GRS04 (PFOS 37%). (2) Sampling location did not contain an appropriate spike level to assess PFOS recovery. Page 10 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 3 Introduction This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze ground water samples collected from various wells located in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; 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 10-30 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 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 5 Reference Substances R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity Use PFBS (predom inantly lin ear) Perfluorobutane sulfonate C 4F 9SO 3 Potassium Salt 3M 1/10/2017 Frozen 101 TCR-121 White Powder 96.7% Target Analyte Reference Standard PFHS (lin ear) Perfluorohexane sulfonate C g F 13SO 3 Sodium Salt Wellington 3/25/2018 Frozen LPFHxSAM08 TCR08-0018 Crystalline 98% Target Analyte Reference Standard R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity Use PFOS (lin ear) Perfluorooctane sulfonate C8F1 7 S O 3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2018 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% Field Matrix Spike Reference Standard PFOS (lin ea r + branched) Perfluorooctane sulfonate C 8F 1 7 S O 3 Potassium Salt CAS #2795-39-3 Wellington . 03/17/2014 . Frozen brPFOSK0708 TCR11-0010 Liquid 99.9% Target Analyte Reference Standard Page 12 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity Use 13c 8-p f o s (lin ear) Sodium Perfluorooctanesulfonate 13C8F17S 0 3'Na+ CAS # MPFC-C-0511 Wellington 05/25/2014 Frozen 092310 TCR11-0016 Liquid 5 pg/mL<1) Internal Standard (1) Custom mixture of seven mass-labeled (13C) perfluoroalkylcarboxylic acids, two mass-labeled (13C ) perfluoroalkylsulfbnates and one mass-labeled (13C) perfluoro-1 -octanesulfonamide. 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. . Table 2. Sample Description Key Code. Exam ple DAL GW 203L DB 110930 S tring Num ber S tring D escriptor 1 S am pling Location 2 Sam ple Type 3 W ell Id e n tifie r 4 W ell Level 5 Sam ple Type 6 S am pling Date Exam ple DAL = Decatur, Alabam a GW= G round w ater Exam ple: 203 R = R esiduum sh a llo w w ater-bearing zone L = B ed rock w ater-bearing zone S = E p ika rst m id dle w ater-bearing zone 0= prim ary sam ple D B =duplicate sam ple LS = lo w spike MS = m id sp ike HS = h ig h spike 110930 = S eptem ber30,2011 Page 13 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 7 Method Summary 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; 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 6, 2011. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Samples that required dilution were prepared as follows: 1:5 dilutions were prepared by diluting 2mL sample with 8 mL of Milli Q water, 1:10 dilutions were prepared by diluting 1mL sample with 9 mL of Milli Q water, 1:20 dilutions were prepared by diluting 0.5mL sample with 9.5mL of Milli Q water, 1:50 dilutions were prepared by diluting 0.2mL sample with 9.8mL of Milli Q, and 1:100 dilutions were prepared by diluting 0.1mL sample with 9.9mL of Milli Q water. Samples may also have been diluted further by varying the injection volume during analysis. Sampling locations DAL GW 317L and DAL GW 328L were prepared for PFOS by removing a 5 mL aliquot and adding an aliquot of a separate internal standard spiking solution (nominal concentration of 1 ng/mL). This same procedure was followed for the laboratory control samples. 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Page 14 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 3. Instrument Parameters. Instrum ent Name A na lytica l M ethod Follow ed A na lysis Date Liqu id C hrom atograph G uard colum n A na lytica l colum n Inje ction Volum e M ass S pectrom eter Ion Source E lectrode P olarity Softw are ETS B uster ETS-8-044.0 10/12/11 Agilent 1100 Prism RP (2.1 mm X 50 mm), 5 g Betasil C 18 (2.1 mm X 100 mm), 5g 2 or 10 gL Applied Biosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 ETS K irk ETS-8-044.0 10/20/11, 10/24/11 Agilent 1200 Betasil C18 (4.6 mm X 100 mm), 5g Betasil C18 (4.6 mm X 100 mm), 5g 10 or 50 gL Applied Biosystems API 5500 Turbo Spray Turbo ion electrode . Negative Analyst 1.5.2 Table 4. Liquid Chromatography Conditions. S te p N um ber 0 1 2 3 4 5 0 1 2 3 4 5 T o ta l T im e (m in ) F lo w R a te (fd /m in ) P e rc e n tA (2 m M a m m o n iu m a c e ta te ) E T S -8 -0 4 4 .0 A n a ly s is 1 0 /1 2 /1 1 0 2.0 14.5 15.5 16.5 20.0 300 300 300 300 300 300 97.0 97.0 5.0 5.0 97.0 97.0 0 2.0 14.5 15.5 16.5 20.0 E T S -8 -0 4 4 .0 A n a ly s is 1 0 /2 0 /1 1 a n d 1 0 /2 A /1 1 750 97.0 750 97.0 . 750 5.0 750 5.0 750 97.0 750 97.0 P e rc e n t B (M e th a n o l) 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 15 of 99 , GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 5. Mass Transitions. A na lyte Reference M aterial S tructure M ass T ransition Q1/Q3 In te rn a l S tandard M ass T ransition Q1/Q3 PFBS L ine ar 299/80 299/99 NA NA PFHS L ine ar 399/80 399/99 NA NA 499/80 PFOS L in e a r+ Branched 499/99 [ ,3CiJPFOS<1> 507/80 499/130 Dwell time was 75 msec (10/12/11 analysis) or 30 msec (10/20/11 and 10/24/11 analysis) for each transition. The individual transitions were summed to produce a `total ion chromatogram" (TIC), which was used for quantitation. NA = Not Applicable (1) Internal standard was only used for the analysis of locations DAL G W 317L and DAL G W 328L for PFOS. 8 Analytical Results 8.1 Calibration 8.1.1 External Standard Calibration -10/12/11 and 10/20/11 analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into Milli Q water. A total of fifteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL were prepared, however, not all analytical runs included all fifteen standards. Low curve points may have been 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. The PFOS reference standard used for the preparation of the calibration standards contained both linear and branched isomers. The samples conained both linear and branched isomers, many with concentrations >100 ng/mL, however, the field matrix spikes were prepared using predominantly linear PFOS. To help minimize any potential analytical bias in the quantitation of linear isomers of PFOS against mixed linear and branched PFOS, the linear PFOS peaks and the branched PFOS peaks were integrated separately. For the linear calibration, only the linear peaks of all samples were integrated, including the calibration curve. The branched calibration was done in the same manner, integrating only the branched isomers. The concentrations of the calibration curve points were based on the percent linear and branched isomers in the standard, 21.1% branched and 78.8% linear. The final calculated concentrations were determined using the summed calculated concentrations of the linear and branched peaks. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. 8.1.2 Internal Standard Calibration -10/24/11 analysis: Sampling locations DAL GW 317L and DAL GW 328L for PFOS were analyzed against a matrixmatched stable isotope internal standard calibration curve. Calibration standards were prepared by Page 16 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. The calibration standards contained an internal standard mix containing 13C8-PFOS at a nominal concentration of 1 ng/mL. A total of thirteen spiked standards ranging from 0.025 ng/mL to 25 ng/mL were analyzed for PFOS. The PFOS reference standard used for the preparation of the calibration standards contained both linear and branched isomers. A quadratic, 1/x weighted, calibration curve of the ratio of the standard peak area counts over the internal standard peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFOS. The PFOS linear and branched isomers were integrated together as one analyte peak and not separately as done for the 10/12/11 and 10/20/11 analyses. These samples did not require the linear and branched isomers to be integrated separately since the samples had low amounts of PFOS and were aided with the addition of internal standard 13C8-PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS for each analytical batch with the exception of the 10/12/11 and 10/20/11 analyses, in which PFOS (linear and branched summed) had an area count RSD of 7.5% in the 10/12/11 analysis and 9.1% in the 10/20/11 analysis. A method deviation is included in Attachment D. 8.3 Limit of Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The LOQs associated with the sample analysis are listed in the table below. Table 6. Limit of Quantitation (LOQ). A n a ly s is D a te 10/12/11 10/20/11 10/24/11 D ilu tio n 1 5 10 20 50 100 500 1 500 1 PFBS L O Q , n g /m L 0.0400 0.200 0.400 0.800 2.00 4.00 20.0 NA NA NA PFHS L O Q , n g /m L 0.0250 0.125 0.250 0.500 1.25 2.50 12.5 0.0250 12.5 NA PFO S L O Q , n g /m L 0.232 1.16 2.32 4.64 11.6 23.2 116 0.0232 11.6 0.0232 NA = Not Applicable; analytical results for 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 reported samples were bracketed by CCVs that met method criteria of 100% 25% with the exception of several CCVs analyzed for PFOS on 10/12/11 which had recoveries greater than 125% (127% 135%). Sample sets bracketed by the non-compliant CCVs include: DAL GW 317L, DAL GW 324L, Page 17 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 DAL GW 327R, DAL GW 328R, DAL GW 328L, DAL GW 330R, DAL GW 330L, DA; GW 331S, DAL GW 335R, and DAL GW GRS04. A method deviation is included with the raw data. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: method procedural blanks, field/trip blanks, and equipment blanks. Method procedural blank results were reviewed and used to evaluate method performance and to determine the LOQ for each analyte. 8.6 Lab Control Spikes (LCSs) Three lab control spike levels were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into 10 mL of Milli Q water or synthetic groundwater to produce the desired concentration. The spiked water samples were then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level should be within 100% 20% with an RSD <20%. For the 10/12/11 and 10/20/11 analyses, the PFOS LCS recovery was based on the sum of the calculated concentrations of the linear and branched isomers integrated separately. All LCSs met acceptance criteria for each analyte except for the 0.2ppb and 2ppb LCSs for PFOS in the 10/20/11 analysis, which had average recoveries of 74.1% and 78.1% respectively. A method deviation is included with the raw data. The following calculations were used to generate data in Table 7 for laboratory control spikes. LCS Percent Recovery = -C--a-l-c--u-l-a--te--d--C--o--n--c-e--n-t-r-a--ti-o--n- ,, 1. 0. .0.%. Spike Concentration standard deviation LCS replicates LCS% RSD = 100% average LCS recovery Table 7. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 10/12/11 External Calibration Lab ID L C S -1 11007-1 L C S -1 11007-2 L C S -1 11007-3 Average %RSD L C S -1 11007-4 L C S -1 11007-5 L C S -1 11007-6 Average % RSD L C S -1 11007-7 L C S -1 11007-8 L C S -1 11007-9 Average %RSD S piked C oncentration (ng/m L) 2.00 2.00 2.00 20.0 20.0 20.0 49.8 49.8 49.8 PFBS C alculated C oncentration (ng/m L) 2.07 2.04 2.10 103% 1.5% 18.4 19.0 19.3 94.6% 2.4% 50.8 49.6 50.5 101% 1.2% % R ecoverv 103 102 105 92.0 95.2 96.5 102 99.6 101 S piked C oncentration (ng/m L) 2.00 2.00 2.00 20.0 20.0 20.0 49.8 49.8 49.8 PFHS C alculated C oncentration (ng/m L) 2.10 2.03 2.09 103% 2.0% 18.3 19.1 18.8 93.7% 2.1% 54.7 50.4 51.0 104% 4.7% % R ecovery 105 101 104 91.6 95.6 93.9 110 101 102 Page 18 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 10/12/11 External Calibration Lab ID L C S -1 11007-1 L C S -1 11007-2 L C S -1 11007-3 Average %RSD L C S -1 11007-4 L C S -1 11007-5 L C S -1 11007-6 Average %RSD L C S -1 11007-7 L C S -1 11007-8 L C S -1 11007-9 Average %RSD S piked C oncentration (ng/m L) PFOS (L in e a r+ B ranched sum m ed) C alculated Cone (Linear) (ng/m L) C alculated Cone (Branched) (ng/m L) 1.85 1.85 1.85 1.44 0.382 1.32 0.354 1.44 0.383 . 95.8% 4.8% 18.5 18.5 18.5 14.4 3.76 15.2 3.95 14.4 3.78 100% 3.1% 46.2 46.2 46.2 35.1 9.70 35.1 9.56 36.1 9.69 97.6% 1.4% % R ecoverv 98.5 90.5 98.5 98.2 104 98.3 97.0 96.7 99.1 ETS-8-044.0 Analyzed 10/20/11 External Calibration Lab ID S piked C oncentration (ng/m L) PFHS C alculated C oncentration (ng/m L) L C S -1 11020-1 2.00 0.174 L C S -1 11020-2 L C S -1 11020-3 . 2.00 2.00 0.172 0.170 Average %RSD 86.0% 0.99% L C S -1 11020-4 2.00 1.76 L C S -1 11020-5 2.00 1.65 L C S -1 11020-6 2.00 1.70 Average % RSD 85.1% 3.1% L C S -1 11020-7 20.0 17.8 L C S -1 11020-8 L C S -1 11020-9 20.0 20.0 16.8 17.4 Average %RSD 86.8% 2.8% "/R ecovery 86.8 86.1 85.1 87.8 82.6 84.8 89.0 84.2 87.1 Page 19 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 10/20/11 External Calibration Lab ID L C S -1 11020-1 L C S -1 11020-2 L C S -1 11020-3 Average % RSD L C S -1 11020-4 L C S -1 11020-5 L C S -1 11020-6 Average % RSD L C S -1 11020-7 L C S -1 11020-8 L C S -1 11020-9 Average %RSD S piked C oncentration (ng/m L) PFOS (L in e a r+ B ranched sum m ed) C alculated Cone (Linear) (ng/m L) C alculated Cone (Branched) (ng/m L) 0.185 0.185 0.185 1.85 1.85 1.85 18.5 18.5 18.5 0.113 0.0320 0.112 0.0299 0.0989 0.0255 74.1% 8.1% (1) 1.16 0.316 1.07 0.305 1.17 0.312 78.1% 4.2 % (1) 13.7 13.0 13.2 3.52 3.40 3.28 90.3% 2.7% %R ecovery 78.4 76.7 67.2 79.8 74.3 80.1 93.1 88.6 89.1 ETS-8-044.0 Analyzed 10/24/11 Internal Standard Calibration Lab ID L C S -1 11024-1 LCS-111024-2 LCS-111024-3 Average %RSD LC S -11 1 0 2 4 4 LCS-111024-5 LCS-111024-6 Average %RSD LCS-111024-7 LCS-111024-8 LCS-111024-9 Average %RSD PFOS (Linear + Branched) S piked C oncentration (ng/m L) C alculated C oncentration (ng/m L) % R ecoverv 0.184 0.184 0.184 0.166 0.166 0.167 90.3% 0.55% 90.0 90.1 90.9 1.84 1.84 1.84 1.72 1.72 1.65 92.3% 2.4% 93.7 93.5 89.7 9.22 9.22 9.22 8.89 8.01 8.91 93.3% 6.0% 96.4 86.9 96.7 (1) LCS average did not meet acceptance criteria of 100 20%. Page 20 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical LCS data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the LCS samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values. The analytical method uncertainty for PFOS when determined by ETS-12012.2 was 18%, however, since the average recovery of the low set of LCS samples analyzed on 10/12/11 had an average recovery of 74.1 %, the analytical uncertainty for this analysis will be expanded for PFOS to 26%. Table 8. Analytical Uncertainty. Analyte Standard Deviation PFBS 6.93 PFHS 9.05 PFOS NA (1) NA = Not Applicable Method Uncertainty 14% 18% , 26% 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 9. Field Matrix Spikes. S a m p lin g L o ca tio n 317L 220R, 220L, 328L 203L, 222R, 227L, 227R, 31 OR, 324L, 327R, 330L, 331S, 335R GRS04, 312R, 330R 328R T rip B la n k S ets 1 and 2 S p ike Level Low FMS High FM S Low FMS High FM S Low FMS High FMS Low FMS High FMS Low FMS High FM S Low FMS Mid FM S High FM S PFBS (ng /m L ) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 PFHS (ng/m L) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 PFOS (ng/m L) 1.00 10.0 10.0 100 100 1000 1000 5000 100 500 10.0 100 1000 FMS Recovery - ^ amP*e Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.) t ^ Spike Concentraron Page 21 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 9 Bata 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 220R (Table 11) - The recovery of the HS for PFOS was 61.9%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFOS to 38%. DAL GW 220L (Table 12) - The recovery of the HS for PFOS was 61.9%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFOS to 38%. DAL GW 222R (Table 13) - The recovery of the HS for PFBS, PFHS, and PFOS was 66.8%, 65.1%, and 56.9%, respectively. Since the LS for PFBS met acceptance criteria, the method uncertainty will not be adjusted for PFBS. Since the HS was the only appropriate spike level for PFHS and PFOS, the analytical uncertainty has been adjusted for PFHS to 35% and for PFOS to 43%. DAL GW 327R (Table 20) - The recovery of the HS for PFBS and PFHS was 65.4% and 69.1 %, respectively. Since the LS for PFBS and PFHS met acceptance criteria, the method uncertainty will not be adjusted. DAL GW 330L (Table 24) - The recovery of the HS for PFBS was 66.1%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFBS to 34%. DAL GW 331S (Table 25) - The recovery of the HS for PFBS was 68.5%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFBS to 32%. DAL GW 335R (Table 26) - The recovery of the HS for PFBS was 69.1%. Since this was the only appropriate spike level, the analytical uncertainty has been adjusted for PFBS to 31%. DAL GW GRS04 (Table 27) - The recovery of the LS for PFOS was 63.0%. Since this was the most appropriate spike level, the analytical uncertainty has been adjusted for PFOS to 37%. Trip Blank 1 (Table 28) - The recovery of the MS for PFOS was 68.0%. Trip Blank 2 (Table 29) - The recovery of the MS and HS for PFOS was 65.9% and 68.9%, respectively. Page 22 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 10. DAL GW 203L 110930 3M UNIS ID Description GLP10-01-02-22-001 GLP10-01-02-22-002 DAL GW203L 0110930 DALGW 203L DB 110930 GLP10-01-02-22-003 GLP10-01-02-22-004 DALGW 203L LS 110930 DALGW 203L HS 110930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 24.3 NA 22.0 NA 106 82.9 819 79.6 23.2 ng/mL 9.9% Concentration (ng/mL) %Recovery 148 NA 135 NA 230 88.5 952 81.1 142 ng/mL 9.2% Concentration (ng/mL) %Recovery 485 NA 470 NA 668 1190 NC 71.2 478 ng/mL 3.1% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/12/11. Table 11. DAL GW 220R110930 3M L IMS ID Description GLP10-01-02-22-005 DAL GW 220R 0110930 GLP10-01-02-22-006 DALGW 220R DB 110930 GLP10-01-02-22-007 DALGW 220R LS 110930 GLP10-01-02-22-008 DALG W 220RHS 110930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 4.69 4.83 12.7 NA NA 79.4 84.4 79.6 4.76 ng/mL 2.9% Concentration (ng/mL) %Recovery 17.7 NA 18.1 NA 25.3 74.0 99.0 81.1 17.9 ng/mL 2.2% Concentration (ng/mL) %Recovery 26.4 NA 28.4 NA 33.4 NC 89.3 61.9<1) 27.4 ng/mL 7.3% m NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 5x and analyzed 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFOS to 38%. Page 23 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 12. DAL GW 220L 110930 3 N IL IN IS ID Description GLP10-01 -02-22-009 GLP10-01-02-22-010 DAL GW 220L 0110930 D ALG W 220LDB 110930 GLP10-01-02-22-011 GLP10-01-02-22-012 DAL G W 220LLS 110930 DALGW 220L HS 110930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 7.91 NA 7.83 NA 15.7 78.3 86.3 78.4 7.87 ng/mL 1.0% Concentration (ng/mL) %Recovery ` 37.8 37.4 45.1 119 NA NA NC 81.4 37.6 ng/mL 1.1% Concentration (ng/mL) %Recovery 46.6 51.7 53.3 111 NA NA NC . 61.9<1) 49.2 ng/mL 10% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 5x and analyzed 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFOS to 38%. Table 13. DAL GW 222R 110930 3M UNIS ID Description GLP10-01-02-22-013 GLP10-01-02-22-014 GLP10-01-02-22-015 GLP10-01-02-22-016 DAL GW 222R 0110930 DAL GW222R DB 110930 DALGW 222R LS 110930 DALGW 222R HS 110930 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 62.4 NA 62.5 NA 149 86.6 730 66.8(1) 62.5 ng/mL 0.16% Concentration (ng/mL) %Recovery 427 431 532 1080 NA NA NC 6 5.1<1) 429 ng/mL 0.93% Concentration (ng/mL) %Recovery 510 NA 512 NA 625 NC 1080 5 6 .9 (1> 511 ng/mL 0 .3 9 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. The analytical uncertainty will be adjusted based on the recovery of the most appropriate spiking level. (2) The analytical uncertainty has been adjusted for PFHS to 35% and for PFOS to 43%. Page 24 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 14. DAL GW 227R110922 PFBS PFHS PFOS 3M U M S ID Description GLP10-01-02-22-017 DAL GW227R 0110922 GLP10-01-02-22-018 DALGW 227R DB 110922 GLP10-01-02-22-019 GLP10-01-02-22-020 DALGW 227RLS 110922. DALGW 227R HS 110922 Average Concentration (ng/mL) %RPD Concentration (ng/mL) YoRecovery 13.1 NA 13.7 NA 95.7 82.3 832 81.9 13.4 ng/mL 4.5% Concentration (ng/mL) YoRecovery 60.3 63.1 NA NA 147 85.3 955 89.3 61.7 ng/mL 4.5% Concentration (ng/mL) %Recovery 584 NA 572 NA 637 NC 1380 80.2 578 ng/mL 2.1% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 10/12/11. Table 15. DAL GW 227L 110922 3M LIM SID Description GLP10-01-02-22-021 GLP10-01-02-22-022 DAL GW227L 0110922 DALGW 227L DB 110922 GLP10-01-02-22-023 DALGW 227L LS 110922 GLP10-01-02-22-024 D ALG W 227LHS 110922 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 258 NA 254 NA 329 NC 966 71.0 256 ng/mL 1.6% Concentration (ng/mL) YoRecovery 68.7 NA 68.3 NA 147 78.5 989 92.1 68.5 ng/mL 0.58% Concentration (ng/mL) YoRecovery 482 NA 465 542 1300 NA NC 82.7 474 ng/mL 3.6% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 10/12/11. For PFBS, the HS was further diluted to 40x. Page 25 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater ' 3rd Quarter Sampling - 2011 Table 16. DAL GW 31OR 110928 3M LIM SID Description GLP10-01-02-22-025 DAL GW 31OR 0110928 GLP10-01 -02-22-026 DAL GW 31OR DB 110928 GLP10-01 -02-22-027 DAL GW 31OR LS 110928 GLP10-01-02-22-028 DAL GW 31OR HS 110928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 716 NA 743 NA 782 NC 1450 72.1 7 30ng/mL 3.7% Concentration (ng/mL) YoRecovery 318 322 395 .1080 NA NA NC 76.0 320 ng/mL 1.3% Concentration (ng/mL) YoRecovery 600 621 692 1360 NA NA NC 75.0 611 ng/mL 3.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 100x and analyzed on 10/12/11. Table 17. DAL GW 312R 110929 3M LIM SID Description GLP10-01 -02-22-029 DAL GW 312R 0110929 GLP10-01-02-22-030 GLP10-01-02-22-031 GLP10-01-02-22-032 DAL GW 312R DB 110929 DAL GW 312R LS 110929 DAL GW 312R HS 110929 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 1130 NA 1150 NA 1910 5260 77.0 82.4 1140 ng/mL 1.8%, Concentration (ng/mL) YoRecovery 829 833 1620 5150 NA NA 78.9 86.4 831 ng/mL 0.48%, Concentration (ng/mL) YoRecovery 1380 1500 2190 5990 NA NA 75.0 91.0 1440 ng/mL 8.3% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10Ox except HS was diluted 500x. Samples analyzed 10/12/11. Page 26 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 18. DAL GW 317L 110928 3M LIM S ID Description GLP10-01-02-22-033 GLP10-01-02-22-034 GLP10-01-02-22-035 DAL GW 317L 0110928 DAL GW 317L DB 110928 DAL GW 317L LS 110928 GLP10-01-02-22-036 DAL GW 317L HS 110928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery <0.0400 NA <0.0400 NA 0.813 81.3 8.37 83.7 <0.0400 ng/mL Concentration (ng/mL) %Recovery 0.103 0.0938 NA NA 0.907 80.9 8.65 85.5 0.0984 ng/mL 9.3% Concentration (ng/mL) XRecovery 0.214 NA 0.196 . NA 0.923 71.8 N A <1) NA (1) 0.205 ng/mL 8.8% N A = Not Applicable Results for PFBS and PFHS reported from 10/12/11 analysis. Results for PFOS reported from 10/24/11 internal standard analysis. (1) Sample was not analyzed since the spike level was not expected to be appropriate as compared to the sample concentration. Table 19. DAL GW 324L 110923 3M LIM SID Description GLP10-01-02-22-037 GLP10-01-02-22-038 GLP10-01-02-22-039 GLP10-01-02-22-040 DAL GW 324L 0110923 DALGW 324L DB 110923 DAL GW 324L LS 110923 DALGW 324L HS 110923 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 70.0 NA 70.0 NA 146 76.0 800 73.0 70.0 ng/mL 0.0% Concentration (ng/mL) %Recovery 82.9 NA 82.1 NA 163 80.5 846 76.4 82.5 ng/mL 0.97% Concentration (ng/mL) %Recovery 212 NA 210 NA 274 NC 999 78.9 211 ng/mL 0.95% N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/12/11. Page 27 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 20. DAL GW 327R 110928 3M LIM S ID Description GLP10-01-02-22-041 DAL GW 327R 0110928 GLP10-01 -02-22-042 DALGW 327R DB 110928 GLP10-01-02-22-043 DAL GW 327R LS 110928 GLP10-01-02-22-044 DALGW 327R HS 110928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 51.4 NA 51.7 NA 135 83.5 706 6 5.4(1) 51.6 ng/mL 0.58% Concentration (ng/mL) YoRecovery 125 NA 127 NA 214 88.0 817 69.1(1) 126 ng/mL 1.6% Concentration (ng/mL) YoRecovery 394 NA 399 NA 485 1140 NC 74.4 397 ng/mL 1.3% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. The analytical uncertainty will be adjusted based on the recovery of the most appropriate spiking level. Table 21. DAL GW 328R 110927 3M LIM SID Description GLP10-01-02-22-045 DAL GW 328R 0110927 GLP10-01-02-22-046 DALGW 328R DB 110927 GLP10-01-02-22-047 DALG W 328RLS 110927 GLP10-01-02-22-048 DALGW 328R HS 110927 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 27.7 NA 28.1 NA 106 78.1 380 70.4 27.9 ng/mL 1.4% Concentration (ng/mL) YoRecovery 57.2 NA 58.5 NA 137 79.2 426 73.6 57.9 ng/mL 2.2% Concentration (ng/mL) YoRecovery 178 NA 178 NA 249 71.5 545 73.5 178 ng/mL 0.28% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 20x and analyzed 10/12/11. Page 28 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 22. DAL GW 328L 110928 3M LIM SID Description GLP10-01 -02-22-049 GLP10-01-02-22-050 GLP10-0102-22051 GLP10 0 1 0 2 - 2 2 0 5 2 DAL GW 328L 0110928 DALGW 328L DB 110928 DAL GW 328LLS 110928 DALGW 328L HS 110928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 40.3 NA 40.3 NA 47.9 115 76.0 74.7 40.3 ng/mL 0.0% Concentration (ng/mL) %Recovery 18.3 18.5 26.7 98.2 NA NA 83.0 79.8 18.4 ng/mL 1.1% Concentration (ng/mL) VoRecovery 1.31 NA 1.26 NA 8.64 73.6 N A (1) N A (1) 1.29 ng/mL 3.9% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 10x and analyzed for PFBS and PFHS on 10/12/11. Results for PFOS reported on undiluted samples analyzed 10/24/11 by internal standard calibration. (1) Sample was not analyzed since the spike level was not expected to be appropriate as compared to the sample concentration. Table 23. DAL GW 330R 110928 3M LIM SID Description GLP10 0 1 0 2 -2 2 0 5 3 DAL GW 330R 0110928 GLP10 0 1 0 2 -2 2 0 5 4 DALGW 330R DB 110928 GLP1001-02-22055 GLP1001-02-22-056 DALG W 330RLS 110928 DALGW 330R HS 110928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) VoRecovery 2070 NA 2060 NA 2780 NC 5980 78.3 3070 ng/mL 0.48% Concentration (ng/mL) VoRecovery 197 NA 194 NA 958 4360 76.3 83.3 196 ng/mL 1.5% Concentration (ng/mL) VoRecovery 600 NA 586 NA 1430 5290 83.7 93.9 593 ng/mL 2.4% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 100x except HS was diluted 500x. Samples analyzed 10/12/11. Page 29 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 24. DAL GW 330L 110928 3M LIM SID Description GLP10-01-02-22-057 DAL GW 330L 0110928 GLP10-01-02-22-058 DALGW 330L DB 110928 GLP10-01-02-22-059 DAL GW 330L LS 110928 GLP10-01-02-22-060 DALGW 330L HS 110928 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 544 NA 515 NA 504 NC 1190 6 6 .1 (1) 530 ng/mL 5.5% m Concentration (ng/mL) YoRecovery 431 NA 437 NA 526 NC 1280 84.6 434 ng/mL f.4% Concentration (ng/mL) YoRecovery 168 NA 170 NA 254 85.0 1070 90.1 169 ng/mL 1.4Yo NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFBS to 34%. Table 25. DAL GW 331S 110929 3M LIM SID Description GLP10-01-02-22-061 DAL GW 331 SO 110929 GLP10-01-02-22-062 D ALG W 331SD B 110929 GLP10-01-02-22-063 D ALG W 331SLS 110929 GLP10-01-02-22-064 DAL GW 331S H S 110929 Average Concentration (ng/mL) YoRPD PFBS PFHS PFOS Concentration (ng/mL) YoRecovery 535 515 596 1210 NA NA NC 6 8 .5 <1) 525 ng/mL 3.8% Concentration (ng/mL) YoRecovery 336 NA . 326 403 NA NC 1090 75.9 331 ng/mL 3.0Yo Concentration (ng/mL) YoRecovery 517 NA 494 NA 598 1310 92.5 80.4 506 ng/mL 4.5% N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 50x and analyzed on 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFBS to 32%. Page 30 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 26. DAL GW 335R 110927 3M L IM S ID Description GLP10-01-02-22-065 DAL GW 335R 0110927 GLP10-01-02-22-066 DALGW 335R DB 110927 GLP10-01-02-22-067 DAL GW 335RLS 110927 GLP10-01-02-22-068 DALGW 335R HS 110927 Average Concentration (ng/mL) %RPD PFBS PFHS PFOS Concentration (ng/mL) %Recovery 735 744 748 1430 NA NA NC 6 9.1(1) 1080 ng/mL 3.7% Concentration (ng/mL) %Recovery 1430 1400 n a (3) 2180 NA NA n a (3) 76.5 1420 ng/mL 2.1% Concentration (ng/mL) YoRecovery 3400 3290 n a (3) 4170 NA NA N A (3> NC 3350 ng/mL 3 .3 % {A) NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. . Samples diluted 50x for PFBS and analyzed on 10/12/11. Samples were diluted 500x for PFHS and PFOS and analyzed on 10/20/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for PFBS to 3 1 % . (3) Sample was not analyzed since the spike level was not expected to be appropriate as compared to the sample concentration. (4) No appropriate spike level was available to assess sample recovery for PFOS. Page 31 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 27. DAL GW GRS04 110930 PFBS PFHS PFOS 3M UNIS ID Description Concentration (ng/mL) %Recovery GLP10-01-02-22-069 GLP10-01-02-22-070 DAL GW GRS04 0 110930 DAL GW GRS04 DB 110930 1720 1660 NA NA GLP10-01-02-22-071 DAL GW GRS04LS 110930 2460 77.0 GLP10-01-02-22-072 DAL GW GRS04 HS 110930 5530 76.8 Average Concentration (ng/mL) %RPD 1690 ng/mL 3.6% Concentration (ng/mL) %Recovery 6220 5890 N A (1) 11800 NA NA N A (1) 115 6060 ng/mL 5.5% Concentration (ng/mL) VoRecovery 1320 1340 NA NA 1960 63.0 (2) 5330 80.0 1330 ng/mL 1.5% p> NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Samples diluted 100x for PFBS and PFOS, except FIS was diluted 500x, and analyzed on 10/12/11. Samples diluted 500x for PFFIS and analyzed on 10/20/11. (1) Sample was not analyzed since the spike level was not expected to be appropriate as compared to the sample concentration. (2) Field matrix spike did not meet method acceptance criteria of 100% 30%. The analytical uncertainty will be adjusted based on the recovery of the most appropriate spiking level. (3) The analytical uncertainty has been adjusted for PFOS to 37%. Table 28. Trip Blank 1 3M UNIS ID GLP10-01-02-22-074 GLP10-01-02-22-075 GLP10-01-02-22-076 GLP10-01 -02-22-077 Description DAL GW TRIP01 0 DAL GW TRIP01 LS DAL GW TRIP01 MS DAL GWTRIP01 HS PFBS PFHS PFOS Concentration (ng/mL) <0.0400 8.18 81.1 867 %Recovery NA 81.8 81.1 86.7 Concentration (ng/mL) <0.0250 8.35 82.3 869 %Recovery NA 83.5 82.3 86.9 Concentration (ng/mL) <0.183 7.98 68.0 727 VoRecovery NA 79.8 6 8 .0 (1) 72.7 N A = Not Applicable FM S Mid diluted 10x, FMS High diluted 100x, and analyzed on 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. Page 32 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Table 29. Trip Blank 2 3M LIM S ID GLP10-01-02-22-078 GLP10-01-02-22-079 GLP10-01-02-22-080 GLP10-01-02-22-081 Description DAL GW TRIP02 0 DAL GW TRIP02 LS DAL GW TRIP02 MS DAL GW TRIP02 HS PFBS PFHS PFOS Concentration (ng/mL) <0.0400 8.09 79.1 838 %Recovery NA 80.9 79.1 83.8 Concentration (rig/mL) <0.0250 8.27 80.1 842 %Recovery NA 82.7 80.1 84.2 Concentration (ng/mL) <0.183 7.94 65.9 689 %Recovery NA 79.4 6 5 .9 (1) 6 8 .9 (1) NA = Not Applicable ' FM S Mid diluted 10x, FMS High diluted 100x, and analyzed on 10/12/11. (1) Field matrix spike did not meet method acceptance criteria of 100% 30%. Table 30. Equipment Rinseate Blanks 3M LIM SID GLP10-01 -02-22-082 GLP10-01-02-22-083 Description DALGW 203L RB 110930 DALGW 220L RB 110930 Sample was analyzed on 10/12/11. PFBS PFHS PFOS Concentration (ng/mL) <0.0400 <0.0400 Concentration (ng/mL) <0.0250 <0.0250 Concentration (ng/mL) <0.232 <0.232 Page 33 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 10 Conclusion Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. 11 ;)fa/Sample Retention All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Attachments Attachment A: Protocol Amendment 22 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 34 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator Page 35 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Attachment A: Protocol A mendment Page 36 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Analytical Protocol: GLP10-01-01 Amendment 22 Study Title Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program PROTOCOL AMENDMENT NO. 22 Amendment Date: September 14, 2011 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-01 Sampling Event Decatur 3rdQuarter Groundwater Sampling Page 1 of 7 Page 37 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 . Analytical Protocol: GLP10-01-01 Amendment 22 This amendment modifies the following portion of protocol: "Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. A mend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples at Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOA (GLP10-01-01). The anticipated sample collection will occur around the timeframe of the week of September 19. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-01-22 and reported as interim report GLP10-01-01-122, (reflecting study GLP10-0101 and amendment -22). R eason: 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 38 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Analytical Protocol: GLP10-01-0f Amendment 22 Amendment Approval Page 3 of 7 Page 39 of 99 G LP10-01-02; Interim Report 22 Analysis of P FBS, PFHS, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Analytical Protocol: G LP10-01-0f Amendment 22 3 M Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Cleston Lange, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions September 14, 2011 Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 22 - Decatur 3rd Quarter 2011 Groundwater Sampling 1 General Project Information Contacts Lab Request Number Six D igit D e p a rtm e n t N u m b e r Project Schedule/Test Dates 3M Sponsor R epresentative Gary Hohenstein 3M EHS Operations 3M Building 224-5W -03 Saint Paul, MN 55144-1000 Phone:(651)737-3570 aa hohenstein@ m m m .com 3M Environm ental Laboratory Managem ent W illiam K. Reagen 3M EHS Opns, Environmental Laboratory 2 6 0 -5 N -1 7 651 733-9739 w krea aen @ m m m .c om Principal Analytical Investigator Cleston Lange . 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cc lana e@ m m m .com . ' Sam pling Coordinator Timothy Frinak W eston Solutions Timothv.frinak@westonsolutions.com Phone: (334)-332-9123 G L P 1 0-01-01-22 Dept #530711, Project #0022674449 Sampling scheduled for the week of Septem ber 19, 2011 . All verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 7 Page 40 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Analytical Protocol: GLP10-01-01 Amendment 22 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze groundwater samples collected from seventeen groundwater wells for Perfluorooctanoic Acid (PFOA). Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples from Decatur, AL will be collected by Weston Solutions personnel the week of September 19, 2011. The 3M Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that results for PFOA are of a known precision and accuracy. The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-01-22. 3 Project Schedule _________ Sample collection bottles will be prepared by the 3M Environmental Laboratory. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival by Friday, September 16, 2011. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ Weston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFOA. . A total of eighteen 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. Two sets of trip blank spikes consisting of reagent-grade water, as well as two additional bottles to be used for the preparation of equipment rinseate blanks, will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. Results from GLP10-01-01-02, GLP10-01-01-09, and GLP10-01-01-17 were used to determine the field matrix spike levels for GLP10-01-01-22 listed in Table 1. Table 1. Sampling Locations and Field Matrix Spike levels. Well No. 317L 220R, 220L, 328L 203L, 222R, 227R, 227L, 310R, 324L, 327R, 330L, and 331S GRS04, 312R, 330R, and 335S 328R Trip Blank Sets 1 and 2 Sample Level Low High Low High Low High Low High Low High Low Mid High Spike Cone. (ng/mL) 1 10 10 100 100 1000 1000 5000 100 500 10 100 1000 Page 5 of 7 Page 41 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Analytical Protocol: GLP10-1-0 Amendment 22 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, GLP10-01-01-09, and GLP1001-01-17), samples GLP10-01-01-22 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 RPLCElectrospray-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 a reference material containing both linear and branched isomers of PFOA. Field matrix spikes will be prepared with a solution prepared with a reference material containing predominantly linear PFOA. Laboratory control samples (LCS) of linear and branched PFOA will be prepared at three concentration levels. 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 42 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Analytical Protocol: GLP10-01-0i Amendment 22 From: Frihak, Timothy R. . Sent: Monday, September 12, 2011 10:48 AM To: Young, Charles T. Cc: Smith, Martin; Johnson, Kevin A.; Missildine, Bret C. Subject: Bottles - GW sampling Decatur, AL , Charlie, The 3,d quarter GW sampling w ill begin next Monday at Decatur. The sampling fo r FCs w ill be inside this time and include the following: 203L 220R 2201 222R 227R 227L 310R 317L 324L 328R 328L 330R 330L 335R GRS04 RW312R RW327R RW331S ' . We will also need M illi-Q w ater and bottles for tw o (2) rinseate blank samples. Page 7 of 7 Page 43 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Attachm ent B: R epresentative S am ple C hrom atogram s and Calibration C urve(s) Page 44 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Printing Date: Wednesday, December 07, 2011 Page 45 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Area, counts Printing Date: Wednesday, December 07, 2011 Page 46 of 99 *** Buster J2930203 GLP10-01 -02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Data printed by STW Printing Time: 10:54:50 AM Printing Date: Wednesday, December 07, 2011 Page 47 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Printing Date: Wednesday, December 07, 2011 Page 48 of 99 '*** Buster J2930203 Printing Time: 11:12:52 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 1 of 5 Page 49 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Printing Date: Wednesday, December 07, 2011 Page 50 of 99 ** Buster J2930203 Data printed by STW Printing Time: 11:12:52 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 3 of 5 Page 51 of 99 * Buster J2930203 Printing Time: 11:12:52 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 4 of 5 Page 52 of 99 *** Buster J2930203 Data printed by STW Printing Time: 11:12:52 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 53 of 99 ** Buster J2930203 Printing Time: 11:08:47 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 54 of 99 Buster J2930203 Data printed by STW Printing Time: 11:08:47 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: bl!1012a.dab Page 55 of 99 *** Buster J2930203 . GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Printing Date: Wednesday, December 07, 2011 Page 56 of 99 Buster J2930203 ( Sample Name: *b111012a097* Semple ID: *GLP1(H>1-02-22-029* Fie: b111012a.wifr Peak Name: *PFOS* Masses): '499.0/99.0 emu.499.0/60.0 amu,499.0/130.0 emu* Comment: "DAL GW 312R0* Annotation: ** Sample Index: 97 Sample Type: Unknown Concentration N/A Calculated Co c: 724. 4.6*5 Acq. Date: 10/13/201 Acq. Tine: 7:15:33 P 4,4*5 Modified: RT Window: Expected RT: Use Relative tT: Yes 30.0 15.3 No min Int. Type: Manual Retention Tim : 15.2 Area : 3096009 CO Height: 4.27e-*005 Start Time: 14.6 End Time: 15.3 42e5 4.0e5 3.8*5 3.6*5 3.4*5 32*5 3.0*5 2.8e5 % 2.6e5 2.4e5 IE 22e5 15.35 15.17 1.0e5 1.6*5 1.4*5 12*5 1.0eS 8.0e4 6.0*4 4.0*4 2.0*4- 0.013.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 ( Sample Name: *b111012a117* Sample ID: *GLP1CW)1-02-22-041* File: "b111012a.wtfT Peak Name: *PFOS* Mass(ee): *499.0/99.0 amu.499.0/80.0 amu,499.0/130.0 amu* Comment: *DAL GW 327R0* Annotation: " Sanple Index: 117 Sample Type: Unknown Concentration : Calculated Cone: n /a 203. ng/mL 2e5- Acq. Date: 10/14/2011 2:16:12 AM Modified: RT Window: Yes 30.0 2.6*5 Expected RT: 15.3 Use Relative RT: Wo 2,4*5 15.37 1520 Int. Type: Manual Retention Time: 15.2 min Area: 1771021 counts Height: 2.51**005 cp* Start Time: 14.9 min End Time: 15.3 ain 2.2*5 13*5 a 1.6*5 1.4*5 12*5 1.0*5 6.0*4 6.0*4 4.0*4 2.0*4 13.5 14.0 Data printed by STW Printing Time: 11:08:47 AM Printing Date: Wednesday, December 07, 2011 143 15.0 Time. 16.0 16.5 17.0 17.5 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 4 of 5 Page 57 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Printing Time: 11:08:47 AM Printing Date: Wednesday December 07 2011 Page 58 of 99 Buster J2930203 Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 1 of 13 Page 59 of 99 Buster J2930203 Data printed by STW Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 2 of 13 Page 60 of 99 ** Buster J2930203 Printing Time: 11:02:09 AM "Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: b!11012a.dab Page 3 of 13 Page 61 of 99 Buster J2930203 Data printed by STW Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 62 of 99 * Buster J2930203 Data printed by STW Printing Time: 11:02:09 AM Printing Date: Wednesday,,December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 5 of 13 Page 63 of 99 Buster J2930203 Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Batch Name: bl11012a.dab Page 64 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name bll1012a.dab Printing Time: 11:02:09 AM Printing Date: Wednesday, December- 07 2011 Page 65 of 99 Buster J2930203 Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 8 of 13 Page 66 of 99 Buster J2930203 Data printed by STW Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: b!11012a.dab Page 9 of 13 Page 67 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07 2011 Page 68 of 99 Buster J2930203 Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011. GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Batch Name: bl11012a.dab Page 69 of 99 * Buster J2930203 Data printed by STW Printing Time: 11:02:09 AM Printing Date: Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Batch Name: blll012a.dab Page 12 of 13 Page 70 of 99 *** Buster J2930203 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Batch Name: b!11012a.dab Printing Time: 11:02:09 AM Printing Date Wednesday. December 07 2011 Page 71 of 99 *ETS-Kirk G LP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFO S in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll020a linear.rdb Page 72 of 99 *ETS-Kirk . G LP10-01 -02; Interim Report 22 Analysis of PFBS, P FH S , and P FO S in Groundwater 3rd Quarter Sampling - 2011 . Results Name: klll020a branched.rdb Wednesday, December 07, 2011 '' Page 73 of 99 *ETS-Kirk GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Results Name: klll020a.rdb Wednesday, December 07, 2011 Page 74 of 99 *ETS-Kirk G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S , and P FO S in Groundwater 3rd Quarter Sampling - 2011 ' Results Name: klll020a linear.rdb Data printed by STW `_ Printing Time: 11:23:25 AM Page 1 of 2 Page 75 of 99 *ETS-Kirk G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 . Results Name: klll020a linear.rdb Data printed by STW Printing Time: 11:23:25 AM Page 2 of 2 Page 76 of 99 ETS-Kirk Data printed by STW Wednesday, December 07, 2011 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S , and P FO S in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll020a branched.rdb Page 1 of 2 Page 77 of 99 G LP10-01-02; Interim Report 22 Analysis of PFBS, P FH S, and P FO S in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll020a branched.rdb Wednesday, December 07, 2011 Page 78 of 99 *ETS-Kirk GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll020a.rdb Printing Time: 11:19:20 AM .- Page 79 of 99 *ETS-Kirk GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 . Results Name: klll020a.rdb Printing Time: 11:19:20 AM . . Page 80 of 99 *ETS-Kirk GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll024a.rdb Analyte Area / IS Area Wednesday, December 07> 2011 ' Page 81 of 99 *ETS-Kirk GLP10-01 -02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Results Name: klll024a.rdb Data printed by STW Wednesday, December 07, 2011 Page 1 of 4 Page 82 of 99 *ETS-Kirk GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 Results Name: k!11024a.rdb Data printed by STW Wednesday, December 07, 2011 Page 2 of 4 Page 83 of 99 *ETS-Kirk I Sample Name: >111024a02S* Sample ID: *11 005-223' File: M11024a.wW Peak Name: *PFOS' Masses): `499.000/99.000 Da,499.000/80.000 Da,499.001 Comment: "Method Blank* Annotation: ** Sample Index: 25 Sample Type: Unknown Concentration: N/A Calculated Cone: <0 Acq. Date: 10/24/2011 Acq. Time: 10:33:38 PH Proc. Algorithm: Specify f Noise Percentage: 50 Peak-Split. Factor: Report Largest Peak: Min. Peak Height: Min. Peak Width: Smoothing Width: RT Expected RT: Use Relative RT: 4 Ye: 0.< 0.< 0 Height: Start Ti End Tim Manual 16.1 min 7215 counts 1.Q7e-*003 cps 15.9 min 16.2 min ISample Name: *k111024a030' Sample ID: ` LCS-111024-4* File: *k111024a.wtr Peak Name: *PFOS` Masses): `499.000/99.000 Da.499.000/80.000 Da,499.000/130.000 Da' Comment *2ppb CCS* Annotation: " Calculated Cone: 1.72 r Acq. Date: 10/25/2011 Acq. Time: 12:20:30 AM Modified: Yes Proc. Algorithm: Specify Para tJoise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 4 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing width: 30.0 16.2 Height: Start Tine: End Time: Data printed by STW Wednesday, December 07, 2011 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll024a.rdb (Sample Name: *k111024a027* Sample 10: 'LCS-111024-1' Peak Name: *PFOS' Mass(es): '499.00V99.000 Da,499.000 Comment *0.2pp6 IC S ' Annotation: ** Sample Index: Sample Type: "" oc ' ration: 0.184 r Calculated Cone: 0.166 r Acq. Date: 10/24/2011 Acq. Time: 11:16:23 PM Modified: Yes Proc. Algorithm: Specify Pari Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 4 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 s< Expected RT: 16.2 mi Use Relative RT: Yes Int. Type: Manual Sample Name: >1110243033' Sample ID: 'LCS-111024-7* Peak Name: *PFOS' Mass(es): *499.000/99.000 Da,49.......... Comment *10ppb ICS* Annotation: " Sample Index: 33 9.22 : 8.89 10/25/2011 1:24:36 AM Base. Sub. Window: Peak-Split. Factoi Report Largest Pei Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 Page 3 of 4 Page 84 of 99 *ETS-Kirk I Sample Name: *k111024a040' Sample ID: 'GLP10-01-02-22-033' Fde:*k111024a.wfr Peak Name: *PFOS' Masses): '499.000/99.000 Da,499.000/80.000 Da,499.000/130.000 D Comment:"DALGW31710* Annotation:" Sample Index: 10 Sample Type: Unknown Concentration: N/A culated Cone: 0.214 ng/raL . Date: 10/25/2011 Acq. Tice: 3:54:12 AH Modified: Yes Proc. Algorithm: Specify Parameter loise Percentage: 50 lase. Sub. Window: 1.00 rain 'eak-Split. Factor: 4 Report Largest Peak: Yes n. Peak Height: 0.00 cps n. Peak Width: 0.00 sec Smoothing width: RT Window: 30.0 Expected RT: Use Relative RT: 1.2*4- 256810 coi 1. BSe+004 15.7 1.1*4- 1.0*4 I 9000.0 8000.0 7000.0 8000.0 5000.0 4000.0 3000.0 2000.0 1000.0- iiM f f lW iit iiiin rii.iim GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Results Name: klll024a.rdb I Sample Name: >1110248044' Sample ID: 'GIP10-01-02-22-049* F4e:M11024a.wtfT Peak Name: 'PFOS' Mass(es): '499.00099.000 Da,499.000/80.000 Da.499.000/130.000 Da* Comment 'DAL GW 328L 0' Annotation: " Sample Index: 44 Sample Type: Unknown Concentration: M/A 7.0e4- Calculated Cone: 1.31 ng/raL Acq. Date: 10/25/2011 Acq. Tine: 5:19:44 AM 6.5*4- Yes Proc. Algorithms: Specify Parr Noise Percentage: SO Base. Sub. Window: 1.00 Peak-Split. Factor: 4 Report Largest Peak Height: 0.00 cps Min. Peak Width: Smoothing width: RT Window: Expected RT: Use Relative RT: Height: Start Tj End Time 7.03e+004 cps Data printed by STW Wednesday, December 07, 2011 Page 4 of 4 Page 85 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Attachm ent C: A nalytical M etho d(s) Page 86 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 3M Environmental Laboratory Method Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q y ^ fo '~} Approved By: --------------------William K. Reagen, Laboratory Manager V* > 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 87 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), 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. ETS-8-044.0 Page 2 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 88 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected in duplicate at the same time from the same location as the sample. The FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sample (LCS) An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples. 3.9 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.10 Limit of Quantitation (LOQ) The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent. The upper limit of quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. ETS-8-044.0 Page 3 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 89 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus. 3.12 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material. 3.13 Stock Standard Solution (SSS) A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound. 3.14 Surrogate A compound similar in chemical composition and behavior to the target analyte(s), but is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality control samples. Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. 3.15 Working Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. 4 Warnings and Cautions 4.1 Health and Safety The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks. ETS-8-044.0 Page 4 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 90 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 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. The previous information is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 91 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: Analyte Transition Monitored PFBA 213 -> 169 PFPeA 263 ->219 PFHA 313-> 26 9 and 313 ->119 PFHpA 363 -> 319, 363 -> 169 and 363 -> 119 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 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 - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (P FP eA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (PFHA - C6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc PerfluorooctanoicAcid (P F O A -C 8 acid); 3M Perfiuorononanoic Acid (P F N A -C 9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (PFDA - C10 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFUnA-C11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P FD oA - 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 92 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 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 fo r 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 499 PFOS (K +)salt correction factor = -- = 0.9275 538 10 mg C8F17S03`K+with purity 90% = 8.35mg C8F17S03_ (10 mg*0.90*0.9275=8.35 mg) 5 pg/mL (5000 ng/mL) mixed working standard--Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/mL mixed working standard--Add 1,25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/mL mixed standard--Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage Conditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 93 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C o n c e n tra tio n o f WS, ng/m L 125 125 125 125 250 250 250 250 5000 5000 5000 V olum e o f WS, pL 10 15 20 30 20 50 100 200 25 50 100 Final Volume o f Calibration Standard (mL o f ASTM Type 1 Water, o r oth e r suitable water) 50 50 50 50 50 50 50 50 50 50 50 Final Concentration o f Calibration Standard, ng/mL (ppb) in ASTM Type 1 Water, o r other suitable water 0.025 0.0375 0.050 0.075 0.100 0.250 0.500 1.00 2.50 5.00 10.0 8 Sample Handling 8.1 Water Sample Preparation This method is applicable to clean water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a, sample aliquot, or filtered. Thoroughly mix sample before removing an aliquot and placing in a labeled plastic autovial. Plastic is preferred over the use of glass autovials, to prevent the possibly of fluorochemical sticking to the glass. Dilute sample, if necessary, with ASTM Type I, HPLC water, or other suitable water. Prepare method QC samples and multiple method blanks and aliquot into labeled plastic autovials. Prepare at least five method blanks. 9 Sample Analysis - LC/MS/MS Analyze the standard curve prior to each set of samples. The standard curve may be plotted using a linear fit, weighted 1/x or unweighted, or by quadratic fil (y = ax2 + bx + c), weighted 1/x or unweighted, using suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not meet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may ETS-8-044.0 Page 8 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 94 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS In Groundwater 3rd Quarter Sampling - 2011 be within 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed. 10 Quality Control 10.1 Data Quality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end of the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. 10.3 Sample Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation of the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-prepared as appropriate. ETS-8-044.0 Page 9 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 95 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the followirig 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. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 96 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Demonstration o f Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary of Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 97 of 99 Attachm ent D: D eviation(s) GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Page 98 of 99 GLP10-01-02; Interim Report 22 Analysis of PFBS, PFHS, and PFOS in Groundwater 3rd Quarter Sampling - 2011 Record of Deviation/Nonconformance I. Identification Study / Project No. GLP10-01-02-22 Date(s) of Occurrence: b111012a, k111020a Document Number: ETS-8-044.0 Deviation type SOP (Check one) Protocol Equipment Procedure 0 Method GPO Other: il. Description (attach extra pages as needed) Method Requirements: 1. S ystem Suitability a re a counts with R S D < 5 % (section 12 .1). 2. FM S recovery within 3 0 % (section 10.6). 3. LCS recovery within 2 0% (section 10.5). 4 . C C V recovery within 2 5 % (section 1 2 .2 ).___________________ Actual procedure/process: 1. T h e system suitability a re a count R S D for P F O S w a s 7 .5 % fo r `b 1 1 1 0 1 2 a P F O S su m ' and 9 .1 % for k 1 110 2 0 a P FO S sum'. 2. The following sampling locations had FM S sam ples outside m ethod acceptance criteria for run b 1 11 0 1 2a: DAL G W 22 0R for P FO S HS (61.9% ), DAL G W 220L for P FO S HS (61.9% ), DAL G W 222R for PFB S HS (66.8% ), PFH S HS (65.1% ), and P FO S HS (56.9% ), DAL G W 327R for PFBS HS (65.4% ) and P FH S HS (6 9.1% ), DAL G W 33 0L for P FB S (6 6.1% ), DAL G W 3 3 1 S for PFB S (6 8.5% ), DAL G W 33 5R for PFB S (69.1% ), DAL G W G R S 04 for P F O S LS (6 3.0% ), TR IP 01 for P F O S MS (6 8.0% ), and T R IP 0 2 for P FO S MS (65.9% ) and HS (68.9% ). 3. The 0.2ppb LCSs had an average recovery of 74.1 % and the 2ppb LCSs had an average recovery of 7 8 .1 % fo r P F O S in run b 1 1 1 0 2 0 a (sum m ed ). 4. Five C C V s fo r P F O S (s u m m ed ) in run b 1 1 1 0 1 2 a had reco veries g reate r than 1 2 5 % (1 2 7 % - 1 3 5 % ).______ III. Actions Takenj ______________________________(s u c h a s a m e n d m e n t is s u e d , S O P re v is io n , e tc .)_____________________________ Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1. T h e system suitability results for P F O S will b e noted in th e final report. 2. S am plin g locations with F M S reco veries outside m eth od a c cep tan ce criteria will be flagg ed in the report and the analytical uncertainty adjusted for the sam ples w here the non-com pliant FM S was the most appropriate spiking concentration. Th e trip blanks w ere also relatively low, especially for P F O S , which m ay explain w hy several sam ple FM S s are low. 3. T h e no n-com pliant L C S s will b e flagg ed in th e final report. 4 . T h e ac curacy o f the C C V s fo r P F O S increased throughout th e run, which suggests in strum ent drift. H ow ever, sin ce the sa m p le concentrations are sim ilar to th at o f previous studies perform ed in th e p ast for _________ this sa m p le set, sa m p les w e re not re-an aly zed .___________________________________________________________ Actions: Halting of Work Client Notification Work Recall Withholding of Report 0 Other: D eviations will be noted in final report. Project Lead/PAI Approval: / fj Study Director (if GLP): j f f i ) K A , j ^ Sponsor Approval (for GLP protocol deviations): NA Technical Reviewer (optional): NA DaW - 7 h i D a te: l & Date: NA Date: NA 7^ Laboratory Department Manager Approval: Date: ^ --------- " " ______________________________________ IV. Authorization to Resume Work W h ere haltin g o f w o rk occurred, resu m p tion o f w o rk m u s t first b e ap p ro v e d b y L ab o rato ry M a n a g e m e n t Laboratory Department Manager Approval: NA Date: NA Deviation No. (assigned by Study Director or Team Leader at the end of study or project) ETS-4-008.7 Page 1 of 1 Documentation of Deviations and Control of Nonconforming Testing Page 99 of 99