Document OpLYEo7OZ8Xmkpnz1Rj7JKXQ

GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 GLP10-01-02: Interim Report 19 - Analysis of PFBS. PFHS. and PFOS in Groundwater Samples Collected at the Off-Site BP Property in Decatur, AL in July 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 W eston Solutions, Inc. 1400 Weston Way W est Chester, PA 19380 Phone: 610-701-3761 Author Susan W olf 3M Environmental Laboratory Interim Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 St. Paul, MN 55144 Project Identification G LP 10-01 -0 2-19 Total Number of Pages 70 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 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 This page has been reserved for specific country requirements. Page 2 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 GLP C o m plia n c e S tatem ent Report Title: Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Off-Site BP Property in Decatur, AL in July 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 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Q uality A ssurance Statement Report Title: Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Groundwater Samples Collected at the Off-Site BP Property in Decatur, AL in July 2011 Study: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 8/12/11, 8/15/11 Phase Data / Report Date Reported to Testing Facility Management Study Director 8/23/11 8/23/11 Date Page 4 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Ta b l e o f C o n te n ts GLP Compliance Statem ent..................................................................................................................3 Quality Assurance Statem ent................................................................................................................4 Table of Contents...................................................................................................................................5 List of Tables..........................................................................................................................................6 1 Study Inform ation............................................................................................................................7 2 Summary......................................................................................................................................... 8 3 Introduction......................................................................................................................................9 4 Test & Control Substances.............................................................................................................9 5 Reference Substances.................................................................................................................. 10 6 Test System .................................................................................................................................. 11 7 Method Summary.......................................................................................................................... 11 7.1 Methods......................................................................................................................... 11 7.2 Sample Collection......................................................................................................... 12 7.3 Sample Preparation...................................................................................................... 12 7.4 A nalysis.........................................................................................................................12 8 Analytical Results.......................................................................................................................... 13 8.1 Calibration...................................................................................................................... 13 8.2 System Suitability.......................................................................................................... 13 8.3 Limit of Quantitation (LOQ)............................................................................................13 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 (FM S).............................................................................................. 17 Page 5 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 9 Data Summary and Discussion....................................................................................................17 10 Conclusion.....................................................................................................................................20 11 Data/Sample Retention................................................................................................................20 12 Attachm ents..................................................................................................................................20 13 Signatures.................................................................................................................................... 21 L ist o f Ta b l e s Table 1. Summarized PFBS, PFHS, and PFOS Results (BP Groundwater, July 2011)................. 9 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.................................................................................. 15 Table 7 continued. Laboratory Control Spike Recovery................................................................. 16 Table 8. Analytical Uncertainty........................................................................................................17 Table 9. Field Matrix Spike Levels.................................................................................................. 17 Table 10. DAL GW BPMW47 110713............................................................................................. 18 Table 11. DAL GW BPMW121 110713........................................................................................... 18 Table 12. Trip Blank........................................................................................................................ 19 Table 13. Rinseate Blank................................................................................................................19 Page 6 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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 St. Paul, MN 55144 Study Personnel W illiam K. Reagen, Ph.D., 3M Laboratory Manager Cleston Lange, Ph.D., Principal Analytical Investigator, (clanqe@mmm.com1: phone (651)-733-9860 Susan Wolf, 3M Analyst Chelsie Grochow, Analyst Kevin Eich, Analyst Kelly Ukes, Analyst Jonathan Steege, Analyst Study Dates Study Initiation: March 8,2010 Interim 19 Experimental Termination: August 3, 2010 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 7 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 12 Summary The 3M Environmental Laboratory received groundwater samples from two different wells located at the Off-Site BP Property in Decatur, AL. A total of thirteen 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 Milli-QTM water and appropriate trip blank spikes, and one equipment rinseate blank. The equipment rinseate blank did not have a FMS sample prepared for determination of PFBS, PFHS, and PFOS recovery. The groundwater samples, trip blanks and equipment rinseate blank associated with GLP10-01-02-19 were received from Weston personnel on July 18,2011. All of the samples were prepared and analyzed for PFBS, PFHS, and PFOS following 3M Environmental Laboratory Method ETS-8-044.0 and conducted under 3M project GLP-10-01-02-19. The average measured PFBS, PFHS, and PFOS concentrations are summarized in Table 1. The equipment rinseate and the trip blank sample were below the lower limit of quantitation (LLOQ), indicating adequate control of sample contamination during shipping and sample collections. The analytical method uncertainties associated with the reported results are: PFBS + 10%, PFHS + 11% and PFOS + 29%. Page 8 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Table 1. Sum m arized PFBS, PFHS, and PFOS R esults (BP G roundw ater, Ju ly 2011). Sampling Location DAL GW BPMW47 110713 DAL GW BPMW121 110713 Trip Blanks (Milli-QTM Water) GLP10-01-02-19 Equipment rinseate blank: DAL GW BPMW121 PFBS Avg. Cone. (ng/mL) RPD 0.188 2.7% <0.0250 <0.0250 <0.0250 PFHS Avg. Cone. (ng/mL) RPD 0.138 2.2% <0.0250 <0.0250 <0.0250 PFOS Avg. Cone. (ng/mL) RPD 0.210 3.8% <0.0400 <0.0400 <0.0400 The analytical method uncertainties associated with the reported results are: PFBS 10%, PFHS 11%, and PFOS 29%. 3 , ilntroductior This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS), in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. This analytical study was conducted to analyze groundwater samples collected from two wells located at the off-site BP property in Decatur, 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 matrix spike samples. Each empty container was marked with a "fill to here" line to produce a final sample volume of 200 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing PFBS (linear), PFHS (linear), and PFOS (linear) prior to being sent to the field for sample collection. All sample bottles included the addition of 180 2-PFBS, 13C3-PFHS, and 13C8-PFOS (internal standard) at a nominal concentration of 1 ng/mL. See section 8.8 of the report for field matrix spike levels. Samples were prepared and analyzed according to the procedure defined in 3M Environmental Laboratory method ETS-8-044.0 "Determination of Perfluorinated Compounds In Water by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". The use of internal standards 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 aqueous equipment rinseate blank. Tables 10-13 summarize the individual sample results and the associated field matrix spike recoveries. All results for the quality control samples prepared and analyzed with the samples are reported and discussed elsewhere in this report There was not a test substance or control substances in the classic sense of a GLP study. This study was purely analytical in nature. Page 9 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 5 Reference Substances Reference Substance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFHS (linear) Perfluorohexane sulfonate C6 F1 3 SO3 Sodium Salt Target Analyte Reference Standard Wellington 04/02/2013 Frozen LPFHxSAM08 TCR08-0018 Crystalline 98% f 'C J PFHS (linear) Sodium Perfiuorohexanesulfonate 13C312C3F13S0 3 Na+ CAS # MPFC-C-0511 Internal Standard Wellington 05/25/2014 Frozen 092310 TCR11-0016 Liquid 5 pg/mL(1) Reference Substance Chemical Name PFOS (linear) Perfluorooctane sulfonate PFOS (linear + branched) Perfluorooctane sulfonate r sCJ PFOS (lin e a l) Sodium Perfluorooctanesulfonate Chemical Formula Identifier Use Source C8F17 SO3 Potassium Salt CAS #2795-39-3 Target Analyte Reference Standard Wellington C8F1 7 SO3 Potassium Salt CAS #2795-39-3 LCS Reference Standard 3M 13C8F17S 0 3'Na+ CAS# MPFC-C-0511 Internal Standard Wellington Expiration Date 10/18/2013 12/14/2016 05/25/2014 Storage Conditions Frozen Frozen Frozen Chemical Lot Number LPFOSKBM06 171 092310 TCR Number TCR08-0001 TCR-696 TCR11-0016 Physical Description Crystalline White Powder Liquid Purity 98% 86.4% 5 pg/mL(1) (1) Custom mixture of seven mass-labeled (13C) perfluoroalkylcarboxylic adds, two mass labeled (13C) perfluoroalkylsulfonates and one mass-labeled (13C) perfluoro-1-octanesulfonamide. Page 10 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Reference Substance Chemical Name Chemical Formula Identifier Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS (predominantly linear) Perfluorobutane sulfonate C4F9S O 3' Potassium Salt Target Analyte Reference Standard 3M 01/10/2017 Frozen 41-2600-8442-5 TCR-121 White Powder 96.7% [1 8 0 2 ] PFBS (linear) [18C>2]-Ammonium Perfluorobutanesulfonate C 4F9S [180 2 ]0 -N H 4 + NA Internal Standard RTI International 03/09/2015 Frozen 11546-107-2 TCR-1009, TCR-1031 Liquid >99% 6 Test System The test systems for this study are groundwater samples collected from wells located in Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real world" samples, not dosed with a specific lot of test substance. Table 2. Sample Description Key Code. String Number Example 1 2 3 4 5 String Descriptor Example DAL GWBPMW470110713 Sampling Location DAL = Decatur, Alabama Well ID GW= Groundwater Sampling Point Example: BPMW47 Sampling Date 110713- July 13,2011 Sample Type 0=prim ary sample DB=duplicate sample LS = low spike MS = m id spike HS = high spike 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 W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Page 11 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 7.2 Sample Collection Samples were collected in 250 m l. NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles associated with GLP10-01-02-19 were returned to the laboratory at ambient conditions on July 18, 2011. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with each cooler of sample collection bottles. 7.3 Sample Preparation Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for analysis. During the preparation of the laboratory control samples, an aliquot of a separate internal standard spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The samples bottles were spiked with an internal standard mix at a nominal concentration of 1 ng/mL prior to being sent to the field for sample collection 7.4 Analysis All study samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the raw data hard copies placed in the final data packet, and are briefly described below. Table 3. Instrument Parameters. Instrument Name Analytical Method Followed Analysis Date Liauld Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software ETSKirk ETS-8-044.0 7/29/11 - PFBS and PFHS Aqilent1200 Betasil C18 (4.6 mm X 100 mm), 5u Betasil C18 (4.6 mm X 100 mm), 5u 25 uL Applied Blosystems API 5500 Turtx) Spray Turtx) ion electrode Negative Analyst 1.5.2 ETSKirk ETS-8-044.0 8/2/11-P F O S Adilent 1200 Betasil C18 (4.6 mm X 100 mm), 5u Betasil C18 (4.6 mm X 100 mm), 5u 25 uL Applied Biosystems API 5500 Turtx) Spray Turbo ion electrode Negative Analyst 1.5.2 Table 4. Liquid Chromatography Conditions. Step Number 0 1 2 3 4 5 Total Time (min) 0 2.0 14.5 15.5 16.5 20.0 Flow Rate (pUmin) Percent A (2 mM ammonium acetate) ETS-8-044.0 Analyzed 7/29/11 and 8/2/11 750 97.0 750 97.0 750 5.0 750 5.0 750 97.0 750 97.0 PercentB (Methanol) 3.0 3.0 95.0 95.0 3.0 3.0 Page 12 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Table 5. Mass Transitions. Analyte Mass Transition Q1/Q3 Reference M aterial Structure Internal Standard Mass Transition Q1/Q3 PFBS 299/80 299/99 Linear [ 1sO J PFBS 303m PFHS 399/80 399/99 Linear [ 13Ci]P FH S 402/80 499/80 PFOS 499/99 Linear [ 13CiJPFO S 507/80 499/130 Dwell time was 30 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 using a stable isotope internal standard calibration curve. Calibration standards were prepared by spiking known amounts of the stock solution containing the target analytes into a laboratory-prepared synthetic groundwater containing calcium and magnesium. A separate internal standard spiking solution was prepared and an aliquot was added at the same level to all calibration standards and laboratory control samples at a nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.025 ng/mL to 100 ng/mL was prepared. Sample DAL GW BPMW47 was quantitated using external calibration due to inconsistent internal standard area counts. A quadratic, 1/x weighted, calibration curve of the standard peak area/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/peak area ratios and the resultant calibration curve confirmed accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes. The correlation coefficient (r) was greater than 0.995 for PFBS, PFHS, and PFOS. 8.2 System Suitability A calibration standard was analyzed four times at the beginning of each analytical sequence to demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was met for PFBS, PFHS, and PFOS. 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 or area ratio are at least twice those of the appropriate blanks. The LOQ for all analytes can be found in Table 6. Page 13 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Table 6. Limit of Quantitation (LOQ). Sampling location DAL GW BPMW47 110713 DAL GW BPMW121 110713 PFBS LOQ, ng/mL 0.0250 0.0250 PFHS LOQ, ng/mL 0.0250 0.0250 PFOS LOQ, ng/mL 0.100 0.0400 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, and PFOS. 8.5 Blanks Three types of blanks were prepared and analyzed with the samples: solvent blanks, trip blanks, and equipment rinseate blanks. Solvent blank results were reviewed and used to evaluate method performance to determine the LOQ for PFBS, PFHS, and PFOS. Trip blanks reflect the shipping and sample collection conditons the sample bottles and samples experience. Equipment rinseate blanks are aqueous samples that reflect the efficiency of equipment cleaning in the field between different sample collections and are proof of no cross contamination of samples from the equipment. 8.6 Lab Control Spikes (LCSs) Low, mid, and high-level lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analyte into Milli Q water or synthetic groundwater 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, average of LCS at each level should be within 100% 20% with an RSD <20%. 7/29/11 Analysis - internal standard calibration: All LCSs met acceptance criteria for PFBS and PFHS. 7/29/11 Analysis - external standard calibration: All LCSs met acceptance criteria for PFBS and PFHS. 8/2/11 Analysis - internal standard calibration: All LCSs met acceptance criteria for PFOS. 8/2/11 Analysis - external standard calibration: The low set of LCS samples for PFOS had an average recovery of 122%. The mid and high sets of LCS samples met acceptance criteria for PFOS. As the reference material used for quantitation of PFOS is predominantly linear, and the PFOS present in the water samples are comprised of both linear and branched isomers, additional LCS samples of PFOS (linear and branched) were prepared at three concentrations in triplicate to evaluate the potential for analytical bias. 8/2/11 Analysis - internal standard calibration: The low, mid, and high linear and branched LCSs had average recoveries of 129%, 122%, and 122%. 8/2/11 Analysis - external standard calibration: The low linear and branched LCS set had an average recovery of 126%. The mid and high sets of LCS samples met acceptance criteria for PFOS. The following calculations were used to generate data in Table 7 for laboratory control spikes. Page 14 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 100Calculated Concentration LCS Percent Recovery = % Spike Concentration LCS% RSD = standard deviation LCS replicates . 1Q0% average LCS recovery Table 7. Laboratory Control Spike Recovery. ETS-8-044.0 Internal standard calibration Analyzed 7/29/11 Lab ID PFBS Spiked Calculated Spiked Concentration Concentration Concentration (ng/mL) (ng/mL) % R ecovery (ng/mL) LCS-110726-1 LCS-110726-2 LCS-110726-3 0.199 0.199 0.199 0.215 0.212 0.224 108 0.199 107 0.199 113 0.199 Average %RSD 109 2.9% LCS-110726-4 LCS-110726-5 LCS-110726-6 1.99 1.99 1.99 2.14 107 1.99 2.02 101 1.99 2.13 107 1.99 Average %RSD 105% 3.3% LCS-110726-7 LCS-110726-8 LCS-110726-9 19.9 19.9 19.9 21.2 106 19.9 21.6 108 19.9 21.6 108 19.9 Average % RSD 107% 1.1% PFHS Calculated Concentration (ng/mL) 0.217 0.216 0.224 110% 1.9% 2.20 2.11 2.19 109% 2.4% 21.3 21.9 21.8 109% 1.6% %Recovery 109 108 112 111 106 110 107 110 110 ETS-8-044.0 External standard calibration Analyzed 7/29/11 PFBS Lab ID Spiked Calculated Spiked Concentration Concentration Concentration (ng/mL) (ng/mL) % R ecovery (ng/mL) LCS-110726-1 LCS-110726-2 LCS-110726-3 0.199 0.199 0.199 0.205 0.201 0.218 103 0.199 101 0.199 110 0.199 Average %RSD 105 4.5% LCS-110726-4 LCS-110726-5 LCS-110726-6 1.99 1.99 1.99 2.07 104 1.99 1.99 100 1.99 2.11 106 1.99 Average %RSD 103% 3.1% LCS-110726-7 LCS-110726-8 LCS-110726-9 19.9 19.9 19.9 19.8 99.7 19.9 20.2 101 19.9 20.6 104 19.9 Average %RSD 102% 2.2% PFHS Calculated Concentration (ng/mL) 0.213 0.208 0.221 108% 2.8% 2.12 2.02 2.07 104% 2.9% 21.0 21.6 21.8 108% 2.1% %Recovery 107 105 111 107 101 104 105 109 109 Page 15 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Table 7 continued. Laboratory Control Spike Recovery. ETS-8-044.0 Internal standard calibration Analyzed 8/2/11 PFOS (lineari PFOS (linear+ branched) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) % R ecovery Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) XRecovery LCS-110726-1 0.199 0.219 110 LCS-110726-10 0.198 0.252 127 LCS-110726-2 0.199 0.211 106 LCS-110726-11 0.198 0.254 138 CCVOO LCS-110726-3 0.199 0.226 114 LCS-110726-12 0.198 0.264 Average %RSD 110% 3.6% Average % RSD 129 % 2 .5 % (1) LCS-110726-4 1.99 2.15 108 LCS-110726-13 1.98 2.29 116 LCS-110726-5 1.99 2.04 103 LCS-110726-14 1.98 2.39 121 LCS-110726-6 1.99 2.13 107 LCS-110726-15 1.98 2.53 128 Average %RSD 106% 2.5% Average %RSD 1 22% 5.0% (1) LCS-110726-7 19.9 21.1 106 LCS-110726-16 19.8 23.0 116 LCS-110726-8 19.9 21.7 109 LCS-110726-17 19.8 24.3 123 LCS-110726-9 19.9 21.4 107 LCS-110726-18 19.8 25.3 128 Average %RSD 107% 1.4% Average %RSD 122 % 4 .9 % <1) ETS-8-044.0 External standard calibration Analyzed 8/2/11 PFOS (linear) PFOS (linear + branched) Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) % R ecovery Lab ID Spiked Calculated Concentration Concentration (ng/mL) (ng/mL) % R ecovery LCS-110726-1 LCS-110726-2 0.199 0.199 0.243 0.241 122 LCS-110726-10 121 LCS-110726-11 0.198 0.198 0.246 0.249 124 126 LCS-110726-3 0.199 0.245 123 LCS-110726-12 0.198 0.251 127 Average %RSD 122% 0.82% (1) Average %RSD 126% 1.2% w LCS-110726-4 LCS-110726-5 LCS-110726-6 1.99 1.99 1.99 1.99 99.9 LCS-110726-13 1.98 2.01 101 LCS-110726-14 1.98 2.09 105 LCS-110726-15 1.98 1.83 92.2 1.69 85.6 1.95 98.4 Average %RSD 102% 2.6% Average %RSD 92.1% 7.0% LCS-110726-7 LCS-110726-8 LCS-110726-9 19.9 19.9 19.9 22.7 114 LCS-110726-16 19.8 21.8 110 LCS-110726-17 19.8 22.2 111 LCS-110726-18 19.8 17.8 90.0 19.7 99.6 18.2 92.1 Average %RSD 112% 1.9% Average %RSD 93.9% 5.4% (1) Trie average recovery did not meet method acceptance criteria of 100% 20%. Page 16 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 8.7 Analytical Method Uncertainty Analytical uncertainty is based on historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which corresponds to a confidence level of 95%. The most recent 50 data points were used to generate the method uncertainty values listed in Table 8. The method uncertainty for PFOS by ETS-12-012-2 was found to be 24%, however, since the highest recovery for the LCSs, the low set of branched and linear LCS, was 129%, the analytical uncertainty assigned to this study for PFOS will be 29%. Table 8. Analytical Uncertainty. Analyte PFBS PFHS PFOS Standard Deviation 5.15 5.33 12.2 Method Uncertainty 10% 11% 29% 8.8 Field Matrix Spikes (FMS) Low, mid, and high 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 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. Table 9. Field Matrix Spike Levels. Sampling Location MW47 MW121 Trip Blank Spike Level Low High Low High Low Mid High PFBS, ng/mL 0.250 1.00 2.00 20.0 0.250 1.00 20.0 PFHS, ng/mL 0.250 1.00 2.00 20.0 0.250 1.00 20.0 PFOS, ng/mL 0.250 1.00 2.00 20.0 0.250 1.00 20.0 FMS Recovery - ^ amP*e Concentration of FMS - Average Concentration:Field Sample & Field Sample Dup.)jqq0/ Spike Concentraton j9 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. Page 17 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Table 10. DAL GW BPMW47 110713<1) PFBS PFHS PFOS 3M U M S ID Description Concentration (ng/mL) %Recovery GLP10-01-02-19-005 DAL GW BPMW47 0 110713 0.190 NA GLP10-01-02-19-006 DAL GW BPMW47 DB 110713 0.185 NA GLP10-01-02-19-007 DAL GW BPMW47 LS 110713 0.435 99.0 GLP10-01-02-19-008 DAL GW BPMW47 HS 110713 1.16 97.3 Average Concentration (ng/mL) %RPD 0.188 ng/mL 2 .r/o Concentration (ng/mL) %Recovery 0.139 NA 0.136 NA 0.408 108 1.13 99.3 0.138 ng/mL 2.2% Concentration (ng/m L) X R e co v ery 0.206 0.214 0.506 NA NA 118 1.36 115 0.210 ng/mL 3.8% NA= Not Applicable (1) Results generated using external standard calibration. Table 11. DAL GW BPMW121 110713<1) PFBS PFHS PFOS 3M U M S ID Description Concentration Concentration (ng/mL) %Recovery (ng/mL) %Recovery GLP10-01-02-19-010 DAL GW BPMW121 0 110713 <0.0250 NA <0.0250 NA GLP10-01-02-19-011 DAL GW BPMW121 DB 110713 GLP10-01-02-19-012 DAL GW BPMW121 LS 110713 <0.0250 2.11 NA <0.0250 106 2.22 NA 111 GLP10-01-02-19-013 DAL GW BPMW121 HS 110713 21.7 109 21.6 108 Average Concentration (ng/mL) %RPD <0.0250 <0.0250 Concentration (ng/mL) XRecovery <0.0400 NA <0.0400 NA 2.15 108 21.7 109 <0.0400 IMA= Not Applicable (1) Results generated using internal standard calibration. Page 18 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Table 12. Trip Blank(1) 3M U M S ID Description GLP10-01-02-19-001 DAL GW TRIP1 0110713 GLP10-01-02-19-002 DALGWTRIP1 LS 110713 GLP10-01-02-19-003 DALGWTRIP1 MS 110713 GLP10-01-02-19-004 DALGWTRIP1 HS 110713 NA = Not Applicable (1) Results generated using internal standard calibration. PFBS PFHS PFOS Concentration (ng/mL) <0.0250 0.263 1.02 21.2 %Recovery NA 105 102 106 Concentration (ng/mL) <0.0250 0.268 1.04 21.5 %Recovery NA 107 104 108 Concentration (ng/mL) <0.0400 0.255 1.02 20.9 "/Recovery NA 102 102 105 Table 13. Rinseate Blank(1> PFBS PFHS PFOS 3M U M S ID Description Concentration Concentration (ng/mL) "/Recovery (ng/mL) GLP10-01-02-19-009 DAL GW BPMW121 RS 110713 <0.0250 NA <0.0250 %Recovery NA Concentration (ng/mL) <0.0400 % R ecovery NA NA = Not Applicable (1) Results generated using internal standard calibration. Page 19 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 10 Conclusion 1 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. 111 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 1 Attachment A: Protocol Amendment 19 (General Project Outline) Attachment B: Representative Chromatograms and Calibration Curves Attachment C: Analytical Method Attachment D: Method Deviation Page 20 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 13 Signatures - _________________vfeg/zey Cleston Lange, Ph.D., 3M Principal Analytical Investigator Date _____________________ Q j/ft/6 vsr'< 2 o /t William K. Reagen, Ph.D., 3M Environmental Laboratory Department Manager Date Page 21 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Attachment A: Protocol A mendment Page 22 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Analytical Protocol: GLP10-01-02 Amendment 19 Study Titte 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. 19 Amendment Date: July 6, 2011 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP1Q-01-02 Sampling Event Decatur Phase 3; Off-Site BP Property Page 1 of 7 Page 23 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Analytical Protocol: GLP10-01-02 Amendment 19 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 TO READ: No changes to the wording of the protocol are required. This am endm ent only addresses and documents the addition of the General Project Outline (GPO) for the collection and analysis o f groundwater samples as part of the 3M Decatur Phase 3 Program for PFOS, PFHS and PFBS (GLP10-01-02). The anticipated sample collection w ill occur around the tim efram e of the week o f July 11, 2011.. The groundwater samples for this sampling event w ill be entered into the 3M Environm ental Laboratory LIMS as project GLP10-01-02-19 and reported as interim report GLP10-01-02-19, (reflecting study GLP10-01-02 and am endm ent-19). Reason: The reason for this am endm ent is to docum ent the General Project Outline (GPO) which describes the anticipate groundwater sam ple collection event for two existing w ells located at an off-site location on the BP Property. The GPO is four pages in length and included as attached to this amendment form. Page 2 of 7 Page 24 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Amendment 19 Amendment Approval William Reagen, EWS Opns Environmental Lab Management L. Jaisimha Kesari P.E., DEE, Study Director Ijnln'y// / o // Date ' Dte Page 3 of 7 Page 25 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Analytical Protocol: GLP10-01-02 Amendment 19 Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: From: cc: Date: Subject: Gary Hohenstein, 3M EHS&Opns Susan Wolf, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Cleston Langey, 3M EHS&Opns; Environmental Lab Jai Kesari, Weston Solutions July 6,2011 Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane sulfonate (PFBS) in Groundwater, Soil and Sedim ent for the 3M Decatur Phase 3 Site-Related M onitoring Program; GLP Interim Report 19 - Decatur Phase 3; O ff Site BP Property 1 General Project Information Contacts Lab Request Number Six Digit Department 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 wkreaaen@mmm.com Principal Analytical Investigator Cleston Lange 3M EHS Opns, Environmental Laboratory 260-5N-17 651 733-9860 cclange@mmm,com Sampling Coordinator Timothy Frlnak Weston Solutions Timothv.frlnak@westonsolutions.com Phone: (334)-332-9123 G L P 1 0-01-02-19 Dept #530711, Project #0022674449 Sampling scheduled for the week of July 11,2011 All verbal and written correspondence will be directed to Gary Hohenstein. Page 4 of 7 Page 26 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Analytical Protocol: GLP10-01-02 Amendment 19 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 two sampling locations for Perfluorobutanesuifonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) from existing w ells located on the BP property. Analyses w ill be conducted under the GLP requirem ents o f EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Groundwater samples w ill be collected by W eston Solutions personnel the week o f July 11, 2011. The 3M Environmental Laboratory w ill prepare the sample bottles with all required spikes to ensure that results for PFBS, PFHS, and PFOS are o f a known precision and accuracy. The final report w ill be submitted to Gary Hohenstein and Jai Kesari upon com pletion under interim report GLP10-01 -02-19. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory for sampling the week o f July 11, 2011. Sample bottles will be shipped in coolers overnight to 3M Decatur for arrival on Friday, July 8,2011. 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 lim it of quantitation will be 0.025 ng/m L (ppb) for PFBS, PFHS, and PFOS. Two sampling locations have been specified. See attachment A for a list of the sampling locations that will be collected for this sampling event For each sampling location, a total of four sample bottles will be collected (sample, sample duplicate, low field matrix spike, and high field matrix spike). The "fill to here" line on each 250 mL Nalgene bottle will be 200 mL. One set of trip blanks consisting of reagent-grade water as well trip blank spikes will be prepared at the 3M Environmental Laboratory and sent to the sampling location with the other bottles. All sample bottles will include the addition o f 180 2-PFBS, 18O rPFHS, and 1 u e-PFOS (internal standard) at a nominal concentration of 1 ng/mL. All sample bottles will also include the addition of 13C4-PFOS (surrogate spike) at a nominal concentration o f 0.1 ng/mL. One additional bottle will be prepared to be used for the preparation of the equipment rinseate blank. A 500mL bottle of laboratory reagent water will be sent with the sample bottles to be used to generate the rinseate blank sample. The table below lists the matrix spike levels that will be prepared. Well No. M W -47 MW-121 Trip Blank Sample Level Low High Low High Low Mid High Spike Cone. (ng/mL) 0.25 1.0 2.0 20 0.25 1.0 20 Page 5 of 7 Page 27 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Analytical Protocol: GLP1O-01-02 Amendment 19 5 Test Methods Samples will be prepared and analyzed by LC/MS/MS following ETS-8-044.G "Determination of Perfluorinated Compounds In W ater by High Performance Liquid Chromatography/Mass Spectrometry Direct Injection Analysis". Alternately, samples may be analyzed by ETS 8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". The data quality objectives for these studies are quantitative results for the target analytes with an analytical accuracy of 10030%. Field matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Where applicable, samples will be analyzed against an internal standard calibration curve. Each curve point will contain isotopically-labeled perfluorocarboxylic acids and perfluorosulfonic acids at a nominal concentration of 1 ng/mL. The calibration curve will 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. 6 Reporting Requirements For each sampling location, the report will contain the results for the sample, sample duplicate, and the field matrix spikes. Trip blank 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 w ill 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 7 Page 28 of 70 Attachment A GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Analytical Protocol: GLP10-01-02 Amendment 19 Bottle request - BP Well Sampling Week of 11 July 2011 Sulfonates levels Y oung, C harles T. to cbjacoby2@ mmm.com, stwolf@ mmm.com, clange@ mmm.com 07/05/2011 01:43 PM "Frinak, Timothy R." Analyses of sulfonates in the BP well groundwater samples should also be performed under GLP10-01-02. Previously determined levels of the sulfonates in 601R (close to MW-47) and 601L (close to MW-121) were: Sample ID D06A0L41-G3 W-601R-0D07A0L92-G0 W-601R-00D6A0L41-G3 W-601L-0D07A0L92-G0 W-601L-0- Sample Date PFBS PFHS PFOS 13-Apr-06 NR 0.0254 ND 20-Sep-07 0.0331 0.0585 0.0649 13-Apr-06 NR 20.8 2.54 20-Sep-07 2.91 17.4 2.83 CThhaanrlkies, Charles T. Young Technical Director Weston Solutions, Inc. 1400 Weston Way (5-2) West Chester, PA 19380 (610) 701-3787 Fax (610) 701-3401 Page 7 of 7 Page 29 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Attachm ent B: R epresentative Sa m ple C hrom atogram s and Calibration C urve(s) Page 30 of 70 *ETS-Kirk k110729a.rdb (PFBS): "Quadratic" Regression ("1 / x" weighting): y = -0.00435 xA2 + 1.29 x + 0.00828 (r = 0.9998) GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb _______________________________________________________________________________ Analyte Cone, / IS Cone.________________________ Data printed by STW Printing Time: 9:39:20 AM Page 1 of 1 Printing Date: Thursday, August 25, 2011 Page 31 of 70 *ETS-Kirk k110729a.rdb (PFHS): "Quadratic" Regression ("1 / x" weighting): y = -0.00359 xA2 + 1.05 x + 0.00651 (r = 0.9997) GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb _______________________________________________________________________________Analyte Cone. / IS Cone.___________ _____________ Data printed by STW Page 1 of 1 Printing Time: 9:39:35 AM Printing Date: Thursday, August 25, 2011 Page 32 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Data printed by STW Printing Time: 9:45:19 AM Printing Date: Thursday, August 25, 2011 Page 1 of 8 Page 33 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Printing Date: Thursday, August 25, 2011 Page 34 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Printing Time: 9:45:19 AM Printing Date Thursday, August 25 2011 Page 35 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Printing Time: 9:45:19 AM Printing Date: Thursday, August 25, 2011 Page 36 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Printing Time: 9:45:19 AM Printing Date: Thursday, August 25, 2011 Page 37 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Printing Date: Thursday, August 25, 2011 Page 38 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Data printed by STW Printing Time: 9:45:19 AM Printing Date: Thursday, August 25, 2011 Page 7 of 8 Page 39 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a.rdb Data printed by STW Printing Time: 9:45:20 AM Printing Date Thursday, August 25 2011 Page 8 of 8 Page 40 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a ext.rdb Printing Date: Thursday, August 25, 2011 Page 41 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a ext.rdb Printing Date: Thursday, August 25, 2011 Page 42 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a ext.rdb Printing Date: Thursday, August 25, 2011 Page 43 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a ext.rdb Printing Time: 9:43:13 AM Printing Date: Thursday, August 25, 2011 Page 44 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0729a ext.rdb Printing Time: 9:43:13 AM Printing Date: Thursday, August 25, 2011 Page 45 of 70 *ETS-Kirk k110802a.rdb (PFOS): "Quadratic" Regression ("1 /x " weighting): y = -0.000876 xA2 + 1.05 x + 0.0177 (r = 0.9989) GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb _______________________________________________________________________________ Analyte Cone. / IS Cone.________________________ Data printed by STW Printing Time: 9:45:52 AM Page 1 of 1 Printing Date: Thursday, August 25, 2011 Page 46 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb Printing Date: Thursday, August 25, 2011 Page 47 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb Printing Date: Thursday, August 25, 2011 Page 48 of 70 ETS-Kirk Data printed by STW Printing Time: 9:47:29 AM Printing Date: Thursday, August 25, 2011 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb Page 49 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb Printing Date: Thursday, August 25, 2011 Page 50 of 70 *ETS-Kirk Sample Name: 'k110802a038' Sample I0:'LC&>110728-I(r Fie: Tc110802.*ir- Peak Name: *PFOS* Maa*(e*):*499.00C9.000Da.499.00a/B0.000Oa,499.000/130.000 Da* I Comment *0.2ppb LCS ECF* Annotation: ** Sample ' ' '* Sample Type: OC Concentration 0.198 r Calculated Cc : 0.252 r 8/3/2011 4:22:49 AM liflec Yes Proc. Algorithm: Specify Par liters - MQ III Noise Percentage: 50 base. Sub. window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 Min. Peak Width: 0.00 Smoothing Width: 0 RT Window: 30.0 se Expected RT: 15.3 ml Use Relative RT: No Height: Start Time: End Time: 184809 counts 1.86e*004 cps 15.8 min GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb SwnplaNam a:VI10802a041* Sample ID: "LCS-110726-13* Fla: *k110602a.MtfT Peak Name: *PFOS* M*se(ea): *499.000/99000 Da,499/100/80.000 Da,499.00Cyi30.000 Da' I Comment *2ppb LCS ECP Annotation: " Sample Index: 42 Sample Type: Concentration: 1.98 Calculated Cone: 2.29 8/3/2011 Acq. Time: 5:26:11 ) Modified: Yes Proc. Algorithm: Specify Noise Percentage: 50 Base. Sub. Window: l.( Peak-Split. Factor Report Largest Peal Min. Peak Height: O.Oi Min. Peak Width: 0.( Smoothing Width: 0 RT Window: 30.0 Expected RT: 16.3 Use Relative RT: No 15*5 1.4*5 1.3e5 Int. Type: Manual Retention Time: 16.2 Area: 1620995 cc Height: 1.74**005 Start Time: End Time: cps 6.0e4 5.0a4 I Sample Name:`V110a02a044* Sample ID: *LCS>110726-16* Fle:"k110e02.wr Peak Name: 'PFOS* Masafee): '499.00cyse.000 Da,499.00CV80.000 Da,499.000/130.000 Oa* Comment "20ppb LCS ECP Annotation: ** Sample Index: 45 : 23.0 r 8/3/2011 6:29:30 AM Modified: Yes Proc. Algorithm: Specify Parameter Noise Percentage: 50 Base. Sub. window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Hln. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 poi RT Window: 30.0 sec Expected RT: 16.3 min Use Relative RT: No Area : Height: Start Time: End Time: Manual e: 16.2 min 17355578 counts 1.70e*006 cps 15.8 min 15a6 1.4*6 1.3e6 1.2*6 1.1e6 1.0*6 9.0*5 8.0*5 7.0*5 6.0*5 5.0*5 45*5 3.0*5 2.0*5 1.0*5 Data printed by STW Printing Time: 9:47:29 AM Printing Date: Thursday, August 25, 2011 14.0 145 I Sample Name: "k110802*052* Sample ID: 'GLP1001-02-1&009' F*:*k110802a.ittr Peak Nama: *PFOS* Ma*a(e): `499.000/99.000 Da.499.000/B0.000 0a.499.00tyi30.000 Da* Comment *DAL GW BPMW121 RS 110713* Armotatjon:- Sample Index: 53 S"ampl'e "Type Unknown Concentration: Calculated Cone: N/A <0 2600 Acq. Date: 8/3/2011 Acq. Time:, 9:18:25 AM Modified: Yes Proc. Algorithm: Specify Parameter Noise Percentage: 50 Base. Sub. Window: 1.00 min Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height: 0.00 cps Min. Peak Width: 0.00 sec Smoothing Width: 0 pol RT Window: 30.0 sec Expected RT: 16.3 min Use Relative RT: No Height: Start Time: End Time: Manual 16.0 7265 cov 8 . 66e *002 15.9 16.2 155 16.0 165 17.0 175 18.0 185 Page 5 of 6 15.5 165 165 i l o 175 18.0 18.5 Page 51 of 70 ETS-Kirk Data printed by STW Printing Time: 9:47:29 AM Printing Date: Thursday, August 25, 2011 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a.rdb Comm ent:'OAL GW BPMW121 011071? Sample Index: 67 Sample Type: Unknown entcatlon: N/A Calculated Cone 0.0237 ng/mL Acq. Date: 6/3/2011 Acq. Time: 1:09 PH Annotation: Modified: Yes Proc. Algorithm: Specify Par. Noise Percentage: 50 e. Sub. Window: 1.00 Peak-Split. Factor: 2 Report Largest Peak: Yes Min. Peak Height . Peak. Width: Smoothing Width: RT Window: Expected RT: Use Rela t n t . Type: Retention Time Height: it Time: End Time: Page 6 of 6 Page 52 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a ext.rdb Printing Date: Thursday, August 25, 2011 Page 53 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a ext.rdb Printing Time: 9:49:53 AM Printing Date: Thursday, August 25, 2011 Page 54 of 70 *ETS-Kirk GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a ext.rdb Printing Time: 9:49:53 AM Printing Date: Thursday, August 25, 2011 Page 55 of 70 *ETS-Kirk Printing Time: 9:49:53 AM Printing Date: Thursday, August 25, 2011 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Results Name: kll0802a ext.-rdb Page 3 of 3 Page 56 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 Attachm ent C: A nalytical M ethod Page 57 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 3M Environm ental Laboratory Method Method of Analysis for the Determination o f Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Method Number: ETS-8-044.0 Adoption Date: Upon Signing Effective Date: Q y j f e 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 58 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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), Perfluorononanoic Acid (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 Water 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 Water by LC/MS/MS; Direct Injection Analysis Page 59 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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 60 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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 Water by LC/MS/MS; Direct Injection Analysis Page 61 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 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 W ater Mobile Phase (B): Methanol Gradient Program: Tim e (min) 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m L/m 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 62 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 6.3 MS/MS System 6.3.1 McxJe: Electrospray Negative ion, MRM mode, monitoring the following transitions: A n a ly te Transition Monitored PFBA 213 -> 169 PFPeA 263 - 2 1 9 PFHA 313 --> 269 and 3 1 3 -> 1 1 9 PFHpA 363 -> 319, 363 -> 169 and 363 -> 119 PFOA 413 -> 369, 413 -> 219 and 413 -> 169 PFNA 463 -> 419, 463 -> 169 and 463 -> 2 1 9 PFDA 513 -> 469, 513 -> 219 and 513 -> 269 PFUnA 563 -> 519, 563 -> 269 and 563 -> 2 1 9 PFDoA 613 -> 569, 613 -> 169 and 613 -> 319 PFBS 299 -> 80 and 299 -> 99 PFHS 399 --^ 80 and 399 --^ 99 PFOS 499 -> 80, 499 -> 99 and 499 -> 130 Multiple transitions for 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 PerfluorooctanoicAcid (P F O A -C 8 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 Perfluorododecanoic Acid (P F D o A -0 1 2 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 W ater by LC/MS/MS; Direct Injection A n a ly s is Page 63 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 The previous inform ation is intended as a guide. Reagents and standards from alternate sources may be used. 7.3 Reagent Preparation 2 mM Ammonium acetate solution (Analysis)--Weigh 0.3 g of Ammonium acetate and dissolve in 2.0 L of reagent water. Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios are maintained. 7.4 Stock Standard Solution (SSS) and Working Standard Solution Preparation The following standard preparation procedure serves as an example. Weighed amounts and final volumes may be changed to suit the needs of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L target analyte SSSs--Weigh out 10 mg of analytical standard (corrected fo r p erce n t s a lt a n d purity) and dilute to 10OmL with methanol or other suitable solvent, in a 10OmL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. m olecular weight of anion salt correction factor m oclecular weight of salt 499 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 64 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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 o f WS, ng/mL 125 125 125 125 250 250 250 250 5000 5000 5000 Volume o f WS, f i . 10 15 20 30 20 50 100 200 25 50 100 Final Volume o f Calibration Standard (mL o f ASTM Type 1Water, or other suitable water) 50 50 50 50 50 50 50 50 50 50 50 Final Concentration o f Calibration Standard, ng/mL (ppb) in ASTM Type 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 65 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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 66 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 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. Recovery = Total analyte found (ng/mL) - Average analyte found in sample (ng/mL) x100 Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of 5% and a retention time RSD of <2% to be compliant. 12.2 Quantitation C alibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 of 11 Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Page 67 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 D em onstration o f S pecificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ng/mL. The LOQ for any specific analyte may vary depending on the evaluation of appropriate blanks and the accuracy of the low-level calibration curve points. Refer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 contains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes and laboratory matrix spikes. 12.5 Precision Samples should be collected in duplicate in the field. The relative percent difference, RPD, should be reported. RPD results greater than 20% will be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary 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 68 of 70 Attachm ent D: D eviation(s) GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS In Water Samples Off-Site BP Property - July 2011 Page 69 of 70 GLP10-01-02; Interim Report 19 Analysis of PFBS, PFHS, and PFOS in Water Samples Off-Site BP Property - July 2011 R ecord of D eviation/N o nco nfo rm ance Study / Project No. 1. Identification Date(s) of Occurrence: Document Number: G LP 10-01 -0 2-19 k110802a and k110802a ext ETS-8-044.0 Deviation type SOP Equipment Procedure 0 Method (Check one) Protocol GPO Other: II. Description (attach extra pages as needed) Method Requirements: 1. LCS average recoveries within 20% (section 10.5). Actual procedure/process: 1. k110802a; internal standard calibration: The low, mid, and high PFOS EOF LCS samples had average recoveries of 129%, 122%, and 122%. k110802a ext; external standard calibration: The low PFOS (linear) LCS had an average recovery of 122%. The low PFOS (linear and branched) LCS had an average recovery of 126%. III. Actions Taken (suchas amendment issued, SOP revision, etc.) Corrective Action ( Yes 0 No) Reference: Acceptability of the nonconforming work: 1. The recoveries for the LCSs (linear + branched) outside method acceptance criteria will be flagged in the final report. All of the LCSs prepared with this study were evaluated by ETS-12-012 to determine the method analytical uncertainty. The analytical uncertainty when evaluated by ETS-12-012 was determined to be 24% for PFOS. However, the analytical uncertainty for this study will be set at 29%, based on the recovery of the low set of linear + branched LCS from run k110802a. Actions: Halting of W ork Client Notification W ork Recall W ithholding of Report 0 O th e r: Deviations will be noted in final report. Project Lead/PAI Approval: f~7 Date: Study Director (if GLP): Sponsor Approval (for GLP protocol deviations): NA Technical Reviewer (optional): NA Date/* Date: Date: NA Laboratory Department ManggerApproval: Date: /M ills ' * > // IV. Authorization to Resume Work _____ Where halting of work occurred, resumption of work must first be approved by Laboratory Management Laboratory Department Manager Approval: NA Date: NA Deviation No. (assigned by Study Director or Team Leader at the end of study or project) ETS-4-008.7 Page 1 of 1 Documentation of Deviations and Control of Nonconforming Testing Pa9e 70 of 70