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GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 GLP10-01-02: Interim Report 16 - Analysis o f PFBS. PFHS. and PFOS in G roundwater Sam ples Collected as Part o f the Avenue A Investigation Area in Decatur. A L in January 2011 Study Title Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan Wolf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP10-01-02-16 Total Number of Pages 61 a ccred ited ! 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 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 This page has been reserved for specific country requirements. GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 GLP C o m p l ia n c e S ta te m e n t Report Title: Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected as Part of the Avenue A Investigation Area in Decatur, AL in January 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. Date Page 3 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Q uality A ssurance Statement Report Title: Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected as Part of the Avenue A Investigation Area in Decatur, AL in January 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 3/ 18/11 Phase Data and Interim Report Date Reported to Testing Facility Management Study Director 3/29/11 3/29/11 Date Page 4 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table of C ontents GLP Compliance Statement................................................................ 3 Quality Assurance Statement................................................................................................................ 4 Table of Contents.................................................................................................................................. 5 List of Tables.......................................................................................................................................... 6 1 Study Information............................................................................................................................ 7 2 Summary......................................................................................................................................... 8 3 Introduction..................................................................................................................................... 8 4 Test & Control Substances............................................................................................................ 9 5 Reference Substances................................................................................................................... 9 6 Test System...................................................................................................................................11 7 Method Summary..........................................................................................................................11 7.1 Methods........................................................................................................................ 11 7.2 Sample Collection..........................................................................................................11 7.3 Sample Preparation....................................................................................................... 11 7.4 Analysis......................................................................................................................... 12 8 Analytical Results..........................................................................................................................13 8.1 Calibration..................................................................................................................... 13 8.2 System Suitability..........................................................................................................13 8.3 Limit of Quantitation (LOQ)........................................................................................... 14 8.4 Continuing Calibration...................................................................................................14 8.5 Blanks............................................................................................................................ 14 8.6 . Lab Control Spikes (LCSs)........................................................................................... 14 8.7 Analytical Method Uncertainty...................................................................................... 17 8.9 Field Matrix Spikes (FMS)..............................................................................................18 9 Data Summary and Discussion.................................................................................................... 18 Page 5 of 61 GLP10-01 -02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 10 Conclusion.................................................................................................................................... 22 11 Data/Sample Retention................................................................................................................22 12 Attachments.................................................................................................................................. 22 13 Signatures..................................................................................................................................... 23 List of Tables Table 1. Summarized PFBS, PFHS, and PFOS Results (Avenue A Investigation, Jan 2011)............8 Table 2. Sample Description Key Code.............................................................................................. 11 Table 3. Instrument Parameters.......................................................................................................... 12 Table 4. Liquid Chromatography Conditions....................................................................................... 12 Table 5. Mass Transitions....................................................................................................................13 Table 6. Limit of Quantitation (LOQ)....................................................................................................14 Table 7. Laboratory Control Spike Recovery...................................................................................... 16 Table 8. Analytical Uncertainty............................................................................................................ 18 Table 9. DAL GW SS22 270111.........................................................................................................19 Table 10. DAL GW SS24 270111.......................................................................................................19 Table 11. DAL GW 21 OR 280111 .......................................................................................................20 Table 12. Trip Blank............................................................................................................................ 20 Table 13. Rinseate Blank.................................................................................................................... 21 Page 6 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 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 William K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanae@mmm.com): phone (651 )-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow; Analyst Jon Steege; Analyst Kevin Eich; Analyst Study Dates Study Initiation: March 8,2010 Interim Report 16 Experimental Termination: March 11, 2011 Interim Report Completion: Date of Interim Report Signing Location of Archives All original raw data and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The reference substance and analytical reference standard retain samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 Page 7 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 2 Summary The 3M Environmental Laboratory received water samples collected as part of the Avenue A Investigation area in Decatur, AL from three sampling locations. A total of twenty-one sample bottles were received at the 3M Environmental Laboratory for perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), and included duplicate water samples from each sampling location, as well as three field matrix spike (FMS) samples for each location. Samples also included one trip blank containing Milli-QTM water and appropriate trip blank spikes, and one equipment rinseate. The equipment rinseate blank did not have FMS samples prepared for determination of PFBS, PFHS, and PFOS recovery. The samples, trip blanks and equipment rinseate blank were received from Weston personnel on February 1,2011. All water samples for this project were logged under GLP10-01-01-16. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01-02-16. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate and trip blank were below the lower limit of quantitation (LLOQ) collected with the water samples for GLP10-01-02-16, indicating adequate control of sample contamination during shipping and sample collections. The PFBS concentration results ranged from 3.39 ng/mL to 43.2 ng/mL. The PFHS concentration ranged from 1.84 ng/mL to 309 ng/mL. The PFOS concentration results ranged from 8.62 ng/mL to 539 ng/mL. Table 1. Summarized PFBS, PFHS, and PFOS Results (Avenue A Investigation, Jan 2011). Sampling Location DAL G W SS22 270111 DAL GW SS24 270111 DAL GW 210R 280111 Trip Blank (M illi-Q TM W ater) Equipm ent rinseate blank PFBS Avg. Cone. (ng/mL) RPD 3.39 5.3% 19.2 3 .1 % 43.2 2.8% <0.0250 <0.0250 PFHS Avg. Cone. (ng/mL) RPD 1.84 6 .5 % 143 2 .8% 309 1.9% <0.0250 <0.0250 PFOS Avg. Cone. (ng/mL) RPD 8.62 1.2% 5 00 5 .8 % (1) 5 39 6 .3 % (2) <0.0300 <0.0300 The analytical method uncertainties associated with the reported results are as follows: PFBS 20%, PFHS 22%, and PFOS 33%. (1) Sampling location did not have an appropriate FMS spike level for PFOS to accurately assess analyte recovery. (2) Sample field matrix spike recovery did not meet acceptance criteria of 100 30% with a recovery of 68.1%. The FMS recovery is within the analytical method uncertainty. 3 Introduction This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was Page 8 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 conducted to analyze ground water samples collected as part of the Avenue A Investigation in Decatur, AL for PFBS, PFHS, and PFOS, in an effort to characterize on-site groundwater conditions. The 3M Environmental Laboratory prepared sample containers (250 mL high-density polyethylene bottles) which were shipped to Decatur, AL Weston personnel prior to field sampling. Sample containers for each sampling location included a field sample, field sample duplicate, and three field spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Table 1 summarizes the average PFBS, PFHS, and PFOS concentrations for the duplicate samples collected, trip blank, and groundwater-equipment rinseate sample. Tables 9-13 summarize the individual sample results and the associated FMS recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report 4- Test &Control Substances There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. 5 Reference Substances R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predom inantly lin ear) Perfluorobutane sulfonate C4 F9 SO3 Potassium Salt 3M 1/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% PFHS (lin ear) Perfluorohexane sulfonate C6 F13SO3 Sodium Salt Wellington 3/25/18 Frozen LPFHxSAM08 TCR08-0018 Crystalline 98% Page 9 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (lin ear) Perfluorooctane sulfonate CBF17 SO3 Potassium Salt CAS #2795-39-3 Wellington 10/18/2013 Frozen LPFOSKBM06 TCR08-0001 Crystalline 98% PFOS (lin e a r + branched) Perfluorooctane sulfonate C8F17SO3 Potassium Salt CAS #2795-39-3 3M 12/14/2016 Frozen 171 TCR-696 White Powder 86.4% R eference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity " C,,-PFOS Perfluorooctane sulfonate C F13 8 17 S O 3 Sodium Salt Wellington 9/28/13 Frozen 092310 TCR10-0048 Liquid 98% Page 10 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 6 Test System The test system for this study are surface water and ground water samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Table 2. Sample Description Key Code. String Number Example 1 2 3 4 5 String Descriptor DAL SWSS24 0270111 Sample Location Sample Type Location ID Sampling Date Sample Type Example DAL=Decatur, Alabama GW=Groundwater Example: SS24 270111 - January 27,2011 0=primary sample DB=duplicate sample LS = low spike MS = mid spike HS = high spike RB = Rinseate Blank 7 Method Summary 7.1 Methods Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". 7.2 Sample Collection Samples were collected in 250 mL NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on February 1, 2011. Samples were stored refrigerated at the laboratory after receipt. The laboratory prepared Trip Blank and Trip Blank field matrix spikes were received with the sample collection bottles. 7.3 Sample Preparation All groundwater samples were initiall prepared by diluting 1mL sample with 9 mLs of Milli-Q water (dilution 1:10). Sampling locations DAL GW SS24 and DAL GW 21OR required further dilution for PFOS and were prepared by diluting 0.1 mL of sample with 9.9 mLs of Milli Q water (dilution 1:100). Trip Blank and Rinseate Samples: Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. Sampling location DAL GW SS22 was analyzed for PFOS by removing a measured volume of sample, adding internal standard, and placing an aliquot of the preapred sample into an autovial for analysis. Page 11 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Table 3. Instrum ent Parameters. Instrument Name Analytical Method Followed Analysis Date Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETS Ginger ETS-8-044.0 2/11/11,2/28/11 Agilent 1100 Prism RP (2.1 mm X 50 mm), 5 u Betasil C18 (2.1 mm X 100 mm), 5u 2or10uL Applied Blosystems API 5000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 ETS Buster ETS-8-044.0 3/10/11 Agilent 1100 Betasil C18 (2.1 mm X 100 mm), 5u Betasil C18 (2.1 mm X 100 mm), 5u 5 uL Applied Blosystems API 4000 Turbo Spray Turbo ion electrode Negative Analyst 1.4.2 Table 4. Liquid Chromatography Conditions. Step Number 0 1 2 3 4 5 0 1 2 3 4 5 Total Time (min) 0 2.0 11.0 14.0 14.5 17.0 0 2.0 11.0 13.5 14.0 17.0 Flow Rate (fdJmin) PercentA (2 mM ammonium acetate) ETS-8-044.0 Anal\rsis (ETS Ginger) 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 ETS-8-044.0 Anahrsis (ETS Buster) 300 97.0 300 97.0 300 5.0 300 5.0 300 97.0 300 97.0 PercentB (Methanol) 3.0 3.0 95.0 95.0 3.0 3.0 3.0 3.0 95.0 95.0 3.0 3.0 Page 12 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 5. Mass Transitions. Analyte Mass Transition Q1/Q3 Reference Material Structure Internal Standard Mass Transition Q1/Q3 PFBS 299/80 299/99 Linear NA NA PFHS 399/80 399/99 Linear NA NA 499/80 PFOS 499/99 Linear [1lCtJPFOS n 507/80 499/130 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. NA = Not Applicable; internal standard not used for quantitation. (1) PFOS internal standard only used for 3/10/11 analysis. 8 Analytical Results 8.1 Calibration 'i 2/11/11 and 2/28/11 Analysis: Samples were analyzed against an external standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into prepared in Milli Q water or Synthetic Groundwater. A total of sixteen spiked standards ranging from 0.025 ng/mL to 100 ng/mL (nominal) were analyzed. Low curve points were disabled as needed to meet calibration acceptance criteria. A quadratic, 1/x weighted, calibration curve of the peak area counts was used to fit the data for each analyte. The data were not forced through . zero during the fitting process. Calculating the standard concentrations using the peak area confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) and a correlation coefficient (r) greater than 0.995, were met for PFBS, PFHS, and PFOS. 3/10/11 Analysis: Sampling location DAL GW SS22 was analyzed against a stable isotope internal standard calibration curve for PFOS. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the same level to all calibration standards and laboratory control samples at a nominal concentration of 1 ng/mL. A calibration curve ranging from 0.025 ng/mL to 100 ng/mL (nominal) was analyzed. Low curve points were disabled for PFOS to meet method accuracy or method blank criteria. The data were not forced through zero during the fitting process. Calculating the standard concentrations using the peak area ratios and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) and a correlation coefficient (r) greater than 0.995, were met for PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of the analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS. Page 13 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 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 nominal LOQ for all analytes can be found in Table 6. Table 6. Limit of Quantitation (LOQ). Analysis Date /2 1 1 / 1 1 2/28/11 3/10/11 NA = Not Applicable Dilution 1 10 100 1 PFBS LOQ, nct/mL 0.0250 0.250 NA NA PFHS LOQ, ng/mL 0.0250 0.250 NA NA PFOS LOQ, ng/mL 0.0300 0.300 2.50 0.250 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%. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: procedural blanks, field/trip blank, and equipment blank. Procedural blank results were reviewed and used to evaluate method performance and to determine the LOQ for each analyte. 8.6 Lab Control Spikes (LCSs) Lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into 10 mL of Milli Q water to produce the desired concentration. The spiked water samples were then prepared and analyzed in the same manner as the samples. The method acceptance criteria states that the average of LCS at each level should be within 100% 20% with an RSD 20%. 2/11/11 Analysis: Three spike levels were prepared and met method acceptance criteria for PFBS, PFHS, and PFOS (linear). 2/28/11 Analysis: Three spike levels were prepared and met method acceptance criteria for PFOS (linear). 3/10/11 Analysis: Two spike levels were prepared and met method acceptance criteria for PFOS (linear). As the reference materials used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear and branched) were prepared to evaluate the potential for analytical bias. 2/11/11 Analysis: Three spike levels LCS (linear + branched) were prepared. The low and mid set of LCS met method acceptance criteria, while the high set of LCS did not meet method acceptance criteria with an average recovery of 133%. 2/28/11 Analysis: Three spike levels LCS (linear + branched) were prepared. The low and mid set of LCS (linear + branched) met method acceptance criteria, while the high set of LCS did not meet method acceptance criteria with an average recovery of 125%. Page 14 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 3/10/11 Analysis: Two spike levels LCS (linear + branched) were prepared and met method acceptance criteria for PFOS. The average recovery of the high set of linear and branched LCS at 125% and 133% suggests a slight bias when quantitating branched isomers of PFOS against a calibration curve of linear PFOS. Therefore, the method uncertainty for this study has been set of 33%. 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 standard deviation LCS replicates LCS% RSD = 100% average LCS recovery Page 15 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 7. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 2/11/11 Lab ID LCS-110210-1 LCS-110210-2 LCS-110210-3 Average %RSD LCS-110210-4 LCS-110210-5 LCS-110210-6 Average %RSD LCS-110210-7 LCS-110210-8 LCS-110210-9 Average %RSD PFBS Spiked Calculated Spiked Concentration Concentration Concentration (ng/mL) (ng/mL) %Recovery (ng/mL) 0.498 0.563 113 0.498 0.498 0.542 109 0.498 0.498 0.581 117 0.498 4.98 4.98 4.98 113% 3.5% 5.37 5.52 5.58 108 111 112 4.98 4.98 4.98 29.9 29.9 29.9 110% 1.9% 29.8 31.1 32.0 99.5 104 107 29.9 29.9 29.9 104% 3.6% PFHS Calculated Concentration (ng/mL) 0.603 0.594 0.599 120% 0.83% 5.61 5.36 5.96 114% 5.3% 30.7 30.8 32.7 105% 3.3% %Recovery 121 119 120 113 108 120 103 103 109 ETS-8-044.0 Analyzed 2/11/11 PFOS (linear) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID LCS-110210-1 LCS-110210-2 LCS-110210-3 0.498 0.498 0.498 0.650 0.587 0.540 130 LCS-110210-10 118 LCS-110210-11 108 LCS-110210-12 Average %RSD 119% 9.3% Average %RSD LCS-110210-4 LCS-110210-5 LCS-110210-6 4.98 4.98 4.98 5.43 4.93 5.86 109 LCS-110210-13 99.1 LCS-110210-14 118 LCS-110210-15 Average %RSD 109% 8.7% Average %RSD LCS-110210-7 29.9 30.8 103 LCS-110210-16 LCS-110210-8 29.9 30.7 103 LCS-110210-17 LCS-110210-9 29.9 32.4 108 LCS-110210-18 Average %RSD 105% 2.8% Average %RSD PFOS (linear + branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery 0.502 0.539 107 0.502 0.585 117 0.502 0.541 108 5.04 5.04 5.04 111% 5.0% 6.15 5.38 5.44 122 107 108 30.2 30.2 30.2 112% 7.5% 40.7 40.4 39.6 135 134 131 133% 1.6%(1) (1) The average recovery did not meet method acceptance criteria of 100% 20%. Page 16 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PF.HS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Analyzed 2/28/11 Lab ID PFOS (linear) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID LCS-110228-1 LCS-110228-2 LCS-110228-3 0.498 0.498 0.498 0.483 0.487 0.427 97.0 LCS-110228-10 97.7 LCS-110228-11 85.6 LCS-110228-12 Average %RSD 93.4% 7.3% Average %RSD LCS-110228-4 LCS-110228-5 LCS-110228-6 Average %RSD 4.98 4.98 4.98 5.27 5.17 5.34 106% 1.4% 106 LCS-110228-13 104 LCS-110228-14 107 LCS-110228-15 Average %RSD LCS-110228-7 LCS-110228-8 LCS-110228-9 Average %RSD 29.9 29.9 29.9 31.3 31.7 31.9 106% 0.94% 105 LCS-110228-16 106 LCS-110228-17 107 LCS-110228-18 Average %RSD PFOS (linear + branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) VoRecovery 0.502 0.502 0.502 0.467 0.475 0.493 93.1 94.6 98.2 95.3% 2.8% 5.04 5.04 5.04 4.88 5.10 4.72 96.7 101 93.6 97.1% 3.8% 30.2 30.2 30.2 40.4 36.1 36.8 125%6.3%(1) 134 119 122 ETS-8-044.0 Analyzed 3/10/11 Lab ID PFOS (linear) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) %Recovery Lab ID LCS-110307-4 LCS-110307-5 LCS-110307-6 Average %RSD 1.99 1.99 1.99 2 .2 2 2.05 2.26 109% 5.2% 1 1 1 LCS-110307-13 103 LCS-110307-14 114 LCS-110307-15 Average %RSD LCS-110307-7 LCS-110307-8 LCS-110307-9 Average %RSD 9.94 9.94 9.94 11 .1 10.7 1 0 .2 107% 4.2% 1 1 2 LCS-110307-16 107 LCS-110307-17 103 LCS-110307-18 Average %RSD PFOS (linear + branched) Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) VoRecovery 2 .0 1 2 .0 1 2 .0 1 2.24 2.23 2.40 114% 4.6% 111 111 120 1 0 .0 1 0 .0 1 0 .0 1 1 .2 1 1 .6 1 1 .0 113% 2.7% 112 116 110 (1) Trie average recovery did not meet method acceptance criteria of 100% 20%. 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the most recent fifty 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 method uncertainty for PFOS by ETS-12012-2 was found to be 17%, however, since the high set of linear and branched LCS had an average recovery of 133%, the analytical uncertainty assigned to this study will be 33%. The method uncertainty values are listed in Table 8. Page 17 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 8. Analytical Uncertainty. Analyte Standard Deviation Method Uncertainty PFBS 10.1 20% PFHS 11.0 22% PFOS N A (1) 33% (1) See section 8.6 for a discussion regarding the method uncertainty for PFOS. 8.8 Field Matrix Spikes (FMS) Low, mid and high field matrix spikes were collected at each sampling point to verify that the analytical method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured volume of field sample to a container spiked by the laboratory with PFBS (linear), PFHS (linear), and PFOS (linear) prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. The nominal spike level for the low field matrix spike was 1.0 ng/mL, the mid field matrix spike was 10 ng/mL, and the high field marix spike was 100 ng/mL for all sampling locations. FMS R e co v e ry - (^amP*e C ncentrat'on f F M S -A ve ra g e Concentration : FieldSam ple& FieldSam pleD up.) jqqo/ Spike Concentraton 9 Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip 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(s) were appropriate for the given matrix and their respective quantitative ranges DAL GW 21OR 280111; The recovery of the HS sample, the only appropriate FMS concentration level for PFOS, was 68.1%. The recovery was within the method uncertainty for PFOS. DAL GW SS24 270111 ; The HS at 97.8 ng/mL was not sufficient to accurately assess recovery for PFOS. Page 18 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 9. DAL GW SS22 270111 PFBS PFHS PFOS 3MUMSID Description Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01 -02-16-006 DAL GW SS22 0 270111 3.30 NA 1.78 NA GLP10-01-02-16-007 DAL GWSS22 DB 270111 3.48 NA 1.90 NA GLP 10-01-02-16-008 GLP10-01-02-16-009 GLP10-01-02-16-010 DAL GWSS22 LS 270111 DAL GWSS22 MS 270111 DAL GWSS22 HS 270111 4.45 1 2 .8 99.5 106 94.1 98.9 3.13 1 2 .0 104 129 102 106 Average Concentration (ng/mL) %RPD 3.39 ng/mL 5.3% 1.84 ng/mL 6.5% NA = Not Applicable NO = Not Calculated; Endogenous concentration greater than 2x spike level. PFBS and PFHS were analyzed by external standard calibration on 2/11/11. PFOS was analyzed by internal standard calibration on 3/10/11. (1) The sample was not analyzed. Concentration (ng/mL) %Recovery 8.57 NA 8.67 NA NA (1) NA (1> 16.5 78.8 N A (1) N A (1) 8.62 ng/mL 1.2% Table 10. DAL GW SS24 270111 PFBS PFHS PFOS 3MLIMSID Description Concentration (ng/mL) %Recovery GLP10-01-02-16-012 GLP10-01-02-16-013 GLP10-01-02-16-014 GLP10-01-02-16-015 GLP10-01-02-16-016 DAL GW SS24 0 270111 DAL GW SS24 DB 270111 DAL GW SS24LS 270111 DAL GW SS24MS 270111 DAL GWSS24 HS 270111 18.9 19.5 2 0 .0 28.6 116 NA NA NC 94.0 99.6 Average Concentration (ng/mL) %RPD 19.2 ng/mL 3.1% N A= Not Applicable NC = Not Calculated; Endogenous concentration greater than 2x spike level. PFBS and PFHS were analyzed 2/11/11. PFOS was analyzed 2/28/11. (1) The sample was not analyzed. (2) Sampling location did not have an appropriate field matrix spike level for PFOS. Concentration (ng/mL) %Recovery 141 NA 145 NA 146 NC 154 NC 234 94.7 143 ng/mL 2.8% Concentration (ng/mL) %Recovery 514 NA 485 NA NA (1) N A (1) NA (1) N A <1) 548 NC 500 ng/mL 5.8% m Page 19 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 11. DAL G W 21 OR 280111 PFBS PFHS PFOS 3MUMSID Description Concentration (ng/mL) %Recovery GLP10-01-02-16-017 DAL GW 21OR 0 280111 43.8 NA GLP10-01-02-16-018 DAL GW 21OR DB 280111 42.6 NA GLP10-01-02-16-019 DAL GW 21OR LS 280111 52.5 NC GLP10-01-02-16-020 GLP10-01-02-16-021 DAL GW 21OR MS 280111 DAL GW 21OR HS 280111 136 95.5 947 90.4 Average Concentration (ng/mL) %RPD N A= Not Applicable NC = Not Calculated; Endogenous concentration greater than 2x spike level. PFBS and PFFIS were analyzed 2/11/11. PFOS was analyzed 2/28/11. (1) The sample was not analyzed. (2) Field matrix spike did not meet method acceptance criteria of 100% 30%. 43.2 ng/mL 2.8% Concentration (ng/mL) %Recovery 312 306 324 402 1280 NA NA NC NC 97.1 309 ng/mL 1.9% Concentration (ng/mL) %Recovery 556 NA 522 NA (1> NA (1> 1220 NA NA (1) NA (1) 68.1 <2> 539 ng/mL 6.3% Table 12. Trip Blank 3MLIMSID GLP10-01-02-16-001 GLP10-01-02-16-002 GLP10-01-02-16-003 GLP10-01-02-16-004 GLP10-01-02-16-005 Description DAL GW TRIP 0 270111 DAL GW TRIP LS 270111 DAL GW TRIP MS 270111 DAL GWTRIPMH 270111 DAL GW TRIP HS 270111 PFBS PFHS PFOS Concentration (ng/mL) <0.0250 1.04 9.88 101 982 %Recovery NA 104 98.8 104 98.2 Concentration (ng/mL) <0.0250 1.18 10.3 108 1040 %Recovery NA 118 103 112 104 Concentration (ng/mL) <0.0300 1.03 9.37 92.8 950 XRecovery NA 103 93.7 94.9 95.0 NA = Not Applicable Page 20 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Table 13. Rinseate Blank 3MUMSID GLP10-01-02-16-011 Description DALGWSS24RB 270111 PFBS PFHS PFOS Concentration (ng/mL) <0.0250 %Recovery NA Concentration (ng/mL) <0.0250 %Recovery NA Concentration (ng/mL) <0.0300 %Recovery NA NA = Not Applicable GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 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. All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. 12 Attachmentsr Attachment A: Protocol Amendment 16 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 22 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 13 Signatures William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 23 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Attachment A: Protocol A mendment Page 24 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Analytical Protocol: GLP10-01-02 Amendment 16 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. 16 Amendment Date: January 25, 2011 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP10-01-02 Sampling Event Avenue A Investigation - Groundwater Sampling Exact Copy of Original z-liJzJi Initial Date Page 1 of 6 Page 25 of 61 GLP10-01-02; Interim Report 16 Analysis o f PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Analytical Protocol: GLP10-Q1-02 Amendment 16 This amendment modifies the following portion of protocol: "Analysis of PFOS, PFHS and PFBS in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program" Protocol reads: No changes to the wording of the protocol are required. AMEND TOread: No changes to the wording of the protocol are required. This amendment only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples from Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection will occur around the timeframe of the week of January 24, 2011. The groundwater samples for this sampling event will be entered into the 3M Environmental Laboratory LIMS as project G L P 10-01-02-16 and reported as interim report G LP10-01-02-06, (reflecting study GLP10-01-02 and amendment -16). Reason: The reason for this amendment is to document the General Project Outline (GPO) which describes the anticipate groundwater sample collection event to be conducted for the 3M Decatur, AL facility. The GPO is four pages in length and included as attached to this amendment form. Page 2 of 6 Page 26 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Analytical Protocol: GLP10-01-02 Amendment 16 Amendment Approval Page 3 of 6 Page 27 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Analytical Protocol: GLP10-01-02 Amendment 16 I khV I Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions Charles Young, Weston Solutions Tim Frinak, Weston Solutions January 25, 2011 Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 16 - Additional Avenue A Sampling; January 2011 1 General Project Information C o n ta c ts Lab Request Number Six D igit Departm ent Num ber Project Schedule/Test Oates 3M S ponsor Representative Gary Hohenstein 3M EHS Operations 3M Building 224-5W-03 Saint Paul. MN 55144-1000 Phone: (651) 737-3570 aahohenstein@ m m m .com 3M Environm ental Laboratory M anagem ent William K. Reagen 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9739 wkreaaen@mmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 ccla n a e fflm m m .c o m Sam pling Coordinator Timothy Frinak Weston Solutions T im othv.frinakfflw estonsolutions.com Phone: (3341-332-9123 GLP10-01-02-16 Dept #530711, Project #0022674449 Sampling scheduled for the week o f January 24, 2011 All verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 6 Page 28 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Analytical Protocol: GLP10-01-02 Amendment 16 2 Background Information and Project Objective(s) The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze groundwater samples collected from three sampling locations for Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) as part of the Avenue A Investigation. Analyses will be conducted under the GLP requirements of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples from Decatur, AL will be collected by Weston Solutions personnel the week of January 24, 2011. The 3M Environmental Laboratory will prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are of a known precision and accuracy. The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report GLP1001-02-16. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week of January 24,2011. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, January 21, 2010. Sample bottles should be stored refrigerated on-site until sample collection. Martin Smith \ Weston Trailer 3M Decatur Plant 1400 State Docks Road Decatur, Alabama 35601 4 Test Parameters The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFBS, PFHS, and PFOS. A total of three sampling locations have been specified. Sampling location descriptions were not available at the time of sample bottle preparation. For each sampling location, a total of five sample bottles will be collected (sample, sample duplicate, low-level field matrix spike, mid-level field matrix spike, and high-level field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One set of trip blanks consisting of reagent-grade water, a low-level trip blank spike, mid-level field spike, mid-high level field spike, and a high-level trip blank spike will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. One additional bottle will be prepared to be used for the preparation of the equipment rinseate blank. A total of twenty-one sample bottles will be prepared. 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 100+30%, Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". Page 5 of 6 Page 29 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Analytical Protocol: GLP10-01-02 Amendment 16 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and the three field matrix spikes. Trip blank and trip blank spikes will 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 time of 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 6 of 6 Page 30 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Attachm ent B: Sam ple C hromatograms and C alibration C urve Page 31 of 61 * * * G i n g e r AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater S a m p te su its Name: g i i 0 2 i i a . r d b *** G in g e r AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Sam pteam its Na me : g i i 0 2 i i a . r d b *** Ginger AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 R e s u l t s Name: g i i 0 2 i i a . r d b *** G in g e r AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples R e s u l t s Name: g i i t m i a . r d b *** G in g e r AG01330509 GLP10-01 -02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 R e s u l t s Name: g i i 0 2 i i a . r d b *** Gin ger AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples R e s u l t s Name: g i i 0 2 i i a . r d b *** G in ger AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples R e s u l t s Name: g i i 0 2 i i a . r d b *** Ginger AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples R e s u l t s Name: g i i i m i a . r d b Printing Time: 10:16:02 AM * * * G i n g e r AG0 1 3 3 0 5 0 9 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Sampteasuits Name: g i . 1 0 2 2 8 a . r a b *** Ginger AG01330509 ISofnpl6Name:-9l10228a019" Sample IO: *10007-27-9' Fil: "g110228a.wifr Peak N am e:` PFOS* Maumee): "499.0/99.0 amu,499,0/80.0 amu,499,0/130.0 amu' Comment *1.0 ng/mL FC aid in Mtfli vietar* Annotation: ** Sample Index: 13 Sample Type: Standard Concent ration: 1.00 g/mL Calculated Cone: 0.951 g/mL Acq. Date: 2/28/2011 Acq. Time: 8:40:20 PM 3.2*5 3.1*5 Modi tied: No Proc. Algorithm: Intel1iQuan - MQI Nc-ise Percentage: 50 Base. Sub. Window : 1.00 min Peak-Split. Facto r: 2 Report Largest Pe ak: No Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 points RT Window: 30.0 s Expected R T : 12.5 m Use Relative RT: No 3.1*5 3.0*5 3.0*5 2.9*5 2.9*5 2.6*5 2.8*5 2.7*5 Int. Type: valley Retention Time: 12.5 m n Area: 1055532 coun s Height: I19000. cps Start Time: 12.4 m n End Time: 12.7 m 2.7*5 2.6e5 2.6*5 2.5*5 2.55 2.4eS 2.4eS 2.3e5 2.3e5 2.2e5 2.2e5 2.1*5 2.1*5 2.0e5 2.0eS 1.9*5 1.8*5 1.6e5 1.7e5 I 1.7e5 f 16e5 S 1.6*5 " 1.5e5 1.5*5 1.4*5 1.4eS 1.3*5 1.3*5 1.2e5 1.2*5 1.1e5 1.1*5 1.0*5 9.5*4 9.0e4 8.5*4 8.0*4 7.5*4 7.0*4 6.5*4 6.0*4 5.5*4 5.0*4 4,5*4 3.5*4 3.0*4 2.5*4 2.0*4 1.5*4 1.0*4 5000.0 0.0 Data printed by CJG Printing Time: 10:23:17 AM GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Results Name: Avenue A Investigation Area; Decatur, AL - Jan 2011________ I Sample Name: "g 1 1 0 2 2 3 a 0 ir Sample ID: 'Solvent Blank* File: "g110228a.vwfT Peak Name: 'PFOS* M achet): *499.0/99,0 amu,499.0/80.0 amu,499.0/130.0 amu* Comment "Milli Q Water TN11-0072* Annotation: ** Sample Index: 11 Sample Type: Unknown culated Cone M/A 0.0110 ng/mL 2700 Acq. Date: Acq. Time: 2/29/2011 S:16:41 PH 2650 Modi tied: c. Algorithm: Ir se Percentage: e. Sub. Window: P-*ak-Spl ic . Factor; Report Largest Pea) . Peak Height: . Peak Width: othing Width: RT Window: Expected RT: s Relative RT: 26002S502500 2450 2400 2350 2300 , Type; Valley 12.5 min 7370 counts 2570. ops 12.5 min 12.6 min 2250 2200 2150 2100 gll0228a.rdb 2050 2000 1950 1900- 1800 1750 1700 1650 1550 1500 1450 I 1400 I 1350 I 1300 1250 1200 1150 1100 1050 1000 950 900 650 800 750 700 12 3 4 Page 1 of 3 5 7 8 9 10 11 12 13 T im *.m in P ago nf Ginger AG01330509 Sample Name: *g110228a032* Sample ID :'L Peak Name: *PFOS* Maasfea): *499.0/99.0 a 1 Comment *5ppb LCS* Annotation: "" Sample Index: 32 Sample Type: QC Concentration: 4.98 ng/mL Calculated Cone: 5.27 ng/mL A e q . Date : 3/1/2011 Acq. Time: 12:34:24 AM Modified: No Proc. Algorithm: IntelliQuan - MQ1I Noise Percentage: 50 Base. Sub. Window : 1.00 min Peak-Split. Facto r: 2 Report Largest Pea k : No Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 poin RT Window: 30.0 sec Expected RT: 12.5 min Use Relative RT: No Int. Type: Valley Retention Time: 12.5 min Area: 5721233 counts Height: 1890000. cps Start Time: 12.5 min End Time: 12.8 min File: "g11022Sa.wtir 0 amu.499.0/130.0 mu' GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Results Avenue A Investigation Area; Decatur, AL - Jan 2011 ISample Name: *g11022Ba04r Sample ID: *LCS-110228-13' Peak Name: 'PFOS* Maes(ee): *499.0/99.0 amu,499.0/80.0 ai Comment *5ppb LCS ECF" Annotation: ** ample Index: 41 Name: gll0228a.rdb Data printed by CJG Printing Time: 10:23:18 AM Page 2 of 3 *** Ginger AG01330509 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples R e s u l t s Name: g i i 0 2 2 8 a . r d b Buster J2930203 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Batch Name: bll0310a.dab b 1 1031 Oa.rdb (PFO S): "Q ua dra tic" R egression ("1 / x " w e igh ting ): y = -0 .0 0 0 4 8 x A2 + 1.34 x + 0 .0 514 (r = 0.9998) 135- 130- 125- 120- 115- 110- 105- 100- 95: 90- 85: (D 8 0 : 0) < 75 J CO 70: (TJ " < 65: a> 6 0 - c < 55: 50: 45- 40- 351 30 J 25: 20- 15- 10- 5- 0- X JX ' s S' s' s '' s'" s *- s'" rS s'' X' s' s' ,S'' yS X S'' S' s' 0 5 10 15 20 25 30 35 40 45 50 55 60 65 A nalyte Cone. / IS Cone. Data printed by STW Printing Time: 9:46:17 AM Printing Date: Thursday, March 17, 2011 s' s '' x S'"'' 70 75 Page 1 of 1 80 s s'' s'"' s' s 85 90 95 100 Page 44 of 61 *** Bu ster J2930203 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples B a t c h Name: b i i 0 3 i 0 a . d a b *** Buster J2 9 3 0 2 0 3 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples B a t c h Name: b i i 0 3 i 0 a . d a b *** Buster J2 9 3 0 2 0 3 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples B a t c h Name: b i i c m o a . d a b GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Attachm ent C: A nalytical M ethod Page 48 of 61 An^ysis^of^FBslr^^^^W^iiGfh^S^sa'mpcsrrsni, for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 3M Environm ental Laboratory Method Method o f Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q y ^ ^ o ~ ] Approved By: -----------William K. Reagen, Laboratory Manager Date ETS-8-044.0 Page 1 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 4 9 of 61 GLP10-01-02; Interim Report 16, , . , c .. , ^ r\A <r\s t^r\A a Analysis of P F B s M i ^ W ^ f f e O h d i S ^ s a 'r t . ^ r e n t , for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 1 Scope and Application This method is to be used to quantify Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector (LC/MS/MS) in clean water samples. Water samples containing heavy particulate may require preparation by an alternate method such as ETS-8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method is considered a performance-based method. Data is considered acceptable as long as the defined QC elements are satisfied. Sample collection is not covered under this analytical procedure. 2 Method Summary Clean aqueous samples are analyzed by direct injection using LC/MS/MS. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. This is a performance-based method. Method accuracy is determined for each sample set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sample be determined using field matrix spikes to verify that the method is applicable to each sample matrix. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. Fortification levels for field matrix spikes and for laboratory matrix spikes should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used to determine the statement of accuracy for analytical results. 3 Definitions 3.1 Calibration Standard A solution prepared by spiking a known volume of the Working Standard (WS) into a predetermined amount of ASTM Type I, HPLC grade water, or other suitable water, and analyzed according to this method. Calibration standards are used to calibrate the instrument response with respect to analyte concentration. 3.2 Laboratory Duplicate Sample (LDS, or Lab Dup) A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared to that of the first aliquot give a measure of the precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures. 3.3 Field Blank (FB)/Trip Blank ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the laboratory and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. The purpose of the FB is to determine if test substances or other interferences are present in the field environment. This sample is also referred to as a Trip Blank. ETS-8-044.0 Page 2 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 50 of 61 GLP10-01-02; Interim Report 16. Analysis of P F B S ,W iS )S ffl P F d Avenue A Investigation Area; Decatur, AL - Jan 2011 for 14 days from 04/04/2011 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) fora 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 51 of 61 An^ysis^of<F^FBs?r^^^^^diritefend^^sa'm^c3r^ent. for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 3.11 Method Blank An aliquot of control matrix that is treated exactly like a laboratory sample including exposure to all glassware, equipment, solvents, and reagents that are used with other laboratory samples. The method blank is used to determine if test substances or other interferences are present in the laboratory environment, the reagents, or the apparatus. 3.12 Sample A sample is an aliquot removed from a larger quantity of material intended to represent the original source material. 3.13 Stock Standard Solution (SSS) A concentrated solution of a single-analyte prepared in the laboratory with an assayed reference compound. 3.14 Surrogate A compound similar in chemical composition and behavior to the target analyte(s), but is not normally found in the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isotopically-labeled substitution. If used, surrogate(s) are added to all samples and quality control samples. Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, preparation, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. 3.15 Working Standard (WS) A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to prepare calibration standards and other required analyte solutions. 4 Warnings and Cautions 4.1 Health and Safety The acute and chronic toxicity of the standards for this method have not been precisely determined; however, each should be treated as a potential health hazard. The analyst should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that might be present. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and vacuum systems. Refer to the appropriate equipment procedure or operator manual for additional information and cautions. 5 Interferences During sample preparation and analysis, major potential contaminant sources are reagents and glassware. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks. ETS-8-044.0 Page 4 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 52 of 61 GLP10-01 -02; Interim Report 16^ , ... . , ,. , , _, . Analysis of pfbsM ^ ^ P ^ im f e g i^ ^ s a f n ^ r e n t , for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 mL plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Time (min) 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (mL/minl 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak Area-quadratic curve fit, 1/x weighted. Run Time: ~ 17 minutes. The previous information is intended as a guide; alternate conditions and equipment may be used provided that data quality objectives are met. ETS-8-044.0 Page 5 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 53 of 61 GLP10-01-02; Interim Report 16, , . . , ., , , Analysis of P F B s . ^ W P ^ m t e o W e f is a 'i i^ r e n t , for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative ion, MRM mode, monitoring the following transitions: Analyte Transition Monitored PFBA 2 1 3 -> 169 PFPeA 263 ->219 PFHA 313 --> 269 and 3 1 3 - 119 PFHpA 363 - 319, 363 -> 169 and 363 -> 119 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 - * 469, 513 - 2 1 9 and 513 -> 269 PFUnA 563 -> 519, 563 - 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --y 80 and 399 --^ 99 PFOS 499 - 80, 499 -> 99 and 499 -> 130 Multiple transitions for monitoring the analytes is an option, as summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased sensitivity. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity. The previous information is intended as a guide, alternate instruments and equipment may be used. 7 Reagents and Standards 7.1 Chemicals Water - Milli-Q, HPLC grade, or other suitably appropriate sources Methanol - HPLC grade Ammonium Acetate - A.C.S. Reagent Grade 7.2 Standards Perfluorobutanoic Acid (P F B A -C 4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar Perfluorohexanoic Acid (P F H A -C 6 acid); Oakwood Products, Inc Perfluoroheptanoic Acid (PFHpA - C7 acid, also known as TDHA, tridecafluoroheptanoic acid); Oakwood Products, Inc Perfluorooctanoic Acid (PFOA - C8 acid); 3M Perfluorononanoic Acid (P F N A -C 9 acid); Oakwood Products, Inc Perfluorodecanoic Acid (P F D A -C 1 0 acid); Oakwood Products, Inc Perfluoroundecanoic Acid (PFU nA-C11 acid); Oakwood Products, Inc Perfluorododecanoic Acid (P FD oA -C 12 acid); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 .of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 54 of 61 An^ysis^of^FBsIr^^^^^Tawi^Gf^nwil^s^mps^^ni, for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 The previous information is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/mL target analyte SSSs--Weigh out 10 mg of analytical standard (corrected fo r percent salt and purity) and dilute to 1OOmL 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. molecular weight of anion salt correction factor moclecular weight of salt PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg C8F17S03'K+with purity 90% = 8.35mg C8F17S0;f (10 mg*0.90*0.9275=8.35 mg) 5 pg/mL (5000 ng/mL) mixed w orking standard--Add 0.5mL each of the 100pg/mL SSSs to a 10mL volumetric flask and bring up to volume with solvent. 250 ng/mL mixed w orking standard--Add 1.25mL of the 5 pg/mL -mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. 125 ng/mL mixed standard--Add 625pL of the 5 pg/mL-mixed working standard solution to a 25mL volumetric flask and bring up to volume with solvent. Storage Conditions-- Store all SSSs and working standards in accordance with laboratory standard operating procedure or in a refrigerator at 42C for a maximum period of 6 months from the date of preparation. 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 55 of 61 GLP10-01-02; Interim Report 16^ , , , , ., , , n*m ^ * Analysis of PFBS^Prl-Tj^i^pF^dSiritfehcjiwi^Sampic^^nt, f o r 1 4 d a y s f r o m 0 4 / 0 4 / 2 0 1 1 Avenue A Investigation Area; Decatur, AL - Jan 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. Concentration of WS, ng/mL 125 125 125 125 250 250 250 250 5000 5000 5000 Volume o f WS, pL 10 15 20 30 20 50 100 200 25 50 100 Final Volume of Calibration Standard (mL of ASTM Type 1Water, or other suitable water) 50 50 50 50 50 50 50 50 50 50 50 Final Concentration of Calibration Standard, ng/mL (ppb) in ASTM Type 1Water, or other suitable water 0.025 0.0375 0.050 0.075 0.100 0.250 0.500 1.00 2.50 5.00 10.0 8 Sample Handling 8.1 Water Sample Preparation This method is applicable to clean water samples. Samples containing heavy particulate may not be suitable for analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a sample aliquot, or filtered. Thoroughly mix sample before removing an aliquot and placing in a labeled plastic autovial. Plastic is preferred over the use of glass autovials, to prevent the possibly of fluorochemical sticking to the glass. Dilute sample, if necessary, with ASTM Type I, HPLC water, or other suitable water. Prepare method QC samples and multiple method blanks and aliquot into labeled plastic autovials. Prepare at least five method blanks. 9 Sample Analysis - LC/MS/MS Analyze the standard curve prior to each set of samples. The standard curve may be plotted using a linear fit, weighted 1/x or unweighted, or by quadratic fil (y = ax2+ bx + c), weighted 1/x or unweighted, using suitable software. The calibration curves may include but should not be forced through zero. The mathematical method used to calculate the calibration curve should be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. High and/or low points may be excluded from the calibration curves to provide a better fit over the range appropriate to the data or because they did not meet the pre-determined acceptance criteria. Low-level curve points should also be excluded if their area counts are not at least twice that of the method and/or solvent blanks. The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may ETS-8-044.0 Page 8 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 56 of 61 An^y^of^Bs^r^^^^^-olaifiyote^nd^ia^sampit^rsni, for 14 days from 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 be within 30%. Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. Calibration verification injections must be within 25% to be considered acceptable. The calibration curve and the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples containing analytes that are quantitated above the concentration of the highest standard in the curve should be further diluted and reanalyzed. 10 Quality Control 10.1 Data Quality Objectives This method and required quality control samples is designed to generate data accurate to 30% with a targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be documented in the raw data and footnoted in the final report. 10.2 Method Blanks Method blanks must be prepared with each analysis batch. At least five method blanks must be prepared. Method blanks may be injected multiple times, but no more than 3 injections should be removed from a single method blank. At a minimum, method blanks are analyzed prior to instrument calibration, prior to the analysis of CCV samples, and at the end of the analytical run. The mean area count for each analyte in the method blanks must be less than 50% of the area count of the LOQ standard. The standard deviation of the area counts of these method blanks should be calculated and reported. If the mean area counts of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria, or alternatively, the method blanks must be evaluated statistically to determine outliers, or technical justification to eliminate one or more results should be made. 10.3 Sample Replicates Samples duplicates are collected in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks. 10.4 Surrogate Spikes Surrogate spikes are not required but may be used on project specific requirements. 10.5 Lab Control Sample Triplicate lab control spikes at a minimum of two different concentrations are to be prepared with each preparation batch. Low lab control spikes should be prepared at concentrations in the range of five to ten times higher than the targeted LOQ and high lab control spikes should be prepared at concentrations near the mid-point of the curve. The relative standard deviation of the control spikes evaluated independently at each concentration level must be less than or equal to 20% and the average recovery must be 80-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-prepared as appropriate. ETS-8-044.0 Page 9 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 57 of 61 AGnLaPly1s0i-s01o-f0p2f; bInste.^rimPi-RIseJpSonrtS1*f6,:GiiyfiVo,fe^nd^il^s.smpies''^nL. f, or .. 14 , days , from ,n , ^ 04/04/2011 Avenue A Investigation Area; Decatur, AL - Jan 2011 10.6 Field Matrix Spikes / Lab Matrix Spikes Recoveries of field matrix spikes and laboratory matrix spikes are anticipated to be between 70% and 130% of the fortified levels. Sample results for spikes outside of 70% to 130%, may be flagged as such (with expanded accuracy statements), or will not be reported due to non-compliant quality control samples. The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous level to be used without justification to determine the statement of accuracy for analytical results. The average of the sample and the field duplicate should be used to calculate the recovery. 11 Data Analysis and Calculations Use the following equation to calculate the amount of analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: (Peak Area - Intercept) Analyte found (ng/mL) = xDF Slope DF = factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate the percent recovery. Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) Recovery = x100 Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of 5% and a retention time RSD of 2% to be compliant. 12.2 Quantitation Calibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 58 of 61 Avenue A Investigation Area; Decatur, AL - Jan 2011 for 14 days from 04/04/2011 Demonstration o f Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary of Changes ETS-8-044.0 Page 11 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 59 of 61 GLP10-01-02; Interim Report 16 Analysis o f PFBS, PFHS, and PFOS In Groundwater Samples Avenue A Investigation Area; Decatur, AL - Jan 2011 Attachm ent D: D eviation(s ) Page 60 of 61 GLP10-01-02; Interim Report 16 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples 1. Identification Study / Project No. ! Date(s) of Occurrence: Document Number: GLP10-01-02-16 g110228a and g110211a ETS-8-044.0 Deviation type SOP Equipment Procedure 0 Method (Check one) Protoco GPO Other: II. Description (attach extra pages as needed) Method Requirements: 1. LCS average recoveries within 20% (section 10.5). 2. FMS recovery within 30% (section 10.6). Actual procedure/process: 1. The average PFOS recovery for the 30 ppb LCS (linear + branched) was 133% (g110211a). The average PFOS recovery for the 30 ppb LCS (linear + branched) was 125% (g110228a). 2. Sampling location 210R; the recovery of the FMS High sample for PFOS was 68.1% (g110228a). III. Actions Taken __________________________ (such as amendment issued, SOP revision, etc.) Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1. The recoveries for the 30 ppb LCS (linear + branched) at 133% and 125% will be flagged in the final report. The last fifty LCSs for PFOS, including the LCS prepared with this study, were evaluated by ETS-12-012 to determine the method analytical uncertainty. The analytical uncertainty when evaluated by ETS-12-012 was determined to be 17% for PFOS. However, the analytical uncertainty for this study will be set at 33%, based on the recovery of the high sets of linear + branched LCS. 2. The FMS High recovery for PFOS will be flagged in the final report. The recovery is within the method uncertainty of 33%. Actions: Halting of Work Client Notification Work Recall Withholding of Report 0 Other: Deviations will be noted in final report. Project Lead/PAI Approval: Study Director (if GLP): ijii J Sponsor Approval (for G IP protocol deviations): NA Technical Reviewer (optional): NA Date: j/ Da,e:# 7 / Date: N A ' Date: NA Laboratory Department_Manager Approval: Date: 4 /9 - P /i/t' o // IV. Authorization to Resume Work Where halting of work occurred, resumption of work must first be approved bv Laboratory Management Laboratory Department Manager Approval: NA Date: NA Deviation N o .______________ (assigned by Study Director o r Team Leader at the end o f study or project) ETS-4-008.7 Page 1 of 1 Documentation of Deviations and Control of Nonconforming Testing Page 61 of 61