Document NEnrKLQ2NXjDoYE3wjrO6wKdp

GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 GLP10-01-02: Interim Report 14 - Analysis of PFBS. PFHS. and PFOS in Groundwater Samples Collected at the BFI Morris Farm Landfill located in Hillsboro. AL in March 2011 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisim ha Kesari P.E., DEE Weston Solutions, Inc. 1400 W eston Way W est Chester, PA 19380 Phone: 610-701-3761 Author Susan W olf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification G LP 10-01 -0 2-14 Total Number of Pages 89 The testing reported herein meet the requirements of ISO/IEC 17025-2005 "General Requirements for the Competence of Testing and Calibration Laboratories", in accordance with the A2LA Certificate #2052.01. Testing that complies with this International Standard also operate in accordance with ISO 9001:2000. Testing Cert #2052.01 Page 1 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 This page has been reserved for specific country requirements. Page 2 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 ' G LP C ompliance Statement Report Title: Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the BFI Morris Farm Landfill located in Hillsboro, AL in March 2011 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: These are environmental samples where there is no specific test substance, no specific test system and no dosing of a test system. The reference substances have not been characterized under the GLPs and the stability under storage conditions at the test site have not been determined under GLPs. Page 3 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Q uality A ssurance S tatement Report Title: Interim Report 14 Analysis o f PFBS, PFHS, and PFOS in Ground W ater Samples Collected at the BFI Morris Farm Landfill in Hillsboro, AL in March 2011 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 4/8/11,4/11/11,4/12/11 Phase Data / Interim Report Date Reported to Testing Facility Management Study Director 4/25/11 4/25/11 Date Page 4 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Ta b le o f C o n ten ts GLP Compliance Statem ent................................................................................................................. 3 Quality Assurance Statement........................ 4 Table of C ontents............... 5 List of Tables.......................................................................................................................................... 6 1 Study Information............................................................................................................................ 8 2 Summary......................................................................................................................................... 9 3 Introduction....................................................................................................................................10 4 Test & Control Substances...........................................................................................................11 5 Reference Substances.................................................................................................................. 11 6 Test System .................................................................................................................................. 13 7 Method Summary............................................................................................... 13 7.1 M ethods........................................................................................................................ 13 7.2 Sample Collection..........................................................................................................13 7.3 Sample Preparation.......................................................................................................14 7.4 Analysis......................................................................................................................... 14 8 Analytical R esults..........................................................................................................................15 8.1 Calibration..................................................................................................................... 15 8.2 System Suitability..........................................................................................................16 8.3 Limit of Quantitation (LO Q )........................................................................................... 16 8.4 Continuing Calibration................................................................................................... 16 8.5 Blanks............................................................................................................................ 16 8.6 Lab Control Spikes (LC Ss)........................................................................................... 16 8.7 Analytical Method Uncertainty...................................................................................... 20 8.8 Field Matrix Spikes (FMS)............................................................................................. 20 8.9 Laboratory Matrix Spikes (LM S)................................................................................... 21 Page 5 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 9 Data Summary and Discussion.................................................................................................... 21 10 Conclusion.................................................................................................................................... 31 11 Data/Sample Retention............................................................................................................... 31 12 Attachm ents.................................................................................................................................. 31 13 Signatures..................................................................................................................................... 32 L ist o f Ta b l e s Table 1. Summarized PFBS, PFHS, and PFOS Results (MFL Groundwater, March 2011)....................... 10 Table 2. Sample Description Key Code........................................................................................................13 Table 3. Instrument Parameters................................................................................................................... 14 Table 4. Liquid Chromatography Conditions................................................................................................ 14 Table 5. Mass Transitions............................................................................................................................. 15 Table 6. Limit of Quantitation (LOQ)............................................................................................................. 16 Table 7. Laboratory Control Spike Recovery................................................................................................ 18 Table 7 continued. Laboratory Control Spike Recovery..............................................................................19 Table 8. Analytical Uncertainty..................................................................................................................... 20 Table 9. DAL GW MFL MW01 0110322 .................................................................................................... 22 Table 10. DAL GW MFL MW01D 0 110322....................................................................................... 22 Table 11. DAL GW MFL MW02 0 110322................................................................................................... 23 Table 12. DAL GW MFL MW02D 0 110322................................................................................................ 23 Table 13. DAL GW MFL MW03 0 110323 .................................................................................................. 24 Table 14. DAL GW MFL MW03D 0 110323................................................................................................ 24 Table 15. DAL GW MFL MW04 0110323................................................................... ...............................25 Table 16. DAL GW MFL MW04D 0 110323................................................................................................ 26 Table 17. DAL GW MFL MW05 0 110323 .................................................................................................. 26 Table 18. DAL GW MFL MW05D 0 110323................................................................................................ 27 Table 19. DAL GW MFL MW10 0110322.................................................................................................. 27 Page 6 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 20. DAL GW MFL MW10D 0 110322............................................................................................... 28 Table 21. DAL GW MFL MW13 0110323 .................................................................................................. 28 Table 22. DAL GW MFL MW13D 0110323............................................................................................... 29 Table 23. Trip B lank.................................................................................................................................... 29 Table 24. Rinseate Blanks.......................................................................................................................... 30 Page 7 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 1 Study Information Sponsor 3M Company Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone: (651) 737-3570 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax:(610)701-7401 j .kesari@westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clange@mmm.com): 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 14 Experimental Termination: April 4,2011 Amended Interim Report Completion: Date of Interim Report Signing Location of Archives A ll 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 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 2 Summary The 3M Environmental Laboratory received groundwater samples from wells located at the BFI Morris Farm Landfill in Hillsboro, AL. A total of sixty sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate groundwater samples from each sampling location. Samples also included two field matrix spike (FMS) samples for each location, one trip blank set containing RO water and appropriate 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. All sample bottles also included the addition of 180 2-PFBS, 13C3-PFHS, and 13C8PFOS (internal standards) and 13C4-PFOS (surrogate spike). The groundwater samples, trip blank and equipment rinseate blank associated with GLP10-01 -02-14 were received from Weston personnel on March 24,2011. All of the samples were prepared and analyzed for PFBS, PFHS, PFOS, and 13C4-PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01 -02-014. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate blank 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 samples ranged from <0.0250 ng/mL to 5.03 ng/mL. The PFHS concentration results for all sample ranged from <0.0250 ng/mL to 12.8 ng/mL. The PFOS concentration results for all sample ranged from <0.0300 ng/mL to 22.5 ng/mL. The analytical method uncertainties associated with the reported results are: PFBS + 15%, PFHS + 11% and PFOS + 23%. For some samples, the method uncertainty was expanded for PFOS to + 36% and expanded for PFHS to + 34%. Page 9 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Table 1. Summarized PFBS, PFHS, and PFOS Results (MFL Groundwater, March 2011). PFBS PFHS PFOS Sampling Location Avg. Cone. (ng/mL) RPD Avg. Cone. (ng/mL) RPD Avg. Cone. (ng/mL) RPD DAL GW MFL MW01 0 110322 <0.0250 <0.0250 <0.0300 [b] DAL GW MFL MW01D 0 110322 0.194 0.52% 0.0533 11% 0.353 16% [b] DAL GW MFL MW02 0 110322 0.194 1.6% 0.467 3.0% 1.42 0.0% DAL GW MFL MW02D 0 110322 0.142 4.2% 0.424 13% 1 . 1 0 0 .0 % DAL GW MFL MW03 0 110323 <0.0250 0.0667 22% [a] 0.209 14% [b] DAL GW MFL MW03D 0 110323 <0.0250 <0.0250 <0.0300 [b] DAL GW MFL MW04 0 110323 1.67 6 .6 % 12.8 15% 22.5 3.1% DAL GW MFL MW04D 0 110323 0.171 10% 0.342 3.2% 0.184 14% [b] DAL GW MFL MW05 0 110323 1.05 1.0% 1.35 5.2% [c] 2.08 1 0 % DAL GW MFL MW05D 0 110323 0.0280 3.2% 0.0323 3.7% <0.0300 [b] DAL GW MFL MW10 0110322 0.0426 12% 0 . 1 2 1 2 1 % [a] 0.242 14% [b] DAL GW MFL MW10D 0 110322 <0.0250 0.0281 15% <0.0300 [b] DAL GW MFL MW13 0 110323 4.13 4.4% 1.27 5.5% 8.28 1 .2 % DAL GW MFL MW13D 0 110323 5.03 17% 1.48 2.0% 8 . 6 8 2 .0 % Trip Blanks (RO Water) <0.0250 <0.0250 <0.0300 [b] GLP10-01-02-14 Equipment rinseate blank: DAL GW MFL MW01 <0.0250 <0.0250 <0.0300 [b] The analytical method uncertainties associated with the reported results are as follows: PFBS 15%, PFHS 11% and PFOS 23%. [a] The RPD did not meet method acceptance criteria of <20%. [bj The analytical uncertainty is been adjusted for PFOS to 36%. See section 8.7 of the report for additional information. fc] The analytical uncertainty is been adjusted for PFHS to 34% based on FMS recovery. |3 Introduction This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze ground water samples collected from various wells located at the BFI Morris Farm Landfill in Hillsboro, AL for PFBS, PFHS, and PFOS in an effort to characterize regional groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL, Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and two field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. Sample bottles were also spiked with internal standard (1.0 ng/mL nominal concentration) and surrogate (0.1 ng/mL nominal concentration). Page 10 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Internal standard was used to aid in the data quality objectives. Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, the trip blank, and equipment rinseate blank. 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. I 4 Test & Control Substances I __j There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. 15 I Referenc_e____S___u__b__ _stances Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predominantly linear) Perfluorobutane sulfonate C4F9SO3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% PFHS (linear) Perfluorohexane sulfonate C6F13SO3 Sodium Salt Wellington 4/2/2013 Frozen LPFHXSAM08 TCR08-0018 Crystalline 98% Page 11 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (linear) Perfluorooctane sulfonate C 8 F17S O 3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity [1802J-PFBS (linear) [180 2 ]-Ammonium Perfluorobutanesulfonate C 4F9S [18C>2]0-NH4+ NA RTI International 03/09/2015 Frozen 11546-107-2 TCR-1032, TCR-1026 Liquid >99% PFOS (linear + branched) Perfluorooctane sulfonate C8 F 17SO 3 Potassium Salt CAS #2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% 13C3-PFHS (linear) Sodium Perfluorohexanesulfonate 13C 312C3F 13S 0 3 Na+ CAS # MPFC-C-0910 Wellington 09/28/2013 Frozen 092310 TCR10-0048 Liquid >98% Page 12 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity 13C8-PFOS (linear) Sodium Perfluorooctanesullbnate 13C8F17S 0 3'Na+ CAS # MPFC-C-0910 Wellington 09/28/2013 Frozen 092310 TCR10-0048 Liquid >98% 13C4-PFOS (linear) Sodium Perfluorooctanesullbnate 13C412C4F17S 03Na+ MPFOS Wellington 09/08/2013 Frozen MPFOS0910 TCR10-0044 Liquid >98% 6 Test System The test systems for this study are ground water samples collected from wells located in Hillsboror, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Table 2. Sample Description Key Code. String Number E xa m p le 1 2 3 4 5 Strina DescriDtor Example DAL GW M FL M W 010110322 S a m p lin g L o c a tio n M FL = M o rris F arm L a n d fill S a m p le T ype G W = G rou n d w a te r W e ll ID E x a m p le : M W 01 S a m p lin g D ate 110322 = M arch 22,2011 S a m p le T ype 0 = p rim a ry s a m p le D B = d u p lic a te sa m p le L S = lo w s p ik e H S = h ig h s p ik e i 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 associated with GLP10-01 -02-14 were returned to the laboratory at ambient conditions on March 24, 2011. Samples were stored refrigerated at the laboratory Page 13 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with each cooler of sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below in Table 3, Table 4 and Table 5. Table 3. In stru m e n t Param eters. Instrument Name Analytical Method Analysis Date Liauid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Ginger ETS-8-044.0 3/28/11-P F B S and PFHS Agilent 1100 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5u 10 uL Applied Biosystems API 5000 Turt Spray Turtx) ion electrode Negative Analyst 1.4.2 ETS McCoy ETS-8-044.0 4/1/11,4/4/11 - PFOS Aqilent 1290 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5u 5nL Applied Biosystems API 5500 Turtx) Spray Turt ion electrode Negative Analyst 1.5.2 Instrument Name Analytical Method Analysis Date Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Kirk ETS-8-044.0 4/4/11 - PFOS Aqilent 1200 Prism RP (4.6 mm X 50 mm), 5 u Betasil C18 (4.6 mm X 100 mm), 5u 25 uL Applied Biosystems API 5500 Turbo Spray Turbo ion electrode Negative Analyst 1.5.2 Page 14 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Table 4. Liquid Chromatography Conditions. S te p Num ber 0 1 2 3 4 5 0 1 2 3 4 5 0 1 2 3 4 5 T o ta l Tim e (m in ) 0 2.0 11.0 14.0 14.5 17.0 0 2.0 14.5 15.5 16.5 20.0 0 2.0 14.5 15.5 16.5 20.0 F lo w R ate (p U m in ) P ercentA (2 m M a m m o n iu m a ce tate ) ETS-8-044.0 Analyzed on ETS Ginger 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 ETS-8-044.0 Analyzed on ETS McCoy 300 90.0 300 90.0 300 5.0 300 5.0 300 90.0 300 90.0 ETS-8-044.0 Anah/zed on ETS Kirk 750 97.0 750 97.0 750 5.0 750 5.0 750 97.0 750 97.0 Table 5. Mass Transitions. P e rc e n tB (M e th a n ol) 3.0 3.0 95.0 95.0 3.0 3.0 10.0 10.0 95.0 95.0 10.0 10.0 3.0 3.0 95.0 95.0 3.0 3.0 A n a ly te M ass T ra n s itio n Q 1/Q 3 R e fe re n ce M a te ria l S tru c tu re In te rn a l S ta n d a rd M ass T ra n s itio n Q 1/Q 3 PFBS 2 9 9 /8 0 2 9 9 /9 9 L in e a r fO J -P F B S 3 0 3 /8 4 PFHS 3 9 9 /8 0 3 9 9 /9 9 L in e a r [ ,3C J-P F H S 4 0 2 /8 0 4 9 9 /8 0 PFOS 4 9 9 /9 9 L in e a r fC d -P F O S 5 0 7 /8 0 4 9 9 /1 3 0 fC J -P F O S su rro g a te 5 0 3 /8 0 L in e a r fC J -P F O S 5 0 7 /8 0 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. 8 Analytical Results 8.1 Calibration Samples were analyzed against an internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into prepared into synthetic groundwater (containing calium and magnesium). A total of fifteen spiked standards Page 15 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 ranging from 0.025 ng/mL to 75 ng/mL (nominal) were prepared, however, not all curve points were included in each analytical batch. Low or high curve points may have been disabled to meet method criteria. A quadratic, 1/x weighted, calibration curve of the peak area ratios 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 for each analytical batch. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, PFOS, and 13C4-PFOS for each analytical batch. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, PFOS, and 13C4-PFOS. 8.3 Limit of Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The LOQ for all analytes can be found in Table 6. Table 6. L im it o f Q u a n tita tio n (LOQ). Analysis Date 3/28/11 4/1/11 4/4/11 (mc110404a) 4/4/11 (k110404a) NA = Not Applicable PFBS LOQ, ng/mL 0.0250 NA NA NA PFHS LOQ, ng/mL 0.0250 NA NA NA PFOS LOQ, ng/mL NA 0.250 0.100 0.0300 8.4 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25% for PFBS, PFHS, PFOS, and 13C4-PFOS. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: procedural blanks, a trip blank and an equipment rinseate blank. Procedural blank results were reviewed and used to evaluate method performance to determine the LOQ for each analyte. The trip blank reflects the shipping and sample collection conditons the sample bottles and samples experience. The equipment rinseate blank is an aqueous sample that reflects the efficiency of equipment cleaning in the field between different sample collections and are proof of no cross contamination of samples from the use of the equipment. 8.6 Lab Control Spikes (LCSs) Lab control samples were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into synthetic groundwater to produce the desired concentration. The spiked water samples were then analyzed in the same manner as the samples. The method acceptance criteria, average of LCS at each level should be within 100% 20% with an RSD 20% . Page 16 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 3/28/11 Analysis: Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate for PFBS and PFHS. The LCSs met acceptance criteria for all three spiking levels. 4/1/11 Analysis: Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate for PFOS (linear). The low set of LCSs were below the limit of quantification, while the mid and high sets of LCS met acceptance criteria. 4/4/11 Analysis (ETS Kirk): Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate for PFOS (linear). The low set of LCSs had a RSD of 23%, while the mid and high sets of LCS met acceptance criteria. 4/4/11 Analysis (ETS McCoy): Low and high-level lab control spikes were prepared and analyzed in triplicate for PFOS (linear). The LCSs met acceptance criteria for both spiking levels. As the reference material used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear and branched) were prepared in triplicate to evaluate the potential for analytical bias. 4/1/11 Analysis: Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate for PFOS (linear and branched). The low set of LCSs were below the limit of quantification, while the mid and high sets of LCS met acceptance criteria. 4/4/11 Analysis (ETS Kirk): Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate for PFOS (linear and branched). The low set of LCSs met acceptance criteria, while the mid (136%) and high-level (133%) did not meet method acceptance crieria. 4/4/11 Analysis (ETS McCoy): Low and high-level lab control spikes were prepared and analyzed in triplicate for PFOS (linear and branched). The LCSs met acceptance criteria for both spiking levels. The 4/4/11 analysis on ETS Kirk indicates a potential analytical bias for samples containing linear and branched isomers of PFOS when analyzed a calibration curve of predominantly linear PFOS. Therefore, samples analyzed on 4/4/11 on ETS Kirk will have an expanded uncertainty for PFOS of 36%, based on the highest average recovery of the linear and branched LCS samples. A method deviation is included with the raw data. The following calculations were used to generate data in Table 7 for laboratory control spikes. ,,, ,, .,, Calculated Concentration LCS Percent Recovery = ------------------------------------- 100% Spike Concentration LCS% RSD = standard deviation LCS replicates . 1Q0% average LCS recovery Page 17 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Table 7. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 3/28/11 PFBS Lab ID Spiked Calculated Spiked Concentration Concentration Concentration (ng/mL) (ng/mL) % R ecoverv (ng/mL) LCS-110325-1 LCS-110325-2 0.198 0.198 0.226 114 0.198 0.256 129 0.198 LCS-110325-3 0.198 0.233 118 0.198 Average %RSD 120 6.5% LCS-110325-4 1.98 2.15 108 1.98 LCS-110325-5 1.98 2.35 119 1.98 LCS-110325-6 1.98 2.16 109 1.98 Average %RSD 112% 5.4% LCS-110325-7 LCS-110325-8 LCS-110325-9 9.94 9.94 9.94 12.2 123 9.94 10.4 105 9.94 11.7 117 9.94 Average %RSD 115% 8.0% PFHS Calculated Concentration (ng/mL) 0.197 0.215 0.206 104% 4.6% 2.13 2.09 2.24 109% 3.3% 10.3 10.6 9.55 102% 5.5% % R ecovery 99.4 109 104 108 106 113 103 107 96.0 ETS-8-044.0 Analyzed 4/1/11 PFOS (lineai) PFOS (lin ear+ branched) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) % R ecoverv LCS-110328-1 0.198 <0.250 NA LCS-110328-10 0.200 <0.250 NA LCS-110328-2 LCS-110328-3 Average %RSD 0.198 0.198 <0.250 <0.250 NA NA LCS-110328-11 NA LCS-110328-12 Average %RSD 0.200 0.200 <0.250 <0.250 NA NA NA LCS-110328-4 LCS-110328-5 LCS-110328-6 1.98 1.98 1.98 2.07 1.98 2.08 105 LCS-110328-13 100 LCS-110328-14 105 LCS-110328-15 2.00 2.00 2.00 2.33 2.35 2.46 117 117 123 Average %RSD 103% 2.8% Average %RSD 119% 2.9% LCS-110328-7 LCS-110328-8 LCS-110328-9 Average %RSD 9.94 9.94 9.94 11.3 11.4 11.1 113% 1.8% 113 LCS-110328-16 115 LCS-110328-17 111 LCS-110328-18 Average %RSD 10.0 10.0 10.0 12.0 11.5 11.5 117% 2.5% 120 115 115 NA = Not Applicable Page 18 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 4/1/11 Lab ID 13C4 PFOS S p ik e d C alculated Concentration C oncentration (ng/m L) (ng/m L) YoRecovery Lab ID 13C4 PFOS S p ik e d C alculated Concentration C oncentration (ng/m L) (ng/m L) % Recovery LC S-110328-1 L C S -1 1032 8-2 L C S -1 1 0 32 8-3 Average %RSD 0.189 0.189 0.189 0.180 0.188 0.184 97.3% 2.3% 95.0 99.4 97.4 L C S -1 10 3 2 8 -1 0 LC S-110328-11 L C S -1 1 0 32 8-12 Average %RSD 0 .1 8 9 0.189 0.189 0 .1 6 5 0 .1 8 6 0 .1 8 3 94.1% 6.5% 87.1 98.5 96.6 L C S -1 10 3 2 8 -4 L C S -1 10 32 8-5 L C S -1 10 32 8-6 Average %RSD 1.89 1.89 1.89 1.77 1.80 1.76 94.0% 1.0% 93.9 95.0 93.2 L C S -1 1 0 32 8-13 L C S -1 1 0 32 8-14 L C S -1 1 0 32 8-15 Average %RSD 1.89 1.89 1.89 1.83 1.78 1.92 97.0% 3.8% 96.4 93.7 101 ETS-8-044.0 Analyzed 4/4/11 (ETS McCoy) Lab ID PFO S (lin eai) S p ik e d C alculated Concentration Concentration (ng/m L) (ng/m L) YoRecovery Lab ID PFO S (lin ear + branched) S p ik e d C alculated Concentration C oncentration (ng/m L) (ng/m L) YoRecovery L C S -1 10 32 8-4 L C S -1 1 0 32 8-5 L C S -1 1 0 32 8-6 Average %RSD L C S -1 1032 8-7 L C S -1 1 0 32 8-8 L C S -1 1 0 32 8-9 Average %RSD 1.98 1.98 1.98 9.94 9.94 9.94 2.11 2.04 2.09 105% 2.0% 11.4 11.7 10.6 113% 5.0% 107 LCS-110328-13 103 LCS-110328-14 106 LCS-110328-15 Average %RSD 115 LCS-110328-16 118 LCS-110328-17 107 LCS-110328-18 Average %RSD 2.00 2.00 2.00 10.0 10.0 10.0 2.48 2.28 2.29 118% 4.7% 11.5 12.1 11.2 116% 4.0% 124 114 115 115 121 112 NA= Not Applicable Page 19 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 4/1/11 (ETS Kirk) PFOS (linear) PFOS (lin ear+ branched) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) % R ecovery LCS-110328-1 LCS-110328-2 LCS-110328-3 0.198 0.198 0.198 0.137 0.157 0.212 69.2 79.0 107 LCS-110328-10 LCS-110328-11 LCS-110328-12 0.200 0.200 0.200 0.245 0.233 0.229 123 117 114 Average %RSD 85.1% 2 3 % Average %RSD 118% 3.9% LCS-110328-4 LCS-110328-5 LCS-110328-6 1.98 1.98 1.98 2.11 2.06 2.05 107 LCS-110328-13 104 LCS-110328-14 104 LCS-110328-15 2.00 2.00 2.00 2.74 2.77 2.63 137 138 132 Average % RSD 105% 1.6% Average %RSD 136% 2.4% (1) LCS-110328-7 LCS-110328-8 LCS-110328-9 9.94 9.94 9.94 11.4 11.2 11.0 115 LCS-110328-16 112 LCS-110328-17 111 LCS-110328-18 10.0 10.0 10.0 13.6 13.1 13.3 136 131 133 Average % RSD 113% 1.8% Average %RSD 133% 1 .9 % 111 (1) Percent recovery did not meet method acceptance criteria of 20%. (2) RSD did not meet method acceptance criteira of 20%. 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values listed in Table 8. For samples analyzed on 4/4/11 on ETS Kirk, the PFOS method uncertainty is expanded to 36%. Table 8. Analytical Uncertainty. Analyte Standard Deviation Method Uncertainty PFBS 7.57 15% PFHS 5.39 11% PFOS 11.7 23% (1) (1) Samples analyzed for PFOS on 4/4/11 on ETS Kirk will have an expanded method uncertainty of 36%. 8.8 Field Matrix Spikes (FMS) Low (1.0 ng/mL) and high (10 ng/mL) field matrix spikes (FMS) were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 100 30% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. Page 20 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 FMS Recovery - (amP^e Concentration o f F M S- Average Concentration: Field Sample & Field Sample Dup.) * jQQy Spike Concentraton 8.9 Laboratory Matrix Spikes (LMS) The high FMS sample spike concentration (10.0 ng/mL) for DAL GW MFL MW04 was not appropriate as compared to the sample concentration for PFOS. The sample set was reanalyzed on 4/4/11 with a 24.9 ng/mL laboratory matrix spike for PFOS. Laboratory matrix spike recoveries within method acceptance criteria of 100 30% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. See section 9 for a discussion of the PFOS results. 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 blank and rinseate blank. Results and average values are rounded to three significant figures according to EPA rounding rules. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of 30%, demonstrate that the method was appropriate for the given matrix and their respective quantitative ranges. DAL GW MFL MW05 - The low-level FMS did meet method acceptance criteria for PFHS with a recovery of 134%, while the high-level FMS met method acceptance criteria with a recovery of 107%. Since the low-level FMS was the more appropriate spike level as compared to the sample concentration, the analytical uncertainty has been adjusted for PFHS to 34%. Page 21 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 9. DAL GW MFL MW01 0 110322 PFBSm PFHS m PFOS 13C rPFO S 3M UNIS ID Description Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01-02-14-017 DAL GW MFL MW01 0 110322 <0.0250 NA <0.0250 NA <0.0300 NA GLP10-01-02-14-018 DAL GW MFL MW01 DB 110322 <0.0250 NA <0.0250 NA <0.0300 NA GLP10-01-02-14-019 DAL GW MFL MW01 LS 110322 1.04 104 1.03 103 0.966 96.6 GLP10-01-02-14-020 DAL GW MFL MW01 HS 110322 9.65 96.5 9.39 93.9 10.2 102 Average Concentration (ng/mL) %RPD or %RSD <0.0250 ng/mL <0.0250 ng/mL <0.0300 ng/mL "ARecovery 99.1 98.6 91.7 87.3 94.2% 6.0% NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for 13C4-PFOS were analyzed on 4/1/11. (3) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. Table 10. DAL GW MFL MW01D 0 110322 PFBS PFHS PFOSm 13Cr PFOS 3NI UNIS ID Description Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery %Recovery GLP10-01-02-14-013 DAL GW MFL MW01D 0 110322 GLP10-01-02-14-014 DAL GW MFL MW01D DB 110322 0.193 0.194 NA 0.0561 NA 0.380 NA NA 0.0505 NA 0.325 NA 93.0 93.4 GLP10-01-02-14-015 DAL GW MFL MW01D LS 110322 1.11 91.7 1.06 101 1.30 94.8 GLP10-01-02-14-016 DAL GW MFL MW01D HS 110322 10.2 100 10.7 106 10.6 102 100 107 Average Concentration (ng/mL) %RPD or %RSD 0.194 ng/mL 0.52% 0.0533 ng/mL 11% 0.353 ng/mL 16% 98.3% 6.6% NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. Page 22 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 11. DAL GW MFL MW02 0 110322 PFBSm PFHS m PFOSm 13C4-PFOSw 3M UNIS ID Description GLP10-01-02-14-021 DAL GW MFL MW02 0 110322 GLP10-01 -02-14-022 DAL GW MFL MW02 DB 110322 GLP10-01-02-14-023 DAL GW MFL MW02 LS 110322 GLP10-01-02-14-024 DAL GW MFL MWQ2 HS 110322 Average Concentration (ng/mL) %RPD or %RSD Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery 0.195 NA 0.474 NA 1.42 NA 0.192 NA 0.460 NA 1.42 NA 1.27 108 1.67 120 2.58 116 10.2 100 10.8 103 11.6 102 0.194 ng/mL 1.6% 0.467 ng/mL 3.0% 1.42 ng/mL 0.0% %Recovery 108 90.6 96.3 98.7 98.4% 7.3% NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS and 13C4-PFOS were analyzed on 4/1/11. Table 12. DAL GW MFL MW02D 0 110322 PFBSm PFHS m PFOSm 13Ct-PFOS w 3M LIM SID Description GLP10-01-02-14-025 GLP10-01-02-14-026 GLP10-01-02-14-027 GLP10-01-02-14-028 DAL GW MFL MW02D 0 110322 DAL GW MFL MW02D DB 110322 DAL GW MFL MW02D LS 110322 DAL GW MFL MWD2D HS 110322 Average Concentration (ng/mL) %RPD or %RSD Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery %Recovery 0.145 NA 0.395 NA 1.10 NA 99.2 0.139 NA 0.452 NA 1.10 NA 94.5 1.22 108 1.47 105 2.20 110 91.0 9.94 98.0 9.72 93.0 10.8 97.0 86.7 0.142 ng/mL 4.2% 0.424 ng/mL 13% 1.10 ng/mL 0.0% 92.8% 5.7% NA = Not Applicable . (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS and 13C4-PFOS were analyzed on 4/1/1 1. Page 23 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 13. DAL GW MFL MW03 0 110323 PFBS PFHS m PFOS 13C4-PFOS 3M UNIS ID Description GLP10-01-02-14-029 DAL GW MFL MW03 0 110323 GLP10-01-02-14-030 DAL GW MFL MW03 DB 110323 GLP10-01-02-14-031 DAL GW MFL MW03 LS 110323 GLP10-01-02-14-032 DAL GW MFL MW03 HS 110323 Average Concentration (ng/mL) %RPD or% RSD Concentration Concentration Concentration (ng/mL) VoRecovery (ng/mL) %Recovery (ng/mL) %>Recovery <0.0250 NA 0.0741 <0.0250 NA 0.0592 NA NA 0.194 0.223 NA NA 0.999 99.9 1.06 99.3 1.28 107 10.9 109 10.8 107 10.1 98.9 <0.0250 ng/mL 0.0667 ng/mL 22% <4> 0.209 ng/mL 14% %Recovery 106 94.6 102 88.5 97.8% 7.9% NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. (4) RPD did not meet acceptance criteria of 100 20%. Table 14. DAL GW MFL MW03D 0 110323 PFBS m PFHSm PFOS 13C rP FO S 3M LIM SID Description Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01-02-14-033 DAL GW MFL MW03D 0 110323 <0.0250 NA <0.0250 NA <0.0300 NA GLP10-01-02-14-034 DAL GW MFL MW03D DB 110323 <0.0250 NA <0.0250 NA <0.0300 NA GLP10-01-02-14-035 DAL GW MFL MW03D LS 110323 GLP10-01-02-14-036 DAL GW MFL MW03D HS 110323 Average Concentration (ng/mL) %RPD or% RSD 1.13 113 10.3 103 <0.0250 ng/mL 1.07 107 9.20 92.0 <0.0250 ng/mL 0.986 98.6 9.97 99.7 <0.0300 ng/mL %>Recovery 99.7 80.4 118 99.2 99.4% 16% NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. Page 24 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Mom's Farm Landfill - MArch 2011 Table 15. DAL GW MFL MW04 0 110323 PFBS m PFHS m PFOS 13C rP FO S P) 3M U M S ID Description Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01-02-14-037 GLP10-01-02-14-038 DAL GW MFL MW04 0 110323 DAL GW MFL MW04 DB 110323 1.61 NA 13.7 NA 22.8 NA 1.72 NA 11.8 NA 22.1 NA GLP10-01-02-14-039 DAL GW MFL MW04 LS 110323 GLP10-01-02-14-040 DAL GW MFL MWD4 HS 110323 GLP10-01-02-14-037 LMS DAL GW MFL MW04; 24.9 ng/mL LMS 2.37 13.0 NA 70.5 113 NA 14.8 23.1 NA NC n a <4> n a (4) 104 33.5 NC NA 53.9 126 Average Concentration (ng/mL) %RPD or %RSD 1.67 ng/mL 16.6% 12.8 ng/mL 15% 22.5 ng/mL 3.1% VoRecovery 90.6 88.0 n a (4) 100 92.6 92.9% 5.8% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples reported for PFBS and PFHS vrere analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS McCoy . (3) Samples reported for 13C4-PFOS were analyzed on 4/1 /1 1. (4) Sample was not analyzed since spiked concentration was not appropriate compared to sample PFOS concentration. Page 25 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 16. DAL GW MFL MW04D 0 110323 PFBS m PFHS PFOS 13Ct-PFOS 3M LIM S ID Description Concentration Concentration Concentration (ng/mL) %Recoveiy (ng/mL) %Recovery (ng/mL) %Recovery %Recovery GLP10-01-02-14-041 DAL GW MFL MW04D 0 110323 GLP10-01-02-14-042 DAL GW MFL MW04D DB 110323 GLP10-01-02-14-043 DAL GW MFL MW04D LS 110323 GLP100102-14-044 DAL GW MFL MW04D HS 110323 Average Concentration (ng/mL) %RPD or %RSD 0.179 NA 0.162 NA 1.13 96.0 10.0 98.3 0.171 ng/mL 10% 0.347 NA 0.336 NA 1.37 103 9.26 89.2 0.342 ng/mL 3.2% 0.196 NA 0.171 NA 1.32 114 10.3 101 0.184 ng/mL 14% 96.3 87.8 93.0 95.9 93.3% 4.2% NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. Table 17. DAL GW MFL MW05 0 110323 3M U M S ID Description GLP10-01-02-14-045 GLP10-01-02-14-046 GLP10-01-02-14-047 GLP1001-02-14-048 DAL GW MFL MW05 0 110323 DAL GW MFL MW05 DB 110323 DAL GW MFL MW05 LS 110323 DAL GW MFL MW05 HS 110323 Average Concentration (ng/mL) %RPD or %RSD PFBSm PFHSm PFOS n Cr PFO S Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %>Recovery 1.04 NA 1.31 NA 2.18 NA 1.05 NA 1.38 NA 1.97 NA 1.79 74.5 2.68 1 3 4 (3) 2.91 NC 10.6 95.6 12.0 107 11.9 98.3 f.05 ng/mL 1.0% 1.35 ng/mL 5.2% (4> 2.08 ng/mL 10% % R ecovery 90.6 103 97.1 111 100% 8.6% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS and 13C4-PFOS were analyzed on 4/1/11. (3) Field matrix spike recovery did not meet method acceptance criteria of 100% 30%. (4) The analytical method uncertainty has been adjusted for PFHS based on the recovery of the most appropriate spike level to 34%. Page 26 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 18. DAL GW MFL MW05D 0 110323 PFBS m PFHS w PFOSm 13C rP FO S p) 3M U M S ID Description Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery VoRecoverv GLP10-01-02-14-049 DAL GW MFL MW05D 0 110323 GLP10-01-02-14-050 DAL GW MFL MW05D DB 110323 GLP10-01-02-14-051 DAL GW MFL MW05D LS 110323 GLP10-01-02-14-052 DAL GW MFL MW05D HS 110323 Average Concentration (ng/mL) %RPD or %RSD 0.0275 NA 0.0284 NA 1.14 111 10.9 109 0.0280 ng/mL 3.2% 0.0329 NA 0.0317 NA 1.16 113 9.61 95.8 0.0323 ng/mL 3 .r/o <0.0300 NA <0.0300 NA 0.982 98.2 10.2 102 <0.0300 ng/mL 93.7 96.4 97.2 101 97.2% 3.3% NA= Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/1 1. Table 19. DAL GW MFL MW10 0 110322 3M LIM S ID Description GLP10-01-02-14-004 DAL GW MFL MW10 0110322 GLP10-01-02-14-005 DAL GW MFL MW10 DB 110322 GLP10-01-02-14-006 DAL GW MFL MW10 LS 110322 GLP10-01-02-14-007 DAL GW MFL MW10 HS 110322 Average Concentration (ng/mL) %RPD or %RSD PFBS w PFHS 01 PFOSm 13C4-PFOSp) Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery 0.0452 NA 0.134 NA 0.259 NA 0.0399 NA 0.108 NA 0.224 NA 1.13 109 1.11 98.9 1.29 105 11.2 112 10.0 98.8 10.4 102 0.0426 ng/mL 12% 0.121 ng/mL 2 1 % (4> 0.242 ng/mL 14% %Recovery 111 98.0 94.5 93.5 99.2% 8.1% N A = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. (4) RPD did not meet acceptance criteria of 100 20%. Page 27 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 20. DAL GW MFL MW10D 0 110322 PFBS m PFHS m PFOS 13Cr PFO S 3M U M S ID Description GLP10-01-02-14-008 GLP10-01-02-14-009 GLP10-01 -02-14-010 GLP10-01-02-14-011 DAL GW MFL MW10D 0 110322 DAL GW MFL MW10D DB 110322 DAL GW MFL MW10D LS 110322 DAL GW MFL MW10D HS 110322 Average Concentration (ng/mL) %RPD Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery <0.0250 NA 0.0259 NA <0.0300 NA <0.0250 NA 0.0302 NA <0.0300 NA 0.958 9.53 95.8 95.3 1.12 10.5 109 0.999 99.9 105 10.2 102 <0.0250 ng/mL 0.0281 ng/mL 15% <0.0300 ng/mL %>Recovery 98.0 99.2 104 97.4 99.6% 2.9% NA = Not Applicable (1) Samples reported forPFBSandPFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. Table 21. DAL GW MFL MW13 0 110323 3M U M S ID Description GLP10-01-02-14-053 DAL GW MFL MW13 0 110323 GLP10-01-02-14-054 DAL GW MFL MW13 DB 110323 GLP10-01-02-14-055 DAL GW MFL MW13 LS 110323 GLP10-01-02-14-056 DAL GW MFL MW13 HS 110323 Average Concentration (ng/mL) %RPD PFBSm PFHSm PFOS 13Cr PFO S Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %>Recovery (ng/mL) %Recovery 4.04 NA 1.23 NA 8.33 NA 4.22 NA 1.30 NA 8.23 NA 5.64 14.0 NC 98.7 2.36 11.0 NC 97.4 10.1 17.8 NC 95.2 4.13 ng/mL 4.4% 1.27 ng/mL 5.5% 8.28 ng/mL 1.2% %Recovery 95.1 99.4 85.9 92.8 93.3% 6.0% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS and 13C4-PFOS were analyzed on 4/1/11. Page 28 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 22. DAL GW MFL MW13D 0 110323 PFBSm PFHS m PFOS 13C rP FO S m 3M U M S ID Description GLP10-01-02-14-057 DAL GW MFL MW13D 0 110323 GLP10-01-02-14-058 DAL GW MFL MW13D DB 110323 GLP10-01-02-14-059 DAL GW MFL MW13D LS 110323 GLP10-01-02-14-060 DAL GW MFL MW13D HS 110323 Average Concentration (ng/mL) %RPD Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery 5.47 4.59 NA 1.49 NA 8.76 NA NA 1.46 NA 8.59 NA 6.56 NC 15.6 106 5.03 ng/mL 17% 2.65 118 11.1 96.3 1.48 ng/mL 2.0% 10.3 NC 17.7 90.3 8.68 ng/mL 2.0% %Recovery 86.4 80.3 90.5 88.3 86.4% 5.0% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration greater than 2x spike level. (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS and 13C4-PFOS were analyzed on 4/1/11. Table 23. Trip Blank 3M U M S ID GLP10-01-02-14-001 GLP10-01-02-14-002 GLP10-01-02-14-003 Description DAL GW Trip 1 DAL GW Trip 1 LS DAL GW Trip 1 HS PFBS m PFHS m PFOSm Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) %Recovery <0.0250 NA <0.0250 NA <0.0300 NA 1.08 108 1.12 112 1.00 100 10.0 99.9 9.90 99.0 9.85 98.5 13C4-PF0S p) %Recovery 97.3 94.9 97.4 NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. Page 29 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Table 24. Rinseate Blanks 3M U M S ID Description GLP10-01-02-14-012 DAL GW MFL MW01 RB 110322 PFBS m PFHSm p ro s Concentration Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery (ng/mL) VoRecovery <0.0250 NA <0.0250 NA <0.0300 NA 13Cr PFOS P) %Recovery 108 NA = Not Applicable (1) Samples reported for PFBS and PFHS were analyzed on 3/28/11. (2) Samples reported for PFOS were analyzed on 4/4/11 on ETS Kirk. (3) Samples reported for 13C4-PFOS were analyzed on 4/1/11. Page 30 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Moms Farm Landfill - MArch 2011 10 Conclusion Laboratory control spikes and field matrix spikes were used to determine the analytical method accuracy and precision for PFBS, PFHS, and PFOS. Analysis was successfully completed following 3M Environmental Laboratory method ETS-8-044.0 described herein. j11 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 14 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Attachment E: Final Study Report Amendment Page 31 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 13 Signatures Cleston Lange, Ph.D., 3M Principal Analytical Investigator Date _____________________________________ 2. / William K^Reagen, Ph.D., 3M Environmental Laboratory Department Manager u// Date Page 32 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Attachment A: Protocol A mendment Page 33 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Analytical Protocol: G LP10-01-02 Am endm ent 14 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. 14 Amendment Date: November 29, 2010 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-02-14 Sampling Event BFI Morris Farm Landfill - Groundwater Sampling Page 1 of 6 Page 34 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Analytical Protocol: G LP10-01-02 Am endm ent 14 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 o f the protocol are required. AMEND TOread: No changes to the wording o f the protocol are required. This amendment only addresses and docum ents 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 fo r PFOS, PFHS and PFBS (GLP10-01-02). The sam pling schedule and final designation o f w ells to be sampled are contingent upon completing an access agreem ent w ith BFI M orris Farm Landfill. The groundwater sam ples fo r this sampling event w ill be entered into the 3M Environmental Laboratory LIMS as project GLP10-01-02-14 and reported as interim report GLP10-01-02-14, (reflecting study GLP10-01-02 and am endm ent -14). Reason: The reason fo r this am endm ent is to docum ent the General Project Outline (GPO) which describes the anticipate groundwater sam ple collection event to be conducted fo r 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 35 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Analytical Protocol: G LP10-01-02 Am endm ent 14 Amendment Approval _____________________________________________ William Reageri, EHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director Date m io Date Page 3 of 6 Page 36 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Analytical Protocol: G LP10-01-02 A m endm ent 14 Environmental Health & Safety Operations, Environmental Laboratory Generai Project Outline To: Gary Hohenstein, 3M EHS&Opns From: Susan Wolf, 3M EHS&Opns; Environmental Lab cc: William Reagen, 3M EHS&Opns; Environmental Lab Cliffton Jacoby, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions Tim Frinak, Weston Solutions Date: November 29,2010 Subject: Analysis o f Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent fo r the 3M Decatur Phase 3 Site-Related M onitoring Program; GLP Interim Report 14 - BFI M orris Farm Landfill G ro u n d w a te r 1 General Project Information Contacts Lab Request Number Six Digit Dpartaient Number Project Schedule/Test Dates 3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone:(651)737-3570 aahohenstein<mmm.com 3M Environmental Laboratory Management William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaenS8mmm.com Principal Analytical Investigator Cieston Lange 3M EHS Opns. Environmental Laboratory 260-5N-17 651 733-9860 cctanaeiammm.com Sampling Coordinator Timothy Frinak Weston Solutions Timothv.frinak(westonsolutions.com Phone: (3341-332-9123 GLP10-01-02-14 Dept #530711, Project #0022674449 To de determined A ll verbal a n d written correspondence will be directed to G a ry Hohenstein. >9 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Analytical Protocol: G LP10-01-02 Amendment 14 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environm ental Lab) w ill receive and analyze groundwater samples collected from m onitoring wells actively m aintained at the BFI M orris Farm Landfill. Each m onitoring station at the facility is constructed with two w ells, one m onitoring the residuum / epikarst groundwater zone and one m onitoring the bedrock groundwater zone. Based on review o f the well locations and groundwater flow patterns for the site, the following w ells have been selected fo r sam pling and the rationale is provided for each selected location: W ell location MW -10 - This well location is upgradient o f the active areas o f the landfill. It is located in the northwest corner o f the property. The location serves as an upgradient groundwater m onitoring point fo r the site. W ell location MW -07 - In a 1996 hydrogeologic investigation, this well location, constructed southwest of the active portions o f the landfill, Indicated upgradient conditions w ith possible seasonal im pact from active areas at the landfill. Later reports indicate the location was subsequently abandoned. As a result, the adjacent w ell location, MW-05, has been selected to provide sim ilar coverage fo r the area. W ell locations MW -1,2, 3, 4, and 13 - These w ell locations are located along the east and south boundaries of the active landfill area and serve as downgradient m onitoring points for the site. Review o f recent groundwater m onitoring reports have indicated sporadic elevated m etals concentrations associated with well locations, MW-01, MW-02, MW-04, and MW-13, suggesting potential im pact from site activities. As a result, these locations are proposed fo r m onitoring downgradient groundwater conditions. Since MW-03 closes a potential data gap on the downgradient side o f the landfill, this location has also been included in the sampling effort. Sampling locations w ill be analyzed fo r of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) as part o f the BFI M orris Farm Landfill groundwater sam pling. Analyses w ill be conducted under the GLP requirem ents of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples from Decatur, AL w ill be collected by W eston Solutions personnel as soon as access is granted. The 3M Environmental Laboratory w ill prepare the sam ple bottles w ith all required spikes to ensure that results fo r PFBS, PFHS, and PFOS are o f a known precision and accuracy. The final report w ill be subm itted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP1001-02-13. 3 Project Schedule ____________________________________ __ Sample collection bottles w ill be prepared by the 3M Environmental Laboratory. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Tuesday, November 30,2010. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ W eston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters_______________________________________________________ The targeted limit of quantitation will be 0.025 ng/m L (ppb) for PFBS, PFHS, and PFOS. A total of fourteen sampling locations have been specified. For each sampling location, a total o f four sample bottles will be collected (sample, sample duplicate, low-level field matrix spike, and high-level field matrix spike). Paae 5 o ft 9 GLP10-01-02; Amended Interim Report 14 . Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Analytical Protocol: G LP10-01-02 Am endm ent 14 The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One set o f trip blanks consisting of reagent-grade water, a low-level trip blank spike, and a high-level trip blank spike w ill be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. The low field matrix spike w ill be prepared at 1 ng/mL and the high field matrix spike at 10 ng/mL. One additional bottle will be prepared to be used for the preparation o f the equipment rinseate blank. In addition to the sample bottles, a 1-L container of Milli Q water will be included to be used for the preparation o f the rinseate blank. All sample bottles will include the addition of 18Or PFBS, 13C3-PFHS, and 13Cr PFOS, (internal standards) at a nominal concentration of 1 ng/mL. All sample bottles will also include the addition o f 13C4-PFOS (surrogate spike) at a nominal concentration o f 0.1 ng/mL. A total of 60 sample bottles w ill be prepared. 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination o f 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 w ill be generated by taking the ratio o f 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 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. 6 Reporting Requirements ________________________ For each sampling location, the report w ill contain the results for the sample, sample duplicate, and the two field matrix spikes. Trip blank and trip blank spikes w ill be reported for the sampling event as will any equipment/rinseate blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the tim e of sample extraction w ill be used to determine the method detection lim it For those sampling locations where the field matrix spike level was not appropriate, due to higher than expected analyte concentrations, a laboratory matrix spike may be prepared and w ill be included in the final report GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 At ta c h m e n t B: R e p r e s e n ta tiv e S a m p l e C h r o m a to g r a m s a n d C a l ib r a tio n C u r ve Page 40 of 89 *** Ginger AG01330509 . GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Date: Thursday, March 31, 2011 Page 41 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Date: Thursday, March 31, 2011 Page 42 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Time: 3:00:41 PM Printing Date: Thursday, March 31, 2011 Page 43 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Time: 3:00:41 PM Printing Date Thursday, March 31 2011 Page 44 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Time: 3:00:42 PM Printing Date: Thursday, March 31, 2011 Page 45 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Time: 3:00:42 PM Printing Date: Thursday, March 31, 2011 Page 46 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: gll0328a.rdb Printing Time: 3:00:42 PM Printing Date Thursday, March 31 2011 Page 47 of 89 *** Ginger AG01330509 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: gl10328a.rdb Data printed by STW Printing Time: 3:00:42 PM Printing Date Thursday, March 31 2011 Page 6 of 6 Page 48 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Page 49 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Page 50 of 89 *ETS-McCoy I SampleName; "mc1104Sl 0 tr S*npta ID:'10007-32-09 FiT'inc110401a.wtfr PeakName: *13C4PFOSSun* Massfaa): *503.000/80.000 Da* Comment*2-5 noAnlFC atdh Synth.Water* Annotation: ** Sample Index: 20 Sample Type: Standard Concentration: 2.39 ng/mL Calculated Cone: 2.40 ng/mL Acq. Date: 4/1/2011 Acq. Tie: 9:22:34 PH Kodlfled: Ho Proc. Algorithm: Specify Parameters - HQ III Hoise Percentage: 50 Base. Sub. Hindou: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Hin. Peak Height: 0.00 cps Hin. Peak Hidth: 0.00 eac Smoothing Hidth: RT Hindou: Expected RT: Use Relative RT: 0 30.0 13.1 Ho points sec ain Int. Type: Retention Area: Height: Base To Base : 13.0 nln 95648 counts 2.5Sc*004 cps GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb I Sample Name:*m c 8 5 5 3 ^ ^ n C T D ^T O 5 3 ^ " FIe:*mc110401a.w1fr " PeakName:*13C4PFOS-Sur* Massfes):*503.000/80.000 Da* Comment ` Method Blank* Annotation: " SSaanmppllae TIynpdee:x: 31 Calculated Cone: Hoiae . Base. Sub. Hindou: Peak-Split. Factor: Report Largest Peak: Hin. Peak Height: Hin. Peak Hidth: Smoothing Hidth: Height: Start Time End Time: 3.76e002 13.0 13.1 11.0 I SampleName: *ine110401a136* Sam pled: IC S -110328-5* F ie: *mc110401a.wiffJ Peak Name:*13C4PFOS-Sun* Masses): *503.000/803X10 Da* Comment *2ppb LCS* Annotation:** Sample Index: 136 Sample Type: QC Concentration: 1.69 ng/mL Calculated Cone: 1.60 ng/mL Acq. Data: 4/3/2011 1.7#4- Acq. Tine: 12:09:50 PH :ols< tage: Base. Sub. Hint Peak-Split. Fector: Report Largest Peak Hin. Peak Height: Hin. Peak Hidth: Smoothing Hidth: Expected RT: s Relat t RT: Retention Tim Area: Height: Start Time: Base To Base 13.1 min 71600 counts I.76S+004 Cps 13.0 min 9000.0 I Sample Name:'mcTUMOlal39* Sample ID:*LCS>110328-8" Fie:Snc110401a.wifr Peak Name:*13C4PFOS-Sun* Masses):503.00tv80.000 Da* Comment *10ppb LCS* Annotation:** ' Sample Index: 139 Sample Type: QC Concentration: 0.00 ng/mL Calculated Cone: 0.00203 ng/mL Acq. Date: 4/3/2011 Acq. Time: 1:11:34 PH Base. Sub. Hindou Peek-Split. Facto: Report Largest Pe> Hin. Peak Height: Hin. Peak Hidth: Smoothing Hidth: RT Hindou: Expected RT: Use Relative RT: Data printed by STW Printing Time: 2:33:35 PM T*rw-m*n12.0 12.6 13.0 13.5 14.6 15.0 15.5 Page 1 of 7 Page 51 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Data printed by STW Printing Time: 2:33:35 PM Page 2 of 7 Page 52 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Data printed by STW Printing Time: 2:33:35 PM Page 3 of 7 - Page 53 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Printing Time: 2:33:35 PM Page 54 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Printing Time: 2:33:36 PM Page 55 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Printing Time: 2:33:36 PM Page 56 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0401a.rdb Data printed by STW Printing Time: 2:33:36 PM Page 7 of 7 Page 57 of 89 *ETS-Kirk GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: kll0404a.rdb Printing Date: Wednesday, May 04, 2011 Page 58 of 89 *ETS-Kirk GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: kll0404a.rdb Data printed by STW Printing Time: 2:38:28 PM Printing Date: Wednesday, May 04 2011 Page 1 of 7 Page 59 of 89 *ETS-Kirk I S tnt Nam: Tc110*0*054` 8arr4atO :*GLPHM 1.02-14-0ir Peak Nama: *13C8PFOS-IS(ISr 507.000/80.000 Oa* Comment*DALGW MFLMW01 0 110322* Annotation:** Sample Index: 54 Simple Type: Unknown Concentration: 0.960 ng/mL 3200 Calculated Cone: N/A Acq. Date: 4/5/2011 Acq. Time: 9:42:11 AM 3000 File: \110404a.w lfr Modified: No Proc. Algori Min. Peak Height: Min. Peak Width: u.00 aec Smoothing Width: 0 pointa RT Window: 30.0 aec Expected AT: 15.3 min Use Relative RT: No Int. Type: Height: Stare Tin End Time: Valley Retention Time: 230.02057e*003counts 15.3 min ieoo 1400 1200- GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: kll0404a.rdb I SampleName:>1104048066* Swnp4elD:*GLP1IV01-02-1443r PeakName: *13C8PFOS-IS<iSr Massfes): *507.000^0.000 0a* Comment "DALGW MFL MW03O0110323* Annotation:** iple Typ. Sample Index: 66 Concentrt: Calcult. Acq. Dat< 3400 Fle:K 110404.w lir Modified: Proc. Algorithm: IntelliQuan - IQA 1 Min. Peak Height: Min. Peak Width: Smoothing Width: Expected RT: 3200 3000 2800- Height: Start Time End Time: : 15.3 min 22996 counts 3.64e003 cps 15.2 min 15.5 min 11|J|.4^ ..^I|II 13.0 133 I 3 8Sample Name:M 10404*071' Sandle tO:*GLP10-01-02-14-041* Fie:> 110404a.PeakName: '1 C PFOS-IS(tsr Masses): *507.000/80.000 Os* Comment *DAL GW MFL MWD4D 0110323' Annotation:" ' Sample Index: 71 Sample Type: Unknown Concentration: 0.960 ng/mL 1300 Calculated Cone: N/A 1250 Acq. Date: Acq. Time: 4/5/2011 2:41:13 PM 1200 Modified: Yes Proc. Algorithm: IntalliQua Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 0 p RT Window: 30.0 Ezpected RT: 15.3 min Use Relative RT : No 1150 1100 1050 1000 Int. Type: Area: Height: End Time: Valley 15.3 min 8723 CC 1.30003 cps 15.5 min 9 14.5 150 153 18.0 163 t7.0 173 130 133 I Sample Name: *k110404a087* SampleID:T.CS-U328-3* F(e:*k110404a.wttr' Peak Nome: *13C8PfOS-IS{ISJ* Masses):*507.00<V80.000 Da* Comment *02pp6 LCS* Annotation: Sample Index: 97 Sample Type: Concentration: 0.951 ng/mL Calculatad Cone: Acq. Date: 4/5/2011 Acq. Time: 9:19:14 PM Modified: No Proc. Algorithm: IntelliQuan - I Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing width: 0 points RT Window: 30.0 sec Expected RT: 15.3 min Area: Height: Start Time: End Time: 4575 counts 7.00e*002 epa 15.3 min 15.5 min . . .. i ilia mufemritf4 150 153 16.0 163 170 173 Tima, min ut i,i 13.0 133 Data printed by STW Printing Time: 2:38:28 PM Printing Date: Wednesday, May 04, 2011 1431 14.67 15.21, 14.0 143 15.0 Page 2 of 7 Page 60 of 89 *ETS-Kirk GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name kll0404a.rdb Data printed by STW Printing Time 2:38:28 PM Printing Date Wednesday, May 04 2011 Page 3 of 7 Page 61 of 89 *ETS-Kirk I Sample Nam; 1(1104040106* SamplID:*LCS-11032-18* 7 le :*1 1 0 4 0 4 a . # r^ Peak Nam: *13C8PFOS4S(ISr Mass<): *507.000/80.000 Da* Comment: 'lOppb LCS ECF* Annotation: ** Sample Index: 106 Sample Type: QC Concentration: 0.954 Calculated Cone: N/A ng/mL 3400' Acq. Date: Acq. Time: 4/1/2011 3:00:24 AH 3200 Modified: Yea Proc. Algorithm: IntelliQuan - IQA Hln. Peak Height: 0.00 epe 3000 2800 Hin. Peak Width: 0.00 aec Smoothing Width: 0 points RT Window: 30.0 sac 2600 Expected RT: IS.3 min Use Relative RT: No 2400 23245 cou 3.39e+003 15.3 15.5 2200 2000 1800 1600 1400 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: kll0404a.rdb ISampleName: *k110404e020* SampleID: 10007-32-6* Fto: *k110404a.wtr Peak Name:*PFOS* Masses): '499.000ra9.000 Da,499.000/80.000 Da,499.000/130.000 Da* Comment *1.0 ngAnL FCetd In Synth.Water* Annotation: ** Sample Type: Concentration: Calculated Cone: Acq. Date: Acq. Time: Modified: Proc. Algorithm: ntelliQuan - IQA II Min. Peak Height: 0.00 eps Min. Peak width: 0.00 sec Smoothing Width: 0 points RT Hindoo: 10.0 sec Expected RT: 15.3 ain Int. Type: Retention Time: Area: 23040 cot Height: 3.31e003 Start Time: 15.3 End time: IS.5 17.72 i iiiljm M l|i/p 1X0 1X5 14.0 14.S 15.0 15.5 16.0 16.5 17.0 17.5 ISample Name:*k110404a029* Sample0:*11 002-20* F8e:M10404a.m4ir Pad: Name: TPOS* Masses): '499.000/99.000 Da,499.000/80.000 Da,499.000/130.000 Da* Sample Index: 29 Sample Type: Unknown Concentration: N/A calculated Cone: <0 Acq. Date: 4/4/2011 Acq. Time: 11:54:33 I Modifie No Proc. AJ IntelliQuan - IQA II Min. Peak Height: Kin. Peak Width: Smoothing Width: RT Window: Expected RT: 2.40e0Q2 epa 15.3 min IS.5 min I SampleName: *k110404e035* Sample ID: 'GLP1IKI1-02-14-004' Fie: *K110404a.w1fr PeakName:*PFOS* Masses): '499.000/99.000 Da,499.000*0.000 Da,499.00M30.000 Da' Comment *DAL GWM Fl MW10 0110322* Annotation: " Sample index: 3S Acq. : 0.259 4/5/2011 2:01:06 hi Modified: Yes Proc. Algorithm: IntelliQuan - l? Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 10.0 sec Expected RT: 15.3 min Use Relative RT: Yes Int. Type: Retention 1 Area: End Time: 13903 COt 1.07**003 15.0 15.5 Data printed by STW Printing Time: 2:38:28 PM Printing Date: Wednesday, May 04, 2011 Page 4 of 7 Page 62 of 89 *ETS-Kirk ISamite N am : >110404*047* Si<4e ID:*GLP10-01-02-14-013* FH: >110404a.wMT Peak N am : *PFOS* Uassfe*): *499.00<y99.000 Da.49900Cy80.000Da,499.000/130.000 Da" Comment *DAL GW MFL M1M>10 0110322* Annotation:* Calculated Cone: 0.380 Acq. Date: 4/5/2011 Acq. Tine: 6:14:31 AM Modified: yea Proc. Algorithm: IntelliQuan Min. Peak Height: 0.00 c Min. Peak Width: 0.00 s Smoothing Width: 0 po RT Window: 10.0 a Expected AT: 15.3 a Use Relative RT: Tea Height: Start Tin End Time: GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: kll0404a.rdb Sampfe Name: >110404*054* Sample ID:*GLP10-01-02-14-017* F*e:*k110404a.wtfT PeakN am : TFOS* Ma*(es): *499.000199.000 Da.499.000/80.000Da.499.0CXV130.000 Comment*OALGW MFLMW01 0110322* Amwtaon:" Sample Index: 54 Sample Type: Unknown Concentration: N/A Calculated Cone: <0 Acq. Date: 4/5/2011 Acq. Time: 8:42:11 AM Modified: No Proc. Algorithm: IntelliQuan - IQA II Min. Peak Height: 0.00 cps Min. Peak. Width: 0.00 sec Smoothing Width: 0 points RT Window: 10.0 sec Expected RT: 15.3 min Use Relative RT: Yea . Type: 13.0 13.5 14.0 14.5 15.0 1S.5 16.0 16.5 17/3 17.5 I S arnie Name:>110404a066* SvnpU ID:*gLp 10-01-02-14-033* Rto: >110404*^46*^ Peak N am :"PFOS* Masafea):*499.000/99.000 Da,499.000/80.000 Da.499.0T' ........ " Comment *DALGWMFIMW03D 0110323* * - - Sample Type: Unknown Concentration: N/A Calculated Cone: 0.00 Acq. Date: 4/5/2011 ng/mL ISample Name:>110404*071* Ssnpto ID: *GLP1001-02-14-04r Fie: "k110404a.wtfT Peak N am : *PFOS* Mass(et):*499.000/99.000 Da,499.000/80.000 Da.499.000/130.000 Da' Comment *OALGW MFL MW04D0 110323* ' - Acq. Time: 2:41:13 PM Modified: Yea Proc. Algorithm: IntelliQuan Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 pole T Wind 15.3 min Use Relative RT: Stare Tim End Time: 3994 counts 3.18e002 cps 15.0 min Data printed by STW Printing Time: 2:38:29 PM Printing Date: Wednesday, May 04, 2011 Page 5 of 7 Page 63 of 89 *ETS-Kirk I SampleNam: >110404*087' Sample tO:IC S -1 103264* Fla: *k110404a.wr Peak Name:TFOS* Masses):*499300/99.000 Da.499.000/80300 Da.499300/130.000Oa* Comment *&2ppt> LCS* Annotation: ** Sample Index: 87 Sample Type; qc Concentration: 0.198 ng/aL Calculated Cone: 0.212 ng/aL Acq. Date: 4/5/2011 Acq. Tine: 8:19:14 PM Modified: No Proc. Algorithm: IntelliQuan - 101 Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 aec Smoothing Hidth: 0 points RT Hindoo: 10.0 sec Expected R 9 RT: Retention 7 Area: Height: Start Tine: Valley 15.4 2232 cot 3.34e+002 I SamfJe Name: *k110404a093* Sample ID:T.CS-110328-0* Fie: *k110404aA6r Peak Name: "PFOS' Mass(ee): '499.000if99.000 Da,499.0Wy80.000 Oa,499.000/130.000 Da' Comment MOppbLCS* Annotation: " Sample Index: 93 Sample Type: 0C Concentration: 9.94 ng/mL Calculated Cone: 11.0 ng/mL Acq. Date: 4/5/2011 Acq. Time: 10:25:52 PM - 7.0*4 6.5*4 6.0*4 5.5*4 Area : Height: Start Time End Time : 56433 counts 8.05e*004 cps 15.3 ain 15.6 ain 5.0*4 . 4.5*4 3.0*4 23*4 2.0*4 13*4 1.0*4 50003 03- Data printed by STW Printing Time: 2:38:29 PM Printing Date: Wednesday, May 04, 2011 GLP10-01-02; Amended Interim Report 14 Analysis of PF8S, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: kll0404a.rdb I Sample Name: M I0404a090* Sample ID:TCS-110328-6* Fie:'k110404*.wKT PeekName: "PFOS* Masses):*499.00<y99.000 Da,499300/80300 Da,499.00<V130.000 Da* Comment *2ppbLCS* /^notation: " Sample Index: 90 Saaple Type: QC Concentration: 1.98 ng/aL Calculated Cone: 2.05 ng/aL 4400 Acq. Date: 4/S/2011 9:2i ) PM 4200 Modified: Proc. Algorithm: I :elliQuan - 1QA 11 Min. Peak Height: Min. Peak Hidth: Smoothing Width: RT Window: Expected RT: 4000 3800 3600 3400 3200 Height: End Time: 28434 counts 4.46e+003 cps IS.3 ain 3000 1 1 1731 133) 133 14.0 143 15.0 153 163 163 17.0 173 I Sample Name:*k110404a100* Sample ID: 1.CS-110328-12' Fie: *k110404a.*6T PeakName:"PFOS* Masses): *499.000199.000 Da.499.000ffi0.000 Da,499300/130.000 Da* Comment *0ippb LCS ECF* Annotation: - Sample Index: 100 Sample Type: QC Concentration: 0.200 ng/mL Min. Peak width: Smoothing Width: RT Window: Expected RT: Retention 1 10131 coo 8.98e+002 15.0 15.5 13 Page 6 of 7 Page 64 of 89 *ETS-Kirk GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name; kll0404a.rdb Data printed by STW Printing Time: 2:38:29 PM Printing Date: Wednesday, May 04, 2011 Page 7 of 7 Page 65 of 89 *ETS-McCoy , GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: mcll0404a.rdb Printing Time: 2:39:09 PM Page 66 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Results Name: mcll0404a.rdb Printing Time: 2:41:05 PM Page 67 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: mcll0404a.rdb Printing Time: 2:41:05 PM Page 68 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: mcll0404a.rdb Printing Time: 2:41:05 PM Page 69 of 89 *ETS-McCoy GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 Results Name: mcll0404a.rdb Data printed by STW Printing Time: 2:41:05 PM Page 4 of 4 Page 70 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 At ta c h m e n t C : A n a ly tic a l M eth o d Page 71 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 3M Environm ental Laboratory Method Method o f Analysis for the Determination o f Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q L j ^ jc , ~j 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 72 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), PerfluorohexanoicAcid (PFHA), Perfluoroheptanoic Acid (PFHpA), PerfluorooctanoicAcid (PFOA), PerfluorononanoicAcid (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (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 W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method is considered a perfo rm an ce-b ased 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 W ater by LC/MS/MS; Direct Injection Analysis Page 73 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected in duplicate at the same time from the same location as the sample. The FDS is handled under identical circumstances and treated exactly the same throughout field and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a measure of the precision associated with sample collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous samples. A known, specific volume of sample must be added to the sample container without rinsing. This may be accomplished by making a "fill to this level" line on the outside of the sample container. The FMS should be spiked between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level is made. The FMS is analyzed to ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation of the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known quantities of the target analytes are added in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a study sample to help determine if the method is in control and whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS are appropriate when expected sample concentrations are not known or may vary. At least one separate, un-spiked sample must be taken at the same time and place as each FMS. 3.7 Laboratory Control Sample (LCS) An aliquot of control matrix to which known quantities of the target analytes are added in the laboratory at the time of sample extraction. At least two levels are included, one generally at the low end of the calibration curve and one near the mid to upper range of the curve. The LCSs are extracted and analyzed exactly like a laboratory sample to determine whether the method is in control. LCSs should be prepared each day samples are extracted. 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot of a sample to which known quantities of target analytes are added in the laboratory. The LMS is analyzed exactly like a laboratory sample to determine whether the sample matrix contributes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LMS corrected for these concentrations. LMSs are optional for analysis of aqueous samples. 3.9 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.10 Limit of Quantitation (LOQ) The lower limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrix-dependent. The upper limit of quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. ETS-8-044.0 Page 3 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 74 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample Including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus. 3.12 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material. 3.13 Stock Standard Solution (SSS) A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound. 3.14 Surrogate A compound similar in chemical composition and behavior to the target analyte(s), but is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality control samples. Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. 3.15 Working Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. 4 Warnings and Cautions 4.1 Health and Safety The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be fam iliar 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 W ater by LC/MS/MS; Direct Injection Analysis Page 75 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 mL plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C 18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Tim e (m ini 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m L/m inl 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area - quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous inform ation is intended as a guide; alternate conditions and equipm ent 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 76 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Moms Farm Landfill - MArch 2011 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative bn, MRM mode, monitoring the following transitions: A n a ly te Transition Monitored PFBA 213 -> 169 PFPeA 263 -219 PFHA 313 --^ 269 and 3 1 3 -> 1 1 9 PFHpA 363 -> 319, 363 -> 169 and 363 -> 1 1 9 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 219 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --^ 80 and 399 --^ 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 M ultiple transitions for m onitoring the analytes is an option, as summing m ultiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use o f one daughter ion is acceptable if method sensitivity is achieved, provided that retention tim e criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals W ater - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (PFBA - C4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (P F H A - 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 PerfluorononanoicAcid (P F N A -C 9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 10 acid); Oakwood Products, Inc PerfluoroundecanoicAcid (PFU nA-C 11 acid); Oakwood Products, Inc PerfluorododecanoicAcid (P F D oA -C 12 acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 of 11 Method of Analysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is Page 77 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 The previous inform ation is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L target analyte SSSs--Weigh out 10 mg of analytical standard (co rrected fo r p e rc e n t s a lt a n d p u rity) and dilute to 10OmL with methanol or other suitable solvent, in a 1OOmL 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. salt correction factor = m olecular weight o f anion m oclecular weight of salt 4QQ PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg CsF^SOs'K* with purity 90% = 8.35mg C8F17S03" (10 mg*0.90*0.9275=8.35 mg) 5 pg/m L (5000 ng/m L) m ixed w orking standard--Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/m L m ixed w orking standard--Add 1 25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/m L m ixed standard--Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage C onditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. ETS-8-044.0 Page 7 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 78 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C o n c e n tra tio n o f W S, n g /m L 125 125 125 125 250 250 250 250 5000 5000 5000 V o lu m e o f W S, fiL 10 15 20 30 20 50 100 200 25 50 100 F in a l V o lu m e o f C a lib ra tio n S ta n d a rd (m L o f A S T M T ype 1 W a te r, o r o th e r s u ita b le w a te r) 50 50 50 50 50 50 50 50 50 50 50 F in a l C o n c e n tra tio n o f C a lib ra tio n S ta n d a rd , n g /m L (p p b ) in A S T M T yp e 1 W ater, o r o th e r s u ita b le w a te r 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 W ater by LC/MS/MS; Direct Injection Analysis Page 79 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 be within 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed. 10 Quality Control 10.1 Data Quality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end of the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. 10.3 Sample Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation of the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-prepared as appropriate. ETS-8-044.0 Page 9 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 80 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011- 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: Analyte found (ng/mL) = (Peak Area - Intercept) xD F Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) x100Recovery = Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of S5% and a retention time RSD of 2% to be compliant. 12.2 Quantitation C alibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 81 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 D em onstration o f S pecificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions R e vision Number Summary of Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis Page 82 of 89 At ta c h m e n t D : D e v ia tio n s GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 Page 83 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 __________Record of Deviation/Nonconformance /. identification Study /Project No. Date(s) of Occurrence: Document Number GLP10-01-02-14 March 14,2011 Protocol Amendment 14 Deviation type SOP Equipment Procedure EJ Method (Check one) E3 Protocol______ GPO______________ Other__________________ ____________________ //. Description (attach extra pages as needed)__________________ Method Requirements: (1) Sample bottles were prepared on i 1/29/10 for sampling to occur as soon as access agreements were obtained. Actual procedure/process: (1) The GPO was revised on March 14,2011 to retted the new sampling date. The initial set of sample bottles were prepared and sent to Weston in Decatur, AL on 11/29/10. At that time, the actual sampling date was not known since access agreements were still being acquired. In early February 2011, the prepared bottles were returned to the 3M Environmental Lab for disposal as the samples had not yet been collected. A new set of sample bottles will be prepared the week of March 14,2011 for sampling the week of March 21,2011. III. Actions Taken _______________________ (suchas amendmentissued, SOPrevision, etc.)_______________________ Corrective Action ( Yes 0 No) Reference: Acceptability o f the nonconforming work: 1) A copy of the revised GPO is attached (3 pages). Actions: Halting ofWork Client Notification Work Recall Withholding of Report Other Project Lead/PAI Approval: Date: 3j)Sr)z,jy Study Director (if GLP): f Date: Sponsor Approval (for GLP pro' deviations):)f/f/iij bate: ^ / ( i Technical Reviewer (optional): NA J Date: NA Laboratory Department Manager Approval: Date: ' ____________________________ ___________________________________________________________ IV. Authorization to Resume Work Wherehaltingofworkoccurred, resumption ofworkmustfirstbe approvedbyLaboratoryManagement Laboratory Department Manager Approval: NA Date: NA Deviation No. (assigned by Study Director or Team Leader a t the end o f study or pmjecfl Page 84 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 f i l Environmental Health & Safety Operations, Environmental Laboratory GoncrsJ OutSIn To: F rom : cc: Date: R e vise d : S ubject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Cliffton Jacoby, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions Tim Frinak, Weston Solutions November 29,2010 March 14,2011 Analysis o f Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent fo r the 3M Decatur Phase 3 Site-Related M onitoring Program; GLP Interim Report 14 - BFI M orris Farm Landfill G roundw ate r 1 General Project Information 3M Sponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul, MN 55144-1000 Phone:(651)737-3570 aahohsnstein mmm.com Contacts Lab Request Number 3M Environmental Laboratory Management William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaen(3)mmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclanoemmm.com Sampling Coordinator Timothy Frinak Weston Solutions Timothv.frinakwestonsolutions.com Phone: (334V332-9123 GLP10-01-02-14 Six Digit Department Number Dept #530711, Project #0022674449 Project Schedule/Test Dates Week of March 21,2011 A ll verbal a n d w ritten correspondence w ill be directed to G ary H ohenstein. Page 2 of 4 Page 85 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 The GPO was revised on March 14,2011 to reflect the new sampling date. 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) w ill receive and analyze groundwater sam ples collected from m onitoring w ells actively m aintained at the BFI M orris Farm Landfill. Each m onitoring station at the facility is constructed with two wells, one m onitoring the residuum / epikarst groundwater zone and one m onitoring the bedrock groundwater zone. Based on review o f the well locations and groundwater flow patterns for the site, the follow ing w ells have been selected for sampling and the rationale is provided for each selected location: W ell location MW-10 - This well location is upgradient o f the active areas o f the landfill. It is located in the northwest com er of the property. The location serves as an upgradient groundwater m onitoring point fo r the site. W ell location MW-07 - In a 1996 hydrogeologic investigation, this well location, constructed southwest of the active portions of the landfill, indicated upgradient conditions w ith possible seasonal im pact from active areas at the landfill. Later reports indicate the location was subsequently abandoned. As a result, the adjacent well location, MW -05, has been selected to provide sim ilar coverage fo r the area. W ell locations MW -1,2, 3, 4, and 13 - These w ell locations are located along the east and south boundaries o f the active landfill area and serve as downgradient m onitoring points fo r the site. Review of recent groundwater m onitoring reports have indicated sporadic elevated metals concentrations associated with w ell locations, MW -01, MW-02, MW-04, and MW-13, suggesting potential im pact from site activities. As a result, these locations are proposed fo r m onitoring downgradient groundwater conditions. Since MW-03 closes a potential data gap on the downgradient side o f the landfill, this location has also been included in the sam pling effort. Sampling locations w ill be analyzed fo r of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) as part of the BFI M orris Farm Landfill groundwater sam pling. 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 as soon as access is granted. The 3M Environm ental Laboratory w ill prepare the sam ple bottles with all required spikes to ensure that results fo r PFBS, PFHS, and PFOS are o f a known precision and accuracy. The final report w ill be subm itted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP1001-02-13. 3 Project Schedule Sample collection bottles will be prepared by the 3M Environmental Laboratory. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival by Friday, March 18,2011. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ W eston T railer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 Page 3 o f4 Page 86 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 4 Test Parameters The targeted lim it of quantitation will be 0.025 ng/m L (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 o f 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. One additional bottle w ill be prepared to be used for the preparation of the equipment rinseate blank. In addition to the sample bottles, a 1-L container of Midi Q water will be included to be used for the preparation of the rinseate blank. All sample bottles w ill include the addition o f 1802-PFBS, 13C3-PFHS, and 13Cs-PFOS, (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 of 0.1 ng/mL. A total o f 60 sample bottles w ill be prepared. 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination o f 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 o f Perfluorinated Adds, 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 of 100+30%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and the two field matrix spikes. Trip blank and trip blank spikes will be reported for the sampling event as w ill any equipment/rinseate blanks prepared in the field. Laboratory control spikes of reagent water prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. Method blanks of reagent water prepared at the time o f sample extraction will be used to determine the method detection limit. For those sampling locations where the field matrix spike level was not appropriate, due to higher than expected analyte concentrations, a laboratory matrix spike may be prepared and will be included in the final report Page 4 of 4 Page 87 of 89 GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS In Groundwater BFI Morris Farm Landfill - MArch 2011 RECORD OF DEVIATION/NONCONFORMANCE I. Identification Study / Project No. G LP10-01-02-14 Date(s) of Occurrence g110328a, k l1 040 4a ......... Document Num ber E T S -8 -0 4 4 .0 Deviation type (Check one) SOP Equipment Procedure 0 Method Protocol GPO _____ O ther II. Description (attach extra pages as needed) Method Requirements: 1. LCS average recoveries and RSD within 20% (section 10.5). 2. FMS recovery within 30% (section 10.6). .3. Sample RPD within 20%. ....................... ............................... ........... ......... Actual procedure/process: 1. The RSD for the lowset ofLCS was 23% for PFOS in run k110404a. The mid and high sets of ECF LCSs for PFOS were 138% and 133% in run k110404a. 2. Sample MW05 Low FMS recovery was 134% for PFHS. (g110328a) 3. Sample MW10 RPD was 21% for PFHS. Sample MW03 RPD was 22% for PFHS. (g110328a) III. Actions Taken (such as amendmentissued SOP revision, etc.) Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1. The recoveries forthe failing LCS (linear + branched) at 138% and 133% wilt be flagged in the final report All LCSs for PFOS prepared with this study were evaluated by ETS-12-012 to determinethe method analytical uncertainty. The analytical uncertainty when evaluated by ETS-12-012 was determined to be 23% for PFOS. However, the analytical uncertainty for the samples in run k110404a wfll be set at 36%, based on the recovery ofthe mid set of linear + branched LCS. 2. The FMS Low recovery fin'PFHS will be flagged in the final report 3. The fouling RPOswill be flagged fo the final report. Actions: Halting of W ork Client Notification W ork Recall Withholding of Report 0 O ther Deviations will be noted in final report Project Lead/PAi Approval: Date: Study Director (if GLP): Sponsor Approval (for GLP protocol deviations): NA Technical Reviewer (optional): NA LaboratQiy Department Manager Approval: j Date. I Date: NA............. ; i Date; IV. Authorisation to Resume Work Where hatting ofworkoccurred resumption ofworkmustttrstbe approved byLaboratory Management Laboratory Department ManagerApproval: NA Date: NA Deviation No. (assigned by S tu d / D frsctcr o r Teem Leader a t the end o f study o r project} ETS-4-QG8.7 P agel of 1 Documentation of Deviations and Control of Nonconforming Testing Page 88 of 89 Attachment E GLP10-01-02; Amended Interim Report 14 Analysis of PFBS, PFHS, and PFOS in Groundwater BFI Morris Farm Landfill - MArch 2011 3M Environmental Laboratory_________________ Final Study Report Amendment Study number: GLP10-01-01-14 . Study title: Analysis of PFOA in Groundwater Samples Collected at the BFI M orris Farm Landfill in Hillsboro, AL in March 2011. Study Director Jaisimha Kesari, P.E., DEE Amendment date: 6/20/11 Amendment number: 1 This amendment m odifies the following portions of the final report: Cover Page (Page 1) - Change the title o f the report from "Analysis of PFOA in Groundwater Samples Collected at the BFI Morris Farm Landfill in Decatur, AL in March 2011", to "Analysis o f PFOA in Groundwater Samples Collected at the BFI M orris Farm Landfill in Hillsboro, AL in March 2011". GLP Compliance Statem ent (Page 3) - Change the title of the report from "Analysis of PFOA in Groundwater Samples Collected at the BFI Morris Farm Landfill in Decatur, AL in March 2011", to "Analysis of PFOA in Groundwater Samples Collected at the BFI Morris Farm Landfill in Hillsboro, AL in March 2011". Q uality Assurance Statem ent (Page 4) - Change the title of the report from "Analysis o f PFOA in Groundwater Samples Collected at the BFI Morris Farm Landfill in Decatur, AL in March 2011", to "Analysis o f PFOA in Groundwater Samples Collected at the BFI Morris Farm Landfill in Hillsboro, AL in March 2011". Section 2 (Page 9) - Changed the location of the BFI Morris Landfill from Decatur, AL to Hillsboro, AL Table 1 (Page 10) - Changed the table heading to indicate MFL Groundwater samples were collected in Hillsboro, AL. Section 3 (Page 10) - Paragraph 1, changed the reference to the location of the BFI Morris Farm Landfill from Decatur, AL to Hillsboro, AL. Section 6 (Page 13) - Paragraph 1, changed the reference to the location of the BFI Morris Farm Landfill from Decatur, AL to Hillsboro, AL. Table 2 (Page 13) - Removed the sample location reference to Decatur, AL Reason fo r the amendment: The location of the BFI Morris Farm was incorrectly identified as being located in Decatur, AL. The BFI Morris Farm is actually located in Hillsboro, AL. Page 1 of 1 Page 89 of 89