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3M Environmental Laboratory POOO3268; Interim Report#4 Analytical Report Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite 600 Series Wells MPI GLP Protocol Number: P0003268 Interim Report#4 Data Requirement 40 CFR Part 792 Author M ichelle D. M alinsky, Ph.D. Phase Completion Date Date o f signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP07-02-02 Total Number of Pages 178 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 1 of 178 3M Environmental Laboratory P0003268; Interim R eports This page has been reserved for specific country requirements. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 2 of 178 3M Environmental Laboratory P0003268; Interim Report84 GLP Compliance Statement Project Title: Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite 600 Series Wells Project Identification Number: GLP07-02-02; MPI Protocol Number P0003268 Interim Report#4 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: Exceptions to GLP compliance: Microsoft Excel was used to electronically document the SPE extractions by method ETS 8 154.3. A hardcopy printout o f the extraction prep sheet was generated and signed by the preparatory analyst on a date after the extraction date. Jaisimha Kesari, P.E., DEE, Study Director Michael A. Santo^ro., Sponsor Representative 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 3 o f 178 3M Environmental Laboratory P0003268; Interim ReprotM Quality Assurance Statement Study Title: Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite 600 Series Wells Study Identification Number: GLP07-02-02; 3M Protocol Number GLP07-02 (MPI Protocol Number P0003268) Interim Report #4 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 study director and management. Inspection Dates Phase 10/09/2007 2/4/2008 through 2/11/2008 In-Phase Data & Report Audit Date Reported To Principal Analytical Investigator Study Study Director Director Management__________ 11/1/2007 1/28/2008 1/28/2008 2/11/2008 2/14/2008 2/13/2008 Date 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 4 of 178 3M Environmental Laboratory P0003268; Interim ReporW4 Table of Contents GLP Compliance Statement.................................................................................................................. 3 Quality Assurance Statement................................................................................................................4 Table of Contents...................................................................................................................................5 List of Tables.......................................................................................................................................... 6 Study Information.................................................................................................................................. 7 Summary and Introduction.....................................................................................................................8 Test Samples/Test System.................................................................................................................. 13 Reference Substances.........................................................................................................................14 Method Summaries..............................................................................................................................15 Preparatory and Analytical Methods.............................................................................................. 15 Analytical Results.................................................................................................................................18 Calibration...................................................................................................................................... 18 ETS 8-44.0.....................................................................................................................................18 ETS 8-154.3.................................................................................................................................. 18 Limit of Quantitation (LOQ)............................................................................................................ 18 Blanks............................................................................................................................................18 Continuing Calibration....................................................................................................................20 Lab Control Spikes (LCSs)............................................................................................................ 22 Sample Duplicates........................................................................................................................ 26 Field Matrix Spikes (FMSs)........................................................................................................... 26 Laboratory Matrix Spikes (LMSs).................................................................................................. 28 Data Summary and Discussion........................................................................................................... 28 Statistical Methods and Calculations................................................................................................... 42 Accuracy and Precision Equations................................................................................................42 Determination of Analytical Method Uncertainty............................................................................ 42 Statement of Conclusion......................................................................................................................43 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 5 of 178 3M Environmental Laboratory P0003268; Interim ReporttM References.......................................................................................................................................... 44 List of Attachments.............................................................................................................................. 44 Signatures............................................................................................................................................ 45 List of Tables Table 1. Sample Results Summary ETS 8-154.3 (SPE Analysis)........................................................ 9 Table 2. Sample Results Summary ETS 8-44.0 (Direct Injection Analysis)........................................ 11 Table 3. Sample Description Key Code.............................................................................................. 14 Table 4. Study Reference Substances................................................................................................14 Table 5. Instrument Parameters.......................................................................................................... 15 Table 6. Liquid Chromatography Program.......................................................................................... 16 Table 7. Mass Transitions................................................................................................................... 16 Table 8. Instrument Parameters.......................................................................................................... 17 Table 9. Liquid Chromatography Program.......................................................................................... 17 Table 10. Mass Transitions................................................................................................................. 17 Table 11. Non-compliant CCV Summary...........................................................................................21 Table 12. Laboratory Control Spike Data: ETS 8-44.0 Analysis Date: 10/8/2007..............................23 Table 13. Laboratory Control Spike Data: ETS 8-44.0 Analysis Date: 10/11/2007............................24 Table 14. Laboratory Control Spike Data: ETS 8-154.3 Analysis Date: 1/8/2008............................ 25 Table 15. Field Matrix Spike Concentrations.......................................................................................27 Table 16. ETS 8-154.3 (SPE) Sample Results with Field Matrix Spike Recoveries.......................... 30 Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with Field Matrix Spike Recoveries..35 Table 18. Method Uncertainties for ETS-8-154.3............................................................................... 42 Table 19. Method Uncertainties for ETS-8-44.0..................................................................................43 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 6 of 178 3M Environmental Laboratory P0003268; Interim Report4 Study Information Sponsor 3M Company Sponsor Representative Michael Santoro Director Regulatory Affairs 3M Bldg. 236-01-B10 Maplewood, MN 55144 Telephone No. (651) 733-6374 FAX No. (651)733-1958 Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Study Location Testing Facility 3M Environmental Health and Safety Operations 3M Center, Bldg. 260-05-N-17 Maplewood, MN 55144 Study Personnel William K. Reagen, Ph.D., 3M Environmental Laboratory Manager Michelle D. Malinsky, Ph.D., Principal Analytical Investigator Cliffton B. Jacoby, Ph.D., 3M Technical Reviewer Zhuojing Liu, Analyst Vallabha Tantry, Analyst Study Dates Interim Experimental Initiation: October 1, 2007 Interim Completion: Date of interim report signing Location of Archives All original raw data, protocol, and 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. All specimens (samples) will be archived according to current 3M Environmental Laboratory operating procedures. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 7 o f <78 3M Environmental Laboratory P0003268; Interim Report#4 Summary and Introduction The 3M Environmental Laboratory analyzed groundwater samples collected offsite from the 3M Decatur, AL facility by Weston Solutions personnel on September 20, 2007. Samples were submitted for analysis under 3M Environmental Laboratory Project Number GLP07-0202. The MPI GLP protocol number is P000P3268: "Analysis of Perfluorobutane sulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctane sulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program". The groundwater samples were initially analyzed for PFBS, PFHS, and PFOS using method ETS 8-44.0 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". The experimental start date was October 1,2007, the day samples were first prepared for analysis by 3M Environmental Laboratory personnel. Samples were initially analyzed by the direct injection method on October 8,2007 and were then reanalyzed on another instrument on October 11,2007 for the following three reasons (1) the data quality objectives for PFOS were not met due to instrument background, (2) several of the samples exhibited high field matrix spike recoveries for PFHS (ranging from 130-150%), and (3) samples from location DAL GW 605L required dilution and preparation of a laboratory matrix spike to determine the sample accuracy. (See the Method Summaries - Preparation section for more detail.) The experimental completion date for the direct injection analysis was October 11, 2007. PFHS field matrix spike recoveries from the second analysis were consistent with the first analysis. Because several samples required uncertainty expansion, all samples were reanalyzed using 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" where the solid phase extraction procedure seemed to minimize matrix interferences/enhancements observed during the direct injection analysis. Samples were extracted using ETS 8-154.3 on January 7,2008 and analyzed on January 8-10,2008. Reanalysis using the SPE methodology was intended to verify that the sample concentrations obtained through direct injection analysis were not exhibiting a matrix induced bias for the sulfonates. Results from both analytical methods are reported. When the resulting sample concentrations from the direct injection analysis are compared to those obtained by the SPE method, excellent agreement is observed. Sample containers were prepared at the 3M Environmental Laboratory. Sample containers for each sampling location included a field sample, field sample duplicate, low field spike and high field spike. Additionally, two equipment rinse blanks and two trip blanks with field spikes were submitted with the samples. Historical values for these locations were provided by Weston Solutions, Inc. and the concentrations of the low and high field spike varied by sample location accordingly. Each empty 500 mL container was marked with a "fill to here" line to produce a final sample volume of 450 mL. Containers designated for field matrix samples were fortified with an appropriate matrix spike solution containing the target analytes prior to being sent to the field for sample collection. Table 1 below summarizes the sample results from the SPE analysis (ETS 8 154.3) and Table 2 summarizes the results from both direct injection analyses (ETS 8-44.0). The average between the sample and the sample duplicate is provided along with the relative percent difference (%RPD) for the SPE results (Table 1). For Table 2, the average between both direct injection analyses and the relative percent standard deviation (%RSD) for the four measurements is provided, when appropriate, for the PFBS and PFHS results. For the PFOS results, only the average and %RPD from the second analysis is provided as the results from the first analysis were not reported. All results for quality control samples prepared and analyzed with the samples will be reported and discussed elsewhere in this report. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 8 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 1. Sample Results Summary ETS 8-154.3 (SPE Analysis). Table 1. Sample Results Summary ETS 8-154.3 (SPE Analysis). mPFBS mPFHS ,vPFOS Sample Description Sample Comment GLP07-02-02-001 DAL GW TRIP1 0 070920 Calculated Cone. (ng/mL) <0.0249 Calculated Cone. (ng/mL) <0.0244 Calculated Cone. (ng/mL) <0.0250 GLP07-02-02-005 GLP07-02-02-006 GLP07-02-02-009 GLP07-02-02-010 GLP07-02-02-013 GLP07-02-02-014 GLP07-02-02-017 GLP07-02-02-018 DAL GW 601R 0 070920 DAL GW 601R DB 070920 Average %RPD DAL GW 601 SO 070920 DAL GW 601S DB 070920 Average %RPD DAL GW 601L 0 070920 DAL GW 601L DB 070920 Average %RPD DAL GW 602S 0 070920 DAL GW602S DB 070920 Average %RPD 0.0350 0.0352 0.0351 0.57 0.0374 0.0323 0.0349 14 2.70 2.66 2.68 1.5 0.169 0.159 0.164 6.1 0.0579 0.0591 0.0585 2.0 0.0547 0.0531 0.0539 3.0 15.9 16.5 16.2 3.7 0.114 0.119 0.116 4.3 0.0663 0.0668 0.0666 0.75 0.103 0.104 0.104 0.97 3.10 3.29 3.20 5.9 0.498 0.547 0.522 9.4 GLP07-02-02-021 DAL GW602L RB 070920 <0.0249 <0.0244 <0.0250 GLP07-02-02-022 GLP07-02-02-023 GLP07-02-02-026 (2)GLP07-02-02-026 dup GLP07-02-02-027 GLP07-02-02-030 GLP07-02-02-031 DAL GW 602L 0 070920 DALGW602L DB 070920 Average %RPD DAL GW 603S 0 070920 DAL GW 603S 0 070920 DAL GW 603S DB 070920 Average %RSD DAL GW 603L 0 070920 DALGW603L DB 070920 Average %RPD 0.0955 0.0966 0.0960 1.1 0.133 (2)0.118 0.131 0.127 6.4 0.0723 0.0676 0.0700 6.6 0.397 0.411 0.404 3.5 0.135 (2,0.126 0.135 0.132 3.9 0.235 0.227 p>0.230 3.5 1.37 1.38 1.37 1.4 0.285 (2)0.275 0.300 0.287 4.4 0.225 0.219 0.222 2.7 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 9 of 178 3M Environmental Laboratory P0003268; Interim R eports Table 1. Sample Results Summary ETS 8-154.3 (SPE Analysis). Continued. <1>PFBS <1>PFHS <1>PFOS Sample Description Sample Comment GLP07-02-02-034 GLP07-02-02-035 GLP07-02-02-038 GLP07-02-02-039 GLP07-02-02-042 GLP07-02-02-043 GLP07-02-02-046 DAL GW604S 0 070920 DAL GW 604S DB 070920 Average %RPD DAL GW604L 0 070920 DALGW604L DB 070920 Average %RPD DAL GW605R 0 070920 DAL GW 605R DB 070920 Average %RPD DAL GW 605L RB 070920 Calculated Cone. (ng/mL) 0.171 0.174 0.172 1.7 0.216 0.214 0.215 0.93 0.0476 0.0425 0.0450 11 <0.0249 Calculated Cone. (ng/mL) 0.220 0.223 0.222 1.4 0.242 0.247 0.244 2.0 <0.0244 <0.0244 <0.0244 NA <0.0244 Calculated Cone. (ng/mL) 0.268 0.272 0.270 1.5 1.01 1.07 1.04 5.8 <0.0250 <0.0250 <0.0250 NA 0.0285 GLP07-02-02-047 GLP07-02-02-048 DAL GW605L 0 070920 DAL GW605L DB 070920 Average %RPD 19.0 17.2 <4>18.1 1.6 28.3 27.1 ,4>27.7 1.8 28.0 29.2 m28.6 3.1 GLP07-02-02-051 DAL GWTRIP2 0 070920 <0.0249 <0.0244 <0.0250 (1) Recoveries of associated field matrix spikes were within 10030%. Sample results considered accurate to within the overall analytical method uncertainty: PFBS: 10021%; PFHS: 100+14%; PFOS: 10015%. (See Determination of Analytical Method Uncertainty section for more information.) (2) Solid sediment was present in the samples from this location. The sediments were not resuspended prior to extraction in the duplicate extraction of GLP07-02-02-026 and all other associated samples and field QC samples. (3) The low level field matrix spike recovery exceeded 10030% (131 %). The sample uncertainty has been expanded to 10050%. (4) A laboratory matrix spike of GLP07-02-02-047 was used to determine the accuracy of the sample results as the field matrix spikes were too low for the given endogenous concentration. The sample results for this location are considered accurate to within the overall analytical method uncertainty: PFBS: 10021%; PFHS: 10014%; PFOS: 10015%. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 10 of 178 3M Environmental Laboratory P0003268; Interim Report#* Table 2. Sample Results Summary ETS 8-44.0 (Direct Injection Analysis). Table 2. Sample Results Summary ETS 8-44.0 (Direct Injection Analysis). (VPFBS (VPFHS <1*PFOS First Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis Second Analysis Sample Description GLP07-02-02-001 GLP07-02-02-001 GLP07-02-02-005 GLP07-02-02-006 GLP07-02-02-005 GLP07-02-02-006 GLP07-02-02-009 GLP07-02-02-010 GLP07-02-02-009 GLP07-02-02-010 GLP07-02-02-013 GLP07-02-02-014 GLP07-02-02-013 GLP07-02-02-014 GLP07-02-02-017 GLP07-02-02-018 GLP07-02-02-017 GLP07-02-02-018 GLP07-02-02-021 GLP07-02-02-021 Sample Comment DAL GWTRIP1 0 070920 DAL GWTRIP1 0 070920 Average %RPD DAL GW 601R 0 070920 DAL GW 601R DB 070920 DAL GW 601R 0 070920 DAL GW 601R DB 070920 Average %RSDor%RPD DAL GW 601S 0 070920 DAL GW 601S DB 070920 DAL GW 601S 0 070920 DAL GW 601S DB 070920 Average %RSD or %RPD DAL GW 601L 0 070920 DAL GW 601L DB 070920 DAL GW 601L 0 070920 DAL GW 601L DB 070920 Average %RSD or %RPD DAL GW 602S 0 070920 DAL GW602S DB 070920 DAL GW 602S 0 070920 DAL GW 602S DB 070920 Average %RSD or %RPD DAL GW602LRB 070920 DAL GW 602L RB 070920 Average %RSD or %RPD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Calculated Cone. (ng/mL) Calculated Cone. (ng/mL) Calculated Cone. (ng/mL) <0.0246 <0.0246 <0.0246 NA 0.0290 0.0300 0.0336 0.0314 0.0310 6.5 0.0309 0.0305 ,4)0.0326 (4)0.0335 w0.0319 (3)<0.0245 (3><0.0245 m<0.0245 NA (3)0.0565 <3)0.0568 (3!0.0595 (3,0.0608 <3>0.0584 3.6 <3)0.0536 (3)0.0535 (3)0.0584 (3)0.0572 (3>0.0557 NR <0.0496 <0.0496 NA NR (2)n r 0.0643 0.0621 0.0632 3.5 (2)n r (2)n r (3)0.0859 (3>0.0936 0.0898 4.5 (S,NR <5,n r 3.08 3.18 193.13 2.3 4.5 16.9 16.6 20.7 20.4 18.6 12 8.6 (2,n r (2)n r 2.35 2.55 2.45 8.2 0.162 0.164 (4)0.173 (4)0.176 m0.169 4.1 <0.0246 (4)<0.0246 <4)<0.0246 NA 0.123 0.131 0.123 0.131 0.127 3.6 <0.0245 <0.0245 <0.0245 NA (2)n r 12)n r 0.422 0.477 0.450 12 (2,n r <0.0496 <0.0496 NA 3M Environmental Laboratory GLP07-Q2-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 11 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 2. Sample Results Summary ETS 8-44.0 (Direct Injection Analysis). (Continued) WPFBS mPFHS <z>PFOS First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis First Analysis First Analysis Second Analysis Second Analysis Sample Description GLP07-02-02-022 GLP07-02-02-023 GLP07-02-02-022 GLP07-02-02-023 GLP07-02-02-026 GLP07-02-02-027 GLP07-02-02-026 GLP07-02-02-027 GLP07-02-02-030 GLP07-02-02-031 GLP07-02-02-030 GLP07-02-02-031 GLP07-02-02-034 GLP07-02-02-035 GLP07-02-02-034 GLP07-02-02-035 GLP07-02-02-038 GLP07-02-02-039 GLP07-02-02-038 GLP07-02-02-039 GLP07-02-02-042 GLP07-02-02-043 GLP07-02-02-042 GLP07-02-02-043 Sample Comment DAL GW602L 0 070920 DAL GW 602L DB 070920 DAL GW602L 0 070920 DAL GW 602L DB 070920 Average %RSD DAL GW603S 0 070920 DAL GW603S DB 070920 DAL GW603S 0 070920 DAL GW 603S DB 070920 Average %RSD or %RPD DAL GW603L 0 070920 DAL GW603L DB 070920 DAL GW603L 0 070920 DAL GW 603L DB 070920 Average %RSD or %RPD DAL GW604S 0 070920 DAL GW604S DB 070920 DAL GW604S 0 070920 DAL GW 604S DB 070920 Average %RSD or %RPD DAL GW604L 0 070920 DAL GW604L DB 070920 DAL GW604L 0 070920 DAL GW604LDB 070920 Average %RSD or %RPD DAL GW605R 0 070920 DAL GW605R DB 070920 DAL GW605R 0 070920 DAL GW605R DB 070920 Average %RSD or %RPD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Calculated Cone. (ng/mL) Calculated Cone. (ng/mL) Calculated Cone. (ng/mL) 0.0912 0.0927 (4,0.0989 <4)0.0938 (4>0.0942 3.S 0.118 0.122 (4)0.119 (4)0.106 m0.116 6.1 0.0679 0.0658 (4)0.0698 (4)0.0667 0.0676 2.5 0.167 0.133 (3)0.170 (3)0.172 ^ 0.160 12 0.222 0.223 (3>0.216 (3)0.203 0.216 4.2 0.0400 0.0458 0.0411 0.0373 0.0411 8.7 0.461 0.455 (3,0.469 (3)0.471 (3)0.464 1.6 (3)0.144 (3)0.164 (3)0.141 (3)0.136 <3)0.146 8.3 (3)0.267 (3)0.271 (3,0.258 (30.261 0.264 2.3 <3)0.255 (3)0.207 (3,0.254 (3)0.265 (3>0.245 11 <3>0.280 (3,0.286 (3>0.267 (3|0.263 m0.274 3.9 l3><0.0245 (3)<0.0245 <0.0245 <0.0245 {3)<0.0245 NA (2)n r <Z)NR 1.10 1.27 1.19 14 <2)n r (2)n r 0.228 0.255 0.242 11 (2>n r (2)n r 0.198 0.191 0.195 3.6 (2)n r (2,n r 0.226 0.231 0.229 2.2 (2)n r (2)n r 0.920 0.901 0.911 2.1 f2)NR (2)n r (3)<0.0496 (3)<0.0496 m<0.0496 NA 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 12 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 2. Sample Results Summary ETS 8-44.0 (Direct Injection Analysis). (Continued) <VPFBS mPFHS (1,2>p f OS Sample Description Sample Comment Dilution Factor Calculated Cone. (ng/mL) Calculated Cone. (ng/mL) Calculated Cone. (ng/mL) First Analysis GLP07-02-02-046 DAL GW605L RB 070920 1 <0.0246 <0.0245 (2)n r Second Analysis GLP07-02-02-046 DAL GW 605L RB 070920 4 (6)<0.0980 ,6)<0.0980 (6)<0.198 First Analysis GLP07-02-02-047 DAL GW 605L 0 070920 1 (5)n r (5)n r (2)n r First Analysis GLP07-02-02-048 DAL GW605L DB 070920 1 <5)n r (5>n r (2)n r Second Analysis GLP07-02-02-047 DAL GW 605L 0 070920 4 19.7 33.9 23.6 Second Analysis GLP07-02-02-048 DALGW605L DB 070920 4 19.0 33.1 24.2 Average m19.4 m33.5 (7)23.9 %RPD 3.6 2.4 2.5 First Analysis GLP07-02-02-051 DAL GWTRIP2 0 070920 1 <0.0246 <0.0245 (2,n r Second Analysis GLP07-02-02-051 DAL GW TRIP2 0 070920 1 <0.0246 (3)<0.0245 <0.0496 Average <0.0246 m<0.0245 <0.0496 %RPD NA NA NA (1) Unless otherwise specified, the recovery of the associated field matrix spikes was within 100+30% indicating that the analytical method was appropriate for the given ground water matrix. Sample results are considered accurate to within the overall method uncertainty: 10025% (PFBS), 10024% (PFHS), and 10029% (PFOS). See Determination of Analytical Method Uncertainty section for more information. Sample results are reported to three significant figures and %RPD or %RSD to two significant figures. Additional significant figures were used to calculate the average, %RPD and %RSD. Values In the raw data may vary slightly due to rounding. (2) No PFOS results from the first analysis were reported as the data quality objectives for the targeted LOQ were not met. (3) Recovery of one or more associated field matrix spikes exceeded 10030%, but was within 10050%. Therefore, sample uncertainty expanded to 100+50%. (4) Sample injection was not bracketed by a compliant CCV injection. Sample uncertainty expanded to 10030%. See Continuing Calibration section for more information. (5) NR=Not reported. No appropriate QC (field matrix spike or lab matrix spike) was analyzed with the samples in the analytical run. Average concentration reflects results from second analysis only. (6) The second analysis unintentionally incorporated a 4-fold dilution resulting in a higher LOQ for the sample analysis. (7) A laboratory matrix spike of GLP07-02-02-047 was used to determine the accuracy of the sample results as the field matrix spikes were too low for the given endogenous concentration. The sample results for this location are considered accurate to within the overall analytical method uncertainty: 10025% (PFBS), 10024% (PFHS), and 10029% (PFOS). Test Samples/Test System Fifty-four sample bottles collected by Weston Solutions, Inc personnel were received at ambient, acceptable conditions at the 3M Environmental Laboratory on September 21,2007. The samples were logged in by 3M Environmental Laboratory personnel and placed in refrigerated storage on September 21, 2007 until they were removed for analysis. Samples were prepared for direct injection analysis first on October 1,2007 and then again on October 11, 2007. Samples were later prepared for SPE analysis on January 7, 2008. The test system for this study is "real world" groundwater samples. The samples have not been dosed with a specific lot of test substance. The table below provides the key code for given sample descriptions. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 13 of 178 3M Environmental Laboratory P0003268; Interim Reports Table 3. Sample Description Key Code. String Number String Descripton 1 General Sampling Location 2 Sample Type 3 Well Number 4 Geologic Unit/Well Type 5 Sample Type 6 Sampling Date Example DAL=Decatur, AL GW=Ground Water Example: 601 S=Epikarst Well L=Limestone (bedrock) well R=Residuum well 0=primary sample volume DB=duplicate sample RB=equipment rlnseate blank TRIP=trlp blank 070920 = September 20, 2007 Reference Substances Table 4 lists the pertinent Information regarding the reference substance used for this study. Table 4. Study Reference Substances._____ ____________________ ______________ Reference Substance PFBS PFHS mPFOS Chemical Name Perfluorobutanesulfonate Perfluorohexanesulfonate Perfluorooctanesulfonate Chemical Formula c 4f 9s o 3k * CeFuSOj'K* CeFuSOjK* Identifier CAS # 29420-49-3 CAS # 3871-99-6 CAS # 2795-39-3 Source Expiration Date Storage Conditions Chemical Lot Number TCR Number 3M 01/18/2017 Frozen Lot 2 TCR-359 3M 2/12/2017 Frozen NB# 120067-69 TCR-83 (SE036) 3M 8/31/2016 (Lot 217) 12/14/2016 (Lot 171) Frozen 217,171 (,)TCR-1166 (Lot 217) (2TCR-696 (Lot 171) Physical Description White Powder White Powder White powder Purity 97.3% 98.6% 86.9% (Lot 217) 86.4% (Lot 171) (1) TCR-1166 was used to prepare calibration standards and lab control spikes for the ETS 8-154.3 analyses (SPE). (2) TCR-696 was used to prepare the field matrix spikes, calibration standards, and lab control spikes for the ETS 8-44.0 analyses (direct inject). 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 14 o f 178 3M Environmental Laboratory P0003268; Interim ReportM Method Summaries Preparatory and Analytical Methods ETS 8-44.0 Preparation All samples, calibration standards, and associated quality control samples were prepared using the procedure outlined in ETS-8-44.0. Briefly, a 0.7 ml. (approximate) aliquot of the water sample, calibration standard, etc. was transferred to a plastic autovial for analysis. Samples were prepared for analysis on October 1, 2007 and were analyzed on October 8, 2007. During this analysis, the solvent blanks began to produce PFOS concentrations higher than the initial LOQ. Additionally, several of the PFHS field matrix spikes were producing recoveries around 130-140%. Furthermore, samples and field spikes associated with DAL GW 605L required dilution and additional QC to verify the concentration. To confirm that these observations were not instrument related and to perform the required dilutions, additional preparation and re-analysis of all samples on another instrument was conducted on October 11,2007. For the second analysis, a laboratory matrix spike was prepared for GLP07-02-02-047 by spiking a separate 10 mL aliquot with a known amount of the target analytes prior to analysis. All samples and spikes associated with location DAL GW 605L (GLP07-02-02-047 through GLP07-02-02-050) required dilution as the concentrations exceeded the upper calibration range. Sample dilution was achieved by using a 25 pL or 10 |iL injection volume against a calibration curve established with a 100 (iL injection volume (analyzed on ETSOIlie). Analysis All sample and quality control extracts were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography program, and the specific mass transitions analyzed are described in the tables below. Table 5. Instrument Parameters. Analysis Date 10/8/2007 Instrument Name ETSMaryAnn Liquid Chromatograph Agilent 1200 Guard column Betasil C8 (4.6 mm X 150 mm), 5 pm Analytical column Betasil C18 (4.6 mm X100 mm), 5 pm Injection Volume 50 pL Mass Spectrometer Applied Biosystem API 5000 Ion Source Turbo Spray Polarity Negative Software Analyst 1.4.2 10/11/2007 ETSOIlie Agilent 1100 Betasil C8 (4.6 mm X 150 mm), 5 pm Betasil C18 (4.6 mm X100 mm), 5 pm 100 pL Applied Biosystem API 4000 Turbo Spray Negative Analyst 1.4.2 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 15 of 178 3M Environmental Laboratory P0003268; Interim ReportM Table 6. Liquid Chromatography Program. Step Number Total Time (min) Flow Rate (fiL/mln) Percent A 2 mM Ammonium Acetate (aq) 0 0.00 1000 97.0 1 0.5 2 11.0 1000 1000 97.0 5.0 3 13.5 1000 5.0 4 13.6 1000 97.0 5 17.0 1000 97.0 Percent B Methanol 3.0 3.0 95.0 95.0 3.0 3.0 Table 7. Mass Transitions. Analyte Mass Transition Q1/Q3 PFBS 299/99 299/80 PFHS 399/99 399/80 PFOS 499/99 499/80 499/130 ETSMaryAnn ETS Olile Dwell Time (msec) Dwelt Time (msec) 150 125 150 125 150 125 150 125 150 125 150 125 150 125 ETS 8-154.3 (SPE) Preparation All samples, calibration standards, and associated quality control samples were prepared using the procedure outlined in ETS-8-154.3. Briefly, a 40 mL aliquot of the sample was loaded onto a pre-conditioned Waters C18 solid phase extraction (SPE) cartridge (Sep-Pak, 1.0 g, 6 cc) using a vacuum manifold. The loaded SPE cartridges were then eluted with 5 mL of methanol. This extraction procedure concentrates the samples by a factor of eight. (Initial volume = 40 mL, final volume = 5 mL). Samples were prepared for analysis on January 7, 2008 and were analyzed on January 8 10, 2008. A laboratory matrix spike was prepared for GLP07-02-02-047 by spiking a separate 40 mL aliquot with a known amount of target analytes prior to analysis. All samples and spikes associated with location DAL GW 601 L (GLP07-02-02-013 through GLP07-02-02-016) and DAL G W 605L (GLP07-02-02-047 through GLP07-02-02-050) required dilution as the concentration of one or more of the analytes exceeded the upper calibration range. Sample dilution was achieved by diluting the final extract 1:10 or 1:25 with methanol prior to analysis. The trip blank spike at approximately 25 ng/mL (GLP07-02-02-053) also required dilution. For this sample, a five-fold dilution was achieved on the instrument by injecting a 2 p.L sample volume against a calibration curve established with a 10 pL injection volume. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 16 of 178 3M Environmental Laboratory P0003268; Interim ReporiM Analysis All sample and quality control extracts were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography program, and the specific mass transitions analyzed are described in the tables below. Table 8. Instrument Parameters. Analysis Date 1/8/2008 Instrument Name ETSStan Liquid Chromatograph Agilent 1100 Guard column Betasil C8 (2.1 mm X 100 mm), 5 pm Analytical column Betas'll C18 (2.1 mm X100 mm), 5 pm Injection Volum e 10 pL Mass Spectrometer Applied Blosystem API 4000 Ion Source Turbo Spray Polarity Negative S o ftw a re Analyst 1.4.2 Table 9. Liquid Chromatography Program. Step Number Total Time (min) Flow Rate (fiL/min) Percent A 2 mM Ammonium Acetate (aq) 0 0.00 300 80.0 1 1.0 300 80.0 2 14.5 300 10.0 3 15.5 300 10.0 4 16.5 300 80.0 5 20.0 300 80.0 Percent B Methanol 20.0 20.0 90.0 90.0 20.0 20.0 Table 10. Mass Transitions. Analyte Mass Transition Q1/Q3 PFBS 299/99 PFHS 299/80 399/99 399/80 PFOS 499/99 499/80 499/130 Dwell Time (msec) 125 125 125 125 125 125 125 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 17 of 178 3M Environmental Laboratory P0003268; Interim ReporttM Analytical Results Calibration ETS 8-44.0 Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into 100 mL of reverse-osmosis purified water. A total of thirteen standards were prepared ranging from 0.025 ng/mL to 50 ng/mL (nominal concentrations). A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The correlation coefficient (r) was greater than 0.998. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed accuracy of each curve point. ETS 8-44.0 requires that each standard used to generate the final calibration should back calculate to within 10025% of the theoretical value (10030% for the LOQ standard). All calibration points used to generate the final calibration curve met this criterion. For the second analysis performed on October 11,2007, separate low and high level calibration curves for PFBS and PFHS were established to achieve a better fit of the calibration standards over a larger calibration range. The low level curves ranged from 0.025 ng/mL to 2.5 ng/mL (nominal) and the high level curves ranged from 0.075 ng/mL to 25 ng/mL (nominal). Values less than 2.5 ng/mL were arbitrarily reported using the low level curve and values greater than 2.5 ng/mL were reported using the high level curve. Results in the overlapping range of 0.075 ng/mL to 2.5 ng/mL were compared and excellent agreement was observed (%RPD <10%). ETS 8-154.3 Extracted calibration standards were prepared by spiking known amounts of methanolic stock solutions containing the target analytes into 40 mL of ASTM Type I water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of eleven spiked standards ranging from 0.025 ng/mL to 10 ng/mL (nominal) were prepared. A quadratic, 1/x weighted, calibration curve was used to fit the data for each analyte. The data were not forced through zero during the fitting process. Calculating the standard concentration using the peak area counts and the resultant calibration curve confirmed the accuracy of each curve point. Each extracted calibration standard used to generate the final calibration curve met the method calibration accuracy requirement of 10025% (LOQ standard 10030%) and included a minimum of six calibration levels. The correlation coefficients (r) were greater than 0.999 for all analytes. Limit of Quantitation (LOQ) The LOQ for this analysis, as defined in ETS-8-44.0 and ETS-8-154.3, is the lowest non zero calibration standard in the curve in which the area counts are at least twice those of the method blank(s) and meets the calibration accuracy requirement described above (10030%). Blanks Depending on the analytical method, various types of blanks were prepared and analyzed with the samples. Each blank type is described and discussed below. ETS 8-44.0 Solvent Blanks For ETS 8-44.0, several blanks of reverse-osmosis purified water were analyzed to assess system contamination and/or instrument carryover. For the direct injection analysis, the solvent blank is equivalent to a method blank. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 18 of 178 3M Environmental Laboratory P0003268; Interim Report#4 October 8, 2007 Analysis For PFBS and PFHS, the average analyte peak area counts for all solvent blanks was less than half the area counts of the calibration standard used to establish the LOQ except during the initial instrument warm-up period prior to analyzing the calibration curve or immediately after analysis of the 50 ng/mL calibration standard. For PFOS, solvent blanks analyzed early in the run exhibited area counts low enough to establish an LOQ of 0.025 ng/mL (nominal); however, as the run progressed PFOS area counts in solvent blanks Increased significantly indicating that the instrument was beginning to show signs of contamination - or that several of the blanks were contaminated. When all the solvent blanks were considered collectively, the LOQ needed to be raised to 0.25 ng/mL to meet the method criterion for the LOQ. As this elevated LOQ was not sufficient for the data quality objectives for this project, all samples and solvent blanks were re-prepared and analyzed on a different instrument on October 11, 2007. No PFOS results were reported from the October 8, 2007 analysis. October 11, 2007 Analysis For PFBS and PFHS, the average analyte peak area counts for all solvent blanks was less than half the area counts of the calibration standard used to establish the LOQ (0.025 ng/mL nominal). For PFOS, the two lowest calibration standards were deactivated to satisfy the method criterion that the average area count for all method blanks considered collectively be less than half the area counts of the LOQ standard. The resultant PFOS LOQ for the second analysis was 0.0496 ng/mL. ETS 8-154.3 Solvent Blanks Several methanol solvent blanks were analyzed to assess system contamination and/or instrument carryover for the SPE analysis. Average analyte peak area counts for all solvent blank samples were less than half the area counts of the calibration standard used to establish the LOQ. Method Blanks Seven method blanks were prepared by loading separate 40 mL of ASTM Type I water onto a C18 SPE cartridge and eluting with 5 mL of methanol using the same extraction procedure as the samples. Method blanks were prepared to evaluate the levels of background contamination in the overall extraction process (laboratory containers, SPE cartridges, etc.) The average area counts for the seven method blanks was determined and compared to the area counts of the LOQ standard. For each analyte, the average area counts of the method blanks were less than the LOQ standard - 0.025 ng/mL (nominal). Equipment Blanks Two aqueous equipment rinseate blanks were submitted as samples: GLP07-02-02-021 and GLP07-02-02-046. The 3M Environmental Laboratory provided two one-liter bottles of ASTM type I water for rinsing. The concentration of these samples was less than the established LOQ for the given analysis day for both PFBS and PFHS. For the SPE analysis, GLP07-02-02-046 produced a PFOS concentration of 0.0285 ng/mL which was very near the LOQ of 0.0250 ng/mL. Trip Blanks Prior to sample collection, two separate sample containers were filled with 450 mL of ASTM Type I water, sealed, and shipped to the sample collection site along with the empty containers. These two sample were analyzed as the field/trip blanks. The trip blank serves as an additional method blank that account for any storage conditions and/or holding time issues that the samples may experience. The resultant concentration for the two field/trip blanks was less than the established LOQ for the given analysis day for all three analytes. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 19 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Continuing Calibration During the course of the analytical sequence, several continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. For the October 8, 2007 direct inject analysis and the January 8, 2008 SPE analyses, all CCVs met the ETS 8-44.0 and ETS 8-154.3 method acceptance criteria for accuracy of 10025% recovery. A few non-compliant CCVs were observed during the October 11,2007 direct inject analysis. For PFOS, the 5.0 ng/mL calibration standard was selected as a CCV standard twice. This standard was excluded from the original calibration curve because it did not meet accuracy requirements. The area counts of the CCV injections were compared to the area counts of the original curve Injection. The first CCV produced area counts 127% of the original and the second CCV produced area counts 110% of the original injection. Since the overall method uncertainty for PFOS is 10029%, the samples bracketed by the first Injection were not assigned an expanded uncertainty as the degree of non-compliance is still within the overall method uncertainty. For PFBS and PFHS, the 5.0 ng/mL calibration standard exceeded the calibration range of the low level curve used to quantitate sample with concentrations less than 2.5 ng/mL (nominal). For PFHS, the instrument software was still able to calculate a concentration for this standard even though the concentration exceeded the upper calibration range. Although these concentrations should be considered estimates, the resultant accuracies for the CCV injections were 109% and 124% which are still within method criteria. Samples bracketed by these two injections were not assigned expanded method uncertainties for PFHS. For PFBS, the area counts of the 5.0 ng/mL CCV injections were compared to the injection of the original curve point. The first and second CCV injections produced area counts 121% and 128% of the original curve point, respectively. Samples with PFBS concentrations reported from the low level curve bracketed by the second injection were assigned an expanded sample uncertainty of 10030% If the associated field matrix spike recoveries met method criteria. The table below summarizes the non-compliant CCVs and actions taken. A method deviation can be found in Attachment D. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 20 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 11. Non-com pliant CCV Summary. Injection Number Analyte %Recovery Samples Bracketed by Non-CompHant CCVs o071011a051 PFBS mNot Calculated GLP07-02-02-009 through GLP07-02-02- 025 o071011a076 PFBS 0>Not Calculated GLP07-02-02-026 through GLP07-02-02- 041 o071011a051 PFHS (2>109% GLP07-02-02-009 through GLP07-02-02- 025 o071011a076 PFHS (2)124% GLP07-02-02-026 through GLP07-02-02- 041 O071011a051 PFOS o071011a076 PFOS p,62.4% p)53.9% GLP07-02-02-009 through GLP07-02-02- 025 GLP07-02-02-026 through GLP07-02-02- 041 Action Taken/Comment Area counts of CCV injection were 121% of the original curve point. No action taken. Samples with PFBS concentrations >2.5 ng/mL were not affected as they were reported from the high level curve. Area counts of CCV injection was 128% of the area counts of the original curve point injection. Samples with PFBS concentrations <2.5 ng/mL were assigned an expanded sample uncertainty of 10030%. Samples with PFBS concentrations >2.5 ng/mL were not affected. Concentration of CCV above the upper limit of quantitation for the low-level curve; however, the estimated accuracy was still within method criteria. No action taken for samples with PFHS concentrations <2.5 ng/mL. Samples with PFHS concentrations >2.5 ng/mL were not affected. Concentration of CCV above the upper limit of quantitation for the low-level curve; however, the estimated accuracy was still within method criteria. No action taken for samples with PFHS concentrations <2.5 ng/mL. Samples with PFHS concentrations >2.5 ng/mL were not affected. Area counts of CCV injection were 127% of the original curve point. Overall method uncertainty for PFOS is 10029%. No action taken. Area counts of CCV injection were 110% of the original curve point. Overall method uncertainty for PFOS is 10029%. No action taken. (1) Curve point selected as a CCV was not used in the final low-level calibration curve. Consequently, the concentration of the CCV exceeded the upper calibration range and a concentration value was not calculated by the software. (2) Curve point selected as a CCV was not used In the final low-level calibration curve. Consequently, the concentration of the CCV exceeded the upper calibration range. However, the software was able to calculate a concentration which should be considered an estimated value. (3) Curve point selected as CCV was originally excluded from the Initial calibration curve because it did not satisfy calibration accuracy requirements (accuracy = 48.9%). 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 21 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Lab Control Spikes (LCSs) ETS 8-44.0 Triplicate low (0.2 ng/mL nominal concentration) and high (4 ng/mL nominal concentration) lab control spikes (LCSs) were prepared each day samples were prepared. LCSs were prepared by spiking known amounts of the target analyte into separate 25 mL aliquots of reverse-osmosis purified water. The spiked water aliquots were then analyzed in the same manner as the samples. Individual LCS results, along with the average and percent RSD for each spike level are presented in the data tables below (Table 12 and Table 13). ETS 8 44.0 requires that each level of LCSs be evaluated independently and meet the following criteria: 10020% (accuracy) and RSD<20%(precision). The low level LCSs analyzed on 10/8/2007 exceeded this criterion for PFHS with an average recovery of 123%. As the overall PFHS method uncertainty is 10024%, this method non-compliance is considered to have minimal impact on the overall data quality of the results reported from this analysis. A method deviation has been issued and can be found in Attachment D. All other LCSs met method acceptance criteria. ETS 8-154.3 Replicate low (0.2 ng/mL nominal concentration) and high (5 ng/mL nominal concentration) lab control spikes were prepared and extracted with samples. LCSs were prepared by spiking known amounts of the analytes into 40 mL of ASTM Type I water to produce the desired concentration. The spiked water samples were extracted and analyzed in the same manner as the samples. Individual LCS results, along with the average and percent RSD are presented below in Table 14. ETS 8-154.3 specifies that the collective average LCS recovery should be within 10020% with a relative standard deviation (RSD)<20%. All LCS data met method criteria. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 22 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 12. Laboratory Control Spike Data: ETS 8-44.0 Analysis Date: 10/8/2007. Analysis Date: 10/8/2007 (VPFBS mPFHS mPFOS Sample Comment Sample ID Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. ICS-071001-001 0.2 ng/mL in RO water 0.197 0.221 112 0.196 0.242 124 0.199 0.202 102 LCS-071001-002 0.2 ng/mL in RO water 0.197 0.228 116 0.196 0.241 123 0.199 0.207 104 LCS-071001-003 0.2 ng/mL in RO water 0.197 0.229 116 0.196 0.243 124 0.199 0.206 104 LCS-071001-004 4 ng/mL in RO water 3.94 4.01 102 3.92 4.25 108 3.97 3.89 97.9 LCS-071001-005 4 ng/mL in RO water 3.94 4.01 102 3.92 4.24 108 3.97 4.03 102 LCS-071001-006 4 ng/mL in RO water 3.94 3.92 99.5 3.92 4.19 107 3.97 3.95 100 Average Low Level Accuracy 115 m123 103 %RSD 1.8 0.30 1.2 Average High Level Accuracy 101 108 100 %RSD 1.3 0.73 1.8 Overall Accuracy 108 116 101 %RSD 7.1 7.4 2.4 (1) Table displays rounded values for all concentration and percent recovery values (3 significant figures) and %RSD (2 significant figures). Reported values may vary slightly from the raw data. (2) Average PFHS LCS recovery for the low-level spikes exceeded method accuracy criteria of 100+20%. A method deviation has been issued. See Attachment D. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 23 of 178 3M Environmental Laboratory P0003268; Interim ReportH4 Table 13. Laboratory Control Spike Data: ETS 8-44.0 Analysis Date: 10/11/2007. Analysis Date: 10/11/2007 (1>PFBS (1IPFHS <1,PFOS Sample Comment Sample ID Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. LCS-071011-001 0.2 ng/mL in RO water 0.197 0.206 105 0.196 0.233 119 0.199 0.209 105 LCS-071011-002 0.2 ng/mL in RO water 0.197 0.198 101 0.196 0.224 114 0.199 0.197 99.0 LCS-071011-003 0.2 ng/mL in RO water 0.197 0.219 111 0.196 0.228 116 0.199 0.206 104 LCS-071011-004 4 ng/mL in RO water 3.94 4.28 109 3.92 4.07 104 3.97 4.01 101 LCS-071011-005 4 ng/mL in RO water 3.94 4.23 107 3.92 4.46 114 3.97 4.10 103 LCS-071011-006 4 ng/mL in RO water 3.94 4.49 114 3.92 4.54 116 3.97 4.53 114 Low Level LCSs 105 116 103 %RSD 5.1 2.0 3.1 High Level LCSs 110 111 106 %RSD 3.2 5.8 6.6 Combined Average 108 114 104 %RSD 4.4 4.6 5.0 (1) Table displays rounded values for all concentration and percent recovery values (3 significant figures) and %RSD (2 significant figures). Reported values may vary slightly from the raw data. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 24 of 178 3M Environmental Laboratory P0003268; Interim RepordU Table 14. Laboratory Control Spike Data: ETS 8-154.3 Analysis Date: 1/8/2008. PFBS PFHS PFOS Sample Comment Sample ID Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. Spiked Cone. (ng/mL) Calc. Cone. (ng/mL) %Rec. LCS-080107-1 LCS-080107-2 LCS-080107-3 LCS-080107-4 LCS-080107-5 LCS-080107-6 LCS-1 (0.2 ng/mL) LCS-2 (0.2 ng/mL) LCS-3 (0.2 ng/mL) LCS-4 (5.0 ng/mL) LCS-5 (5.0 ng/mL) LCS-6 (5.0 ng/mL) 0.199 0.206 103 0.195 0.207 106 0.200 0.205 102 0.199 0.216 108 0.195 0.207 106 0.200 0.207 103 0.199 0.217 109 0.195 0.206 105 0.200 0.206 103 4.99 5.06 101 4.89 5.01 103 5.01 5.18 103 4.99 5.00 100 4.89 4.84 99.1 5.01 5.15 103 4.99 4.99 100 4.89 4.96 102 5.01 5.24 105 Average 104 103 103 %RSD 3.8 2.7 0.77 (1) Table displays rounded values for all concentration and percent recovery values (3 significant figures) and %RSD (2 significant figures). Reported values may vary slightly from the raw data. 3U Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 25 of 178 3M Environmental Laboratory P0003268; Interim ReportM Sample Duplicates All sample locations were collected in duplicate; therefore, laboratory duplicates were not prepared for a given analysis except for GLP07-02-02-026 (DAL GW603S) for analysis by method ETS 8-154.3. Sample and associated field spikes from this location exhibited some solid sediments that clogged the SPE cartridge during the extraction. (Samples were thoroughly mixed prior to aliquoting the 40 mL for extraction which resuspended the visible solids.) A complete extraction of GLP07-02-02-026 was achieved, but not for the other samples from this location. GLP07-02-02-026 through GLP07-02-02-029 were then re extracted, but the samples were not shaken prior to aliquoting the 40 mL which did not resuspend the solids. The GLP07-02-02-026 dup represents the extraction where the solids were not resuspended prior to extraction. The relative percent difference (%RPD) or relative standard deviation (%RSD) for each sample and sample duplicate is provided in Tables 1, 2,16, and 17. The %RPD or %RSD for each location was less than 20%. Field Matrix Spikes (FMSs) Low level and high level field matrix spikes were collected at each sampling location to verify that the analytical method is applicable to the sample matrix. (Additional mid-level spikes were prepared for the Trip Blank spikes.) Field matrix spike recoveries within 10030% confirm that "unknown" components in the sample matrix do not interfere with the analysis of the analytes of interest. The low and high level spike concentrations varied depending on the historical concentration of the sample location. Both ETS-8-44.0 and ETS 8-154.3 state that targeted fortification levels of field matrix spike levels should be between 0.5 and 10 times the endogenous level to be used to determine the statement of accuracy for the sample results without further justification. The table below lists the final concentrations of the low and high spikes for each location. Field matrix spike recoveries are reported in the Data Summary and Discussion section below in Table 16 and Table 17. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 26 of 178 3M Environmental Laboratory P0003268; Interim Repori#4 Table 15. Field Matrix Spike Concentrations. 3MUMS Sample ID Sample Location Low Spike Concentration (ng/mL) PFBS PFHS PFOS GLP07-01-02-001 thru -004 DALGWTRIP1 0.250 0.262 0.245 GLP07-01-02-005 thru -008 DAL GW 601R 0.250 0.262 0.245 GLP07-01-02-009 thru -012 GLP07-01-02-013 thru -016 DAL GW 601S DAL GW 601L 0.250 0.250 0.262 0.262 0.245 0.245 GLP07-01-017 thru-020 DALGW602S 0.500 0.525 0.490 n)GLP07-01-021 DALGW602LRB NA NA NA GLP07-01-022 thru-025 DALGW602L 0.500 0.525 0.490 GLP07-01-026 thru -029 GLP07-01-030 thru-033 GLP07-01-034 thru-037 DALGW603S DALGW603L DALGW604S 0.250 0.250 0.250 0.262 0.262 0.262 0.245 0.245 0.245 GLP07-01-038 thru-041 DALGW604L 0.250 0.262 0.245 GLP07-01-042 thru-045 ,'*GLP07-01-046 GLP07-01-047 thru-050 DALGW605R DALGW605L RB DALGW605L 0.250 NA 0.500 0.262 NA 0.525 0.245 NA 0.490 GLP07-01-051 thru -054 DALGWTRIP2 2.50 2.62 (1) Field matrix spikes were not prepared for the equipment rinseate sample. 2.45 Mid Spte Concentration (ng/mL) PFBS PFHS PFOS 0.500 NA NA NA NA 0.525 NA NA NA NA 0.490 NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA NA 5.00 5.25 4.90 High Spte Concentration (ng/mL) PFBS PFHS PFOS 0.999 1.05 0.979 0.999 1.05 0.979 0.999 1.05 0.979 25.0 26.2 24.5 5.00 5.25 4.90 NA NA NA 5.00 5.25 4.90 2.50 2.62 2.45 2.50 2.62 2.45 0.999 1.05 0.979 5.00 5.25 4.90 0.999 1.05 0.979 NA NA NA 5.00 5.25 4.90 25.0 26.2 24.5 [Cone. FMS sample(-^T-) - (Average Cone, of Sample/Sample Dup(-- )] FMS Spike Recovery = _________________mL___________________________________ mL 100% Spike Amount (ng/mL) 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 27 of 178 3M Environmental Laboratory P0003268; Interim ReportM Laboratory Matrix Spikes (LMSs) A separate laboratory matrix spike was prepared for GLP07-02-02-047 as the two field matrix spikes prepared for this location were less than half the resultant endogenous concentration. A 100 ng/mL (nominal) spike was prepared by spiking a known amount of the target analytes into a separate aliquot of the sample. The LMS was used to assess the sample accuracy for this sample location. The LMS recovery is presented in the Data Summary and Discussion section below. [Cone. LMS sample(-iy-) - (Cone. GLP07 - 02 - 02 - 047(^9-)] LMS Spike Recovery ---------------------------- ----------------------------------------------- WL--* 100% Spike Amount (-- ) Data Summary and Discussion ETS 8-154.3 Table 16 below summarizes the ETS 8-154.3 sample results and field matrix spike (FMS) recoveries for each sample submitted. The table provides the average concentration and the relative percent difference (RPD) of the sample and sample duplicate. Results and average values are rounded to three significant figures. Percent relative difference (%RPD) values are rounded to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of 10030% demonstrate that the analytical method is appropriate for the given matrix. If the low level spike amount was less than half the resultant endogenous concentration, the FMS recovery was not reported as the spike level was not appropriate for the given sample concentration. However, if the spike concentration was greater than 10 times the endogenous concentration, the spike recoveries were calculated and reported. The spike level range of 0.5 to 10 times the endogenous concentration listed in ETS 8-154.3 is intended to be a guideline with the lower range limit a more critical factor for accurate quantitation than the upper limit. A method deviation has been issued that addresses the acceptability of reporting recoveries from spikes that exceed the upper range and can be found in Attachment D. With the exception of the low PFHS spike for DAL GW 603L, all reportable field matrix spike or lab matrix spike recoveries were within 10030%; therefore, the results were considered accurate to within the overall analytical method uncertainty of 10021% (PFBS), 10014% (PFHS) and 10015% (PFOS). See Determination o f Analytical Method Uncertainty for more information. The PFHS sample uncertainty for DAL GW 603L was expanded to 10050% to account for the 131% recovery of the low level field matrix spike. ETS 8-44.0 Table 17 below summarizes the ETS 8-44.0 direct injection sample results and field matrix spike (FMS) recoveries for each sample submitted. The table displays results from both the October 8, 2007 and October 11, 2007 analyses. The average between both direct injection analyses and the relative percent standard deviation (%RSD) for the four measurements is provided, when appropriate, for the PFBS and PFHS results. For the PFOS results, only the average and %RPD from the second analysis is provided as the results from the first analysis were not reported as data quality objectives for the LOQ were not met. The concentrations and average value are provided to three significant figures. Percent relative difference (%RPD) or relative standard deviation (%RSD) are provided to two significant figures. Because of rounding, values may vary slightly from those listed in the raw data. Field matrix spikes meeting the method acceptance criteria of 10030% demonstrate that 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 28 o f 178 3M Environmental Laboratory P0003268; Interim Report84 the analytical method is appropriate for the given matrix. If the low level spike amount was less than half the resultant endogenous concentration, the FMS recovery was not reported as the spike level was not appropriate for the given sample concentration. However, if the spike concentration was greater than 10 times the endogenous concentration, the spike recoveries were calculated and reported. The spike level range of 0.5 to 10 times the endogenous concentration listed in ETS 8-44.0 is intended to be a guideline with the lower range limit a more critical factor for accurate quantitation than the upper limit. A method deviation has been issued that addresses the acceptability of reporting recoveries from spikes that exceed the upper range and can be found in Attachment D. Samples with appropriate field matrix spike or lab matrix spike recoveries within 10030%; were considered accurate to within the overall analytical method uncertainty of 10025% (PFBS), 10024% (PFHS) and 10029% (PFOS). See Determination o f Analytical Method Uncertainty for more information. Several of the PFHS field matrix spike recoveries exceeded 10030% with recoveries consistently trending high between 130 and 150%. With the exception of DAL GW 604S (137% high spike) and DAL GW 604L (132% low spike), all PFBS field matrix spike or lab matrix spike recoveries met method acceptance criteria. Three samples exhibited non-compliant recoveries for PFOS: DAL GW 601S (59.3% low spike), DAL GW602S (65.5% low spike), and DAL GW605R (49.8% low spike, 58.4% high spike). All affected samples described above have been assigned an expanded sample uncertainty of 10050%. As discussed previously in the Continuing Calibration section, additional sample results for PFBS (footnoted) were assigned an expanded uncertainty of 10030% because they were bracketed by non-compliant CCV injections. Reanalysis of all samples confirmed the high spike recoveries for PFHS observed during the first analysis. Because several samples required uncertainty expansion, all samples were reanalyzed using the ETS 8-154.3 method where the solid phase extraction procedure seemed to minimize matrix interferences/enhancements observed during the direct injection analysis. However, when the resulting sample concentrations from the direct injection analysis are compared to those obtained by the SPE method, excellent agreement is observed in general. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 29 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 16. ETS 8-154.3 (SPE) Sample Results with Field Matrix Spike Recoveries. Table 16. ETS 8-154.3 (SPE) Results with QC. mPFBS Sample Description GLP07-02-02-001 GLP07-02-02-002 GLP07-02-02-003 GLP07-02-02-004 GLP07-02-02-005 GLP07-02-02-006 GLP07-02-02-007 GLP07-02-02-008 GLP07-02-02-009 GLP07-02-02-010 GLP07-02-02-011 GLP07-02-02-012 Sample Comment DALGWTRIP1 0 070920 DAL GW TRIP1 LS 070920 DAL GWTRIP1 MS 070920 DALGWTRIP1 HS 070920 Average %RPD DAL GW 601R 0 070920 DAL GW 601R DB 070920 DAL GW 601RLS 070920 DAL GW 601R HS 070920 Average %RPD DAL GW 601 SO 070920 DAL GW 601S DB 070920 DAL GW 601SLS 070920 DAL GW 601S HS 070920 Average %RPD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 Calculated Cone. (ng/mL) <0.0249 0.297 0.598 1.14 NA NA 0.0350 0.0352 0.333 1.21 0.0351 0.57 0.0374 0.0323 0.332 1.23 0.0349 14 %Recovery NA 119 120 115 NA NA 119 118 NA NA 119 120 ,VPFHS Calculated Cone. (ng/mL) <0.0244 0.313 0.621 1.26 NA NA 0.0579 0.0591 0.371 1.26 0.0585 2.0 0.0547 0.0531 0.372 1.31 0.0539 3.0 %Recovery NA 119 118 120 NA NA 119 114 NA NA 121 120 <'>PFOS Calculated Cone. (ng/mL) <0.0250 0.263 0.531 1.12 NA NA 0.0663 0.0668 0.323 1.11 0.0666 0.75 0.103 0.104 0.325 1.10 0.104 0.97 %Recovery NA 107 108 114 NA NA 105 106 NA NA 90.5 102 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 30 of 178 3M Environmental Laboratory P0003268; Interim ReporttU Table 16. ETS 8-154.3 (SPE) Results with QC. (Continued) Sample Description GLP07-02-02-013 GLP07-02-02-014 GLP07-02-02-015 GLP07-02-02-016 GLP07-02-02-017 GLP07-02-02-018 GLP07-02-02-019 GLP07-02-02-020 Sample Comment DAL GW 601 LO 070920 DAL GW 601L DB 070920 DAL GW 601LLS 070920 DAL GW 601L HS 070920 Average %RPD DAL GW 602S 0 070920 DAL GW602S DB 070920 DAL GW 602S LS 070920 DAL GW 602S HS 070920 Average %RPD Dilution Factor 10 10 10 10 1 1 1 1 mPFBS Calculated Cone. (ng/mL) 2.70 2.66 3.08 27.1 2.68 1.5 0.169 0.159 0.606 5.51 0.164 6.1 %Recovery NA NA NR 97.8 NA NA 88.5 107 (VPFHS Calculated Cone. (ng/mL) 15.9 16.5 17.1 40.1 16.2 3.7 0.114 0.119 0.605 5.73 0.116 4.3 %Recovery NA NA NR 91.0 NA NA 93.0 107 (1>PFOS Calculated Cone. (ng/mL) 3.10 3.29 3.52 26.2 3.20 5.9 0.498 0.547 0.895 5.69 0.522 9.4 %Recovery NA NA NR 94.0 NA NA 76.1 106 GLP07-02-02-021 DAL GW 602L RB 070920 1 <0.0249 NA <0.0244 NA <0.0250 NA GLP07-02-02-022 GLP07'02-02-023 GLP07-02-02-024 GLP07-02-02-025 DAL GW 602L 0 070920 DAL GW 602L DB 070920 DALGW 602LLS 070920 DAL GW 602L HS 070920 Average %RPD 1 0.0955 1 0.0966 1 0.669 1 5.14 0.0960 1.1 NA NA 115 101 0.397 0.411 1.01 5.96 0.404 3.5 NA NA 115 106 1.37 1.38 1.89 6.71 1.37 1.4 NA NA 104 109 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 31 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 16. ETS 8-154.3 (SPE) Results with QC. (Continued) Sample Description GLP07-02-02-026 GLP07-02-02-026 dup GLP07-02-02-027 GLP07-02-02-028 GLP07-02-02-029 GLP07-02-02-030 GLP07-02-02-031 GLP07-02-02-032 GLP07-02-02-033 GLP07-02-02-034 GLP07-02-02-035 GLP07-02-02-036 GLP07-02-02-037 Sample Comment DAL GW 603S 0 070920 DAL GW 603S 0 070920 DAL GW 603S DB 070920 DALGW603S LS 070920 DAL GW 603S HS 070920 Average %RSD DAL GW 603L 0 070920 DAL GW603L DB 070920 DAL GW603L LS 070920 DAL GW 603L HS 070920 Average %RPD DAL GW 604S 0 070920 DAL GW 604S DB 070920 DAL GW 604S LS 070920 DAL GW604S HS 070920 Average %RPD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 1 mPFBS Calculated Cone. (ng/mL) 0.133 (2)0.118 0.131 0.420 2.88 0.127 6.4 0.0723 0.0676 0.361 2.75 0.0700 6.6 0.171 0.174 0.456 1.36 0.172 1.7 %Recovery NA NA NA 117 110 NA NA 116 108 NA NA 114 119 mPFHS Calculated Cone. (ng/mL) 0.135 |2)0.126 0.135 0.436 3.16 0.132 3.9 0.235 0.227 0.575 3.20 m0.230 3.5 0.220 0.223 0.539 1.44 0.222 1.4 "/Recovery NA NA NA 116 115 NA NA |3>131 113 NA NA 121 116 mPFOS Calculated Cone. (ng/mL) 0.285 t2|0.275 0.300 0.510 2.68 0.287 4.4 0.225 0.219 0.499 2.79 0.222 2.7 0.268 0.272 0.487 1.24 0.270 1.5 %Recovery NA NA NA 91.2 97.8 NA NA 113 105 NA NA 88.6 99.1 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 32 of 178 3M Environmental Laboratory P0003268; Interim Repor&4 Table 16. ETS 8-154.3 (SPE) Results with QC. (Continued) Sample Description GLP07-02-02-038 GLP07-02-02-039 GLP07-02-02-040 GLP07-02-02-041 GLP07-02-02-042 GLP07-02-02-043 GLP07-02-02-044 GLP07-02-02-045 Sample Comment DAL GW 604L 0 070920 DALGW604L DB 070920 DAL GW604L LS 070920 DAL GW 604L HS 070920 Average %RPD DAL GW 605R 0 070920 DAL GW 605R DB 070920 DAL GW 605R LS 070920 DAL GW605R HS 070920 Average %RPD Dilution Factor 1 1 1 1 1 1 1 1 mPFBS Calculated Cone. (ng/mL) 0.216 0.214 0.488 5.34 0.215 0.93 0.0476 0.0425 0.326 1.22 0.0450 11 %Recoveiy NA NA 109 103 NA NA 112 118 mPFHS Calculated Cone. (ng/mL) 0.242 0.247 0.554 5.84 0.244 2.0 <0.0244 <0.0244 0.305 1.20 <0.0244 NA %Recovery NA NA 118 106 NA NA 116 114 mPFOS Calculated Cone. (ng/mL) 1.01 1.07 1.28 5.98 1.04 5.8 <0.0250 <0.0250 0.173 0.899 <0.0250 NA %Recovery NA NA NR 101 NA NA 70.7 91.8 GLP07-02-02-046 DAL GW 605L RB 070920 1 <0.0249 NA <0.0244 NA 0.0285 NA GLP07-02-02-047 GLP07-02-02-048 GLP07-02-02-049 GLP07-02-02-050 GLP07-02-02-047 LMS DAL GW 605L 0 070920 DAL GW 605L DB 070920 DAL GW 605LLS 070920 DAL GW 605L HS 070920 DAL GW 605L 0 070920 Average %RPD 10 19.0 NA 10 17.2 NA 10 17.5 NR 10 18.1 NR 25 122 ,4)103 <4>18.1 1.6 28.3 NA 28.0 27.1 NA 29.2 26.6 NR 28.3 26.8 NR 29.0 120 (4)93.8 125 27.7 28.6 1.8 3.1 NA NA NR NR ,4)96.9 3M Environmental Laboratory GLPQ7-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 33 of 178 3M Environmental Laboratory P0003268; Interim Reportit4 Table 16. ETS 8-154.3 (SPE) Results with QC. (Continued) Sample Description GLP07-02-02-051 GLP07-02-02-052 (5|GLP07-02-02-054 ,s,GLP07-02-02-053 Sample Comment DAL GW TRIP2 0 070920 DAL GW TRIP2 LS 070920 DAL GW TRIP2 HS 070920 DAL GWTRIP2 MS 070920 Dilution Factor 1 1 1 5 (1,PFBS Calculated Cone. (ng/mL) <0.0249 2.64 (5,5.26 (S,21.5 %Recovery NA 106 105 86.1 <VPFHS Calculated Cone. (ng/mL) <0.0244 2.85 (5,5.57 (5)26.3 %Recovery NA 108 106 100 WpFOS Calculated Cone. (ng/mL) <0.0250 2.65 |5)5.38 (S|26.0 %Recovery NA 108 110 106 (1) Except when otherwise specified, recoveries of associated field matrix spikes were within 10030%. Sample results considered accurate to within the overall analytical method uncertainty: PFBS: 10021%; PFHS: 10014%; PFOS: 10015% (See Determination of Analytical Method Uncertainty section for more information.) (2) Solid sediment was present in the samples from this location. The sediments were not re-suspended prior to extraction in the duplicate extraction of GLP07-02-02-026 and all other associated samples and field QC samples (GLP07-02-02-027 through GLP07-02-02-029). (3) The low level field matrix spike recovery exceeded 10030% (131%). The sample uncertainty has been expanded to 100+50%. (4) A laboratory matrix spike of GLP07-02-02-047 was used to determine the accuracy of the sample results as the field matrix spikes were too low for the given endogenous concentration. The sample results for this location are considered accurate to within the overall analytical method uncertainty: PFBS: 10021%, PFHS: 10014%; PFOS: 10015%. (5) Sample descriptions for GLP07-02-02-053 and -054 were mislabeled when entered into the LIMS system. The sample bottle assigned to GLP07-02-02-053 contained the high level spike and the bottle assigned to GLP07-02-02-054 contained the mid level spike according to the 3M Environmental Lab label affixed to the bottle during bottle preparation. NR=Not reportable. Spike level was less than half the endogenous concentration and not considered appropriate for the given sample. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 34 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with Field Matrix Spike Recoveries. Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (V PFBS (V PFHS Sample Name First Analysis 10/8/2007 Second Analysis 10/11/2007 First Analysis 10/8/2007 Second Analysis 10/11/2007 Sample Description Sample Comment GLP07-02-02-001 GLP07-02-02-002 GLP07-02-02-003 GLP07-02-02-004 GLP07-02-02-001 GLP07-02-02-002 GLP07-02-02-003 GLP07-02-02-004 DAL GWTRIP1 0 070920 DAL GWTRIP1 LS 070920 DAL GWTRIP1 MS 070920 DAL GWTRIP1 HS 070920 DAL GWTRIP1 0 070920 DAL GWTRIP1 LS 070920 DAL GWTRIP1 MS 070920 DAL GWTRIP1 HS 070920 GLP07-02r02-005 GLP07-02-02-006 GLP07-02-02-007 GLP07-02-02-008 GLP07-02-02-005 GLP07-02-02-006 GLP07-02-02-007 GLP07-02-02-008 Average %RSD DAL GW 601R 0 070920 DAL GW 601R DB 070920 DAL GW 601R LS 070920 DAL GW 601R HS 070920 DAL GW 601R 0 070920 DAL GW 601R DB 070920 DAL GW 601RLS 070920 DAL GW 601R HS 070920 Average %RSD or %RPD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Calculated Cone. (ng/mL) <0.0246 0.284 0.576 1.15 <0.0246 0.292 0.559 1.28 <0.0246 NA 0.0290 0.0300 0.317 1.13 0.0336 0.0314 0.330 1.15 0.0310 6.5 `/,,Recovery NA 114 115 115 NA 117 112 128 NA NA 115 110 NA NA 119 112 Calculated Cone. (ng/mL) <0.0245 |3)0.347 13)0.691 (3)1.42 <0.0245 |3|0.344 |3|0.706 |3|1.38 m<0.0245 NA 0.0565 0.0568 0.398 |3)1.43 0.0595 0.0608 |3|0.400 (3) 1.47 m0.0584 3.6 %Recovery NA 0 )132 (5 )1 3 2 |3,135 NA <3,131 (3|134 (3|131 NA NA 130 <3)131 NA NA (3|129 (3*134 (1,2} PFOS Calculated Cone. (ng/mL) <2,n r |2)n r (2)n r (2,n r <0.0496 0.288 0.531 1.24 <0.0496 NA (2)n r (2|n r ,2)n r (2|n r 0.0643 0.0621 0.305 1.01 0.0632 3.5 `/,,Recovery NA NA NA NA NA 118 108 127 NA NA NA NA NA NA 98.8 96.7 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 35 of 178 3M Environmental Laboratory P0003268; Interim RepordU Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (Continued) Sample Name First Analysis 10/8/2007 Second Analysis 10/11/2007 First Analysis 10/8/2007 Second Analysis 10/11/2007 Sample Description Sample Comment GLP07-02-02-009 GLP07-02-02-010 GLP07-02-02-011 GLP07-02-02-012 GLP07-02-02-009 GLP07-02-02-010 GLP07-02-02-011 GLP07-02-02-012 GLP07-02-02-013 GLP07-02-02-014 GLP07-02-02-015 GLP07-02-02-016 GLP07-02-02-013 GLP07-02-02-014 GLP07-02-02-015 GLP07-02-02-016 DAL GW 601 SO 070920 DAL GW 601S DB 070920 DAL GW 601S LS 070920 DAL GW 601S HS 070920 DAL GW 601 SO 070920 DAL GW 601S DB 070920 DAL GW601SLS 070920 DAL GW 601S HS 070920 Average %RSD DAL GW 601L0 070920 DAL GW 601L DB 070920 DAL GW 601LLS 070920 DAL GW601L HS 070920 DAL GW 601L0 070920 DAL GW 601L DB 070920 DAL GW 601 LLS 070920 DAL GW 601L HS 070920 Average %RSD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 2 1 1 1 4 (V PFBS Calculated Cone. (ng/mL) 0.0309 0.0305 0.324 1.20 |4)0.0326 <4|0.0335 |4|0.339 ,4|1.31 0.0319 4.5 <5,n r (5)n r IS)NR |5)>u lo q 3.08 3.18 3.23 29.9 fS)3.13 3.2 %Recovery NA NA 117 117 NA NA 123 128 NA NA NR NA NA NA NR 107 m PFHS Calculated Cone. (ng/mL) 0.0536 0.0535 |3)0.400 (3)1.47 0.0584 0.0572 |3|0.409 |3)1.47 (3|0.0557 4.5 16.9 16.6 16.9 48.5 20.7 20.4 21.1 51.4 18.6 12 %Recovery NA NA (3)132 (3|135 NA NA (3|134 |3)134 NA NA NR 121 NA NA NR 118 (ulPFOS Calculated Cone. (ng/mL) (2|n r |2|n r (2,n r (2|n r (S)0.0859 (8)0.0936 0.235 0.923 m0.0898 8.6 t2|NR |2|NR (2)n r |2|n r 2.35 2.55 2.78 28.8 2.45 8.2 %Recovery NA NA NA NA NA NA |3|59.3 85.1 NA NA NA NA NA NA NR 108 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 36 of 178 3M Environmental Laboratory P0003268; Interim ReportH4 Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (Continued) Sample Name First Analysis 10/8/2007 Second Analysis 10/11/2007 First Analysis Second Analysis Sample Description Sample Comment GLP07-02-02-017 GLP07-02-02-018 GLP07-02-02-019 GLP07-02-02-020 GLP07-02-02-017 GLP07-02-02-018 DAL GW 602S 0 070920 DAL GW602S DB 070920 DAL GW 602S LS 070920 DAL GW602S HS 070920 DAL GW 602S0 070920 DAL GW 602S DB 070920 GLP07-02-02-019 GLP07-02-02-020 GLP07-02-02-021 GLP07-02-02-021 DAL GW 602S LS 070920 DALGW602S HS 070920 Average %RSD DAL GW 602L RB 070920 DAL GW 602L RB 070920 Dilution Factor 1 1 1 1 1 1 1 1 1 1 (1) PFBS Calculated Cone. (ng/mL) 0.162 0.164 0.613 5.39 <4|o.173 (4|0.176 (4)0.648 5.67 w0.169 4.1 <0.0246 (4|<0.0246 %Recovery NA NA 90.0 105 NA NA 94.8 110 NA NA (V PFHS Calculated Cone. (ng/mL) 0.123 0.131 0.665 6.32 0.123 0.131 0.644 6.87 0.127 3.6 <0.0245 <0.0245 "/,,Recovery NA NA 103 118 NA NA 98.5 128 NA NA (1,2) PFOS Calculated Cone. (ng/mL) |2|n r (2|n r (2)n r (2)n r 0.422 0.477 (3|0.770 4.45 m0.450 12 (2|n r <0.0496 %Recovery NA NA NA NA NA NA (3|65.5 81.7 NA NA First Analysis GLP07-02-02-022 DAL GW 602L 0 070920 1 0.0912 10/8/2007 GLP07-02-02-023 DAL GW 602L DB 070920 1 0.0927 GLP07-02-02-024 DAL GW602L LS 070920 1 0.646 GLP07-02-02-025 DAL GW602L HS 070920 1 5.22 Second Analysis GLP07-02-02-022 DAL GW 602L 0 070920 1 (4)0.0989 10/11/2007 GLP07-02-02-023 DAL GW602L DB 070920 1 (4)0.0938 GLP07-02-02-024 DAL GW602LLS 070920 1 (4|0.672 GLP07-02-02-025 DAL GW602L HS 070920 1 6.14 Average <4>0.0942 %RSD 3.5 NA NA 111 103 NA NA 115 121 0.461 0.455 1.11 6.40 0.469 0.471 <3)1.21 (3)7.54 0.464 1.6 NA NA 124 113 NA NA (3 )1 4 1 (3)135 (2|n r |2)n r (2,n r <2|n r 1.10 1.27 1.57 5.66 1.19 14 NA NA NA NA NA NA 78.6 91.4 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 37 of 178 3M Environmental Laboratory P0003268; Interim ReportM Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (Continued) (V PFBS Sample Name First Analysis 10/8/2007 Second Analysis 10/11/2007 First Analysis 10/8/2007 Second Analysis 10/11/2007 Sample Description Sample Comment GLP07-02-02-026 GLP07-02-02-027 GLP07-02-02-028 GLP07-02-02-029 DAL GW 603S 0 070920 DAL GW603S DB 070920 DAL GW603S LS 070920 DAL GW603S HS 070920 GLP07-02-02-026 GLP07-02-02-027 GLP07-02-02-028 GLP07-02-02-029 GLP07-02-02-030 GLP07-02-02-031 GLP07-02-02-032 GLP07-02-02-033 GLP07-02-02-030 GLP07-02-02-031 GLP07-02-02-032 GLP07-02-02-033 DAL GW603S 0 070920 DAL GW603S DB 070920 DAL GW603S LS 070920 DAL GW603S HS 070920 Average %RSD DAL GW 603L 0 070920 DAL GW603L DB 070920 DAL GW603LLS 070920 DAL GW603LHS 070920 DAL GW 603L 0 070920 DAL GW603L DB 070920 DAL GW 603LLS 070920 DAL GW603LHS 070920 Average %RSD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Calculated Cone. (ng/mL) 0.118 0.122 0.409 2.93 |4,0.119 |4)0.106 (4)0.382 3.12 <4>0.116 6.1 0.0679 0.0658 0.367 2.90 (4|0.0698 (4)0.0667 |4|0.394 (4|2.14 ,4,0.0676 2.5 %Recovery NA NA 116 113 NA NA 108 120 NA NA 120 113 NA NA 130 83.0 (V PFHS Calculated Cone. (ng/mL) 0.144 0.164 <3,0.511 3.48 0.141 0.136 0.461 |3,3.66 p,0.146 8.3 0.267 0.271 |3|0.652 |3|3.75 0.258 0.261 |3|0.641 2.95 m0.264 2.3 %Recovery NA NA ,3)136 127 NA NA 123 (3)134 NA NA |3)146 <3)133 NA NA ,3|145 102 (1 2 ) PFOS Calculated Cone. (ng/mL) <2)NR (2)n r |2)n r (2)n r 0.228 0.255 0.421 2.29 0.242 11 (2)n r |2)n r (2|n r (2|n r 0.198 0.191 0.433 2.00 0.105 3.6 %Recovery NA NA NA NA NA NA 73.3 83.7 NA NA NA NA NA NA 97.4 73.8 3U Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 38 of 178 3M Environmental Laboratory P0003268; Interim Report&4 Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (Continued) (VPFBS Sample Name First Analysis 10/8/2007 Second Analysis 10/11/2007 First Analysis 10/8/2007 Second Analysis 10/11/2007 Sample Description Sample Comment GLP07-02-02-034 GLP07-02-02-035 GLP07-02-02-036 GLP07-02-02-037 GLP07-02-02-034 GLP07-02-02-035 GLP07-02-02-036 GLP07-02-02-037 GLP07-02-02-038 GLP07-02-02-039 GLP07-02-02-040 GLP07-02-02-041 GLP07-02-02-038 GLP07-02-02-039 GLP07-02-02-040 GLP07-02-02-041 DAL GW 604S 0 070920 DAL GW604S DB 070920 DAL GW604S LS 070920 DAL GW 604S HS 070920 DAL GW 604S 0 070920 DAL GW604S DB 070920 DAL GW604S LS 070920 DALGW604S HS 070920 Average %RSD DAL GW 604L 0 070920 DAL GW 604L DB 070920 DAL GW 604LLS 070920 DAL GW 604L HS 070920 DAL GW 604L 0 070920 DAL GW 604L DB 070920 DAL GW 604L LS 070920 DAL GW604L HS 070920 Average %RSD Dilution Factor 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Calculated Cone. (ng/mL) 0.167 0.133 0.473 1.36 |3|0.170 |3)0.172 0.465 1.54 m0.160 12 0.222 0.223 0.518 5.52 (3|0.216 (3|0.203 0.538 6.41 m0.216 4.2 "/Recovery NA NA 129 121 NA NA 118 |3)137 NA NA 118 106 NA NA |3)132 124 (VPFHS Calculated Cone. (ng/mL) 0.255 0.207 |3)0.617 (3)1.69 0.254 0.265 |3)0.626 |3)1.80 m0.24S 11 0.280 0.286 0.634 6.73 0.267 0.263 (3,0.642 |3)7.60 (3>0.274 3.9 "/Recovery NA NA (3)147 <3)139 NA NA |3)140 (3)147 NA NA |3)134 123 NA NA (3)144 |3)140 (U)PFOS Calculated Cone. (ng/mL) (2|n r (2)n r (2)n r |2)n r 0.226 0.231 0.404 1.04 0.229 2.2 (2)n r (2,n r (2)n r (2|n r 0.920 0.901 1.04 5.07 0.911 2.1 %Recovery NA NA NA NA NA NA 71.7 82.9 NA NA NA NA NA NA NR 85.0 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 39 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (Continued) (V PFBS Sample Name First Analysis 10/8/2007 Second Analysis 10/11/2007 First Analysis Second Analysis First Analysis 10/8/2007 Second Analysis 10/11/2007 Sample Description Sample Comment GLP07-02-02-042 GLP07-02-02-043 GLP07-02-02-044 GLP07-02-02-045 GLP07-02-02-042 GLP07-02-02-043 GLP07-02-02-044 GLP07-02-02-045 GLP07-02-02-046 GLP07-02-02-046 GLP07-02-02-047 GLP07-02-02-048 GLP07-02-02-049 GLP07-02-02-050 GLP07-02-02-047 GLP07-02-02-048 GLP07-02-02-049 GLP07-02-02-050 GLP07-02-02-047 LMS DAL GW 605R 0 070920 DAL GW 605R DB 070920 DAL GW 605RLS 070920 DAL GW605R HS 070920 DAL GW 605R 0 070920 DAL GW 605R DB 070920 DAL GW605R LS 070920 DALGW 605RHS 070920 Average %RSD DALGW605L RB 070920 DAL GW 605L RB 070920 DAL GW 605L0 070920 DALGW605L DB 070920 DAL GW 605L LS 070920 DAL GW 605L HS 070920 DAL GW 605L 0 070920 DAL GW605L DB 070920 DAL GW 605LLS 070920 DAL GW605L HS 070920 DALGW605L HS 070920 Average %RPD Dilution Factor 1 1 1 1 1 1 1 1 1 4 1 1 1 1 4 4 4 4 Calculated Cone. (ng/mL) 0.0400 0.0458 0.342 1.27 0.0411 0.0373 0.238 1.04 0.0411 8.7 <0.0246 (6)<0.0980 |S,NR (5)n r |S)NR (5)n r m19.7 ,7|19.0 19.5 19.6 10 125 <5J`19.4 3.6 "/Recovery NA NA 120 123 NA NA 79.6 100 NA NA NA NA NA NA NA NA NR NR (7|107 (V PFHS Calculated Cone. (ng/mL) <0.0245 <0.0245 <3)0.358 (3)1.48 <0.0245 <0.0245 0.252 1.25 <0.0245 NA <0.0245 (6,<0.0980 <5|n r (5|n r |5|n r |5|n r m33.9 (7|33.1 32.3 32.5 %Recovery NA NA ,3)136 (3|140 NA NA 96.0 119 NA NA NA NA NA NA NA NA NR NR 153 <57>33.S 2.4 ,7)122 <1,2} PFOS Calculated Cone. (ng/mL) (2|n r <2|n r <2|n r |2|n r <0.0496 <0.0496 (3)0.122 |3,0.572 (3)<0.0496 NA <2,n r (6)<0.198 (2|n r <2|n r (2|n r |2|n r <7)23.6 m24.2 22.8 23.4 /Recovery NA NA NA NA NA NA (3)49.8 (3)58.4 NA NA NC NC NC NC NA NA NR NR 133 17123.9 2.5 |7,110 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 40 of 178 3M Environmental Laboratory P0003268; Interim Repori#4 Table 17. ETS 8-44.0 (Direct Inject Analyses) Sample Results with QC. (Continued) ft)PFBS ft)PFHS f1,Z)PFOS Sample Name Sample Description Sample Comment Dilution Factor Calculated Cone. (ng/mL) %Recovery Calculated Cone. (ng/mL) "/Recovery Calculated Cone. (ng/mL) %Recovery First Analysis GLP07-02-02-051 DAL GW TRIP2 0 070920 1 <0.0246 NA <0.0245 NA |2)n r NA 10/8/2007 GLP07-02-02-052 DAL GWTRIP2 LS 070920 1 2.77 111 3.24 123 (2|n r NA (8|GLP07-02-02-054 DAL GWTRIP2 HS 070920 2 (8|5.61 112 (8)6.67 127 (2|n r NA (8|GLP07-02-02-053 DAL GWTRIP2 MS 070920 1 (8)>u lo q NC (8)>u lo q NC |2)n r NA Second Analysis GLP07-02-02-051 DAL GWTRIP2 0 070920 1 <0.0246 NA <0.0245 NA <0.0496 NA 10/11/2007 GLP07-02-02-052 DAL GWTRIP2LS 070920 1 3.08 123 (3)3.59 |3)137 2.94 120 (8)GLP07-02-02-054 (8)GLP07-02-02-053 DAL GWTRIP2 HS 070920 DAL GWTRIP2 MS 070920 4 4 6.45 28.3 129 (3)7.60 ,3)145 6.09 113 (3|37.2 (31142 28.2 124 115 Average <0.0246 Pl<0.0245 <0.0496 %RPD NA NA NA (1) Unless otherwise specified, the recovery of the associated field matrix spikes was within 10030% indicating that the analytical method was appropriate for the given ground water matrix. Sample results are considered accurate to within the overall method uncertainty:10025% (PFBS), 10024% (PFHS), and 10029% (PFOS). See Determination of Analytical Method Uncertainty section for more information. Sample results are reported to three significant figures and %RPD to two significant figures. Additional significant figures were used to calculate the average, %RPD, %RSD, and %recovery. Values in the raw data may vary slightly due to rounding. (2) NR=Not reportable. No PFOS results from the first analysis were reported as the data quality objectives for the targeted LOQ were not met. (3) Recovery of one or more associated field matrix spikes exceeded 10030%, but was within 10050%. Therefore, sample uncertainty expanded to 10050%. (4) Sample injection was not bracketed by a compliant CCV injection. Sample uncertainty expanded to 10030%. See Continuing Calibration section for more information. (5) NR=Not reportable as no appropriate QC (field matrix spike or lab matrix spike) was analyzed with the samples in the analytical run. The reported average sample concentration reflects the results from the second analysis only. (6) The second analysis unintentionally incorporated a 4-fold dilution resulting in a higher LOQ for the sample analysis. (7) A laboratory matrix spike of GLP07-02-02-047 was used to determine the accuracy of the sample results as the field matrix spikes were too low for the given endogenous concentration. The sample results for this location are considered accurate to within the overall analytical method uncertainty: 10025% (PFBS), 100+24% (PFHS), and 10029% (PFOS). (8) Sample descriptions for GLP07-02-02-053 and -054 were mislabeled when entered into the LIMS system. The sample bottle assigned to GLP07-02-02-053 contained the high level spike and the bottle assigned to GLP07-02-02-054 contained the mid level spike according to the 3M Environmental Lab label affixed to the bottle during bottle preparation. >ULOQ = greater than the upper limit of quantitation. NC = Not calculated. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 41 of 178 3M Environmental Laboratory P0003268; Interim ReporiM Statistical Methods and Calculations Statistical methods used to interpret sample results include averages and standard deviations. The Analyst software programs calculated sample concentrations using resultant analyte peak areas and the established quadratic, 1/x weighted, calibration curve. Sample calculations and equations used to report method accuracy and precision are described below. Accuracy and Precision Equations ,LCS _Percen.t _Recovery = -C--a--lc--u--la--t-e-d---C--o--n--c-e--n-t-r-a--t-i-o-n- 100% Spike Concentration o%/RDSoDn(/RDeilat -tive So.tandjard, Dn evi.a.t.ion.) = -s-t-a--n--d-a--r-d--d--e--v-i-a--t-io--n--o--f--r-e-p- -li-c--a-t-e--s-* 100% replicate average 0%/ DRPr .D^(/Rneil.a-tive Pr,ercen.t Difference), ---A--b-s--o--lu--t-e--d--i-f-fe--r-e--n--c-e---b-e--t-w--e--e-n---s-a--m--p--le---d-u- p-l-i-c-a--t-e--s-*.1. 0. 0. .%. average sample concentration Determination of Analytical Method Uncertainty The analytical method uncertainty for PFBS, PFHS, and PFOS was determined using historical data that was control charted to evaluate the method accuracy and precision. (Analytical method uncertainty and control chart procedures are outlined in ETS 12-12.2 "Estimation of Uncertainty of Measurements" and ETS 4-026.2 "Control Charts for Laboratory Analyses". The control chart for ETS-8-044.0 and ETS-8-154.3 consists of all laboratory control spike recoveries (in %) for data generated and reported using the given method. The last fifty historical data points (including the points generated in this study) were extracted from the control chart and the overall average and standard deviation were determined for each analyte. The expanded uncertainty was then determined by multiplying the standard deviation by a factor of 2, which corresponds to the 95% confidence level. This expanded analytical method uncertainty (95% confidence level) was used to assign the overall analytical method uncertainty to the final results presented in Tables 1,2,16, and 17. Table 18. Method Uncertainties for ETS-8-154.3. Analyte PFBS Average LCS Recovery (last 50 points) 100% Standard Deviation of LCS Recoveries 10.5% 2* Standard Deviation of LCS Recoveries 21.0% Reported Analytical Method Uncertainty 10021% PFHS 97.5% 7.12% 14.2% 10014% PFOS 99.3% 7.52% 15.0% 10015% 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 42 of 178 3M Environmental Laboratory P0003268; Interim ReportM Table 19. Method Uncertainties for ETS-8-44.0. Analyte PFBS Average LCS Recovery (last 50 points) 103% Standard Deviation of LCS Recoveries 12.4% 2* Standard Deviation of LCS Recoveries 24.8% Reported Analytical Method Uncertainty 10025% PFHS 108% 12.0% 24.0% 10024% PFOS 115% 14.0% 28.0% 10028% Statement of Conclusion Sample results were summarized in Table 1 and Table 16 (ETS 8-154.3 SPE) and Table 2 and Table 17 (ETS 8-44.0 Direct Inject). Historical lab control spike recoveries recorded in the method's control chart were used to determine the overall analytical method uncertainty. Sample results with field matrix spike recoveries within 10030% were considered to be accurate within the stated method uncertainty. Samples with field spike recoveries exceeding 10030% were assigned an expanded uncertainty of 10050%. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 43 of 178 3M Environmental Laboratory PO003268; Interim ReporttM References ETS 8-44.0 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis". 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". ETS 12-012.2 "Estimation of Uncertainty of Measurements". ETS 4-026.2 "Control Charts for Laboratory Analyses". List of Attachments Attachment A: Selected Chromatograms and Calibration Curves Attachment B: Extraction and Analytical Methods Attachment C: Protocol and Protocol Amendments Attachment D: Protocol and/or Method Deviations 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 44 of 178 Signatures 3M Environmental Laboratory P0003268; Interim Reporttt4 ----------------- ------------------------------------------- g * William K. Reagen, Ph.D. 3M Environmental Laboratory Manager Date 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 45 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Attachment A: Sample Chromatograms and Calibration Curves 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 46 of 178 V1660305 3M Environmental Laboratory P0003268; Interim Report#4 Results Name: s080108a.rdb V1660305 Results Name: s080108a.rdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 47 of 178 Stan V166030S 3M Environmental Laboratory P0003268; Interim Report#* Results Name: s080108a.rdb 'Stan V1660305 Results Name: sOSOlOSa.tdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 48 of 178 V1660305 3M Environmental Laboratory P0003268; Interim Report#4 Resulta Name: s080108a.rdb V1660305 Results Name: s080108a.rdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 49 of 178 Stan V1660305 3M Environmental Laboratory P0003268; Interim Report#4 Results Name: s080108a.tdb " Stan V166Q30S Results Name; aQ8Ql08a.tdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 50 of 178 "Stan VI660305 3M Environmental Laboratory P0003268; Interim ReportM Results Name: aOBOlOBa.rdb Stan VI660305 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 51 of 178 scan V16603S 3M Environmental Laboratory P0003268; Interim Report#4 Results Name! s080108a.rdb 'scan VI660305 Results Name: s080108a.rdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 52 of 178 V1660305 3M Environmental Laboratory P0003268; Interim Report#4 V1660305 Results Name: sOBOl08a.tdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 53 of 178 Stan V1660305 3M Environmental Laboratory P0003268; Interim Report#4 VI660305 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 54 of 178 V1660305 3M Environmental Laboratory P0003268; Interim Reports V166035 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 55 of 178 V1660305 3M Environmental Laboratory P0003268; Interim Report#4 Results Name: s080108a.rdb Stan V1660305 Results Name: 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 56 of 178 in V1660305 3M Environmental Laboratory P0003268; Interim Report#4 Results Name! s080106a.rdb Stan V1660305 Results Name: s080108a.rdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 57 of 178 VI660305 3M Environmental Laboratory P0003268; Interim ReporW4 Results Nene: sOSOlOSa.tdb 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 58 o f 178 **Stan V1660305 3M Environmental Laboratory P0003268; Interim Report#4 Results Name: s080108a.rdb 3M Environmental Laboratory Printing Date: Wednesday, February 06, 2008 GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 59 of 178 **Stan V1660305 3M Environmental Laboratory P0003268; Interim Report84 Results Name: s080108a.rdb Page 1 of 1 3M Environmental Laboratory Printing Time: 2:42:30 PM Printing Date; Wednesday, February 06, 2008 GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 60 of 178 Stan V1660305 3M Environmental Laboratory P0003268; Interim ReporbU Results Name: s080108a.rdb Page 1 Qf 1 3M Environmental Laboratory Printing Time: 2:43:54 PM Printing Date: Wednesday, February 06, 2008 GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 61 of 178 3M Environmental Laboratory P0003268; Interim Report#* Attachment B: Extraction and A nalytical Methods 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 62 of 178 US if current, for 1.\ cays from 0.n 6/2:0 0 ? 3M Environmental Laboratory P0003268; Interim Report#4 3M Environmental 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 L j ^ f o " ] Approved By: William K. Reagen, Laboratory Manager 'O 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 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 63 o f 178 Document may am use? if current, for 14 days from 04/16/200? 3M Environmental Laboratory P0003268; Interim Reporttf4 1 Scope and Application This method is to be used to quantity Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Add (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (PFUnA), PerfluorododecanoicAcid (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 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 64 of 178 Document rnay be use*! if ctmomm for 14 days from 04/16; 3M Environmental Laboratory P0003268; Interim Reports 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 rfthe 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 lim it 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 lim it 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 o f 11 Method of Analysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 65 of 178 Document may fo: used, if current, for 14 days from 04/16/2007 3M Environmental Laboratory P0003268; interim ReportfU 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 o f Analysis fo r the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 66 of 178 Doch if - ' n 3M Environmental Laboratory P0003268; Interim ReportM Parts and supplies that contain Teflon should be avoided or minimized due to the possibility of interference and/or contamination. These may include, but are not limited to: wash bottles, Teflon lined caps, autovial caps, HPLC parts, etc. The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended to make calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to two solvents and equipped with a variable volume injector capable of Injecting 5-100 pL connected to a tandem Mass Spectrometer (LC/MS/MS). I Analytical balance capable of reading to 0.0001 g A device to collect raw data for peak integration and quantitation 15-mL and 50-mL disposable polypropylene centrifuge tubes. Gas tight syringes, 25pL, 50pL, 100pL, 250pL, 500pL, 1000pL. 1 mL plastic HPLC autovial. Disposable pipettes, polypropylene or glass as appropriate Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 6.2 Chromatographic System Guard Column: Prism RP, 4.6 mm x 50 mm, 5 pm Analytical Column: Betasil C 18,4.6 mm x 100 mm, 5 pm Temperature: 10C Mobile Phase (A): 2 mM Ammonium Acetate in Water Mobile Phase (B): Methanol Gradient Program: Tim e (m ini 0.0 0.5 11.0 13.5 13.6 17.0 %A 97 97 5 5 97 97 %B 3 3 95 95 3 3 Flow Rate (m L/m inl 1.0 1.0 1.0 1.0 1.0 1.0 Injection Volume: 100 pL. Quantitation: Peak A rea-quadratic curve fit, 1/x weighted. RunTime: ~ 1 7 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 o f 11 Method of Analysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection Analysis 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Weils (Sulfonates) Page 67 of 178 'ooumeni: may oe used, if current, for 'M days from 04/16/200? 3M Environmental Laboratory P0003268; Interim Report#4 6.3 MS/MS System 6.3.1 Mode: Electrospray Ngative ion, MRM mode, monitoring the following transitions: A n a ly te Transition Monitored PFBA 213 --> 169 PFPeA 2 6 3 -> 2 1 9 PFHA 3 1 3 -> 2 6 9 and 3 1 3 -> 119 PFHpA 363 -> 3 1 9 , 3 6 3 -> 169 and 3 6 3 -> 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 M ultiple transitions for m onitoring the analytes is an option, as summing m ultiple transitions may provide quantitation o f isom ers that more closely m atches 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 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 PerfluorobutanoicAcid (P F B A -C 4 acid); Oakwood Products, Inc Perfluoropentanoic Acid (PFPeA - C5 acid, also known as NFPA, nonafluoropentanoic acid); Alfa Aesar PerfluorohexanoicAcid (P F H A -C 6 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 PerfluorononanoicAdd (P F N A - C9 add); Oakwood Products, Inc PerfluorodecanoicAdd (P F D A -C 1 0a dd); Oakwood Products, Inc PerfluoroundecanoicAcid (P FU nA-C 11 acid); Oakwood Products, Inc PerfluorododecanoicAcid (P F D oA - C12 add); Oakwood Products, Inc Perfluorobutanesulfonate (PFBS - C4 sulfonate); 3M Perfluorohexanesulfonate (PFHS - C6 sulfonate); 3M Perfluorooctanesulfonate (PFOS - C8 sulfonate); 3M ETS-8-044.0 Page 6 o f 11 Method of Analysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 68 of 178 fient may be user acurra"-, for 14 days fre e 04/16/2007 3M Environmental Laboratory P0003268; Interim ReportM 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 targe t analyte SSSs--Weigh out 10 mg of analytical standard (corrected for percent salt and purity) and dilute to 100mL with methanol or other suitable solvent, in a 100mL volumetric flask. Transfer to a 125mL LDPE bottle or other suitable container. Prepare a separate solution for each analyte. Expiration dates and storage conditions of stock solutions should be assigned in accordance with laboratory standard operating procedure. An example of purity and salt correction is given below for PFOS. m olecular weight of anion salt correction factor = m oclecular weight of salt PFOS (K +)salt correction factor = = 0.9275 10 mg CsF^SOs'K* with purity 90% = 8.35mg C8F,7S03" (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 10Opg/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 o f 11 Method of A nalysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 69 of 178 Document may be used, if current, for 14 days fron; 04/16/200? 3M Environmental Laboratory P0003268; Interim ReporttU 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, HPLC water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C oncentration o f WS, ng/m L 125 125 125 125 250 250 250 250 5000 5000 5000 V olum e o f WS, fjL 10 15 20 30 20 50 100 200 25 50 100 F in al V olum e o f C alibration Standard (mL o f ASTM T y p e i W ater; o r o th e r su itab le water) 50 50 50 50 50 50 50 50 50 50 50 Final C oncentration o f C alibration Standard, ng/m L (ppb) in A S TM Type 1Water, o r o th e r su itab le w ater 0 .0 2 5 0 .0 3 7 5 0 .0 5 0 0 .0 7 5 0 .1 0 0 0 .2 5 0 0 .5 0 0 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 o f 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 o f 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 o f Analysis fo r the Determ ination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a lysis 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 70 of 178 Document rnay be i.::tacl, if current, for 14 days from 1 3M Environmental Laboratory P0003268; Interim Report#4 be within 30%. Justification for exclusion of calibration curve points w ill 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 w ill 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. A t 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 w ill 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 o f Analysis fo r the Determ ination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a lysis 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 71 of 178 jocurnent may be used, if current: for 14 days from 04/16/201 3M Environmental Laboratory P0003268; Interim Report#4 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 w ill 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 tim es 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 = x 100 Analyte added (ng/mL) 12 Method Performance Any method performance parameters that are not achieved must be considered in the evaluation of the data. Nonconformance to any specified parameters must be described and discussed if the Technical Manager (nonGLP study) or Study Director (GLP study) chooses to report the data. If criteria listed in this method performance section are not met, maintenance may be performed on the system and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. If data are to be reported when performance criteria have not been met, the data must be footnoted on tables and discussed in the text of the report. 12.1 System Suitability System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are injected at the beginning of each analytical run prior to the calibration curve. Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of S5% and a retention time RSD of <2% to be compliant. 12.2 Quantitation C alibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. CCV Perform ance: The calibration standards that are interspersed throughout the analytical sequence are evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples that are bracketed by CCVs not meeting these criteria must be reanalyzed. ETS-8-044.0 Page 10 o f 11 Method of Analysis for the Determ ination o f Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 72 of 178 Document may be used, if current for 14 davs from 04/18/2007 3M Environmental Laboratory P0003268; Interim ReportM D em onstration o f S p e cificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response of unique ions. 12.3 Sensitivity The targeted lim it o f 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% w ill be flagged in the report, but will not be excluded from reporting. The requirement for replicates excludes field blanks or rinse blanks. Section 10 contains additional information regarding the required precision of laboratory control spikes. 13 Pollution Prevention and Waste Management Waste generated when performing this method will be disposed of appropriately. The original samples will be archived at the 3M Environmental Laboratory in accordance with internal procedures. 14 Records Each data package generated for a study must include all supporting information for reconstruction of the data. Information for the data package must include, but is not limited to the following items: study or project number, sample and standard prep sheets/records, instrument run log (instrument batch records, instrument acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data calculations. 15 Affected Documents None. 16 Revisions Revision Number Summary o f Changes ETS-8-044.0 Page 11 o f 11 Method of Analysis for the Determ ination of Perfluorinated Compounds in W ater by LC/MS/MS; Direct Injection A n a ly s is 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Weils (Sulfonates) Page 73 of 178 Document may be used, bourrent, for 14 days from 3M Environmental Laboratory P0003268; Interim Reportff4 3M Environmental Laboratory Method Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry Method Number: ETS-8-154,3 Adoption Date: 28 Apr 2000 Revision Date: Upon Signing Effective Date: 6 % ( z H / o 7 Approved By: William K. Reagen Manager Date ETS-8-154.3 Page 1 of 20 Determination of Peifluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 74 o f 178 Docur'iient may be used, beurren'e for 14 days Tram 0?/24/.200 3M Environmental Laboratory P0003268; Interim ReportH4 1 Scope and Application This method describes the extraction of target analytes from water matrices using solid phase extraction (SPE) followed by separation, identification, and quantitation using high-performance liquid chromatography mass spectrometry (HPLC/MS) or tandem mass spectrometry (HPLC/MS/MS). This method has been validated for perfluorooctane sulfonate (PFOS), perfluorooctane sulfonylamlde (FOSA), and perfluorooctanoate (PFOA) in groundwater, surface water, and drinking water samples. This method is considered a performance-based method and may be applied to the determination of other perfluorinated acids, alcohols, amides, and sulfonates in sim ilar matrices, as long as the defined QC elements are satisfied and with the understanding that the method is not validated for compounds outside the scope of the original protocol. This method is based in part on the 3M Environmental Laboratory report E01-0454, "Method of Analysis for the Determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water", as developed and validated by Exygen Research (formerly Centre Analytical Laboratories, Inc.). This method was originally validated using a 40 mL sample aliquot for extraction and a final elution volume of 5 mL. These volumes may be changed on a per project basis to meet the data quality objectives set forth by the project lead. Acceptable recoveries of laboratory quality control samples will demonstrate that the extraction and elution volumes do not impact the validity of the method. Sample collection is not covered under this analytical procedure. 2 Method Summary W ater samples are collected from a site of interest and shipped to the analytical facility. Perfluorinated acids, alcohols, amides, and sulfonates are extracted from aliquots of the water samples using solid phase extraction (SPE) cartridges. The compounds are eluted from the SPE cartridge, using methanol. Separation, identification, and measurement are accomplished by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) analysis. High-performance liquid chromatography/mass spectrometry (HPLC/MS) may be used if the defined QC elements are satisfied and meets the data quality objectives outlined in the general project outline for the given project. The concentration of each identified component is measured by comparing the MS response of the quantitation ion (or summed total of multiple ions) produced by that compound to the MS response of the quantitation ion (or summed total of multiple ions) produced by the same compound in an extracted calibration standard (external standard). 3 Definitions 3.1 SPE cartridge A column containing an open solvent reservoir, retaining frit, sorbent bed, retaining frit, and luer tip. The sorbent bed is bonded silica which is designed to selectively retain or elute the compounds of interest depending on the solvent conditions. The compounds of interest can be separated from the water matrices and introduced into an appropriate solvent for analysis. 3.2 Analytical Sample A portion of an extracted laboratory sample prepared for analysis. ETS-8-154.3 Page 2 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 75 o f 178 Document may oe used, If currer;-:, for 14 clays from 08/24/2007 3M Environmental Laboratory P0003268; Interim ReporW4 3.3 Calibration Standard An aqueous solution prepared by spiking a known volume of the Working Standard (WS) into a predetermined amount of ASTM type I water, HPLC grade reagent water, or other suitable water (i.e. matrix water), and extracting the solution according to this method. The calibration standard solutions are used to calibrate the instrument response with respect to analyte concentration. 3.4 Laboratory Duplicate Sample (LDS) A laboratory duplicate sample is a separate aliquot of a sample, taken in the analytical laboratory that is extracted and 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. 3.5 Field Blank (FB)/Trip Blank ASTM Type I water, HPLC grade reagent water, or other suitable water, Is 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 o f 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. 3.6 Field Duplicate Sample (FDS) A sample collected in duplicate at the same time from the same location as the sample. The FDS is placed 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. 3.7 Field Matrix Spike (FMS) A sample to which known quantities of the target analytes are added to the sample bottle in the field or In the laboratory before the bottles are sent to the field. 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 at approximately 0.5-10 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. Typically a low and a high spike are prepared for each sampling location. The FMS is analyzed to ascertain if matrix effects or sample holding time contributes bias to the analytical results. 3.8 Field Spike Control Sample (FSCS)/Trip Blank Matrix Spike An aliquot of ASTM Type I water (HPLC grade reagent water or other suitable water may used) to which known quantities of the target analytes are added in the field at the time of sample collection (at an appropriate concentration to be determined by the project lead) or in the laboratory prior to the shipment of the collection bottles. The FSCS is extracted and analyzed exactly like a sample to determine whether a loss of analyte could be attributed to holding time, sample storage and/or shipment issues. A low and high FSCS may be appropriate when expected sample concentrations are not known. This sample may also be referred to as Trip Blank Matrix Spike. 3.9 Laboratory Control Sample (LCS) An aliquot of ASTM Type I water (HPLC grade reagent water or other suitable water may used) 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 ETS-8-154.3 Page 3 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 76 of 178 Docihm,..:.;"^: may be used, If current, be Id days fro,a fddia4/2C}07 3M Environmental Laboratory P0003268; Interim Report#4 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. 3.10 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 extracted and 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. 3.11 Laboratory Sample A portion or aliquot of a sample received from the field for testing. 3.12 Limit of Quantitation (LOQ) The lower lim it 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 matrixdependent. The upper lim it of quatitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitatied 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. 3.13 Method Blank An aliquot of ASTM Type I water (HPLC grade reagent water or other suitable water may used) 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. 3.14 Sample A sample is a small portion collected from a larger quantity of material intended to represent the original source material. 3.15 Stock Standard Solution (SSS) A concentrated solution of a single analyte prepared in the laboratory with an assayed reference compound. 3.16 Surrogate A compound sim ilar to the target analyte(s) in chemical composition and behavior that 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 (except solvent blanks and half of the prepared method blanks). Surrogate(s) are added to quantitatively evaluate the entire analytical procedure including sample collection, extraction, and analysis. Inclusion of a surrogate analyte is an optional quality control measure and is NOT required. The project lead should indicate in the general project outline/protocol whether or not a surrogate compound will be part of the analysis. ETS-8-154.3 Page 4 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 77 of 178 D o c u m e n t may be used, if current, for 14 days from 04/24/200? 3M Environmental Laboratory P0003268; Interim ReportW4 3.17 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. Unknown samples may contain high concentrations of volatile toxic compounds. Sample containers should be opened in a hood and handled with gloves to prevent exposure. The laboratory is responsible for maintaining a safe work environment and a current awareness of local regulations regarding the handling o f 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 too, 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 extraction and analysis, be aware of potential contaminant sources from reagents and solid phase extraction devices. All materials used in the analyses shall be demonstrated to be free from interferences under conditions of analysis by running method blanks. 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 Materials Note: Brand names, suppliers, and part numbers are for illustrative purposes only. Equivalent performance may be achieved using apparatus and materials other than those specified here. Demonstration of equivalent performance (quality control samples meeting method acceptance criteria) is the responsibility of the laboratory performing the analysis. 6.1 Instrumentation Balance, analytical (display at least O.OOOIg), Mettler HPLC/MS/MS or HPLC/MS system, as described in Section 10. 6.2 Supplies and Materials. ETS-8-154.3 Page 5 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 78 o f 178 Document mav be used, if current, for 1.f rDys from 08/2/820. 3M Environmental Laboratory P0003268; Interim Report#4 Sample collection bottles--LDPE (e.g., NalgeneTM) narrow-mouth bottles with screw cap. Note: Do not use Teflon bottles or Teflon lined caps. Coolers or boxes for sample shipment. AutoTrace automated SPE workstation, Caliper Life Sciences. A manual SPE manifold with vacuum pump may be used if desired. Supplies for the manual SPE manifold are included below.) Vacuum pump, Biichi. Visiprep vacuum manifold, Supelco. 15mL disposable polypropylene centrifuge tubes, VWR. 50mL disposable polypropylene centrifuge tubes, VWR Sep Pak Vac 6cc (1g) tC18 cartridges (part # WAT 036795), Waters. (Cartridges with other amount or types of sorbent material may be used depending on the data quality objectives of the project.) 15 mL disposable culture tubes (17 x 100 mm), VWR (Cat. No. 60818-626). Disposable micropipettes (50-1 OOpL, 100-200pL), Drummond. Class A pipettes and volumetric flasks, various. LDPE narrow-mouth bottles, Nalgene (volumes may vary depending on analytical needs). 2 mL clear HPLC vial kit (cat# 5181-3400), Agilent/Hewlett Packard. Standard lab equipment (graduated cylinders, disposable tubes, etc.), various. 7 Reagents and Standards Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent performance may be achieved using chemicals obtained from other suppliers. Do not use a lesser grade of chemical than those listed. 7.1 Chemicals Methanol (MeOH), HPLC grade, JT Baker, Catalog No. JT9093-2. Ammonium Acetate, Reagent grade, Sigma-Aldrich, Catalog No. A-7330. ASTM Type I Water, prepared in-house (HPLC grade reagent water or other suitable water may also be used) Sodium Thiosulfate, Reagent grade, JT Baker. 7.2 Standards PFBA, Heptafluorobutyric Acid, (C4 Perfluorinated Acid) NFPA, NonafluoropentanoicAcid (C5 Perfluorinated Acid) PFHA, Perfluorohexanoic Add (C6 Perfluorinated Acid) TDHA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid) PFOA, Ammonium perfluorooctanoate, (C8 Perfluorinated Acid) C9Add, HeptadecafluorononanoicAcid PFDA, Nonadecafluorodecanoic Acid (C10 Perfluorinated Add) ETS-8-154.3 Page 6 of 20 Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In W ater By solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 79 of 178 Document may bo used, if current, for 14 days from 08/ 24/ 200? 3M Environmental Laboratory P0003268; Interim Report#4 Ch Acid, PerfluoroundecanoicAcid C i2Acid, PerfluorododecanoicAcid FBSA, Perfluorobutanesulfonamide FOSA, Perfluorooctanesulfbnylamide PFBS, Potassium Perfluorobutanesulfonate PFHS, Perfluorohexanesulfbnate PFOS, Potassium perfluorooctanesulfonate THPFOS, 1H, 1H, 2H, 2H-perfluorooctanesulfonicAcid THPFDS, IH, IH, 2H, 2H-perfluorodecanesulfonic Acid PFOA [1,2-13C], 13C isotopically labeled perfluorooctanoic acid, Perkin Elmer PFOS [180 2], 1S0 2 isotopically labeled Ammonium Perfluoroocatanesulfbnate Others as required. 7.3 Reagent Preparation 250 mg/mL sodium thiosulfate solution -- Dissolve 25g of sodium thiosulfate in 100 mL reagent water. 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 o f a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/m L targe t analyte SSSs--Weigh out 10 mg of analytical standard (corrected for percent salt and purity} and dilute to 100mL with methanol or other suitable solvent, in a 100mL 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 439 PFOS (K +)salt correction factor = ---- = 0.9275 538 10 mg CaF^SOj'K* with purity 90% = 8.35mg C8F17S03' (10 mg*0.90*0.9275=8.35 mg) 1 pg/m L (1000 ng/m L) m ixed w orking standard--Add 1.OmL each of the 10Opg/mL SSSs to a 1OOmL volumetric flask and bring up to volume with solvent. 0.1 pg/m L (100 ng/m L) m ixed w orking standard--Add 10.OmL of the 1.Opg/mL-mixed working standard solution to a 100m l volumetric flask and bring up to volume with solvent. ETS-8-154.3 Page 7 of 20 Determination of Perfiuorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 80 of 178 Document may be used, if current, for 14 deys from 08/24/200?" 3M Environmental Laboratory P0003268; Interim ReportH4 0.01 pg/m L (10 ng/m L) m ixed standard--Add 10.0mL of the 0.1pg/mL-mixed working standard solution to a 10OmL 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 o f 6 months from the date of preparation. 7.5 Calibration Standards Using the working standards described above, prepare calibration solutions in ASTM Type I water, or other suitable water, using the following table as a guideline. Note: Volumes of water and working standards may be adjusted to meet the data quality objectives addressed in the general project outline. Calibration levels other than those listed below can be prepared as needed. C oncentration o f WS, ng/m L V olum e o f WS, - F in al V olum e o f C alibration S tandard (mL o f A S TM Type 1 W ater, o r o th e r su itab le water) F inal C oncentration o f C alibration Standard, ng/m L (ppb) in A STM Type 1 Water, o r o th e r su itab le w ater 100 10 40 0 .0 2 5 100 20 40 0 .0 5 0 100 40 40 0 .1 0 0 100 100 40 0 .2 5 0 1000 20 40 0 .5 0 0 1000 40 40 1.00 1000 100 40 2.50 10000 20 40 5.00 10000 40 40 10.0 10000 100 40 2 5 .0 The calibration standards are processed through the entire extraction procedure (Section 11), identical to the laboratory samples. The concentration of the calibration standard in the final extract depends on the volume extracted and the final elution volume. Final sample concentration factor = Volume extracted (mL)/Elution Volume (mL) Storage Conditions-- Store all extracted calibration standards in 15mL polypropylene tubes or in labeled autovials at 42C. After analysis, archive all extracted standards with the sample extracts in accordance with laboratory standard operating procedures. 8 Sample Collection Bottle Preparation For most projects, sample collection bottles are prepared by 3M Environmental Laboratory personnel before they are shipped to the collection site. Typically, four separate collection bottles are associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field matrix spike. Depending on the scope of the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not uncommon for additional mid level field matrix spikes to be collected if the expected sample concentrations are truly unknown or could span a large concentration range. Low-density polyethylene (LDPE) wide-mouth Nalgene bottles are used for the sample collection containers. (Volumes of the bottles may vary depending on how much sample is required to meet ETS-8-154.3 Page 8 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 81 of 178 Docum.. niay be used, if current, fer s4 days from 0S/24/20u/ 3M Environmental Laboratory P0003268; Interim Report#4 data quality objectives.) The interiors of the Nalgene bottles may be rinsed multiple times with acetone and methanol and allowed to dry before adding the appropriate spikes. Note: rinsing of the bottles Is optional and is not required. The project lead will communicate what the final collection volume will be and a corresponding "fill to here" line is drawn on the exterior of the bottle using a permanent marker. Typically, placement of the "fill to here" line Is done by using a marker template. Alternatively, bottles with pre-marked volume indicators may be purchased. For the sample bottles designated for matrix spikes, an appropriate volume of matrix spiking solution is added to the empty bottle. The volume of spike solution added should produce the desired final concentration of target analytes once the bottle is filled with sample to the "fill to here line". (If a surrogate is included for the project, the surrogate compound should also be added to the matrix spikes). The matrix spiking solution should be prepared in a suitable solvent and contains all of the target (and surrogate if applicable) analytes; however, multiple spike solutions may be used if an appropriate mixed component standard is not available. The matrix spiking solution is often the same as the working standards used to create the calibration standards. An example of a bottle spike is given below. "Fill to here" volume = 450 mL (A 500 mL Nalgene bottle is used) Desired Field Spike Concentration = 0.1 ng/mL 45pL of a 1 pg/mL spiking solution (containing the target analytes) is added to the bottle and the bottle cap promptly sealed If analysis of a surrogate analyte Is included in the project objectives, the preparatory analyst should also add an appropriate volume of surrogate standard solution to all the bottles designated as samples or field duplicate samples. All bottles should be clearly labeled to Indicate its Intended use as a sample/field sample duplicate, low spike, or high spike. If each location has different designated spike levels, the label should also clearly indicate the sample location designation. Generally, a set of bottles for a given collection site are then grouped together in plastic bags for organizational purposes. For each collection event, at least one set of trip blank and trip blank matrix spikes are prepared. The number of trip blank sets required for a given project w ill be communicated by the project lead. For the trip blank, the surrogate spike Is added to the bottle (if included) and then ASTM Type I water (HPLC grade reagent water or other suitable water may used) is added to the "fill to here" line. The bottle cap is replaced and tape may be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding the appropriate volume of matrix spiking solution, filling the bottle to the desired volume with the appropriate water and replacing and sealing the cap. The preparatory analyst should document bottle preparation in a Note to File or on a sample preparation worksheet. The Note to File should include the following information: date prepared, total number of bottles prepared, number of sample sites, the standard identification numbers and spike volumes used to prepare spiked bottles, the "fill to here" volume, and any other pertinent information needed for reconstructibility of the data. The Note to File will be included In the final data package for the project. ETS-8-154.3 Page 9 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 82 of 178 Document may be used, beurrent, for 14 days from 04/24/200 3M Environmental Laboratory P0003268; Interim Report#4 9 Quality Control and Data Quality Objectives Analytical results of the FB, FMS, LMS, FD, and FSCS should be evaluated at the conclusion of the study to help Interpret the quality of sample data. Analytical results for these control/duplicate samples must be reported with the sample data. 9.1 Solvent Blanks Solvent blanks are analyzed with each sample set to determine contamination or carryover. In general, solvent blanks should have area counts that are less than 50% of the area count of the lowest calibration standard. Solvent blanks should be analyzed prior to and following each calibration curve, each set of system suitability samples, and after no more than 10 unknown sample extracts. If instrument carryover is a problem, consecutive solvent blanks may be necessary. In this case, the area counts of the solvent blanks should return to <50% of the lowest calibration standard prior to the injection of further standards or samples. 9.2 Method Blanks A method blank consists of an aliquot of ASTM Type I water (HPLC grade reagent water, or other suitable water may be used) equal in volume to the samples, and extracted in the same manner as the samples. At least five method blanks should be prepared and analyzed each day that extractions are performed for a particular study or project. Method blanks must be interspersed throughout the extraction batch and analyzed interspersed throughout the analytical sequence. The average area counts for each analyte must be less than 50% o f the area count o f the LOQ standard. The standard deviation of the area counts should be calculated. A specific %RSD acceptance criteria is not specified but is assessed on a batch basis. If the mean area counts of the method blank exceed 50% of the LOQ standard, then the LOQ must be raised to the first standard level in the curve that meets criteria. Method blanks may be eliminated if technical justification can be provided (e.g. the method blank was analyzed after an unexpectedly high level sample). If any method blanks are removed from the LOQ determination, document in the raw data and report as appropriate. 9.3 Laboratory Sample Replicates / Field Duplicate Sample Depending on the scope of the project, all or selected samples may be extracted at least in duplicate, and in triplicate if difficulties were encountered in the sampling and/or holding conditions of the samples. If field sample replicates are collected, duplicate and triplicate extractions of an individual sample may not be required. The relative percent difference (RPD) of duplicate samples or relative standard deviation (RSD) should be less than 20% for the precision o f sample preparation and analysis to be considered in control. Replicate samples not meeting the 20% method criteria will be reviewed and evaluated on a case by case basis. 9.4 Laboratory Matrix Spikes (LMSs) LMSs are performed if FMSs have previously been performed for the sample matrix. Alternatively, LMSs are performed for a sample matrix if the FMS levels were not appropriate for determining spike recoveries relative to endogenous levels. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared for each sample and analyzed to determine the matrix effect on spike recovery efficiency of each target analyte. Lab matrix spike recoveries should fall within 30% of expected values. LMS concentrations should be prepared at approximately 0.5-10 times the endogenous concentration or approximately 4-10 times the LOQ concentration o f each analyte. ETS-8-154.3 Page 10 of 20 Determination of Perfluorinated Adds, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 83 of 178 Do):.onen may ou usee!, it current tor 14 d: rrom u /2 4 -o :0 0 t 3M Environmental Laboratory P0003268; Interim Report#4 9.5 Laboratory Control Spike (LCS) Lab control spikes are prepared for each extraction batch to determine method accuracy and precision. LCSs should be prepared at a minimum of two levels and in triplicate. Low lab control spikes should be prepared at a concentration in the range of approximately four to ten times higher than the targeted LOQ and the high lab control spikes should be prepared at a concentration near the mid-point of the calibration curve. For each target analyte, the percent relative standard deviation (method precision) o f the pooled control spikes must be less than or equal to 20% and the average recovery (method accuracy) must be 80-120%. Sample data for target analytes outside of the laboratory control spike acceptance criteria are not reportable. 9.6 Field Matrix Spikes (FMSs) FMSs are prepared for each sample and analyzed to determine the matrix effect and sample holding time on spike recovery efficiency of each target analyte. Generally, each sample location represents a different sample and sample matrix. FMS samples are a sample to which known quantities of the target analytes are added to the sample bottle in the field or in the laboratory before the bottles are sent to the field. Typically a low and a high FMS are prepared for each sampling location. The ratio of endogenous analyte to field spike concentration that is appropriate to assess accuracy is defined as approximately 0.5 to 10 times the expected sample concentration. For example, if the endogenous level of analyte in the sample is expected to be 1.0 ng/mL, the appropriate range for FMS used to assess accuracy of results would be approximately 0.5 ng/mL to 10 ng/mL. For samples that are expected to have endogenous analytes present at or below the targeted LOQ, the appropriate range for FMS would be approximately 4 to 10 times the LOQ concentration. For example, if the analyte LOQ is 0.025 ng/mL, the appropriate range for low level FMS would be 0.1 ng/mL to 0.25 ng/mL. 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. Field matrix spike method acceptance criteria are recoveries within 30% of the expected value. If FMS recovery Is outside of 30% of the expected value or could not be assessed because the FMS was spiked at an inappropriate level, the sample result is reported as NR, where NR is defined as "Not Reportable". For data reportability, a sample may be re-extracted and re analyzed or an alternate analytical method may be applied to the sample. Alternatively, resampling and reanalysis of a new sample may be completed. If re-extraction, resampling, and re-analysis fail to meet the FMS acceptance criteria, the sample result will be reported as "NR" (not reported due to noncompliant QC results). Exceptions to the 30% FMS acceptance criteria for data reportability are as follows: 1. ) If FMS recovery could not be assessed because FMS's were at an inappropriate level, then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within 30% the data are reportable but flagged as not meeting the FMS method acceptance criteria. 2. ) If multiple FMS's were prepared on a sample and the closest FMS level to the reported sample meets the 30% acceptance criteria but additional FMS's are outside the 30% acceptance range, the data are reportable but flagged with an expanded uncertainty and as not meeting FMS method acceptance criteria. 3. ) If the FMS recoveries are outside of the 30% acceptance range but at least 20 acceptable historical reportable FMS sample results are available, the data may be reported but flagged with an expanded uncertainty and as not meeting FMS criteria. 10 Calibration and Standardization ETS-8-154.3 Page 11 o f 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 84 of 178 Document may be used, if current for 14 (lays Dorn 08/24/ 3M Environmental Laboratory P0003268; Interim Report#4 10.1 Instrument Setup Note: In this example, an Applied Biosystems Sciex API 4000 Tandem Mass Spectrometer (LC/MS/MS) is used. Other brands o f LC/MS/MSs as well as single quadrupole mass spectrometers (LC/MS) may be used as long as the method criteria are met. Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent performance may be achieved using apparatus and materials other than those specified here, but demonstration of equivalent performance that meets the requirements of this method is the responsibility of the laboratory. The operator must optimize and document the equipment and settings used. Establish the LC/MS/MS system and operating conditions equivalent to the following: Mass Spec: Applied Biosystems API 4000 Ion Source: Turbo Ion Spray (ABS) Mode: Electrospray Negative Scan Type: MRM (Multiple Reaction Monitoring) Harvard infusion pump (Harvard Instruments), fortuning Computer: DellDHM Software: Windows 2000 or W ndows XP, Analyst 1.4.1 HPLC: Agilent Series 1100 Agilent Quaternary Pump Agilent Vacuum Degasser Agilent Autosampler Agilent Column Oven Note: One or more C18 HPLC analytical columns (2.1 mm x 100 mm, 5pm or 2.1 mm x 50 mm, 5pm) may be attached on-line after the purge valve and before the sample injection port to retard and separate any residue contaminants that may be in the mobile phase and/or HPLC system. HPLC Column: Betasil C 1 8 , 2.1mm x 100mm, 5pm (ThermoElectron Corporation) Column Temperature: 35C Injection Volume: 5pL Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3) Mobile Phase (B): Methanol ETS-8-154.3 Page 12 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 85 of 178 Document may be used, if current, for 14 days from 03/24/200' 3M Environmental Laboratory P0003268; Interim ReportM Liquid Chromatography Gradient Program. Step Number 0 1 2 3 4 5 Total Time (min) 0 1.0 14.5 15.5 16.5 20.0 Flow Rate (/JJm in) 300 300 300 300 300 300 Percent A (2 m M am m onium acetate) 80.0 80.0 10.0 10.0 80.0 80.0 Percent B (M e thanol) 20.0 20.0 90.0 90.0 20.0 20.0 Note: Other HPLC gradients may be used as long as the method criteria and project data quality objectives are met. It may be necessary to adjust the HPLC gradient in order to optimize instalment performance. Columns with different dimensions (e.g. 2.1mm x 30mm) and columns from different manufacturers (Keystone Betasil C18 eta) may be used. M ass Transitions M onitored. A n a ly te Mass Transition Q1 (amu) P F B A (C .A dd) N F P A (Cs A d d ) P F H A (Ce Add) 213.0 262.9 3 1 3 .0 TDHA (C7 Add) PF O A (Ca A d d) CsAdd 362.9 4 1 3 .0 4 6 3 .0 ______________________________ Mass Transition Q3 (amu) D eclustering P o te n tia l 169.0 219.0 2 6 8 .7 ,1 1 8 .9 3 1 8 .7 .1 6 8 .8 ,1 1 8 .9 3 6 8 .9 ,2 1 9 .0 .1 6 9 .0 4 1 8 .7 ,1 6 8 .9 ,2 1 8 .9 -30 -30 -45 -35 -45 -45 C ,0Add On Add C 12 A d d FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS P F O A 1 , 2 ,3C1 P F o s [ " 'e y 512.9 563.0 613.0 297.7 497.9 298.9 398.9 498.9 426.9 526.9 414.9 503.0 4 6 8 .8 ,2 1 8 .9 ,2 6 9 .1 518.7, 268.9,218.8 568.7,168.9, 318.7 78.0 77.9 98.9, 79.9 98.9, 80.0 8 0 .0 .9 8 .8 ,1 3 0 .0 4 0 6 .8 ,8 0 .9 5 0 6 .7 .8 1 .0 369.8 1 0 3 .0 ,8 4 .0 -35 -45 -50 -55 -90 -65 -95 -120 -70 -70 -40 -100 ETS-8-154.3 Page 13 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 86 of 178 Document: may be used, ii current or 'in days frurn Cmd/24/20ud 3M Environmental Laboratory P0003268; Interim ReporW4 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 analyte signal. The use of one daughter ion is acceptable if method sensitivity is achieved, provided that retention time criteria are met to assure adequate specificity. W hile the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is suggested for PFOS. Quantitation may be performed using the total ion chromatogram (TIC) for a given analyte. For example, the PFOA TIC would sum all three of the monitored transitions. Use of the suggested primary ion is recommended. Retention times may vary slightly, on a dayto-day basis, depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the standards are interspersed throughout the analytical run. 10.2 Method Acquisition Parameters The following values are provided as an example of method acquisition parameters for a single period, single experiment method using the Sciex instrumentation. Actual values may vary from instrument to instrument. Also, these values may be changed from time to time in order to optimize for greatest sensitivity. If a multiple period is used, each period may have different gas, temperature, and ion spray voltages. Curtain Gas (CUR) Collision Gas (CADI lonSprav Voltage (IS) Temperature (TEM) Gas 1 (Nebulizer) GS1 Gas 2 (Turbo Gas) GS2 Interface Heater (Ihe) Entrance Potential (EP) 15.0 Hiah -4500 450.0 35.0 45.0 ON -10 10.3 C alibration Curve Analyze the standard curve prior to each set of samples. The validated method specifies that the standard curve should be plotted using a linear fit, weighted 1/x or unweighted. However, the standard curve may also be plotted by quadratic fit (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. If the calibration curve does not meet acceptance criteria, perform routine maintenance or prepare a new standard curve (if necessary) and reanalyze. For purposes of accuracy when quantitating low levels of analyte, it may be necessary to use the low end of the calibration curve rather than the full range. For example, when attempting to quantitate approximately 0.05 ng/mL of analyte, generate a calibration curve consisting of the standards from 0.025 ng/mL to 10.0 ng/mL rather than the full range of the curve (0.025 ng/mL to 25.00 ng/mL). This will reduce inaccuracy attributed to linear regression weighting of high concentration standards. 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. Any curve point may be rejected due to a bad injection ETS-8-154.3 Page 14 o f 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 87 of 178 If CU ! ' 3M Environmental Laboratory P0003268; Interim ReportM : or failing to meet accuracy requirements of 25% (and 30% for the LLOQ). Justification for exclusion o f calibration curve points will be noted in the raw data. A minimum of 6 points w ill be used to construct the calibration curve. No more than 25% of the total extracted calibration standards should be excluded. This does not pertain to low and high levels that may need to be disabled to achieve an accurate curve In the concentration range of the samples, rather, this is intended to apply to mid curve points only. 10.4 Continuing Calibration Verification (CCV) Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze a mid-range calibration standard, one o f 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. 10.5 System Suitability A minimum of three system suitability samples will be injected at the beginning of each analytical run, prior to the analysis of the calibration curve. Typically these samples are at a concentration near the mid-level of the calibration curve are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of S5% and a retention time RSD of 2% to be compliant. 11 Procedures 11.1 Extraction Scheme The following steps represent a typica l extraction scheme. Sample extraction volumes and final elution volumes may be adjusted to meet data quality objectives. Allow samples to equilibrate to room temperature. Thoroughly mix samples by gently inverting the sample bottle. Measure a 40mL representative aliquot of the well-mixed sample into a 50mL polypropylene centrifuge tubes (Spike the lab matrix spikes as required*, replace lid and mix well). Alternate volumes may be used depending on the scope of the project. Use a consistent sample volume for all extractions and document on the sample prep sheet. Add 40pL of 250 mg/mL sodium thiosulfate solution to 40mL of sample. Adjust the amount of sodium thiosulfate solution added if alternate sample volumes are used. Thoroughly mix sample. Note: * Samples may need to be prescreened to determine an appropriate matrix spike level (typically approximately 0.5 to 10 times the sample concentration). Alternatively the samples could be spiked at more than one level, allowing for the inappropriate spike level to be eliminated. Condition the C18 SPE cartridges (1g, 6mL) by passing approximately 10mL methanol (at a minimum) followed by approximately 50mL (at a minimum) ASTM Type I water. Do not let column run dry. If column does run dry, recondition. SPE cartridges cannot be over conditioned. Load the analytical sample onto the C18 SPE cartridge. Once the entire sample has loaded onto the cartridge, isolate the cartridge from the vacuum and wait until all samples on the vacuum manifold have been loaded. Discard eluate. Open manifold valves and pull a vacuum on the SPE cartridges for approximately 3 minutes to remove residual water from the SPE cartridge. Elute with exactly 5 mL of 100% methanol. Collect eluate into graduated 15mL polypropylene centrifuge tubes. This is the target elution fraction (final volume approximately 4.5 mL as not all of the solvent w ill leave the SPE column. This will not affect the calculations in any way since the ETS-8-154.3 Page 15 o f 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 88 of 178 Document may do used, if current, for 14 days from 08/24/2007 3M Environmental Laboratory P0003268; Interim ReportM curve is also extracted). Note: the elution volume may be altered to meet project needs. The same elution volume needs to be used for all samples, calibration standards, and QO samples. Intersperse the method blanks throughout the extraction batch. Transfer well-mixed aliquots of the final extract to labeled autovials. Analyze a portion of the target elution fraction eluent using negative electrospray HPLC/MS/MS or HPLC/MS. Note: Samples are concentrated by a factor of eight during the extraction; Initial Vol = 40mL -> Final Vol. = 5mL. , 11.2 Sample Analysis Set up analysis sample queue. Method blanks must be interspersed throughout the analytical sequence. Inject the same volume (between 5~25pL) of each standard, analytical sample and blank into the instrument (unless an on-instrument sample dilution is desired). A ll sample extracts with a concentration > ULOQ must be diluted and reanalyzed. If dilution of the final extract fails to produce acceptable results (e.g. poor MS recoveries) dilute the original sample and re-extract. 12 Data Analysis and Calculations The chromatography analysis software will typically calculate the amount of target analyte in the sample extracts using the established calibration curve. Calculate the percent recovery of the LCS using the following equation: LCS% recovery ---SL-p-C-i-kS-e-C-C-o-o-n-nc-c-e-en-n-tt-rr-aa-t-ti-ioo-n-n-(-(424i-^-)) *100% mL Calculate the percent recovery of the FSCS using the following equation: FSCS% recovery -FS-S-p-iC-k-Se--CC--o-o-nn-c-c-ee-nn--tt-rr-aa-tt-ii-oo-nn--((443|^--)-)*100% Calculate the percent recovery of the FMS using the following equation: FMS % recovery = _F_M__S_C_o_n_c_e_n_t_r_at_i_on__( 4miL-_) _-_A_v_e_r_a_g_e_C_o_n_c_e_n_t_ra_t_io_n__o_f_S_a_m__p_le_/_S_a_m_p_l_e_D_u_p_l_ic_a_t_e_( Spike Concentration Cmn-5aL-) 4miL-) * 100% ETS-8-154.3 Page 16 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 89 of 178 3M Environmental Laboratory P0003268; Interim ReportM 13 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 project lead 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 determined by the analyst/project lead. 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. 13.1 System Suitability A minimum of three system suitability samples will be injected at the beginning of each analytical run. These samples are run prior to the calibration curve. The system suitability injections must have area counts with an RSD of 5% and a retention time RSD of s2% to be compliant. 13.2 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 o f the LLOQ, which may be within 30%. D em onstration o f S pe cificity: Specificity is demonstrated by chromatographic retention time (within 3% of standard) and the mass spectral response of unique ions. 13.3 Sensitivity S olvent Blanks and M ethod Blanks: Solvent and method blank area counts must be < 50% that of the lowest standard used in the calibration curve. Solvent blanks analyzed after high level samples or calibration standards may have area counts greater than 50% of the lowest standard from instrument carryover as long as subsequent solvent blanks analyzed before the next sample/QC sample demonstrate that the instrument carryover is decreasing back to expected levels. L im its o f Q uantitation (LOQ): The lower LOQ (LLOQ) is the lowest non-zero active standard in the calibration curve; the peak area o f the LLOQ must be at least 2X that of the method blank(s). By definition, the measured value of the LLOQ must be within 30% of the theoretical value. 13.4 Accuracy CCV Perform ance: 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. LCS recoveries should be within 25% to be considered acceptable and to verify that the method is in control on a given day. Lab C ontrol Spikes: The average recovery of the pooled LCSs for each target analyte should be within 80-120% and the percent relative standard deviation of the recoveries must be less than or equal to 20%. 13.5 Precision R eproducibility: Reproducibility of the method is defined by the results of duplicate or triplicate analysis of samples. A RPD or RSD of s 20% w ill be considered acceptable for replicate lab control spikes. Because field sample duplicates account for variability in sample location (as well as variability in the extraction procedure), RPD or RSD values may be higher. Report the RPD or ETS-8-154.3 Page 17 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 90 of 178 Document may be used, if current for 14 days from 03/ 24/2 3M Environmental Laboratory P0003268; Interim ReportM RSD of sample/field duplicates and discuss in the report if greater than 20% and the impact on field matrix spike recoveries, if any. 13.6 Analytical Method Uncertainty / Data Acceptability Analytical method uncertainty may be defined and reported in one of two ways. The first approach uses historical LCS data that is control charted and is used to evaluate method accuracy and precision, based on procedures defined In ETS-12-012. In ETS-12-012, a detailed estimation of uncertainty measurements was performed on ETS-8-231.2, "Solid Phase Extraction and Analysis of Perfluorinated Acids, Alcohol, Amides, Sulfonates and other Fluorlnated Compounds by High Performance Liquid Chromatography/Mass Spectrometry". The procedure outlined in this method utilizes the same preparation and analysis steps as those identified in ETS-8-231.2. In that evaluation it was determined that the use o f control charts was an acceptable approach to determining analytical method uncertainty. A t least twenty data points are required when using this method for determining analytical uncertainty. The method uncertainty is defined as 2x the standard deviation of the percent recoveries of the pooled lab control spikes. While all LCS data points are control charted, only the most recent fifty data points are used for determining the method uncertainty. When less than twenty LCS data points have been generated for a given analyte, the batch LCS and FMS QC determine the data acceptability. If FMSs meet the 30% recovery criteria at a level appropriate to the endogenous level, and the LCS meet the 20% recovery criteria, then the uncertainty of the data is deemed accurate to within 10020%. If FMS do not meet the 30% recovery criteria, and historical FMS data does not exist, the analytical uncertainty is evaluated on a case-by-case basis and a discussion included in the final analytical report. 14 Pollution Prevention and Waste Management Sample extract waste and flammable solvent is discarded in high BTU containers, and glass pipette waste is discarded in broken glass containers located in the laboratory. 15 Records Each data package generated for a study must include all supporting information for reconstructibility 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. 16 Attachments None. 17 References "Method of Analysis for the Determination of Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) in Water", E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania, January 2000. E01-0454: Validation report for the "Method of Analysis for the Determination o f Perfluorooctane sulfonate (PFOS), Perfluorooctane sulfonylamide (PFOSA), and Perfluorooctanoate (POAA) In ETS-8-154.3 Page 18 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 91 of 178 Document mav be used, if current, for 14 days from 08/24/2007 3M Environmental Laboratory P0003268; Interim ReporttU W ater', E. Wickremesinhe and J. Flaherty, Study Number 023-002, Centre Analytical Laboratories, Inc., State College, Pennsylvania. 18 Affected Documents None. 19 Revisions Revision Number Summary of Changes 1 Updated to the new format. Changed Title. Section 1: States the validation of 3 analytes, removes reference to EPA document that's no longer applicable. Section 2: Provided for the extraction of more than the 3 validated analytes, allows the use of a LC/MS system, not only the LS/MS/MS previously mentioned. Section 3: Revised definitions for field matrix spike, field control spike, LLOQ, method blank, and MDL. Section 5: Reworded the interferences, added recommendation to use disposable pipettes. Section 6: Re-categorized and pared down. Section 7: Changed storage time to 6 months. Added more calibration points to the table. Section 8Added statement addressing labeling requirements and spiking procedures. Expanded section 8.8. Section 9: New Section Section 10: Changed some of the parameters in the tables. Allowed for use of different instrumentation. Added information from section 12 of previous version, extensively revised. Section 11 (section 9 in previous version): Clarification of wash step, stated exact volume ofeluate is 5 mL, revised standardization process, removed requirement to use LC/MS/MS. Section 12 (section 13 in previous version: no changes Section 13 (section 14 in previous version): Extensively rewritten. Section 14 (section 15 in previous version): no changes Section 15 (section 16 in previous version): Minor changes to recording requirements. Section 16 (section 17 in previous version): Removed attachment. Section 17 (section 18 in previous version): Removed reference to EPA document that no longer applied to this SOP. Section 18: New section. 2 Section 1: Added emphasis that the method is a performance-based method. Added statement that this method does not cover sample collection. Section 2: Removed statement that samples are shipped cold as this is no longer the practice. Removed reference to specific C18 SPE cartridge. Added statement that other extraction and elution volumes may be used. Section 3. Minor edits/clarifications to several definitions. Added surrogate and SPE cartridge as a definition. Removed references to LOD and MDL as this ETS-8-154.3 Page 19 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 92 of 178 DcrJurneru may he used, if current, fos 14 days from 3M Environmental Laboratory P0003268; Interim ReportU laboratory does not report LCD and/or MDL values. Section 6. Added reference to automated SPE workstation. OSection 7. Added additional analytes and updated standard preparation examples. Section 8. Removed verbiage that pertained to sample collection as the 3M Environmental Lab personnel typically do not collect samples. Addressed sample bottle preparation. Section 9. Changed method blank criteria, LMS and FMS acceptance criteria from 100+25% to 10030%, and LCS criteria where pooled recoveries are used to determine acceptance. Section 10. Updated all example instrument conditions for Sciex instrumentation removed Micromass references Section 11. Clarified extraction procedure - removed inclusion of a 40% methanol wash step. Section 12. Minor edits. Section 13. Added section on determination of analytical uncertainty and changed performance criteria as appropriate. 3 Section 11.1. Added use of sodium thiosulfate ETS-8-154.3 Page 20 of 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 93 of 178 3M Environmental Laboratory P0003268; Interim ReportM Attachment C: Protocol and Protocol A mendments 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 94 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 STUDY PROTOCOL Study Title: PeFrfisluho,AranonoadPclyetCrasiflnsaluemosofusrPloMUtheimsreoifxnanlautgietnooLer(rPsoCiubnF/lMugOfotPSaSnrn)/aMoeitngesSur(WalPffmooFarntHeathrSt,ee),S(3aPoMniFld,BDSSee)dc,aimtuernt, MEPxIyLRIeMseSarPcrhoStotucodlyNNuummbbeerr:.:P00103073.0226189 Performing Laboratory: MPI Research, Inc. State College 3058 Research Drive State College, PA 16801 Phone:(814)272-1039 Sponsor Representative: Michael A. Santoro Director of Regulatory Affairs 3M Building 023 6-01-B-10 St. Paul, MN 55144 Phone: (651) 733-6374 Page 1 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 95 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 DISTRIBUTION: 1) Jaisimha Kesari, Study Director, Weston Solutions, Inc. 2) Karen Risha, Principal Investigator, MPI Research, Inc. 3) Michael A. Santoro, Sponsor Representative, 3M Company 4) MPI Research Quality Assurance Unit Page 2 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 96 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 PROTOCOL APPROVAL Study Title: P(AFPrinsoFhagHl,rySaasnm)is,daoCnfdlPaPmereifrlfu'Jluo.'oirforiobgouLctafta.n/neMessuSul/ilMofonSnaatfetoe(rP(tPhFFeBO3S?S)*,)iPDinereWfnlutaoaterror.Mh:Seexonailtn.oeSrsieundlgiimoneantte, MExPy1LRJMesSeaPrcrohtoSctuodl yNNumumbebre:rP: 000103372.062819 APPROVALS JWaiessitmonhaSKoleustaiorin,sStudy Director Date M3MichCaoeml Apa.nSyant Sponsor Representative Date / -J W J -tff- Date Page 3 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 97 of 178 3M Environmental Laboratory P0003268; Interim ReportU4 ExyLIMS Protocol Number: P0003268 TABLE OF CONTENTS TITLE PAGE..................................................................................................................................................................1 D IST R IB U T IO N ............................................................................................................................................................ 2 PROTOCOL APPROVAL............................................................................................................................................3 TABLE OF CONTENTS..............................................................................................................................................4 INTRODUCTION.......................................................................................................................................................... 5 TEST MATERIALS......................................................................................................................................................5 OBJECTIVE...................................................................................................................................................................6 TESTING FACILITY................................................................................................................................................... 7 STUDY DIRECTOR..................................................................................................................................................... 7 SPONSOR REPRESENTATIVE.................................................................................................................................7 PRINCIPAL INVESTIGATOR...................................................................................................................................7 PROPOSED EXPERIMENTAL START AND TERMINATION DATES..........................................................8 IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM.............................................................. 8 SAMPLE PROCUREMENT, RECEIPT AND RETENTION................................................................................8 SAMPLE IDENTIFICATION.....................................................................................................................................9 ANALYTICAL PROCEDURE SUMMARY............................................................................................................9 VERIFICATION OF ANALYTICAL PROCEDURE.............................................................................................. 10 METHOD FOR CONTROL OF B U S .......................................................................................................................11 STATISTICAL METHODS.........................................................................................................................................11 GLP STATEMENT.......................................................................................................................................................11 REPORT..........................................................................................................................................................................12 SAFETY AND HEALTH.............................................................................................................................................13 AMENDMENTS TO PROTOCOL.............................................................................................................................13 DATA RECORD KEEPING........................................................................................................................................13 QUALITY ASSURANCE............................................................................................................................................14 RETENTION OF DATA AND ARCHIVING.......................................................................................................... 14 APPENDIX I, ANALYTICAL METHODS...............................................................................................................15 Page 4 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 98 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 INTRODUCTION The purpose of this study is to perform analysis for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) in water, soil, sediment, fish, and clams using LC/MS/MS for the 3M Decatur Monitoring Program. The study will be audited for compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by the Quality Assurance Unit of MPI Research. TEST MATERIALS The test materials are perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS). PFBS Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt ^FSCVK*) Transitions Monitored: 299 -> 80,99 Structure: FFFF 3 FFFF PFCHhSemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (CFuSOa'K*) Transitions Monitored: 399 -* 80, 99 Structure: F F F FF F FFF FFF 3 PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CgF^C^lC) Transitions Monitored: 499 - 80, 99 PageS of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 99 of 178 3M Environmental Laboratory P0003268; Interim Reports ExyLlMS Protocol Number: P0003268 Structure: FFF F FF FFFFFFFF 3 OBJECTIVE The purpose o f this study is to perform analysis for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) in water, soil, sediment, fish, and clams for the 3M Decatur Monitoring Program using the current versions of the following 3M Company and MPI Research analytical methods: ETS-8-012: "Method of Analysis for the Determination o f 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) in Water, Soil and Sediment by LC/MS/MS" V0001780: "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS" V0001781: "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS" V0001782: A"Mciedth(PodFOoAf A) innalSyesdisimfoerntthbeyDLeCte/MrmSi/nMatSio"n of Perfluorooctanoic V0001783: "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS" The primary analytical method for the analysis of the water, soil, and sediment samples is the ETS-8-012 method. In instances where quantitative analytical results are not obtained by this method, the Study Director may direct the performing laboratory to analyze the samples by alternate methods (V0001780 for water samples, V0001781 for soil samples, and V0001782 for sediment samples). Page 6 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 100 of 178 TESTING FACILITY M(foPrImRereslyeaErxchyg, eInncR. esearch, Inc.) State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 Fax:(814)231-1580 STUDY DIRECTOR Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j .kesari@westonsolutions.com SPONSOR REPRESENTATIVE Michael A. Santoro 3M Company Director of Regulatory Affairs 3M Building 0236-01-B-10 St. Paul, MN 55144 Phone: (651) 733-6374 PRINCIPAL INVESTIGATOR Karen Risha MPI Research, Inc. State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 karen.risha@mpiresearch.com 3M Environmental Laboratory P0003268; Interim ReportH ExyLIMS Protocol Number: P0003268 Page 7of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 101 of 178 3M Environmental Laboratory P0003268; Interim ReporttU ExyLIMS Protocol Number: P0003268 DPRAOTEPOS SED EXPERIMENTAL START AND TERMINATION It is proposed that the analytical portion of this study be conducted from June 14, 2007 to December 31, 2007. The actual experimental start and termination dates will be included in the interim reports and the final report. IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM The following are the test systems for this study: Water (groundwater and surface water) Soil Sediment Fish Clams The samples will be collected by Weston Solutions. The control samples will be purchased and prepared by the testing facility. Purchase and processing details for the control samples will be included in the appropriate interim report and/or final report associated with this study. The analysis of PFBS, PFHS, and PFOS are included in a voluntary effort by 3M to gain additional characterization of samples collected to comply with the 3M Letter of Intent (LOI) with the U.S. EPA to collect PFOA data. Additional samples not part of the LOI may be analyzed at the discretion of the Study Director. SAMPLE PROCUREMENT, RECEIPT AND RETENTION Water, soil, sediment, fish, and clam samples are being received at MPI Research directly from Weston Solutions. The details of sample procurement procedures for this study are outlined in the 3M work plan entitled "Phase 2 Work Plan for Sampling Environmental Media for PFOA at the 3M Decatur, AL Plant." The number and types of samples received and analyzed will vary depending on data needs for additional characterization of PFBS, PFHS, and PFOS concentrations in various environmental media and availability in the bfieelddo.cuTmheentotetadlinnutmhebearpporfosparmiapteleisnrteerciemivreedpoarntdaasnsoaclyiazteeddfworitehatchhismsatutrdiyx. will Water, soil, and sediment samples will be used as received at MPI Research. These samples will be homogenized before the extraction process by vigorously shaking the sample bottles. These samples will be stored refrigerated at 2C-8C. Fish and clam samples will be processed according Page 8 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 102 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 to the appropriate analytical method (see Appendix I). These samples will be stored frozen at < -10C. The receipt and processing of the samples will be documented in the appropriate interim report and raw data associated with the study. SAMPLE IDENTIFICATION Prior to analysis, each sample will be assigned a laboratory sample reference number. The reference number will be unique and will distinguish each laboratory sample that is processed throughout the analytical procedure. Chromatographic data will be identified by the laboratory sample reference number. Sample storage conditions and locations will be documented throughout the study. ANALYTICAL PROCEDURE SUMMARY References: ETS-8-012: "Method of Analysis for the Determination of 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) in Water, Soil and Sediment by LC/MS/MS" V0001780: "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS" V0001781: "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS" V0001782: "Method of Analysis for the Determination of Perfluorooctanoic V0001783: A"Mciedth(PodFOoAf A) innalSyesdisimfoerntthbeyDLeCte/MrmSi/nMatSio"n of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS" The primary analytical method for the analysis of the water, soil, and sediment samples is the ETS-8-012 method. In instances where quantitative analytical results are not obtained by this method, the Study Director may direct the performing laboratory to analyze the samples by alternate methods (V0001780 for water samples, V0001781 for soil samples, and V0001782 for sediment samples). Page 9 o fS7 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 103 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 The above referenced methods are to be followed for the analysis o f the samples with the following exceptions: If sludge samples are received by MPI Research to be included in the study, the sludge samples will be extracted and analyzed following the method for soil samples. If necessary for the preparation of appropriate standards levels, alternate weights of test material and alternate volumes o f suitable solvent (acetonitrile, methanol, etc.) may be used. If necessary, the duplicate bottle of a water sample may be used in an extraction if the primary bottle does not have enough volume available. VERIFICATION OF ANALYTICAL PROCEDURE A laboratory control sample will be used for the preparation of fortified control samples. The test substance will be made into solutions as per the method, and added to the matrices via a micropipette. For water sampling, MPI Research will supply one bottle per sample collected. The bottles will be 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottles. These bottles have been routinely used for fluorochemical sample collection at the testing facility and have been shown to be free of PFBS, PFHS and PFOS. Samples will be added to each container to a volumetric fill line at 200 mL. A field duplicate, a low field spike, a mid field spike (optional, at the discretion of the Study Director), and a high field spike of each sample will be collected. The low, mid (optional), and high field spike bottles will contain PFBS, PFHS and PFOS as well as perfluorooctanoic acid (PFOA) and 1,2-13C perfluorooctanoic acid (13C PFOA, optional). PFOA and 13C PFOA (optional) are included in the solutions used to spike the samples. The results for PFOA and 13C PFOA (optional) will not be reported in this study. MPI Research will supply one field blank (control water) and two or three field blank spikes (control water fortified with PFBS, PFHS and PFOS at a low, mid (optional) and high level) for every twenty aqueous samples collected. At the testing facility, each water sample (excluding field duplicates and field spikes) may be extracted in duplicate and may also be fortified at a low, mid (optional), and high concentration and processed through the described procedure. The use of the in lab duplicate and the in lab fortified spikes is not a requirement but may be requested to determine method accuracy and to check for bias at the discretion of the Study Director. For soil, sediment, fish, and clams, MPI Research will supply one 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottle per sample collected or atoztihpe-sseaaml bpaleg.loAcaltlioconn. taSianmerps/lbesagwsilulsbede afodrdesadmtopleeaccohllceocnttioaninewrilolrbbeasghiinpptehde Page 10 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 104 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 field. At the testing facility, each sample will be extracted in duplicate and will also be fortified at a known concentration with PFBS, PFHS and PFOS at a low, mid (optional, at the discretion of the Study Director), and high level and processed through the described procedure to determine method accuracy and to check for bias. Low, mid, and high spiking levels for each matrix are defined below: Matrix Low PFOA Mid PFOA High PFOA Spiking Levels Spiking Levels Spiking Level Water 0.25 ng/mL 5.0 ng/mL 100 ng/mL Soil 2 ng/g 40 ng/g 800 ng/g Sediment 2 ng/g 40 ng/g 800 ng/g Fish 2 ng/g 40 ng/g - Clams 2 ng/g_____ 40 ng/g - Low, mid and high spiking levels of the analytes for each matrix may be altered depending on sample size, sample availability, and/or to cover analyte concentrations expected in the samples. In instances where the expected analyte concentrations exceed the relevant range of the lower level spikes, the lower level spikes may be deferred. Recoveries are anticipated to be between 70% and 130% of the fortified levels; however, the exact precision and accuracy will be determined by the analysis of the quality control samples described above. A statement of accuracy will be included in the appropriate interim report. METHOD FOR CONTROL OF BIAS Control of bias will be addressed by taking representative sub-samples from a homogeneous mixture of each matrix from untreated control samples, and by analyzing at least two levels of fortifications. STATISTICAL METHODS Statistics will be limited to those specified in the subject methods and to the calculation of average recoveries, as applicable. GLP STATEMENT All aspects of this study shall be performed and reported in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The final report or data package (supplied to the Sponsor) shall contain a statement that Page 11 of57 3M Environmental Laboratory QLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 105 of 178 3M Environmental Laboratory P0003268; Interim Reporm ExyLIMS Protocol Number: P0003268 the study was conducted in compliance with current and applicable GLP standards and will outline any deviations in the study from those standards. RThepisressetnattaetmiveen.t will be signed by the Study Director and Sponsor REPORT Interim reports will be prepared by the principal investigator or their designee for specific sampling sites and sample matrices due to the size of the data sets and the phased nature o f sample collection activities. A final report will be prepared by the principal investigator or their designee at the conclusion of the study. All reports will include, but will not be limited to, the following: The name and address of the Study Director, Sponsor Representative, and of the testing facility. A statement of GLP compliance (any related documentation, such as chain-of-custody records, must be in the study records). The signed and dated statement by the MPI Research Quality Assurance Unit regarding dates of study inspections and dates findings were reported to the Study Director and Management. A description of the exact analytical conditions employed in the study. If the subject method was followed exactly, it is necessary to include only a copy of the analytical method. Any modifications to this method will be incorporated into the report. If the method is photo-reduced, the project number and page number must be included on each page. Description of the instrumentation used and operating conditions. All results from all sets analyzed. Control and fortified samples will be identified and the data table will include sample number and fortification level. Representative chromatograms for each analyte in each matrix, including chromatograms of a standard and a control sample, and a chromatogram at a fortification level. The location of the analyte peaks will be clearly identified in all chromatograms. All circumstances that may have affected the quality or integrity of the data will be documented in the report. Locations where raw data, interim reports, and the final report are to be archived. Page 12 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Weils (Sulfonates) Page 106 of 178 3M Environmental Laboratory P0003268; interim Report#4 ExyLIMS Protocol Number: P0003268 Additions or corrections to the final report shall be in the form of an amendment signed by the Study Director. The amendment shall clearly identify that part of the report that is being altered and the reasons for the alterations. The amendment will be signed and dated by the Study Director and the Sponsor Representative. All applicable requirements for reporting of study results as per 40 CFR 792.185. SAFETY AND HEALTH Laboratory personnel will practice good sanitation and health habits. Every reasonable precaution shall be taken to prevent inadvertent exposure of personnel and the environment to the test or reference substance(s). AMENDMENTS TO PROTOCOL All significant changes to the analytical protocol outlined here will be expressed in writing, signed and dated by the Study Director and Sponsor Representative. Amendments usually will be issued prior to initiation of study plan change. However, when a change is required without sufficient time for the issue of a written amendment, that change may be effected verbally with supporting documentation signed and dated by the Study Director and followed with a written amendment as soon as possible. In this case, the effective date of the written amendment will be the date of the documented change. Copies of the signed amendments will be appended to all distributed study plan copies. The original amendment will be maintained with the original study plan. Any deviations from the study plan or from the analytical method as provided will be documented and reported promptly to the Sponsor Representative. DATA RECORD KEEPING Records to be maintained include the following (as appropriate): Sample tracking sheet(s) HSaismtoprlye raencdeipprtepreacroartdiosn, sotforstaagnedhairsdtosr(ys,toacnkd, cfohratiinfiscaotfiocnu,stcoadliybration) Description of any modifications to the method Instrument run sheets, bench-sheets or logs Analytical data tables All chromatographic and instrumental conditions Page 13 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 107 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Sample extraction and analysis dates A complete listing of study personnel, signatures and initials Chronological presentation of all study correspondence Any other documentation necessary for the reconstruction of the study Chromatograms- All chromatograms will contain the following: oSfaminptelreeisdt,enantidficinajteiocnti,oninnjeucmtiobnerdcaotrer,easrproonwdionrgottohtehreinrudnic.ation of the area Additionally, fortifications will include the amount of analyte added and the sample number of the sample that was fortified. Analytical standard chromatograms will additionally include the concentration (e.g., pg/mL). As part of the documentation the following sheets will be included in each analytical set: a run sheet listing the samples to be run in the set, and an instrument conditions sheet describing the instrument type and operating conditions. QUALITY ASSURANCE The QA Unit o f MPI Research will inspect the study at intervals adequate to assure compliance with GLP's, and will report the findings of audits to the Study Director, MPI Research Management, and the Sponsor Representative. RETENTION OF DATA AND ARCHIVING All hard copy raw data, including, but not limited to, the original chromatograms, worksheets, correspondence, and results shall be included with the data package submitted to the Study Director. These will be archived with the original study plan, amendments, final report, and all pertinent information from the Sponsor. The testing facility shall keep all electronic raw data and any instrument, equipment, and storage logs for the period of time specified in 40 CFR 792.195. An exact copy of the materials submitted to the study director will also be kept at MPI Research, State College. MPI Research will obtain permission from the study director before discarding or returning samples. Page 4 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Weils (Sulfonates) Page 108 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 APPENDIX I ANALYTICAL METHODS ETS-8-012: "Method of Analysis for the Determination of 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) in Water, Soil and Sediment by LC/MS/MS" V0001780 "Method of Analysis for the Determination of Perfluorooctanoic V0001781 A"Mciedth(PodFOoAf A) innaWlysaitserfobrythLeCD/MetSer/MmSin"ation of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS" V0001782 "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" V0001783 "Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS" Page 15 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 109 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 3M Environmental Laboratory . M ethod . Method ofAnalysis for the Determination of PerfluorobutanoleAcid (PFBA), PerfluoropentanolcAdd (PFPeA), Perfluorohexanolc Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (PFO), Perfluorononanoic Acid (PFNA), Perfluorodecanolc Acid(PFDA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid(PFDoA), Perfiuorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment byLC/MS/MS MethodNumber: ETS-8-01Z1 Adoption Date: Upon Signing Effective Date: Approved By: Date ETS-8-012.1 Page I o f 12 M atta) of Anafyds for Iha Oataiminatfon o f PortfciorobutanoteAdd (PFBA), Pacfluoropanlanolc Add (PFPaA). Parduorehaxanaic Add (PFHA). PerfluoraftapUAofe Add (PFHpA). purfuorooctanoie Add (PFOA). Ferfluorononarwlc Add (PFNA). P a rA ttradecftae Add (PFDA), ParDuofoundacanoic Add (PFUnA). Pcrfuorododacanote Add (PFOoa). P arfuorebutanaaiiifotuta (PFBS). Perduorohexanasuftnata (PFHS). and PartluoroocfsnaiuWMtata (PFOS) to Watar, Sod and Sadimanf by COUSAIS Page 6 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 110 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 1 Scopo and Application This method is to be used to quantity Perfiuarobutanolc Add (PFBA), Perfiuoropentanoic Add (PFPeA), Periluorahexanoic Add (PFHAJ, Perfluoroheptanaic Acid (PFHpA), Pedluoisodenoic Acid (PFOA), Peritoononanoic Add (PFNA), Perfiuorcdecanoic Acid (PFOA), Perfiuoroundecanoic Acid (PFUnA). Perfluorododecanoic Add (PFDoA), PerfluoroOutanesutfonate (PF8S), Pertluorohaxanesutfonate (PFHS), and Perfluoraoctanesulfbnale (PFOS) by High Performance Liquid Chromatography coupled to a tandem Mass Spedromebic Detector (IC/MS/MS) in water, soil and sediment. The method is designed to target a lower limit o( quantitation (LOQ) of0.025 ngfmL (water) and 020 ng/g (soil and sediment). 2 Method S u m m a r y _________________________________ Aqueous samples are mixed with equal volumes ofacetonitrile, thoroughly mitred, centrifuged if necessary, and alquated lor analysis by LC/MS/MS. Similarly, one-gram aliquots of soil and sediments are mixed with 80:20 acetonitrfle:water mixture, thoroughly mixed, centrifuged, and liquated for analysis by LCIMS/MS. . 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 lor each sample be determined using field matrix spikes (aqueous samples) or laboratory matrix spikes (soil and sediment) to verify that the method is applicable to each sample matrix. Sample results for spikes outside o f 70% to 130%, will not be reported due to noncompient quality control samples. Fortification levels for field matrix spikes and lor laboratory matrix spikes should be at least 50% of the endogenous level end 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 ct the Working Standard (WS) into a predetermined amount of ASTM type I or HPLC grade water, diluted with acetonitrile, end analyzed according (o this method. Calibration standards are used to caibrate 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 extracted and analyzed separately with identical procedures. Analysis of LDSs compared to that ol the first. aliquot give a measure of the precision associated with laboratory procedures, but not with sample collector!, preservation, or storage procedures. . 3.3 Field Blank (FB)/Trlp Blank ASTM Type I or HPLC grade water pieced in a sample container In the laboratoryarrd treated as a sample In all respects, Including exposure to sampling site conditions, storage, preservation end all analytical procedures. The purpose of the FB is to determine it test substances or other interferences are present in the field environment This sample Is also referred to as a Trip Blank. Trip blanks are not a requirement (or soil or sediment samples. 3.4 Field Duplicate Sample (FDS, Field Dup) A sample collected in dupieate at the seme time from the same location as the sample. The FDS is placed under identical circumstances and treated exactly the same throughout field and laboratory procedures. BTS-S-012.1 Page 3 o f 12 Method o f A ra ly s li for Iho O elem rlnatlon of PerfluofoUuUnolc A dd (PFBA), PorfluoroponUnoie Add (P FP tA ), Perfluorotrexanotc A dd (PFHa ). P erfluoroheplande A dd (PFHpA). P erSudroocuitde A dd (PFOA). PotSuoranonanofc Add (PFNA). Perituorodeconofc A dd (PFOA), Pofltuoroundecondc A dd (PFUnA). Pertuerododecsnofc A cd (PFOaA), Periluorobutaneeulfonalo (PFBS), Pcrfluorohexanesdlonate (PFHS). and PeriluorooctaneM jIfonate (PFOS) in W olor, S d l and Sediment by LC/MSiMS Page 17 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) P a g e lli of 178 3M Environmental Laboratory P0003268; Interim Reports ExyLIMS Protocol Number: P0003268 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 taborslory before the bodies 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' fineon the outside of the sample container. The FMS should be spited between approximately 50% and 10 times the expected analyte concentration in the sample. If the expected range of analyte concentrations Is unknown, multiple spkes at varying levels may be prepared to increase the likelihood that a spike at an appropriate'level is made. The FMS is analyzed lo ascertain if any matrix effects, interferences, or stability issues may complicate the interpretation ofthe sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) An aliquot ofASTM Type I.or HPLC grade waterlo which known quantities of the target analytes are added in the laboratory prior to the shipment ofthe colecfion bottles. The FSCS Is extracted and analyzed exactly like a 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 ate not known or may vary. At least one separate, urvepiked sample must be taken at the same time and placeas each FMS. . 3.7 Laboratory Control Sample (LCS) ' An aliquot of control matrix to which known quantities of the target analytes ate added in the laboratory at the time of sample extraction. At least two levels are Included, one generally at the lew end ofthe 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 ofa sampleto which known quantities oftarget analytes are added in the laboratory. The LMS is extracted and analyzed exactly like a laboratory sample to determina whether the sample matrix contrfoutes bias to the analytical results. The endogenous concentrations of the analytes in the sample matrix must be determined in a separate elquot and the measured values In the LMS corrected for these concentrations. LMSs are required for soils and sediments and are optional for analysis of aqueous samples. 3.9 Laboratory Sample . A portion or aliquot ofa 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 concilions. 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 upperlimitof quantitation (ULOQ) for a dataset is the highest concentration that can be reliably quantitated within the specified limits of precision and accuracy during mutine operating conditions. The highest standard in the calibration curve that meets method criteria is defined as the ULOQ. ETS-8-012.1 Page 3 o f 12 Method o f Analysis fo r the Determ ination of Periluorobtdandc A dd (PFBA), Perfuoropentanotc Add (PFPeAJ, Periiuorohexanoic A dd (PFHA, Perfluoroheptanotc A dd (PFHpA), Perduoroodanoie A dd {PFOAi. Periluoronananolc Add fPFNA), Perfluorodecandc A dd (PFDA), Parituoroundecaholo A dd (PFUnA), Pertuorododacandc A dd (PFDoA), Periluorobutanesulfonate fPFBS), Periluorohexeneaulfonate (PFHS), and Periluoroodanesutronate (PFOS) In W ater, S d l and Sediment by LC/MStMS Page 18 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 112 o f 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 3.11 Method Blank .. An aliquot of conlrol matrix that is treated exactly Ike 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 ofa single-analyte prepared in the laboratorywith an assayed reference compound. 3.14 Surrogate A compound similar to the target analyte(s) in chemical composition and behavior that Is ra t normally found In the sample(s). A surrogate compound is typically a target analyte with at least one atom containing an isolopically labeled substitution. If used, surrogates) are added to all samples and quality control samples (except solvent blanks and half of the prepared method blanks).' Surrogate(s) era added to quantitatively evaluate the entire analytical procedure including sample collection, sanction, and analysts. Inclusion o f a surrogate analyte is an optionalquality control measure and is NOT required. 3.15 Working Standard (WS) A solution of severe! 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 safely glasses to prevent exposure to chemicals that might be present. The laboratory is responsible for maintaining a safe work environment and a outrent 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 a) personnelnvotvod in these analyses. 4.2 Cautions ' . The analyst must be familiar with the laboratory equipment and poteribalhazards including, but not United to, the use of solvents, pressurized gas and solvent Ones, high voltage, and vacuum systems. Refer to the appropriate equipment procedure oroperatormanualfor additionalinformation and cautions. 5 Interferences During extraction and analysis, major potential contaminant sources are reagents and glassware. AHmaterials used in the analyses shall be demonstrated to be free from interferences under condib'ons of analysis by running method blanks. ETS-8-01Z.1 Page 4 o r 12 Method of analysis fo r the Determ ination o f Partiuorotm unolc Add IPFBA), PerfluoropeM anolc A dd {PFPeA), Pertiuorohexanolc Add (PFHAJ, Perttuorohepranolc Add <PFHpA). Perfluoroedanole A dd (PFOA). PeiSuerononenoie A dd (PFNA). Perfluorodecenore A dd (PFOA). PertiuoroundecanolcAdd IPFU nnt. PerSuorododecendcAdd (PPOoAI. P erfU erotrutenetdlbnets (PF6 S). Pemuorehexanasulfonale (PFHS). and PeiSuoreodeneturlanete (PFOS) In w ater. Seti and Sedim anl by LCMSrMS Page 19 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 113 of 178 3M Environmental Laboratory P0003268; Interim ReporttM ExyLIMS Protocol Number: P0003268 Parts and supplies that contain Teflon should be avoided or minimeed due lo the possibility of interference andibr contamination. These may include, but aie 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 calrbration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high performance liquid chromatograph capable of pumping up to 2 solvents and equipped with a variable volume injector capable of injecting 5-200 pL connected to a tandem Mass Spectrometer (IC/MSfMS). Applied Biosystems SciexAPI 5000 instrumentation is required lo meetthe LOQs of0.025 ngtotL (water) and 0.20 ngfg (sol and sediment). If analyte concentrations require dilutions for one or more analytes that preclude the targeted LOQs from being reached, Applied Biosystems Sciex API 1000 instrumentation may be utilized since the LOQs will already be raised. ' Analytical balance capable of reading to 0.0001 gram. - A device to colled raw data for peak Integration and quantitation. 15-mL and 50-m l disposable polypropylene centrifuge tubes. Disposable micropipettes (10-20 pL, 25-50 pL. 50-100 pL. 100-200 p i). 125-mLLDPE narrow-mouth bottles, 2-mL dear HPLC vial kit. ' Disposable pipettes, polypropyleneor glass as appropriate. Ultrasonic bath. Centrifuge capable ofspinning 15-mL and 50-mL polypropylene tubes at 3000 tpm. 6.2 Chromatographic System ' Analytical Column: Luna 3 pm C8 (2) Mercury (Phenomenex), 2 mm x 4 mm. 3 pm (PIN: OOM-4245QO-CE) Temperature: 35*C Mobile Phase (A):2 mM Ammonium Acetate In Writer Mobile Phase (B): Methanol Gradient Program: Bm aim ip) %A %B 0.0 90 10 0.5 90 10 2.0 10 90 5.0 10 so 5.1 0 100 6.0 0 100 6.1 90 10 10.0 90 10 Injection Vokime: 5 pL (can be increased to as much as 50 pi). Flow Rato ' rmUmlni 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Quantitation: Peak Area - external standard calibration curve, 1Atweighted. ETS-8-012.1 Pages o f 12 Method ofAnetyilM toethe Determ ination o r PcrituorobuUnolc Add (PFBAJ. Perfluaropenranofc A dd (PFPeA), pedtuorahexanoie A dd (PFHA), P erftierotieplanolc A dd (PFHpA). PeiSuorooctonolc Add (PFOA), Partuorontew nolc A dd (PFNA). P erS uorodranolc A dd (PFOA). PeriluoraundecendcAdd (PFUnA), Porfluarododecondc Add (PFOoA), Perfluorabulsnesulfonato (PFBS), Perikiorohexaneautlgnale (PFHS). end P n ilu o ro o d s n n d to n itt (PFOS) In W ater. Soil and Sedim ent try IC/MSTMS Page 20 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 114 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 RunTime: -1 0 minutes. The previous Information is intended as a guide: alternate conditions and equipment may be used provided that data quality objectives are met. . 6.3 MS/MS System 6.3.1 Mode: Electrospray Negative MRMmode, monloring thefotadng transitions: Analvte Transition Monitored PFBA 213 -* 169 PFPeA 263 -* 219 PFHA 313 -.2 6 9 and 313 - 119 PFHpA . 363 - 319.363 169 and 363 - 119 PFOA 413 369.413 - 219 and 413 - 169 PFNA 463 -> 419. 463 -+ 169 and 463 -> 219 pfda 513 -> 469. 513 - 219 and 513 - . 269 PFUnA 563 - 519. 563 -> 269 and 563 ->219 PFDoA 613 -* 569.613 - 169 and 613 - 319 PFBS 299 -.8 0 and 299 -.9 9 PFHS 399 - 80 and 399 - t 99 PFOS 499 -+ 80.499 99 and 499 -> 130 Multiple transitions for monitoring the analytes is an option because summing multiple transitions may provide quantitation of isomers that more closely matches NMR data and may have the added benefit of increased anaiyte signal. 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 end equipment may be used. - 7 Reagents and Standards __ Water-HPLC grade Methanol- HPLC grade Ammonium Acetate-A.C.S. Reagent Grade Acetonitrile - HPLC grade PertiuorobutanoicAdd (PFBA) - Oakwood Products, Inc PeriluorcpentanoicAdd (PFPeA) - Sigma-AJdrich Perfluorohexandic Add (PFHA) - Oakwood Products. Inc PeriluoroheptanoicAcid (PFHpA) - Oakwood Products, Inc Perfluorooctanoic Acid (PFOA) - Oakwood Products. Inc Perftuonononanoic Add (PFNA) - Oakwood Products, Inc PerffuorodecanoicAcid (PFDAJ- Oakwood Products, (nc Perfluoroundecanoic Add (PFUnA)- Oakwood Products, Inc Perfluorododecanoic Acid (PFDoA)- Oakwood Products. Inc . ETS-6-012.1 P a g e io f 12 M etflod c iA nalyse fo r the D eterm intticn o fP artuorebdanolc A dd (PFBA). Perfluoropentanoic A do (PFPeA), Pertuoronexanofc Add (PFHA), P eritoroheptandc A dd (PFHpA). PailuoroocUnow A dd (PFOA), PerSuorononande A dd (PFNA), P eritorodecanolc Add (PFOA). Partluoroundecande Add (PFUnA). PerSuorododecandc A dd (PFDoA), Parfluorobutanetutfonate (PFBS), P erilu cro /ito in e w lfo n a te (PFHS), and PerSuorooctaneuifonale (PFOS) In W ater, Soil and Sedim ent by IC/M SA4S Page 21 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 115 of 178 3M Environmental Laboratory P0003268; interim Report#4 ExyLIMS Protocol Number: P0003268 Perfluorobutanesulfonate (PFBS) - 3M Perfluorohexanesulfonate (PFHS)- 3M PerfluoraodanBsuttonata (PFOS)- FfuKa . . The previous Information is intended as a guide. Reagents and standards from alternate sources may be used. 8 Sample Handling _____________ . 8.1 W ater Sample Extraction 8.1.1 Measure 10 mLofsampleintoa 5(PmLpolypropylene ccntrifoge tube. FottiiicaEcnsaretobedoneanNs point, i necessary. Odervolumes and containers may be usedasappropriate. 8.1.2 Add 10mLolacetonitrile tothe sample inthe centrifogetube. Captightly and shake. 8.1.3 Sonicate sample far*2 hours at loom temperature. Thisstep is optional, but is recommended if particutales appearto be present . 8.1.4 Centrifuge fcr -10 minutesat-3COOrpm. Thisstep is optional, butis recommended if samples are sonicated. - 8.1.5 8.1.6 Transfer a porticnofthe supernatantto anautosamplervialforanalysis. Di/uts sample, ifnecessary, w ifi 50:50acefcnitniewater ' 8 2 Soil and Sediment Extraction 82.1 Welghl g ofsample intoa15wnlpolypropylene centrifugetube. Fortifications are to be done at thispoint, if necessary. 822 Add 8 mb o f8020 aaetontrilewaferto the samplein the cenbtluge tube. Cap rightly and shalre 82.3 Sonicate samplefor-2 hours atroomtemperature. 82.4 Centrifogefor-10mlnutesat-3000rpm. 82.5 Transfera portion ofthe supernatantto anautosa/rplervalfor analysis. 82.8 Dilutesampleifneoessaiy,w9h50:50acetonj|ijeniieter. 827 Analyze samples usingetectrosprayLOMSMS Other weights and volumes can be used as long as the QC elements specified in this method are satisfied and all sample preparation procedures may be reconstructed. 9 Sample Analysis LC/MS/MS ' ETS-8-012.1 Page 7 o f 12 Method o f Analysis for lb s Determ ination o f PefftuorotniU noic A de (PFBAJ, PerSiioropentanolc A dd (PFPeA). Potfhjotghexsnold A dd (PFHA). P srftioroheptanofc Add (PFHpA), P edluoioM arioic A dd (PFOAJ, ParSuerononanolc A dd (PFNA). Pentuoradecanob A dd (PFOAJ. Perltuoroiardeeanolc Add (PFUnA). PerSuorodedecandc A dd (PFDoAJ, P eduorobvtanesullonala (PFBS). AarSuorohezanendonala (PFHSl, and Perduontoosnssulftinafs (PFOS) to Weur. Sell and Sadlmenr try LOUSIUS Page 22 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 116 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyUMS Protocol Number: P0003268 9.1.1 A minimum ofsixcalibrationlevelsmustbepresentin thefinalcaibration curve. 9.12 An entire setofralbraSon standards is injectedat the beginningafasample setpriorto sample analysis. As analternative; anentiresetofealbalion standards mayhe injected atthebeginningofa samplesetWowed by catbralion standards interspersedevery 5-10 samples (to acoountfora second setofstandards). In either case, cafbratron standardsora conlruiig calibrationverification standard must bracketthe lin t sampleand tie last sample. Analyticalstudiosmay only roquirethatan iniialcalixation curve be analyzed priorto samplesand thatthe oontinuedaccuracy otthe initialcalbation curve be conftmed bytie analystsof continuing caibration verification standards. Thesame approachshouldbe usedthroughouttfie entire study unless reasons aredocumentedandtechnicaljustificationto changeis approved priorto sampleanalysis. 9.1.3 The standardcun* Is plotted by quadraticit (y * a*8+bx+c),weighted 1Acor unweighted, orusinga inear fit. weighted 1At, usingsuitable software. Thecafbraton curves mayincludebutshould notbe forced through zero. The mathematical methcd usedtoralculatethe caibration curve should be applied coraistently throughouta study. Anychangeshould be documented In the law data.' 9.1.4 Samplescontainrrganatytas thatare quantitatedabove(heconcentration ofdie higheststandardin (he curveshouldbe firrtherdilutedand reanalyzedorre-iyscted usinga smafcrvolume. 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 (water) or 0.20 ng/g, wet weight (soil and sediment). Any deviations from the quality control measures speled out belowwill be documented In the raw data and footnoted in the final report 10.2 Blanks 102.1 Method Blank Method blanks mustbe prepared with each extraction batch. A range of three to seven method blanks must be prepared. These method blanks must be interspersed throughout the extraction batch and analyzed interspersed throughoutthe analytical sequence. ' ' . 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. 1922 Solvent Blank Solvent blanks must be analyzed throughout the analytical sequence. Solvent blanks that show area counts greater than 50% of the area counts of the LOQ standard must be evaluated to determine If analytical results are significantly Impacted by sample cany-over or an unacceptable buildup ofanalyte in the kistrumental background. 10.3 Sample Replicates Samples should be prepared in duplicate In the lab (soil and sediment) or collected In duplicate in the field (water). The relative percent difference, RPD, should be reported. RPD results greater than 20% (water) or ETS-8-012.1 Page I of 12 Method o f A M lysis for the Determination o f Pertuorobudnoie A dd (P fBA), PerfluoropenUnote A dd (PFPeA), P crftorohexftnolc ' A dd (PFHA), P srfluorotoplanoic A dd (PFHpA), Pe/fluoroodenoie A dd (PFOA). PerfluorononanoJc A dd (PFNA). PortHwodecanoic A dd (PFDA), Perluoroundecanoie Add (PFUnA), P eriluorododecanolc Add (PFDoA). Perfluorobulaneaulto n a l* (PFBS), P erfluorahesannuffonet* (PPHS), end Periluorooctaneiuffenafe (PFQS) In Wfeter, Sofl and S etfm enl by L&M &M S Page 23 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 117 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 30% (soil and sediment) will be flagged in the report but will not be excluded from reporting. The requirement for replicates excludes field blanks and rinse 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 extraction batch. Low lab control spikes should be prepared at concentrations in the range offive to ten times higher than the targeted LQ 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 for these six pooled control samples must be less than or equal to 20% and the average reoovery must be 00-120%. If the above criteria are not met, the entire set of samples should be re-injected or re-extracted as appropriate. 10.6 Field Matrix SpJkas / Lab Matrix Spikes Recoveries of field matrix spikes (aqueous samples) and laboratory matrix spikes (soils and sediments) are anticipated to be between 70% and 130% of the fortified levels. If the recoveries of the spikes fall outside the acceptable range, the sample result w il be reported as *NR' (not reported due to non-compliant QC results). The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the endogenous levelto be used withoutjustification to determine the statement ofaccuracy for analytical resuis. The average ofthe sample and the lab dupficate (soils and sediment) or field duplicate (water) should be used to calculate the recovery. 10.7 Standard Preparation - 10.7.1 StandardStock Solutions Prepare individual stock solutions of each analyte at -1000 pgfrnL by weighing 100 mg ofanalytical standard (corrected for purity and salt content if necessary) and dilute to 100 mL with methanol or acetonitrile In separata 100-mL volumetric flasks. For purity correction, take the amount of analyte that is needed for weighing (l.e.100 mg) and divide by the purity in decimalform (Le. 99.6% * 0.996). The result is the weightthat is needed to make the solution corrected for purity (i.e. weigh 100.4 mg). For sail correction, calculate the salt content by taking the molecular weightof the target compound (i.e. PFOS * 499) end dividing by the molecular weight of the entire compound (Le. PFOS potassium salt (CftFnSQrlf 538). The result is the salt content in decimal form (i.e. 0.9275). Take the amount of analyte that is needed for weighing (Le. 100 mg) and divide by th salt content in decimal form. The result is the weight that is needed to make the solution corrected for salt content (Le. weigh 107.8 mg). Store alt stock solutions in appropriate containers and at appropriate storage conditions for up to 6 months from the dale ofpreparation. ' - Alternate stock solution concentrations can be made, If necessary, using alternative masses and volumes. 10.7.2 StandardFortification Solutions A 10 pg/mL mixed fortification solution containing aBof the analytes is prepared by bringing 1 mL of each of the 1000 pgftnL stock solutions to a final volume of 100 mL w ih acetonitrile in a 100-mL volumetric flask. A 1.0 pg/mL mixed fortification solution containing all ofthe anstytes is prepared by bringing 10 mL of the 10 pgfoiL mbced solution to a final volume of 100 with acetonitrile in a 100-mL volumetric flask. A 0.1 pg/nt. mixed fortification solution containing all of the analytes is prepared by bringing 10 mL of the 1.0 pg/mL mixed solution to a final volume of 100 with acetonitrile in a 100-mL volumetric flask. A 0.01 pg/mL mixed fortification solution containing all of the analytes Is prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with acetonitrile in a 100-mL volumetric flask. Store aBfortification standards up to 6 months from the date of preparation . ETS-8-012.1 Page 9 o ft 2 Method o f Analysis for the DetermineSon oTPerfluorobutanoie Add (PFBA). Periluoropentanole A dd (PFPeA). Peffluorohexandc A dd (PFHA), PerSuoroheptandc Add (PFHpA), P e rtW w cu n o lc A dd (PFOA). Perfluorononanoic A dd (PFNA), Peifluorodecanoie A dd (PFOA). Perfluoroundeeanoic Add (PFUnA). Perttorododecenolc Add (PFDoA). Perduorobutaneeulfonaie (PFBS). P aritorohexenesiifonete (PFHS). end PertiuorooctanesuUbnale (PFOS) in W ater, S oli and Sediment by LC/MS/MS Page 24 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 118 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Alternate fortification solution concentrations can be made, If necessary, likewise, alternative volumes may be used. 10.8 Instrument Calibration 10.8.1 LC/MS/MScatbrstion standards are prepared ejdemaliy in 50:50acetonffle:waterand am used to construct the calibration curves forthewater, sod,and sedimentprocedures. 10.8-2 Thefofloring is a typicalexampleofacafibiaticn set AtemateoraddSonafooneerttatiorts may beprepared as.needed. Concentration Initiai Solution Final Concentration of of Initial Solution Aliquoted Volume (ng/mL) (mL) 100 5 Final Solution Volume (mL) 100 Calibration Standard (ng/mL) 5.0 100 2.5 . 100 2.5 10 10 . 100 s 10 100 1.0 0.5 - 2.S 1 10 10 100 100 0.25 0.1 0.5 10 100 0.05 1 2.5 100 0.025 Store all calibration standards for up to three months. Alternate volumes and concentrations of standards may be prepared as needed. . 11 Data Analysis and Calculations Use the (Mowing equation to calculate the amount of analyte found (in ngAnL, based on peak area) using the standard curve (linear regression parameters) generated by an appropriate software program: Analyte found (ng/mL). < P ** A r1-In te rc u t),, pF Slope DF a 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 percentrecovery. Recove , Total analyte found (ng/mL)-Average analyte found In sample (ng/mL) Analyte added (ngfaL) Use the Mowing equation to convertthe amountofanalyte found in ng/mL to ng/g (ppb). fpund, bi Analyte found(ng/mt) Volume extracted (mL) Sample weight (g) * Use the following equation to calculate the amount ofanalyte found in ppb basedon dry weight Analyte found (ppb) dry weight * Analyte found (ppb) x [100% / total solids (%}} 12 Method Performance ETS-e-012.1 Page 10 o f 12 Method of Analyala fo r the Determ ination o f Pertuorabutanole Add (PFBA), PerfluoropenUnolc A dd (PFPeA), Perfluo ra tiexanolc Add (PFHA). Perfluoroheptanoic A dd (PFHpA). Perfluorooctanole Add (PFOA), Perfluorononenolc A dd (PFNA), Pertuorodecenoic Acid (PFOA), Perfluoraundecanoic Add (PPUnA). Perflgoradodecanolc A dd (PFDoA), PeflhJorobvUneautfonate (PFBS). Perfluarahexaneaulfonate (PPKS). and PerfluorooctanesuHOnale (PFOS) In VW ier, Soil and Sedim ent by LC/MSMS Page 25 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 119 of 178 3M Environmental Laboratory P0003268; Interim R eporm ExyLIMS Protocol Number: P0003268 Any method performance parameter that are not achieved must be considered in the evaluation o( the data. Nonconformance to any specified parameters must be described end discussed If the Technical Manager(notv CLP study) or Study Director (GLP study) chooses to reportthe data. If criteria Isted in this method performance section are not met maintenance may be performed on the system and samples reanalyzed, orother actions taken as appropriate. Documentall 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 ofthe report 12.1 System Suitability -. . System Suitability standards are not a required component of this method. If required by protocol or by the technical manager, a minimum of three system suitability samples are Injected at the beginning of each analytical run prior to the calibration curve Typically these samples are at a concentration near the mid level of the calibration curve and are repeated injections from one autosampler vial. The system suitability injections must have area counts with an RSD of S5%and a retention bme RSO of 2% to be compliant 12.2 Quantitation . Calibration Curve; The coefficient of determination (r1) value for the calibration cunre must be greater than or equal to 0.985. The concentration of each point in die curve must back calculate to be within 125% of the theoretical concentration with the exception of the LLOQ, which may be within 130%. Calbration curve points that are not at the high or low end ofthe curve maynot be deactivated. CCV Performance: The continued accuracy of the calibration curve must be demonstrated by analyzing continuing caEbratkm verification (CCV) standards. Each CCV may be a calibration curve point that is reinjected or a separately prepared standard, and is typically near the middle of the calibration curve. Alternative concentrations or multiple concentrations may be chosen depending on project requirements. Not more than ten samples or spites may be analyzed between the Initial calibration and a CCV or bracketing CCVs. The accuracy of each analyte must be within 25% ofthe theoretical value. Samples that are bracketed by CCVs not meeting these criteria mustbe reanalyzed. Demonstration o f Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of standard) and the mass spectral response ofunique ions. 12.3 Sensitivity The targeted limit of quantitation for all analytes is 0.025 ngftnL (water) and 0.20 ng/g (soils and sediments, wet weight). The LOQ for any specific analyte may vary depending on the evaluation ofappropriate blanks and the accuracy ofthe low-level calibration curve posits. Refer to Section 10for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate data that are accurate to +/-30%. Section 10 oontains additional information regarding the required accuracy of laboratory control spikes, field matrix spikes (water samples) and laboratorymatrix spikes (soils and sediments). 12.5 Precision Samples should be prepared in duplicate in (he bib (soil and sediment) or coDectsd in duplicate in the held (aqueous). The relative percentdilteienes.RPD, should be reported. RPD results greater than 20% (rater) or 30% (soil and sediment) will be flagged in the report, but win not be excluded from reporting. The requirement lor replicates excludes field blanks or rinse blanks Section 10 contains additional information regarding the requited precision o f laboratory control spires. -1--3----P-o--l-lu--t-io--n---P-r---v-e--n-t-i-o-n---a-n--d--W---a-s-t-eTMSa-nWagTem---e--n--t--------------------- Page 11 o f 12--------------- M itto d 0lA m ))'3l3 fo r Deleim ination JP ertuerobttanofcA cid {PF&AJ, Ptriluoropcntanote A dd (PFPA). P erflgorghvdnote Acid (PFHA). Pe^uoroheotm otc A dd (PFHpA), P t/fluorooeU ndc Acid <PFOA), Pfluorononnotc A dd (PFNA). P erfluorodtcanoic AchJ (PFDA), Perfluoroum tecsnoic Add (PFUnA), Perfcjorododacanoic Add (PFDoA), PerfluorobutorouSTonat (P fB5J. P erftuoroftexA netulfoftde (PFHS), and Pariluorood*flesu)k>nate'{PFC$) in W sler. Soi) and Seifl/nenJ by LC/MS/MS Page 26 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 120 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 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 interna! procedures. 14 Records_________________ Each data package generated far a study must include all supporting infarmatfan far reconstruction o fthe data Information far the data package must include, but is not imited to the blowing items: study or project number, sample and standard prep sheets/racords, instrument run log (instrument batch records, instrument acquisition method, summarypages), instrument results files, chromatograms, calfarafion curves, and data calculations. 15' References Exygen Research Analytical Method 1/0003305-1 details method development and verification of recovery far multiple analytes In groundwater, surface water, soil, and sediment. This will be archived as part of E06-0549. 16 Affected Documents_________________ None. 17 Revisions*1 Revision Number Revision Description Revision Date 1 The sonfcation and centrifagallon steps ofthe watersample preparationwere 11/10/06 made optional. The accuracy requirements ofthe analytical balance were updated. The method was updated to allow the use ofa linear 1htweighted calibration curve. The table of required daughter ions for the analytes was updated. The method was updated to allow different sample volumesto be extracted and to allow efifferent standard bottles and storage conditions to be used. Calibration requirements were updated to shewthat analyzing continuing calibration verification standards at one concentration was an acceptable alternative to reinjecting all curve points used to construct the calibration curve. Minorwording changes were made throughout ETS-8-012.1 Page 12 o f 13 Method o fAnalysis for the DeterminoUan o f PertkiorQbutanaie Acid (PFBA) porituoropenranoic Add (PFPcA). Pe/Suorohecanalc A dd (PFHAI. Perfluaroheptm aic A dd (PFHpA), P trfluorooeU nolc A dd IPPQA}, Pwlluorononanoic A dd (PFNA>, PorSuwodtcanolc A dd (PFOA). PerSuaroundecsndc Add (PFUrtA). PsrSudradodscanoic A dd (PFDoA), Perfluorabutanesulfansro (PFBS). Pertluarohoxanosuironats (PFHS), and Psrllugiooctarwsulfanata <PFOS) In W ater, Sod and Sadimam by LCIMSIMS Page 27 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 121 of 178 3M Environmental Laboratory P0003268; Interim Reporttt4 ExyLIMS Protocol Number: P0003268 Page 28 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 122 of 178 3M Environmental Laboratory P0003268; Interim Reporttt4 ExyLIMS Protocol Number: P0003268 AMNeAthLodYNTuImCbAeLr: MV0E0T01H7O80D Method of Analysis for the DeterminbaytiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water Analytical Testing Facility: SE30txa5yt8egeRCnoeRslleeeagsreeca,hrPcDAhriv16e801 Approved By: TPaeuchl nCiocanlnLolelaydeCr, -- LC-MS, E'xygen Research Date / /JoVhicne PFrlaehsiedretynt, Op/erations, Exygen Research Date Total Pages: 7 Page 29 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 123 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number VOOOI780 | Method ofAnalysis for the DeAterNmAinLaYtiLoTCnIC/oMAfSPL/eMmrfSleuotrhooocdtanoic Acid (PFOA) in Water by 1.0 Scope TaScphieidsctmrboyemthHeotirdgichisDtPoeetebrfceotoremmr (apLnlCocey/MedLSif/qMouriStdh)eiCnihsworoalatmetirao.tnogarnadphqyuanctoiutaptlieodn otof paerftlaunodreomoctaMnoasics 2.0 Safety 22..12 CAprolewncsaauuyltstioothnbses.earpvperosapfreialtaebMorSatDoSrybperfaocrteicheas.ndling any chemical for proper safety 3.0 Sample Requirement 333...132 33..34 3.6 pNAAAmSSteraalotnmiolmmnyjlsspeueppaaceatslmlmetrsaee.astmsppt4caullpo0neerslelsdetpml.oesmrtrcLohectucedioosoenstsfnutsbrtapieepeinefsnrgrtrtoihinnsgcioaasgeertmdraonpaunueptarteeglreedduthsieslcfyedwolsedrmhfisloeoflioxsruxbhrtlwerdoetadhaucstebltbepdieoreeefxnbcsot.aierrafmeailcelcbpoedtleinweoitisnnern.idg.ftushgateoemdspaealmeqtdup-il3fliio0nbrg0rea0pxteltrarpanmtcotfiooforrnor.toh-mi3s 4.0 Reagents and Standards 4444....1324 WPAMemearfttmhleuaroon-nrooiHluom-PctLHaACnPcoLgeicCtraaAtdgeecr-aiddAe-.CS.iSg.mRae-AaglednritcGhrade 3.0 Instrument and Equipment 5.1 5555555555..........783514912610 2ADAA51ADsp1Wo052Lmniuils5dsamvalmhppctLeo-leemioooyvpLLgnrcsnstisiLhticapladdnsceSebbeiieaLassepeltlctlretppDeqopetebHooeurpsPmPcafdssiiPoEop(laaapia1trcLlpbbkeonlmn0relletCocVaeet0adcaeper-tpvapnsrti1wcao.rcoiopc0aaanwleeil6lw0yytpdth-s0pkapecmldbirricma(ptqoo5alo.Le(upp0tvuMlai-yyoagtda1hlrlfaf)neeioOsabrdnnctrsOebCoheepal1Sutr1eeccdtL0opl8aeeie,-mvenknn1sSoc1g.tt0atPirr0lt0rnuiit0oEoofftmuu-pgem20cggLrge0.aaeeer0)0rptai,0etttnuhtruuwr0ijiLobbed0(i)cneecLgt1.ahssteCao..pgsdnr/a..MidbcslpaqSepou/aMsaoabnbSfltei'l)tep.aouttfiimopinsnp..jiencgtinugp5t-o2002 Page 2 of7 Page 30 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 124 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001780 ______________________ analytical method______________________ Method ofAnalysis forthe DeterminatiLoCn/oMfSP/eMrfSluorooclanoic Acid (PFOA) in Water by 55..1132 SCPeEntrviafucgueumcapmaabnliefoolfds.pinning SOmLpolypropylene tubes at 3000 rpm. 6.0 Chromatographic System 6.1 6666....3542 GMMT(APernoo/amNabbdlpii:iylleee8etnir2caPPt5athhPul0aarrC5oess-eeg:o0rl((5ua3AB2mm0)1):n3C:::0F)l2MuomeptMhhaasnAeomlRmPo(KnieuymstAonceetSacteieinntiWfica)t,e2r.1 mm x SOmm, 5p Tim2208el20...O.f0.050minl %2266655555A 3377355555 FfmloUw00000.....m33333Riantte 666...876 RQInuujenacnTttiiiotmanteiVo:no-:lu2Pm3eeam:kin1A5urtepeasL.-(ceaxntebrneailnsctraenadsaedrdtocaalisbmrauticohnacsu5rv0ep.L). TophteimabizoevtehceoHndPiLtiConssyastreemin.tendedas aguideand maybechanged in order to 7.0 MS/MS System 7.1 Mode: ElectrosprayNegativeMRMmode, monitoring413 ->369 m/z. TophteimaibzoevtehecMonSdMitiSonsysstaerme.intended as a guide and may be changed in order to 8.0 Preparation ofSolutions 8.1 MobilePhase 8.1.1 a2mmmMoniaummmaocnetiautmetoac1e0ta0t0eminLwoaftweratiesr.prepared by adding 0.154 g of Alternate volumes maybe prepared. Page 3 oft Page 31 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 125 of 178 3M Environmental Laboratory P0003268; Interim Reportai ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V00017SO Method ofAnalysis forthe DetAeNrmAinLaYtiLToCnIC/oMAfSPL/eMrMfSluEoTrHooOctDanoicAcid (PFOA) in Water by 9.0 Standard Preparation 9.1 S999999.t.....111a111.n.....546312daramamadfATAiAmomm1APnrp0hoferS1L1LeLp0e0a1tem12a2tthr.p.mo.ho0o1n550oo0as1acaat1fntfxL2fprmmhkponplotei5tygteh/cgomhgplLhLFot/kaem/le/digimemaomnfcLLia/sat1Lrn1amLe1ttLDnaLtDt.0leoi0lh0adLfLyPcPfs10oeffippoDtkco1of2EE4gafgfropar25r0Pno't/pstt/trgbb5im.iCiimodrtErmf1ffoo/o-iteialmiifimLctntuLcpcLbfiarttacipdaltlaaLonLScseietasLttgrotidoa.i.ioo(tatosLo/oDnitcllltlmoonieuannuiDuooPo.nlortttrLsuniesPsniEirofoooostoeH.in-ssolnnlsclbou1utoulotoabntutttel0tolbitoiouitduoto0otiltltaotoeannetiniflop.nooefafofoongsin.ironnfff/faropPamaiPPtrnluflaoFeFFPLarvvOOlmitOFootaooyvAlAlOAauu)fboxfmmAeliPaiiiinussmsnFeseamppdtpOiulooosrrermAedereffvpeopppior11ldpaaabfeul00rrurepyti001eeenerma0dddiwwwrota0eeobbbdeiidrttwyyyieohh1gofbibbfb0hfrtmmyr0hrriii6gini1eennnbmmetgt0ghghgmrr0eLaiaiaii1nnotnnnnth0gwowgonggoairlltmninih1t11tiaiohgnhs00ng0tl StandardCalibration Solutions 9.2.1 9.2.2 LTcipdarCheelein/pbMtarfiraocSetal/idllMootanwoSsissnntcaageamneliddipsbealredarasd.t.tsiyopanircesatlpanreodxcaaemrdsspseleda:retahdrpodrueitpgioahnreathdlecionenxHctrePancLttrCiaotniwopnarsteormc.eadyTurhbeee, Final Concentration Fortification Volume o f Concentration o f Calibration o f Fortification Volume Fortified Control Calibration Standard ID Solution (ppb) (ML) Semole (m L) StM dard (ppt)* (exam ple) 0 0 40 0 XCmmddyy-0 I0 too 40 25 XCm m ddyy-l 10 200 40 50 XCmmddyy-2 10 400 40 too XCmmddyyO 100 too 40 250 XCmmddyy-4 100 200 40 500 XCmmddyy-5 * cXTohCnec*ee=txnoettoxrratarctaitocetnde,dcdocunaeclietbo4nr0tatr0htaietoicnoonsntoacnfednthatreradct.4iao0lniborafttihoenssttaannddaar1rd0d0di0sureiqnugatlhteoXe8xCxtmriatmsctidinodinvtiva(-Sl6PE). Page 4 of 7 Page 32 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 126 of 178 3M Environmental Laboratory P0003268; Interim Report&i ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V001780 Method ofAnalysis for theDeAteNrmAinLaYtiLToCnIC/oMAfSPL/eMrMfSlEuoTrHooOctDanoic Acid (PFOA) in Water by 9.2.3 9.2.4 9.2.3 nAsaSAeettltoe2tzedroeereCfrndoasa.tlttolasente6avdxnoatCdrrlauad,crmsudtpeeedxsstootcarlaanutcwldtiitboeocrdnoaw.nt(eicroeeenkansgts.retaantntidobanlrsadnoskfi)nstma1nu5ds-matrbLdesppmorlaeyypparbroeepdpyrlweepnitaehrteuedbaceahss 10.0 Batch Set Up 10.1 10.2 ocpiREnornaeonetcqhcthureeroidebrqlueasaumgrtaaceflelhnoinrttryetotsiccfaforofssevosnadeurtmrrrfyoaiapenltfllceod(eskrmapntehneloxatedwhtnrbolanaafdcobttccreohbodtr.lhanait(cnsoteykrpnpyrtiourcdajsauetilicnplotylgn.ics2aH0t(ePlosLarbaCnledcwsossna)pttiremkore)lussatswnpiidinlklceltb)uwedotesopraeetvcaeilgferieiaefnsdytt 11.0 Sample Extraction 11.1 11.2 1111..34 11.5 LAMCEmfi1no5olontilueoxalnamatodledswSwyLiusOztweearipeloedmmilot)ns4bhl.paLy0ymltp-ehpm55rpeooolmLnlepCymsyLcpouLluorefosonnsSifp1dnaePy0HimgtcEl0iPeeoep%nnLlncleeetaeCrcmrdiocttfwrerreuCointgdaashittegptrapeierntSrfoasuuoPr(ybgtl-(E.ieLeIos2cnCtCg(aud/fo,rMbroitnofre6lilapSssdela//mcg(sMmvfteeLooc.Sp$rl))l.ut.DeimbmfDyidysLeicoalp=uaso*anrteds5fnodsetemeienlllteduuoLgteaa)4cdtt.e1eo0,.0lrmuienmmpLtoLlnawcgrmeuirtanheldtidhduwraayaantnteoeddlr 12.0 Chromatography 12.1 12.2 12.3 12.4 gcUe(mbifASaILntonaxenetosCntullajntgaeelierns/oelbairacMytnedrscwrctlazbnpnacaitSetetneteeitorehidnid/dreduordMeisgsaennnsebrfsccSoatdyoasaaslmftfunsrmelbaoePitspddttbnaereyxhFlentdreostedawOaaardsatfaettm.aarsieAicmndneoreetotdscanhne.xacuoldemtnoynnercsArtatvuatucdereacnoeaesrnntbvstslracfedidypeyelbadbeytaosleralo5itrnoaibiccd-tnfctdfhhf1raiseoaaiole0aenalristnxmbirgtfsosastiqrerasrrananatteuastom.ymtdagtacisanorpantapbteerdtnlntalddeseiealdnts,searsdis.dasilotsttanaiasasaenorstjAmntndent.ifuddcsnp.iisaavnttlmeiarereejEndddenruLgsxaoscsspa)nttira1tir.nelmdtoma/trexencpsuIatfroethnrownrseiredenrtaedceetstieiiaeibcftbtgvsdaivoheesehtneeenaeagdt,drmnrciiiynannaasedcprgannncnaad5mllditrsoeu-nrede1apdfncgss,0tflepuetioeeidoteromrl.xsvnelaiafotneukarmlswtsasateoeactpvtrttatlseeeahbheoreladleeesestlf Psge 5 of 7 Page 33 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 127 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygeo Research Method Number V0001780 ______________________ analytical method______________________ Method ofAnalysis forthe DetenninatiLoOnMofSP/eMrfSluorooctanoic Acid (PFOA) in Waterby 12.3 evsSoxeafcrmtsewuepsadlercseatrasleiynsbsdprtaoaertnmidso.ernessshptaoonundlsdaersdnsohctoonuexcldecnebeterdaftuisorttanhneudrsaidrndiglurMteesdapsoasnnLdsyernse.xan3Aa.3lnyyz(oedsra.emqupilveaslethnat)t 13.0 Acceptance Criteria 13.1 13.2 13.3 13.4 13.3 13.6 R2TsaeaHARdMbtwEiomeC1nhtnxp0nalhea3freoanh4jaeucep.rtutene0car4w9yrinioesltrcrg%rdorno%uh19tonkraetehavcamcdo3ek2bnptvrotTliacewdednstreeyodeasolrerai.deeorihr(ttinisraodmnbbtioste,Rewotich.bottlmsreoglou,Jaaauttaiatnrnrihnai.nlolufttmamnt2sdieiivkrsh(mfonoasts0u3Teatsaeeannenctb.ns6lpPyohm9donummre9astFes8etnoebcabpanhtuulO3satotalee4nleeaemrs.sme)ntveov1Adlntetn.wsydfaule3axuufIsntttalexsniaicsh)hfhsumocrcteacthtpeIoeedaaritamnlfeobiseeltwbulekseecedcunpefudeencevrtdosoorlrtuaetatstdeeon2upniadnlomtlspr(bt0nfatinaas.eabeRrbfey%rdnskduofinegerasa)nIdraesealtnreokmftttsrnxrteohtsotPdmmrifebtatoppoeeomrsfFc-hebttaailntefroeoOkeeetttuecxraarahrhrsneetsclAnitrnreeetaotaxrtadeseaahdifdasdnhssloablaaccastsisypuajouneolbntattscpullsoaloeugtarslyairtsttaltndcSaklsfhmeieltizdlomuOt.dis-etctveibetuepolssobnifadeiearnxnratlcrnAelu.attsemlgtssbaddioitlimrstoo/nrildoearurLgcoennityuetnocbsmoufahrne,tmutteenurareedtomturavtehmatbdshtiesfsltxoPeetla.eenoi3eitiaysxcdteFtnntr6nrfazhbeireOein9dcedeteaxegeohobcdeadAtxetapitawen.y.crhssfntmendpearpeaedetrautswlrsiuhnearariteckseabihintibt-tifesiobtfhreeenloteranel7ldaxlogodnaitiL,0tmmtmimnu,lro-Ositwakctmohmi1tnisatcoaatQreh3sinsinuteudw,0itcipa.ddslsloHeu%maedit,attntrrhhuIhr7tvptetfaedhbgbhhoi0enlinnneeeseeeeas.ft 14.0 Calculations 14.1 bgUeasnseeedrtahtoeendfopblelyoatwkhieanrMgeaea)qssuuaLstiyinongnxtthsooefctsawtlacanurdelaaptrerdotgchruearmvame: o(luinnteaorfrPeFgOreAssifoonunpdara(imnentge/rLs), PFOA found (ng/L) = (Peak tffigsjlUopienteiSSP-fl x DF DF = factorby which the final volume was diluted, ifnecessary. Page 6 of7 Page 34 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 128 of 178 3M Environmental Laboratory P0003268; Interim ReportH4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number VO00I780 | ANALYTICAL METHOD Method ofAnalysis for theDeterminatiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water by 14.2 tFhoerfsoallmowpliensgfeoqrtuiafiteiodnwtoitchaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp.rior to extraction, use Recovery (%) - [totalanalytefound(ng/L) analytefoundincontrol(ng/L)] ^ analyte added (ng/L) Pge7of7 Page 35 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 129 of 178 3M Environmental Laboratory P0003268; Interim R eports ExyLIMS Protocol Number: P0003268 AMNeAthLodYNTuImCbAeLr: MV0E0T01H78O1D Method of Analysis for the DeterminaLtiCon/MoSf /PMerSftuorooctanoic Acid (PFOA) in Soil by Analytical Testing Facility: SE30txa5yt8egeCRnoeRslleeeagsreeca,hrPcDAhri1v6e801 Approved By: TPaeuchl nCiocnalnoLlelayder, LC-MS, Exygen Research DatelolzAt/O-/ Date Total Pages: 7 Page 36 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 130 o f 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001781 ANALYTICAL METHOD [ MethodofAnalysis for the DeterminaIt.iCon/MoSf/PMerSfluorooctanoic Acid (PFOA) in Soil by 1.0 Scope TaScphieidsctmrboyemtheHotrdigichisDtPoeetebrfceotoermmr (apLnlCocye/MedLSif/qMouriStdh)eiCnihssoroolialm.tiaotnogarnadphqyuancotiutaptlieodn otof paerftlaunodroemoctaMnoasics 2.0 Safety 22..21 pACrolewncasauuytlsitootnhbses.earpvperosapfreialtaebMorSatDorSybperfaocrteicheas.ndling any chemical for proper safely 3.0 SampleRequirement 333...123 33..43 ANSSAtperaalomtomlmljepsseppaaaeclmlsmrtee.atspptc1ulloe3erselstpgl.oemrrooceutcfdiesotetsnssbriteepnfsrgrtaohimgcioseerprdnolaueeutreegfeddhoselrydwesxhmfioltolriruxablscedeotdiioslbbnpse.eeafcmoirafpelilleebodsew.iinendgtshateomspaelmeqdupilflioinbrgreapxteltarantcotfioorrno.tohmis 4.0 Reagents andStandards 4444....3142 AMWPemeratfmthleuaoron-nroHiouloP-mcLtHaACnPcoLgeitCrcaaAtdgeecr-aiddAe-.CS.iSg.mRae-aAglednritcGhrade 3.0 Instrument and Equipment 5.1 555555555355............1118972513641320 UA2DSWDAA5A1s1lio05P2luLimintalsds5EtrvmamhptpoceL-aeleimooopvvysLLrgncsosnisaitLhtpicaalddncnscSeeebbiiuieaLassetceplltucltrpepepDqoeetbmbooHeurpsmPPacafssdiiPtooE(amlappaih1actrLklbbep.olnam0nrtlleeCoVncte0eaacdeapeir-atppfsnvrt1iwoc.caroopoic0aalanwleeli6d0lwyytpdth.0-spkpacemldibrcrim(aptqooa5l.oL(euppt0v1uMaiyy-oagtad1hlflrfan)eeoi0sarbdntncr0seCboheeupa1SltrlLecdect0opl8eeai.-emvennnk1sSctogtt0.a0Ptrirlt0OrnutiioEoofftm-puugem2c0gLgrge0aa.eeer)0Orptai,t0ettnhturuuwri0ijLobbde0(i)nceecgLt1.hassteCao..psgdnr/a..MidbscplaqSeopu/MsaaoabnbSflteil)tep.aouttiifmopisnnp..jiencgtinugp3t-o2020 Page 2 of 7 Page 37 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 131 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 E*yen Research Method Number VOOOI78I | ANALYTICALMETHOD MethodofAnalysis forthe DeteiminaLtiCon/MoSf/PMerSfluorooctanoic Acid (PFOA) in Soil by 55..1154 CWernistrti-faucgtieocnasphaabkleer.ofspinning50 mLpolypropylene tubes at 5000 ipm. 6.0 Chromatographic System 6.1 66..32 GMM(ATPernoo/amNabbdlpii;iylleeee8tnir2caPPta5thhPul0aarr5Coess-ee:go0rl((5au3BA2mm0))1":nC3:::0F)l2MuomeptMhhaasnAeomlRmPo(KnieuymstoAnceetSacteieinntiWfica)t,e2r.1 mm x 50 mm, 5p Tim2208e120....(.00050mini %6662255555A %3377355555B F(mloL00w000./....33333mRiantle 666...867 RIQnuujenacnTttiiiotmanteiV:ono-:lu2Pm3eeam:kin1Au5rtepeasL.-(ceaxntebrneailnsctraenadsaerddtocaalsibmrauticohnacsu5rv0ep.L). TophteimabizoevtehceoHndPiLtiConssysatreemin.tended as a guide and maybe changed in order to 7.0 MS/MS System 7.1 MPFoOdeA:.ElectrosprayNegativeMRM mode, monitoring 413 -->369 m/z for TophteimabizoevethceoMndSitMioSnssyasrteemin.tended as a guide and maybechanged in order to 8.0 Preparation ofSolutions 8.1 Mobile Phase 8.1.1 a2mmmMoniaummmaocneituamte taoce1t0a0te0minLwoaftewraitserp.repared by adding 0.154 g of Alternate volumes maybe prepared. Page 3 of7 Page 38 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 132 of 178 3M Environmental Laboratory P0003268; Interim Reporm ExyLIMS Protocol Number: P0003268 Exygeo Research Method Number VOO1781 ANALYTICAL METHOD | Method ofAnalysis forthe DeterminaLtiCon/MoSf/PMerSfluorooctanoic Acid (PFOA) in Soil by 9.0 StandardPreparation 9.1 999999S......t111111a......n654231darTmafAmmaAimaAAmP1odrnph0orfeL0L1L1epSe0at1em1a22t.hrpt.m.h10oono550osoa01aattan1ffxc2fLprhommnpploe{ki5ttgyecomghglhhp/LLk/toaFml/ee/diemgiammncfioLLaa/stL1n1aLm1erttnLaLDDt.0elto0l0hdaLiyLcfsfPP01oefpfpoDitkfo1o24EEcgaforgfp52rrPa0ntp/osrtt/gibb5mCt.iiotmEdrmrf1i/ffioo-etiolmafiimLicutptLLccbianfrttacptiaaalLldnoLsicteaeSLsttrgotidoai.it.oa(toLsoooD/inllcttlomnoeauilnniDuoouPo.nolrttrLsueinstnsPEiroofisootoe.oEi-oslnsnllbcosun1touultoaobnutt0ltettiobltouoiitodut0ooitlttlaoonetateinnfilonp.oeofoaffonosgi.niornfnff/faropPamiPaPrtnlufaleoFFFaLPrvvOOlmtiOFoootaoyvAAallAOfuub)oxfmemPlAiiiaiiunsmssFnseemaptdppOuiloosorerrmreAdeeffvpepoppiodr11lapaafbeul00rerrupyit100eeenrema0ddidwwwroa0teeobbbdeiidrtwtyyyiehho1gofibbbb0hffrtmmyhrri0rig6iiniee1nnnbmemgtt0mhhgggrr0eLaaaiiii1notnnnnnth0ognwogoggwarilltnminhi111taoitihgsn0nh0g0tl 9.2 Standard Calibration Solutions 9.2.1 9.2.2 TpciLdarhCeeleinp/bMtafrircoaSeatldi/lloMotanwoSsissnntacgaemaneliddipsbealerdarasd.t.tsiyopanircesatlpanreodxcaaemrsdspseldea:rteahdrpodrueitpgioahnretahdlecionenxHctreaPncLttriCaotniwonpasrteormc.eadyuTrbheee, * oTcXCSofhoConFlenuco=cteerie111xtno111eni0000nt00f0txt000rrircata(arapcttatiiptiooceobtnnd)ne,dcdocuFnaeoclVriettbo(oin442211pfrl0000t0i00tauLcrh000000tmaa)iettoeiiconoonnsntocaFfneoSndtrhVattairmerfoadicloteu.4444444ialdome0000000lniC(ebmooronaLffttr)tioholensstCtSaaontnaCnddncaaadelrF1rina25d1bd25i0rt500n0rr50d0d00aai0a0s(tlutiiporeooinqnnt)ugo*aftlhteoXXXXeXXX8SxCxCCCCCCC(tteaamrmmmmmmixanltimmmammmmcsdbmtardddiddddianrodpdddddddtinyiylyyyyytoeiyyIyyyyya)n(D-------Sl1325046PE). Page 4 of 7 Page 39 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 133 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001781 MethodofAnalysis for theDeAteNrmAiLnYaLtTiCoInC/MoASfL/PMeMrSfEluToHroOocDtanoic Acid (PFOA) in Soil by 9.2.3 9.2.4 9.2.3 nASsaAeettlote2tzedroeereCfrndoasa.ttltoalsentea6vdxn'oaCtdrlruaad,cmrsudtpeeedxsstootcarlaanutwcltdiitbooecrdnowa.nt(eicroeeenkansgts.retaantnitodbanlrsadnoskfi)nstma1nu5ds-amtrbLdespmporlaeyypparbroeepdpyrlweepnitaehrteuedabceahss 10.0 Batch Set Up 10.1 10.2 iRocpEnornaeontecqhcthurereoiedrbqaluesaugmrtaeacflenlhionttrryetoctscioaffofsinseovstadurremorrfaylipane(tfllcmeodeskreanpttenhholxadeowtnrdblnaaafcbobttclrceoahotdrnh.anki(tcsoteuyrpnspyritionrdcajgauetlcipl3otyl.nimcs2aL0te(lsooarfbanmledcesostsnh)ptairmknooeulsls)tswapiniinlkdlcelb)tuwedtoesopraeetvcaielgferieiaefnsdytt 11.0 Sample Extraction 11.1 111111...342 1111..56 11.7 11.8 11.9 nceBATCCfEALWIoleSeroleruondlnueaeinalanadmndtntoidttlrdeggeerwsyi3Lihif.dfztf(wueeimt,udpeohSdrgirgeoLnetsetecbhelhgapyatyomtevfulphn-ooafobtS5rpetcrufmo)leluemb~e.psCmetmsea1ylhLtiismL0hsludeeeotaspmnoaSinsuf1lnneaPeoiaHp0gdnmcEln0iPueaem%tnputonLnlctelleitodeaCtxsrcmrr4iatsat5fow0rwresuhto0inotegada-shmnlk3etgmplateie)0hernLctr.Lasue0oo(ybb0nl~w(pa.ce1Lototas2ihpCtlnCgh(wydma/df,prMoinri.onwrit6ldsoilpaSoaetlp/sm/ctnsMaoyevteecLnrlocdSet5i)li)nc.iuo.naCebmmntDyeucLsetheohfpneoaSoantkrPs5fro3e~siEtfe0mriunIllfeSuLggcomtaea)rmc.trL1e-otti01runliuipb5dunmmoegttemsloeLnys.i.(pgnrfmruoruoaDnertpdettiidhsyusf.raclyayenatneroaddesl 12.0 Chromatography 12.1 12.2 12.3 bSAaiLmInnnetCntuajgaeens/lirMctyndestzbpnnaSeteeirthin/ddrrMeisgsensescoaSdaasmlfunmebPspddteyelFetesowdOaastfet.meiAmneetonh.xcaueontenrArvatareecoennrtscafeydpaldeyo3laoitn-bcic1fcdrha0aailanltsisibgtsoaasernmantato.mtdpiasoalptretnaldseln,.esdasstAasaaetrmntsd.fdaipavnlmreeEdauxaoslstntretrdmmarnpcufoatroseretrtiedctviecebfdsio,eetenaadncninaesdeanncanmldtrurtdiapdrstfleeioeodmslnlieonutalwtsteootvfttebahhlleesel Page 5 of7 Page 40 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 134 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001781 ANALYTICAL METHOD | MethodofAnalysis for the Determination ofPerfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS 12.4 12.5 Sgvse(cUeftooxaxeeaosfllcnrtmelitrseeobawaupercwrclsaadlacitertenteoceesiddeaourtdsaaelnnbiyrnsfcbtysospdarfttsrolaaeaoetittnrmanbrxihdsnodrtea.eardrnaateaarsiscsdsonrehtptdsncaeaoooldmnuyncnsdltsuutcddeaaeasrrnsvbtsldnideeybsboatcshertlroooaidtnneftuhfsioecxleoedarecnmxrfnebtiqetrarrsereusadtyaatgacftnurntaisbeeodtnrtedaistnadthsnariseuddiltotnarisasaonsjdirnenntdiiudcn.lgisutnatreiertMjendedersLgsdcsapp)tiasoia1n.etsonn/erLxnssdIatyenherwirdnsene.eexsaaeiitbtngav3hseAanhe.aegl3dtrnmyriiyannyz(cpronegad5ldsirseo-na.e1ecgfms,q0uepeuptroe.sxvilaavfeterkmsasaalcaepthtranlseeeartedae)stt 13.0 Acceptance Criteria 13.1 13.2 13.3 13.4 13.5 13.6 EHT2sRawteiaAeRMdbm1Cohntnpx0nrhl3aeaafonejeh4aurpce.teu0tenrcawy4i9oirnelstrrcrr%g%dnoouh1o9ratnkeethccavamdoekn3p2btvTaorcltiedwednstreyesedoaloerraiee.dohirr(ttrinsaidonbmbstio,tReewotic.htbotrlmegsloo,uauaaJtatanitrhrninlialnf.toutmamdn2tiesiivrkshom(fosnats0ua3eTatesaennnetbc.nyslPp6omh9dounmmeras9tFse8teenocabbpnhtauuOl5seatolateel4enaemrs.sevn)metovAl1ndtnte.wsyadfeula3xIuusfnltttaxseniusafhihhcsm)orlcccaehttpeaIoeedartialmnobfetsiweleublekseececduenpfdueedncvresotoorltreautatdsteon2neupaidnolmtlbsrpt(0tninfaaas.bareRefbyed%knrdusofiengreasna)rIdeeaslatonerkttmftnxrsrtoehosPtmtmdierfbtapotpeoeorfmF-schebttaailneftroeoOkeeteecttauxrhaarhrrsentenstAlcrnrieeetaroataxtdeesaahfddiadnhssoslaablaccsatyisspajuolunoetbnatctusplsloaelougstlayarsttrtialtdcnJalshikmfleteziodlOum.idtstt-evecbiuoetlpesoifdsnbaeiaernrntaxlcAn.raelusttemglsdsbtadiiotilmrsotnoidr/leorrauoLcgeninyteutnbocofmuneashr,mtetuetnurarteomedturmhvtaetashtbedisflsxetetPlaoeno3eii.eiaytscdettxnFnt6rnfrhazebreieinO9cededtexageoeobhcdaedAtexitpaenatcyw.r.hssfntmedpnaepreeedartsualtwrisuhareianretkcsebathiinbit-tiiesffbtorheeenolteraelnl7adxlognodaitiLt,0mmtimmu,nlrotO-iswactkhmoim1ntisatocaatQehr3isnsitunudew,citi0pa.dlsHdsloeuma%edi,ttatntrruhhIh7vrttpetfgaehhbbdhie0olninnneeeeeessea.ft Page 6 of 7 Page 41 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 13S of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number VOOOI78I 1 ANALYTICAL METHOD Method ofAnalysis for theDeterminaLtiCon/MoSf/FMerSfluorooctanoic Acid (PFOA) in Soil by 14.0 Calculations 14.1 bgUaessneeedtrhaeotendfopblleyoawtkhienagrMeaea)qsusuasLtiiynongnxtthsooefctsawtlacanurdelaaptrerdotgchruearmavme: o(luinnteaorfrPeFgOreAssifoonunpdar(aimnentge/rLs), PFOAfound(ng/L) (Peakaresalo-pientercept! x DF DF = factorby which the finalvolumewas diluted, ifnecessary. 14.2 Fthoerfsoalmlopwliensgfeoqrtuiafiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp.rior to extraction, use Recovery(%) = [ totalanalytefound(ng/L) - analytefoundincontrol(ng/L)] ,^ analyte added (ng/L) 14.3 nUgs/egt(hpepbf)o.llowing equation to convert the amount of PFOA found in ng/L to PFOA found(ppb) - (PFOA founsdafmnpa/lLe)wxeivgohltu(m5eg)extracted (0.04L)1 14.4 bUasseedthoenfdorlylowweinigghte.quation to calculate the amount of PFOA found in ppb PFOA found(ppb) dryweight = PFOAfound (ppb) x [100%/ total solids(%)] Page 7 ofr Page 42 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 136 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 AMNeAthLodYNTuImCbAeLr: MV0E0T01H7O82D Method of Analysis for the SDeedteimrmenintabtyioLnCo/fMPSer/MlluSorooctanoic A' cid (PFOA) in Analytical TestingFacility: 3ES0txa5yt8egeCRnoeRslleeeagsreeca,hrPcDAhriv16e801 Approved By: PTaeuclhnCiocanlnLolelayder, LC-MS, ExygenResearch g//y /( I / f/JVVohicne PFrlaehsiedretynt, Operations, Exygen Research DatelO lzb fa 'i Date 'L Total Pages: 7 Page 43 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 137 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 ANALYTICAL METHOD Method ofAnalysis for the DeterminatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 1.0 Scope TaScphieidsctmrboyemtheHotridgichisDtPeoetebrcfeotoremrm(apLnlCocey/MedLSif/qMouriStdh)eiCnihssoreoldamitmiaoetnongta.rnadphqyuancotiutaptlieodn otof paerftlaunodroemoctaMnoasics 2.0 Safety 22..12 pCArolewncsaauuyltstiootnhbses.earpvperosapfreialtaebMorSatDoSrybperfaocrteicheas.ndling any chemical for proper safely 3.0 Sample Requirement 333...132 33..54 pSAASNteraalmotolmmjlpsseeppaaceallmmtrsee.atspptc3ullo0eerslestplg.oemrrcooetucfidsoettesnsbsrteipenfsrrtgoahimgcioseerpdrnolaueeutreegefddohselrydwsehmxfilootlirruxablscedeetdidosbibnpmee.efeconiraftelilesboadewmiinenpdgletshsat.eomspaelmeqdupilfliionbrgreapxteltarantcotfioorrno.tohmis 4.0 Reagents and Standards 44444.....13425 PWAMAemceraefttmhlteuiarcoon-nArooiHlucoim-PcdtLHaA-CnPcRoLgeieCtcraaagAtdgeeecrn-aitddAge-.rCaSd.iSeg.mRae-aAgtednritcGhrade 5.0 Instrument and Equipment 5.1 55$55555555...........11791854236120 SA2D5WAADAsp11oP05L2muinilasdsE5tmvamhptpcoLe-eleiooovvmypLLrgncsnsasitihticaLpaldcdnscSeebbeuiiLeaaesselptluclterptDeppqoetmebooeHuprmsPPcadfssiiPoEm(oaplpaai1atckLltbpbeoalnm0nrtelleConVctee0aadceaiper-pafpvtsnrt1iowcc.aopooric0laaanlelweid60lyywtpdt.h0s-pkpcaelmdcirbri(maptqoo5al.o(Leupp0tvIMuaiyy-goaadt1llfrha)fneeio0sardtbnnc0rsCeboeehupa1lS1treLccde0top8leeai-,emvenn1nkSs1cog0tt.aPt0irrl0rtnuiit0Eooffotm-uupgem2c0ggLgrea0.aeeer0)r0tpai,t0eltnurthuuwr0iijLobdbe0(i)cnegecLt1.hassteCao..psgdnr/.a.MidbcspalqSepou/aMsaoabn.bSlfteil)tep.aouttiifmopinsnp..jiencgtinugp$t-o2002 Page 2of7 Page 44 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 138 o f 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygeo Research Method Number VOOO1782 ANALYTICAL METHOD Method ofAnalysis fortheDeterminatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 555...111453 WCVeornritstert-ixfaeucrgt.ieocnasphaabkleer.ofspinning 50 mLpolypropylene tubes at 3000 ipm. 6.0 Chromatographic System 6.1 6666....5342 AMGM(TPnero/oamaNbbdlpy:iiilleet8eeinrc2aPPta5thhPlu0aarrC5oess-oee;g0lr((5u3aBA2mm0)1)n:3C:::0F)lM2umoeptMhhaanAsoemlRmPo(nKiuemystAonceetSatceieinntiWfica)t,er2.1 nun x SO nun, 5p Tim2208e120....f00.050minl /26662.55555A %3733755555B Flow Rate Im L00000/.....m33333in) 666...786 QRInuujenacnTttiiiotmanteiVo:no-:lu2Pm3eeam:kin1A5urtepeasL.-(ceaxntebrneailnsctraenadsaerddtocaalisbmrauticohnacsu5rv0ep. L). TophteimabizoevethceoHndPiLtiConssyasrteemin.tendedas a guide andmaybe changed inorder to 7.0 MS/MS System 7.1 MPFoOdAe:. ElectrosprayNegativeMRMmode, monitoring 413 -* 369 m /z for TophteimabizoevethceoMndSitMioSnssyasrteeimnt.endedas a guide and maybechanged in order to 8.0 Preparation of Solutions 8.1 Mobile Phase 8.1.1 a2mmmMoniaummmaocneituamte taoce1t0a0te0 minLwoaftewratiesrp. repared by adding 0.154 g of Page 3 of7 Page 45 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 139 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 |_M_e_t_h_o_d_o__f_A_n_a_l_y_s_is__fo_r_t_heADNeAteLrYmTinIaCtiAoLnLCoM/fMPESeTr/MfHluSOorDo_o_c_ta_n_o_i_c_A__c_id__(P__F_O_A__)_i_n_S_e_d_i_m_e_n_t__by 8.2 Extraction Solutions 8.2.1 11%000acmetLicoafcwidatienr.water is prepared by adding 10 mL of acetic acid to Alternate volumes maybe prepared. ' 9.0 Standard Preparation 9.1 9999S99......t111111a......n165432daramTAmiamaAAPommfA1dnrp0hrfeo1LeLILSep001ate12m2athp.tr.m.ho0S1n5ooo00oasa1aatfnt1cfxLfr2pmmhnopploekt5titgyecohgghmlhpL/Lt/okamlFe//eidiemgmamcnfiLLoas/aLt1na1mL1tetrLnLaDD.tl0oet00lhadLiLycsPfP10ffefpooDptkoco12fEEag4frfogpa5r2rPn0to/spttr/gbtbi5m.idCoiEmtrmifr1fo/fo-iotiealmiifmLictutLcLcbnprifattactdiaplalLoLanicseetSastLtgortidoia..i(ottoaoLson/oDicltllmtooneliunanDouiuoP.onlortrtLsutsniePsEinrfiooosotoeoE.i-oslnslnclbsonu1uotulotobantutt0teltoilbtoiouitdout0otoiltltoaontaetneinfilonp.ooefaoffoonsg.inrionfnfff/arpoamiPaPPrtnulflaoeFFFLarvvPOliOOmtootaoFoyvAlAAlaOufub)oxfmPmeliAiiaiiunsssmFnesemapppdOtiulosoorrremAdeereffvpeppopio11rldaaapbfuel00rrrueypit00ee1enermadd0diwwwrota0eeobbbediidrwttyyiyehhog1obfibbbh0ftmrfmyhrr0riingii6i1eennnbmtmeg0thggghmrr0eaLiaaiii1nnntnnonth0gowogngogwairlltmninih111tiatoighns0hg0n0tl 9.2 Standard Calibration Solutions 9.2.1 9.2.2 TLohfCet/hMefoS0l/.l1MowpSignc/gmaliiLsbrfaaottriyotipnfiiccsataatlinoednxaasrmdolspulateiro:enap.dredpitaiorendalincomnectehnatnraotliovnias dilution may be SooCflouFntoicorentinf(tinrcagatt/iimoonnL) 1111520000000 V(om11l112u0000Lm) e Dil(umteLd) to 11111to00000o00000 Con(ncFgei/nnmtarlLat)ion 1020510.....25000.0 Page 4 of7 Page 46 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 140 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 MethodofAnalysis for the DeteArmNiAnaLtiYoLnTCoIC/fMPASeLr/MflMuSoEroToHcOtanDoic Acid (PFOA) in Sediment by 9.2.3 9.2.4 nASaettloet2edrereCndaa.tltolec6vaolCilbu,rmuapteisotonanssidtxacnmodnoacnrdethnsstir.nati1o2nSs-mofLstLaDndPaErdnsamrroayw-bmeopurethpabroetdtlaess 10,0 Batch Set Up 10.1 10.2 ciRoEnoneanteqchchueeiunrbqentaurmttaracetelhiianottytonesdsaffs(soslaaucrmborfanipcentlolrcedonesltarpeonlxaaldntnsrdlpaafciobktrteoewdtr)haotit(osotyrvpuyperniordctijruafeeylpcaltlypt.iecrd2oa0tceecsodoruannrtlaredlosslrsse)pcimkofevouserstrtiwyfitinefloldcrlbutedhateespbaekatcnticlofehiwae.sdnt 11.0 Sample Extraction 11.1 11.2 1111..34 11.5 11.6 111111...879 11.10 11.11 11.12 11.13 ACnAecmCCDAEffeSCLWAfW1ooloele5PeoloeudoendudilnlueaernnnalElncandadmadtdo-tositudttarldtedgr6heerwwyecitL3ni2tiihif.edf0haztt5fw(tute0ecUsii,rudhpeeoodotg5d.tmimregghoertnmnlesembicbheelleigadLpcyenayayLmtettgtmoclp-nhuhhuotao2stel25rhttpeeebeuecoef).eo00faldteemcstfeptshCnm.umtu.om1saylihanomb%binnumLlnuCdLeLleeedweosspassntaaStiootsl1CoiphlennceaaaPteoff0p,aehdgtmtuc-E0HnHnti--2evi4e%m1tnpo33ScPPno0ocl1tll0Pme0iLtLaoer0.axtr8mctE0r0thcCiCLe.ottfo5wm0i0errexudc0inowwtoesdtga,rtLhshpalpafrgaemacapltetmmnm)mthetoanrrte.eLdisusepofesrderybf,fletg((w(Sp.oscehd1v~Le-hororPsaaioCamln-~22n(tEgCy(r1ek2d/2fot,epdMrdoeiec0il0nngrrtxr6.laaiooloatS,mmoroenlapppt6mC/cnndlrMnii/y/vetinensosmLddlofledeauuSel5tgol)lccLnttsu.eeaee))ihCwemb)cm.n.d.ssaty.b.rucLekCDDtoityehshepn"ooontSoeepaoltPaslf5tnnraenehbsisEooclefcmiesouatutntltiitauLncggolslttwteeoaahege)nettt.rmcer1etcciato1r0ssueoon0inhtiolbdllndmudamuuageftakcmmosaeLctLetted.hoinrn(.ogdemfnmrnorrfdaDiueueor5tidsttntntr0iihhthiusfoodadcaaay-mnnarkntr3teyeyhroeoaL0dddeslrl Page 5 of 7 Page 47 of57 3M Environmental Laboratory QLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 141 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number VOOOI7S2 |____________ ;_____________ ANALYTICAL METHOD_______________________ | Method ofAnalysis forthe DetenninatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 12.0 Chromatography 12.1 12.2 12.3 12.4 12.5 gvseSUbbsssimLaSAInotxttneeenaetCaaasnjufanrcjtmgaenenntews/sneelwicdMdductypnerdeetatlaasaaizdblnnaieSorerrtrtneeitrcdneddhsen/niddeaMdrstrssiegaassenl)eeisiny.rnfsmsvScoabioasanpdlsmerafntusrametoaareIPtesdydpsttytrnanmyhreiadFelnsosesemboaSd.Oepaednrtstefe-emaie.apiA1tsmsnsnrtrhlieh0ohsptdeanea.xeacoueoljrnssdontyuenncerAadretclatsctuamerdean.tecaoenrevrdtspvbsscaddfeneeplyeasldeeroo,ychsolayasilttofontbci.cicnncfeudarhSataoeacaxhlli-lAidnraletsci1sebibrtgnaes0sobraqrebmrteanntearuetaedots.atdgpinag'fiatosaoaunrlimsitneeortnnarttadsaitnplnlnthss,tnsealiesedieuteasdntotratariasssa.agnnonrtimdnradnnd(doufidttg.palSiiosaufvvrmlrtirdteMeaeenadeasnu,sLgdaoscapdssnairmcseot1aanndmsomt/nnreuLxudpsdafuefsoynsreoowrnstrerntsrltteemcte.lbxisioarefiftcbeeogunwadi3oeeArahsne.ntesd3tltdhneydcaiiaenbnasteyz(rangoeencsbodmfedldsrtyoiufraic.ranepdcfsmoccqtfttluepniaaeoeupodreldlrlaviliinsliavebnbonepkassardrlwtseaetealoaertttvtlsrihinattaeooeehahoartslnadnle)etestfl 13.0 Acceptance Criteria 13.1 13.2 13.3 13.4 13.5 sTadHeiCMsRobtewEA1nht0axpnal3hfarehojanaem.ecputren0ec94rrwniiyotlrgcorror%dhpu19koraetehmvaccodl3ek2pnvetroTeadedncsertadseralerimde.oeorth(iirasrmbdotbesRn,weiotu.lotgosemrtlouau,2tsnaaarnrh.nolftautitmdsteiinkv(mbfshsoot0T3ssateaeaecnnbt.6lyphmo9omumonPer9sets8neebocpaFbutulat5sttoa4elleOresmas.me)nvo1evttie.nsAdfaun3leausxInuflasxenhssfi)cuomatcrdhcptaoeIaradtmiloitwseefbetbuakceeucdpneunfdelecodtolorrteadesdaenopn2uvdolstpbtda(0taneifabaerRbefyrinl%dksoinfeeesarnda)reeltankottmsexnrtghostoPmmneifottpreoporFc-fhteabtifaielnroeoOkraetttecxaarerhhtesltrAitncereoeedxraaessearafadsedsahsallactcssspityujutolobttptauchlomosgelautsrlaiasttlnadthcaklfsetlnuiodld.utittscevsibeuostlasoifnebt0irarntarAclnuatesb.mtblssdioa2iiltmoentoodrielurgoecnytnnetrubonshroaeunemeeutganerudtmr-oarhmttve/baistesmftoPlexaetl3eenoiiiayxttFsdent6LrtrrafnzhbireOiea9,dcedtxeegecohbcedAattaxetitpa.weyh.rceshfmntnepdpedareeaeratsurnul.isneaartiekcsehabntibt-tiefiotahereenloreane7loadxgondiLtn,0tmtmiu,lrOeo-tiswtacmh1imwtnsatacoQahe3isnitnudui,0tpc.idlbdsseloHu%eadt,ltanrrahuI7rvetttnfedghbhhbo0neikneeeseaeesf.t Page 6 o f 7 Page 48 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 142 of 178 3M Environmental Laboratory P0003268; interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 ANALYTICAL METHOD Method ofAnalysis forthe DeterminatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 13.6 Rane4tae%nnatliwyotniitchatiinlmrauennsatbnheaetlnwytteihceeanlsersuttanmn.duiasftrdrbeseteranentadinoanslaytmizmepdel.edsrifmtuesxtceneodtsdthriifstlimmoitrewitthhainn 14.0 Calculations 14.1 bUgaessneeedtrhaoetenfdopblleyoawtkhienagrMeeaaq)susuaLstiiynongnxttohsoecfatswltcaaunrldeaatperrdothgceruaarmvme:o(ulninteoafrPrFeOgrAessfoiounndpa(irnamnge/tmerLs), PFOAfound(ng/mL) = (Peak arseloap-eintercept) x DF DF = factorby which the final volumewas diluted, ifnecessary. 14.2 Fthoerfsoalmlopwliensgfeoqrtuiafiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp.rior to extraction, use Recovery(%) " ( totalanalytefound(ng/mL) analytefoundincontrol(ng/mL)] ^ analyte added (ng/mL) 14.3 Ungs/egt(hpepbfo).llowingequation to convert the amount ofPFOA found in ng/mL to PFOA found (ppb)= (PFOA fousnadm/pnlge/mwLei)gxhtf(inSagl)volume (5 mL)l 14.4 Ufosuendthienfpoplblobwaisnegdeoqnudartyiowne(iigfhnt.ecessary) to calculate the amount of PFOA PFOA found (ppb) dryweight " PFOA found(ppb) x [100%/ total solids(%)] Page 7 of7 Page 49 o f57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 143 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 AMNeAthLodYNTuImCbAeLr: MV0E0T01H7O83D Method of Analysis for the DeatnedrmCilnaamtisobnyoLf CPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish Analytical Testing Facility: SE30txa5yt8egeCRnoeRslleeeasgreeca,hrPcDhAri1v6e801 Approved By: TPaeuchl nCiocnalnLolelayder, LC-MS, ExygenResearch Date ''VJoichien/ oPFrlae?hsiedretynt, Operations, Exygen Research Date TotalPages: 8 Page SOof 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 144 of 176 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V000178} I ANALYTICAL method Method ofAnalysis forthe DetermCilnamatisobnyoLfCPe/MrflSu/oMroSoctanoicAcid (PFOA) in Fish and 1.0 Scope TaScphieidsctmbroyemthHeotirdgichisDtPeoetebrfceotoremrm(apLnlCocey/MedLSif/qMouriStdh)eiCnihsforisolahmtiaaontnodgacrnlaadpmhqsyu.ancotiutaptlieodn otofpearftlaunodroemoctaMnoasics 2.0 Safety 22..12 pCArolewncsaauuyltstiootnhbses.earpvperosapfreialtaebMorSatDoSrybperfaocrteichesa.ndling any chemical for proper safety 3.0 Sample Requirement 33..12 3.3 pSaaAsSfornunaatooabdmmjlldleeyippcmalspleltsiee.rsaatos.tvc2iceoso0ehnlslgoo.seupocolertfdiSnaoteenbnasidenltpphsraaroofnomrcmodcepzeodelpsguensleraefencdossietrzboweeertxhaiwfltogelriraetebhcsetaoeidmovxsrnetpyprr.ealniecccisitegfi.ihoientndP.tlfiaonrPcoleaztahlectlehneoewstshastmaeofmropfarrplgoilneezcgesaunripbnnslotaaicnlnmontpdfitolmiaeoriexntiiehndoriessaf . 4.0 Reagents and Standards 4444444444444.............11314526117891302 WCTPMAFALDSS1-eloiu-aacmiOoelArmrlpteiftruebcmchtelsiereoauostrcataonicn-onohgnlnnleirryeoe(Ht(ooibr-6l1alluloidiPn0(2-lmc-cRi6eL-0cLt10Haea-H-ChAcC0-4anlP2PiHoc0g0og-dL0eLrNe0irPmo0Ctc-anCaHLmsdtemAtRigCee2slggeacrehesrr--aniagsaa)hddhegddrRA)-ea)-eee--e.dRn-RCaeSRteg.eRiSgaeegaerga.nmgaageRtdgeaengee-enntraAntatggtdlgrgedeagrrnradaritdaecdGdeheerade 5.0 Instrument and Equipment 5.1 55..32 AAAjsioLnldavhceleioyvgnntihticnsceeaeptclqoetbeurcafdioolpatrlpolnmeecacdaetntwcarcaaneiwptdhaeldbimaqaleutvMaioadfrafoisracrsebhpaSlrdeeopaimvenkcogatiltrntuoootmgem0grea.er0ptai0enthr0ijoe0(ncLc1atCaopgn/ra.MdbclaqSepu/MaaobnSfltei)tp.aoutifmoinnp.jiencgtinugp 5t-o2020 Page 2of 8 Page SI of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 14S of 178 3M Environmental Laboratory P0003268; Interim R eporm ExyLIMS Protocol Number: P0003268 Exygcn Research Method NumberV0001783 | ANALYTICAL METHOD | MethodofAnalysis for the DetermCilnaamtisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and 5555555555555.............19111158671411324650 WDA52DSCTR11105P2i2eiruiomsss5inE5mtmtssppoaLt-utmoorrtpLmLmiauyscsifLcabpalLdudieetbbzeeipgiiLvasseolstleeeaptrepDrnea(p.ocoH2mpsrPosass-i0hP(rpaEspaim1acahbLbaetr0knabltloLCoete0eaplrep)er-r.eppvs.1ir(d.pooooiS0aellwffu0lyytlsp0sa-ppkpmseirr(ipktolo5n.ocsLpp0nou.yy-iat1nclhlnee0agdnbnt0.5eoeu10ntLcct0oleem,-e.nn1s1NLtt0.0rr00iip0ff5uu-op72gglLy01ee)0p7,ttur7uuwoL)bb.pi)eety.hssl..edniseptousbaebsleatti2p0s0. 0 ipm. 6.0 Chromatographic System 6.1 6666....5234 TM(MGAPerno/omaNabbdlp:iiyilleeee8tnri2caPPt5athPhul0aarrC5oess-e:ego0rl((5ua3AB2mm01)):n3C:::0F)lM2uomeptMhhaasnAeomlRmPo(KnieuymstoAnceetSacteieinntiWfica)t,e2r.1 mmx SOmm, 5p Tim220e8120...(0..0050mini %6662255555A %3377355555B F(mloLw00000/.....m33333Riante) 666...876 RQInuujenacnTttiiiotmanteiV:ono~:lu2Pm3eeam:kinA1u5rtepeasL.-(ceaxntebrneailnsctraenadsaerddtocaalsibmrauticohnacsu5rv0ep. L). TophteimabizoevtehceoHndPiLtiConssyastreemin.tended asa guide and maybe changed in order to Page 3 of8 Page 52 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 146 of 178 3M Environmental Laboratory P0003268; Interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001783 Method ofAnalysis forthe DeAteNrmCAilLnaamYtisTobInCyoALfCLPe/MMrflSEu/oTMrHoSoOcDtanoic Acid (PFOA) in Fish and 7.0 MS/MS System 7.1 PMFoOdAe:. ElectrosprayNegative MRMmode, monitoring413 - 369 m/z for TophteimabizoevethceoMndSiMtioSnssyasrteemin.tended as a guide and may bechanged inorder to 8.0 PreparationofSolutions 8.1 Mobile Phase 8.1.1 a2mmmMonaiummmaocneituamtetaoce1t0a0te0imnLwoaftewraitserp.repared by adding 0.154 g of 8.2 Extraction Solutions 8.2.1 8.2.2 o2a3c%f0di%diamisDnceoti1hmr0by0eilctdmhiaycLclhdilodiocfrihmnolsomeirtlohaesntahinelaaotnnloo.elaiinfsintpoarlleupveaonrleeudmisbepyordefip1sa0sroemldvLibnwygi2bthrgitnooglfuineagnsce3o.rmbiLc Alternate volumes maybe prepared. 9.0 Standard Preparation 9.1 StandardStock/Fottification Solution 9.1.1 9.1.2 .9.1.3 9.1.4 9.1.5 TPAmommiafmAAa1niprr0hfeLeLo1ep00aet1amt2phr.m.hno.o150osaa10aattfn1r2fxLhmnolpepto5iythceomgghlpLtkkoelm/id/egiamcmnfiLas/anta1Lm1tetnLaLDl.ote0Ll0ahdyLcsP01oefDfptk1of2Eao4fgpfo2P5rnr0s"op/gtr5tbdoE.Cmitrirm1/-foiftaelmmifiiuLtbprLcicfatdtcpiLLaolaaniceasLgotrttd(a.itotiaLsn/ocDliotmtloeoiaDoniunooP.lonrrtuLnPesfErnistsooe-Eo.issoc1nolbsltoultubonoa0uetlttobotluitd0itutoitloltootaeteinflniopn.eooaffong.sroinonf/fapfromiaPrntuPlfaoeFLarFvPilOmttoOoFaoyvlAaOfA)uobxfPmleaAiiiunsimFnssemadOptiuloposermAdrrefvpeeoiplord1pbfapue0laryeutpi10reenrmae0dwiwrdto0aeoebedidrbwitye1hgoyoifb0bhftrmfy0hbriinig6re1nmmbiget0nhgmrr0eLgaiai1tnnnoith0ngowwognagirlmntiinh1ttoaihghgn0s1lt Page 4 of 8 Page 53 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 800 Series Wells (Sulfonates) Page 147 of 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Melhod Numb VOOO1783 f Method ofAnalysis for theDeAteNrmCAilLnalmartiTsobInCyoaLfLCPe/MMrflSEu/oTMrHoSoOcDtanoic Acid (PFOA) in Fish and 9.2 Standard Calibration Solutions 9.2.1 9.2.2 pTLorfhCetep/hMaefroSe1ld/l.Mo0awpsSignnc/gemaelidiLsberdfaao.ttriytoipnfiiccsaatatlinoednxaasrmdoslpualteiro:enap.dredpitairoendalincomnectehnatnraotliovnias dilution may be S99oo..C22lfuo..F34tnio00oc0r.eO.ntlll0.0.in..0AanSOOOf.02(lt5tiewtr55cloea2tatetdr/tierimoeCondnanLa.tlt)olec6vaolVCilb(uo,m52lrm111lIu..a.uO0000L50ptem)isoteonanssidtxacnmodnoDacnrid(eltmu11t1111hsnot000000sLteo000000i.rdn)attio1o2n5s-mofLsCtLaoD(nnH00000dcP.F.000.e0..a000E..iOn000nr/020md1t52a01r55nsSl5Laat)miroroanyw-bme opurethpabroedttleass 10.0 Batch Set Up 10.1 10.2 ociREnonaenetcqhchueeiunbrqentaurmttaracetelhiianottytonesdsfafs(soslacaurmobrfanipcentlorlcedonesltarpeonlxaaldtnnsrdlapafciobktertoewdrt)haotit(osotyrpvuypreniordctijrauefelycpaltyltp.iecrd2oa0cteecsodoruanrnltaerdolsslrss)epcimokfoveusresttriwyfiiinefllodclrbutedahetespbaekatcnticlofehiwae.sdnt 11.0 Sample Extraction 11.1 11111111....3542 11.6 PdeScdPA(tfWPhofiairailaotmdyellarehccalbrnd.coikeektngoeiwtr32ifhnhatzyt0b0hen,yheydeadlem5amdsant2cbiLtLuigncdoh0yrbhe-neoodeel1ommdfodsfrfiyargLeet1aioicitdnf2conhseLr,S5enigaoatlCtrPonazoteofnEh-neonprmrNieneeliltwteartLHrSu(iizcsinlitbPlejeeathe.herEmtrpl.aoseifaendpClteouaDuidslnorareebtti--srinnnsesm1ehsddciehseanaaieaqmmhatkstrsipounoodeo)ie.elduoxnoudan3rfsntl.wc0tilDnihoelaeiwafenrtmllrwnwyl.aao)ciLs.sirzgtokRthihehelsseieupnttns2mho.a.sfbelcelnygaytDpsi(psohefkrownleaosrorpinisrf-ntcyiolhshssaohltaiisemlan2kka,npg0elpel2werlomdefwicwgtotfeeLhrlinlstaty-thihtoso1lrekiiflbc5fsuceuam.teohmfgnoegleeeuirtenhemlotua,3ununtn02ebcsos%eteelo.gs,,, Page 5 of 8 Page 54 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 148 o f 178 3M Environmental Laboratory P0003268; Interim Report#4 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001783 ______________________ANALYTICAL METHOD______________________ MethodofAnalysis for theDetermCilnaamtisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fishand 11.7 11.8 11.9 111111...111120 11.13 11.14 11.15 11.16 1111..1178 eTtMAAPetDHtsfSACPDtfCfhhhhvoxalraolhdnaeeeoedeeeaamreaatsasrndarccnmkdnpcp-sska-tkplaetat1eesioaey1rc.2orneesnf3imarit0z1ts0ge0afttifiaph-rteh0uuorureh4-etemett-emmmgensnghshetsaphmhet.aiieeehadLirfiuseznaemn-zitarLataebunepstueeohorepmhprhextaerexttpxe-eefeleslahtoddsptwesstdrsaprehrSvuia.fls.aSfcaneieOacocflOotcfeucdaalphtelraatattfscsuomedosgomsi-koefmdznknafn1rt1ptLneLloagie.oiefa-0rntnttnelone,orsoeHpapzdiCkcmsifflbslotoeoeasPtaetkroasylhLrutlcriLy.wnylctalterpf-lhepaCrooopneeoi1hordrrlndscrfroluo0atsodvatdo-aupsspttmpiiitomcoeiagncrythyn1aeiltoeghlumoeilshgtyemnethosnehtnS2uienuaoihLnexbeenslPetueidmrusC/iiegtEdonnartrasetS/uSLiimtugemaMtxslaoPbecPbestrtdponeEooSreoEiyiwiilasrslnsnfl/seaeuscvceMicptc2.utmcotvtwoeohoioh%moS.lanlnsrtuinenup.hniai.mtsttmzoeabtah1athersi-nlt2ientnCraeeachnuSticoaeifpboofnntoenrSimeilrigtbgpllrdOo.ptue(iLee-nesaccecsdt3amatstnaossamr0.m<htiimLt-cnlhaspaips4sbhkdfenleil0creiaedeiconeizpreeonCme.naeleanutttd)dttmhrda.hi--etspftee2e2fhuetmal00eehgaani0l0anroesud-kn0tu0iasonotrthtuhirielarantpbtpnihptsomaeimdoneeel.f 12.0 Chromatography 12.1 12.2 12.3 12.4 ImteLgvUSsisasAihnnnaaoineetCtsteunjmjmafnraheeeet/ssnlereewMeccppyutdsrnrnttllzlsabpaeaeeSitdtetrdreenicshce/erddsr.aMeoaeedisesssnalsfetaeiyssSrfo.cabdtA,eaaosmlfrutmtsresaecssPpttdotvtmaaahyehFlieafemnleosedei.Onarctsdnbeypm.aaaiArmbnlalnsar5eoieldttba.cat-auigels1roonnnyiearAc0nrndtntttaure.inaaseonorrsiatscvbafnnditSpmavlaeyegytolsnescaapitltn,odbcniialcnodheanrfdnaaoaeirscfadnnldtsraer(iatgssrdontaareeoqsrndtntntmreou.sdaatmgsaiaucstamerrnitrucseteotadttuossilnn,ttessusadfbtisaenubotoaeastibtselnortmleidfoonntfiuohpinw.ifgvsrnelmteieeeccMandraulfaogLussliasnpirreditsbs1ndbecemstr/reyoLdpxafsaonarotyerawierndrdnoctectdexnasisetbcfitheldgiaoiei3teesbaehntn.dtwosr3tbdacaitnfaeasenet(nagdrisniegoodntmdaintrannrojrneapdneecfctdflqsivuiepostnaouiertlergomnavilirdaonvnnyesakalwtads)eonyl5.aiavedn-rrtaena1hbdeIrlatl0neaesaes)lt Page 6 of8 Page 55 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 149 of 178 3M Environmental Laboratory P0003268; interim ReportM ExyLIMS Protocol Number: P0003268 Exygen Research Method Number VOOOI7S3 ______________ Method ofAnalysis for the DeAteNrmCAilLnamaYtisTobInCyoALfCLP/eMMrilSEu/oTMrHoSoOcDta_n_o_ic__A_c_i_d_(_P_F_O__A_)__in__F_is_h__a_n_d 12.S Sexacmepedlesrtaenspdoarndseresshpoounlsdesnsohtoeuxldcebeedfustrathnedradrdilurteesdpoanndserse.anaAlnyzyedsa.mples that 13.0 Acceptance Criteria 13.1 13.2 13.3 13.4 13.5 13.6 aTR2asmEHeAbmMRtdoCnthp0nhlaearf4oenuhaueper.tutneacw9ysi4rnoiestr%ngrdoroht9otn1kreeahcavmncok2pbt3vlortiTswaceodnyreedoeaerloriaetotriri(rnstatioinbtmbs,oReeewcthiootbtlreolxsga,Jatautiaantfrinchnrlani.ottmmasntes2iieirkvh(oaaofmnteus0e3aTseanemnnetdcn.sy6plPo9hdomurmap92ssttFe8ebencnahblta0uul$Oseoaeatlaeeen4m%r.sss)ntmelvno1Adtw.tnyfduseal3ufuttoIsnthaesxnihihfahs)mcocrfteoactepteIodaarintutmlfsbieewhllubseklceecpnefdeeuderncsoetvoorrtutaeattstobneeunpanimodlotsr(ltepniftnaa.asateRerbfudeaksdnrotrinrgehasIa)nlseecadlatfenotmrtk-nanrstoesetrdPtrmifblunoppatoeioxmsFechmbbtttalinrtfooeeOeekrrterutabhaanrarsenecsnAlriectetaaaoetxtseadiidrtfhnodoshsslebaacasaioaspsnujnodluebtastunlploflaou.gysarlttsrisltncsalis0mzhkefteitdmotutdsea-.tevcai5upeetldnoisfbsaneeianaxrtlc.ndreldptsetmlsdtsbaiioaliasrptorodrloarrurcebginnduetondcfomuasr,hmsttustenurateodetuevthaaihtbtdeistfsxnlteoePlhene.ii3etycjsdextaFnter6azhebreitncO9cedeetaegoothbcdcdeeAtetp.ateaonyw.c.shdnempnaeue.detearutlwlhsauraierndtsebaiithbnisifibtfroenoltebraellnl7ogndiateiLmm,0imm,nlotiO-wekomhmiin1attxaQrehs3nsiuecw,cti0.apdlsslHuumi%eat,tttrhhdurhIvttptebeaehfgihheolnnnndeeeaee.eft 14.0 Calculations 14.1 UbgaessneeedtrhaeotenfdoplbleyoawtkhineagrMeeaaq)susuaLstiiyonnngxttohsoecfatslwtcauanrldaetaeprrdtohgceruaarmmve:ou(lnitneoafrPrFeOgrAesfsoiounndp(airnamnge/tmerLs), PFOA found (ng/mL) = (Peakaresalo-pientercept) 14.2 nUgs/egt(hpepbfo).llowing equation to convert the amount ofPFOA found in ng/mL to PFOAfound(ppb)- fPFOAfounds(anmtt/pmleLw) eXigfihnta(lgv)olume ImLl x DF1 DF factorby which the final volume was diluted, ifnecessary. Page 7 ofS Page 56 of57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 150 of 178 3M Environmental Laboratory P0003268; Interim Reporttt4 ExyLIMS Protocol Number: P0003268 ExygenResearch MethodNumber V0001783 | ANAtA'TIC.VL METHOD Method ofAnalysisfor the DetemCiilnaamtisobnyoIfCP/eMrfSlu/oMroSoctanoicAcid (PFOA) in Fish and 14.3 Fthoerfsoalmlowpliensgfeoqrtuifaiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp.rior to extraction, use Recovery(%) = | totalanalytefound(ng^g) - analytefoundincontrol (ng/g)] analyte added (ng/g) Page 8 of8 Page 57 of 57 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 151 of 178 3M Environmental Laboratory P0003268; Interim ReportM Exygen Protocol P0003268 Amendment 1 Study Title "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program" PROTOCOL AMENDMENT NO. 1 Amendment Date: August 24, 2007 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP07-0003 Page 1of 4 Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 152 of 178 3M Environmental Laboratory P0003268; Interim Reporttt4 Exygen Protocol P0003268 Amendment 1 This amendment modifies the following portion of protocol: "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in W ater, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program" Protocol reads: Testing Facility MPI Research, Inc. (formerly Exygen Research, Inc.) State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 Fax: (814) 231-1580 A m en d to r ead : Testing Facility MPI Research, Inc. (formerly Exygen Research, Inc.) State College 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 Fax: (814) 231-1580 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Reason: Addlton of the 3M Environmental Laboratory as a testing facility allows samples to be sent to the 3M Environmental Laboratory for analysis. The initial sample analysis is outlined in the attached General Project Outline (GPO) authored by Michelle Malinsky, 3M Principal Analytical Investigator. Page 2 of 4 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 153 of 178 3M Environmental Laboratory P0003268; Interim ReportM Exygen Protocol P0003268 Amendment 1 Protocol reads: Analytical Procedure Summary References: ETS-8-12,0: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfiuoropentanoic 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) in Water, Soil and Sediment by LC/MS/MS A m e n d to r ead : Analytical Procedure Summary References'. ETS-8-12: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfiuoropentanoic 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) in Water, Soil and Sediment by LC/MS/MS ETS-8-154: Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry ETS-8-044: Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis Reason: These additional 3M Environmental Laboratory methods allow samples to be analyzed by other methods If deemed appropriate by the 3M principal analytical investigator and 3M Environmental Laboratory management. Page 3 of 4 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 154 of 178 3M Environmental Laboratory P0003268; Interim ReportH Amendment Approval Michael A. Sanjdro, SponsorRepresentative Exygen Protocol P0003268 Amendment 2 l'f a /)7 Date M. L icihi ei illMe D.l l iM..ai'lJini s,.k.Jyli,JPhD.. Principal Analytical Investigator ... ... 'Dl at/ X'-t EHS pns Environmental Lab Management JaisimhaKesari P.E., DEE, StudyDirector Date Date Page 3 o f3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 155 of 178 3M Environmental Laboratory P0003268; Interim ReportM Amendment Approval Exygen ProtoAcomlePn0d0m0e3n2t682 Michael A. Santo, Sponsor Representative Date Miche:i Epa! Analytical investigator Jaisimisa 'Resati P.E., DEE. Study Director Date Page 3 of 3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 156 of 178 3M Environmental Laboratory P0003268; Interim ReportM Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: Gary Hohenstein, 3M EHS&Opns; From: cc: Michelle Mallnsky, 3M EHS&Opns; Environmental Lab Kent Lindstrom, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Dale Bacon, 3M EHS&Opns; Environmental Lab Casey Howell, QAI, 3M EHS&Opns; Environmental Lab Tim Frinak, Weston Solutions, Inc. Jai Kesari, Weston Solutions, Inc. Date: Subject: August 23,2007 Decatur Off-site Surface Water and Sediment Sampling week of August 27,2007 under GLP Protocol P3268 (3M Environmental Laboratory Request GLP07-003) 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 157 of 178 3M Environmental Laboratory P0003268; Interim Report#4 1 General Project Information Project C oordinators) GLP Study Director GLP S ponsor Representative Analytical Facility Management Lab Request Number Six Digit Department Number Project Scheduie/Test Dates 3M Overall P ro je ct C oordinator Gary Hohenstein 3M EHS Operationo 42-2E-27 651-778-5150 gahohenstein@mmm.com Field Sam pling C oordinator Tim Frinak Weston Solutions, Inc. 3M A nalytical P roject Management Kent Lindstrom 3M EHS Opns, Environmental Laboratory 260-5N-17 651-733-9882 kr1indstrommmm.com Principal Analytical Investigator Michelle Malinsky 3M EHS Opns, Environmental Laboratory 260-5N-17 651-733-9859 mmallnskvOmmm.com Jaisim ha Kesari Weston Solutions, Inc. 1400 Weston Way Westchester, PA 19380 Michael A. Santoro 3M Company W illiam K. Reagen 3M Environm ental Laboratory Manager 3M EHS Opns, Environmental Laboratory 260-5N-17 651-733-9739 wkreagen@mmm.com GLP07-0002 530711 Sampling to Commence on August 28, 2007 All verbal and written correspondence will be directed to Gary Hohenstein. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 158 of 178 3M Environmental Laboratory P0003268; Interim Reportm 2 Background Information and Project Objectlve(s) On August 28,2007, personnel from Weston Solutions, Inc. will collect sediment and surface water samples from an off-site location near the 3M Decatur facility. The EHS Operations Environmental Laboratory will analyze the water samples for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) under GLP study GLP07-0003 (MPI Protocol #P3268). The final report will be submitted to Gary Hohenstein upon completion. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory professional services personnel for arrival in Decatur, AL no later than Monday August 27, 2007. Collection bottles will be sent to the Weston Solutions, Inc. office located at the 3M Decatur facility. 4 Test Parameters 4.1 Water Samples Estimated reporting limits will be 0.025ng/mL (ppb) for the three target analytes. A total of five sample sites have been specified. For each sampling location, a total of four or five sample bottles will be collected (sample, sample duplicate, low-level field matrix spike, mid-level matrix spike when appropriate, and high-level matrix spike). The "fill to here" line on each 500 mL Nalgene bottle will be 450 mL. The table below provides the spike levels associated with each location. Additionally, Weston has requested two bottles for equipment rinseate samples. Additionally, three trip blank sets consisting of reagent-grade water, a low-level trip blank spike, mid-level trip blank spike, and a high-level trip blank spike will be prepared at the 3M Env. Laboratory and sent to the sampling location with the other bottles. Three trip blank sets will allow for samples to be sent back to the laboratory in three separate shipments if necessary. A total of 37 sample bottles will be prepared. Additionally, the lab will send two one-liter bottles of reagent grade water to be used for equipment rinsing. Table 1. Sam ple Locations and Spike Levels fo r S urface W ater Sam ples. Sam ple Loca tio n West Pond Location 1 *H istoricai PFBS Cone. (ng/m L) NA *H is to ric a l PFHS Cone. (ng/m L) NA *H is to ric a l PFOS Cone. (ng/m Lf NA L o w Spike Cone. (ng/m L) 0.25 West Pond Location 2 NA NA NA 0.25 East Pond Location 1 7.63 61.8 437 10 East Pond Location 2 7.63 61.8 437 10 Swamp Location 1 (Emergent Marsh) 7.63 61.8 437 10 Equipment Rinseate 1 NA NA NA **NA Equipment Rinseate 2 NA NA NA **NA Trip Blank Set 1 NA NA NA 0.25 Trip BJank Set 2 NA NA NA 0.25 Trip Blank Set 3 NA NA NA 0.25 Maximum surface water concentrations within the ` East Pond" sampling area. "Equipm ent Rinseates do not require field matrix spikes. M id S pike Cone. (ng/m L) NA NA 100 100 100 **NA **NA 10 10 10 H ig h Spike Cone. (ng/m L) 5.0 5.0 500 500 500 **NA **NA 500 500 500 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 159 of 178 3M Environmental Laboratory P0003268; Interim ReporttM 4.2 Sediment Samples Estimated reporting limits will be 0.20 ng/g for sediment samples. A total of 39 primary field sediment samples will be collected. Duplicate sediment samples will be collected for four selected locations. Weston has requested two extra sediment collection bottles. Matrix spikes for sediment will be prepared in the laboratory. Each location will have only one sample bottle. If a blank sediment matrix is available, two sediment trip blanks will be sent to the facility with the bottles. 5 Test Methods 5.1 Water Samples Water samples will be extracted and analyzed by LC/MS/MS using procedures outlined in 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 has been validated for PFOS; however, specific quality control samples analyzed with the samples will be used to determine overall method precision and accuracy for all analytes. 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. Additional water analysis methods that may be used if deemed appropriate by the PAI and 3M laboratory management include the following: ETS 8-44 "Method of Analysis for the Determination of Perfluorinated Compounds In Water by LC/MS/MS; Direct Injection Analysis" ETS 8-12 "Method of Analysis for the Determination of PerfluorobutanoicAcid (PFBA), PerfluoropentanoicAdd (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid (PFHpA), PerfluorooctanoicAcId (PFOA), PerfluorononanoicAcid (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (PFUnA), PerfluorododecanoicAcid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment by LC/MS/MS. 5.2 Sediment Samples Sediment samples will be extracted and analyzed by LC/MS/MS using procedures outlined in ETS 8-12 "Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), PerfluoropentanoicAdd (PFPeA), Perfluorohexanoic Add (PFHA), Perfluoroheptanoic Acid (PFHpA), PerfluorooctanoicAdd (PFOA), PerfluorononanoicAcid (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (PFUnA), PerfluorododecanoicAcid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment by LC/MS/MS". If a blank sediment matrix is available, an extracted calibration curve will be prepared to analyze the sample extracts. If not, sample extracts may be analyzed against a calibration curve prepared using the solvent mix used to extract the samples. If necessary, a curve may be prepared using a sample sediment that was screened and determined to have low levels of the target analyte. Lab matrix spikes will be prepared for each sample. Lab matrix spikes not yielding recoveries within 10030% will be addressed in the report and the final accuracy statement may be adjusted accordingly. Laboratory duplicates will be prepared for each sample. The four field duplicates collected will assess sample collection precision. 6 Reporting Requirements 6.1 Water Samples For each sampling location, the report will contain the results for the sample, sample duplicate, and the two (or three) field matrix spikes. Trip blank(s) and associated trip blank spikes will also be reported. Laboratory control 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 160 of 178 3M Environmental Laboratory P0003268; Interim Report#* 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. 6.2 Sediment Samples For each sample location, the report will contain the results for the sample, laboratory duplicate, field duplicate if appropriate, and the prepared laboratory matrix spike(s). If a blank sediment matrix is available, lab control spikes prepared at the time of sample extraction will also be reported and used to evaluate the overall method accuracy and precision. 7 Attachments None. GLP protocol is available upon request. Not attached due to Hie size limitations. 8 E-mail Communications 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 161 of 178 3M Environmental Laboratory P0003268; Interim ReportM "Young, Chartes T." <Charies.Young@WestonSol utions.com> 08/22/2007 03:32 PM To "Kent Lindstrom" <krlindstrom@mmm.com> "Michelle Malinsky" <mmalinsky@mmm.com> cc "Kesari, Jai" <J.Kesari@WestonSolutlons.com> "Frinak, Timothy R." <T.Frinak@WestonSolutions.com> bcc | History: Subject P3267 / P3268 Decatur off-site SW/SD sampling been3 This message has replied to. Kent and Michelle: The off-site sediment (SD) and surface water (SW) samples to be collected at Decatur starting on Tuesday 8/28 and analyzed under the GLP Protocols P3267 and P3268 include the following: 39 primary sediment samples 4 field duplicate sediment samples Please add two spare bottles for the sediments 5 surface water samples 2 Equipment rinseate samples 3 Trip blank samples Of the SW samples, 2 are from a location upgradient of sources It is anticipated that only 0.25 and 5 ng/mL spikes would be required for these "West Pond" samples. Based on earlier sampling, the maximum SW concentrations within the "East Pond" sampling area were 526 ppb PFOA, 7.63 ppb PFBS, 61.8 ppb PFHS and 437 ppb PFOS. Current concentrations may be lower than previous so low range coverage by field spikes will be necessary in the event that concentrations have dropped appreciably. I will provide information that may be helpful in determining lab spiking levels for the sediments in a subsequent email. Thanks, Charlie Charles T. Young fTWW(1a64ex1eec00sshx0t)t7noCW74nic00haeS11elso-stD3tloeu7nirrt8,ieWo7cPntAaosyr,1(I94n-3c2.8)0 CONFIDENTIALITY: This e-mail and attachments may contain information which is confidential and proprietary. Disclosure or use of any such information without the written permission of W eston Solutions, Inc. is strictly prohibited. If you received this e-mail in error, please notify the sender by return e-mail and delete this e-mail from your system. Thank You. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 162 of 178 3M Environmental Laboratory P0003268; Interim ReportM Exygen Protocol P0003268 Amendment 2 Study Title "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program" PROTOCOL AMENDMENT NO. 2 Amendment Date: Septembers, 2007 Performing Laboratory 3M Environmental, Health, and Safety Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55144-1000 Laboratory Project Identification GLP07-02 Page 1 of 3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 163 o f 178 3M Environmental Laboratory P0003268; Interim ReporttU Exygen Protocol P0003268 Amendment 2 This amendment modifies the following portion of protocol: "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program" P rotocol A m endm ent 1 reads: Laboratory Project Identification GLP07-0003 A m en d to r ead : Laboratory Project Identification GLP07-02 Reason: When the original GLP project was created using the 3M Environmental Laboratory's Laboratory Information Management System (LIMS), the wrong project template was used. With the correct template, all samples collected under protocol P0003268 and analyzed at the 3M Environmental Lab will be logged in under GLP program number GLP07-02. Samples from individual sampling events or different subcategories of samples (i.e. water vs. sediment) will be logged under separate projects under the same GLP program number. For example, the sediment samples collected on August 28-29, 2007 will be logged under GLP project number GLP07-02-01. Samples from the next event will be logged under project number GLP07-02-02. The new GLP program template allows for easier sample tracking and management when numerous samples will be collected over an extended period of time. Page 2 of 3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 164 o f 178 3M Environmental Laboratory P0003268; Interim ReporW4 Amendment Approval Exygen Protocol P0003268 Amendment 2 Michael A. Santoro, Sponsor Representative " l -,/V n . M idhelle D, M a lin .. sk yh , |j%' .D ., Prir^ijjal ___________________________ Analytical Investigator Date tat EHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director Date Date Page 3 of3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 165 of 178 3M Environmental Laboratory P0003268; Interim Reporttf4 Amendment Approval m j d . Michael A. Sandro, Sponsor Representative Exygen Protocol P0003268 Amendment 2 i / MDate'7 4 Michelle D. Malinsky, f h,D,, Principal Analytical Investigator Dat EHS Opus Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director Date Date Page 3 of3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 166 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Amendrrssnt Approval Exygen Protocol P003268 Amendment 2 Michael A. Saatto, Sponsor Representative Date Mite!leI), s'a! Analytical Investigator Date Page 3 of 3 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 167 of 178 3M Environmental Laboratory POOO3268; Interim Reporttu Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: Gary Hohenstein, 3M EHS&Opns; From: cc: Michelle Malinsky, 3M EHS&Opns; Environmental Lab Kent Lindstrom, 3M EHS&Opns; Environmental Lab William Reagen, 3M EHS&Opns; Environmental Lab Dale Bacon, 3M EHS&Opns; Environmental Lab Casey Howell, QAI, 3M EHS&Opns; Environmental Lab Tim FrinaK, Weston Solutions, Inc. Jai Kesari, Weston Solutions, Inc. Date: Subject: September 10,2007 Decatur groundwater samples from off-site 600 series wells (MPI Protocol P3268; 3M GLP Program GLP07-02) 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 168 of 178 3M Environmental Laboratory P0003268; Interim ReportiU 1 General Project Information Project C oordinators) GLP Study Director GLP S ponsor Representative Facility Management Lab Request Number Six Digit Department Number Project Schedule/Test Dates 3M Overall P roject Gary Hohenstein 3M EHS Operationo 42-2E-27 651-778-5150 gahohenstein@mmm.com Field Sampling C oordinator Tim Frinak Weston Solutions, Inc. 3M A nalytical P roject Management Kent Lindstrom 3M EHS Opns, Environmental Laboratory 260-5N-17 651-733-9882 krtindsirom@mmm.com Principal Analytical Investigator Michelle Malinsky 3M EHS Opns, Environmental Laboratory 260-5N-17 651-733-9859 mmalinskv@mmm.com Jaisimha Kesari Weston Solutions, Inc. 1400 Weston Way Westchester, PA 19380 Michael A. Santoro 3M Company W illiam K. Reagen 3M Environm ental Laboratory Manager 3M EHS Opns, Environmental Laboratory 260-5N-17 651-733-9739 wkreagen@mmm.com GLP07-02-02 530711 Sampling to commence the week o f September 17,2007 All verbal and written correspondence will be directed to Gary Hohenstein. 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 169 of 178 3M Environmental Laboratory P0003268; Interim ReporttU 2 Background Information and Project Objective(s) Personnel from Weston Solutions, Inc. will collect groundwater samples from off-site 600 series wells located near the 3M Decatur facility. The EHS Operations Environmental Laboratory will analyze the water samples for perfluorobutanesulfonate (PFBS), perfluorohexanesulfbnate (PFHS), and perfluorooctanesulfonate (PFOS) under 3M GLP program number GLP07-02 (MPI Protocol #P3268). The final report will be submitted to Gary Hohenstein upon completion. 3 Project Schedule Sample collection bottles will be prepared by 3M Environmental Laboratory professional services personnel for estimated arrival in Decatur, AL on Friday September 14,2007. Collection bottles will be sent to the Weston Solutions, Inc. office located at the 3M Decatur facility. 4 Test Parameters 4.1 Water Samples Estimated reporting limits will be 0.025ng/mL (ppb) for PFOA. A total of fourteen sample sites have been specified. For each sampling location, a total of four bottles will be collected (sample, sample duplicate, low-level field matrix spike, and high-level matrix spike). The "fill to here" line on each 500 mL Nalgene bottle will be 450 mL. The table below provides the spike levels associated with each location. Additionally, Weston has requested two bottles for equipment rinseate samples. Additionally, two trip blank sets consisting of reagent-grade water, a low-level trip blank spike, mid-level trip blank spike, and a high-level trip blank spike will be prepared at the 3M Env. Laboratory and sent to the sampling location with the other bottles. A total of 66 sample bottles will be prepared. Additionally, the lab will send two one-liter bottles of reagent grade water to be used for equipment rinsing. Table 1. Sam ple Locations and Spike Levels for Surface W ater Sam ples. S a m p le L o c a tio n /W e ll ID 601R 610S 601L H isto rica l PFBS C oncentration (no/m L) NR NR NR H isto rica l PFHS C oncentration (ng/m L) 0.0254 0.0292 20.8 H istorica l PFOS C oncentration (no/m L) <0.025 0.0344 2.54 L o w Spike C oncentration (ng/m L) 0.25 0.25 0.25 602R 0.221 0.115 0.193 0.5 602S 602L 0.192 0.115 0.137 0.461 0.577 1.77 0.5 0.5 603R 603S 603L 0.204 0.1 0.0441 0.329 0.106 0.0461 0.120 0.255 0.182 0.25 0.25 0.25 604R 604S 0.119 0 .1 18/NR 0.146 0.213/0.159 0.919 0.271 / 0.0548 0.5 0.25 604L 0.178/NR 0.275/0.211 0.945 / 0.727 0.25 605R 605L 0.0677 <0.025 0.0418 <0.025 0.0257 <0.025 0.25 0.25 H igh Spike C oncentration (nct/mL) 1 1 25 5 5 5 2.5 2.5 2.5 2.5 1.0 5.0 1 1 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 170 of 178 3M Environmental Laboratory P0003268; Interim ReporW4 ` Equipment Rinseates do not require field matrix spikes. Trip B lank Set 1: Low spike: 0.25 ng/mL; Mid spike: 0.5 ng/mL; High Spike: 1.0 ng/mL Trip B lank Set 2: Low spike: 2.5 ng/mL; Mid spike: 5.0 ng/mL; High Spike: 25 ng/mL 5 Test Methods 5.1 Water Samples Water samples will be extracted and analyzed by LC/MS/MS using procedures outlined in 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 has been validated for PFOA; however, specific quality control samples analyzed with the samples will be used to determine overall method precision and accuracy. The data quality objectives for these studies are quantitative results for the target analyte 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. Additional water analysis methods that may be used if deemed appropriate by the PAI and 3M laboratory management include the following: ETS 8-44 "Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct Injection Analysis" ETS 8-12 "Method of Analysis for the Determination of PerfluorobutanoicAcid (PFBA), Perfluoropentanoic Add (PFPeA), PerfluorohexanoicAcid (PFHA), Perfluoroheptanoic Acid (PFHpA), PerfluorooctanoicAdd (PFOA), PerfluorononanoicAcid (PFNA), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Add (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, and Sediment by LC/MS/MS. 6 Reporting Requirements 6.1 Water Samples For each sampling location, the report will contain the results for the sample, sample duplicate, and the two (or three) field matrix spikes. Trip blank(s) and assodated trip blank spikes will also be reported. 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 predsion. 7 Attachments None. GLP protocol is available upon request. Not attached due to file size limitations. 8 E-mail Communications 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 171 of 178 3M Environmental Laboratory P0003268; Interim Reporttt4 "Young, Charles T." <Charles.Young@WestonSol utions.com> 09/07/2007 02:07 PM To "Kent Lindstrom" <krlindstrom@mmm.com> "Michelle Malinsky" <mmalinsky@mmm.com> cc "Frinak, Timothy R." <T.Frinak@WestonSolutions.com> bcc History: Subject Last Sampling Round for Decatur 600 series wells prior to abandonment 1% This message has been forwarded. Kent and Michelle: The fourteen 600 series off-site wells at Decatur are scheduled for sampling prior to well abandonment. The following excerpt from the attached spreadsheet shows earlier analytical data for these wells and should be used to determine appropriate spiking ranges for PFBS, PFHS, PFOS and PFOA. Analyses will be under the GLP protocols P3267 and P2368. In addition to bottle sets for samples from each of the 14 wells, two equipment rinseate blank bottles and Milli-Q water and two trip blank bottle sets should be provided for the QC samples. Sampling will be performed by Tim Frinak during the week of September 17. Can the bottle sets be prepped and shipped later next week for Friday September 14 arrival at Decatur? DOfefc-asittuer,6A00lasbearmiesawells Groundwater PFBS, PFHS, PFOS and PFOA Concentrations Well ID 660011SR 666666660000000021233243SLLLRRRS 604S 604L 660055LR Sample ID DDAALL--GGWW--660011RS--00--006600441133 DDDDDDDAAAAAAALLLLLLL-------GGGGGGGWWWWWWW-------666666600000001233223LSRRSLL-------0000000-------000000066666660000000444444411111113323333 DDDDDAAAAALLLLL-----GGGGGWWWWWS---S666--60006044404LRS4S-L--00-0-0---000-0-066606000614441211210220311 DDAALL--GGWW--660055RL--00--006600441122 Sample Date 13-Apr-06 1133--AApprr--0066 111333---AAAppprrr---000666 11113332----AAAApppprrrr----00006666 00111122----ADDApeepccrr----00006666 1122--AApprr--0066 [kApvpebr,angge/PmFLB)S |NR NNRR 0000000.......12121102401911454291 NN00..RR117188 N0.D0677 (Apvpebr,angge/PmFLH) S 0.0254 02.00.8292 0000000.......4311110614342015676961 00000.....2220111745135198 ND NngD/m=LNot detected at or above Limit of Quantitation (LOQ) of 0.025 A(pvpebr,angge/PmFLO) S ND 200...150943344 000001......2519175278715792 00000.....29007742251545778 ND Thanks, Charlie 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 172 of 178 3M Environmental Laboratory P0003268; Interim Report#4 Charles T. Young WTWf(1a64ex1eec00sshx0t)t7noC7W4nic00haeS11els-ost3Dtloeu7nirrt8,ieW7ocPntAaosyr,1(I94n-3c28.)0 CONFIDENTIALITY: This e-mail and attachments may contain information which is confidential and proprietary. Disclosure or use of any such information without the written permission of W eston Solutions, Inc. is strictly prohibited. If you received this e-mail in error, please notify the sender by return e-mail and delete this e-mail from your system. Thank You. Off-site Stk welts GW alt constituents;^ 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 173 of 178 Attachment D: M ethod Deviations 3M Environmental Laboratory P0003268; Interim ReportM 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 174 o f 178 3M Environmental Laboratory P0003268; Interim Reports 3M Confidential ....... ........... Record of Nonco n fo r m ance / Deviation' _________ _______________................ ,..........L id e n tification _ _ _ * Study m o je No. GLP07-02-02 " ' *ofte{irS~dccun-enoe:' ' ^ S S m e n ilu m b e r: October 11,2007 : ETS-S-44,0 Deviation type O SOP P Equipment P rocedure`" 0 Method (Check om ) D Protocol G P O ________ o th e r;.................... ___ : ` !- i t - B r n t m ^ o n : Method Reqairemeisis: _______________________ ____________ ETS 8-44.0 Section 12.2 ... ......... ....................................................... CCV Performance: The accuracy of the CCV injection must be within 25% of the theoretical concentration {30% for the LOG standard). Samples not bracketed by compliant CCVs must be reanalyzed. Actual procadurc/process: The table attached to the end of this deviation record documents the non-oompftant CCV injections and We actions taken. Bracketed samples were not reanalyzed. This table was also presented and discussed in the report ///. Actions Taken ............ ......... ............ .. _s5 ''. . * a'" nyjT.-y io% SOPmmpn, eiey _ Corrective Action- ( O Yes 0 No) Reference: .............................. | A cceptability o f fee nonconform ing work: j Results were reported without reanalysis as the degree o f non-compliance was deemed minimal when the overall method uncertainty was considered. CCV failures did not significantly impact the overall data tobies; quality objectives of the project When appropriate, affected samples were assigned an expanded ! uncertainty. Results in summary and full QC were flagged appropriately. j Actions: O Halting of W ork D Client Notification O Work-Race# Withholding of Report S O ther Deviation addressed in report ' j Recorded by: Michelle D. Matinsky> Date: 01/28/2008 GLP Study Din Authorization: i Sponsor Apprcv Protocols):,(4i^v-'0 4/& Technical Manager Approval iifharan9 ofwikcrworxra^t iatad); /V. A u th o riz a tio n to Resume Work .......... W:<amHaitmy of -vark ceemeC r/w .-x .; ;.v,r v-~t he try :/ Technical Manager Approvai: mmDate:/ / Date: . / Datea:* ` i ''vai Management Date: Deviation Mo, 1_______ a s s ig n e d b y S tu d y D ir e c to r o r P r o je c t L e a d a t th e m id o f s tu d y o r p r o je c t) ETS-4-08.4 Page 1 of 2 Attachment A: Record of Nonconformance I Deviation form Documentation of Deviations and Control of Nonconforming Testing 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 175 of 178 3M Environmental Laboratory P0003268; Interim ReporttU 3M Confidential Record of Nonconformance / Deviation Non-CompUamt CCV injections. "T fa jm io n A n a ly te 1 % tU & m r y N um ber .j____ oonotm ost PFBS '' Mot C afcu W sd S a m p le s B m e k a tw l b y Mon-Compliant C C f j i Action T a k a n tQ a m n m tt G L P 07 4J M 2 -C 5 tti!w g h S U = 0 7 -oe - 025 A re s a n t e o t C C V ^ e tfe itw e ro 1 2 1 % o fth e original cu rve point No *o rr ta k en . Samples w ith P F S S a m ce n iraB o tis > 2 .5 flgftnL w e n ot a ffe c te d a s fie y w e re rep o rted fe w th e high fa rc e u rs ; 00710118078 PFBS N ot C afcu feted 6 L P e 7 -0 2 -0 2 -0 2 8 ro u g h <3LF7-d2-C i2- 041 A re * s u ite o f O G V in je c te Vsas 1 2 8 % o f th e a tm ro a rs tS o f tfir i s r is p te iu p e W in jection. S a m p le s *S h P F S S c t e h < S :5 ngfm L w w e a s s a d a n e g m te S s w te e isrK srtjan ty of 1 0 0 *3 . I n t e l # PF8S c o n ce n tra tio n s > 2 .5 r 0 m L m m w A a ffe c te d . o ffiH O tle O S V ;PFKS 1085t G IP 0 7 .0 2 -0 2 -Q S throug h G U fo m - O - 025 C ra c a n tra fc n o f C C V s ts o w i * u p p e r ! * o f tju a r ite w a f a H ie f e w * ! c a v a ; how ew w , th e e s trr a ite i a c e u ra ty m s s tfi aatSts o w ih o d a te te N o (& n te !o m te fs te s tP F H S c o n c e n tra te < 2 5 n g frn l. S am p le s w ith P F H S c o n cen tratio n s 2 5 n g ffflt w s ra n o t affected ; O 0 7 t0 1 1 a 0 7 6 PFHS *1 2 4 % G tW -0 2 -0 2 -0 2 6 through G L P O 7-02- 2- 041 C s n c en S s iio n o f C K V stro ve th e tip p e r S m t o f qu arsttafcn fo r th e l o w * * ! c a v e ; h o r , th e e s S m a W w x u ra s y w a s s ttl! w rh in rn e ih s d C rite ria N o e ir a S a ifa ife s ffin p te w S h P h H S c o n c e n ta tte s < 2 ,8 n g to L S am p le s w ith P F H S co n cen tratio n s > 2 .5 n g frn l w e re n o t affe cted . O 0 m i1 t 5 1 oQ 71 l1aO ?6 PFOS pros oi6 2 4 % ** 5 3 .9 % G L P 07 4J 2 -C 2 00 8 throug h G U =07- 24S 2- 825 A re a counts o f C C V ir^ecricrr w e re 127% o f th e origan! curve, point. O v e ra l'm e fto d uncertainty f a PFOS i 1 0 0 *2 9 % . hte a d k m ta k e n . G L P O r-O 2 O 2-0 through G L 7 . M 2 - 041 M a s co u n ts o f C C V injedsfcn w e re !T 0 % o ith e nrrgins' cu rve p o in t O vtsrali m eth o d u ncertainty f a P T O S is 1 0 0 *2 8 % . N o a c to n ta k e n . -opper as the(1) CavspiSsi*cM .asaecV' n i b S M te w *w s ! a ta tte n & C!^Sf,vtt*<ntiwilonofaC C V e aected ih * q a t o ic n ra n g e and a c o n s p ira tio n v a lu e n ot te c u ia is d b y softw are. (2) 0iavepin**teia&3ssaCGV*t usJiiiSte*naialeuetctbaa!m<m. Coeseir!y, 83tan<iti!aBo(i{thBCCV e x oe s d e rt B is u p p e r c a s s a tio n ra n g e. H o w s w r. th e so ftw are w as aisle io lo t e t e a c o n c e n tra ti w hich t if a t e to c o n s irfa e d 3) as CCV originallyC s v e pom setedw f w as s tu d e d to r n th e n is i c a S M c m c u rv e te a ts s e * d id not satis fy E jr a fc n a tx w ra c y rs q riw ro e m s fa e c u ra c y ** 4 8 ,8 % ). FTS-4-08.4 Page 2 o f 2 Attachment A: Record o f Nonconformance! Deviation form Documentation of Deviations and Control of Nonconforming Testing 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 176 of 178 3M Environmental Laboratory P0003268; Interim Reportm 13M Confidential Record of Nonconformance Deviation S tuoy/P roject No. G1P07-02-02 Deviation type SOP (Check e r s ) Q .Protocol Method SetpimtnoRls: I, itientHication Dates) of Occurrence; 10/4/2007- Equipment Procedure O GPC H. Description Document Number E tS 8-44.0 Method O tter: " Section 10JS-Lab C ontrol Sample .................'.... . , The relatve standard deviation of the control spikes evaluated independently at each concentration level must be loss than or equai 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. { Actual precedure/precess; l The low fevei PFHS IC Ss analyzed on 10/8/2007 produced an average-recovery ef 123% with a %RSD j of 0.30. The entire set of samples was not reanalyzed. j ... Actions Taken !___;............ _ .................... (smmjis smmdm m l istued, SOP mvisisn. me.; j Corrective o n { ' Yes 0 No) Refennc: A cceptafeilityofthenottG onfom iing w o it: Average low-favel LCS recovery of 123% was stilt within the overall PFHS method uncertainty of 100424%, Recoveries m m included in the centra! chart used to determine uncertainty, impact to data quaiity objectives considered minimal Most samples were assigned am expanded uncertainty for PFHS due to FMS recoveries exceeding 130% ..................................... ........................... Actions: Halting o f Work O Client Notification Work Recati O Withholding of Report : 0 O ften Method Deviation addressed in final resort l - ..... : ' .I" I ....... ?Recorded by: Michette O. Matmsky . ; . Date; 1/28/2008 I GLP Study Director Authorization; i ?Sponsor Approvai (GLP Protocols); ,. . TechnicalI . V\cMiM<y *j Manager Approvai cif 9 <*wo* wo*res^l -cm; at: MewA 1'st Date; ' j IV. Authorization to Resume Work I ,. ` 'P 'f'&iSO.of w frj 1 c p rr -w r; by Technical Management j Technical Manager'Approved: Date: j Deviation No. ( a s s ig n e d b y S tu d y S im c p r o r P r o je c t L e a d a t th e e n d o f s tu d y o r p r o je c t} Print Dare: 1/28/2008 Page 1 of 1 Print Tima; 11:32:02 AM ETS-4-08.4 Attachment A: Record o f Nonconformance / Deviation form Documentation of Deviations and Control of Nonconforming Testing 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 177 of 178 3M Environmental Laboratory P0003268; Interim ReportfU 3M:Confidential _ ___ Recoup of Nonconformance /deviation ............................ f. Idehtifica&en ___ ________ Study /P roject No. ' Oaiefs) of Occurrence:" D w a itrie S K m b e r '~ GLP0?*Q2-O2 All dates samples analyzed ET5-8-154.3 & E7B-B-44.0 Deviation type O SOP (Checkom) Protocol ' O Equipment Procedure * 0 Method O GPO_______ O Other: ___ .___________ _____ ________ __ ___ _____ ____ JL_ D m stjp&m ..;___ ____ ...___ ____ _ _ M e th o d R e q u ire m e n t: '" ETS 8-154.3 Secfcrs a e fie ld Matrix Spikes/TS 8-44.0 Section 10.6 ' ..................... j The targeted fortification levels should be at least 50% of the endogenous level and less that 10 times the endogenous level to be used withoutjustification to determine the statement of accuracy for analytical results. j Actual prmMumfptoems: t All spike levels that were less than 0.5 times the endogenous tevei were listed as "NR' (not reportable); 1 however, spike levels greater than 10 times the endogenous tevei were not flagged nine data tables as not reportable......................... ,, . M__________ ,______ ____ _________________________ A ctions Taken .... ....... ........ ............. (SiKh a$ enmrnSiiim i issued SOP m iston, etc.) .... .._____ ___________ C o rre c tiv e A ctio n ( Yes i l No) R eferance: i .................. ... j A c c e p ta b ility o f th e n o n c o n fo rm in g w o rk : . ........... The spiking range provided in the method is intended to be a guideline. The lower limit is considered more critical for assigning the sample accuracy as it is more difficult to accurately quantitate a recovery for a small change in overall concentration when foe sample is spiked. The upper limit is provided to prevent samples being spiked with an ''excessive'' concentration were foe amount attributed to the sample is negligible. For this report {in general), if a spike level exceeded 1'tSXthe endogenous concentration, the tew level spike was within the target range and produced an acceptable recovery untess otherwise noted. If the tow ievel spike did not meet criteria, the sample resist was assigned an expanded uncertainty. .................... ............. Actions: Hatting of Work O Client Notification O Work Recall Withholding of Report 3 Other: Deviation addressed In report Recorded by: Michaile O. Maiinsky Date: fg/200# j G IP Study'Director Authodzai liM i Date Sponsor Approval (GLP Protocols); ! Technical Manager Approval (ifhaltingofwarotatkmsltiaraei mcam: { IV. Autr-orizatien to Rsuma Work | _ riftcsc '\.tu vrj c< . v o ..n rt ftutsf fe e m. m pm vtK: % ; f Technical Manager Approval: Date: i Date: ; Date: I . ................................... .... .......................... ..... ........................... ...... .J Deviation No. _____ 3 ( a s s ig n e d b y S tu d y D ir e c to r o r P r o je c t I s a d a t th e e n t i a t O M y o t p ra je e j? ETS-4-08.4 Page 1 of 1 Attachment A: Record of-Nonconformance / Deviation form Documentation of Deviations and Control of Nonconforoing Testing 3M Environmental Laboratory GLP07-02-02, Decatur Offsite 600 Series Wells (Sulfonates) Page 178 o f 178