Document mb2ondrLLVG2eokE7ZNYoE2YO

GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 GLP10-01-02: Interim Report 18 - Analysis of PFBS. PFHS. and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIAl located in Decatur. AL in June 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 Jaisim ha Kesari P.E., DEE W eston Solutions, Inc. 1400 W eston Way W est Chester, PA 19380 Phone: 610-701-3761 Author Susan W olf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 St. Paul, MN 55144 Project Identification G LP 10-01 -0 2-18 Total Number of Pages 113 The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052.01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. Testing Cert #2052.01 Page 1 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 This page has been reserved for specific country requirements. Page 2 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 GLP Compliance Statement Report Title: Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) in Decatur, AL in June 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 Date Page 3 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Q uality A ssurance Statement Report Title: Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Former Sludge Incorporation Area (FSIA) in Decatur, AL in June 2011 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 8/18/11 -8 /1 9 /1 1 Phase Data / Report Date Reported to Testing Facility Management Study Director 8/25/11 8/25/11 Date Page 4 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 Table of Contents GLP Compliance Statem ent.................................................................. !............................................. 3 Quality Assurance Statem ent.............................................................................................................. 4 Table of Contents................................................................................................................................. 5 List of Tables......................................................................................................................................... 6 1 Study Inform ation.............................................................. 8 2 Summary.........................................................................................................................................9 3 Introduction....................................................................................................................................11 4 Test & Control Substances...........................................................................................................11 5 Reference Substances..................................................................................................................12 6 Test System ..................................................................................................................................13 7 Method Summary..........................................................................................................................13 7.1 Methods.........................................................................................................................13 7.2 Sample Collection......................................................................................................... 13 7.3 Sample Preparation...................................................................................................... 13 7.4 Analysis.........................................................................................................................14 8 Analytical Results..........................................................................................................................15 8.1 Calibration......................................................................................................................15 8.2 System Suitability.......................................................................................................... 15 8.3 Limit of Quantitation (LOQ)........................................................................................... 16 8.4 Continuing Calibration................................................................................................... 16 8.5 Blanks............................................................................................................................16 8.6 Lab Control Spikes (LCSs)..................................... 16 8.7 .Analytical Method Uncertainty......................................................................................20 8.9 Field Matrix Spikes (FM S)..............................................................................................21 9 Data Summary and Discussion................................................................................................... 21 Page 5 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 10 Conclusion.....................................................................................................................................39 11 Data/Sample Retention............................................................................................................... 39 12 Attachm ents..................................................................................................................................39 13 Signatures.................................................................................................................................... 40 List of Tables Table 1. Summarized PFBS, PFHS, and PFOS Results (FSIA Groundwater, June 2011)........ 10 Table 2. Sample Description Key Code....................................................................................... 13 Table 3. Instrument Parameters................................................................................................... 14 Table 4. Liquid Chromatography Conditions................................................................................ 14 Tables. Mass Transitions.............................................................................................................15 Table 6. Limit of Quantitation (LOQ).............................................................................................16 Table 7. Laboratory Control Spike Recovery................................................................................18 Table 8. Analytical Uncertainty..................................................................................................... 20 Table 9. Field Matrix Spike Levels................................................................................................21 Table 10. DAL GW 130R 110630 ............................................................................................. 23 Table 11. DAL GW 130S 110630...............................................................................................23 Table 12. DAL GW 130L 110630............................................................................................... 24 Table 13. DAL GW 131R 110622 ............................................................................................. 24 Table 14. DAL GW 131S 110622............................................................................................... 25 Table 15. DAL GW 131L 110622.............................................................................................. 25 Table 16. DAL GW 133R 116030.............................................................................................. 26 Table 17. DAL GW 133S 110630............................................................................................... 26 Table 18. D ALG W 133L110630............................................................................................... 27 Table 19. DAL GW 134R 110628 ............................................................................................. 27 Table 20. DALGW 134S 110628............................................................................................... 28 Table 21. DAL GW 134L110628............................................................................................... 28 Page 6 of 113 Table 22. DAL GW 135R 110628... Table 23. DAL GW 135S 110628.... Table24. DAL GW 135L110628.... Table 25. DAL GW 136S 110630.... Table 26. DAL GW 136L110630.... Table 27. DAL GW 137S 110624.... Table 28. DAL GW 137L 110624.... Table 29. DAL GW 138S 110630.... T able30. D ALG W 138L110630.... Table 31. DAL GW 138R 110630 ... Table 32. DAL GW CW26C 110622 Table 33. DAL GW CW 26L110622. Table 34. DAL GW 140R 110622 .... Table 35. DAL GW 141R 110630.... Table 36. DAL GW 142R 110622.... Table 37. DAL GW 143R 110622 .... Table 38. DAL GW 144S 110628.... Table 39. Trip Blank 1 .................... Table 40. Trip Blank 2 .................... Table 41. Rinseate Blanks............. GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 29 29 30 30 31 31 32 32 33 33 34 34 35 35 36 36 .37 .37 ,38 .38 Page 7 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone:(610)701-3761 Fax: (610) 701-7401 j.kesari@ w estonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 St. Paul, MN 55144 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanae@mmm.com): phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow, Analyst Kevin Eich, Analyst Kelly Ukes, Analyst Jonathan Steege, Analyst Study Dates Study Initiation: March 8,2010 Interim 18 Experimental Termination: August 3,2010 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 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -Ju n e 2011 The 3M Environmental Laboratory received groundwater samples from wells located at the Former Sludge Incorporation Area (FSIA) in Decatur, AL, representing twenty-eight different sampling locations. A total of one hundred fifty-four sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each sampling location. Samples also included at least two field matrix spike (FMS) samples for each location, two trip blank sets containing Milli-QTM water and appropriate trip blank spikes, and two equipment rinseate blanks. The equipment rinseate blanks did not have FMS samples prepared for determination of PFBS, PFHS, and PFOS recovery. The groundwater samples, trip blanks and two equipment rinseate blanks associated with GLP10-0102-18 were received from Weston personnel on July 8, 2011. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01-02-18. Many of the groundwater samples required dilution to attain PFBS, PFHS, and/or PFOS concentrations within the range of the curve, in some instances up to 100-fold dilution were required. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate from DAL GW 130L and the trip blank sample were below the lower limit of quantitation (LLOQ) for PFBS, PFHS, and PFOS, indicating adequate control of sample contamination during shipping and sample collections. The equipment rinseate from sample DAL GW 133S for PFOS was just above the LLOQ at 0.0478 ng/mL, while PFBS and PFHS were below the lower limit of quantitation (LLOQ). The PFBS concentration results for all groundwater samples ranged from 0.0391 ng/mL to 74.3 ng/mL. The PFHS concentration results for all groundwater samples ranged from 0.0806 ng/mL to 844 ng/mL. The PFOS concentration results for all groundwater samples ranged from 0.483 ng/mL to 1510 ng/mL. The analytical method uncertainties associated with the reported results are: PFBS + 11%, PFHS + 14% and PFOS + 36%. For some samples, the method uncertainty was expanded for PFOS. Page 9 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 1. Summarized PFBS, PFHS, and PFOS Results (FSIA Groundwater, June 2011). Sampling Location DAL G W 130R 110630 DAL G W 130S 110630 D A L G W 13 0 L 110630 DAL G W 131R 110622 DAL G W 131S 110622 DAL G W 131L 110622 DAL G W 133R 110630 DAL G W 133S 110630 DAL G W 133L 110630 DAL G W 134R 110628 DAL G W 134S 110628 DAL G W 134L 110628 DAL G W 135R 110628 DAL G W 135S 110628 DAL G W 135L 110628 DAL G W 136S 110630 DAL G W 136L 110630 DAL G W 137S 110624 DAL G W 137L 110624 DAL G W 138R 110630 DAL G W 138S 110630 DAL G W 138L 110630 DAL G W CW 26C 110622 DAL G W C W 26L 110622 DAL G W 140R 110622 DAL G W 141R 110630 DAL G W 142R 110622 DAL G W 143R 110622 DAL G W 144S 110628 Trip Blanks (Milli-QTM Water) D A LG W 130L RB 110630 D A LG W 133S RB 110630 PFBS Avg. Cone. (ng/mL) RPD 16.3 1 .8 % 3.53 0.0% 1.67 1 .8 % 54.9 3.5% 0.894 4 .6% 3.42 1 .2% 4.79 3.8% 9.08 1 .4% 6.67 0.45% 51.4 1 .4% 0.258 2 .3% 11.8 6 .8 % 74.3 1.6% 1.21 0 .8 3 % 9.69 0.83% 3.69 1 .1% 2.33 0.43% 0.107 2.8% 0.0826 1.9% 8.01 0 .0 % 4.57 0.66% 0.0391 2 .8 % 8.23 0.73% 13.5 0.74% 1.59 1 .3 % 0.0431 2.8% 1.69 0 .0 % 1.66 2 .4% 1.66 4 .2 % <0.0250 <0.0250 <0.0250 PFHS Avg. Cone. (ng/mL) RPD 125 0.0% 29.8 0.34% 13.6 2 .2 % 304 4.6% 5.07 7.5% 21.6 1.9% 33.1 3 .0 % 67.2 0.74% 46.9 1.7% 483 0.62% 3.09 2.3% 111 1 3 % 844 3.7% 8.06 2.2% 71.0 2.5% 25.8 0.78% 16.0 1 .3% 0.0806 2.0% 0.107 0.94% 39.2 0.26% 23.2 0 .0% 0.113 0.89% 67.8 1.6% 105 1.0% 17.8 1 .1 % 0.296 1.7% 10.2 3 .0 % 6.06 3.8% 7.14 3.9% <0.0250 <0.0250 <0.0250 PFOS Avg. Cone. (ng/mL) RPD 450 4.4% 97.6 5.0% 63.7 5.3% 1510 3.3% 5.37 2 .1% 32.4 1 .5 % (1) 42.6 7.3% 195 1.0% 146 4 .8 % <2) 1060 13% 13.3 0 .0 % 4 9 3 2 2 % <3) 969 11% N R <4> 57.6 7 .3 % <1) 116 0.87% 69 .0 1 0 % (1) 0.483 6 .4% 1.96 2 .6 % 347 0.58% 199 4.5% 0.851 2.6% 398 0.0% 934 4.9% 128 13% 3.00 3.0% 85.5 6.8% 23.8 3.4% 29.0 3 .8 % (1) <0.100 <0.0400 0.0478 The analytical method uncertainties associated with the reported results are: PFBS 11%, PFHS 14%, and PFOS 36%. (1) The analytical uncertainty has been adjusted for PFOS based on FMS recovery fo r DAL GW 131L to 39%, DAL GW 135L to 37%, DAL GW 136L to 41 %, and DAL GW 144S to 37%. (2) The low field m atrix spike for PFOS had a recovery that >200%, while the high field m atrix spike met method acceptance criteria. , (3) The RPD did not meet method acceptance criteria o f 20%. (4) NR = Not Reported; Recovery o f the only appropriate field m atrix spike was >200%. See section 9 of the report for additional inform ation. Page 10 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze groundwater samples collected from various wells located at the Former Sludge Incorporation Area (FSIA) in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on site groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and a minimum of two field matrix 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. Sample bottles for select sampling locations were fortified with internal standard prior to sample collection to aid in sample analysis. These included sampling locations: DAL GW 134S, DAL GW 135S, DAL GW 136R, DAL GW 137R, DAL GW 137S, DAL GW 137L, DAL GW 138L, Trip Blank samples, and equipment rinseate blanks. Where applicable, internal standards were used to aid in the data quality objectives. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, the trip blank, and the aqueous equipment rinseate blank samples. Tables 10-41 summarize the individual sample results and the associated field matrix spike recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report , 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 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -J u n e 2011 R eference Substance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Num ber TCR Number Physical Description Purity PFBS (predom inantly lin ear) Perfluorobutane sulfonate C4F9SO 3 Potassium Salt Target Analyte Reference Standard 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 W hite Powder 96.7% PFHS (lin ear) Perfluorohexane sulfonate C 6 F13SO 3 Sodium Salt Target Analyte Reference Standard W ellington 4/2/2013 Frozen LPFHXSAM08 TCR08-0018 C ry stallin e 98% R eference Substance Chemical Name PFOS (lin ear) Perfluorooctane sulfonate PFOS (lin ea r + branched) Perfluorooctane sulfonate 15Ca-PFOS Sodium Perfluorooctanesulfonate Chemical Formula Identifier Use Source C 8 F17SO 3 Potassium Salt CAS #2795-39-3 Target Analyte Reference Standard W ellington C 8F 1 7 S O 3 Potassium Salt CAS #2795-39-3 LCS Reference Standard 3M 13C 8F 17S 0 3'N a + CAS # MPFC-C-0511 Internal Standard W ellington Expiration Date 10/18/2013 12/14/2016 05/25/2014 Storage Conditions Frozen Frozen Frozen Chemical Lot Num ber LPFOSKBM06 171 092310 TCR Number TCR08-0001 T C R -6 9 6 TC R 11-0016 Physical Description C ry stallin e W hite Powder Liquid Purity 98% 86.4% (1) Custom mixture o f seven mass-labeled (13C) perfluoroalkytcarboxylic adds, two mass labeled (,3C) perfluoroalkylsulfonates and one mass-labeled (13C) perfluoro-1-octanesulfbnamide. 5 p g /m L (1) Page 12 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS In W ater Samples F S IA -J u n e 2011 The test systems for this study are groundwater samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Table 2. Sample Description Key Code. String Number E x a m p le 1 2 3 4 5 6 String Descriptor DAL G W 1 3 1 R 0 110622 S a m p lin g L o c a tio n W e ll ID S a m p lin g P o in t W e ll L e v e l S a m p lin g D a te S a m p le T yp e Example D A L = D e c a tu r, A la b a m a G W = G ro u n d w ater E x a m p le : 131 R = R e s id u m s h a llo w w a te r-b e a rin g zo n e L = B e d ro c k w a te r-b e a rin g zo n e S = E p ik a rs t m id d le w a te r-b e a rin g zo n e 110622 = J u n e 2 2 ,2 0 1 1 0 = p rim a ry s a m p le D B = d u p lic a te s a m p le L S = lo w s p ik e M S = m id s p ik e H S = h ig h s p ik e f, iiW iS K if 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles associated with GLP10-01-02-18 were returned to the laboratory at ambient conditions on July 8, 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 each cooler of sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Samples that required dilution were prepared by dilutions of 1mL sample with 9 mLs of Milli Q water (dilution 1:10). Samples requiring a 1:100 dilution were prepared by adding 0.1 mL sample to 9.9 mLs of MilliQ water. Samples associated with sampling locations DAL GW 143R and DAL GW 144S were spiked with internal standard by adding an aliquot of internal standard stock solution into 10 mLs of sample. Internal standard was added to aid on the quanitation of the samples. Page 13 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Table 3. Instrument Parameters. Instrum ent Name A n a lytica l M ethod Follow ed A nalysis Date L iquid C hrom atograph G uard colum n A n a lytica l colum n Injection Volum e M ass Spectrom eter Ion S ource E lectrode P olarity S oftw are E T S K irk ETS-8-044.0 7/20/11 - PFBS, PFHS, and PFOS Aqilent 1200 Prism RP (2.1 mm X 50 mm), 5 n Betasil C18 (2.1 mm X 100 mm), 5p 2 o r1 0 (iL Applied Biosystems API 5500 Turbo Spray Turbo ion electrode Negative Analyst 1.5.2 E T S K irk ETS-8-044.0 7/29/1 la n d 8/2/11 -P F O S Agilent 1200 Betasil C18 (4.6 mm X 100 mm), 5u Betasil C18 (4.6 mm X 100 mm), 5u 25 uL Applied Biosystems API 5500 Turbo Spray Turbo ion electrode Negative Analyst 1.5.2 Table 4. Liquid Chromatography Conditions. S tep Num ber 0 1 2 3 4 5 0 1 2 3 4 5 T o ta l T im e (m in ) 0 2.0 14.5 15.5 16.5 20.0 0 2.0 14.5 15.5 16.5 20.0 F lo w R a te (fd Jm in ) P ercen tA (2 m M a m m o n iu m a c e ta te ) ETS-8-044.0 Analyzed 7/20/11 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 ETS-8-044.0 Analyzed 7/29/11 and 8/2/11 750 97.0 750 97.0 750 5.0 750 5.0 750 97.0 750 97.0 P ercen 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 14 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 Table 5. Mass Transitions. A n a ly te M a s s T ra n s itio n Q 1 /Q 3 R e fe re n c e M a te ria l S tru c tu re In te rn a l S ta n d a rd M a s s T ra n s itio n Q 1 /Q 3 PFBS 2 9 9 /8 0 2 9 9 /9 9 L in e a r NA NA PFHS 3 9 9 /8 0 3 9 9 /9 9 L in e a r NA NA 4 9 9 /8 0 PFO S 4 9 9 /9 9 L in e a r [ 13C tJ -P F O S (1> 5 0 7 /8 0 4 9 9 /1 3 0 Dwell tim e w a s 30 m se c fo r each transition. T he individual transitions w e re su m m e d to pro d u ce a "total ion chrom atogram " (TIC), which w as used for quantitation. (1 ) Internal standard w a s only used fo r PF O S fo r sam pling locations D A L G W 135S, D A L G W 137S, DAL G W 137L, DAL G W 138L, DAL G W 144R and DAL G W 143S. 8 Analytical Results 8.1 Calibration Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into prepared in Milli Q water. A total of fifteen spiked standards ranging from 0.025 ng/ml_ to 100 ng/mL (nominal) were analyzed. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. For sampling locations DAL GW 135S, DAL GW 137S, DAL GW 137L, DAL GW 138L, DAL GW 143R, DAL GW 144R and rinseate blanks for PFOS: Samples were analyzed using a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the same level to all calibration standards and laboratory control samples at a nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.025 ng/mL to 100 ng/mL was prepared. 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 ratios and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of each analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS with the exception of the external calibration of the synthetic water curve which had an area count RSD of 9.3%. Other QC items were used to assess data accuracy Page 15 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples FSIA - June 2011 including calib ra tio n cu rve p o in t a ccuracy, cu rve fit criteria, C C V s, an d LC S, all m e e tin g m eth o d a c c e p ta n c e criteria. A m e th o d d e via tio n is in clu de d w ith th e ra w data. 8.3 Limit of Quantitation (LOQ) T h e LO Q fo r this a n a lysis is th e lo w e st n o n -zero calibration sta n da rd in th e cu rve th a t m e e ts linearity and a ccu ra cy requirem ents and fo r w hich th e area counts o r area ratio are at least tw ice those o f the a p p ro p ria te b la n ks. T h e L O Q fo r all a n a ly te s ca n be fo u n d in T a b le 6. Table 6. Lim it o f Q uantita tion (LO Q ). A n a ly s is D a te 7/20/11 Analysis external calibration 7/29/11 Analysis external calibration 7/29/11 Analysis internal standard calibration 8/2/11 Analysis internal standard calibration NA = Not Applicable D ilu tio n 1 5 10 50 100 1 10 100 1 1 PFBS L O Q , n g /m L 0.0250 0.125 0.250 1.25 2.50 NA NA NA NA NA PFHS L O Q , n g /m L 0.0250 0.125 0.250 1.25 2.50 NA NA NA NA NA PFO S L O Q , n g /m L 0.100 0.500 1.00 5.00 10.0 1.00 10.0 100 0.100 0.0400 8.4 Continuing Calibration D uring th e co u rse o f each analytical sequence, continuing calibration verification sa m p le s (C C V s) w e re a n a ly z e d to c o n firm th a t th e in s tru m e n t re s p o n s e a n d th e initial c a lib ra tio n c u rv e w e re still in co n tro l. A ll C C V s m et m ethod criteria o f 100% 25% fo r PFBS , P FH S , and P F O S except fo r the external calibration o f th e syn th etic w a te r curve w h e re tw o C C V s had recoveries o u tside m eth o d acce p ta n ce criteria o f 100% 25% fo r P F O S . T h e tw o n o n-com pliant C C V s did not b ra cke t a ny sa m p le s reported herein. 8.5 Blanks T w o types o f blanks w e re prepared and analyzed w ith th e sam ples: m ethod blanks and field/trip blanks. M ethod blank results w ere review ed and used to evaluate m ethod perform ance and to determ ine the LO Q fo r each analyte 8.6 Lab Control Spikes (LCSs) Low, m id, an d high-level la b control sp ike s w e re p re pared an d a n a lyzed in trip lica te w ith e ach p re p a ra tio n set. L C S s w e re p re p a re d b y spikin g kn o w n a m o u n ts o f th e a n a lyte into M illi Q w a te r o r synthetic g ro undw ater to produce the desired concentration. T he spiked w a te r sam ples w ere then p re p a re d a n d a n a ly z e d in th e s a m e m a n n e r a s th e s a m p le s. T h e m e th o d a c c e p ta n c e crite ria , a ve ra g e o f LC S at each level should be w ithin 100% 20% w ith an R S D <20% . 7/20/11 A nalysis: A ll LC S s m e t acceptance criteria fo r PFBS, PFH S , and PFO S . Page 16 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 7/29/11 Analysis - internal calibration: The low set of LCS samples for PFOS had an average recovery of 126%. The mid and high sets of LCS samples met acceptance criteria for PFOS. 7/29/11 Analysis - external calibration: The low set of LCS samples for PFOS were spiked below the LOQ. The mid and high sets of LCS samples met acceptance criteria for PFOS. 8/2/11 Analysis - All LCSs met acceptance criteria for PFOS. As the reference material used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear and branched) were prepared at three concentrations in triplicate to evaluate the potential for analytical bias. 7/20/11 Analysis: All linear and branched PFOS LCSs met acceptance criteria. 7/29/11 Analysis - internal calibration: The low set of LCS samples (linear and branched) for PFOS had an average recovery of 136% and the high set had an average recovery of 122%. The mid set of LCS samples met acceptance criteria for PFOS. 7/29/11 Analysis - external calibration: The low set of LCS samples (linear and branched) for PFOS were spiked below the LOQ. The mid and high sets of LCS samples met acceptance criteria for PFOS. 8/2/11 Analysis: The low, mid, and high linear and branched LCSs had average recoveries of 129%, 122%, and 122%. The following calculations were used to generate data in Table 7 for laboratory control spikes. 100C alculated Concentration LCS Percent Recovery = % Spike Concentration standard deviation LCS replicates LCS% RSD = 100% average LCS recovery Page 17 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 Table 7. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 7/20/11 External standard calibration PFBS L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry S p ik e d C o n c e n tra tio n (n g /m L ) LC S -110714-1 LC S-110714-2 LC S-110714-3 Average %RSD 0.498 0.498 0.498 0.507 0.514 0.514 103 0.56% 102 103 103 0.498 0.498 0.498 LC S-110714-4 LC S-110714-5 LC S-110714-6 4.98 4.98 4.98 5.14 103 4.98 5.14 103 4.98 5.13 103 4.98 Average %RSD 103% 0.0% LC S-110714-7 LC S-110714-8 LC S-110714-9 29.9 29.9 29.9 29.9 29.0 29.5 100 96.8 98.8 29.9 29.9 29.9 Average %RSD 98.5% 1.6% PFHS C a lc u la te d C o n c e n tra tio n (n g /m L ) 0.524 0.526 0.537 106% 1.4% 5.21 5.30 5.20 105% 1.0% 30.1 28.6 29.8 98.8% 2.9% % R ec o v e ry 105 106 108 105 106 104 101 95.6 99.7 ETS-8-044.0 Analyzed 7/20/11 External standard calibration P F O S (lin e a r) P F O S (lin e a r+ b ra n c h e d ) L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) !' R e c o v e r y L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry LC S -110714-1 LC S-110714-2 LC S -110714-3 Average %RSD 0.498 0.498 0.498 0.427 0.432 0.448 87.5% 2.4% 85.8 86.8 89.9 LC S-110714-10 LC S -110714-11 LC S-110714-12 Average %RSD 0.495 0.495 0.495 0.469 0.460 0.437 92.0% 3.6% 94.7 92.9 88.3 LC S-110714-4 LC S-110714-5 LC S-110714-6 Average %RSD 4.98 4.98 4.98 4.93 4.92 4.72 97.5% 2.5% 98.9 98.8 94.7 LC S -110714-13 LC S -110714-14 LC S-110714-15 Average %RSD 4.96 4.96 4.96 4.14 4.33 4.46 86.9% 3.7% 83.5 87.3 89.9 LC S-110714-7 LC S-110714-8 LC S-110714-9 Average %RSD 29.9 29.9 29.9 30.5 28.5 29.6 98.7% 3.4% 102 95.2 98.9 LC S-110714-16 LC S-110714-17 LC S-110714-18 Average %RSD 29.8 29.8 29.8 29.4 29.3 28.5 97.5% 1.7% 98.6 98.3 95.6 Page 18 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -J u n e 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 7/29/11 Internal standard calibration P F O S (lin e a r) P F O S (lin e a r+ b ra n c h e d ) L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry LC S -110726-1 LC S-110726-2 LC S-110726-3 Average %RSD 0.199 0.199 0.199 0.257 0.248 0.250 12 6% 1 .8 % (1) 129 LC S-110726-10 125 LC S -110726-11 125 LC S-110726-12 Average %RSD 0.198 0.198 0.198 0.272 0.264 0.271 1 3 6 % 1 .7 % (1) 137 133 137 LC S-110726-4 L C S -1 10726-5 LC S-110726-6 Average %RSD 1.99 1.99 1.99 2.11 2.00 2.11 104% 2.8% 106 LC S-110726-13 101 L C S -1 10726-14 106 LC S-110726-15 Average %RSD 1.98 1.98 1.98 2.26 2.34 2.47 119% 4.7% 114 118 125 LC S-110726-7 LC S-110726-8 LC S-110726-9 Average %RSD 19.9 19.9 19.9 20.8 21.4 21.1 106% 0.94% 105 LC S-110726-16 107 LC S -110726-17 106 LC S-110726-18 Average %RSD 19.8 19.8 19.8 22.9 24.1 25.6 122% 5 .3 % <1) 116 122 129 ETS-8-044.0 Analyzed 7/29/11 External standard calibration P F O S (lin e a r) P F O S (lin e a r+ b ra n c h e d ) L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry L C S -1 10726-4 LC S-110726-5 LC S-110726-6 Average %RSD 1.99 1.99 1.99 2.07 2.08 2.04 104% 0.56% 104 LC S-110726-13 104 LC S-110726-14 103 LC S-110726-15 Average %RSD 1.98 1.98 1.98 2.04 2.04 2.27 107% 6.5% 103 103 115 LC S-110726-7 LC S-110726-8 LC S-110726-9 Average %RSD 19.9 19.9 19.9 21.4 21.7 20.1 106% 3.9% 107 LC S-110726-16 109 LC S-110726-17 101 L C S -1 10726-18 Average %RSD 19.8 19.8 19.8 17.2 19.2 17.2 90.3% 6.6% 87.1 97.1 86.6 (1) The average recovery did not meet method acceptance criteria o f 100% 20%. Page 19 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples FSIA - June 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 8/2/11 Internal standard calibration P F O S (lin e a r) P F O S (lin e a r+ b ra n c h e d ) L a b ID S p ik e d C o n c e n tra tio n (n g /m L ) C a lc u la te d C o n c e n tra tio n (n g /m L ) % R ec o v e ry L a b ID S p ik e d C a lc u la te d C o n c e n tra tio n C o n c e n tra tio n (n g /m L ) (n g /m L ) V o R eco very LC S -110726-1 LC S-110726-2 LC S-110726-3 Average %RSD 0.199 0.199 0.199 0.219 0.211 0.226 110% 3.6% 110 LC S-110726-10 106 LC S -110726-11 114 LC S-110726-12 Average %RSD 0.198 0.198 0.198 0.252 0.254 0.264 129% 2 .5 % (1> 127 128 133 LC S-110726-4 LC S-110726-5 LC S-110726-6 Average %RSD 1.99 1.99 1.99 2.15 2.04 2.13 106% 2.5% 108 LC S-110726-13 103 LC S-110726-14 107 LC S-110726-15 Average %RSD 1.98 1.98 1.98 2.29 2.39 2.53 122% 5 .0 % <1) 116 121 128 L C S -1 10726-7 L C S -1 10726-8 LC S-110726-9 Average %RSD 19.9 19.9 19.9 21.1 21.7 21.4 107% 1.4% 106 LC S-110726-16 109 LC S-110726-17 107 LC S-110726-18 Average %RSD 19.8 19.8 19.8 23.0 24.3 25.3 1 2 2 % 4 .9 % <1) 116 123 128 (1) The average recovery did not meet method acceptance criteria of 100% 20%. 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values listed in Table 8. The method uncertainty for PFOS by ETS-12-012-2 was found to be 28%, however, since the low set of linear and branched LCS had an average recovery of 136%, the analytical uncertainty assigned to this study for PFOS will be 36%. Table 8. Analytical Uncertainty. Analyte Standard Deviation PFBS 5.59 PFHS 7.12 PFOS NA = Not Applicable NA Method Uncertainty 11% 14% 36% Page 20 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 8.8 Field Matrix Spikes (FMS) Low, mid, and high field matrix spikes (FMS) were collected at each sampling point (low and high FMS only at 131R, 134R, and 135R) 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% confimi 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 M atrix S pike Levels. S am pling Location 134S, 135S, 136R, 137R, 137S, 137L, 138L 130L, 131S, 131L, 133R, 135L, 136S, 136L, 141R, 142R, 143R, 144S 130R, 130S, 133S, 133L, 134L, 138R, 138S, CW26C, CW26L, 140R 131R, 134R, 135R Trip Blank S pike Level Low Mid High Low Mid High Low M id High Low High Low Mid M id-H ig h High PFBS, ng/m L 0.102 1.02 10.2 1.02 10.2 102 10.2 102 510 102 1972 1.02 10.2 102 510 PFHS, ng/m L 0.102 1.02 10.2 1.02 10.2 102 10.2 102 510 102 2000 1.02 10.2 102 510 PFOS, ng/m L 0.0985 0.985 9.85 0.985 9.85 98.5 9.85 98.5 493 98.5 2000 0.985 9.85 98.5 493 FMS R ecovery- (Sample Concentration o f FM S-Average Concentration :Field Sample & Field Sample Dup.) *jqq0// Spike Concentraton The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks and rinseate blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges. DAL GW 130L - The recovery of the high FMS sample for PFOS was 68.3%. The high spike, the only appropriate spike level as compared to the sample concentration, is still within the analytical uncertainty of 100% 36%. No additional adjustment will be made to the analytical uncertainty. DAL GW 131L - The recovery of the high FMS sample for PFOS was 61.2%. Since the high spike was the only appropriate spike level as compared to the sample concentration, the analytical uncertainty has been adjusted for PFOS to 100% 39%. Page 21 o f 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 DAL GW 133L - The recovery of the mid FMS sample for PFOS was 231 %. The high FMS sample met acceptance criteria with a recovery of 92.1%. Since both spiking levels were appropriate as compared to the sample concentration, the sample set will be reported and footnoted. DAL GW 134L - The sample RPD was 22% for PFOS. DAL GW 135S - The recovery of the high FMS sample for PFOS was 224%. Since the high spike was the only appropriate spike level as compared to the sample concentration, the sample set will not be reported since the FMS recovery was greater than 100% 50%. DAL GW 135L - The recovery of the high FMS sample for PFOS was 63.4%. Since the high spike was the only appropriate spike level as compared to the sample concentration, the analytical uncertainty has been adjusted for PFOS to 100% 37%. DAL GW 136L - The recovery of the high FMS sample for PFOS was 58.9%. Since the high spike was the only appropriate spike level as compared to the sample concentration, the analytical uncertainty has been adjusted for PFOS to 100% 41 %. DAL GW 141R - The recovery of the high FMS sample for PFOS was 65.6%. The mid FMS sample met method acceptance criteria. Since the mid spike was the most appropriate spike level as compared to the sample concentration, the analytical uncertainty will not be jadjusted for PFOS. DAL GW 142R - The recovery of the high FMS sample for PFOS was 68.5%. The high spike, the only appropriate spike level as compared to the sample concentration, is still within the analytical uncertainty of 100% 36%. No additional adjustment will be made to the analytical uncertainty. DAL GW 144S - The recovery of the high FMS sample for PFOS was 63.5%. Since the high spike was the only appropriate spike level as compared to the sample concentration, the analytical uncertainty has been adjusted for PFOS to 100% 37%. Page 22 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS In W ater Samples F S IA -J u n e 2011 Table 10. DAL GW 130R 110630 3 M U M S ID D e s c rip tio n G L P 1 0-01-02-18-006 G L P 1 0-01-02-18-007 G L P 1 0-01-02-18-008 G L P 1 0 -0 1 -0 2 -1 8 -00 9 G L P 1 0 -0 1 -0 2 -1 8 -01 0 DAL GW 130R 0110630 DAL G W 130R DB 110630 DAL G W 130R LS 110630 DAL G W 130R MS 110630 D A LG W 130R HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 16.4 16.1 NA NA 25.0 85.8 110 501 91.9 95.0 1 6 .3 n g /m L 1 .8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 125 125 131 218 629 NA NA NC 91.2 98.8 1 2 5 n g /m L 0 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 440 NA 460 NA 501 NC 492 NC 853 81.8 4 5 0 n g /m L 4 .4 % NA = Not Applicable NC = Not Calculated; the endogenous sample concentration Is greater than 2x the spike level. Reported results from external standard calibration. 11Table . DAL GW 130S 110630 3 M U M S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -0 1 1 G L P 1 0 -0 1 -0 2 -1 8 -01 2 G L P 1 0 -0 1 -0 2 -1 8 -01 3 G L P 1 0 -0 1 -0 2 -1 8 -01 4 G L P 10-01 -02-18-015 DAL G W 130S 0110630 DAL G W 130S DB 110630 DAL G W 130S LS 110630 D A LG W 130S MS 110630 D A LG W 130S H S 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 3.53 3.53 13.7 NA NA 100 102 96.5 504 98.4 3 .5 3 n g /m L 0 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 29.8 29.7 39.9 130 577 NA NA NC 98.3 107 2 9 .8 n g /m L 0 .3 4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 100 95.1 113 185 466 NA NA NC 88.8 74.8 9 7 .6 n g /m L 5 .0 % NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. Reported results from external standard calibration. Page 23 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS In W ater Samples F S IA -J u n e 2011 Table 12. DAL GW 130L 110630 3 M L IM S ID D e s c rip tio n G LP 10-01-02-18-016 G LP 10-01-02-18-017 G LP 10-01-02-18-018 G LP 10-01-02-18-019 G LP 10-01-02-18-020 DAL G W 130L 0110630 D A L G W 1 3 0 L DB 110630 D A L G W 1 3 0 L LS 110630 D A L G W 1 3 0 L M S 110630 D A L G W 1 3 0 L HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 1 .6 8 NA 1 .6 5 NA 2.7 7 108 1 2 .4 105 98 .2 9 4 .6 1 .6 7 n g /m L 1 .8 % C o n c e n tra tio n (n g /m L ) % R ecoverv 1 3 .7 1 3 .4 NA NA 1 5 .2 NC 2 4 .1 114 103 9 8 .5 1 3 .6 n g /m L 2 .2 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 6 2 .0 NA 6 5 .4 NA 7 2 .0 NC 7 2 .4 NC 131 6 8 . 3 (1) 63.7 n g /m L 5.3% NA = Not Applicable NO = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. Reported results from external standard calibration. (1) FMS did not meet acceptance criteria of 10030%. The recovery is within the analytical uncertainty. Table 13. DAL GW 131R 110622 3 M L IM S ID D e s c rip tio n G LP 10-01-02-18-021 DAL G W 131R 0110622 G LP 10-01-02-18-022 DAL G W 131R DB 110622 G LP 10-01-02-18-023 D AL G W 131R LS 110622 G LP 10-01-02-18-024 DAL G W 131R H S 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry C o n c e n tra tio n (n g /m L ) % R ec o v e ry C o n c e n tra tio n (n g /m L ) % R ec o v e ry 53.9 NA 5 5 .8 NA 157 100 1880 9 2 .6 5 4 .9 n g /m L 3.5% 297 NA 311 N A 414 NC 2200 94 .8 3 0 4 n g /m L 4 .6 % 1530 NA 1480 NA N A (1) N A (1) 3200 84 .8 1 5 1 0 n g /m L 3 .3 % NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. Reported results from external standard calibration. (1) FMS not analyzed since spike level was not appropriate in comparison to the sample concentration. Page 24 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 14. DAL GW 131S 110622 3 M U M S ID D e s c rip tio n GLP10-01-02-18-025 DAL G W 131S 0110622 GLP10-01-02-18-026 D A L G W 1 3 1 S D B 110622 GLP10-01-02-18-027 D A L G W 1 3 1 S L S 110622 G L P 1 0 -0 1 -0 2 -1 8 -02 8 G L P 1 0-01-02-18-029 D A LG W 131S MS 110622 D A L G W 1 3 1 S H S 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.914 0.873 1.93 10.9 98.9 NA NA 102 98.1 96.1 0 .8 9 4 n g /m L 4 .6 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 5.26 4.88 6.07 15.2 104 NA NA NC 99.3 97.0 5 .0 7 n g /m L 7 .5 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 5.31 5.42 6.27 13.1 80.3 NA NA NC 78.5 76.1 5 .3 7 n g /m L 2 .1 % NA = Not Applicable NC = Not Calculated; the endogenous sample concentration is greater than 2x the spike level. Reported results from external standard calibration. Table 15. DAL GW 131L 110622 3 M U M S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -03 0 GLP10-01-02-18-031 G L P 1 0 -0 1 -0 2 -1 8 -03 2 G L P 1 0 -0 1 -0 2 -1 8 -03 3 G L P 1 0 -0 1 -0 2 -1 8 -03 4 DAL G W 131L 0110622 DAL G W 131L DB 110622 DAL G W 131LLS 110622 DAL G W 131L MS 110622 DAL G W 131LH S 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 3.40 3.44 4.44 13.8 102 NA NA NC 102 96.6 3 .4 2 n g /m L 1 .2 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 21.4 21.8 22.8 32.8 120 NA NA NC NC 96.5 2 1 .6 n g /m L 1 .9 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 32.6 32.1 30.5 NA NA NC 42.0 92.6 NC 6 1 .2 <1) 3 2 .4 n g /m L 1 .5 % m NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS did not m eet acceptance criteria o f 10030%. The analytical uncertainty for PFOS has been adjusted for FMS recovery to 39%. Page 25 o f 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -Ju n e 2011 Table 16. DAL GW 133R 116030 3 N IU N IS ID D e s c rip tio n GLP10-01-02-18-045 DAL G W 133R 0110630 G L P 1 0 -01-02-18-046 G L P 1 0 -01-02-18-047 G L P 1 0 -01-02-18-048 D A LG W 133R DB 110630 D A LG W 133R LS 110630 D A LG W 133R MS 110630 GLP10-01-02-18-049 D A L G W 1 3 3 R HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) X R e c o v ery 4.70 4.88 5.62 14.3 98.9 NA NA NC 93.2 92.3 4 .7 9 n g /m L 3 .8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 32.6 33.6 32.0 41.7 130 NA NA NC NC 95.0 3 3 .1 n g /m L 3 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 44.1 NA 41.0 37.5 51.3 111 NA NC NC 6 9 .5 <1) 4 2 .6 n g /m L 7 .3 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS did not meet acceptance criteria of 10030%. The recovery Is within the analytical uncertainty Table 17. DAL GW 133S 110630 3 M U N IS ID D e s c rip tio n G L P 1 0 -Q 1-02-18-040 GLP10-01-02-18-041 G L P 1 0-01-02-18-042 DAL G W 133S 0110630 D A L G W 1 3 3 S D B 110630 DAL G W 133SLS 110630 GLP10-01-02-18-043 DAL G W 133S MS 110630 GLP10-01-02-18-044 D A L G W 1 3 3 S H S 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 9.01 9.14 18.9 NA NA 96.3 105 94.0 487 93.7 9 .0 8 n g /m L 1 .4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 66.9 67.4 76.2 167 551 NA NA NC 97.9 94.9 6 7 .2 n g /m L 0 .7 4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 196 194 202 265 585 NA NA NC 71.1 79.2 1 9 5 n g /m L 1 .0 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Page 26 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Table 18. DAL GW 133L 110630 3 IU U M S ID D e s c rip tio n G L P 1 0-01-02-18-035 G L P 1 0-01-02-18-036 G L P 1 0-01-02-18-037 G L P 1 0-01-02-18-038 DAL GW 133L 0110630 DAL GW 133LD B 110630 D A LG W 133L LS 110630 D A LG W 133L MS 110630 GLP10-01-02-18-039 DAL G W 133L HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R e co very 6.68 NA 6.65 17.2 107 487 NA 103 98.4 94.2 6 .6 7 n g /m L 0 .4 5 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 47.3 46.5 61.6 164 543 NA NA NC 115 97.3 4 6 .9 n g /m L 1 .7 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 149 142 N A (1) 373 599 NA NA N A (1) 2 3 1 <2) 92.1 1 4 6 n g /m L 4 .8 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) Not Analyzed; The LS was not analyzed since it was not expected to be appropriate as compared to the sample concentration. (2) Field matrix spike did not meet method acceptance criteria of 10030%. No adjustment was made to the analytical uncertainty since both spike levels were appropriate as compared to the sample concentration. Table 19. DAL GW 134R110628 3 M L IM S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -05 0 GLP10-01 -02-18-051 DAL G W 134R 0110628 D A LG W 134R DB 110628 G L P 1 0 -0 1 -0 2 -1 8 -05 2 G LP10-01 -02-18-053 DAL G W 134RLS 110628 D A LG W 134R HS 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 51.7 51.0 NA NA 150 1890 96.7 93.2 5 1 .4 n g /m L 1 .4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 484 NA 481 NA 588 2360 NC 93.9 4 8 3 n g /m L 0 .6 2 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 996 1130 1040 2870 NA NA NC 90.4 1 0 6 0 n g /m L 1 3 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Page 27 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 20. DALGW 134S 110628 3 M U M S ID D e s c rip tio n G L P 1 0-01-0 2 -1 8 -05 9 GLP10-01-02-18-060 G L P 1 0-01-02-18-061 G L P 1 0 -0 1 -0 2 -1 8 -06 2 G L P 1 0-01-0 2 -1 8 -06 3 DAL G W 134S 0110628 DAL G W 134S DB 110628 DAL G W 134S LS 110628 DAL G W 134S MS 110628 DAL G W 134S HS 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.255 NA 0.261 0.371 1.23 10.8 NA NC 95.3 103 0 .2 5 8 n g /m L 2 .3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 3.05 3.12 3.12 4.08 14.0 NA NA NC NC 107 3 .0 9 n g /m L 2 .3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 13.3 NA 13.3 12.6 14.6 24.9 NA NC NC 118 1 3 .3 n g /m L 0 .0 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Table 21. DAL GW 134L 110628 3 M U M S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -0 5 4 G L P 1 0-01-0 2 -1 8 -05 5 GLP1001-02-18-056 G L P 1 0 -0 1 -02-18-057 G L P 1 0 -0 1 -02-18-058 DAL GW 134L 0110628 D A LG W 134L DB 110628 DAL G W 134LLS 110628 D A LG W 134L MS 110628 D A LG W 134L HS 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 11.4 12.2 NA NA 22.0 100 108 94.3 479 91.6 1 1 .8 n g /m L 6 .8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 104 NA 118 NA 127 NC 216 103 586 93.1 11 1 n g /m L 1 3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 438 NA 547 NA 469 NC 534 NC 897 82.1 4 9 3 n g /m L 2 2 % m NA= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) RPD did not meet acceptance criteria of 20%. Page 28 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 22. DAL GW 135R110628 3 M L IM S ID D e s c rip tio n GLP10-01-02-18-079 DAL G W 135R 0110628 G L P 1 0 -0 1 -0 2 -1 8 -08 0 G L P 1 0 -0 1 -02-18-081 D A LG W 135R DB 110628 DAL G W 135R LS 110628 GLP10-01-02-18-083 D A L G W 1 3 5 R HS 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) 1 % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 74.9 NA 73.7 172 NA 95.8 1840 89.5 7 4 .3 n g /m L 1 .6 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 859 828 927 2620 NA NA NC 88.8 8 4 4 n g /m L 3 .7 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 1020 917 1070 2480 NA NA NC 75.6 9 6 9 n g /m L 1 1 % N A= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Table 23. DAL GW 135S 110628 3 M U M S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -06 9 G LP10-01 -02-18-070 DAL G W 135S 0110628 D A LG W 135S DB 110628 G L P 1 0-01-02-18-071 G L P 1 0 -0 1 -0 2 -1 8 -07 2 G L P 1 0 -0 1 -0 2 -1 8 -07 3 DAL G W 135S LS 110628 DAL GW 135S MS 110628 DAL G W 135SH S 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 1.20 1.21 NA NA 1.41 2.21 10.5 NC 98.5 91.1 1 .2 1 n g /m L 0 .8 3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 7.97 8.15 8.86 9.22 19.1 NA NA NC NC 108 8 .0 6 n g /m L 2 .2 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results for PFBS and PFHS are from external standard calibration. PFOS was analyzed by both internal standard and external standard calibration with the results from both analyses being not reportable. (1) Not Reported; the most appropriate field m atrix spike recovery was greater than 100% 50%. Page 29 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 24. DAL GW 135L 110628 3 M L IM S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -07 4 G L P 1 0 -01-02-18-075 G L P 1 0 -01-02-18-076 G L P 1 0 -0 1 -0 2 -1 8 -07 7 G L P 1 0-01-02-18-078 DAL G W 135L 0110628 D A LG W 135L DB 110628 D A LG W 135L LS 110628 DAL G W 135L MS 110628 DAL G W 135LH S 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 9.73 9.65 10.6 19.9 109 NA NA NC 100 97.4 9 .6 9 n g /m L 0 .8 3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 71.9 70.1 NA NA 73.9 84.0 176 NC NC 103 7 1 .0 n g /m L 2 .5 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 55.5 59.7 NA NA 48.1 57.8 120 NC NC 6 3 .4 <1) 5 7 .6 n g /m L 7 .3 % <1> N A= Not Applicable NO = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS did not meet acceptance criteria of 10030%. The analytical uncertainty for PFOS has been adjusted for FMS recovery to 37%. Table 25. DAL GW 136S 110630 3 M L IM S ID D e s c rip tio n G L P 1 0-01-02-18-088 G L P 1 0-01-02-18-089 G L P 1 0-01-02-18-090 GLP10-01-02-18-091 G L P 1 0 -0 1 -0 2 -1 8 -09 2 DAL G W 136S 0110630 DAL G W 136S DB 110630 DAL G W 136S LS 110630 DAL G W 136S MS 110630 DAL G W 136S HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 3.71 NA 3.67 4.61 13.2 99.8 NA NC 93.2 94.2 3 .6 9 n g /m L 1 .1 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 25.9 25.7 26.7 35.2 125 NA NA NC NC 97.3 2 5 .8 n g /m L 0 .7 8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 115 NA 116 NA 120 NC 118 NC 187 72.6 1 1 6 n g /m L 0 .8 7 % NA= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Page 30 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 26. DAL GW 136L 110630 3 M U N IS ID D e s c rip tio n GLP10-01-02-18-084 DAL G W 136L 0 110630 G L P 1 0-01-0 2 -1 8 -08 5 G L P 1 0-01-0 2 -1 8 -08 6 G L P 1 0 -0 1 -02-1 8 -1 5 5 G L P 1 0 0 1 -0 2 -1 8 -0 8 7 D A LG W 136L DB 110630 DAL G W 136L LS 110630 DAL G W 136L MS 110630 DAL G W 136L HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e rv 2.33 NA 2.32 NA 3.32 12.5 NC 99.8 101 96.7 2 .3 3 n g /m L 0 .4 3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 15.9 NA 16.1 NA 17.0 26.3 115 NC 101 97.1 1 6 .0 n g /m L 1 .3 % C o n c e n tra tio n (n g /m L ) V o R eco very 72.4 NA 65.5 NA 73.6 84.8 127 NC NC 5 8 .9 (1) 6 9 .0 n g /m L 1 0 % (1> NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS did not m eet acceptance criteria of 10ftt30% . The analytical uncertainty fo r PFOS has been adjusted for FMS recovery to 41 %. Table 27. DAL GW 137S 110624 3 M L IM S ID D e s c rip tio n G L P 1 0-01 -0 2 -1 8 -09 3 G L P 1 0-01 -0 2 -1 8 -09 4 G L P 1 0 -0 1 -0 2 -1 8 -09 5 G L P 1 0 -0 1 -0 2 -1 8 -09 6 G L P 1 0-01 -0 2 -1 8 -09 7 DAL G W 137S 0110624 D ALG W 137S DB 110624 DAL G W 137S LS 110624 DAL G W 137S MS 110624 DAL G W 137S HS 110624 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.108 0.105 0.215 1.05 9.68 NA NA 106 92.5 93.9 0 .1 0 7 n g /m L 2 .8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.0814 0.0798 0.184 1.06 9.86 NA NA 101 96.0 95.9 0 .0 8 0 6 n g /m L 2 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.498 0.467 0.569 1.42 10.2 NA NA NC 95.2 98.7 0 .4 8 3 n g /m L 6 .4 % NA= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results for PFBS and PFHS are from external standard calibration. Reported results for PFOS are from internal standard calibration. Page 31 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS In W ater Samples F S IA - June 2011 Table 28. DAL GW 137L 110624 3 M L IM S ID D e s c rip tio n G L P 1 0 -01-02-18-098 G L P 1 0 -0 1 -0 2 -1 8 -09 9 G L P 1 0 -0 1 -0 2 -1 8 -10 0 G L P 1 0-01-02-18-101 G L P 1 0 -0 1 -0 2 -1 8 -10 2 DAL G W 137L 0110624 D A LG W 137L DB 110624 D A LG W 137L LS 110624 D A LG W 137L MS 110624 DAL G W 137L HS 110624 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.0834 0.0818 0.189 1.06 9.70 NA NA 104 95.8 94.3 0 .0 8 2 6 n g /m L 1 .9 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.106 0.107 NA NA 0.213 1.10 10.0 104 97.4 97.0 0 .1 0 7 n g /m L 0 .9 4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 1.93 1.98 NA NA 2.01 2.96 12.0 NC 102 102 1 .9 6 n g /m L 2 .6 % N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results for PFBS and PFHS are from external standard calibration. Reported results for PFOS are from internal standard calibration. Table 29. DAL GW 138S 110630 3 M L IM S ID D e s c rip tio n G LP 10-01 -02-18-113 D A L G W 138S 0 1 1 0 6 3 0 G LP 10-01 -02-18-114 G LP 10-01 -02-18-115 DAL G W 138S DB 110630 DAL G W 138S LS 110630 G LP10-01-02-18-116 DAL G W 138S M S 110630 G LP 10-01 -02-18-117 D AL G W 138S HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 4.55 NA 4.58 14.5 NA 97.4 96.8 90.4 488 94.8 4 .5 7 n g /m L 0 .6 6 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 23.2 23.2 33.4 117 528 NA NA NC 92.0 99.0 2 3 .2 n g /m L 0 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 194 NA 203 NA 221 NC 269 NC 593 80.1 1 9 9 n g /m L 4 .5 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Page 32 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Table 30. DAL GW 138L 110630 3 M L IM S ID D e s c rip tio n G LP 10 0 1 -0 2 -1 8 -1 0 8 G L P 1 0-01-02-18-109 G L P 1 0-01-0 2 -1 8 -11 0 G L P 1 0-01-02-18-111 G LP10-01 -02-18-112 DAL GW 138L 0110630 D A LG W 138L DB 110630 D A LG W 138L LS 110630 D A LG W 138L MS 110630 D A LG W 138L HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S - C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.0385 0.0396 0.135 0.973 9.06 NA NA 94.1 91.6 88.4 0 .0 3 9 1 n g /m L 2 .8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.112 0.113 0.213 1.08 9.82 NA NA 98.5 94.9 95.2 0 .1 1 3 n g /m L 0 .8 9 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 0.840 0.862 NA NA 1.04 1.82 10.8 NC 98.4 101 0 .8 5 1 n g /m L 2 .6 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results for PFBS and PFHS are from external standard calibration. Reported results for PFOS are from internal standard calibration. Table 31. DAL GW 138R110630 3 M L IM S ID D e s c rip tio n GLP10-01 -02-18-103 G L P 1 0 -0 1 -02-18-104 GLP10-01 -02-18-105 DAL G W 138R 0110630 D A LG W 138R DB 110630 DAL G W 138RLS 110630 G LP10-01 -02-18-106 G LP10-01 -02-18-107 D A LG W 138R MS 110630 D A LG W 138R HS 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 8.01 8.01 17.7 NA NA 95.0 97.8 88.0 462 89.0 8 .0 1 n g /m L 0 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 39.1 39.2 48.8 134 515 NA NA NC 93.0 93.3 3 9 .2 n g /m L 0 .2 6 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 348 NA 346 NA 340 NC 405 NC 731 78.0 3 4 7 n g /m L 0 .5 8 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Page 33 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 32. DAL GW CW26C 110622 PFBS PFHS PFO S 3 M U M S ID D e s c rip tio n G L P 1 0-01-02-18-118 G L P 1 0-01-02-18-119 G L P 1 0-01-02-18-120 G L P 1 0-01-02-18-121 G L P 1 0-01-0 2 -1 8 -12 2 DAL G W CW26C 0 110622 DAL G W CW 26C DB 110622 DAL G W CW26C LS 110622 DAL G W CW 26C MS 110622 DAL G W CW 26C HS 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D C o n c e n tra tio n (n g /m L ) % R ec o v e ry 8.26 NA 8.20 18.1 NA 96.8 106 95.9 480 92.5 8 .2 3 n g /m L 0 .7 3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 68.3 67.2 77.0 166 563 NA NA NC 96.3 97.1 6 7 .8 n g /m L i 1 .6 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 398 NA 398 NA 384 NC 499 NC 839 89.5 3 9 8 n g /m L 0 .0 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Table 33. DAL GW CW26L 110622 PFBS PFHS PFO S 3 M U M S ID D e s c rip tio n GLP10-01-02-18-123 DAL G W CW 26L 0110622 GLP10-01-02-18-124 DAL G W CW 26L DB 110622 G L P 1 0-01 -0 2 -1 8 -12 5 G L P 1 0-01 -0 2 -1 8 -12 6 G L P 1 0-01-02-18-127 DAL G W CW 26L LS 110622 DAL G W CW 26L MS 110622 DAL G W CW26L HS 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D C o n c e n tra tio n (n g /m L ) % R ec o v e ry 13.4 NA 13.5 NA 23.0 107 501 93.6 91.7 95.6 1 3 .5 n g /m L 0 .7 4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 104 NA 105 NA 115 NC 202 95.6 599 97.0 1 0 5 n g /m L 1 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 911 NA 957 NA 925 985 1410 NC NC 96.6 9 3 4 n g /m L 4 .9 % N A= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Page 34 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -Ju n e 2011 Table 34. DAL GW 140R 110622 3 M U M S ID D e s c rip tio n G LP10-01-02-18-128 G LP10-01-02-18-129 G LP10-01-02-18-130 G LP10-01-02-18-131 G LP10-01-02-18-132 DAL G W 140R 0110622 D A LG W 140R DB 110622 DAL G W 140R LS 110622 D A LG W 140R MS 110622 D A LG W 140R HS 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) V o R eco very 1.58 NA 1.60 11.3 101 477 NA 95.2 97.5 93.2 1 .5 9 n g /m L 1 .3 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 17.7 17.9 27.8 119 508 NA NA 98.0 99.2 96.1 1 7 .8 n g /m L t 1 .1 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 119 NA 136 NA 125 NC 210 83.8 598 95.5 1 2 8 n g /m L 1 3 % IMA= Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. Table 35. DAL GW 141R 110630 3 M L IM S ID D e s c rip tio n G LP1001-02-18-135 G LP10-01-02-18-136 GLP1Q-01-02-18-137 GLP10-01-02-18-138 GLP1OO1-02-18-139 DAL G W 141R 0 110630 DAL G W 141R D B 110630 DAL G W 141RLS 110630 D AL G W 141 R M S 110630 DAL G W 141R H S 110630 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % >R ecovery 0.0437 0.0425 0.992 9.49 94.7 NA NA 93.0 92.6 92.8 0 .0 4 3 1 n g /m L 2 .8 % C o n c e n tra tio n (n g /m L ) V o R eco very 0.298 0.293 NA NA 1.30 10.0 99.1 98.5 95.1 96.9 0 .2 9 6 n g /m L 1 .7 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 3.04 2.95 3.94 10.0 67.6 NA NA NC 71.1 6 5 .6 (1) 3 .0 0 n g /m L 3 .0 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS did not m eet acceptance criteria o f 10030%. The recovery is within the analytical uncertainty. Page 35 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Table 36. DAL GW 142R110622 3 M U M S ID D e s c rip tio n GLP10-01-02-18-140 DAL G W 142R 0110622 G LP10-01-02-18-141 G LP10-01 -02-18-142 G LP10-01 -02-18-143 GLP10-01-02-18-144 D A LG W 142R DB 110622 DAL G W 142R LS 110622 D A LG W 142R MS 110622 D A LG W 142R HS 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % >R ecovery 1.69 1.69 2.62 11.4 97.0 NA NA 91.2 95.2 93.4 1 .6 9 n g /m L 0 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 10.0 NA 10.3 11.1 19.6 109 NA NC 92.6 96.9 1 0 .2 n g /m L 3 .0 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 82.6 88.4 NA NA 89.3 85.2 153 NC NC 6 8 .5 <1) 8 5 .5 n g /m L 6 .8 % NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS did not m eet acceptance criteria of 10030%. The recovery is within the analytical uncertainty. Table 37. DAL GW 143R110622 PFBS PFHS PFO S 3 M L IM S ID D e s c rip tio n G LP10-01 -02-18-145 G L P 1 0 -0 1 -02-18-146 G L P 1 0 -0 1 -0 2 -1 8 -14 7 G LP10-01-02-18-148 G L P 1 0 -01-02-18-149 DAL G W 143R 0110622 D A LG W 143R DB 110622 D A L G W 1 4 3 R L S 110622 D A LG W 143R M S 110622 D A LG W 143R HS 110622 A v e ra g e C o n c e n tra tio n (n g /m L ) 1 % R P D C o n c e n tra tio n (n g /m L ) % R ec o v e ry 1.64 1.68 2.62 10.9 96.0 NA NA 94.1 90.6 92.5 1 .6 6 n g /m L 2 .4 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 5.94 6.17 7.04 15.4 106 NA NA NC 91.6 98.0 6.06 n g /m L 3 .8 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 23.4 24.2 NA NA N A <1) 32.3 123 N A <1) NC 101 2 3 .8 n g /m L 3 .4 % N A = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS not analyzed since spike level was not appropriate in comparison to the sample concentration. Page 36 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Table 38. DAL GW 144S 110628 3 M U M S ID D e s c rip tio n G L P 1 0 -0 1 -0 2 -1 8 -15 0 GLP10-01-02-18-151 G L P 1 0-01-02-18-152 DAL G W 144S 0110628 DAL G W 144S DB 110628 DAL G W 144SLS 110628 G L P 1 0-01-02-18-153 G L P 1 0 -01-02-18-154 DAL G W 144S MS 110628 DAL G W 144SH S 110628 A v e ra g e C o n c e n tra tio n (n g /m L ) % R P D PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) % R ec o v e ry 1.69 1.62 2.55 11.4 91.4 NA NA 87.7 95.5 88.0 1 .6 6 n g /m L 4 .2 % C o n c e n tra tio n (n g /m L ) % R ec o v e ry 7.28 7.00 7.99 17.1 98.5 NA NA NC 97.6 89.6 7 .1 4 n g /m L 3 .9 % C o n c e n tra tio n (n g /m L ) X R e c o v ery 29.5 28.4 N A <1) 37.0 91.5 NA NA N A (1) NC 6 3 .5 (2> 2 9 .0 n g /m L 3 .8 % NA = Not Applicable NO = Not Calculated; Endogenous sample concentration greater than 2x spike level. Reported results from external standard calibration. (1) FMS not analyzed since spike level was not appropriate in comparison to the sample concentration. (2) FMS did not meet acceptance criteria o f 10Qt30%. The analytical uncertainty for PFOS has been adjusted fo r FMS recovery to 37%. Table 39. Trip Blank 1 3 M U N IS ID G L P 1 0 -01-02-18-064 G L P 1 0 -01-02-18-065 G L P 1 0 -0 1 -0 2 -1 8 -06 6 G L P 1 0-01-0 2 -1 8 -06 7 G L P 1 0 -0 1 -0 2 -1 8 -06 8 D e s c rip tio n Trip Blank S et 1 Sample Trip Blank S et 1 LS Trip Blank S et 1 MS Trip Blank S et 1 MHS Trip Blank S et 1 HS NA = Not Applicable Reported results from external standard calibration. PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) <0.0250 1.05 10.3 102 508 % R ec o v e ry NA 103 101 100 99.6 C o n c e n tra tio n (n g /m L ) <0.0250 1.10 10.9 105 523 % R ec o v e ry NA 108 107 103 103 C o n c e n tra tio n (n g /m L ) <0.100 1.01 9.45 102 381 X R e c o v ery NA 103 95.9 104 77.4 Page 37 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -Ju n e 2011 Table 40. Trip Blank 2 3 M L IM S ID G LP10-01-02-18-001 G LP10-01-02-18-002 GLP10-01-02-18-003 G L P 1 0 -0 1 -0 2 -1 8 -00 4 G L P 1 0 -0 1 -0 2 -1 8 -00 5 D e s c rip tio n Trip Blank S et 2 Sam ple Trip Blank Set 2 LS Trip Blank Set 2 MS Trip Blank Set 2 MHS Trip Blank Set 2 HS NA = Not Applicable Reported results from external standard calibration. Table 41. Rinseate Blanks PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) <0.0250 0.995 9.62 93.0 459 % R ec o v e ry NA 97.5 94.3 91.2 90.0 C o n c e n tra tio n (n g /m L ) <0.0250 1.01 9.98 95.2 ATI % R ec o v e ry NA 99.0 97.8 93.3 93.5 C o n c e n tra tio n (n g /m L ) <0.100 0.903 8.39 91.2 344 % R eco very NA 91.7 85.2 92.6 69.8 3 M L IM S ID G L P 1 0 -0 1 -0 2 -1 8 -13 3 G L P 1 0 -0 1 -0 2 -1 8 -13 4 D e s c rip tio n D A L G W 1 3 0 L R B 110630 D A L G W 1 3 3 S R B 110630 PFBS PFHS PFO S C o n c e n tra tio n (n g /m L ) <0.0250 <0.0250 % R ec o v e ry NA NA C o n c e n tra tio n (n g /m L ) <0.0250 <0.0250 % R ec o v e ry NA NA C o n c e n tra tio n (n g /m L ) <0.0400 0.0478 % R eco very NA NA NA = Not Applicable Reported results for PFBS and PFHS are from external standard calibration. Reported results for PFOS are from internal standard calibration. Page 38 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 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. All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. Attachment A: Protocol Amendment 18 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 39 o f 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Cleston LangerPh.D., 3M Principal Analytical Investigator ik h ]Z t J ) Date William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 40 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Attachment A : Protocol A mendment Page 41 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Analytical Protocol: G LP10-01-02 Amendment 18 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program PROTOCOL AMENDMENT NO. 18 Amendment Date: June 15,2011 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-02 Sampling Event Former Sludge Incorporation Area (FSIA) Groundwater Page 1 of 8 Page 42 o f 113 GLP10-01-02; Interim R eport 18 A nalysis o f PFBS, PFHS, and PFOS In W ater Sam ples F S IA -J u n e 2011 Analytical Protocol: G LP10-01-02 Amendment 18 This amendment modifies the following portion of protocol: "Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. Amend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples from Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe during the week of June 20,2011. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-02-18 and reported as interim report GLP10-01-0218, (reflecting study GLP10-01-02 and amendment-18). Reason: The reason for this amendment is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The GPO is five pages in length and included as attached to this amendment form. Page 2 of 8 Page 43 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS In W ater Samples FSIA - June 2011 Analytical Protocol: G LP10-01-02 Amendment 18 Amendment Approval Gestori C. Lange, Principal Analytical Investigator William Reagen, EHS Opns Environmental Lab Management JI&(.A// Jaisimha Kesari P.BfDEE, Study Director Date Date Page 3 of 8 Page 44 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 Analytical Protocol: GLP10-01-Q2 Amendment 18 wmm Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: Gary Hohertstein, 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 June 15,2011 Analysis of Perfluorooctane Sulfonate (PFOS), Perfiuorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 18 - Former Sludge Incorporation Area (FSIA) Groundwater - June 2011 Sampling 1 General Project Information Contacts Lab Request Number Six Digit Department Number Project Scheduledrat Dates 3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 aahohensteiniSmmm.com 3M Environmental Laboratory Management William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaoeniffimmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclanaeiffimmm.com Sampling Coordinator Timothy Frinak Weston Solutions Timothv.frinakiffiwestonsolutions.com Phone: <3341-332-9123 G IP10-01-02-18 Dept #530711. Project #0022674449 Sampling scheduled for the week of June 20,2011 All verbal and written correspondence will be directed to G ary Hohenstein. Page 4 of 8 Page 45 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Analytical Protocol: G LP10-01-02 Amendment 18 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze groundwater samples collected from twenty-seven groundwater wells for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) from the Former Sludge Incorporation Area (FSIA). Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples from Decatur, AL will be collected by Weston Solutions personnel the week of June 15,2011. The 3M Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are of a known precision and accuracy. The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP10-01-0218. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of June 20, 2011. Sample bottles will be shipped in coolers overnight to 3M Decaturfor arrival on Friday, June 17,2011. 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 PFBS, PFHS, and PFOS. A total of thirty-one sampling locations have been specified. For each sampling location, a sample, sample duplicate and a minimum of two field matrix spikes will be collected. Table 1 indicates the well ID and corresponding field spike levels. The *1111to here" line on each 250 mL Nalgene bottlewill be 200 mL. Two sets of trip blanks consisting of reagent-grade water, a low-level trip blank spike, mid-level field spike, mid-high field spike, and a high-level trip blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. Two additional bottles will be prepared to be used for the preparation ofthe equipment rinseate blanks. A1-L container of laboratory reagent water will be provided for the collection of the equipment rinseate blanks. Based on the results from previously collected samples from the FSIA (GLP10-01-02-07 and GLP10-01-02-11), mostsampling locations will require dilutionwith laboratory reagentwater prior to sample analysis. However, sampling locations identified in Set 1 of Table 1 are expected to contain PFBS, PFHS, and PFOS concentrations <10 ng/mL. For samples collected from these sampling locations, toe sample, sample duplicate and field matrix spikeswill contain the addition of internal standard 1<tOrPFBS, " CyPFHS, and 13CrPFOS, at a nominal concentration of 1 ng/mL, as will the trip blanks samples, trip blank low spikes, and two equipment rinseate blanks. The additional of internal standardswill be used to aid in toe analysis ofthe samples. A total of 169 sample bottles will be prepared. Page 5 of 8 Page 46 o f 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Analytical Protocol: G LP10-01-02 Amendment 18 Table 1. Sampling Locations and Field Matrix Spike levels. Set# Well No. Sample Level 1 134S, 135S, 136R, 137R, 137S, 137Land 138L 130L, 131S, 131L, 133R, 2 135L.136S, 136L 141R, 142R, 143R and 144R 130R, 130S, 133S, 133L, 3 134L, 138R, 138S, CW26C, CW26L and 140R 4 131R, 134R and 135R 5 Trip Blank Sets 1 and 2 Low Mid High Low Mid Hiah Low Mid High Low Hiah Low Mid Mid-Hiah High Spike Cone (ng/mL) 0.1 1.0 10 1 10 100 10 100 500 100 2000 1 10 100 500 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". The data quality objectives for these studies are quantitative results for foe target analytes with an analytical accuracy of 10030%. Field matrix spites not yielding recoveries within 10030% will be addressed in foe reportand foe final accuracy statement may be adjusted accordingly. Based on foe results from previously collected samples from foe FSIA (GLP10-01-02-07), most sampling locations will require dilution with laboratory reagent water priorto sample analysis by ETS-8-044.0. For samples containing internal standard: samples will be analyzed against an internal standard calibration curve. Each curve pointwill contain isotopically-labeied perfluorocarboxylic acids and perfluorosulfonic acids at a nominal concentration of 1 ng/mL. The calibration curve will be generated by taking foe ratio ofthe standard peak area counts over the internal standard peak area counts to fitthe data for each analyte. Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry"or ETS-8-110.1 "Method ofAnalysis for foe Determination of Perfluorinated Compounds in Water, Soil and Sediment by LC/MS/MS*. 6 Reporting Requirements For each sampling location, foe report will contain foe results for foe sample, sample duplicate, and field matrix spikes. Trip blank and trip blank spikes will be reported for the sampling event as win any equipment/rinseate blanks prepared in the field. Laboratory control spikes of reagentwater prepared at the time of sample preparation will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagentwater prepared at the time of sample preparation will be used to determine foe method detection Omit For those sampling locationswhere foe field matrix spice level was not appropriate, due to higherthan expected analyte concentrations, a laboratory matrix spike may be prepared and will be included in the final report Page 6 of 8 Page 47 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS In W ater Samples FSIA - June 2011 Analytical Protocol: G LP10-01-02 Amendment 18 7 Email Correspondence Quarterly GW sampling - Decatur Former Sludge Incorporation Area Wells Young, Charles T. to : s tw o tf@ m m m .c o m 06/13/201102:14 PM Cc: " Frinak, T im o th y R." , " Sm ith, M a rtin " Sue: WESTON w ill b e perform ing q u arterly gro un d w ater sam pling o f th e fo rm er sludge incorporation area (FSIA) w ells beginning on June 2 0 ,2 0 1 1 . The attached w ord docum ent shows th e FSIA w ells (highlighted in yello w ) th a t w ill be sam pled fo r fluorochem ical analyses.under G LP10-01 -01 and G LP10-01-02. It also shows sam pling schedule fo r o th e r q uarterly sam pling (and conventional param eters) Also attached is a spreadsheet sum m ary ta b le fro m th e m ost recen t (N o v-2010) round a t th e FSIA w ells. In addition to th e p rim ary/d u p licate/sp ike b ottles, w e w ill need bottles and M illi-Q w a te r fo r th e tw o equipm ent rlnseate blanks th a t w ill b e collected. Thanks, C h a rlie Charles T. Young Technical D irector W eston Solutions, Inc. 1400 W eston W ay (5 -2 ) W est Chester, PA 19380 (6 1 0 )7 0 1 -3 7 8 7 Fax (610) 701-3401 Page 7 of 8 Page 48 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -Ju n e 2011 Analytical Protocol: G LP10-01-02 Amendment 18 Quarterly GW Monitoring 201L 203L* 204L 206L 209L 211R 212R 212D 213R 213S 215R First and Third Quarter Monitoring Program 215D 223R 306R 328R* 216R 225R 307L 328L* 217R 225L 308R 330R* 217S 226R 31OR* 330L* 217D 226L 311R 332S 218R 227R* 313R 335R* 218L 227L* 315R 501 220R* 228R 317L* 503 220L* 228L 319L 507 221R 229R 324L* 51OR 222R* 229L 325L 510L 511S 512R 512L GRS04*3 RW312R* RW327R* RW331S* 201L 203L 211R 212R 212D 213R 213S 217R 217S 217D Second and Fourth Quarter Monitoring Program 218R 324L 131S** 136R** 218L 325L 131L** 136S** 222R 332S 133R** 136L** 223R 335R 133S** 137R** 229R 512R 133L** 137S** 229L 512L 134R** 137L** 305R 130R** 134S** 138R** 307L 130S** 134L** 138S** 313R 130L** 135R** 138L** 315R 131R** 135S** CW26C** 135L** CW26L** 140R** 141R** 142R** 143R** 144R** Monitoring wells will be analyzed lor VO Cs and isopropyl ether using EPA Method 8260 unless otherwise indicated. (*) Monitoring wells will be analyzed for PFOA, and VO Cs / isopropyl etherusing EPA Method 8260. (**) Monitoreig wells will be analyzed for PFOA. aOne sample will be collected from the closed landfill (SW M U4) groundwater extraction system for VO C and PFOA analysis. RW indicate recovery wells used in active grow dw ater extraction systems. Page 8 of 8 Page 49 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Attachment B : Representative Sam ple C hromatograms and Calibr atio n C urve(s) Page 50 of 113 Workstation: ETSKIRK GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Time: 2:05:58 PM Printing Date: Wednesday, July 27, 2011 Page 51 o f 113 Workstation: ETSKIRK GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Time: 2:07:54 PM Printing Date: Wednesday, July 27, 2011 Page 52 of 113 Workstation: ETSKIRK GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Time: 2:07:19 PM Printing Date: Wednesday, July 27, 2011 Page 53 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Time: 12:06:00 PM Printing Date: Tuesday, September Page 54 of 113 *ETS-Kirk Sample Nam: >110720*035' Sample 10:*LCS-110714-7* Fie: *k110720a.MfT I Peak Name: "PFBS' Maaa(as): *299-000/80.000 Da,299.000/99.000 Da* Comment: *30pp LCS* Annotation: " Sample Index: 35 Sample Type: QC Concentration: 29.9 Calculated C o m Acq. Date: Acq. Time: Modified: Yes Proc. Algorithm: Specify Par Noise Percentage: 50 Base. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 3 Expected RT: 13.2ml Use Relative RT: No Int. Type: Manual Retention Time: 13.2 min Area: '31344694 c Height: 5.63e+006 cps Start Time: 13.0 min End Time: 13.9 min I t 1 [ Sample Nam#: T<110720*045" Sample ID:*LCS-110714-13* FUe:*k110720a.wHT Peak Name: *PF8S* Masses): *299.000/80.000 Da.299.000/99.000 Oa* SamCpolmemeInntd:e^xp:pb LCS E4C5F* Annotation: ** Sample Type: QC Concentration: 0.00 ng/mL Calculated Cone: 0.0539 ng/mL Acq. Date: 7/21/2011 Acq. Time: 12:42:49 AM Modified: Proc. Algorithm: Specify Parameters - MQ III Noise Percentage 50 Base. Sub. Window : 1.00 min Peak-Split. Facte Report Largest Peak: Yes Min. Peak Height 0 . 0 0 cps Min. Peak Width: 0 . 00 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: 13.2 min Use Relative RT: Int. Type: Valley Retention Time: 13.2 min Area: 79581 counts Height: 1 .17e+004 cps Start Time: 13.0 min End Time: 13.5 min 1.15*4 1.10*4 1.05*4 1.00*4 9500.00 9000.00 8500.00 8000.00 7500.00 7000.00 5500.00 & 2s- 6000.00 TJ 1 5500.00 5000.00 4500.00 4000.00 3500.00 3000.00 2500.00 2000.00 1500.00 1000.00 50 0.00 11.0 11.5 Data printed by STW Printing Time: 12:06:00 PM Printing Date: Tuesday, September 06, 2011 12.0 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb I Sample Name: K110720a042* Sample ID: IC S -1 10714-10* File: *k110720a. Peak Name: *PFBS* Ma(*a): *299.000/80.000 Da.299.000/99.000 Da* Comment *0.5ppb LCS ECF* Annotation: " Simple Index: 42 Sample Type: QC Concentration: 0.00 ng/mL Calculated Cone: 0.00377 ng/mL Acq. Date: 7/20/2011 Acq. Time: 11:39:53 PM Modified: No Proc. Algorithm: Specify Parameters - Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT ; Rele : RT: Height: Start Time: End Time: .556+003 cps I Sample Name:*k110720*048" Sample ID;*LCS-110714-18" Ftte;*k110720a.wr Peak Name: *PFBS* Masses): *299.000/80.000 Da.299.000/99.000 Da' Comment *30ppb LCS ECF* Annotation: ** Sample Index: 49 Sample Type: QC Concentration: Calculated Cone: 0.00 ng/mL 0.323 na/mL 8>5#4 Acq. Date: 7/21/2011 ' Acq. Time: Modified: 1:45:41 AM 6.0e4 SOProc. Algorithm: Specify Par. ,C6rs - MQ III Noise Percentage: Base. Sub. Window: 1.00 Peak-Split. Facto: Report Largest Pe Min. Peak Height: 0.00 cps 5 .0*4 - Min. Peak Width: Smoothing Width: RT Window: 0 points 4.5*4- Expected RT 13.2 min : Relat : RT: Int. Type: 4.0*4- Retention Time: 13.2 min Area: 41 662 counts Height: ' 69e+004 cps & 3.5*4 Start Time: End Time: 12.9 min 1 3.0*4 2.5*4 2.0*4 1.5*4 1.0*4- 5000.0 0.0- Page 2 of 29 Page 55 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Data printed by STW Printing Time: 12:06:00 PM Printing Date: Tuesday, September 06 2011 Page 3 of 29 Page 56 o f 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS In W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 57 of 113 ETS-Kirk Data printed by STW Printing Time: 12:06:01 PM Printing Date: Tuesday, September 06, 2011 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Page 58 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Time 12:06:01 PM Printing Date: Tuesday, September 06, 2011 Page 59 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 60 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Time: 12:06:01 PM Printing Date: Tuesday, September 06, Page 61 o f 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in Water Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 62 of 113 *ETS-Kirk Data printed by STW Printing Time: 12:06:01 PM Printing Date: Tuesday, September 06, 2011 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -Ju n e 2011 Results Name: kll0720a.rdb I Sample Name: T<110720a145* Sample ID: GLP10-01-02-1S-066' Fite: Peak Name: *PFBS* Mass(ee): '299.000/80.000 Da,299.000/99.000 Da' Comment T rip Blank Sal 1 MS* Annotation: " Sample Index: 145 Sample Type: Unknown Concentration: N/A Calculated Cone: 10.3 ng/mL Acq. Date: 7/22/2011 Acq. Time: 11:41:15 AM Modified: Yes Proc. Algorithm: Specify Parameters - MQ H I Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: 13.2 min Use Relative RT: No Retenti Area : Height: Manual e: 13.1 rain 13821158 counts 2.15e006 cps 13.0 rain 13.8 min Sample Name:*V1107kta02F~ Sample ID:'SolventBtank* >1107208. Peak Name: *PFHS* Maaa(ea): *399.000/99.000 Da,399.000/80.000 Da* Comment >4Si Q Vtoter TN11-0238" Annotation: " Sample Index: 28 Sample Type: Unknown Concentration: N/A Calculated Cone: < 0 Acq. Date: - 7/20/2011 Acq. Time: 6:46:26 PM Modified: No Proc. Algorithm: Specify Parameters - M Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor Report Largest Peal Peak Height: 0 . 0 0 cps Min. Peak Width: Smoothing Width: RT Window: Expected RT: Use Relative RT: Height: Start Time: End Time: Base To Base 14.9 min 12075 counts 2.03e*003 cps Page 10 of 29 Page 63 of 113 *ETS-Kirk Sample Nam: >1107208029* Sample ID:'LCS-110714-1" Fle:*k110720a.wir I P*ak Name: 'PFHS' Masses): "399.000,-99.000 Da.399.000/80.000 Oa* I Comment: "0.5ppb LCS" Annotation: *" Sample Index: 29 Sample Type: QC Concentration: 0.498 ng/mL Calculated Cone: 0.524 ng/mL Acq. Date: 7/20/2011 1.20e5 Acq. Time: 7:07:21 PM 1.15e5 Modified: Yes Proc. Algorithm: Specify Paramet' Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 : Expected RT: 14.9 Use Relative RT: I.IOeS 1.05*5 1.00*5 9.50*4 9.00*4 8.50*4 8.00*4 7.50*4 Retention Time: 7 .0 " 6.50*4 8I 6.00*4 = 5.50*4 5.00*4 4.50*4 4.00*4 3.50*4 3.00*4 2.50*4 2.00*4 1.50*4 1.00*4 sooaoo 0.00 12.5 ( Sample Name: *k110720*035" Sample ID: *LCS-110714-7* Fle:Tc110720a.wlfr Peak Name: 'PFHS* Masses): *399.000/99.000 Da.399.000/80.000 Da* Comment: *30ppb LCS* Annotation: ** Sample Index: 35 Sample Type: C Concentration: 29.9 ng/mL Calculated Cone: 30.1 ng/mL Acq. Date: 7/20/2011 6 Acq. Time: 9:13:06 PM Modified: No Proc. Algorithm: Specify Parameters - M0 III Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Larqest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: Smoothing Width: 0.00 sec 0 points RT Window: 30.0 sec Expected RT: 14.9 min Use Relative RT: No g 4 4 Height : Start Tiro, End Time: 41799969 C 5.74e+006 cps 14.7 min 15.2 min GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll072Oa.rdb I Sample Nam*: *k110720a032* Sampl*ID:*LCS-110714-4* F I*: "k110720*.v4fr Peak Nam*: 'PFHS* Masses): *399.000/99.000 Da.399.000/80.000 Da* Comment *Sppb LCS* Annotation: ** Sample Index: 32 Calculated Cone: 5.21 ng/mL Acq. Date: 7/20/2011 Acq. Time: 8:10:12 PM Modified: No Proc. Algorithm: Specify Parameters - MQ III Noise Percentage: Base. Sub. Window: Peak-Split. Factor: 50 1.00 2 min Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 sec I RT: ! RT: Int. Type: Retention Time: Height: Start Tim, End Time: 1.15*6 1.10*6 1.05*6 1.00*6 9.50*5 9.00*5 6.50*5 6.00*5 7.50*5 7.00*5 6.50*5 ' 6.00*5 5.50*5 5.00*5 4.50*5 4.00*5 3.50*5 3.00*5 2.50*5 2.00*5 1.50*5 1.00*5 5.00*4 0.00 12.5 I Sample Name: >110720*042" Sample ID: *LCS-110714-10* Flte:*k110720a.vWr Peak Nam*: `PFHS* Masses}: "399.000/99.000 Da.399.000/80.000 Da* Comment "O.Sppb LCS ECF* Annotation: ** Sample Index: 42 Sample Type: C Concentration: 0.00 ng/mL Calcuiated Cone: 0.0245 ncr/mL AAccqq.. TDiamtee:: 71/12:03/92:05131 PM 6500- Modified: No Proc. Algorithm: Specify Parameter: Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: Min. Peak Width: 0.00 cps 0 .0 0 sec Smoothing Width: RT Window: 30.0 Expected RT: : Relai : RT: 14.5 15.0 15.5 16.0 16.5 17.0 12.5 13.0 13.5 14.0 14.5 ' 15.0 15.5 16.0 16.5 17.0 Data printed by STW Printing Time: 12:06:01 PM Printing Date: Tuesday, September 06, 2011 Page 11 of 29 Page 64 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Time: 12:06:01 PM Printing Date: Tuesday, September 06, 2011 Page 65 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 66 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Time: 12:06:02 PM Printing Date: Tuesday, September 06, Page 67 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 68 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Data printed by STW Printing Time: 12:06:02 PM Printing Date: Tuesday, September 06 2011 Page 16 of 29 Page 69 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 70 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -June 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 71 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 72 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 73 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0720a.rdb Data printed by STW Printing Time: 12:06:02 PM Printing Date Tuesday September 06 2011 Page 21 of 29 Page 74 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb ISampteNam:T<110720#Oer SampleID:'GLP1&01-02-18-006' FU*:1 Peak Naim: *PFOS* Maskat): '499.000f99.000 Da.499.000/80.000 Da,49 Comment*DALGW 130R0110630(d 1:100)' Annotation:' Sample Index: 61 Sample Type: Unknown Concentration: N/A 22e5-i Calculated Cone: 440. ng/mL Acq. Date: 7/21/2011 Zl $ Acq. Time: 6:18:06 AM 2.0*5- Modified: Yes Proc. Algorithm: Specify Parameter: 1.9*5 Noise Percentage: Base. Sub. Window: SO 1.00 min 1.8*5- Peak-Split. Factor: 2 Report Largest Peak: Yes 1.7*5- Peak Height: Min. Peak Width: cps 1.6*5 Smoothing Width: RT Window: 1.5*5- Expected RT: Use Relative RT: 1.4*5 Height: Start Time End Time: le: 15.7 min 3140308 counts 1.3*5 1.2*51.1*5 1.0*5- 9.0*4- 8.0*4- 7.0*4- 6.0*4- 5.0*4- 4.0*4- 3.0*4- 2.0*4- 1.0*4- 13.5 14.0 I Sample Name: 1(110720a07S' Sample ID: 'GLP1Q01-02-18-016" File:T<110720a.wMT Peak Name: 'PFOS* Mass(*8): '499.000f99.000 Da,499.000/80.000 Oa,499.000/130.000 Da' Comment:*DALGW130L 0110630(dl 1:10)* Annotation:' Sample Index: 75 Sample Type: Unknown Concentration: N/A Calculated Cone: 62.0 Acq. Date: 7/21/2011 ng/mL 3-2e5' Acq. Time: 11:11:52 AM Modified: Yes Proc. Algorithm: Specify Paramet- Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 8 Report Largest Peak: Yes Min. Peak Height: - M0 III 3.0*5 Min. Peak Width: Smoothing Width: s Relative RT: 30.0 15.9 Base To Ba3 e 1.4*5 1.2*5 1.0*5 8.0*4 6.0*4 4.0*4 20*4 0.0 Data printed by STW Printing Time: 12:06:02 PM Printing Date: Tuesday, September 06, 2011 Sample Nam*: 1(1107208070' Sampl* ID:'GLP1Q01-02-18-01 f FUe:1 Peak Name: 'PFOS* Mass(as): '499.000/99.000 Da,499.000/80.000 Da,4! Comment *DAL GW 130S 0 110630 (d31:10)* Annotation:" Sample Index: 70 Sample Type: Unknown njlate. N/A 100. ng/mL 5 .2*5 - 5 .0*5 - Modified: Yes Proc. Algorithm: Specify Parameters - MQ III Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 6 Report Largest Peak: Yes Min. Peak Height: Min. Peak Width; Smoothing Width: RT Window: : Expected RT: Use Rela s RT: 4 .8*5 4 .6*5 4 .4*5 4.2*54.0*53.8*53.6*53.4*53.2*5- 7070817 cc 5.24e+005 15.3 16.4 3.0*52.8*526*52.4*5- 2.2*5- 20*51.6*5- 1.6*5- 1.4*5- IAS- 1.0*5- 8.0*4- 135 14.0 I Sample Name: K110720a08T Sample ID: 'GIP1001-02-18-02S' File: *k11072Oa.wtr Peak Name: 'PFOS* Mass(*a): '499.000/99.000 Da.499.000/80.000 Da,499.000/130.000 Da' Comment *D A LGW 131S0110622 (dQ1:10)' Annotation:" Sample Index: 88 Sample Type: Unknown Concentration: N/A Calculated Cone: 5.31 ng/mL Acq. Date: Acq. Time: 7/21/2011 3:44:45 PM 3.2*4- mtage: 90 Base. Sub. Window: 1.00 min Peak-Split. Factor: 3 Report Largest Peak: Yes Min. Peak Height: Min. Peak Width: 0.00 cps 0.00 3ec Smoothing Width; 0 pol RT Window: 30.0 3ec Expected RT: 15.9 Relai ! RT: Base To Base Height : Start Time: End Time: 15.0 15.5 16.0 16.5 17.0 1 7 5 18.0 Page 22 of 29 15.0 15.S 16.0 165 17.0 17.5 18.0 ---- 15.0 15.5 16.0 165 17.0 1 7 5 18.0 Page 75 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS In W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Date: Tuesday, September 06, 2011 Page 76 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Printing Time: 12:06:02 PM . Printing Date: Tuesday, September 06, Page 77 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Sample Type: Concentration Calculated v Acq. Date: Acq. Time: Specify Parametei Noise Per-centage: SO Base. Sub . Window: 1 .0 0 min Peak-Spli t. Factor: 3 Repor t La rgest Peak: Yes Kin. Peak Height: 0 .0 0 cps Min. Peak Width: 0.00 Smoothing Width: 0 poll Base To Base Retention Time: 15.7 min Area: 3605106 counts Height: 2.71e+00S cps Start Time: 15.3 min End Time: 16.3 min 2.9*5 2.5*5 2.4*5 2.3*5 2-2*5 2.1*5 2.0*5 1.0*5 1.8*5 1.7*5 1.6*5 1 1.5*5 1.4*5 1.3*5 1 1.2*5 1.1*5 1.0*5 9.0*4 8.0*4 7.0*4 6.0*4 5.0*4 4.0*4 3.0*4 2.0*4 1.0*4 0.0 13.5 14.0 ( Sample Nam*: '*110720*166' Sample ID: 'Gl.P10-01-02-18-079- File: 1(110720a.*4r Peak Name:'PFOS* Mashas): '499.00CV99.000 Da,499.000/B0.000 Da.499.00CV130.000 Da* Comment: "DAL GW135R 0110628 (da 1:100)' Annotation: ~ Sample Index: 166 . Sample Type: Unknown Concentration: N/A Calculated Cone: 1020. ng/mL 65*5- Acq. Date: 7/22/2011 '1 Acq. Time: 7:01:56 PM Modified: Yes Proc. Algorithm: Specify Parameter: Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 7 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 poll RT Window: 30.0 3 ec Expected RT; 15.9 min Use Relative RT: No 6.0*5 5.5*5 5.0*5 45*5 Int Type: Base To Base ntlon Time: 15.7 mil : 7191513 count; Height: 6.80e+005 ops Start Tim 15.3 End Time: 4.0*5 3.5*5 3.0*5 25*5 2.0*5 Data printed by STW Printing Time: 12:06:03 PM Printing Date: Tuesday, September 06, 2011 15.0 15.5 16.0 16.5 17.0 17.5 18.0 Time, min 155 155 t6.0 165 175 175 185 I Semple Nam*: 1(110720*157* Sample ID: 'GLPIDOI42-18-074' FUe:"k110720a.wtfr Peak Nam*: 'PFOS* Ma*s(e9): *499.000/99.000 Da.499.CXXV80.000 Da,499.000/130.000 Da* Comment *DAL GW 13 5L 0110628 (dl 1:10)* Annotation: ** Sample Index: 157 Sample Type: Unknown Concentration: Calculated Cone: N/A 55.5 ng/mL 4.2*5- Acq. Date: Acq. Time: 7/22/2011 3:53:03 PM 4.0*5 Modified: Yes Proc. Algorithm: Specify Parameters - MQ III Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Spilt. 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: Use Relai s RT: Mar.< il 15.6 min 3951824 counts 4.266+005 cps 15.3 min 16.0 min 3.8*5 3.8*5 3.4*5 3.2*5 3.0*5 2.8*5 2.6*5 2.4*5 2.2*5 2.0*5 1.8*5 1.8*5 1.4*5 1.2*5 1.0*5 8.0*4 6.0*4 4.0*4 Z0*4 0.0 135 14.0 I Sample Name: *k110720a1>9* Sample ID: 'GLP10-01-02-18-088* FUa:*k110720a.wttr Peak Name: ` PFOS* Masses): *499.000/99.000 Da.499.000/80.000 Da,499.000/130.000 Da* Comment *DAL GW 136S 0110830 (dll 1:10)* Annotation: ** Sample Index: 179 Sample Type: Unknown Concentration: N/A Calculated Cone: 115. ng/mL Acq. Date: Acq. Time: 7/22/2011 11:35:01 PM BdeS 1 ; Per< Base. Sub. Window: Peak-Split. Factor: Report Largest Peal Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: 30.0 Expected RT: 25.9 Use Relative RT ailn Int. Type : Manual Retention Time: 15.8 min 095614 counts Height : 6.40e+00S cps Start Time: 15.4 min End Time: 16.4 min 4.0*5 3.5*5 i 3.0*5 25*5 2.0*5 1.5*5 1.0*5 5.0*4 15.0 15.5 16.0 16 5 17.0 1 7 5 18.0 135 145 145 15.0 155 165 165 175 175 185 Page 25 of 29 Page 78 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples FSIA - June 2011 Results Name: kll0720a.rdb u d id p i iiiu e u uy D in Printing Time: 12:06:03 PM Printing Date: Tuesday, September 06, 2011 Page 26 of 29 Page 79 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb I SampleNem*:T<110720a207* Sampl* tD:"GLP1001-02-18-108* FUe:<V110720a.wtr Peak Name: *PF0S* Masses): 499.00tV99.000 Da,499.000/80.000 Da,499.00CV130.000 Da* Comment: *0ALGW138L 0110630* Annotation:' Sample Index: 207 Sample Type: Unknown Concentration: N/A Calculated Cone: 0.339 ng/mL 1.Se4 Acq. Date: 7/23/2011 ' Acq. Time: 9:22:54 AM 18*4 Modified: Yes Proc. Algorithm: Specify Parameters - M0 III Noise Percentage: 50 Base. Sub. Window: 1 .0 0 min Peak-Split.Factor: 4 Report Largest Peak: Yes Min, Peak Height: 0 .0 0 cps Min. Peak Width: 0 .'' Smoothing Width: 0 RT Window: 30.0 Expected RT: min : RT: No Base To Basi 1.74 1.6*4 f .5 * 4 1.4*4 1.3*4 12*4 1.1*4 1.0 9000.0 8000.0 7000.0 6000.0 5000.0 4000.0 3000.0 2000.0 1000.0 0Ql 13.5 14.0 14.5 rSample Name: "k110720a22r Sample ID: "GLP10-01-02-18-118" File: "k110720a.wir Peak Name:'PFOS* Mass(ea): *499.000/99.000 Da.499.000/80.000 Da.499.000/130.000 Da" I Comment:-0ALOWCW26C 0110622(dH1:10)' Annotation:- Sample Index: 221 Sample Type: Unknown Concentration: N/A Calculated Cone: 398. ng/mL Acq. Date: 7/23/2011 3.6*5 Acq. Time: 2:16:52 PM 3.4e5 Modified: Yes Proc. Algorithm: Specify Parameters - M0 III Noise Percentage so Base. Sub. Window: 1.00 min Peak-Split. Factor: 6 Report Largest P< ak: Yes Min. Peak Height 0 .0 0 cps Min. Peak Width: 0 .0 0 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: 15.9 min Use Relative RT: No 3.2e5 3.0*5 28*9 2.6*5 2.4*5 Int. Type: Base To Base Retention Time: 15.8 min Area: 5630287 counts Height: 3 74e*005 cps Start Time: 15.4 min End Time: 16.4 min 2.2*5 & 2.0*5 S 1.8*5 1 1.6*5 1.4*5 1.2*5 1.0*5 8.0*4 6.0*4 4.0*4 2.0*4 0.0 Data printed by STW Printing Time: 12:06:03 PM Printing Date: Tuesday, September 06, 15.0 15.0 15.5 158 16.0 16.0 l/.lUs. 18.5 17.0 17.5 168 17.0 178 18.0 18.0 I Sample Name: "kl 10720a212" Sample ID; *GLP104)1-02-18-113* Ffe>: :*k110720a.wtr Peak Name: *PFOS* Maw{): *499.000/99.000 Da.499.00tV80.000 Da,,499.000/130.000 Da* Comment*DAL GW 138S 0110630(491:10)* Annotation:" Sample Index: 212 Sample Type: Unknown Concentration: N/A Calculated Cone: 194. ng/mL e-e Acq. Date: 7/23/2011 ' Acq. Time: 11:09:02 AM 1.10e$ Nois< Pere Base. Sub. Window: Peak-Split. Factor: Report Largest Peak: Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: 3( Expected RT: : Rela : RT: Height : Start Time: End Time: 15.8 min 13359050 count3 1.19e+006 cps 2 III 1.056 1.00a6 9.50e5 9.00a5 8.50*5 8.00*5 780*5 7.00e5 | 6.50*5 ^ 6.00*5 | 5.50e5 5.00e5 4.50*5 4.00*5 3.50*5 3.00*5 2.50*5 2.00*5 180*5 I.OOeS 5.00*4 0.00 138 14.0 Sample Name:*k110720*226" Sample ID: 'GLP10-0102-18-123* File:*k110720a.wir Peak Name: *PFOS* Masses): `499.000/99.000 Da,499.000/80.000 Da.499.000/130.000 Da* Comment *DAl GW CW26L 0110622 (dQ 1:10)* Arvtotatkm: " Sample Index: 226 Sample Type: Unknown Concentration: Calculated Cone: N/A 911. na/mL 98e5 Acq. Date: Acq. Time: 7/23/2011 ' 4:01:39 PM g.OeS Modified: Yes Proc. Algorithm: Specify Parameter: Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 6 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 poir RT Window: 30.0 sec Expected RT: 15.9 min Use Relative RT: No 6.5e5 8.0a5 7.5*5 7.0*5 6.5*5 6.0*5 Int. Type: Base To Base Retention Tim i: 15 .8 min Area: 12573911 i >unts Height: 9 . 58e +005 Start Time: min End Time: min 5.5*5 & 5.0*5 t S 4.5*5 4.0*5 3.5*5 3.0e5 2.5*5 2.0*5 1.5*5 1.0*5 5.0*4 0.0 Page 27 of 29 15.0 158 16.0 168 17.0 1 7 8 18.0 15.0 15.5 16.0 168 17.0 17 8 16.0 Page 80 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb Sample Nam*: >1107208237* Sample ID: *GLP1(H)1-02-18-123' File: "k110720a.tfl* I Peak Name: *PFOS* Masses): *489.00099.000 0a,499.000/80.000 Da,499.000/130.000 Da* Comment: *DAL GW 140R 0110622 (dil 1:10)* Annotation: ** Sample Index: 237 Sample Type: Unknown Concentration: N/A Calculated Cone: 119. Acq. Date: 7/23/201 Acq. Time: 7:52:16 Modified.- Yes Proc. Algorithm: Specify Parametei Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 pol RT Window: 30.0 3ec Expected F : Retai : RT: Int. Type: Manual Retention Time: 15.7 min Area: 6325647 counts 3.0*5 I 2.5eS 13.5 14.0 ( SampleName: 1c110720a25r Sample ID: *GlP104>1-02-1S-14Cr FBe:aV110720a.wirr Peak Name: *PFOS* Masses): *499.000/99.000 Da,499.000/80.000 Da.499.000/130.000 Da* Comment: "DAL GW 142R 0110622 (dil 1:10)* Annotation: *" Sample Index: 251 Sample Type: Unknown Concentration: Calculated Cone: N/A 82.6 ng/mL 5.2*5 Acq. Date: 7/24/2011 5.0*5 Acq. Time: 12:46:29 AM 4.8*5 Modified: Yes Proc. Algorithm: Specify Parameter: Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 poir RT Window: 30.0 sec Expected RT: : Rela< : RT: No Int. Type: Retention 1 Area : Height: Manual ie: 15.8 min 5636738 counts S.27e+005 cps 4.6*5 4.4*5 4.2*5 4.0*5 3.8*5 3.6 3.4*5 3.2*5 3.0*5 2.8*5 2.6*5 2.4*5 22*5 2.0*5 15*5 1.6*5 1.4*5 12*5 1.0*5 8.0*4 8.0*4 4.0*4 2.0*4 0.0- Data printed by STW Printing Time: 12:06:03 PM Printing Date: Tuesday, September 06, 2011 15.0 15.5 15.0 15.5 17.0 17.5 15.0 Sample Name: '*110720*246' Sample ID: *GLP10-01-02-18-135* FUe:"l Peak Name: 'PFOS* Masa(es): *499.000/99.000 Da,499.0r 00/80.000 Da,4S Comment*OALGW 141R0110530* Annotation:^ Sample Index: 246 Sample Type: Unknown Concentration: N/A ' Calculated Cone: 3.04 ng/mL Acq. Pate: 7/23/2011 2.1*5 Acq. Time: 11:01:17 PM 2.0e5 Modified: Yes Proc. Algorithm: Specify Parameters - M Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split.Factor: 2 Report Largest Peak: Min. Peak Height: 0.00 Min. Peak Width: 0. Smoothing Width: 0 RT Window: 30.0 Expected RT: : Rel. s RT: 1.9*5 1.6*5 1.7*5 1.6*5 1.5*5 1.4*5 1.3*5 Height : Start Time: End Time: 1.2*5 1.1*5 1.0*5 9.0*4 8.0*4 7.0*4 6.0*4 5.0*4 4.0*4 3.0*4 2.0*4 1.0*4 0.0 135 14.0 I Sample Name: 1(110720*260* Sample ID: *GLP10-01-02*18-145* File: Td 10720a.wtfT Peak Nam#: "PFOS* Masses): `499.000/99.000 Da,499.000/80.000 Da,499.000/130.000 Comment 'DAL GW 143R 0110622 (dB 1:10)* Annotation:' Sample Index: 260 Sample Type: Unknown Concentration: N/A Calculated Cone: 17.6 ng/mL Acq. Date: 7/24/2011 Acq. Time: 3:55:38 AM Modified: Yes Proc. Algorithm: Specify Parameters - MQ III Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 6 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Mln. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: 15.9 min Use Relative RT: No Height : Start Time: End Time: 15.7 1274SS0 co 9.82e+004 cps min 15.0 15.5 16.0 16.5 17.0 17.5 18.0 Time.mln __ Page 28 of 29 15.0 15.5 15.0 165 17.0 17.5 18.0 Page 81 of 113 *ETS-Kirk I Sample Name:"V110720a265* Sampte ID: "GIP10-01-02-18-1SO- Fite: "k110720a.wir Peak Nan: ` PFOS* Masses): `499.000/99.000 Da,499.000/80.000 Da,499.00Ck/130.000 Da" Comment:"DALGW 144S 0110628(dB 1:10)" Annotation:" Sample Index: 265 Sample Type: Unknown Concentration: N/A 4.6*4- Calculated Cone: 8.69 ng/mL Acq. Date: 7/24/2011 4.4*4- Acq. Time: 5:40:48 AM 4.2*4- Modified: Yes Proc. Algorithm: Specify Parameters - M0 H I 4.0*4 Noise Percentage: Base. Sub. Window : 50 1 .0 0 min 3.8*4 Peak-Split, facto r: 5 Report Largest Peak: Yes 3.6*4 Min. Peak Height: Min. Peak Width: 0 .0 0 cps 0 .0 0 sec 3.4*4 Smoothing Width: RT Window: 0 points 30.0 aec 3.2*4 Expected RT: Use Relative RT: 15.9 min No 3.0*4 Int. Type: Base To Base 2.8*4 Retention Time: 15.7 min 2.6*4 Area: Height: 623012 counts 4 .65e+004 cps & 2.4*4 Start Time: End Time: 15.4 min 1 6 .2 min |f 2.2*4 2.0*4 1S.66 1.8*4 1.6*4- 1.4*4- 1.2*4- 1.0*4- 8000.0- 6000.0- 4000.0- 2000.0 - 0.0 I....................I............................ '"filili 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0 17.5 _____________ Tim*, min Data printed by STW Printing Time: 12:06:03 PM Printing Date: Tuesday, September 06, 2011 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0720a.rdb I Sample Name: *k110720a145"Sample IO: 'G IP 10-01-02*11 Peak Name: *PFOS* Maes(es): `499.000/99.000 Da,499.001 Comment Trip Stank Set 1 MS* Annotation: " 9.5e5 Modified: No 9.0e5 Proc. Algorithm: Specify Parameters - MQ III se Percentage: 50 8.5e5 :e. Sub. Window: 1.00 Peak-Split. Factor: 2 min 8.0e5 Report Largest Peak: Yes i. Peak Height: 0.00 cps 7.5*5 Min. Peak Width: Smoothing Width: 0.00 sec 0 points 7.0e5 RT Window: 30.0 sec Expected RT: 15.9 : Relative RT: No min 6.5e5 .. Type: 6.0e5 Retention 1 Area: Height : 6661651 counts 1.00e+006 cps 15.7 min g, S.5e5 f 505 16.1 min 1 4.5e5 4.0e5 3.5e5 3.0e5 2.5*5 2.0e5 1.5e5 1.0*5 5.0*4 0.0 15 81 Page 29 of 29 I Page 82 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b.rdb Data printed by STW Printing Time: 12:08:22 PM Printing Date: Tuesday, September 06, 2011 Page 1 of 1 Page 83 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b.rdb Printing Date: Tuesday, September 06, 2011 Page 84 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in Water Samples F S IA - June 2011 Results Name: kll0729b.rdb Printing Date: Tuesday, September 06, 2011 Page 85 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0729b.rdb Data printed by STW Printing Time: 12:10:58 PM . Printing Date: Tuesday, September 06 2011 Page 3 of 7 Page 86 o f 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: k!10729b.rdb Printing Time: 12:10:58 PM Printing Date: Tuesday, September 06, 2011 Page 87 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b.rdb Printing Date: Tuesday, September 06, 2011 Page 88 of 113 *ETS-Kirk Sample ame: "kl 107296047" Sample ID: *LCS-110726-16* Flte:` vTl0729b.wirr Peak Name: 'PFOS* Masses): '499.000/99.000 Da,499.000/80.000 Da,499.00(V13( Comment *20ppb LCS ECF* Annotation: ** Sample Index: 47 Sample Type: QC Concentration: 19.8 ng/mL Calculated Cone: 22.9 ng/mL Acq. Date: 7/31/2011 Acq. Time: 9:25:45 AM Modified: Yes Proc. Algorithm: Specify Parameters - MO 1 Noise Percentage: So Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 3ec Expected RT: 16.2 min Use Relative RT: No Height: Start Time End Time: 16527493 counts 1 .66e*006 cps 15.8 min 14.0 14.5 I Sample Name: *k110729b081` Sample ID: *GLP1CwD1-02-18-09S* File: *k110729b.wltr Peak Name: *PFOS* Masses): *499.000/99.000 Da,499.000/80.000 Da,499.000/130.000 Comment: *DAL GW 137L 0110624* Annotation: " Sample Index: 81 Sample Type: Unknown Concentration: N/A Calculated Cone: 1.9: Acq. Date: 7/31/21 Acq. Time: 9:24:59 PM Yes Specify Parametej Noise Per er.tage: 50 Base. Sub Window 1.00 min Peak-Spll . Facto : 2 Report Largest Pe k: Yes Min. Peak Height: Min. Peak Width: 0.00.00 cps 3 sec Smoothing Width: 0 points RT Window 30.0 sec Expected RT: 16.2 rain Use Relat ve RT: No Int. Type Manual Retention Time: 16.1 min Area : 2172452 co nts Height: 2 43e+005 cps Start Tim* 15.8 min End Time: 16.4 min fr if H1 15.5 15.0 16.5 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b.rdb SampaNama:*k110729b072* Sample ID: 'G LP10-01-02-18-093* File: Tel 10729b.wtfT Peak Name:'PFOS* Masses): '499.000/99.000 Da,499.000/80.000 Da,499.000/130.000 Comment"DALGW137S 011062-r Annotation:" Sample Index: 72 Sample Type: Unknown Concentration: N/A Calculated Cone: 0.498 [ 7/31/2011 Acq. Time: 6:14:27 PM Modified: Yes Proc. Algorithm: Specify Parameters Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: Smoothing Width: 0.00 sec 0 RT Window: 30.0 Expected RT: 16.2 Use Relative RT: No Int. Type: Manual 1 counts 004 cps .5.8 min .6.3 min 1 # 1 I Sample Name: *k110729b086* Sample ID: "GLPlb4142-1i Peak Name: "PFOS* Masses): *499.000/99.000 Da,499.0T Comment "DAL GW 13810110630* Annotation: ~ Sample Index: 86 Sample Type: Unknown Concentration: N/A Calculated Cone: 0.840 no/mL Acq. Date: 7/31/2011 Acq. Time: 11:10:47PM Modified: Yes Proc. Algorithm: Specify Parameters - MQ Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 3ec Smoothing Width: 0 points RT Window: 30.0 sec Expected RT: 16.2 min Use Relative RT: No Int. Type: Manual Height : Start Time: End Time: Data printed by STW Printing Time: 12:10:58 PM Printing Date: Tuesday, September 06, 2011 Page 6 of 7 15.5 16.0 16.5 17.0 17.5 18.0 185 Page 89 of 113 ETS-Kirk Printing Time: 12:10:58 PM Printing Date: Tuesday, September 06, 2011 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b.rdb Page 90 of 113 Workstation : ETSKIRK GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b ext.rdb Printing Time: 12:04:36 PM Printing Date: Wednesday, August 03, 2011 Page 91 of 113 `ETS-Kirk 10comment nemtL f c eta n syrrth. water Sample Index: 19 Sample Type: Standard Concentration 10.0 ng/mL Calculated 9.09 ng/mL Acq. Date: 7/30/2011 Acq. Time: Annotation: Modified: Proc. Algorithm: ! Percentage: Base. Sub. Window: Peak-Split. Factor: Report Largert Peak: Min. Peak Height: n. Peak Width: Smoothing Width: RT Window: Expected RT: ! Relative RT GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b ext.rdb Data printed by STW Printing Time: 12:13:00 PM Printing Date: Tuesday, September 06, 2011 Page 1 of 2 Page 92 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0729b ext.rdb [ Sample Nam*: "kl 107296044* Sample ID: IC S -1 10728-13" File: *k110729b.wir Peak Name: *PFOS* Msaa(*e): *499.000/99.000 De,499.000/80.000 Da.499.OOCV130.000 Da* Comment *2ppb LCS ECF* Annotation: ** Sample Index Sample Type: Concentratici 1.98 r Calculated C< 2.04 r Acq. Date: 7/31/2011 Acq. Time: 8:22:25 AM Modified: Proc. Algorithm: Noise Percentage: Base. Sub. Window: Peak-Split. Factor: Report Largest Peak: Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: 3. Expected RT: Use Relative RT: l 1.00 min Mani Time: 16.1 min 1464074 counts Height: 1.53e*00S cps Start Time 15.8 min End Time: 16.3 min I Sample Name: K 1107296047" Sample ID: "L C W 10726-16" File: "k110729b.wtr Peak Name: 'PFOS* Meea(es): *499.000/99.000 Da.499.000/80.000 Da.499.000/130.000 Da* Comment *20ppb LCS ECF* Annotation: ** Sample Inde) Sample Type; Concentrator 19.8 Calculated C< 17.2 Acq. Date: 7/31/2011 Acq. Time: 9:25:45 A Modified: 1 Proc. Algorithm: Spe< Noise Percentage: Base. Sub. Window: Peak-Split. Factor: Report Largest Peak: Min. Peak Height: Min. Peak Width: Smoothing Width: RT Window: 3< Expected RT: ] Use Relative RT: t Int Type: Mam Retention Time; 16.1 min Area: 16S1S14S counts Height: 1.S6e+006 cps Start Time: 15.8 min End Time: 16.4 min - 1 i i 7.0e5 6.0*5 5.0*5 4.0*5- 3.0*5- 2.0*5- I.OeS- 1S.0 15.5 16.0 165 17.0 175 18.0 165 I Sample Name: K110729b055* Sample ID: *GLP104)14)2*18-021* File: *1 1 0 7 2 9 6 *!? Peak Name: 'PFOS* Masses): ' 499.00Cy99.000 Da,499.000/30.000 Da.499.000/130.000 Da* Comment: *DAL GW 131R 0110622 (dll 1:100)* Annotation: ** Sample Index: 55 Sample Type: Unknown Concentration: N/A Calculated Cone: 1530. ng/mL Acq. Date: 7/31/2011 Acq. Time: 12:14:44 PM Modified: Yes Proc. Algorithm: Specify Parameters - M0 III Noise Percentage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes n. Peak Height cps Kin. Peak Width: Smoothing Width: points RT Window: 30.0 Expected RT: 16.2 min Height : Start Time: End Time: Manual 16.0 min 68726S counts 1,30e+006 15.7 min 16.4 min 6.50*5 8.00*5 7.50eS 8- 7.00*5 6.50*5 1 6.00*5 5.50*5 0.0 Data printed by STW Printing Time: 12:13:00 PM Printing Date: Tuesday, September 06, 2011 Page 2 of 2 Page 93 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in Water Samples F S IA - June 2011 Results Name: kll0802a.rdb Printing Date: Tuesday, September 06, 2011 Page 94 o f 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: kll0802a.rdb Printing Time 12:15:38 PM Printing Date: Tuesday September 06 2011 Page 95 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA - June 2011 Results Name: Jcll0802a.rdb Printing Time: 12:15:38 PM Printing Date: Tuesday, September 06, Page 96 of 113 *ETS-Kirk Sample Name: 1(110602807?* Sample ID: "GLP1001-02-18-133* Peak Name: *13C8PFOS-IS(IS)* Masses): *507.000/80.000 Da* Comment: "DAL GW 130L RB 110630* Annotation: ** Sample Index: 73 Sample Type: Unknown Concentration: 0.960 ng/mL Calculated Cone: N/A Acq. Date: 8/3/2011 2.0*5 Acq. Tine: 4:21:05 PH 1.9*5 Yea IntelliQuan - It 1.8*5 0.00: 0.00 epa Min. Peak Width: sec Smoothing Width: 0 points 1.7*5 RT Window: Expected RT: 30.0 sec 16.2 min 1.6*5 No 1.5*5 FUe:*k110602a.wffT 1.4*5 1.3*5 End Time: 1.2*5 1.1*5 1.0*5 9.0*4 8.0*4 7.0*4 6.0*4 5.0*4 4.0*4 3.0*4 2.0*4 1.0*4 0.014.0 14.5 Sample Name: *kl10802a013* Sample ID: *11 003-25-5* F4e:*k110802a.wtr Peak Name: *PFOS* Mass/): *499.000/99.000 Da,499.000/80.000 Da,499.00CV130.000 Da* Comment: *0.1 ng/ml FC ctd In Synth. Water" Annotation: ** Sample Index: '' 0.100Sample Type: Concentration: Standard r Calculated Cone: 0.0965 r Acq. Date: 8/2/2011 Acq. Time: 7:35:09 PM Modified: No Proc. Algorithm: Specify Parameters - HO III Noise Percentage: 50 Base. Sub. Window: I.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 see Expected RT: : Ret; ! RT: Height : Start Time: End Time: Valley 16.2 min 77242 counts 1.30e+ 004 cps Data printed by STW Printing Time: 12:15:39 PM Printing Date: Tuesday, September 06, GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0802a.rdb Sample Nam*: "k110802a073* Sample ID: "GLP100102-18-134* Peak Nam*: *13C8PFOS4S(IS)* Masses): "507.000/80.000 Da* Comment "DALGW 133SRB110630* Annotation:- Sample Index: 74 Sample Type: Unknown Calc: 0.960 N/A ng/mL 2.1*5 8/3/2011 2.0*5 Fite: "k110802a.wtr Modified: Yes Proc. Algorithm: : itelllQua Min. Peak Height: 0. 00 Min. Peak Width: 0.00 Smoothing Width: RT Window: Expected RT: Use Relative RT: 1.9*5 1.8*5 1.7*5 1.6*5 1.5*5 1.4*5 1.3*5 1.2*5 1.1*5 1.0*5 9.0*4 6.0*4 7.0*4 6.0*4 5.0*4 4.0*4 14.0 14.5 Sample Name:*k110602*023* Sample ID:*11 005-129* FDe:*k110802a.wtr Peak Name: *PFOS* Masses): *499.000/99.000 Da,499.000/80.000 Da,499.000/130.000 Da* Comment "Method Blank* Annotation: ** Sample Index: 24 Sample Type: Unknown Concentration: N/A Calculated Cone: <0 Acq. Date: 8/2/2011 Acq. Time: .11:06:09 PM Modified: Yes Proc. Algorithm: Specify Parameters Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.0( Min. Peak Width: 0.0( Smoothing Width: 0 RT Window: 30.0 Expected RT: 16.3 Use Relative RT: No Height : Start Time: End Time: Manual 16.2 16450 col 2.16e+003 16.0 16.3 16.0 16.5 17.0 17.5 16.0 16.5 Tima, min 16.0 16.5 Page 3 of 5 Page 97 of 113 *ETS-Kirk GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -June 2011 Results Name: kll0802a.rdb Data printed by STW Printing Time: 12:15:39 PM Printing Date: Tuesday, September 06, 2011 Page 4 of 5 Page 98 of 113 *ETS-Kirk I Sample Name: -Vll0602a041* Sample b : 'LC S -1 1 0 7 2 9 -ir Fife: *k110802* ttifT Peak Name: 'PFOS' Maaa(aa): '499.00CV99.000 Da,499.000^0.000 0a.499.0(XV13< Comment: *2ppb LCS ECF* Annotation: Sample Index: 42 Sample Type: QC Concentrate :ulated c Acq. Date: Acq. Time: Modified: Yes Proe. Algorithm: Specify Parameters :ntage: SO Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height Min. Peak Width: Smoothing Width: RT Window: Expected RT: GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Results Name: kll0802a.rdb Data printed by STW Printing Time: 12:15:39 PM Printing Date: Tuesday, September 06, 2011 Page 5 of 5 Page 99 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in Water Samples F S IA -J u n e 2011 A t ta c h m e n t C: A n a ly tic a l M e th o d Page 100 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA'- June 2011 onIII B-- M- "-a--m---e--m--a-iILaisoRRiovy Method Method o f Analysis for the Determination o f Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q y ^ Approved By: W illiam K. Reagen, Laboratory M anager Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 101 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples FSIA - June 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 Perfluoroodanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. W ater samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In 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 102 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS In W ater Samples FSIA - June 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 Lim it 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 103 o f 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 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 104 of 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 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 C 18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Time /m ini 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 im L/m inl 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous inform ation is intended as a guide; alternate conditions and 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 105 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative bn, MRM mode, monitoring the following transitions: A n a ly te Transition Monitored PFBA 213 -> 169 PFPeA 263 ->219 PFHA 3 1 3 -> 2 6 9 and 3 1 3 -> 11 9 PFHpA 363 -> 319, 363 -> 169 and 363 -> 1 1 9 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 219 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --^ 80 and 399 --^ 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 M ultiple transitions for monitoring the analytes is an option, as summing m ultiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use o f one daughter ion is acceptable if method sensitivity is achieved, provided that retention tim e criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals W ater - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (PFBA - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (P F H A -C 6acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (PFNA - C9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 10acid); Oakwood Products, Inc PerfluoroundecanoicAcid (PFU nA-C 11 acid); Oakwood Products, Inc PerfluorododecanoicAcid (P F D oA -C 12 acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 of 11 Method of Analysis fo r the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a lysis Page 106 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS In W ater Samples F S IA -J u n e 2011 The previous inform ation is intended as a guide. Reagents and standards from alternate sources may be used. . 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)-- Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L 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. m olecular weight of anion salt correction factor m oclecular weight of salt PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg CsF^SOs'K* with purity 90% = 8.35mg C8F17S03- (10 mg*0.90*0.9275=8.35 mg) 5 pg/m L (5000 ng/m L) m ixed w orking standard-- Add 0.5ml_ each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/m L m ixed w orking standard-- Add 1,25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/m L m ixed standard-- Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 107 of 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 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/mL 125 125 125 125 250 250 250 250 5000 5000 5000 Volum e o f WS, pL 10 15 20 30 20 50 100 200 25 50 100 Final Volum e o f Calibration Standard (mL o f A STM Type 1 Water, or other suitable water) 50 50 50 50 50 50 50 50 50 50 50 Final Concentration o f Calibration Standard, ng/m L (ppb) in A STM 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 108 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 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 109 o f 113 GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: (Peak Area - Intercept) Analyte found (ng/mL) = xDF Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. 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 C alibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or . equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 110 o f 113 GLP10-01-02; Interim Report 18 Analysis of PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 D em onstration o f S pecificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary o f Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 111 o f 113 A tta c h m e n t D: D evia tio n (s ) GLP10-01-02; Interim Report 18 Analysis o f PFBS, PFHS, and PFOS in W ater Samples F S IA -J u n e 2011 Page 112 of 113 GLP10-01 -02; Interim Report 18 RECORD OF D E V IA T IO N /N O N W M m " " 08^ TM TM ? " I. Id e n tific a tio n Study / Project No. G L P 1 0-01-02-18 Date(s) of Occurrence: k110729b, k110802a Docum ent Number: E T S -8 -0 4 4 .0 Deviation type (C heck one) SOP Protocol Equipm ent Procedure 0 M ethod GPO Other: II. D e s c rip tio n (a tta c h e x tra p a g e s a s n e e d e d ) Method Requirements: 1. LCS average recoveries within 20% (section 10.5). 2. FMS recovery within 30% (section 10.6). 3. RPD within 20% (section 10.3). 4. System suitability peak area RSD 5% and retention time RSD <2%. Actual procedure/process: 1. k110729b (internal calibration): The low set of PFOS ECF LCS samples had an average recovery of 136% and the high set of ECF LCS samples had an average recovery of 122%. k110802a: The low, mid, and high PFOS ECF LCS samples had average recoveries of 129%, 122%, and 122%. 2. The following samples had FMS recoveries less than 70% for PFOS: 130L, 131L, 135L, 136L, 141R, 142R, and 144S. Samples 133L and 135S had FMS samples greater than 150% for PFOS. 3. Sample 134L had an RPD of 22% for PFOS. 4. k110729b (external calibration): The peak area RSD for PFOS was 9.3%.____________________________ III. A ctions Taken ______________________________(su ch a s a m e n d m e n t iss u e d , S O P revision , etc.) C orrective A ction ( Yes 0 No) Reference: A cceptability o f the nonconform ing w ork: 1. The recoveries for the non-compliant LCSs (linear + branched) will be flagged in the final report. All of the LCSs prepared with this study were evaluated by ETS-12-012 to determine the method analytical uncertainty. The analytical uncertainty when evaluated by ETS-12-012 was determined to be 28% for PFOS. Flowever, the analytical uncertainty for this study will be set at 36%, based on the recovery of the low set of linear + branched LCS from run k110729b. 2. The non-compliant FMS recoveries for PFOS will be flagged in the final report. If necessary, the method uncertainty will be expanded for samples with FMS recovery less than 64%. Samples 133L and 135S will not be reported for PFOS due to the FMS recoveries being outside the 50% acceptance criteria. 3. The PFOS RPD for sample 134L will be flagged in the final report. 4. Other QC Items were used to assess data accuracy for PFOS - calibration curve point accuracy, curve fit ________ criteria, CCVs, and LCS, all meeting method acceptance criteria.____________________________________ Actions: Halting of W ork Client Notification W ork Recall 0 O ther: Deviations will be noted in final report. W ithholding o f Report Project Lead/PAI Approval: Study Director (if GLP): Sponsor Approval (for GUP protocol deviations): NA Technical Reviewer (optional): NA Laboratory DepartmentJVIanager Approval: In Date: Date: Date: NA Date: IV. A uthorization to R esum e W ork W here halting o f w ork occurred, resum ption o f w ork m ust first b e a p p ro v ed b y Lab oratory M a n a g em e nt Laboratory Department Manager Approval: NA Date: NA Deviation No. (assigned by Study Director or Team Leader at the end o f study or project) E T S -4 -0 0 8 .7 Page 1 of 1 D ocum entation o f Deviations and Control o f N onconform ing Testing Page 113 of 113