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GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 GLP10-01-02. Interim Report 13: Analysis o f PFBS. PFHS. and PFOS in Groundwater Samples Collected at the Morgan County Landfill located in Decatur. AL in November 2010 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan Wolf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01-02-13 Total Number of Pages 67 The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052.01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. Certificate #2052.01 Page 1 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 This page has been reserved for specific country requirements. Page 2 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 G LP C o m pliance Statement Report Title: GLP10-01-02, Interim Report 13. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Morgan County Landfill located in Decatur, AL in November 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 SiteRelated 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. Hohenstein, Sponsor Representative Jaisimha Kesari, P.E., DEE, Study Director Date Date Page 3 of 67 GLP10-01 -02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Q u ality A ssurance Statement Report Title: GLP10-01-02, Interim Report 13. Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Morgan County Landfill located in Decatur, AL in November 2010 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 SiteRelated Monitoring Program. This report and the accompanying data were audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated below. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 1/5/11-1/7/11 Phase Data / Final Report Date Reported to Testing Facility Management Study Director 1/20/11 1/20/11 Date Page 4 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Ta b le of C ontents GLP Compliance Statement................................................................................................................. 3 Quality Assurance Statement................................................................................................................ 4 Table of Contents.................................................................................................................................. 5 List of Tables.......................................................................................................................................... 6 1 Study Information............................................................................................................................ 8 2 Summary......................................................................................................................................... 9 3 Introduction................................................................................................................................... 10 4 Test & Control Substances.......................................................................................................... 10 5 Reference Substances................................................................................................................. 11 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......................................................................................................................... 13 8 Analytical Results......................................................................................................................... 15 8.1 Calibration..................................................................................................................... 15 8.2 System Suitability......................................................................................................... 15 8.3 Limit of Quantitation (LOQ)...........................................................................................15 8.4 Continuing Calibration...................................................................................................15 8.5 Blanks............................................................................................................................15 8.6 Lab Control Spikes (LCSs)...........................................................................................16 8.7 Analytical Method Uncertainty......................................................................................20 8.8 Field Matrix Spikes (FMS).............................................................................................20 Page 5 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 9 Data Summary and Discussion................................................................................................... 20 10 Conclusion....................................................................................................................................29 11 Data/Sample Retention................................................................................................................ 29 12 Attachments..................................................................................................................................29 13 Signatures..................................................................................................................................... 30 L ist of Ta b le s Table 1. Summarized PFBS, PFHS, and PFOS Results (Morgan County Landfill Groundwater, Decatur, AL, November 2010).................................................................................................... 9 Table 2. Instalment Parameters........................................................................................................ 14 Table 3. Liquid Chromatography Conditions..................................................................................... 14 Table 4. Mass Transitions..................................................................................................................14 Table 5. Limit of Quantitation (LOQ)................................................................................................ 15 Table 6. Laboratory Control Spike Recovery.....................................................................................17 Table 7. Analytical Uncertainty.......................................................................................................... 20 Table 8. Field Matrix Spike Levels.....................................................................................................20 Table 9. DAL GW MCL MW 1B 101110..........................................................................................21 Table 10. DAL GW MCL MW 11101110..........................................................................................21 Table 11.DAL GW MCL MW 1S 101110........................................................................................... 22 Table 12.DAL GW MCL MW 2B 101110........................................................................................... 22 Table 13. DAL GW MCL MW 21101110..........................................................................................23 Table 14. DAL GW MCL MW 3B 101110.........................................................................................23 Table 15. DAL GW MCL MW 31101110..........................................................................................24 Table 16. DALGW MCL MW 3S 101110........................................................................................24 Table 17. DALGW MCL MW 4B 101110........................................................................................25 Table 18. DAL GW MCL MW 41101110...........................................................................................25 Table 19. DAL GW MCL MW 4S 101110....................................................................................... 26 Table 20. DAL GW MCL MW 13B 101111..................................................................................... 26 Page 6 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table21. D A LG W M C LM W 131101111...................................................................................... 27 Table 22. DAL GW MCL MW 13S 101111...................................................................................... 27 Table 23. Trip Blank........................................................................................................................ 28 Table 24. DAL GW 602S RB 101029............................................................................................. 28 Page 7 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 1 Study Information Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone:(651)737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j.kesari@westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel William K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanqe@mmm.com1: phone (651)-733-9860 Susan Wolf, 3M Analyst Kevin Eich; Analyst Chelsie Grochow; Analyst Jonathan Steege; Analyst Study Dates Study Initiation: March 8, 2010 Interim Report 13 Experimental Termination: December 15,2010 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 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located at the Morgan County Landfill located in Decatur, AL, representing fourteen different sampling locations. A total of sixty sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS) analysis, and included duplicate groundwater samples from each sampling location. Samples also included two field matrix spike (FMS) samples for each location, one trip blank containing Milli-QTM water, two trip blank spikes, and one equipment rinseate blank. The equipment rinseate blank did not have FMS samples prepared for determination of PFBS, PFHS, and PFOS recovery. The groundwater samples, trip blanks and one equipment rinseate blank were collected by Weston personnel on November 10-11, 2010 and received on November 12, 2010. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01-02-13. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate and the trip blank were below the lower limit of quantitation (LLOQ), indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results for all ground waters ranged from <0.0250 ng/mL to 2.26 ng/mL. The PFHS concentration results for all ground waters ranged from <0.0250 ng/mL to 3.28 ng/mL. The PFOS concentration results for all ground waters ranged from <0.0250 ng/mL to 14.8 ng/mL. The method uncertainty for PFBS is 16%, PFHS 13%, and PFOS 30%. Table 1. Summarized PFBS, PFHS, and PFOS Results (Morgan County Landfill Groundwater, Decatur, AL, November 2010) Avg. PFBS Avg. PFHS Sample ID Concentration Concentration (nq/mL) RPD (ng/mL) RPD DAL GW MCL MW 1B 101110 2.26 25% [al 3.28 22% [al DAL GW MCL M W 11101110 0.493 11% 0.966 9.1% DAL GW MCL MW 1S 101110 1.77 19% 2.23 20% DAL GW MCL MW 2B 101110 1.24 1.6% 1.38 2.2% DAL GW MCL M W 21101110 2.06 3.4% 1.38 2.2% DAL GW MCL MW 3B 101110 0.0381 12% 0.0326 3.7% DAL GW MCL M W 31101110 0.0279 0.72% 0.0324 8.0% DAL GW MCL MW 3S 101110 <0.0250 <0.0250 DAL GW MCL MW 4B 101110 <0.0250 <0.0250 DAL GW MCL M W 41101110 <0.0250 <0.0250 DAL GW MCL MW 4S 101110 <0.0250 <0.0250 DAL GW MCL MW13B 101111 0.0987 4.7% 0.0717 1.5% DAL GW MCL MW13I 101111 0.0843 7.6% 0.0526 4.4% DAL GW MCL MW13S 101111 0.0957 4.2% 0.0559 8.4% Trip Blank (Milli-QTM Water) < 0.0250 < 0.0250 Equipment rinseate blanks < 0.0250 < 0.0250 N/A; not applicable [a] The sample/sample duplicate RPD was >20%. [b] Analytical uncertainty has been adjusted for FMS recovery for PFOS to 35%. Avg. PFOS Concentration (ng/mL) RPD 7.40 30% [al 1.47 13% 6.42 20% 14.8 2.0% [bl 5.20 16% 0.283 7.4% 0.262 0.38% 0.0306 16% 0.0475 15% 0.144 4.9% 0.256 5.9% < 0.0250 < 0.0250 < 0.0250 < 0.0250 < 0.0250 Page 9 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 3 Introduction This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze ground water samples collected from off-site wells located in Decatur, AL for PFBS, PFHS, and PFOS in an effort to characterize on-site groundwater conditions. The 3M Environmental Laboratory prepared sample bottles (250 mL high-density polyethylene) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets for each groundwater sampling location included a field sample, field sample duplicate, and two field spike samples. Each empty container for groundwater samplings was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS, PFHS, and PFOS prior to being sent to the field for sample collection. All sample bottles also included the addition of internal standards 180 2PFBS, 180 2-PFHS, and 13C4-PFOS at a nominal concentration of 1 ng/mL. All sample bottles also included the addition of surrogate spike 13C4-PFOS at a nominal concentration of 0.1 ng/mL. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds in Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate groundwater samples collected, the trip blank, and equipment rinseate samples. Tables 9-24 summarize the individual sample results and the associated FMS recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report. 4 Test & Control Substances There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. Page 10 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 5 Reference Substances The analytical reference substances used for this study are listed below. R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predom inantly linear) Perfluorobutane sulfonate C 4 F9SO3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% PFOS (lin ear) Perfluorooctane sulfonate C 8 F17SO 3 Potassium Salt CAS # 2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFHS (lin ear) Perfluorohexane sulfonate C 6 F13SO 3 Sodium Salt Wellington 4/2/2013 Frozen LPFHxSAM08 TCR08-0018 Crystalline 98% PFOS (lin ea r + branched) Perfluorooctane sulfonate C8F1 7 S O 3 Potassium Salt CAS # 2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% Page 11 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 1, o 2-p f b s Labeled - Perfluorobutane sulfonate C4F9S[1802]0- Ammonium Salt RTI International 3/9/2015 Frozen 11546-107-2 TCR-1022, TCR-1028, TCR- 1033, and TCR-1038 Liquid 99% 1'O r PFHS Labeled - Perfluorohexane sulfonate C6F13S[1802]160Sodium Salt Wellington 04/29/2013 Frozen MPFC-C-0410 TCR10-0037 Liquid NA(1) R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 13C ,-P F O S Perfluorooctane sulfonate 13C8F17s o 3 Sodium Salt Wellington 04/29/2013 Frozen MPFC-C-0410 TCR10-0037, TCR10-0044, and TCR09-0076 Liquid NA(1) (1) Compound is part of a custom mixture of mass-labeled perfluorinated compounds at a concentration of 5.0 pg/mL. Page 12 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 6 Test System There was not a test system for this study in the classic sense of a GLP study. This study was conducted for analysis of ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" environmental samples. Sample Description Key Code. String Number Example 1 2 3 4 5 6 7 String Descriptor Example DAL GWMCL MW4S 0101110 Sample Location DAL= Decatur, Alabama Sample Type GW= Groundwater Well Location MCL = Morgan County Landfill Well ID Well Level Example: MW4 S = Shallow well 1= Interface well B = Bedrock well Sample Type 0 = primary sample DB = duplicate sample LS = low spike RB = Rinseate Blank Sampling Date 101110 = November 11, 2010 7 Method Summary 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on November 12, 2010. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spike samples were sent with the sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below in Table 2, Table 3 and Table 4. Page 13 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 2. Instrument Parameters. Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS MaryAnn ETS-8-044.0 11/23/10 Agilent 1200 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5n 10 uL Applied Biosystems API 5000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 3. Liquid Chromatography Conditions. ETS Ginger ETS-8-044.0 12/15/10 Agilent 1100 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 m m X 100 mm), 5u 10 uL Applied Biosvstems API 5000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Step Number Total Time (min) 00 1 2.0 2 14.5 3 15.5 4 16.5 5 20.0 00 1 1.0 2 11.0 3 13.5 4 14.0 5 17.0 Flow Rate (pL/min) Percent A (2 mM ammonium acetate) ETS-8-044.0 - 1 1 /23/10 Analysis 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 ET S -8-044.0-12/15/10 Analysis 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 PercentB (Methanol) 3.0 3.0 95.0 95.0 3.0 3.0 3.0 3.0 95.0 95.0 3.0 3.0 Table 4. Mass Transitions. Analyte Mass Transition Q1/Q3 Internal Standard Mass Transition Q1/Q3 PFBS 299/80 299/99 f 'OJPFBS 303/84 PFHS 399/99 399/80 ro jP F H S 403/84 499/99 PFOS 499/80 f 'CJPFOS 507/80 499/130 13CrPFOS Surrogate 503/80 C3c jpfo s 507/80 Dwell time was 50 msec for each transition. The individual transitions were summed to produce a "total ion chromatogram" (TIC), which was used for quantitation. Page 14 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 8 Analytical Results 8.1 Calibration Samples were analyzed against a stable isotope matrix-matched internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into laboratory prepared synthetic groundwater containing calcium and magnesium. A total of thirteen spiked standards ranging from 0.025 ng/mL to 50 ng/mL (nominal) analyzed on 11/23/10 and ten spiked standards ranging from 0.025 ng/mL to 5.0 ng/mL (nominal) analyzed on 12/15/10. Low curve points were disabled for PFOS on 11/23/10 to meet method blank criteria. Aquadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. 8.2 System S uitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. All analytes met the acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak ratio and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, PFOS, and 13C4-PFOS. 8.3 Lim it o f Q uantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The nominal LOQ for all analytes can be found in Table 5. Table 5. L im it o f Q uantitation (LOQ). Analysis Date 11/23/10 12/15/10 N/A - Not Applicable PFBS LOQ, ng/mL 0.0250 N/A PFHS LOQ, ng/mL 0.0250 N/A PFOS LOQ, ng/mL 0.250 0.0250 8.4 C ontinuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All reported sample results were bracketed by CCVs that met method criteria of 100% 25% with the exception of sampling location DAL GW MCL 21101110, which was bracketed by a CCV for PFOS that had a recovery of 149%. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: method blanks, trip blanks and equipment rinseate blanks. Method blank results were reviewed and used to evaluate method performance to determine the LOQ for each analyte. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience. Equipment rinseate blanks are aqueous samples that reflect the efficiency of equipment cleaning in the field between different sample collections and are proof of no cross contamination of samples from the equipment. Page 15 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - november 2010 8.6 Lab Control Spikes (LCSs) 11/23/10 Analysis: Lab control spikes were prepared and analyzed in triplicate at three levels for PFBS, PFHS, and PFOS, and at two levels for 13C4-PFOS. LCSs were prepared by spiking known amounts of the target analytes into 10 mL of laboratory prepared synthetic groundwater to produce the desired concentration. The spiked water samples were then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level within 100% + 20% with an RSD <20%, were met for PFBS and PFHS. The low level LCS for PFOS could not be calculated as the detected concentration was below the limit of quantitation. The mid and high level LCS met method acceptance crteria. 12/15/10 Analysis: Lab control spikes were prepared and analyzed in triplicate at two levels for PFOS. LCSs were prepared by spiking known amounts of the target analytes into 10 mL of laboratory prepared synthetic groundwater to produce the desired concentration. The spiked water samples were then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level within 100% 20% with an RSD <20%, were met for PFOS. As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of linear and branched isomers, additional LCS samples of linear and branched PFOS were prepared at a minimum of two concentrations to evaluate the potential for analytical bias. 11/23/10 Analysis: Three LCS levels were prepared an anlzyed in tripcalte. The low level linear and branched LCS could not be calcualted as the detected concentration was below the limit of quantitation. The mid level linear and branched LCS had an average recovery of 136% and the high level had an average recovery of 133%. A new set of linear and branched stock standards were prepared, with new LCS prepared at the same three concentration levels. The new LCS were analyzed at the end of the analytical run. Two of the low level linear and branched LCS could not be calcualted as the detected concentration was below the limit of quantitation. One replicate at the low level had a recovery of 152%, while both the new mid and high level linear and branched LCS met method acceptance criteria with average recvoeries of 114%. The mid and high level LCS concentrations were more appropriate as compared to the sample concentrations reported from this run. A method deviation is included in the raw data. 12/15/10 Analysis: Two LCS levels were prepared and anlyzed in triplicate. Both LCS level of linear and branched PFOS met method acceptance criteria. All LCS results were used in the determination of method analytical uncertainty in section 8.7. The following calculations were used to generate data in Table 6 for laboratory control spikes: LCS Percent Recovery Calculated Concentration --------------------------------------- 100% Spike Concentration LCS% RSD = standard deviation LCS replicates 100% average LCS recovery Page 16 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 6. Laboratory Control Spike Recovery. ETS-8-044.0 Lab ID LCS-101115-1 LCS-101115-2 LCS-101115-3 Average %RSD LCS-101115-4 LCS-101115-5 LCS-101115-6 Average %RSD Spiked Concentration (nq/mL) 0.0948 0.0948 0.0948 '3Cr PFOS Calculated Concentration (nq/mL) 0.114 0.112 0.110 0.940 0.940 0.940 118% 1.7% 0.990 1.03 1.02 108% 2.1% %Recovery 120 118 116 105 109 109 ETS-8-044.0 Analyzed 11/23/10 Lab ID Spiked Concentration (nq/mL) PFBS Calculated Concentration (nq/mL) %Recoveiy Spiked Concentration (nq/mL) PFHS Calculated Concentration (nq/mL) LCS-101115-1 LCS-101115-2 LCS-101115-3 0.198 0.198 0.198 0.168 0.205 0.212 84.6 103 107 0.198 0.198 0.198 0.189 0.219 0.229 Average %RSD LCS-101115-4 LCS-101115-5 LCS-101115-6 1.96 1.96 1.96 98.2% 12% 1.85 2.13 2.04 94.2 109 104 1.97 1.97 1.97 108% 9.9% 2.01 2.37 2.27 Average %RSD LCS-101115-7 LCS-101115-8 LCS-101115-9 9.94 9.94 9.94 102% 7.4% 9.10 10.8 10.5 91.5 108 106 9.95 9.95 9.95 112% 8.3% 10.1 12.0 11.9 Average %RSD 102% 8.8% 113% 9.4% (1) N/A = Not Applicable; A recovery could not be calculated as the detected value was below the limit of quantitation. (2) Laboratory control sample did not meet method acceptance criteria of 100% 20%. %Recovery 95.5 111 116 102 120 115 101 120 119 Spiked Concentration (nq/mL) 0.198 0.198 0.198 1.96 1.96 1.96 9.94 9.94 9.94 PFOS (lineai) Calculated Concentration (ng/mL) <0.250 <0.250 <0.250 N /A '1 1.96 2.31 2.18 110% 8.3% 10.4 12.0 12.3 116% 8.5% %Recovery N/A N/A N/A 100 118 111 105 121 123 Page 17 of 67 GLP10-01-02; Interim Report 13 . Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 11/23/10 Lab ID LCS-101115-10 LCS-101115-11 LCS-101115-12 Average %RSD LCS-101115-13 LCS-101115-14 LCS-101115-15 Average %RSD LCS-101115-16 LCS-101115-17 LCS-101115-18 Average %RSD PFOS (linear+ branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) `/Recovery Lab ID 0.196 0.196 0.196 <0.250 <0.250 <0.250 N/A LCS-101120-1 N/A LCS-101120-2 N/A LCS-101120-3 N/A12' Average %RSD 1.97 2.63 134 LCS-101120-4 1.97 2.63 134 LCS-101120-5 1.97 2.73 139 LCS-101120-6 9.90 9.90 9.90 136% 2.1% m 12.9 13.3 13.4 Average %RSD 130 LCS-101120-7 134 LCS-101120-8 135 LCS-101120-9 133% 2.2% B Average %RSD PFOS (linear+ branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery 0.196 0.196 0.196 0.298 <0.250 <0.250 152 N/A N/A N/A'1' 1.97 2.03 1.97 2.34 1.97 2.29 103 119 116 9.90 9.90 9.90 113% 7.5% 10.3 11.7 11.7 105 118 118 114% 6.6% (1) N/A = Not Applicable; A recovery could not be calculated as the detected value was below the limit of quantitation. (2) Laboratory control sample did not meet method acceptance criteria of 100% 20%. Page 18 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 6 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 12/15/10 Lab ID LCS-101215-1 LCS-101215-2 LCS-101215-3 Average %RSD LCS-101215-4 LCS-101215-5 LCS-101215-6 Average %RSD PFOS (linear + branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID 0.198 0.198 0.198 0.139 0.172 0.162 70.3 86.8 81.9 LCS-101215-7 LCS-101215-8 LCS-101215-9 79.7% 11% 1.98 1.63 1.98 1.94 1.98 1.92 82.5 97.9 96.7 Average %RSD LCS-101215-10 LCS-101215-11 LCS-101215-12 92.4% 9.3% Average %RSD PFOS (linear+ branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery 0.196 0.196 0.196 0.207 0.214 0.200 106 109 102 106% 3.3% 1.97 2.20 1.97 2.18 1.97 2.17 112 111 110 111% 0.90% (1) N/A = Not Applicable; A recovery could not be calculated as the detected value was below the limit of quantitation. (2) Laboratory control sample did not meet method acceptance criteria of 100% 20%. Page 19 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 8.7 A nalytical 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%. Table 7. A nalytical U ncertainty. Analyte PFBS PFHS PFOS Standard Deviation 8.02 6.27 15.2 Method Uncertainty 16% 13% 30% 8.8 Field Matrix Spikes (FMS) A field matrix spike sample was collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% 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 8. Field M atrix Spike Levels. Sampling Location All sampling locations - Low Spike All sampling locations - High Spike PFBS, ng/mL 0.970 9.72 PFHS, ng/mL 0.960 9.61 PFOS, ng/mL 0.980 9.78 FMS Recovery - ^ amP*e Concentration of FM S- Average Concentration : Field Sample & Field Sample Dup.) *jqq0/ Spike Concentraton 9 Data Summary and Discussion' . " The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks and rinseate blanks. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges. DAL GW MCL MW 2B 101110 - The HS recovery for PFOS was 135%. This was the only appropriate spike level for this sampling location. The analytical uncertainty has been adjusted for the sampling location for PFOS to 35%. Page 20 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 9. DAL GW MCL MW 1B 101110 PFBS PFHS PFOS 13C4-PFOS 3MUMSID GLP10-01-02-13-001 GLP10-01-02-13-002 GLP10-01-02-13-003 GLP 10-01 -02-13-004 Description DAL GW MCL MW 1B 0 101110 DAL GW MCL MW1BDB 101110 DAL GW MCL MW1BLS 101110 DAL GW MCL MW1B HS 101110 Concentration Concentration (ng/mL) YoRecovery (ng/mL) 1.98 NA 2.92 2.54 NA 3.63 3.17 NC 4.09 12.8 108 13.9 %Recovery NA NA NC 111 Concentration (ng/mL) 6.29 8.50 7.49 17.6 %Recovery NA NA NC 104 %Recovery 98.2 90.2 99.9 94.7 Average Concentration (ng/mL) %RPD/RSD 2.26 ng/mL 25% m 3.28 ng/mL 22% m 7.40 ng/mL 30% 95.7% 4.5% NA = Not Applicable (1) The sample/sample duplicate RPD was 220%. Table 10. DAL GW MCL MW 11101110 3MLIMSID GLP10-01-02-13-005 GLP10-01-02-13-006 GLP10-01-02-13-007 GLP10-01-02-13-008 Description DAL GW MCL MW 110 101110 DAL GW MCL MW 11 DB 101110 DAL GW MCL MW 11 LS 101110 DAL GW MCL MW 11 HS 101110 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (ng/mL) 0.520 0.466 1.72 11.5 %Recovery NA NA 126 113 Concentration (ng/mL) 1.01 0.922 2.16 12.3 YoRecovery NA NA 124 118 Concentration (ng/mL) 1.56 1.37 2.61 12.9 YoRecovery NA NA 117 117 YoRecovery 95.6 96.0 95.6 101 0.493 ng/mL 11% 0.966 ng/mL 9.1% 1.47 ng/mL 13% 97.1% 2.8% NA = Not Applicable Page 21 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 11. DAL GW MCL MW 1S 101110 PFBS PFHS PFOS 13C4-PFOS 3M LIMS ID GLP10-01-02-13-009 GLP10-01-02-13-010 GLP10-01-02-13-011 GLP10-01-02-13-012 Description DAL GW MCL MW 1S0 101110 DAL GW MCL MW1S DB 101110 DAL GW MCL MW1S LS 101110 DAL GW MCL MW 1S HS 101110 Concentration Concentration (ng/mL) %Recovery (ng/mL) 1.93 NA 2.45 1.60 NA 2.00 2.84 111 3.32 12.8 114 13.7 %Recovery NA NA NC 119 Concentration (ng/mL) 7.05 5.78 7.21 17.7 %Recovery NA NA NC 115 %Recovery 87.7 98.0 99.1 97.9 Average Concentration (ng/mL) %RPD/RSD 1.77 ng/mL 19% 2.23 ng/mL 20% 6.42 ng/mL 20% 95.6% 5.6% NA = Not Applicable Table 12. DAL GW MCL MW 2B 101110 - PFBS PFHS PFOS 13C4-PFOS 3MLIMSID GLP10-01-02-13-013 GLP10-01-02-13-014 GLP10-01-02-13-015 GLP10-01-02-13-016 Description DAL GW MCL MW2B0 101110 DAL GW MCL MW 2B DB 101110 DAL GW MCL MW2B LS 101110 DAL GW MCL MW2B HS 101110 Concentration (ng/mL) 1.25 1.23 2.42 12.1 Concentration %Recovery (ng/mL) NA 1.36 NA 1.39 122 ' 2.61 112 12.7 %Recovery NA NA 129 118 Concentration (ng/mL) 14.6 14.9 16.2 28.0 %Recovery NA NA NC 135 (1) %Recovery 102 97.1 100 99.9 Average Concentration (ng/mL) %RPD/RSD 1.24 ng/mL 1.6% 1.38 ng/mL 2.2% 14.8 ng/mL 2.0% 99.7% 1.9% N A = Not Applicable (1) Field matrix spike recovery did not meet method acceptance criteria of 100% 30%. (2) The analytical uncertainty has been adjusted for FMS recovery to 100% 35%. Page 22 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 13. DAL GW MCL MW 21101110 3M UNIS ID GLP10-01-02-13-017 GLP10-01-02-13-018 GLP10-01-02-13-019 GLP10-01-02-13-020 Description DAL GW MCL MW2I 0 101110 DAL GW MCL MW2I DB 101110 DAL GW MCL MW2I LS 101110 DAL GW MCL MW 2I HS 101110 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOSm 13C4-PFOS Concentration Concentration (ng/mL) %Recovery (ng/mL) 2.09 NA 1.39 2.02 NA 1.36 3.16 NC 2.54 12.8 111 12.2 %Recovery NA NA 121 113 Concentration (ng/mL) 5.61 4.78 6.17 17.0 %Recovery NA NA NC 121 %Recovery 96.3 96.0 97.7 103 2.06 ng/mL 3.4% 1.38 ng/mL 2.2% ' 5.20 ng/mL 16% 98.3% 3.5% N A= Not Applicable (1) Samples were bracketed by a CCV that outside method acceptance criteria with a recovery of 149%. Table 14. DAL GW MCL MW 3B 101110 PFBS PFHS PFOS 13C4-PFOS 3MUMSID GLP10-01-02-13-021 GLP10-01-02-13-022 GLP10-01-02-13-023 GLP 10-01-02-13-024 Description DAL GW MCL MW 3B 0 101110 DAL GW MCL MW 3B DB 101110 DAL GW MCL MW 3B LS 101110 DAL GW MCL MW 3B HS 101110 Concentration Concentration (ng/mL) %Recovery (ng/mL) 0.0403 NA 0.0332 0.0359 NA 0.0320 1.22 122 1.21 11.4 117 11.4 %Recovery NA NA 123 118 Concentration (ng/mL) 0.293 0.272 1.22 NA 01 %>Recovery NA NA 95.7 NA (1) %,Recovery 101 98.3 98.2 99.6 Average Concentration (ng/mL) %RPD/RSD 0.0381 ng/mL 12% 0.0326 ng/mL 3.7% 0.283 ng/mL 7.4% 99.4% 1.6% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Page 23 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 15. DAL GW MCL MW 31101110 3MUMSID GLP10-01-02-13-025 GLP10-01-02-13-026 GLP10-01-02-13-027 GLP10-01-02-13-028 Description DAL GW MCL MW 3I 0 101110 DAL GW MCL MW 3I DB 101110 DAL GW MCL MW3I LS 101110 DAL GW MCL MW3I HS 101110 Average Concentration (ng/mL) %RPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (ng/mL) 0.0278 0.0280 1.19 11.2 %Recovery NA NA 120 115 Concentration (ng/mL) 0.0311 0.0337 1.26 11.1 %Recovery NA NA 128 115 Concentration (ng/mL) 0.261 0.262 1.24 NA(1) %Recovery NA NA 99.8 NA (1> %Recovery 96.5 98.0 101 103 0.0279 ng/mL 0.72% 0.0324 ng/mL 8.0% 0.262 ng/mL 0.38% 99.5% 2.9% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Table 16. DAL GW MCL MW 3S 101110 PFBS PFHS PFOS 13C4-PFOS 3M UNIS ID GLP10-01-02-13-029 GLP10-01-02-13-030 GLP10-01-02-13-031 GLP10-01-02-13-032 Description DAL GW MCL MW 3S 0 101110 DAL GW MCL MW3S DB 101110 DAL GW MCL MW3S LS 101110 DAL GW MCL MW3S HS 101110 Concentration Concentration (ng/mL) %Recovery (ng/mL) <0.0250 NA <0.0250 <0.0250 NA <0.0250 1.22 126 1.23 11.3 116 11.2 %Recovery NA NA 128 117 Concentration (ng/mL) 0.0331 0.0281 0.980 NA(1) %Recovery NA NA 96.9 NA(1> %Recovery 94.7 101 104 101 Average Concentration (ng/mL) %RPD/RSD <0.0250 ng/mL <0.0250 ng/mL 0.0306 ng/mL 16% 100% 4.0% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Page 24 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 17. DAL GW MCL MW 4B 101110 PFBS PFHS PFOS 13C4-PFOS 3M UNIS ID GLP10-01-02-13-033 GLP10-01-02-13-034 GLP10-01-02-13-035 GLP10-01-02-13-036 Description DAL GW MCL MW 4B 0 101110 DAL GW MCL MW 4B DB 101110 DAL GW MCL MW 4B LS 101110 DAL GW MCL MW4BHS 101110 Concentration (ng/mL) "/Recovery <0.0250 NA <0.0250 NA 1.19 123 11.1 114 Concentration (ng/mL) <0.0250 <0.0250 1.23 11.4 "/Recovery NA NA 128 119 Concentration (ng/mL) 0.0511 0.0439 0.991 NA(1) %Recovery NA NA 96.3 N A (1) %Recovery 101 102 102 106 Average Concentration (ng/mL) %RPD/RSD <0.0250 ng/mL <0.0250 ng/mL 0.0475 ng/mL 15% 103% 2.2% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Table 18. DAL GW MCL MW 41101110 3M UNIS ID GLP10-01-02-13-037 GLP10-01-02-13-038 GLP10-01-02-13-039 GLP10-01-02-13-040 Description DAL GWMCL MW 4I0 101110 DAL GWMCL MW4I DB 101110 DAL GWMCL MW4I LS 101110 DAL GWMCL MW4I HS 101110 Average Concentration (ng/mL) "ARPD/RSD PFBS PFHS PFOS 13C4-PFOS Concentration (ng/mL) <0.0250 <0.0250 1.18 11.7 "/Recovery NA NA 122 120 Concentration (ng/mL) <0.0250 <0.0250 1.20 11.7 %Recovery NA NA 125 122 Concentration (ng/mL) 0.147 0.140 1.11 NA 01 %Recovery NA NA 98.6 NA<1) %Recovery 99.9 98.0 98.1 102 . <0.0250 ng/mL <0.0250 ng/mL 0.144 ng/mL 4.9% 99.5% 1.9% NA = Not Applicable ' (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Page 25 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 19. DAL GW MCL MW 4S 101110 PFBS PFHS PFOS 13C4-PFOS 3MLIMSID GLP10-01-02-13-041 GLP10-01-02-13-042 GLP10-01-02-13-043 GLP10-01-02-13-044 Description DAL GW MCL MW 4S0 101110 DAL GW MCL MW4S DB 101110 DAL GW MCL MW4S LS 101110 DAL GW MCL MW4S HS 101110 Concentration Concentration (ng/mL) %Recovery (ng/mL) <0.0250 NA <0.0250 <0.0250 NA <0.0250 1.21 125 1.23 11.7 120 11.7 %Recovery NA NA 128 122 Concentration (ng/mL) 0.263 0.248 1.11 N A (1) %Recovery NA NA 87.2 NA (1) %Recovery 102 99.3 106 104 Average Concentration (ng/mL) %RPD/RSD <0.0250 ng/mL <0.0250 ng/mL 0.256 ng/mL 5.9% 103% 2.8% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Table 20. DAL GW MCL MW 13B 101111 PFBS PFHS PFOS 13C4-PFOS 3MUMSID GLP10-01-02-13-045 GLP10-01-02-13-046 GLP10-01-02-13-047 GLP10-01-02-13-048 Description DAL GW MCL MW 13B0 101111 DAL GW MCL MW13B DB 101111 DAL GW MCL MW13B LS 101111 DAL GW MCL MW13B HS 101111 Concentration (ng/mL) %Recovery 0.0964 NA 0.101 NA 1.31 125 10.9 111 Concentration (ng/mL) 0.0711 0.0722 1.31 11.2 %Recovery NA NA 129 116 Concentration (ng/mL) <0.0250 <0.0250 0.987 N A (1> %Recovery NA NA 101 NA (1) %Recovery 104 99.2 98.9 99.8 Average Concentration (ng/mL) %RPD/RSD 0.0987 ng/mL 4.7% 0.0717 ng/mL 1.5% <0.0250 ng/mL 101% 2.6% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Page 26 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 21. DAL GW MCL MW 131101111 PFBS PFHS PFOS 13C4-PFOS 3MUMSID GLP10-01-02-13-049 GLP10-01-02-13-050 GLP10-01-02-13-051 GLP10-01-02-13-052 Description DAL GW MCL MW 13I 0 101111 DAL GW MCL MW 131 DB 101111 DAL GW MCL MW 131 LS 101111 DAL GW MCL MW 131 HS 101111 Concentration (ng/mL) %Recovery 0.0875 NA 0.0811 NA 1.29 124 11.3 115 Concentration (ng/mL) 0.0537 0.0514 1.29 11.7 %Recovery NA NA 129 121 Concentration (ng/mL) <0.0250 <0.0250 0.955 NA(1) %Recovery NA NA 97.4 NA <1> XRecovery 99.1 99.9 100 100 Average Concentration (ng/mL) %RPD/RSD 0.0843ng/mL 7.6% 0.0526 ng/mL 4.4% 0.0250 ng/mL 99.9% 0.59% . NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Table 22. DAL GW MCL MW 13S 101111 PFBS PFHS PFOS 13C4-PFOS 3MUMSID GLP10-01-02-13-053 GLP10-01-02-13-054 GLP10-01-02-13-055 GLP10-01-02-13-056 Description DAL GW MCL MW 13S0 101111 DAL GW MCL MW13S DB 101111 DAL GW MCL MW 13S LS 101111 DAL GW MCL MW 13S HS 101111 Concentration (ng/mL) %Recovery 0.0977 NA 0.0937 NA 1.27 121 11.6 118 Concentration (ng/mL) 0.0582 0.0535 1.25 11.5 %Recovery NA NA 124 119 Concentration (ng/mL) <0.0250 <0.0250 0.943 NA (1) %Recovery NA NA 96.2 N A (1) %>Recovery 104 105 98.7 103 Average Concentration (ng/mL) %oRPD/RSD 0.0957 ng/mL 4.2% 0.0559 ng/mL 8.4% <0.0250 ng/mL 103% 2.7% NA = Not Applicable (1) Sample set was analyzed for PFOS on 12/15/10. The high field matrix spike sample was not analyzed in this run. Page 27 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Table 23. Trip Blank 3M UNIS ID GLP10-01-01-13-058 GLP10-01-01-13-059 GLP10-01-01-13-059 GLP10-01-01-13-060 Description Trip Blank Sample Trip Blank Low Spike Trip Blank Low Spike Trip Blank High Spike NA = Not Applicable (1) Results reported from analytical run 11/23/10. (2) Results reported from analytical run for PFOS on 12/15/10. PFBS PFHS Concentration Concentration (ng/mL) VoRecovery (ng/mL) <0.0250 <1) NA <0.0250(1> 1.18 <1) 122 1.23 (1) NA NA NA 11.5 <1> 118 11.6 <1) %Recovery NA 128 NA 121 PFOS Concentration (ng/mL) <0.0250 <2> 0.936 <2) 1.12 (1) 10.9 (1) VoRecovery NA 95.5 114 111 Table 24. DAL GW 602S RB 101029 3MLIMSID GLP10-01-01-13-057 Description DAL GW MCL MW2I RB 101110 N A = Not Applicable (1) Results reported from analytical run 11/23/10. (2) Results reported from analytical run for PFOS on 12/15/10. PFBS PFHS PFOS Concentration (ng/mL) <0.0250 <1) Concentration Concentration (ng/mL) (ng/mL) <0.0250 (1) <0.0250 <2) Page 28 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 10 Conclusion Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. 11 Data/Sample Retention . All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Attachments Attachment A: Protocol Amendment 13 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 29 of 67 GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator 7 Date William K. Reagen, Ph.D., 3M Environmental Laboratory Manager 3 / J fo 'o // Date Page 30 of 67 Attachment A GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples M o w n County Amendment 13 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. 13 Amendment Date: November 9, 2010 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-02-13 Sampling Event Morgan County Landfill - Groundwater Sampling Exact Copy of Original Date \ Page 1 of 6 Page 31 of 67 Attachment A GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County -02 Amendment 13 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. A mend to read: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis o f groundwater samples from Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe of November 10-11, 2010. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory UMS as project GLP10-01-02-13 and reported as interim report GLP10-01-02-13, (reflecting study GLP10-01-02 and am endm ent-13). Raason: 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 three pages in length and included as attached to this amendment form. Page 2 of 6 Page 32 of 67 Attachment A GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County L a r ^ ^ r Amendment 13 Amendment Approval Page 3 o f 6 Page 33 of 67 Attachment A GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples , Morgan County Amendment 13 Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From : cc: Date; S ubject: Gary Hohensiein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab W iliam Reagen, 3M EHS&Opns; Environmentei Lab Cliffton Jacoby, 3M EHS&Opns; Environmental Lab Jai Kesari, W eston Solutions Charles Young, Weston Solutions Tim Frinak, Weston Solutions November 9, 2010 Analysis o f Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 1 3 -M o rg a n County Landfill G ro u n d w a te r 1 Generai Project Information C o n ta c ts Lab Request Number Six D igit D epartm ent Num ber P roject Schedule/Test Dates 3M S ponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 aahohensteinrammm.com 3M Environm ental Laboratory M anagem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wk reaaenrShnmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cd anae m m m .com Sam pling C oordinator Timothy Frinak Weston Solutions Timothv.frinakrSiwestonsolutions.com Phone: (334K532-9123 GLP10-01-02-13 Dept #530711, Project #0022674449 Sampling scheduled for November 10-11,2010 All verbal and written correspondence will be directed fo Gary Hohenstein. -. Page 4 of 6 Page 34 of 67 Attachment A GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples C O M , L F M V o2 Amendment 13 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) w ill receive and analyze groundwater samples collected from five m onitoring stations. Each monitoring station at the facility is constructed with two to three wells, m onitoring the residuum, the interm ediate zone (epikarst) and bedrock. Based on review of the well locations and groundwater flow patterns for the site, the follow ing wells have been selected for sampling and the rationale is provided for each selected location: MW-1 (S, I, B); MW-2 (I, B); MW-3 (S, I, B); and MW -4 (S, I, B) - These eleven wells represent downgradient com pliance wells for the facility which, based on groundwater contours, m onitor flow from most o f the active landfill area. W ell designations are: S-shallow well, I - interface well, and B - Bedrock well. MW -13 (S, I, B) - This well cluster represents an upgradient monitoring point to the landfill and serves as a background monitoring point. Sampling locations w ill be analyzed for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfiuorooctanesuifonate (PFOS) as part of the Morgan County Landfill groundwater sampling. Analyses w ill be conducted under the GLP requirem ents o f EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater sam ples from Decatur, AL w ill be collected by W eston Solutions personnel November 10-11, 2010. The 3M Environm ental Laboratory will prepare the sample bottles w ith 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-Q1-02-13. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling November 10-11, 2010. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Wednesday, November 10, 2010. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ W eston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabam a 35601 , . 4 Test Parameters The targeted limit o f quantitation will be 0.025 ng/mL (ppb) for PFBS, PFHS, and PFOS. A total of fourteen sampling locations have been specified. For each sampling location, a total of four sample bottles will be collected (sample, sample duplicate, low-level field matrix spike, and high-level field matrix spike).The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One set of trip blanks consisting of reagent-grade water, a low-level trip blank 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. The low field matrix spike will be prepared at 1 ng/mL and the high field matrix spike at 10 ng/mL. Two additional bottles will be prepared to be used for the preparation of the equipment rinseate blanks. In addition to the sample bottles, a 1-L container of Milli Q water will be included to be used for the preparation of the rinseate blanks. All sample bottles will include the addition of 13Oz-PFBS, 180 2-PFHS, and 13C4-PFOS, 1802-PFBS (internal standards) at a nominal concentration of 1 ng/mL. All sample bottles will also include the addition of 13C4-PFOS (surrogate spike) at a nominal concentration o f 0.1 ng/mL. A total o f 61 sample bottles will be prepared. Page 5 of 6 Page 35 of 67 Attachment A GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Amendment 13 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Where applicable, samples will be analyzed against an internal standard calibration curve. Each curve point will contain isotopically-labeled PFBS, PFHS, and PFOS at a nominal concentration of 1 ng/mL. The calibration curve will be generated by taking the ratio of the standard peak area counts over the internal standard peak area counts to fit the data for each analyte. Laboratory control samples prepared with the samples must have an average recovery within 10020% and a RSD 20%. The data quality objective for this study is quantitative results for the target analytes with an analytical accuracy o f 10030%. Field matrix spikes not yielding recoveries within 1003Q% will be addressed in foe report and the final accuracy statement may be adjusted accordingly. 6 Reporting Requirements For each sampling location, the report will contain foe results for foe sample, sample duplicate, and the two field matrix spikes. Trip blank and trip blank spikes will be reported for foe sampling event as will any equipment/rinseate blanks prepared in foe field. Laboratory control spikes of reagent water prepared at foe time of sample extraction will also be reported and used to evaluate foe overall method accuracy and precision. Method blanks of reagent water prepared at foe time of sample extraction will be used to determine foe method detection limit. For those sampling locations where foe field matrix spike level was not appropriate, due to higher than expected analyte concentrations, a laboratory matrix spike may be prepared and will be included in foe final report. Page 6 of 6 Page 36 of 67 ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Ana|y m 9 i f f Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:10:20 AM Printing Date: Wednesday, January 26, 2011 Page 1 of 1 Page 37 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Anat y ? &8 l ? f 1 Gr oundwat er Samples Morgan County Landfill, Decatur, AL - November 2010 m 10 1 1 2 3 a .rd b (PFH S): "Q ua d ra tic" Regression ("1 l x " w eighting): y = -0.00591 x A2 + 1.19 x + 0.0 15 2 (r = 0.9996) 48 46 44 42 40 38 36 34 32 30 0<D3 2 8 < CO 26 0fl>3 2 4 < 3Q^> 22 <(c0 20 18 16 14- > 0 '' 5 '' 10 15 20 ' 25 30 35 40 45 50 Analyte Cone. / IS Cone. Data worked up by STW Printing Time: 11:10:34 AM Page 1 of 1 Printing Date: Wednesday, January 26, 2011 Page 38 of 67 *TS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Ana' mei ET1 Gr oundwat er Samples Morgan County Landfill, Decatur, AL - November 2010 Analyte Area / IS Area Data worked up by STW Printing Time: 11:10:50 AM Printing Date: Wednesday, January 26, 2011 Page 1 of 1 Page 39 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Ana|y^ssgf P f f ^ P F f ^ g r ^ F O ^ Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:11:12 AM Printing Date: Wednesday, January 26, 2011 Page 1 of 1 Page 40 of 67 Attachment B Data worked up by STW Printing Time: 11:13:20 AM Printing Date: Wednesday, January 26, 2011 GLP10-01-02; Interim Report 13 Ana| y i ? M f G r o u n d w a t e r Samples Morgan County Landfill, Decatur, AL - November 2010 Page 1 of 9 Page 41 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Ana|y , m g ^ f E ^ P F h ^ 0^ P 3FOpdp Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Printing Date: Wednesday, January 26, 2011 Page 42 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 A n a ' y ^ g f P f B S ^ P F ^ g ^ ^ O ^ p Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:13:21 AM Printing Date: Wednesday, January 26, 2011 Page 3 of 9 Page 43 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Anat y ? M ? f ' Gr oundwat er Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:13:21 AM Printing Date: Wednesday, January 26, 2011 Page 4 of 9 Page 44 of 67 *ETS-Mary Ann Attachment B Printing Time: 11:13:22 AM Printing Date: Wednesday, January 26, 2011 GLP10-01-02; Interim Report 13 Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Page 45 of 67 Attachment B Printing Time: 11:13:22 AM Printing Date: Wednesday, January 26, 2011 GLP10-01-02; Interim Report 13 A H a ' m g l P f B ^ P F h ^ G r o u n d w a t e r Samples Morgan County Landfill, Decatur, AL - November 2010 Page 6 of 9 Page 46 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Anal y , M j r i t i a S 5 i ^ ? a i P Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:13:22 AM Printing Date: Wednesday, January 26, 2011 Page 47 of 67 *ETS-Mary Ann Attachment B GLP10-01-02; Interim Report 13 Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:13:23 AM Printing Date: Wednesday, January 26, 2011 Page 8 of 9 Page 48 of 67 *ETS-Mary Ann Attachment B Data worked up by STW Printing Time: 11:13:23 AM Printing Date: Wednesday, January 26, 2011 GLP10-01-02; Interim Report 13 Ana|yMss 9 iE f Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Page 9 of 9 Page 49 of 67 Ginger AG01330509 Attachment B g 1 0 1 2 1 5 a .rd b (PFO S ): "Q ua d ra tic" R egression ("1 / x " w e ighting): y = -0.0 5 1 2 xA2 + 1.74 x + 0 .0 1 9 (r = 0.9995) 7.9 7.5 H 7.0 6.5 6.0 5.5 5 .0 Ca>O 4.5 < CO CaO) 4 .0 : < flj 3 .5 ro 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0 0.5 1.0 Data worked up by STW Printing Time: 11:14:33 AM Printing Date: Wednesday, January 26, 2011 1.5 2.0 2.5 3.0 ' Analyte Cone. / IS Cone. GLP10-01-02; Interim Report 13 Ana|y m 8 i f f Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 3.5 Page 1 of 1 4.0 4.5 5.0 Page 50 of 67 * * * Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 13 AnalV |? M P f jP5EOpdp Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:14:56 AM Printing Date: Wednesday, January 26, 2011 Page 1 of 1 Page 51 of 67 *** Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 13 P f H| i ^ i^ O p d iP Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:16:51 AM Printing Date: Wednesday, January 26, 2011 Page 1 of 4 Page 52 of 67 *** Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 13 A n a l y s t P f BS^PFH^ g p d F O ^ Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:16:52 AM Printing Date: Wednesday, January 26, 2011 Page 53 of 67 *** Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 13 Ana|y ^ ss 8 i S ^ i p5^?di5' Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Printing Date: Wednesday, January 26, 2011 Page 54 of 67 **+ Ginger AG01330509 Attachment B GLP10-01-02; Interim Report 13 A n a iy ^ g ^ f Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Data worked up by STW Printing Time: 11:16:53 AM Printing Date: Wednesday, January 26, 2011 Page 4 of 4 Page 55 of 67 Attachment C Document rH^ikSE8tM6 sef#., for 14 days from 01/26/20 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 3M Environmental Laboratory Method Method of 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 Approved By: W illiam K. Reagen, Laboratory Manager 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 56 of 67 Attachment C Document s&jsaerst, for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfiuorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. 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 57 of 67 Attachment C Document WriferiHi sfejssiefat, for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected In duplicate at the same time from the same location as the sample. The FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sample (LCS) An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples. 3.9 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.10 Lim it o f 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 58 of 67 Attachment C Document ntayibariiesieriferiifisejrctert, for 14 days from 01/28/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus. 3.12 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material. 3.13 Stock Standard Solution (SSS) A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound. 3.14 Surrogate A compound similar in chemical composition and behavior to the target analyte(s), but is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality control samples. Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. 3.15 W orking 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 59 of 67 Attachment C Document sfepaeral;, for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrum entation 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 Chrom atographic 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 (min) 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m L/m in) 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak A rea-quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous information is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 60 of 67 Attachment C Document 36jf<&ef8t, for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: Analyte Transition Monitored PFBA 213 --> 169 PFPeA 263 -> 2 1 9 PFHA 3 1 3 -> 2 6 9 and 313 -> 1 1 9 PFHpA 363 -> 319, 363 -> 169 and 363 -> 119 PFOA 413 ->369, 413 -> 2 1 9 and 413 -> 1 6 9 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 --> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --^ 80 and 399 -- 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 Multiple transitions for monitoring the analytes is an option, as summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals Water - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (P F B A - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (PFHA - C6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (P F N A -C 9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (PFDA - C10 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFUnA - C11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P FD oA -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 for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 61 of 67 Attachment C Document nijikaiwwferiifi e&tsrierat, for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 The previous information is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)-- Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and W orking Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/mL target analyte SSSs-- Weigh out 10 mg of analytical standard (corrected for percent salt and purity) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An'example of purity and salt correction is given below for PFOS. molecular weight of anion salt correction factor moclecular weight of salt PFOS (K +)salt correction factor = -- = 0.9275 538 10 mg CsF^SOs'K" with purity 90% = 8.35mg C8F17S03" (10 mg*0.90*0.9275=8.35 mg) 5 pg/mL (5000 ng/mL) mixed working standard-- Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/mL mixed working standard-- Add 1,25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/mL mixed standard-- Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage Conditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection , Analysis Page 62 of 67 Attachment C Document Basset*, for 14 day: from 01/ :6/2 011 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. Concentration of WS, ng/mL 125 125 125 125 250 250 250 250 5000 5000 5000 Volume of WS, pL Final Volume of Calibration Standard (ml of ASTM Type 1Water, or other suitable water) 10 50 15 50 20 50 30 50 20 50 50 50 100 50 200 50 25 50 50 50 100 50 Final Concentration of Calibration Standard, ng/mL (ppb) in ASTM Type 1Water, or 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 W ater 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 63 of 67 Attachment C Document ntjfiCF0i megrim sepnetsL for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 be within 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed. 10 Quality Control 10.1 Data Quality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end of the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. 10.3 Sample Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation of the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-prepared as appropriate. s 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 64 of 67 Attachment C Document nifiiMMSi6aferitii s^reta!, for 14 days from 01/26/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: . . . . .. . . . (Peak Area-Intercept) Analyte found (ng/mL) = --------------------------- -- x DF 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 S uitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of <5% and a retention time RSD of <2% to be compliant. 12.2 Quantitation Calibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 65 of 67 Attachment C Document netfitw#*6riferiifi s^retst, for 14 days from 01/28/2011 Analysis of PFBS, PFHS and PFOS in Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Demonstration o f Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 A ccuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix . spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary of Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 66 of 67  M c M ^ ntial GLP10-01-02; Interim Report 13 Analysis of PFBS, PFHS and PFOS In Groundwater Samples Morgan County Landfill, Decatur, AL - November 2010 Record of Deviation/Nonconformance I. Identification Study / Project No. GLP10-01-02-13 \ Date(s) of Occurrence: i m101123a and g101215a Deviation type SOP (Check one) Protocol Equipment Procedure 0 Method 0 GPO Other: II. Description (attach extra pages as needed) Method Requirements: (1) LCS average recovery of 100% 20%. (2) Sample/Sample Duplicate RPD 20% . (3) Field matrix spike recovery of 100% 30%. Document Number: ETS-8-044.0 A ctual p roce d u re /p ro ce ss:................................................................................................................... (1) LCS average recovery for both sets of linear and branched PFOS were outside method acceptance criteria with average recoveries of 136% and 133%. (2) The RPD values for PFBS, PFHS, and PFOS for one sampling location were >20%. (3) The recovery of the high FMS sample for DAL GW MCL MW 2B 101110 was 135%. III. Actions Taken _________________________ (such a s a m e n d m e n t issued, S O P revision, etc.)_________________________ Corrective Action ( Yes 0 No) Reference: A cceptability o f the n o n co nform ing work:_____________________________ _____ _____ (1) It was suspected that the ECF stock standard used to prepare the linear+branched LCs may have become contaminated. A new linear and branched stock standard was prepared, with new LCS prepared at the same three concentration levels. Two of the low level linear and branched LCS could not be calculated as the detected concentration was below the limit of quantitation. One replicate at the low level had a recovery of 152%, while both the new mid and high level linear and branched LCS met method acceptance criteria with average recoveries of 114%. The mid and high level LCS concentrations were more appropriate as compared to the sample concentrations reported from this run. All LCS were used in the determination of method uncertainty. (2) Sampling location DAL GW MCL ME 1B 101110 had RPD values >20% for all three analytes. The results will be footnoted in the data tables. (3) The high FMS sample was the only appropriate spike level for PFOS for this sampling location. The analytical uncertainty will be adjusted to 35%. 0 Other: Deviations will be noted in final report. Project Lead/PAI Approval: S is a ri W olf Study Director (if GLP): W O k i h l ^ S p onsor A pproval (for G LP p ro to co l deviations): NA Technical Reviewer (optional): NA Date: l i b i l i Date: g M h Date: NA Date: NA Laboratory Departm ent M anager Approval: Date: -- _ ..... IV. Authorization to Resume Work 3 Lo/ / W h ere halting o f w ork occurred, resum ption o f work m u st first b e approved b y L aboratory M an ag em en t Laboratory Departm ent M anager Approval: NA Date: NA Deviation N o .______________ (assigned by Study Director or Team Leader at the end of study or project) Attachment A ETS-4-008.7 Page 1 of 1 Documentation of Deviations and Control of Nonconforming Testing Page 67 of 67