Document nM8e6Vm2859wR9L7QK6aV0Yw

Interim Report #5-Analvsis of PFBS. PFHS. and PFOS from 3M Decatur Offsite 605 Series Wells - April 2008 Study Title 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 MPI Protocol Number: P00003268 Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE W eston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Author Susan W olf 3M Environmental Laboratory Report Completion Date Date of signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 Maplewood, MN 55144 Project Identification GLP07-02-03 Total Number of Pages 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 This page has been reserved for specific country requirements. Page 2 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 GLP Compliance Statement Report Title: Interim Report #5-Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite 605 Series Wells-April 2008 Project Identification Number: GLP07-02-03 Study Title: "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" MPI GLP Protocol Number P0003268 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: Some o f the reference substances used to prepare the calibration standard mix have expired. The expired neat materials have been sent out for recertification and are not expected to have any impact on the results contained in this report. Jaisimha Kesari, P.E., DEE, Study Director Page 3 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Quality A ssurance Statement Report Title: Interim Report #5-Analysis of PFBS, PFHS, and PFOS from 3M Decatur Offsite 605 Series Wells-April 2008 Project Identification Number: GLP07-02-03 Study Title: "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" MPI GLP Protocol Number P0003268 This analytical phase was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Inspection Dates 4/10/08,4/11/08, 4/14/08 Phase Data and Report Date Reported to Principal Analytical In v e s tig a to r Study Director's Management Study Director 4/16/08 4/21/08 4/21/08 r-/-oT Date Page 4 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Table of Contents GLP Compliance Statem ent......................................................................................................................3 Quality Assurance Statement.....................................................................................................................4 Table of C ontents....................................................................................................................................... 5 List of Tables................................................................................................................................................6 Study Information........................................................................................................................................ 7 Summary and Introduction.........................................................................................................................8 Test & Control Substances........................................................................................................................9 Reference Substances............................................................................................................................... 9 Test System.................................................................................................................................................9 Method Sum mary..................................................................................................................................... 10 Sample Collection.............................................................................................................................. 10 Sample Preparation........................................................................................................................... 10 Analysis............................................................................................................................................... 10 Analytical R esults..................................................................................................................................... 11 Calibration........................................................................................................................................... 11 System Suitability............................................................................................................................... 11 Limit of Quantitation (LOQ)................................................................................................................12 Continuing Calibration........................................................................................................................ 12 Blanks................................................................................................................................................. 12 Lab Control Spikes (LCSs)....................................................... 12 Determination of Analytical Method Uncertainty...............................................................................14 Field Matrix Spikes (FMS).................................................................................................................. 14 Data Summary and Discussion.........................................................................................;.................... 15 Statistical Methods and Calculations...................................................................................................... 18 Page 5 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Statement of Conclusion.......................................................................................................................... 18 References.................................................................................................................................................18 List of Attachm ents................................................................................................................................... 18 Signatures.................................................................................................................................................. 19 List of Tables Table 1. Sample Results Summary......................................................................................................... 8 Table 2. Study Reference Substances.....................................................................................................9 Table 3. Sample Description Key Code.................................................................................................. 9 Table 4. Instrument Parameters............................................................................................................ 10 Table 5. Liquid Chromatography Conditions.........................................................................................11 Table 6. Mass Transitions...................................................................................................................... 11 Table 7. Laboratory Control Spike Recovery........................................................................................13 Table 8. Analytical Method Uncertainty.................................................................................................14 Table 9. Field Matrix Spike Concentrations.......................................................................................... 15 Table 10. DAL G W 605L 080401.......................................................................................................... 16 Table 11. DAL GW 605R 080401..........................................................................................................16 Table 12. Field Blank Samples..............................................................................................................17 Page 6 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Study Information Sponsor 3M Company Sponsor Representative Michael Santoro Director Regulatory Affairs 3M Bldg 236-01-B10 Maplewood, MN 55144 Phone; (651) 733-1958 masantoro@mmm.com Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 .kesari@westonsolutions.com Study Location Testing Facility 3M EHS Operations 3M Environmental Laboratory Building 260-5N-17 Maplewood, MN 55106 Study Personnel William K. Reagen, Ph.D., 3M Laboratory Manager Michelle Malinsky, PhD., Principal Analytical Investigator Susan Wolf, Report Author Cliffton B. Jacoby, Ph.D., 3M Technical Review Zhuojing Liu; Analyst Study Dates Interim Analytical Initiation: April 3, 2008 Interim Analytical Completion: April 5, 2008 Interim Report Completion: Date of Interim Report Signing Location of Archives All original raw data, protocol, and the analytical report have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792. All samples (specimens) will be retained and archived according to current 3M Environmental Laboratory standard operating procedures. Page 7 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Summary and Introduction The 3M Environmental Laboratory analyzed groundwater samples collected offsite from the 3M Decatur, AL facility by Weston Solutions personnel on April 1,2008. Samples were submitted for analysis under 3M Environmental Laboratory Project Number GLP07-02-03. The GLP protocol number is P0003268: ""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 analyzed for PFBS, PFHS, and PFOS using method ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry". The experimental start date was April 3, 2008, the day samples were first prepared for analysis by 3M Environmental Laboratory personnel. The experimental completion date was April 5,2008. Sample collection containers were prepared at the 3M Environmental Laboratory. Sample containers for each sampling location included a field sample, field sample duplicate, low field spike, mid field matrix spike, and a high field spike. Additionally, one equipment rinse blank and one trip blank with field spikes were submitted with the samples. 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 PFBS, PFHS, and PFOS prior to being sent to the field for sample collection. Table 1 below summarizes the sample results. The average between the sample and the sample duplicate is provided along with the relative percent difference (%RPD), if applicable. All results for quality control samples prepared and analyzed with the samples will be provided and discussed elsewhere in this report. Table 1. Sample Results Summary111. 3M LIMS ID Sample Description GLP07-02-03-001 DAL G W 605L 0 080401 GLP07-02-03-002 DAL G W 605L DB 080401 PFBS Concentration (ng/mL 2.89 2.95 Average 2 .9 2 GLP07-02-03-006 G LP 0 7-02-03-007 %RPD Sample/Sample Duplicate DAL G W 605R 0 080401 D A L G W 6 0 5 R DB 080401 2.1 0.0481 0.0501 Average 0.0491 % RPD Sample/Sample Duplicate 4.1 PFHS Concentration (ng/mL 4.27 4.28 4 .2 8 0 .2 3 0.0248 0.0275 0 .0 2 6 2 10 PFOS Concentration (ng/mL) 4.13 4.01 4 .0 7 2.9 <0.0261 <0.0261 < 0 .0 2 6 1 NA NA = Not Applicable (1) Samples were extracted by solid phase extraction using method ETS-8-154.3 on April 3, 2008 and analyzed on April 4-5, 2008. The analytical method uncertainties associated with the reported results are as follows: PFBS 100% 18%, PFHS 100% 14%, and PFOS 100% 22%. Page 8 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Test & Control Substances There was no test substance or control substances for this analytical phase in the classic sense. The study was purely analytical in nature. All materials used for this study are listed below and were reference materials as described herein. Reference Substances Table 2 lists the pertinent information regarding the reference substance used for this study. Table 2. Study Reference Substances. Reference Substance Chemical Name Chemical Formula Identifier Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFBS Perfluorobutanesulfonate C jF 9 S O 3 Potassium Salt, CAS #29420-49-3 3M 01/10/2017 Frozen 101 TCR-121 W hite powder 96.7% PFHS Perfluorohexanesulfonate PFOS Perfluorooctane sulfonate C 6F 1 3 S O 3 Potassium Salt, CAS #3871-99-6 3M CsF 17 S O 3 Potassium Salt, CAS #2795-39-3 3M 02/12/2017 12/14/2016 Frozen Frozen NB 120067-69 171 TCR-083 TCR-696 W hite powder W hite powder 98.6% 86.4 Test System The test system for this study is water samples from 3M Decatur offsite wells collected April 1, 2008 by Weston Solutions, Inc. personnel. Samples for this study are "real world'' samples, not dosed with a specific lot of test substance. Table 3. Sample Description Key Code. String Number 1 2 3 4 5 String Descriptor General Sampling Location Sample Type Well Number Sample Type Sampling Date Example DAL= Decatur, Alabama GW= Ground Water 605R = 605 residuum well 605L = 605 limestone bedrock well 0=primary sample DB=duplicate sample LS=low spike MS = m id spike HS = high spike RB=equipment rinse blank 080401= April 1,2008 Page 9 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Method Summary Preparatory and Analytical Methods Sample Collection Samples were collected in 500 ml. NalgeneTM (high-density polyethylene) bottles prepared at the 3M Environmental Laboratory. Sample bottles were returned to the laboratory at ambient conditions on April 3, 2008. Samples were stored refrigerated at the laboratory after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with the collection bottles. Sample Preparation All samples, calibration standards, and associated quality control samples were extracted using ETS-8-154.3 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry". Briefly, 40 mL of sample were loaded onto a pre-conditioned Waters Sep-Pak tC18 solid-phase extraction (SPE) cartridge (1 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 April 3, 2008 and were analyzed on April 4-5, 2008. Analysis All samples and quality control samples were analyzed for PFBS, PFHS, and PFOS using high performance liquid chromatography/ tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are described in the tables below. Table 4. Instrument Parameters. Instrument Name Liquid Chromatograph Guard column Analytical column Injection Volume Mass Spectrometer Ion Source Electrode Polarity Software E TS Stan Agilent 1100 Betasil C18 (100 mm X 2.1 mm), 5 u B etasilC 18(100m m X 2.1 mm), 5 u 5 nL Applied Biosystems API 4000 Turbo Spray Z-spray Negative Analyst 1.4.2 Page 10 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Table 5. Liquid Chromatography Conditions. Step Number 0 1 2 3 4 5 Total Time (m in ) 0 2.0 14.5 15.5 16.5 20.0 Flow Rate (p L/m in ) 300 300 300 300 300 300 Percent A (2 m M ammonium acetate) 90 90 10 10 90 90 Percent B (Methanol) 10 10 90 90 10 10 Table 6. Mass Transitions. Analyte PFBS PFHS PFOS Mass Transition Q1/Q3 299/80 299/99 399/99 399/80 499/99 499/80 499/130 Dwell Time (msec) 125 125 125 125 125 125 125 A nalytical Results Calibration Calibration standards were prepared by spiking known amounts of stock solutions containing the target analytes into 40 mL of laboratory water. Each spiked water standard was then extracted in the same manner as the collected samples. A total of twelve spiked standards ranging from 0.025 ng/mL to 25 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 accuracy of each curve point. Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method calibration accuracy requirements of 10025% (10030% for the lowest curve point) were met for all analytes in each analytical batch. The correlation coefficients (r) were greater than 0.995 for all analytes in each analysis. System Suitability The 1.0 ng/mL extracted-calibration standard was analyzed at least three times at the beginning of the analytical sequence to demonstrate overall system suitability. All analytes met the acceptance criteria of less than or equal to 5% relative standard deviation (RSD) for peak area and less than or equal to 2% RSD for retention time for the opening system suitability injections. Page 11 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Limit of Quantitation (LOQ) The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity and accuracy requirements and for which the area counts are at least twice those of the appropriate blanks. The LOQs for this analysis are listed below. Table 7. Limit of Quantitation (LOQ). A nalyte PFBS PFHS PFOS LOQ, ng/m L 0.0252 0.0245 0.0261 Continuing Calibration During the course of each analytical sequence, continuing calibration verification samples (CCVs) were analyzed to confirm that the instrument response and the initial calibration curve were still in control. All CCVs met method criteria of 100% 25%. Blanks Four types of blanks were prepared and analyzed with the samples: solvent blanks, method blanks, equipment blanks, and field/trip blanks. Each blank type is described below. Solvent Blanks Several blanks of methanol were analyzed to assess system contamination and/or instrument carryover. Analyte peak area counts in solvent blank samples were less than half the area counts of the calibration standard used to establish the LOQ. Method Blanks Five method blanks were prepared and analyzed with the samples. The average analyte peak area counts in the method blank samples were less than half the area counts of the calibration standard used to establish the LOQ. Equipment Blank One aqueous equipment rinseate blank was submitted as a sample: GLP07-02-03-015. The 3M Environmental Laboratory provided two one-liter bottles of ASTM type I water for rinsing. The resultant PFBS, PFHS, and PFOS concentrations were below the analytical LOQs listed in Table 7. Trip Blank Prior to sample collection, one separate sample container was filled with 450 mL of reverseosmosis purified water, sealed, and shipped to the sample collection site along with the empty containers. This sample was analyzed as the field/trip blank. 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 PFBS, PFHS, and PFOS concentrations were below the analytical LOQs listed in Table 7. Lab Control Spikes (LCSs) Low and mid-level lab control spikes were prepared and analyzed in triplicate with each preparation set. LCSs were prepared by spiking known amounts of the analytes into laboratory water to produce the desired concentration. The spiked water samples were then prepared and analyzed in the same Page 12 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 manner as the samples. Analysis of triplicate LCSs at the two specified levels cross-validates the analytical method as used here for any modifications/deviations from method and ETS-8-154.3. All LCSs were used in the determination of analytical uncertainty. Table 8. Laboratory Control Spike Recovery Lab ID PFBS PFHS Spiked C a lc u la te d Spiked C a lc u la te d Concentration Concentration Concentration Concentration (n g /m L ) (ng/mL) % Recovery (ng/mL) (n g /m L ) % R ecovery L C S -08 0403-1 LC S -080403-2 LC S -080403-3 LC S -080403-4 LC S -080403-5 LC S -080403-6 0.202 0.202 0.202 5.04 5.04 5.04 0.220 0.225 0.216 5.09 5.10 5.16 109 0.196 111 0.196 107 0.196 101 4 .9 0 101 4 .9 0 102 4.90 0.204 0.210 0.200 4.87 4.88 4.82 104 107 102 99.5 99.6 98.4 Average %RSD 105% 4.2% 102% 3.2% Lab ID PFOS Spiked Calculated Concentration Concentration (n g /m L ) (ng/mL) % R ecovery LCS-080403-1 LC S -080403-2 LC S -0 8 0 4 0 3 -3 LC S -0 8 0 4 0 3 -4 LC S -080403-5 LC S -080403-6 0.209 0.209 0.209 5.22 5.22 5.22 0.192 0.197 0.196 5.06 4.95 5.12 91.9 94.1 93.6 97.0 94.9 98.1 Average %RSD 94.9% 2.4% Page 13 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Determination of Analytical Method Uncertainty The analytical uncertainty was determined based on historical QC data that is used to evaluate method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The analytical uncertainty was determined by the statistical evaluation of the recoveries for the individual analyte recovery as determined for laboratory matrix spiked samples. The standard deviation was calculated for the set of recovery results (in %). The expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which correspond with a confidence level of 95%. A minimum of twenty data points is needed to determine method uncertainty by this method. Table 9. Analytical Method Uncertainty Analyte PFBS PFHS PFOS Number of data points (n) used for determining uncertainty values 50 50 50 Mean Recovery Standard Deviation Method Uncertainty (%) (%) (%) 101 101 98.8 8.82 6 .9 9 1 1 .0 18 14 22 Field Matrix Spikes (FMS) Low, mid, and high field matrix spikes were collected at each sampling point (with the exception of the rinse blank) to verify that the analytical method is applicable to the collected matrix. Field matrix spikes are generated by adding a measured volume of field sample to a container spiked by the laboratory with the target analytes prior to shipping sample containers for sample collection. Field matrix spike recoveries within method acceptance criteria of 10030% confirm that "unknown" components in the sample matrix do not significantly interfere with the extraction and analysis of the analytes of interest. Sampling location DAL GW 605R purged less than three volumes with a total quantity of 1.5 gallons. As a result, the well could not provide adequate water to meet the volume requirements for all sample bottles provided for this location. The sample, duplicate, and low spike bottles were filled to the line, while the mid and high field matrix spike bottles were filled approximately 50%. The volume collected for the mid and high field matrix spikes was determined and the field matrix spike concentrations were adjusted appropriately. [Cone. FMS sample(-- )- (Average C one.of Sam ple/Sam pleDup(-- )] FM S Spike Recovery = mL ___ ______ ______mL 1 100% Spike Amount (ng/mL) MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Table 10. Field Matrix Spike Concentrations. Location Description Low Field Matrix Spike D A L G W 6 0 5 L Mid Field Matrix Spike High Field Matrix Spike Low Field Matrix Spike D A L G W 6 0 5 R Mid Field M atrix Spike<1) High Field M atrix Spike(1> Low Field Matrix Spike Trip Blank Mid Field Matrix Spike High Field Matrix Spike Final Concentration (ng/m L) PFBS 0.224 4.48 89.6 0.224 6.65 181 0.224 4.48 89.6 PFHS 0.218 4.35 87.0 0.218 6.46 176 0.218 4.35 87.0 PFOS 0.232 4.64 92.9 0.232 6.90 187 0.232 4.64 92.9 (1) Bottle was filled below the fill line. The sample volume was determined and the field matrix spike true values were adjusted appropriately. Data Summary and Discussion The tables below summarize the sample results and field matrix spike recoveries for the sampling locations as well as the Trip Blanks. 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 according to EPA rounding rules. Relative percent difference 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 low FMS recovery was not reported as the spike level was not appropriate for the given sample concentration. All reportable field matrix spike recoveries were within 10030%; therefore, the results were considered accurate to within the overall analytical method uncertainty for PFBS of 10018%, PFHS 100%14%, and PFOS 100%22% (see Determination o f Analytical Method Uncertainty for more information.). Page 15 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Table 11. DAL GW 605L 080401. PFBS PFHS PFOS 3M U M S ID Description Concentration (ng/mL) % R ecovery GLP07-02-03-001 DAL G W 605L 0 080401 GLP07-02-03-002 D A LG W 605L DB 080401 GLP07-02-03-003 DAL G W 605LLS 080401 GLP07-02-03-004 D A L G W 60 5L M S 080401 GLP07-02-03-005 D A L G W 6 0 5 L HS 08 0401 (1:20 dilution) 2.89 2.95 3.18 7.14 91.5 NA NA NC 94.2 98.9 Average Concentration (ng/mL) %RPD 2.92 n g /m l+ 2.1% Concentration C o n c e n tra tio n (n g /m L ) % Recovery (ng/mL) %Recovery 4.27 NA 4.13 NA 4.28 NA 4.01 NA 4.51 NC 4.26 NC 8.33 93.2 8.30 91.1 88.9 97.2 92.6 95.3 4.28 n g /m l 0.23% 4.07 ng/m Lt 2.9% NA = Not Applicable NC = Not Calculated; Endogenous sample concentration is greater than 2x spike level. Table 12. DAL GW 605R 080401. PFBS PFHS PFOS 3M U M S ID Description GLP07-02-03-006 GLP07-02-03-007 GLP07-02-03-008 G LP 0 7-02-03-009 G LP 0 7-02-03-010 DAL G W 605R 0 080401 D A L G W 60 5R DB 080401 DAL G W 605R LS 080401 DAL GW 605R MS 080401 DAL G W 6 0 5 R HS 080401 (1:20 dilution) Average Concentration (ng/mL) % RPD Concentration (ng/mL) 0.0481 0.0501 0.284 6.370 175 % R ecovery NA NA 105 95.0 96.8 0.0491ng/mL 4.1% Concentration C o n c e n tra tio n (n g /m L ) %Recovery (ng/mL) %Recovery 0.0248 NA <0.0261 NA 0.0275 NA <0.0261 NA 0.231 94.2 0.194 83.5 5.93 91.4 5.21 75.5 168 95.7 165 88.0 0.0262 n g /m l 10% <0.0261 ng/mL NA = Not Applicable Page 16 of 130 M PI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Table 13. Field Blank Samples. 3M U M S ID G LP 0 7-02 -03 -011 G LP 07-02-03-012 G LP 07-02-03-013 G LP 07-02-03-014 GLP07-02-03-015 PFBS PFHS PFOS Description DAL G W TRIP 0 080401 DAL G W TRIP LS 080401 DAL G W TRIP MS 080401 DAL G W TRIP HS -080401 (1:20 dilution) D A LG W 605L RB Concentration (n g /m L ) <0.0252 0.226 4.41 88.4 <0.0252 % R ecovery NA 101 98.4 98.7 NA C o n c e n tra tio n C o n c e n tra tio n (n g /m L ) %Recovery (ng/mL) % R ecovery <0.0245 NA <0.0261 NA 0.210 96.5 0.201 86.6 4.31 99.1 4.22 90.9 85.7 98.5 86.4 93.0 <0.0245 NA <0.0261 NA NA = Not Applicable Page 17 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 , ___ r. Calculated Concentration LCS Percent Recovery = --------------------------------------- 100% Spike Concentration o%/oRcSrD^ ,(rR, el,ative Standard ^Deviat*ion*) = -s--t-a--n-d--a--r-d---d--e--v--ia--t-i-o--n---o--f--r-e- p--li-c--a--t-e--s- *. 1. 0. .0.%. replicate average i . Absolute difference between sample duplicates . . . . . . % RPD (Relative Percent Difference) = --------------------------------------------------- -------- ----------- * 100% average sample concentration Statement of Conclusion Sample results were summarized in Table 1. Historical values of lab control spikes for this method recorded in the laboratory'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. All remaining samples and associated project data (hardcopy and electronic) will be archived according to 3M Environmental Laboratory standard operating procedures. References ETS 8-154.3; "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates in Water by Solid Phase Extractions and High Performance Liquid Chromatography/Mass Spectrometry". ETS 4-026.2; "Control Charts for Laboratory Analyses". ETS 12-012.2; "Estimation of Uncertainty of Measurements". List of Attachments Attachment A: Selected Chromatograms and Calibration Curves Attachment B: Extraction and Analytical Method Attachment C: Protocol and Protocol Amendments Page 18 of 130 Signatures MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 William K. Reagen, Ph.D. 3M Environmental Laboratory Manager <9 Date Page 19 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Attachment A: Selected Chromatograms and Calibration Curve Page 20 of 130 Stan API4000 V1660305 Printing Date: Monday, April 07, 2008 M PI Protocol P00003268; Interim Report #5 Results Name: s0 8 0 4 0 4 a .rdb 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 [ Sample Harm:`*060404*031' S*mpto ID: t.CS-060403-4- Fie: *s080404.vrfr Peak Nama: *PFBS TE* Mass(**): *288.3/79.8 amu.298.9/89.Oamu* I Comma. *5A ppb extracted LCS* Annotation:- anple Index: 31 `pie Type: Calculated Cor Acq. D.te: Acq. Tine: Hud tiled: RT Window: Expected RT: U.*e Relative I Iftt. Type: Height: Page 1 of 6 Page 21 of 130 ** * Stan API 4 000 V1660305 MPI Protocol P00003268; Interim Report #5 Results Name: s080404a.rdb 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; Apnl 2008 Page 22 of 130 Stan AP 14 000 V1660305 ISampb Name: **0#0404a02(r Sample ID:*C-080402-008* Fib: *080404a.wifr Peak Narr: 'PFHS TIC* Masa(aa): *399X1/793 amj.399.0/99.0 amu* Comment: *1D pp6 extracted curve point* Annotation: ** RT Window: Expected Rt Une Reletiv Printing Time: 13:26:36 Printing Date: Monday, April 07, 2008 M PI Protocol P00003268; Interim Report #5 Results Name: sO,iso4 o4 a . rdb 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Page 23 of 130 Stan A P I 4000 V1660305 Int. Typ*: RuLfentiun T. 4 Printing Time: 13:26:36 Printing Date: Monday, April 07, 2008 6 Results Name MPI Protocol P00003268; Interim Report #5 sO 804 0 4 a .rdb 3 M Pr0j eCt GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 I Sample Name: "*0e0404a039" Sandte 10; GLP07-02-03-OOV Fla: *s060404a.wirr Peak Mams; *PFHS TIC* Mass(et): *399.0/79J amu.399.(V99.0 amu* Comment: *DAL GW 605L 0* Annotation: " 3n.pl Index: 39 Height: ' irt Tine. I Tim: !: 14.5 mir AtOiCSs count: 792000. cp Page 4 of 6 Page 24 of 130 Stan API4000 V1660305 Printing Date: Monday, April 07, 2008 MPI Protocol P00003268; Interim Report #5 Results Name: s080404a . rdb 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Page 25 of 130 Stan A P I 4000 V1660305 Printing Time: 13:26:37 Printing Date: Monday, April 07, 2008 MPI Protocol P00003268; Interim Report #5 Results Name: 3080404a.r,h 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ISample Nam*: "s060404a039* Sample ID: GLP07-02-03-001' FS*: *s060404a.v*ir Peak Nam*: 'PFOSTIC' Mass(*s): '49699.2 amu,496.9/130.0 amu.49860.0 amu* Comment: 'DAL QW 6051 O' Annotation: " Itird: H e ig h t: irt Tir.e: I Time: Page 6 of 6 Page 26 of 130 *** Stan API4000 V1660305 MPI Protocol P00003268; Interim Report #5 Results Name: sO 80.04a.rdb 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Page 27 of 130 *** Stan API 4000 V1660305 MPI Protocol P00003268; Interim Report #5 Results Name: s080404a.rdb 3M Project G LP07-02-03 Decatur Offsite 605 Senes Wells; Apnl 2008 Page 28 of 130 ***Stan API4000 V1660305 MPI Protocol P00003268; Interim Report #5 Results Name: =0 8 0 , 0 , a.rdb 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; Apnl 2008 Page 29 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Attachment B: Extraction and A nalytical Methods Page 30 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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: Q f r f t Y / O 7 Approved By: William K. Reagen Manager Date E T S -8 -1 5 4 .3 Page 1 of 20 D eterm ination o f Perfluorinated Acids, Alcohols, Am ides, and Sulfonates In W ater By so lid P hase Extraction and High Perform ance Liquid C hrom atography/M ass Spectrom etry Page 31 of 130 Document may be used, if current, for 14 days from 04/ MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 perfiuorooctane sulfonate (PFOS), perfluorooctane sulfonylamide (FOSA), and perfluorooctanoate (PFOA) in groundwater, surface water, and drinking water samples. This method is considered a perform ance-based method and may be applied to the determination of other perfluorinated acids, alcohols, amides, and sulfonates in similar 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 n o t covered under this analytical procedure. 2 Method Summary Water 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. E T S -8-154.3 Page 2 of 20 D e te rm in a tio n o f P erfluorinated A cids, A lco h o ls, A m id e s, a n d S u lfo n a te s In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 32 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 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. 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 Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry Page 33 of 130 Document may be used, If current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 limit of quantitation (LLOQ) for a dataset is the lowest concentration that can be reliably quantitated within the specified limits of precision and accuracy during routine operating conditions. To simplify data reporting, the LLOQ is generally selected as the lowest non-zero standard in the calibration curve that meets method criteria. Sample LLOQs are matrixdependent. The upper limit 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 similar 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. E T S -8-154.3 Page 4 of 20 D e te rm in a tio n o f P e rflu o rin a te d A cid s, A lc o h o ls , A m id e s , a n d S u lfo n a te s In W a te r B y S o lid P h a se E xtraction and H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 34 of 130 Document may be used, if current for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 of the chemicals used in this method. A reference file of material safety data sheets (MSDS) should be available to all personnel involved in these analyses. 4.2 Cautions The analyst must be familiar with the laboratory equipment and potential hazards including, but not limited 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 0.0001 g), Mettler HPLC/MS/MS or HPLC/MS system, as described in Section 10. 6.2 Supplies and Materials. E T S -8-154.3 Page 5 of 20 D e te rm in a tio n o f P e rflu o rin a te d A cid s, A lc o h o ls , A m id e s , a n d S u lfo n a te s In W a te r B y S o lid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 35 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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, Buchi. 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, Nonafluoropentanoic Acid (C5 Perfluorinated Acid) PFHA, Perfluorohexanoic Acid (C6 Perfluorinated Acid) TDHA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid) PFOA, Ammonium perfluorooctanoate, (C8 Perfluorinated Acid) C9Acid, Heptadecafluorononanoic Acid PFDA, Nonadecafluorodecanoic Acid (C10 Perfluorinated Acid) E T S -8 -1 54.3 Page 6 of 20 D e te rm in a tio n o f P erfluorinated A cids, A lcohols, A m id e s, an d S u lfo n a tes In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 36 of 130 O'. -nay be used, if current for 14 days from MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Cn Add, Perfluoroundecanoic Add C12Add, PerfluorododecanoicAdd FBSA, Perfluorobutanesulfonamide FOSA, Perfluorooctanesulfonylamide PFBS, Potassium Perfluorobutanesulfonate PFHS, Perfluorohexanesulfonate PFOS, Potassium perfluorooctanesulfonate THPFOS, 1H, 1H, 2H, 2H-perfluorooctanesulfonic Add THPFDS, IH, IH, 2H, 2H-perfiuorodecanesulfonic Add PFOA [1,2-13C], 13C isotopically labeled perfluorooctanoic add, Perkin Elmer PFOS [180 2], 1b0 2 isotopically labeled Ammonium Perfluoroocatanesulfonate 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 of a particular study. For example, pL volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate levels. 100 pg/mL target analyte SSSs--Weigh out 10 mg of analytical standard (corrected fo r percen t s a lt a nd p urity) 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. ,, .. , . molecular weight o f anion salt correction factor = -------------------------------------- moclecular weight of salt 499 PFOS (K +)salt correction factor = ------= 0.9275 538 10 mg C8Fi7S03'K+with purity 90% = 8.35mg C8F17S0;f (10 mg*0.90*0.9275=8.35 mg) 1 pg/mL (1000 ng/mL) mixed working standard--Add lO m L each of the 100pg/mL SSSs to a 10OmL volumetric flask and bring up to volume with solvent. 0.1 pg/mL (100 ng/mL) mixed working standard--Add 10.0mL of the 1.0pg/mL-mixed working standard solution to a 100mL volumetric flask and bring up to volume with solvent. E T S -8-154.3 Page 7 of 20 D e te rm in a tio n o f P e rflu orin a ted A cids, A lcohols, A m id e s, an d S u lfo n a tes In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 37 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 0.01 pg/m L (10 ng/mL) m ixed standard-- Add 10.0mL of the 0.1|jg/mL-mixed working standard solution to a 100mL 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. 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 o n cen tratio n o f WS, ng/mL Volume o f WS, ML Final Volume o f Calibration Standard (mL o f A STM Type 1 Water, or other suitable water) Final Concentration of Calibration Standard, ng/mL (ppb) in A STM Type 1 Water, o r other suitable water 100 10 100 20 100 40 100 100 40 40 40 40 0.025 0.050 0.100 0.250 1000 1000 20 40 40 40 0.500 1.00 1000 10000 10000 100 20 40 40 40 40 2.50 5.00 10.0 10000 100 40 25.0 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 E T S -8-154.3 Page 8 of 20 D e te rm in a tio n o f P erflu orin a ted A cid s, A lco h o ls, A m id e s, a n d S u lfo n a tes In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 38 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 will 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. E T S -8-154.3 Page 9 of 20 D e te rm in a tio n o f P e rflu o rin a te d A c id s , A lc o h o ls , A m id e s , a n d S u lfo n a te s In W a te r B y s o lid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 39 of 130 Document may be used, if current, for 14 days from 04/17/200 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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% of the area count of 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 of 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 of each analyte. E T S -8-154.3 Page 10 o f 20 D e te rm in a tio n o f P erfluorinated A cids, A lco h o ls, A m id e s, an d S u lfo n a tes In W a te r B y s o lid P h a se E xtraction and H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 40 of 130 Document may be used, If current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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) of 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 E T S -8 -1 54.3 P a g e 11 o f 20 D e te rm in a tio n o f P erfluorinated A cids, A lco h o ls, A m id e s, a n d S u lfo n a te s In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 41 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 10.1 Instrument Setup Note: In this example, an Applied Biosystems Sciex API 4000 Tandem Mass Spectrometer (LC/MS/MS) is used. Other brands of LC/MS/MSs as well as single q ua drup le 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: Dell DHM Software: Windows 2000 or Windows 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 E T S -8-154.3 Page 12 o f 20 D e te rm in a tio n o f P erfluorinated A cid s, A lco h o ls, A m id e s, an d S u lfo n a tes In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 42 of 130 Document may be used, if current, for 14 days from 04/17/2008 Liquid Chromatography Gradient Program. Step Number 0 1 2 3 4 5 Total Time (m in ) 0 1.0 14.5 15.5 16.5 20.0 Flow Rate (fd/m in) 300 300 300 300 300 300 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Percent A (2 m M ammonium acetate) 80.0 80.0 10.0 10.0 80.0 80.0 Percent B (Methanol) 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 instrument performance. Columns with different dimensions (e.g. 2.1 mm x 30mm) and columns from different manufacturers (Keystone Betasil C18 etc.) may be used. Mass Transitions Monitored. Analyte Mass Transition Q1 (amu) PFBA (CaAcid) NFPA (C5 Acid) 213.0 262.9 PFHA (Ce Acid) 313.0 TDHA (C7 Acid) 362.9 PFOA (C$ Acid) 413.0 Cg Acid 463.0 Mass Transition Q3 (amu) 169.0 219.0 268.7,118.9 318.7,168.8,118.9 368.9,219.0.169.0 418.7,168.9, 218.9 Declustering Potential -30 -30 -45 -35 -45 -45 C10 Acid C11 Acid C12 Acid FBSA FOSA PFBS PFHS PFOS THPFOS THPFDS PFOA [1 ,2 13C1 PFOS [ 1802l 512.9 563.0 613.0 297.7 497.9 298.9 398.9 498.9 426.9 526.9 414.9 503.0 468.8,218.9,269.1 518.7,268.9, 218.8 568.7,168.9, 318.7 78.0 77.9 98.9, 79.9 98.9, 80.0 80.0, 98.8,130.0 406.8, 80.9 506.7, 81.0 369.8 103.0, 84.0 -35 -45 -50 -55 -90 -65 -95 -120 -70 -70 -40 -100 E T S -8 -1 54.3 Page 13 o f 20 D e te rm in a tio n o f P erflu orin a ted A cids, A lcohols, A m id e s, an d S u lfo n a tes In W a te r B y Solid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 43 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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. While 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 (CAD) lonSpray Voltage (IS) Temperature (TEM) Gas 1 (Nebulizer) GS1 Gas 2 (Turbo Gas) GS2 Interface Heater (Ihe) Entrance Potential (EP) 15.0 High -4500 450.0 35.0 45.0 ON -10 10.3 Calibration 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 E T S -8-154.3 Page 14 o f 20 D e te rm in a tio n o f P e rflu o rin a te d A cid s, A lc o h o ls , A m id e s , a n d S u lfo n a te s In W a te r B y S o lid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 44 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 or failing to meet accuracy requirements of 25% (and 30% for the LLOQ). Justification for exclusion of calibration curve points will be noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. 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 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. 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 5% and a retention time RSD of 2% to be compliant. 11 Procedures 11.1 Extraction Scheme The following steps represent a typical 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 will leave the SPE column. This will not affect the calculations in any way since the E T S -8 -1 54.3 Page 15 o f 20 D e te rm in a tio n o f P erfluorinated A cids, A lco h o ls, A m id e s, a n d S u lfo n a tes In W a te r B y S olid P h a se E xtraction and H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 45 of 130 Document may be used, if current for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 QC 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). All 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 Concentration (-^-) LCS% recovery = -S--p-i-k--e--C--o--n-c--e-n--t-r-a-t-i-o--n--(*--mn1-gL=0-0)% Calculate the percent recovery of the FSCS using the following equation: FSCS Concentration (--^-) FSCS% recovery = -S--p-i-k--e--C--o--n--c-e-n--t-r-a-t-i-o--n--(---m2ng^L----) *100% Calculate the percent recovery of the FMS using the following equation: FMS % recovery = FMS Concentration (--mng=L-_)_-_A__vS_ep_ria_kg_ee_C_C_oo_nn_cc_ee_nn_tt_rra_at_tiio_o_nn_(_o--m_nf_gL--S_a_)m__p_l_e_/S__a_m_p_l_e_D__u_p_l_ic_a_t_e_(nm-g-L-- ) * 100% E T S -8-154.3 Page 16 of 20 D e te rm in a tio n o f P erfluorinated A cids, A lco h o ls, A m id e s, an d S u lfo n a tes In W a te r B y Solid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 46 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 <2% to be compliant. 13.2 Quantitation Calibration Curve: The coefficient of determination (r2) value for the calibration curve must be greater than or equal to 0.990. Each point in the curve must be within 25% of the theoretical concentration with the exception of the LLOQ, which may be within 30%. Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (within 3% of standard) and the mass spectral response of unique ions. 13.3 Sensitivity Solvent Blanks and Method 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. Limits of Quantitation (LOQ): The lower LOQ (LLOQ) is the lowest non-zero active standard in the calibration curve; the peak area of 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 Performance: 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 Control 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 Reproducibility: Reproducibility of the method is defined by the results of duplicate or triplicate analysis of samples. A RPD or RSD of < 20% will 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 o f 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry Page 47 of 130 icument nr- : ''''days from MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 Fluorinated 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 of control charts was an acceptable approach to determining analytical method uncertainty. At least twenty data points are required when using this method for determining analytical uncertainty. The method uncertainty is defined as 2xthe 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 of 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 Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry . Page 48 of 130 jocume ; i3 y u CU H t; n t 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Water", 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 o f 3 analytes, removes reference to EPA document that's no longer applicable. Section 2: Provided fo r the extraction o f more than the 3 validated analytes, allows the use o f a LC/MS system, not only the LS/MS/MS previously mentioned. Section 3: Revised definitions fo r field matrix spike, field control spike, LLOQ, m ethod 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 8:Added statement addressing labeling requirements and spiking procedures. Expanded section 8.8. Section 9: N ew Section Section 10: Changed some o f the param eters in the tables. Allow ed fo r use o f different instrumentation. Added information from section 12 o f previous version, extensively revised. Section 11 (section 9 in previous version): Clarification o f wash step, stated exact volume o fe lu a te is 5 mL, revised standardization process, rem oved 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): M inor 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: A dded emphasis that the m ethod is a perform ance-based method. A dded statement that this m ethod 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 m ay be used. Section 3. M inor edits/clarifications to several definitions. A dded surrogate and SPE cartridge as a definition. Removed references to LOD and MDL as this ETS-8-154.3 Page 19 o f 20 Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry Page 49 of 130 Document may be used, if current, for 14 days from 04/17/2008 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 laboratory does not report LCD and/or MDL values. Section 6. Added reference to automated SPE workstation. OSection 1. 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 m ethod blank criteria, LMS and FM S 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 fo r Sciex instrumentation removed Micromass references Section 11. Clarified extraction procedure - rem oved inclusion o f a 40% methanol wash step. Section 12. M inor edits. Section 13. A dded section on determination o f analytical uncertainty and changed performance criteria as appropriate. 3 Section 11.1. Added use o f sodium thiosulfate E T S -8 -1 54.3 Page 20 of 20 D e te rm in a tio n o f P e rflu orin a ted A cids, A lco h o ls, A m id e s, an d S u lfo n a tes In W a te r B y S olid P h a se E xtraction an d H igh P e rfo rm a n ce Liquid C h ro m a to g ra p h y/M a ss S p e ctro m e try Page 50 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Attachment C: Protocol and Protocol A mendments Page 51 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 STUDY PROTOCOL Study Title: PeFrfisluho,AranonoadPclyetCrasiflnsaluemosoufsrlPofUhoesrneifxanlautgenoLer(PsoCubF/lMuOfotSaSnn)/aMeitnesSu(WlPffooFarntHeathrSt,ee),S(3aPoMniFld,BDSSee)dc,aimtuernt, Monitoring Program MEPxIyLRIeMseSarPchroStotucodlyNNuummbbeerr:.: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 0236-01-B-10 St. Paul, MN 55144 Phone: (651) 733-6374 Page 1 o f 57 Page 52 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 o f 57 Page 53 of 130 MPI Protocol P00003268; Intrim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 E xyL IM S Protocol Number: P0003268 PROTOCOL APPROVAL Study Title: Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate . (PFHS), and Perfluorooctanesulfonate (PFOS) in Water. Soil. Sediment, PFrisohg,raamnd Clam.:. `J.'ing LC/MS/MS for the Dtresur M onitoring MP1 Research Study Number: 0137.0219 ExyLIMS Protocol Number: P0003268 APPROV. Jaisimha Kesari, Study Director Weston Solutions Michael A. Sant(qIro, Sponsor Representative 3M Company taren Rispa, Principal Investigator MPI Research, Inc. Date ofe/ie|p'7 Date /& Date' Page 3 of57 Page 54 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 TABLE OF CONTENTS TITLE PAGE.......................................................................................................................................................1 DISTRIBUTION................................................................................................................................................. 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 BIAS...............................................................................................................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 f 57 Page 55 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 (C4F9SO3TC) Transitions Monitored: 299 - 80,99 Structure: FFFF FFFF 3 PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (CFuSCVlO 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 (CgFivSCbTO Transitions Monitored: 499 - 80, 99 Page S o f57 Page 56 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLlMS Protocol Number: P0003268 Structure: FFFFFF FF FFFFFFFF 3 OBJECTIVE The purpose of 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 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: 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 o f 57 Page 57 of 130 TESTING FACILITY M(foPrImReerslyeaErcxhy,geInncR. 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 jF.akxe:sa(r6i1@0)w7e0st1o-n74so0l1utions.com SPONSOR REPRESENTATIVE Michael A. Santoro 3DMireCctoomr poafnRyegulatory 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 kPahroenne.:ri(s8h1a4@) m27p2ir-1es0e3a9rch.com MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Page 7 o f 57 Page 58 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 field. The total number of samples received and analyzed for each matrix will be documented in the appropriate interim report associated with this study. 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 o f 57 Page 59 of 130 MPI Protocol P00003268; Intrim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 to the appropriate analytical method (see Appendix I). These samples will be stored frozen at < -10C. aTphperorperciaetipetintaenrdimprreopcoerstsainngd roafw tdhaetasaasmsopclieastedwwillithbtehedsotcuudmy.ented in the SAMPLE IDENTIFICATION Pnurimorbetro. anTahlyesisr,efeearcehncseamnpulmebwerillwbiellabsseigunnediquaelaabnodratwoirlyl sdaimstpinleguriesfhereeancche laboratory sample that is processed throughout the analytical procedure. nCuhmrobmera.tographic data will be identified by the laboratory sample reference sStaumdyp.le storage conditions and locations will be documented throughout the ANALYTICAL PROCEDURE SUMMARY RETefSe-r8e-n0c1e2s:: PA("PMecFriefdHltuhpooArdo),h(oPefPFxAeaBrnnfAoalu)il,cyosriosAocfcPotiarednrtfohliue(cPoDrFAoeHtpceieArdnm)t,a(inPnaoFPtiOeicorAnfl)uo,ofrAPPoecheriredffpllutuaoonrrooo(nibPcouFntPaaAnenAcooiii)dcc, PP(APeecFrriffdDlluuoooArroo),hu(PnexdFaeNncAaesn)u,olifcoPnAearPctfeieldur(ofP(lruPFooFHbrUuoStdn)a,eAncae)an,snudPolfiePocrenfrlauftloeuroAordocoioddcteacnaenso(u(PiPclFfFoDABnAcaSit))de,, V0001780: V0001781: V0001782: V0001783: A"AAA"""(PMMMMccccFiiiieeeeddddOtttthhhh(((S(PPPPoooo)ddddFFFFinOOOOooooWAAAAffff AAAA))))aiintiinnnnnnneaaaarFWlSSlll,yyyyeioSsssssadiiioiihltssssieimblarffffnyooaooebdrnrrrnLydtttttCChhhhLbSleeee/yCaeMmdDDDDL/MiSeeesemC/ttttbMSeeee/eMrrryr/nMmSmmmtLS"iiiiSb/CnnnnM"yaaaa/MttttLSiiiioooo"CSnnnn//MMooooffffSSPPPP"/MeeeerrrrSffffllll"uuuuoooorrrr.ooooooooccccttttaaaannnnooooiiiicccc prTsaeehsmreufoplptrlsremismairniasegrtynhoaelatnEbaoolTbyrSttaait-cio8anr-le0ydm12ebttoymhoetdathhnifsoaodlrmy.tzeheItehnaoitndnha,setltyahsnseiacsemSostpfuwltdehhsyeerwDebaiyqrteeurca,tanolsttroeitirmlan,taiaavtnyeeddasinmeradeelciytmthtioetchdnaeslt (V0001780 for water samples, V0001781 for soil samples, and V0001782 for sediment samples). Page 9 o f 57 Page 60 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 The above referenced methods are to be followed for the analysis of 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 Imwfeneiteghchoetdsssfaoorryfsfotoeirlststhamme apptrleeerspi.aalratainodn oafltaeprpnraoteprivaotelusmtaensdaordfsslueivtaeblsl,ealstoerlvneantet I(efaxctnreeatcocentsiiostarnirliyef,,tmhtheeetphdraiumnpoallir,cyaetbteco.t)btmoletatdlyeobeosefnuaosetwdha.atvere esnamoupglhe vmoaluymbeeauvsaeidlabinle.an VERIFICATION OF ANALYTICAL PROCEDURE mAcoentltharbooodlr,saaatnomdrpyaledcsdo.endtTrtoohlethstaeemsmtpaslteurbicwsetisallnvcibaeeawumilsliecdbroepfomirpaetdthteee.inptroepsaorlauttiioonnsoafsfopretrifitehde FcmooolrluetcwhteadtHe.rDPTsaEhme pbbloointttgtll,eess.MwPiIllTRbheeessee5a0r0bcohmttlLwesipllrhesaculvepeapnlebydeeonSncei/rSobpuoettictnleePlyrpeemruiseesrdamwipfdoleer fluorochemical sample collection at the testing facility and have been shown atcsaoponhnidkibtgeaheh,iingaffehrirmeeleftidiodeolsadfpfieivksPlodpeFliuksBopmefSike,ebteaorPcti(hFctolHpesfstiaSlimlownlapiialnnlllede,cwaoaPtntiFlttlh2Oae0biSn0ed.iPcmsocFLlrSBle.eatScmit,oAepnPdlF.efoisHefTltSdwhheiedallnSulodtpbuwleiPdc,yFamatODdei,Sddireaed(acosltoptowwtori)oe,neflliaaaenclal)dhds, pPfffs(oioooeFerrplrluOtdtfeiiltfvAouiiboeeno,lndraraysolnow)okptuwicwttsti(heeoaicnldnnolPtnaoyFntltio)croBa.otqSslapub,wcieePPkioadFFerutOeHestpr(hASsP)oearFaamtnaeOsnandpddAmdleitP)npwsFll3coetOaCohsno.SlidlsrePacsTttFtth1euhOar,dd2eeAl.-eyo1r.w3AefCis(,etMoulmptldpthPtsieieIbdorfltnfRao(elaonruselptkos)iPterniaFsoogapronOrcifceakahAtleca)isiwnnlaaioc(nitnclliydlduco,dnshe1ueta3airdCpgccoihphldiPlnwlywFe(aavOo1ttten3heeAlCerer) cirdsnaoeuqmnplauclpbeieclnseadttetrued(apettlxiaiooccnnaldduteaedtnmeiandrnagmdpyirfntoihaeecellesmdosinseedtbldhuaeobptdhlffircooaoarrcutttceiiguffshiireeaddtachnysedapatdinkfediaesecsltrdolioisbcwsenhp,doeitckpmkearisodfr)oceerqmd(ubouaiiprrayteesi.mobaneteTanthlht)ee,exbtuudratsiansemcdctroeaedhfytitigbohihnnee of the Study Director. pFatorozertichplse-eosasienlaa,emldsbpeaSdlegcim.il/oSeAcnpaltetl,icocfoPnisn.rhet,amSiaanienmerdrpsw/lcbeildsaaemgwsmsil,ulosMubetdePhaIfHodRrdDeesPsadeEmatorpbcloeehtatcclweohlipllceleocrnstuistoaapnimpnlewpyrlieloolcnrboebella5esgc0ht0iienpdpmtehoLder Page 10 o f 57 Page 61 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 aaawfinneilddllodlwtp.aor,lsocAmochteiebdscteshke(feodofporttretthiisobfrtinoiienauadsggl.,ahftaattachitkelhintdeyoe,dwsicensraciccrbhoeetndiscoapenmnrotoprcflaeettdihwouenrielSlwttubiotdehdyeePxtDFetrirBrmaeScci,tntePoedrFm)Hi,neSatdnhaudonpddhliiacPgcahFctuOelreSaavnceadylt 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 2ng/g 40 ng/g 800 ng/g SeCdFliaimsmhesnt 2 ng/g 40 ng/g 800 ng/g 2 ng/g 40 ng/g 2 ng/g 40 ng/g - aLlotewre, dmdiedpeannddinhgigohn sspaimkipnlge sliezvee,lssaomfptlheeavaanialalybtielistyf,oarneda/ocrhtomactorviexrmanaaylybtee caloonwnacelyertneltercvaoetnliocsnepnsitkreeaxstpimoencatsyeedbxecidneeedftehrterheesdar.melepvleasn.t raInngeinostfatnhceeslowwehrerleevethlespeixkpese,cttehde Rlaaencevcaceulolyrsvsa;eicsrhyioeowwsfielatlvhrebeere,aqitnnuhctaeilcluiietdpxyeaadtccetoidnnptttrrhoeoeclbiasespioapnmbreopatpwnlrediesaetandececisn7uc0trre%airbcimyeadwnredaiplbloo1rb3vte.0e%.detAoerfmstthianeteedmfoberntyitfitehodef METHOD FOR CONTROL OF BIAS ahCnooamnltyorzgoilennogefaobtuilsaesamswtixitltwlurboeeleoavfdedelsarecoshsfemfdoarbttriyfiixtcaafktriioonmngsr.uenptrreesaetnedtactiovnetrsoulbs-asammppleless, afrnodmbya STATISTICAL METHODS cSatalctuisltaitcisonwoilfl abveerliamgeiterdectoovetrhioesse, asspaecpipfiliecdabinle.the subject methods and to the GLP STATEMENT rEAePlplAoarstTpoeSrcCdtsAatoafGptoahocisdkasgLtueadb(ysoursaphtpaollrileybdPetropaetcrhtfieocerSmpSoetndasnoadnra)drsdrhseapl4ol0rctoeCndFtaiRninc7ao9m2st.paltieaTmnhecenetfwitnhitaahlt Page 11 o f 57 Page 62 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 RtsThtheaepnisrdseatsurseddtnasyttaeawtmnivadeesn.wtciolwlndoiluulctltiebndee ainsnigycnodemedvpialbitaiynoncesthiewnittShhteucdustyrurdeDnytifrraeoncmtdortahpoapsnleidcastbaSlnepdoaGnrsLdosPr. REPORT Interim reports will be prepared by the principal investigator or their designee pafonrredpsatphreeecdipfbihcyasstaehdme ppnraliitnnugcriepsiaotlefsinsaavnmedsptsilgaeamctooprllleeocmrttiahotenriircaedcsetidsviuigtenieetsoe. tahtAethsfeiiznceaolonrcfeltpuhoseriotdnawtoailflstehbtees study. All reports will include, but will not be limited to, the following: Tofhtehneatmesetinagndfaacdilditrye.ss of the Study Director, Sponsor Representative, and cAhasitna-toefm-ceunsttoodfy GreLcoPrdcso,mmpulsitanbceein(athneystruedlayterdecodrodcsu).mentation, such as TUtohnteihtesrieSggtnauerdddyianDngidrdeadctateotserdoafnstdsatutMedmayneianngtsepbmeycetntihot.ensMaPnIdRdaetseesarfcinhdQinugaslwityerAesrseuproarntecde Antcinhoucepmdoyesrbuspeocborrfjrieapatchnttteiedodmnpaienanotaghtfleooytndthtiuhcewameelaxbrsmeaeprcfeoottmrhlaltouo.ndswat.lIeybfdtAeitcheniaenxylacmclcmuoteldnotyehdd,doiiiftdtioiconiaisnstesniapoeecnhcmhsoetpsptosloaa-ogrryteeyhed.diustocimneindetc,thhletuohddseteuwpodrinyoll.ljyebcIeatf Description of the instrumentation used and operating conditions. Aidlelnrtiefsiuedltsanfrdomthealdlasteatstaabnlealwyzileldi.ncCluodnetrsoalmapnlde fnourmtifbieedr asnadmpfolerstifwicialltiobne 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. Adaltlacwiricllumbestdaonccuems etnhatetdminaythhearveepoarftf.ected the quality or integrity of the Larocchaitvieodn.s where raw data, interim reports, and the final report are to be Page 12 o f 57 Page 63 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 iAadmdednenittidifoymnteshnatotrspiagcrontrerodefcbtthiyoenthrseeptooSrtttuhdtehyaftDiniisraelbcetroienrpg.oratTltheshreeadallmabneendditmnheetnrhteeasshfooanrlmsl cfoloerfatrhaleny Dalitreercattoiornasn. d tTheheSpaomnseonrdRmeepnrtesweniltlatbivee.signed and dated by the Study A79l2l .a1p8p5l.icable requirements for reporting of study results as per 40 CFR SAFETY AND HEALTH Laboratory personnel will practice good sanitation and health habits. Eesuxvbpesortsyaunrcreee(asos)of.npaebrlseonpnreelcaauntdiontheshaenllvirboenmtaeknetntotothperetveestntorinraedfveerretnecnet AMENDMENTS TO PROTOCOL RAexelplprresesisgseennditfaicitniavnewt.riActhimnagne,ngdesismgnetneodtstahunesduaadlnlayatlewydtiilclbabyletpihsresoutSoetdcuopdlryiooDurtitlroiencientdoitriahateinroden Sowpfioslltnusdboyer pthlaeniscshuaenogef.aHworwitteevnera,mwehnednmaencth, atnhagtecihsarnegqeuimreadywbiteheofuftecstuefdficvieernbtatlilmy ewiftohr mRseocsfoutfhreueflipapelgtdopnhcriynwogetoiarsedvepet.ldeinlansatCstgndawuopatdiitprcdtvyehooioeevpp.cosialuifdaeomneswtf.dh.ertenihwAttewTtaienlthrnslyiiieotgbdtnaneeomeenrvddseiiogiaangcaimtdnnumimoaeemnendlenesdnnadmftamtmreneoadedenmsnntadtsdntwsmohdaowietelenrlnisdelttblpuaeobswdbreyytitphlealpodeptlsahbsppdnieeerabnotolemmdeSr.etaopfudriftdnolItyyttmnohatieaotnDthhledltiiedrhsodeecaiccswunStatmoaripstirlehboey,nntuiatsttctnehehoaddderel DATA RECORD KEEPING R ecoSradmsptolebteramckaiinngtasihneeedt(isn)clude the following (as appropriate): HDIAASnaenlislsmstatcrcolpruyhrilmtrypeiocteramianeonltcanddetroiopaupgtrnfatreaasprtnhpeaaycebhroealimecrttssdiooa,sdnnb,idesfontiifconcarshstatta-irgosnuehndmehsaeiertstndostotstoarh(rlysec,tlooomacgnneksddt,ihtcfoiohodrantisinfiscaotfiocnu,stcoadliybration) Page 13 o f 57 Page 64 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 AASCahncmryoopmonlteophlleeoerxgttedircoalaicclsuttpiimonrnegesnaeotnnafdttsaitoatuinnodanynlyeopcsefiesrasssdlolaansrttnyeusefdlo,yrscitgohnrearreteuscproeonsnsdatnreundccitenioitniaolsf the study Chromatograms- All chromatograms will contain the following: . AocacAtAiSnhoonfandssennamtiadpncdrlslyieuapatiyttetnrimmltiiroettcioecrnepaonisaanaldlstflett,l.eistlonaynehcntn,toues:idtnmff(adiaoednciob.rniadgrcettjtuai.uirei,ofnromciondpcntfsaseig,ohntt/sniihmetocnhaeehnnjLettersseui)coaolt.mitwnmmsidotbitapienlenhltslroeegcdigrcntfatriohochbtaraelleimrlu,tnoedswagswsaerpaimrtonsthowhnpgewfediollesiirolnanhstrsmigetfteooiraotettuodusdhbmdn.tewehitretienriolioultnrfnnudbtaanyieilcn.pnlaiyaentlticyhoaltennuienddsocaeelofddtu,pdtdhieaenerednaedataaitrnncahehndgea QUALITY ASSURANCE TashseurQeAcoUmnpitliaonfcMe PwIitRhesGeLarPc'hs,wainlldiwnsipllecrtepthoretstthuedyfinatdiinntgesrvoaflsauaddietqsutaotethtoe Study Director, MPI Research Management, and the Sponsor Representative. RETENTION OF DATA AND ARCHIVING wiwAcnhiilfrttlohhormmthhtaahaertetodidogaonrtrcaaifomgrppoisnaym,caklwtrahoasgerwteukSdsspuhydobeanemtpstaolsi,atr,nt.ec,idnocartlrmouedetshnpinedognmS,dteuenbdntuycst,eD, finrianoenatcdltolrrrie.mespuiTotlrehttdse,sseahtnowad,lilllatbhblleeepainoerrcrctlihuigniidvneeenaddtl 7Teaq9lhsu2oei.p1bt9mee5sekt.nientpAg,tnaafntaedcMxialPiscttItyoRrcsaoehgpsaeeylalrloockfghets,ehpSeftoamartlealttCheeerloeilaclpeltsergroesin.uoidbcmoriatftwetdimdtaoetatshpaenescdtiufiadenydydiiinnresct4rt0ourmCweFniRtll, dMisPcIardRiensgeaorrcrhetuwrnililngosbatmaipnlesp. ermission from the study director before Page 14 o f 57 Page 65 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 A P P E N D IX I ANALYTICAL METHODS ETS-8-012: "Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA), Perfluorohexanoic Acid (PFHA), Perfluoroheptanoic Acid PP((APPeecFFrriffdHDlluuopooAArroo)),,uh(PnePxdFeaeNrncfAaelusn)uo,orlifcoooPnAceatrPctafeienlduro(ofPi(lcruPFooFHbArUuoSctdn)ia,deAncae)a(n,sPnudPoFlfiePOocrenfArlauf)tl,oeuroPAordecoroiofddcluetaocnaroensno(u(PoiPclnFfFoaDABnnAcaoSiti))dce,, V0001780: (PFOS) in Water, Soil and Sediment by LC/MS/MS" "Method of Analysis for the Determination of Perfluorooctanoic V0001781: V0001782: A""AMMcciieeddtthh((PPooddFFOOooAAff AA)) iinnnnaaWSllyyossaiiiltssebrffyoobrrLyttChhLee/CMDD/MSee/ttMSeerr/MSmm"iiSnn"aattiioonn of of Perfluorooctanoic Perfluorooctanoic V0001783: AA"Mcciieddth((PPodFFOOoAAf A)) iinnnaFSlyeissdihsimafnoedrnttChbleyamDLesCtbe/MrymLSi/CnMa/MtSio"Sn/MofSP"erfluorooctanoic Page 15 o f 57 Page 66 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 3M Environmental Laboratory . Method . Method o f Analysis for the Determination o f Perfluorobutanolc A cid (PFBA), Perfluoropentanolc A cid (PFPeAj, Perfluorohexanoic A cid (PFHA), Perfluoroheptanolc Acid (PFHpA), Perfluorooctanolc Acid (PFOA), Perftuorononanoic Acid (PFHA), Perfluorodecanolc A cid (PFOA), Perfluoroundecanoic Acid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesultonate (PFBS), Perfluoroheitanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS . Method Number: ETS-S-012.1 Adoption Date: Upon Signing Effective Date: Approved By: W ilia m K. Reagen, Technical M anager Date ETS-8-012.1 Page I of 12 Method of Analysis lor Ihe Determination or Partition}butanoic Add (PFBA), Pertluoropentanolc Add (PFPeA), Parduorohannotc Add (PFHA). Perfluoroftepunoic Add (PFHoA). PerHuorooctanoic Add (PFOA), Perftuorononanoic Add (PFNA). Pertuorodecanoic Add (PFOA), PeiHuoroundecanoic Acid (PFUnA), Pertuorododecanoie Add (PFOoA). Poifluorobutanesutfonata (PFBS), Peifluorohexanasulfonate (PFHS), aifo Perfluorgodanesutfonate (PFOS)in Water. Soil and Sediment by IC/MS/US Page 16 o f 57 Page 67 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 1 Scope and Application This method is to b e used to quantity Periluorobutanoic Acid (P F B A ), Perfluoropentanoic A d d {P FP eA ), Perfluorohexandc Acid (P FH A ), Petfluoroheptandc Acid (PFH pA ), Perfluorooctanoic Acid (PFOA), Periiuorononanoic A d d (P F N A ), Periluorodecanoic A cid (P F D A ), Perfiuoroundecanoic Acid (P FU nA ), Perfluorcdcdecanoic Acid (PFD oA ), Perfluorobutanesulfonate (P F 6S ). Perfluorohexanesulfonate (P FH S ). and Perfluorooctanesutfonate (P F O S ) by High Perform ance Liquid Chrom atography coupled to a tandem M ass Spectrcm etric Detector (L C /M S /M S ) in water, soil and sedim ent. T h e m ethod is designed to target a tower limit of quantitation (L O Q ) o f 0 .0 2 5 ng/m L (water) and 0.20 ng/g (soil and sediment). 2 Method Summary___________________________________ ___________________ A queous sam ples are mixed with equal volumes o f acetonitrile, thoroughly m ixed, centrifuged if necessary, and aliquoted for analysis by L C /M S /M S . Similarly, one-gram aliquots o f soil and sedim ents a re m ixed with 80:20 acetonitrlletwater mixture, thoroughly mixed, centrifuged, and afiquoted for analysis by L C /M S /M S , This Is a perform ance-based method. Method accuracy is determ ined for each sam ple set using multiple laboratory control spikes at multiple concentrations. This method also requires that the precision and accuracy for each sam ple b e determ ined using field matrix spikes (aqueous sam ples) or laboratory m atrix spikes (soil and sedim ent) to verify that the m ethod is applicable to each sam ple m atrix S am ple results for 6pikes outside o f 7 0 % to 130% , will not be reported due to non-compfiant quality control sam ples. Fortification levels for field matrix spikes and for laboratory m atrix spikes should b e a t le a s t 5 0 % o f the endogenous level and less than 1 0 tim es th e endogenous level to b e used to determ ine th e statem ent of accuracy for analytical results. ' 3 Definitions 3.1 Calibration Standard . A solution prepared by spiking a known volume of the W orking S tandard (W S> into a predeterm ined am ount of A S T M type I o r H P L C grade water, diluted with acetonitrile, 8nd analyzed according to this m ethod. 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 sam ple is a separate aliquot o f a sam ple taken in th e analytical laboratory that is extracted and analyzed separately with identical procedures. Analysis o f L D S s com pared to that of th e first. aliquot give a m easure o f the precision associated with laboratory procedures, but not with sam ple collection, preservation, or .storage procedures. . 3.3 Field Blank (FB)nfrip Blank A S T M T y p e I o r H P L C grad e w ater placed in a sam ple container in the laboratory-and treated a s a sam ple in all respects, including exposure to sampling site conditions, storage, preservation and all analytical procedures. T h e purpose o f th e FB is to determ ine if test substances or other interferences a re present in the field environm ent This sam ple is also referred to as a Trip Blank. Trip blanks are not a requirem ent for soil or sediment samples. ' 3.4 Field Duplicate Sample (FDS, Field Dup) A sam ple collected in duplicate a t the sam e time from th e sa m e location a s the sam ple. T h e F D S is placed u nder identical circumstances and treated exactly the sam e throughout field and laboratory procedures. 6TS-8-012.1 P a g e 2 o f 12 M elted of Analysis for (he (^termination of Perfluorobutanolc Add (PFBA), Perfluoropentanoic Add (PFPeA), Perlluorohexanolc A dd (PFHA). Perfluoroheptanoie Add (PFHpA). Perfluorooctanoic Add (PFOA). Perfluorononenolc Add (PFNA). Perfluorodecanoic Acid (PFOA), Perfiuoroundecanoic Add (PFUnA). PerHuorododecanoic Add (PFDoA), Perfluorobutanesuifonaie (PF65). PerfluorohesanesUfonste (PFHS). and Perfluoroodanesutfonate (PFOS) in Water, Soil and Sediment by LC/MS/MS Page 17 o f 57 Page 68 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Analysis of the F D S com parad to that o f the first sample gives a m easure o f th e precision associated with sam ple collection, preservation and storage, as well as with laboratory procedures. 3.5 Field Matrix Spike (FMS) - A sam ple to which known quantities o f the target analytes are added to the sam ple bottle In th e laboratory before the bottles a re sent to the field for collection o f aqueous sam ples. A known, specific volum e o f sample m ust be added to the sam ple container without rinsing. This m ay b e accomplished by m aking a 'fill to this level* line on the outside o f the sam ple container. T he F M S should b e spiked betw een approxim ately 5 0 % and TO times the expected analyte concentration in (he sample. If the expected range o f analyte concentrations is unknown, multiple spikes at varying levels may b e prepared to increase the likelihood that a spike 8t an appropriate'level Is m ade. T h e F M S is analyzed to ascertain if an y m atrix effects, interferences, o r stability issues m ay complicate the interpretation o f the sample analysis. 3.6 Trip Blank Spike (Field Spike Control Sample, FSCS) A n aliquot o f A S T M T ype I. or H P L C grade water to which known quantities o f the target analytes are added in th e laboratory prior to the shipment o f the eoOection bottles. T h e F S C S Is extracted and analyzed exactly like a sam ple to help determ ine if the method is in control and w hether a loss o f analyte could b e attributed to holding time, sample storage and/or shipment issues. A low and high F S C S are appropriate w hen expected sample concentrations are not known or m ay vary. At least one separate, urvspiked sam ple m ust b e taken at the sa m e time and place as ea c h F M S . 3.7 Laboratory Control Sample (LCS) ' A n aliquot of control matrix to which known quantities o f the target analytes are added in the laboratory at the time o f sample extraction. At least two levels are included, one generally at the low end o f the caDbration curve and one near the mid to upper range of the curve. T h e LC S s are extracted and analyzed exactly like a laboratory sample to determ ine w hether the method is in control. L C S s should b e prepared ea c h d a y samples are extracted. . 3.8 Laboratory Matrix Spike (LMS) A laboratory matrix spike is an aliquot o f a sample to which known quantities o f target analytes a re ad d ed In the laboratory. T he L M S is extracted an d analyzed exactly like a laboratory sam ple to determ ine w hether the sam ple matrix contributes bias to the analytical results. T h e endogenous concentrations o f th e analytes in the sam ple matrix m ust be determined in a seprete aliquot-and the m easured values in th e L M S corrected for these concentrations. L M $ s a re required ter soils and sedim ents and are optional te r analysis of aqueous samples. . 3.9 Laboratory Sample . A portion or aliquot of a sam ple received from the field for testing. 3.10 Limit of Quantitation (LOQ) T h e lower limit o f quantitation (L L O Q ) for a dataset is the lowest concentration that can b e reliably quantitated within the specified limits o f precision and accuracy during routine operating condftions. T o simplify data reporting, the L LO Q is generally selected a s the lowest non-zero standard in the calibration curve that m eets method criteria. Sam ple LLO Q s a re m atrix-dependent ' T h e upper limit of quantitation (U L O Q ) for a dataset is the highest concentration that can b e reliably quantitated within the specified limits o f precision and accuracy during routine operating conditions. T h e highest standard In the calibration curve that m eets method crteria is defined as the U LO Q . - 6 T S -8 -0 1 2 .1 P a g e 3 o f 12 Method oTAnaiysU tor trie Determination of Perfluorobi/tandc A dd (PFBA), Perfluoropentanoic A dd (PFPeA), Perfluororiexanolc Add (PFHAJ, Pertuoroheptanoic Add (PFHpA). Pertuorooctanoic Add (PFOA). Perfluorononanole Add (PFNA), Perfluprodecanolc Add (PFDA), Pernuoroundecahde Add (PFlInA), Pertuorododeeandc Add (PFOoA), Perfluoiobutanesutfonate (PFBS), Perftjorahexsneautfonate (PFHS), and Perflvoroodeneiulionale (PFOS) in Water, Soil and Sediment by LC/MS/MS Page 18 o f 57 Page 69 of 130 MPI Protocol P00003268; Intrim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 3.11 Method Blank .. A n aliquot o f control m atrix that is treated exactly like a laboratory sam ple Including exposure to all glassware, equipm ent solvents, and reagents that are used with other laboratory sam ples. T h e m ethod blank is used to determ ine If test substances or other Interferences are present in the laboratory environm ent th e reagents, o r the apparatus. 3.12 Sample A sam ple is a n aliquot removed from a larger quantity of material Intended to represent the original source m aterial 3.13 Stock Standard Solution (SSS) A concentrated solution o f a single-analyte prepared in the laboratory with an assayed reference com pound. 3.14 Surrogate A compound similar to the target analyte(s) in chemical composition and behavior that Is not normally found In the sem ple/s). A surrogate compound is typically a target analyte with at least o ne atom containing an isotopically labeled substitution. If used, surrogate^) are added to all sam ples end quality control sam ples (except solvent blanks and half o f the prepared method b la n k s ).' Surrogate(s) a re ad d ed to quantitatively evaluate the entire analytical procedure including sample collection, attraction, and analysis. Inclusion o f a surrogate analyte is an optional quality control m easure and is N O T required. 3.15 Workl ng Standard (WS) A solution o f several analytes prepared in the laboratory from S S S s and diluted a s n e ed ed to prepare calibration standards an d other required analyte solutions. . 4 Warnings and Cautions_________________________________________________ 4.1 Health and Safety The acute and chronic toxicity o f the standards fo r this m ethod have not been precisely determ ined; however, each should b e treated as a potential health hazard. T he analyst should w e a r gloves, a lab coat, a nd safety glasses to prevent exposure to chem icals that m ight be present T h e laboratory is responsible tor maintaining a safe work environment and a current aw areness o f local regulations regarding th e handling ot the chemicals used In this method. A reference tile of m aterial safety data sheets (M S D S ) should be available to all personnel involved in.these analyses. 4.2 Cautions . T h e analyst must be familiar with the laboratory equipment and potential h a zard s including, but not limited to, the use of solvents, pressurized gas and solvent lines, high ireltage, and vacuum systems. R e fe r to the appropriate equipm ent procedure or operator m anual for additional information and cautions. 5 Interferences During extraction and analysis, major potential contaminant sources a re reagents end glassware. All materials used in the analyses shall be demonstrated to b e b e e from interferences under conditions o f analysis by running method blanks. E T S -8 -0 1 2 .1 P a g e 4 o f 12 Method of Analysis for lire Determination of Perilvorotrufanolc Add (PFBA), Perfluoropentanolc Add (PFPeA), Pertluorohexwiclc Add (PFHA). Parltuoroheplandc Add (PFHpA). Pemuoroodanole Add (PFQA), Perftuorononanoic Add tPFNA}. Perfiuorodecsnore Add fPFDAJ, Perftuoroundecanolc Add (PFUnA). Perfluorododecandc Add (PFDoA), PeriTuorobvfanesulfOnate {PFBS), PerfluorohexanasulfdTste fPFHS), and Pcrifuoroodsnesulfonete (PFOS) hi water. Soil and Sediment by LCTMSrMS Page 19 of57 Page 70 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 Parts and supplies that contain T eflo n should be avoided or minimized d ue to the possibility o f interference a n d A x contamination. These m ay include, but are not limited to: w ash bottles, T e flo n * lined caps, autovial caps, H P L C parts, etc. T h e use o f disposable micropipettes or pipettes to aliquot standard solutions is recom m ended to m ake calibration standards and matrix spikes. 6 Instrumentation, Supplies, and Equipment 6.1 Instrumentation and Equipment A high perform ance liquid chromatograph capable o f pumping up to 2 solvents and equipped with a variable volum e injector capable of injecting 5 -2 0 0 p i connected to a tandem M ass Spectrom eter (IC /M S /M S ). Applied Biosystems Sciex A P I 5 0 0 0 instrumentation is required to m eet the L O Q s o f 0 .0 2 5 n g frn l (w ater) a n d 0 .2 0 ng/g (s o i and sediment). If analyte concentrations require dilutions for o ne o r m ore Bnalytes that preclude the targeted L O Q s from being reached, A pplied Biosystems Sciex A P I 4 0 0 0 instrumentation m a y b e utilized since the LO Q s will already b e raised. ' Analytical balance capable o f reading to 0.0 0 0 1 gram. - A device to collect raw data for peak integration and quantitation. 15 - m l and 5 0 -m l disposable polypropylene centrifuge tubes. Disposable micropipettes (1 0 -2 0 p i , 2 5 -5 0 pl_ 50-100 pL, 100-200 p i) . 1 2 5 -m l LD P E narrow-mouth bottles. ' 2-m L d e a r H P L C vial kit. ' Disposable pipettes, polypropylene or glass as appropriate. Ultrasonic bath. Centrifuge capable o f spinning 15-m L an d 50-m L polypropylene tubes at 3 0 0 0 rpm. 6.2 Chromatographic System {PIN:Analytical Column: Luna 3 pm C 8 (2) M ercury (Phenomenex), 2 m m x 4 m m . 3 p m 00M -4245O 0Q E ) Temperature: 35*C M obile P h ase (A): 2 m M Am m onium Acetate in W ater Mobile Phase (B): Methanol ' Gradient Program: Tim e (m ini %A %B 0.0 90 10 0.5 90 10 2.0 10 90 5.0 10 90 5.1 0 100 6.0 0 100 6.1 90 10 10.0 90 10 Injection Volume: 5 pL (can be Increased to as much as SO pL). ' F(lmowUmRiant)e 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Quantitation: P eak A r e a -e x te r n a l standard calibration curve, frit weighted. E T S -8 -0 1 2 .1 Page 5 o fl2 Method of Analysis for the Determination of Pedluorebubnoie Ada (P fBA). pertuoropentenoie Add (PFPeA). Pertuorohexanoic Add (PFKA). Perftuoroheptanolc Add (PFHpA). PertuorocclanolcAcldiPFOA), Perflyorononanolc Add (PFNA). Perfluorodecanolc Add (PFOA), Perfluoroundecanoic Add (PFUnA), Porfluorododecanolc Add (PFOoA). Perfluortfutanesulfonate (PFBS), Pertuwohexaneaurtonasa (PFHS). and Perfluorooctanesuiionale (PFOS) tn Water. Soil and Sediment 0y CC/M&MS Page 20 o f 57 Page 71 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Run Time: - 1 0 minutes. T h e previous inform ation is in tended as a guide: a ltern ate conditions a n d eq u ip m en t m a y b e used provided that data quality objectives are met. - 6.3 MS/MS System 6.3.1 M o d e Electrospray Negative M R M mode, monftoring the following transitions A n a ly te Transition M onitored PFBA 213 - * 169 PFPeA 263 -* 219 PFHA PFHpA . -*3 1 3 -*> 2 6 9 an d 3 1 3 - H 1 9 363 - * 319. 363 169 and 363 -* 1 1 9 PFOA 413 -+ 369.413 -> 219 and 413 -> 169 PFNA 463 - t 419. 4 6 3 -* 169 and 463 -> 219 PFDA 5 1 3 - 4 6 9 , 5 1 3 2 1 9 an d 5 1 3 - > 2 6 9 PFUnA 563 - 519. 563 - * 269 and 563 -+ 219 PFDoA 613 -> 569. 613 - * 169 and 613 319' PFBS 299 - 80 and 299 - * 99 PFHS 399 - * 80 and 399 - * 99 PFOS 499 - 80. 499 - * 99 and 499 - 130 M ultiple transitions for m onitoring th e analytes is a n option b e c a u s e sum m ing m ultiple transitions m ay provide quantitation of isomers that more closely m atches N M R data and m ay have the ad d e d b en efit o f increased analyte signal. T h e u se o f .one d au g h ter ion is ac c e p ta b le if m ethod sensitivity is ach ie v e d , provided that retention tim e criteria a re m e t to a s su re a d e q u a te specificity. T h e p revious inform ation Is Intended as a guide, alte rn a te instrum ents a n d e q u ip m e n t m a y be used. - 7 Reagents and Standards W ater - H P IC grade Methanbf - H P IC grade Ammonium A cetate -A .C .S . Reagent Grade Acetonitrile - H P L C grade Perfluorobutancic A d d (P F B A ) - Oakwood Products. Inc Perfluoropentanoic A d d (P F P eA ) - Sigma-AJdrich Perfluorohexanoic Acid (P F H A ) - Oakwood Products, Inc Perfluoroheptanoic A d d (P F H p A ) - Oakwood Products, Inc Perfluorooctanoic Acid (P F O A ) - O akw ood Products, Inc Perfiuorononandc A d d (P F N A ) - Oakwood Products, Inc Perituorodecanoic Acid (P F O A ) - Oakwood Products, Inc Perfluoroundecanoic Acid (P F U n A ) - Oakwood Products, Inc Perfluorododecanoic Acid (P F D o A ) Oakwood Products, Inc . ' . . ETS-8-012.1 Page of 12 Msiftod of Anafysla for tne Determination of Perftuoro&uiBnolc Add (PFBA). Perfluoropentanoic Add (PFPeA). Perfluoronexsnoic Add (PFHA). Perfluoroheptsnaic Add (PFHpA). Perfluorooctanoic Add (PFOA), Perfluoranonanoic Add (PFNA), Perfluoredecanolc Add (PFOA), Perfluoroundecanoic Add (PFUnA). Perfluorododecanoic Add (PFDoA). PerfluoroSutaneauNonate (PFBS), PerfluoroMexanesuifonate (PFHS), and Perfluoroodanesul'onale (PFOS) In Water, Soil and Sediment by IC/MS/MS Page 21 o f 57 Page 72 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Perfluorobutanesulfonate (PFBS) - 3M Perfiuofohexanesulfonate (P F H S )- 3M Perfluorooctanesulfonate (PFO S) - Fluka . . T h e previous information is in tended as a guide. R ea g e n ts and s tan d ard s from a lte rn a te sources m ay be used. 8 Sample Handling _____________________ . 8.1 Water Sample Extraction 8.1.1 Measure 1 0 m L of sample into a 50-m L polypropylene centrifuge tube. Fortifications are to be done 81 this point, if necessary. Other volumes and containers m ay be used as appropriate. 8 .1 2 A d d lO m L o faceto n M e to th e s a m p le in th e c e n trifu g e tu b e . C ap tightly and shake. 8.1.3 Sonicate sample for - 2 hours at room temperature. This step is optional, but is recommended ff particulates appear to b e present . 8.1.4 Centrifuge far - 1 0 minutes at -3 0 0 0 rp m This step s optional, but is recommended if samples are sonicated. ' 8.1.5 Transfer a portion o f the supernatant to an autosampler via) for analysis. ' 8.1.6 Dilute sample, if necessaty, with 50:50 aoetanitrileiwater. 8.2 Soil and Sediment Extraction 6.2.1 822 W eigh 1 g of sample into a 15-mL polypropylene centrifuge tube. Fortifications a re te b e done a t this point, if necessary. Add 6 m l o f 80.20 acetonitrilew a te r to (he sample in the centrifuge tube. C ap tightly and shake. 8.2.3 Sonicate sample for 2 hours at room temperature. 8.2.4 Centrifuge for - 1 0 minutes a t -3 0 0 0 rpm. 8 2 5 Transfer a portion o f the supernatant to an autosampfervisi for analysis. 8 2 6 Dilute sample, if necessary, wfth 50:50 acetcntotie.water. 827 Analyze samples using electrospray IC /M S /M S O ther weights and volumes can b e used as long a$ the Q C elem ents specified in this method are satisfied and ell sample preparation procedures m a y be reconstructed. 9 Sample Analysis - LC/MS/MS E T S -8 -0 1 2 .1 P a g e ? o f 12 Method of Analyst for the Determination of Perfluorobulanolc Add (PFBA), Perfluoropentanole Add (PFPeA), Perihjoroheunoic Add (PFHA). Perfluoroheptanolc Add (PFHpA), Perfluorooctarioic Add (PFOA), Pedluoronongndc A dd (PFMA). PerfluorodecanoJc Add (PFOA). Periluoroundeeanolc Add (PFUnA), Perfluarododecanolc Add (PFDoA). Pertuorobutanesulfonate (PFBS), Perihiorohexanesdronate (PFHS), and Pertluorccaanesulfonate (PFOS) bi WWer. SoHand Sodlmenl by LC/MSTMS Page 22 o f 57 Page 73 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 9.1.1 A minimum of six calibration levels must be present in the final calibration curve. 9 .1 2 An entire set of calferation standards is injected a t the beginning of a sample set prior to sample analysis. As an alternative, an entire set of calferation standards m ay be injected at the beginning of a sample set followed - by calibration standards Interspersed every 5-10 samples (to account for a second set o f standards). In either case, calibration standards or a c o n tm n g calibration verification standard must bracket the first sample and the last sample. Analytical studies m ay only require that a n initial cafibration curve b e analyzed prior to samples and that the continued accuracy of the initial calbraticn curve be confirmed by the analysis of continuing cafbration verification standards. T he sam e approach should be used throughoutthe entire study unless reasons are documented 8nd technical justification to change is approved prior to sample analysis. 9.1.3 T he standard curve is plotted by quadratic f t (y * a x * + b x * c ) , weighted 1Aco r unweighted, o r using a linear ft, weighted lo u s in g suitable software. The calibration curves may include but should not ba forced through zero. T he mathematical method used to calculate the calibration curve should b e applied consistently throughout a study. Any change should be documented In the raw data. 9.1.4 Samples containing analytes that are quantitated above the concentration o f the highest standard in the curve should b e further diluted and reanalyzed or re-injected using a smallervolume. 10 Quality Control______ 10.1 Data Quality Objectives. This m ethod and required quality control samples is designed to generate d ata accurate to + /-3 0 % with a targeted L O Q o f 0 .0 2 5 ng/mL (water) or 0 .2 0 ng/g, Wet weight (soil and sedim ent). A n y deviations from the quality control m easures spefled out below will be docum ented In the raw d ata and footnoted in the final report 10.2 Blanks 1 0 2 .1 Method Stank M ethod blanks m ust b e prepared with each extraction batch. A range of th ree to seven method blanks m ust be prepared. T h ese method blanks must be interspersed throughout th e extraction batch and analyzed interspersed throughout the analytical sequence. ' ' . T h e m e a n a re a count for each analyte in the m ethod blanks m ust b e less than 5 0 % o f the are a count o f the LO Q standard. T he standard deviation o f the area counts of th ese m ethod blanks should be ' calculated and reported. If-th e m ean a re a counts o f the method blanks exceed 5 0 % o f the LOQ standard, then .the LO Q m ust be raised to the. first standard level in the curve that m eets criteria or alternatively, the method blanks must b e evaluated statistically to determ ine outliers o r technical justification to eliminate o ne or more results should b e m ade. 1 0 2 2 Solvent Blank 1 Solvent blanks must be analyzed throughout the analytical sequence. Solvent blanks that show area counts greater than 50% o f the are a counts o f the LO Q standard m ust b e evaluated to determ ine if analytical results are significantly impacted by sam ple carry-over or an unacceptable buildup o f analyte In the instrumental background. 10.3 Sample Replicates . Sam ples should b e prepared in duplicate In the lab (soil and sediment) or collected in duplicate In the field (w ater). T h e relative percent difference, R P D , should b e reported. R P D results g reater than 2 0 % (water) or E T 5 -8 -0 1 2 .1 P a g e 8 o fi2 Method ot Anatytis tor the Determination ot Perfluorcbuttnde Acid (PFBA), Perfluoropentanolc Add (PFPeA), PerRuorohezanoic ' Add (PFHA), Perfluorohepianolc Add (PFHpA). Perfluorooctanoic Add (PFOA). Perfluorononanolc Add (PFNA), Perttuo/odecanoic Add (PFDA), Perfluoroundeeanoic Add (PFUnA). Pertuorododecandc Add (PFDoA), Pertuorobutanesutfonaie (PFBS), Perfluorghexanesulfonate (PFHS). and Pertuorodttaneaulionate (PFOS) In water, Sod and Sediment by LC/MSrMS Page 23 o f 57 Page 74 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 30% (soil and sedim ent) will be flagged in the report, but win not be excluded from reporting. T h e requirem ent fo r replicates excludes field blanks a nd rinse blanks. . 10.4 Surrogate Spikes Surrogate spikes are not required but m ay be used on project specific requirem ents. 10.5 Lab Control Sample the rangeT rip lic a te lab control spikes a t a m in im u m o f tw o d iffe re n t concentrations a re to b e p re p a re d w ith each e xtra c tio n batch . Low Jab control spikes should be prepared a t concentrations in o f five to ten times h igher than the targeted IO Q and high lab control spikes should be prepared a t concentrations ne a r th e mid point o f th e curve. The relative standard deviation o f the control spikes fo r these six pooled control sam ples must- be less than or equal to 20% a nd the average recovery m ust be 80-120% , If the above criteria are not m et, th e entire set o f sam ples should be re-injected o r re-extracted as appropriate. - 10.6 Field Matrix Spikes / Lab Matrix Spikes R ecoveries o f field m atrix spikes (aqueous sam ples) a nd laboratory m atrix spikes (soils a nd sedim ents) are anticipated to be betw een 70% and 130% o f the fortified levels. If the recoveries o f th e spikes fa ll outside the a c c e p ta b le range, th e sa m p le re su lt wSI b e repo rte d as 'N R * (n o t reported d u e to no n -c o m p lia n t Q C results). T h e targeted fortification levels should be a t least 50% o f th e endogenous level and less th a n 10 tim es the e n d o g e n o u s le ve l to be u sed w ith o u t ju stifica tio n to de te rm in e th e s tatem ent o f a c c u ra c y fo r a n a lytica l results. T h e ave ra g e o f th e sam ple and the lab dupGcate (sons and sedim ent) o r field duplicate (w ater) should be used to calculate the recovery. . 10.7 Standard Preparation 10.7.1 S tandard Stock Solutions ' Prepare individual stock solutions o f each analyte at *1 0 0 0 pg/m L by w eighing 100 m g o f analytical standard (corrected fo r purity and salt' c o n te n t if necessary) and dilute to 100 m L w ith m ethanol o r acetonitrile in separate 1 0 0 -m l volum etric flasks. F o r purity correction, take the am ount o f analyte that is needed for w e ig h in g (l.e .1 0 0 m g ) a n d divide b y th e purity in d e cim a l fo rm (.e. 9 9 .6 % 0 .9 9 6 ). T h e result is th e w e ig h t that is n e e d e d to m a ke th e solution corrected for purity (i.e. w eigh 100.4 m g). F o r salt correction, calculate th e salt co n te n t b y taking the m olecular w eight o f the target com pound (i.e. PFO S = 49 9 ) a nd dividing b y the m olecular w e ig h t o f th e en tire co m p o u n d (i.e. P F O S p o ta ssiu m sa lt (C eF nS O yK * $38). T h e re su lt is th e sa lt c o n te n t in d e cim a l fo rm (i.e. 0,9275). T ake th e am o u n t o f analyte th a t is needed for w eig h in g (i.e. 100 m g ) and divide by the sa lt co n te n t in decim al form. The result is (he w eight th a t is needed to m ake the solution corrected fo r salt content (L a w eigh 107.8 mg). Store ail stock solutions in appropriate containers and a t appropriate storage - conditions fo r up to 6 m onths from the date o f preparation. ' - A lternate stock solution concentrations can be m ade, If necessary, using alternative m asses an d volum es. 10.7.2 Standard Fortification Solutions A 10 p g /m l m ixed fortification solution containing all o f the analytes is prepared b y bringing 1 m L o f each o f the 1000 p g fo iL stock solutions to a final volum e o f 100 m L w ith acetonitrile in a 1 0 0-m L volum etric flask. A 1.0 100p g / m l m ix e d fortifica tio n solution con ta in in g a ll o f th e a n a lyte s is p re p a re d b y b rin g in g 10 m L o f th e 1 0 pg /m L m ix e d so lution to a fin a l volum e o f 100 w ith acetonitrile in a - m l volum etric flask. A 0.1 p g/m L m ixed fortification solution containing all o f th e analytes is prepared b y bringing 10 m L o f th e 1.0 p g /m l m ixed solution lo a fin a l volum e o f 100 w ith acetonitrile in a 1 0 0 * n l volum etric flask. A 0 .0 1 pgfrnL m ixed fortification solution c o n ta in in g all o f th e a n a lyte s is p re p a re d b y b rin g in g 1 0 m l o f th e 0.1 p g /m L s o lu tio n to a fin a l v o lu m e o f 100 w ith acetonitrile in a 100-m L volum etric flask. Store all fortification standards up to 6 m onths fro m the date o f preparation . ' ETS--Q12.1 Page 9 o f U Method o f Analyelt for tno Determination Of Perfluorobutanoic Add (PFBA). Perfluoropentanoic Add (PFPeA). Perfluorohexanoie Add (PFHAJ, PerfluoroheptanolcAdd (PFKpA), Perfluorooctanolc Add (PFOA). Perfluorononanoic Add (PFNA). PerSuorodecandc Add (PFOA), Perfluoroundecanolc Add (PFUnA). Perituorododecanoic Add (PFOoA). PeriUiorobutaneauifonate (PFBS). Perfluorohexanejiifonate (PFHS). and Perftuorooctanesulfonate (PFOS) in Water, Soil and Sediment by IC/MS/MS Page 24 o f 57 Page 75 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Alternate fortification solution concentrations can b e m ade, if necessary. L kew .se, alternative volumes m ay be used. 10.8 Instrument Calibration 10.8.1 LC/M S/M S calibration standards are prepared externally in SOSO acetonibilewaterand are used to construct Ifte calibration curves for the water, soil, and sediment procedures. 10.8.2 The tokwring a a typical exam ple of a caibratior s e t A tem ate or additional concentrations m ay be prepared as. needed. . C oncentration Initial Solution of Initial Solution Aliquoted Volum e (ng/m L) (m L) 100 5 Final Solution Volum e (mL) 100 Final Concentration of Calibration Standard (ng/m L) 5.0 100 10 5 2.5 2.5 10 10 10 100 100 100 100 2 .5 1.0 0 .5 0.25 1 10 100 0.1 0.5 10 100 0.05 1 2.5 100 0 .0 2 5 Store all calibration standards for up to three months. Alternate volumes and concentrations o f standards m ay be prepared as heeded. . 11 Data Analysis and Calculations U se the following equation to calculate the amount o f analyte found (in ng/mL, b ased on peak a re a ) using the standard curve (linear regression param eters) generated by an appropriate software program : A nalytefound(ng/m l) J P ea^ .^ - J .ij,) 9fcepl) D F Slope DP = factor by which the final volume w as diluted, if necessary. For sam ples fortified with known amounts o f analyte prior to extraction, use th e following equation to calculate the percent recovery. - Recove T o tal an a ly te found (ng/m L) - A v erag e analyte found In sam ple (n g /m L ) ^ ^ Analyte added (ng/hiL) U s e th e following equation to convert the amount of analyte round in ng/mL to ng/g (ppb). Analyte found (ppb) - A n a ly te fo undtnB'm L> W lu m e extracted (m L ) S em ple weight (g) ' ' U se the following equation to calculate the amount o f analyte found in ppb based on dry w eight. A n alyte found (ppb) dry w eight = A n a ly te found (p p b ) x [1 0 0 % / total solids (% )] 12 Method Performance E T S - -0 1 2 .1 Page 10 of 12 Method erf Analysis tor the Determination of Perftuorobutanolc Acid (PFBA). Perfluofopenlarrolc Add (PFPeA), Perfluorohexanolc Add (PFHA), PenVoroheptanolc Add (PFHpA). Perfluoroocunolc Add (PFOA), Perfluorononanoie A dd (PFNA), Perfuorodeeanolc Add {PFOA), Perfluoroundacanoic Add (PFUnA), Perfuorododecsnoic Add (PFDoA), PerflucrctJuUnesulfonat (PFBS). Perftuorohesanasuiionate (PFKS). and Perfluoroodanesuffonete (PFOS) In Water, Soil and Sediment by LC/MSfMS Page 25 o f 57 Page 76 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 A n y method perform ance param eters that are not achieved m ust be considered in the evaluation o f the data. Nonconform ance to an y specified param eters must be described and discussed ff the Technical M an ag er (nonG L P study) or Study Director (G L P study) chooses to report th e data. ff criteria listed in this m ethod performance section are not met. m aintenance m ay b e perform ed on th e system and sam ples reanalyzed, o r other actions taken as appropriate. Docum ent ail actions in the raw d ata. . If data are to b e reported w hen performance criteria have not been m et, th e date m ust b e footnoted on tables and discussed in the text o f the report 12.1 System Suitability . System Suitability standards a re not a required component o f this m ethod. If required by protocol o r by the technical m anager, a m inimum o f three system suitability sam ples a re injected at the beginning of each analytical run prior to the calibration curve. Typically these sam ples are a t a concentration near th e m id level of S2% th e calibration curve and a re repeated injections from o ne autosam pler vial. T h e system suitability injections ' m ust have are a counts with an R S D of 5% and a retention tim e R S D of to be compliant 12.2 Quantitation . {t3)C alib ra tio n C u rv e : T h e coefficient o f determination value for the calibration curve must be g reater than or equal to 0 .9 8 3 . T h e concentration o f each point in th e curve must back calculate to b e within 2 5 % o f the theoretical concentration with the exception o f the LLO Q , which m ay b e within 3 0 % . Calibration curve points that a re not a t the high or low end o f the curve may not be deactivated. C C V P e rfo rm a n c e : T h e oontinued accuracy of the calibration curve m ust b e dem onstrated b y analyzing continuing- calibration verification (C C V ) standards. Each C C V m ay b e a calibration curve point that is reinjected or a separately prepared standard, and is typically near the m iddle o f the calibration curve. Alternative concentrations or multiple concentrations m ay be chosen depending on project requirements. Not more than ten sampfes o r spikes m ay be analyzed between the initial calibration and a C C V o r bracketing CCVs. T h e accuracy o f each analyte must be vrithin 2 5 % of the theoretical value. Sam ples that are bracketed by C C V s not m eeting th ese criteria m ust be reanalyzed. D e m o n s tra tio n o f S p ecificity: Specificity is demonstrated by chromatographic retention tim e (within 4 % of standard) and the m ass spectral response of unique ions. 12.3 Sensitivity T h e targeted limit o f quantitation for all analytes is 0.0 2 5 n g /m l (w ater) an d 0 .2 0 ng/g (soils an d sedim ents, w et weight). T h e L O Q for any specific anatyte m ay vary depending on the evaluation o f appropriate blanks and the accuracy of the low-level calibration curve paints. R efer to Section 10 for additional details. 12.4 Accuracy This method and required quality control samples are designed to generate d a ta that a re accurate to + /-30% . Section 1 0 contains additional information regarding th e required accuracy o f laboratory control spikes,'field matrix spikes (w ater sam ples) and laboratory matrix spices (soils and sediments). 12.5 Precision Sam ples should b e prepared in duplicate in the tab (soil and sediment) o r collected in duplicate in the field (aqueous). T he relative percent difference, R PD , should be reported. R P D results g reater than 2 0 % (w ater) o r 30% (soil and sedim ent) will b e flagged in the report, but wffl not b e excluded from reporting. T h e requirement for replicates excludes field blanks or rinse blanks. Section 1 0 contains additional information regarding the required precision o f laboratory control spikes. 13 Pollution Prevention and Waste Management ~ ET5-B-012.1 " ofP a g e M 12 Method of Arat/sls tor the Determination of Perfluorobulanote Add (PFBA), Perfuoropentanofc Add (PFPeA), Perfborohexanoie Acid (PFKA), Pert!uorohepianole Add (PFHpA), Pertluoroodanoic Add (PFOAJ, Pertiuoranonanolc Add (PFNA). Perfluorodecanofe Add (PFOA), Perltuoroundecanoic Add (PFUnA), Perftuorododscanoic Add (PFOaA). Perfluorabutoneaulfonate (PFBS). Perttuorohexsneauflonale (PFKS). and Perflucroodaneaujtonate`|PFOS) in Water, Soil and Sediment by IC/MS/MS Page 26 o f57 Page 77 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 W a s te generated w hen performing this method will be disposed o f appropriately. T h e original sam ples will be archived at the 3 M Environmental Laboratory in accordance with internal procedures. 14 Records Each d ata package generated for a study m ust include all supporting information fo r reconstruction o f th e d a ta Information for the d ata package m ust include, but is not limited to the following items: study o r project number, sam ple and standard prep sheets/racords, instrument run log (instrument batch records, instrument acquisition method, sum m ary pages), Instrument results files, chromatograms, calibration curves, and data calculations. 15 References_____________________________________ '__________ ___ Exygen Research Analytical Method V 0003305-1 details method developm ent and verification o f recovery for multiple analytes In groundwater, surface water, soil, and sedim ent. This will be archived a s part of E 06-0 5 4 9 . 16 Affected Documents_________________ None. 17 Revisions R e v is io n Number Revision Description Revision D ate 1 Th e sonication and centrifugation steps o f the w ater sam ple preparation w e re 11/10/06 m ade optional. T he accuracy requirements of the analytical balance w ere updated. T he method w as updated to allow the use of a linear l/x w eighted calibration curve. T h e table of required daughter ions for the analytes w as updated. T h e method w as updated to allow different sample volumes to b e extracted and to allow different standard bottles and storage conditions to b e used. Calibration requirements w e re updated to show that analyzing continuing calibration verification standards at one ' concentration w as an acceptable alternative to reinjecting all curve points used to construct the calibration curve. M inor wording changes w ere m ade throughout ETS--012.1 P a g e ! 2 o f 12 Method o f Analysis tor the Determination of Periluorofautanolc Acid (PFBA), Perfluoropentanoic Add (PFPeA), Pertuorohexanolc Add (PFHA). Periluoroheptanofc Add (PFHpA), Perfluoreoclanclc Add (PFOA), Perfluorononanoie Add (PFNA), Perfluorodecanolc Add (PFOA), PerfluoroundecanolcAcid (PFUnA). Peril jorododecanoic Add (PFDoA), Perfluorobutanesulfonate (PFBS). Periluorohexanesulfonate (PFHS), and Pertluoroodanesulfonate (PFOS) In Water, Soil and Sediment fay LC/MSIMS Page 27 o f 57 Page 78 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Page 28 o f 57 Page 79 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 ANALYTICAL METHOD Method Number: V0001780 Method of Analysis for the DeterminbaytiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water Analytical Testing Facility: E3S0txa5yt8egeRCneoRslleeeasgreeca.hrPcDAhriv16e801 Approved By: C.-- \jv~t______________ TPaeuchl nCiocanlnLolelayder, LC-MS, E'xygen Research _DaitoeJzaM / /Jo2vVh;i.cneFPlraehsied:rrettyynt, Op/erations, Exygen Research Date Total Pages: 7 Page 29 o f 57 Page 80 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V000I780 _______________________________ A N A L Y T IC A L m e t h o d _______________________________ Method of Analysis for the DeterminatiLoCn/oMfSP/eMrfSluorooclanoic Acid (PFOA) in Water by 1.0 Scope TaScphieidsctmrboyemthHeotirdgichisDtPeoetebrfceotoremrm(apLnlCocey/MedLSi/fqMouriSdth)eiCnishworoalatmetirao.tnogarnadphqyuanctoiutaptlieodn otof paer/tlaunodroemoctaMnoasics 2.0 Safety 22..21 CAolwnsauylst othbesearpvperosapfreialtaebMorSatDoSrybperfaocrteichesa.ndling any chemical for proper safety precautions. 3.0 Sample Requirement 333...132 33..54 3.6 AAmNSSAteaaltonmilmmnylsspueppaaaetsllmemsraeeastmsppt4caullpon0eersleldsetlpm.oesmrtrcLhocetueciodosoenstsnfutsbratpieepeinefsnrgrrttoiihnnscgioagaseetrmdraonpaunuepatrteeglreeddtuhsiesclfydewolsedrhmifslooefliosxruxhbrtlwerdoetadhaucstelbtebpdieoereefxbncsota.ierrafmeailcelcpbeodtnleiweoitisnrnen.idg.futshgateeomdspaealmeqtdup-i3lfliio0nbrg0rea0pxteltrarpanmtcotfiooforrnor.toh~mi5s project. 4.0 Reagents and Standards 4444....1234 WPAMemeartftmheluaroon-nroioHluom-PctLHaACnPcoLgeiCctraaAtdgeecr-aiddAe-.CS.iSg.mRae-AaglednritcGhrade 5.0 Instrument and Equipment 5.1 5555555555..........178234569110 2ADDAA51spW1Ao502Lmniiulssad5ammtvhpptceLo-leeoooiymvpLLrgncssntisithicLaapldndsceSebbeiieLaasseellptctlreetDppqopeteboHoeurmpsPPcafdssiiPoEo(plaaapia1ctLrlkbbpeolnm0rnlelteCocVeet0adaceaper-tapvpsntr1iwc.acropoioc0aaanellwei60lwpyytdth0s-pakpecmldbirrmc(iaptooq5la.oeL(pput0vuMlayyi-ogatad1llhfraf)nee0oisradnnbctr0sebCeeohupa1lSt1rLedccet0op8leeai,e-menvnnk1sSc1gott.0atrriP0lr0ntiitu0oEoffotmuup-gem20cggLgre0.aeaeer0)0rtpai,0etttnuthruuwr0ijLiobbed0(i)neceLcg1t.hssateCa.o.pgsdnr/a..MidbcspalqSeopu/saMaoabnbSlfteil)te.paouttifimopinsnp..jiencgtinugp5-to2002 Page 2 of 7 Page 30 o f 57 Page 81 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001760 ANALYTICAL m e t h o d _________________________ Method of Analysis for the DeterminatiLoCn/oMfSP/eMriSluorooctanoic Acid (PFOA) in Water by 55..1132 CSPenEtrvifaucgueumcapmaabnliefoolfds.pinning 50 mL polypropylene lubes at 3000 rpm. 6.0 Chromatographic System 6.1 A(Pn/Nal:yt8i2ca5l0C5-o0l5u2m1n3:0F) luophase RP (Keystone Scientific), 2.1 mm x 50 mm, 5p 66..32 MMGTerooambbdpiiilleeeenraPPtthhPuaarreosse:egr((a3ABm0)):C:: M2 metMhanAoml monium Acetate in Water Tim22e08120.....(00050mini %22665555A 65 %7733355555B FfmloLw00000/.....m33333Riaht)e 666...876 RIQnuujenacnTttiiiotmanteiVo: no-:lu2mP3eeam:kin1A5urtepeasL.-(ceaxntebrneailnsctraenadseadrdtocaalsibmrauticohnacsu5rv0ep. L). TophteimabizoevethceoHndPiLtiConssyastreemin.tended as a guide and may be changed in order to 7.0 MS/MS System 7.1 Mode: Electrospray Negative MRM mode, monitoring 413 -+ 369 m/z. TophteimaibzoevtehecMonSdMitiSonssystaerme .intended as a guide and may be changed in order to 8.0 Preparation of Solutions 8.1 Mobile Phase 8.1.1 a2mmmMoniaummmaocneituamte taoce1t0a0te0 minLwoaftewraitserp. repared by adding 0.154 g of Alternate volumes may be prepared. Page 3 ofr Page 3 1 o f 57 Page 82 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001780 ANALYTICAL METHOD Method of Analysis for the DeterminatiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water by 9.0 Standard Preparation 9.1 99999S9......t111111a......n546312darAmamafATaAAm1omimPdrnp0hofre11LLeLpS0e0eat1m1a22thr.pt.mho.0n31o30ooosa01aaatf1tncfxL2frphmmonptploke3ityhgtecomgghplh/LLto/keaFlm/e/diigmeammcnfoLLia/satL1na1mLret1tLnaLDDt.le0tol0h0adiLLycfPPsf10oeffpopiDtk1oof2EEc4afgrgopf25rr0aPtnosp/trt/gbi5bmt.CiiomdEtrfmr1iff/oi-otieolamiifmicLtuLtccpbLfiranttacpitdalalaLonLcsiteeasSLttgroitdoa.i.iot(aotoLs/oonDitlclmtlnooieualnniuOoouPo.olnrttLrsnuseitPnsEiriofosootoe.oEi-nossllnlcsbonu1utoulotoabnuttttl0etliobotiouitduoto0otiltltoatoneanteiniflonp.oeofofafoonsgin.irofnnff/fraPopPamaiPtrnluflFoaFeFLParvvOOlimtOFootaooyvAAlOAlauuf)boxfmmAePliiaiiiunssmsnFeseampdppOtiuloosorrermAeedreffvpepoppior11dlaapabfeul00rrruepyit001eeenermad0ddiwwwrota0eeobbbdeiidrttwyyiyeohh1gofbibb0bfhrtfmmyhri0rrign6iiie1ennnbmemgtt0hgghgmrr0eaLiaaiii1nntnonnnth0ogwogwnggoarilltmniinh1t11tiaoihghsn00ng0tl 9.2 Standard Calibration Solutions 9.2.1 cLaCli/bMraSt/iMonSstcaanldibarradtsioanrestparnodcaersdssedartehrporuegpharethdeinexHtrPacLtCionwpartoerc.eduTrhee, 9.2.2 Tidheentfiocalllotwoisnagmipsleas.typical example: additional concentrations may be prepared as needed. F in a l Concentration Fortification Volum e o f C oncentration o f C alibration o f Fortification V olum e Fortified Control C alibration Standard ID Solution (ppb) (p L ) Sam ple (m L ) Standard ip p t)* (exam ple) 00 to too to 200 10 400 100 to o 40 40 40 40 40 0 XCm m ddyy-Q 25 XC m m ddyy-1 so X C m m ddyy-2 too XC m m ddyy-3 250 X C m m ddyy-4 100 200 40 500 XCm m ddyy*5 * The etxotoracted concen40tr0ation of the c4a0libration standar1d00i0s equal toXfiCxmitms dindivtiva-l6 concentration, due to the concentration of the standard during the extraction (SPE). XC = extracted calibration standard. Page 4 o f 7 Page 32 o f 57 Page 83 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001780 ________________________ ANALYTICAL METHOD________________________ Method of Analysis for the DeterminatiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water by 9.2.3 9.2.4 9.2.3 AasASettltot2zeorereCfrnoasattltoalsente6avdxnoatCdrlrauda, cmrsudtpeeedxsstootcarlanautcwldtiitboeocrdnoaw.nt(eicroeeenkansgts.retaantntiodbnalrsadnoskfi)nstma1nu5ds-amt rbdLespmporlaeyypparbroeepdpyrlweepnitaehrteuedbaceahss needed. 10.0 Batch Set Up 10.1 oEnaechrebaagtcehntocfosnatmroplle(smeexthtroadctebdla(ntykpiucsailnlyg 2H0PoLrClewssa)temr)usatnidncltuwdoe aretalgeeanstt 10.2 cpiRnoreontqhctureeoidrlquesumraafellointrryettsicafoifseovsdruerrfyaianetflcoderkapnthnloaedwnblnaafobtccrohotr.hanitcsoerpnyrtordajueticpotln.icsate(lsabandcosnptirkoels spike) will be to verify specified 11.0 Sample Extraction 11.1 11.2 1111..34 11.5 mCLEAMfi1no5olonitluexoalnamtaodledswwSyLiusOztweearipeloedmmilon)ts4hbl.paLy0ymltpe~hpm5rp5eooolmLnlpeCmysyLcpoiLlsuorefoosnnsSifp1deanP0yHimgtcE0liPeeope%nnLlnlceeteCaercmrdioctftwrereruCointgdaahsitetgprapeierntSrfoausuoPr(ybglt~(E.ie1Leos2nCctC(gadu/fo,rMrboitnoferl6laipSssedla//mcgs(MmvtfeeLooc.Sp5r)l)l.ut.eDimmbfDyidysLeicolap*uasonarted5fsondsteemeienlllteuduoLgtaea)4ctd.te1e0o,0.lrmiuenmmpLtoLlnawcgrmeuirtanheldtidhudwraayaantetnoeddlr 12.0 Chromatography 12.1 12.2 12.3 12.4 Ue(cgbfAISLamitnonxaeneotCsntlulajntageeleir/nsoelabiraMcytndescrwrctlzabpnnacaitSetetneetertoiheind/idddreuoMrdeisgsaennnsebrsfcScoatdyoaasaslmfftsumnrelbaoetPispdtdtabnerexyhFlendrtetsoeadwOaaardstaafettm.aarsieAicmdnneoreeottdscanhne.xcauoldemtonynnrecsArttavuutdacereacoenesarnntbvstsrlacfedidypeyelabdbeytaosleraol5itrnoaibcicd-tnfctdfhrfh1asioeaaioel0eanalrtsinmxibrgtfsosastqirerarasnrnaattueasmtoy.mtdagtaciasonpnratapbeterntdlntalddeeisealdnt,ssearsdi.sadsitlosttnaiasaasaenorstjAmntndent.iufddcsn.piisatvantlmeiarereejnEdddenrugLsoaxscsspna)tritat1ni.reldmtomat/erxenpcsauIftroetrhnowrnseiredenrteadceetstieiiaeicftbbtgvdaisvhoeeeshteneeneaagdt,drrmnciiiynananasedcrpgannncnaad5mldlitrsoeun-rede1apdfncgss,t0fleueptieoieotdreorm.lxsvnelaiafotneukarmslwstastaeoeactpvtrtatltseeeabhehoreladleeseestlf Page 5 of7 Page 33 o f 57 Page 84 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001780 | ANALYTICAL m e t h o d I Method of Analysis for the DeterminatiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water by 12.3 evsSoxeafcrmtsewupesadlercesatraseliynsbspdrtoaaerntmdiso.ernessshptaoonundlsdaersdnsohctooneuxcldecnebeterdaftusiortatnhnedursaidrndiglurMteesdapsoasnnLsdyernse.xan3Aa.l3nyyz(oesdra.emqpulievsalethnat)t 13.0 Acceptance Criteria 13.1 Cofhr4o1m3aatmogur.amThmeu4s1t 3shaomwuappaereanktocfoarrdesapuognhdtesrtoionthaet P3F6O9 Aamauniforno,mwahiplaerethnet 13.2 13.3 tedbmMR1hnla3eeuaetu0ciinstgrro%htkehvokbtcednseesoreohrionbtewoibtlsoouaatnnainlofndivk(fnss3asaecbl6Pmdoume9FnepauOstaelnrs.emvoAdtsaluIntlashfu)sohtpeaartoietlekeeccupndveoolrtdsenenilsrtbtasebaerynoinegnsdltretsrehstPmeatpem-FhtaieeOekutxarresnAtlitroxtahfasbalacassylenttplseositrld5kfeeo.0et-vcuoesaenxtrAlsmgsbtdirn/doeauLgyetncser,tteremdttmahdhbitoea.eeeitxnnrrabieicdtxaehcetieawn.sfpnepetwrieatkehnb-ebeelel7xoaL0tunlrO-iatkm1scQ3istidt0i.asoe%m,nI7ptfho0lieeasf 13.4 13.5 TewHiAEnxhraonjcreerwyolcruarteccednvToadeteelr.derirdsb,e.tmrl,taahuttmieisootanntyontsocabttaloenenedfexufaxicmrccedilebeudenfdorte2udo0(nRf%df)reotxoomftrofbartecthhtceeeaadlcstiobtacatlraatcaliluitsbitloniarcnuataitmoilocnbonueurorvstfletoiasetnfhrdegebaexycrntdareuaslricsbattithreneadagdttiostchmntoaenuucdslHudtarurvgbdbeeees. 13.6 Rastp0eap.tn9erdo9nap2trirodi(ansRtoe2trimtsht0eee.sp9rs8ebl5eem)tv.wuasentetInfsbeectsatoaltfniabdksraeaamnrtdiopstnloeasnraseddhsjuousluastlsmtdpifbnaleelslstrreuomamunutaesslnitydtzeneoodtpt.heedrsareitfitolnimm, oiatrsne,d ththene than an4a%nalwytiitchainl raunnatnhaelnyttihcealserut nm.uIsft rbeeternetainoanlytizmede.drift exceeds this limit within 14.0 Calculations 14.1 UbgaessneeedrthateoendfopblelyoawtkhieanrgMeaea)qssuuaLstiiynongnxtthsooefctsawtlacanurdelaaptredrotghcruearmvame: o(luinnteaorf rPeFgOreAssifoonunpdar(aimn entge/rLs), PFOA found (ng/L) = (Peak aresalo-pientercept! x DF DF = factor by which the final volume was diluted, if necessary. Pase 6 of 7 Page 34 o f 57 Page 85 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001780 1 ANALYTICAL m e t h o d Method of Analysis for the DeterminatiLoCn/oMfSP/eMrfSluorooctanoic Acid (PFOA) in Water by 14.2 Fthoerfsoalmlopwliensgfeoqrtuiafiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp. rior to extraction, use Recovery (%) = f total analyte found (ng/L) - analyte found in control (ng/L)] ^ analyte added (ng/L) Page 7 of7 Page 35 o f 57 Page 86 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLlMS Protocol Number: P0003268 ANALYTICAL METHOD Method Number: V000178! Method of Analysis for the DeterminaLtiCon/MoSf/PMerSfluorooctanolc Acid (PFOA) in Soil by Analytical Testing Facility: Exygen Research S30ta5t8e RCeoslleeagrec,hPDAriv16e801 Approved By: TPaeuclhnCiocanlnLolelayder, LCC-M-Si, ELxy'gen Research Date|0 lz A ,M Date Total Pages: 7 Page 36 o f 57 Page 87 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygea Research Method Number V000178I _______________________ ANALYTICAL METHOD________________________ Method of Analysis for the DeterminaLtiCon/MoSf /PMerSfluorooctanoic Acid (PFOA) in Soil by 1.0 Scope TaScphieidsctmrboyemtheHotridgichisDtPeoetebrfceotoermrm(apLnlCocye/MedLSif/qMouriStdh)eiCnihssoroolialm.tiaotnogarnadphqyuanctoiutaptlieodn otof paerftlaunodroemoctaMnoasics 2.0 Safety 22..12 pACrolewncasauuyltsitootnhbses.earpvperosapfreialtaebMorSatDorSybperfaocrteicheas.ndling any chemical for proper safety 3.0 Sample Requirement 333...123 33..54 NASAStperaaolmtolmmljspseeppaaaecllmmsrtee.atspptcu1lloe5erselstplg.oemrrocoetucfdiseottesnssbrtiepenfsrgrtaohimgcioseeprdrnolaueeutreegfeddhoselrdywesxhmfioltolriruxablscedeotdiiolsbbnpse.eeafcmoirafpeillelebodsew.iinendgtshateomspaelmeqdupilfliionbrgreapxteltarantcotfioorrno.tohmis 4.0 Reagents and Standards 4444....1342 AWMPemearfttmhleuaroon-nroioHulom-PctLHaACnPcoLegitcCraaAtdegecr-aiddAe-.CS.iSg.mRae-aAglednritcGhrade 5.0 Instrument and Equipment 5.1 555555......567234 D5AA1Asp1o052Linlds5mmvahpce-lemoiovyLLgnsnitLhtciaddnscebiieaLsslpeclteppDqoetbooeurmPcafssdioEoaalpiactrblbpolnmnrlleeoceeaacdaperptpnritwcopraoocaanewelliwyytpdths-ppaemldbrr(miaooq5aloeppu0tvuMayiy-oatd1hllfrafee0oisarnbnc0rsebeoehupalStrLccedetopleeai,emvennnks1cogtt.arr0tiltrniiut0offootmuu-gem20gggre0a.eeer00pati0tetunthuuir0Ljobbe0()neeccL1,ssatCao..pgnr/a.MdbcalqSepu/aMaobnSfltei)tp.aoutifmoinnp.jiencgtinugp 5t-o2002 555555......1891111032 2DAUWSPilumtasEtrptoLaeopvsrcsosiaaplnceSbeuiaelctuetrpembHpsPaiPt(maph1Lke.a0tCVnt0ei-asvf1.oci0al6d0l.0kcicpt.L(lga)ndtC1l08-1S0P0EpcLa)r,trwidigthesd.isposable tips. Page 2 of 7 Page 37 o f 57 Page 88 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 Exygen Research Method Number V000178I | ANALYTICAL METHOD Method of Analysis for the DeterminaLtiCon/MoSf /PMerSfluorooctanoic Acid (PFOA) in Soil by 55..1154 CWernistrt-ifaucgtieocnasphaabkleero. f spinning 50 mL polypropylene tubes at 5000 rpm. 6.0 Chromatographic System 6.1 66..23 TM(AGMPern/ooamNabbdlp:iiyilleete8enir2caPPta5thhPul0aarr5Coess-ee:go0rl5((ua3AB2mm0)1):n3C:::0F) l2MuomeptMhhaasnAeomlRmP o(KnieuymstoAnceetSacteieinntiWfica)t,e2r .1 mm x 50 mm, Sp Time (min) 0.0 228102....0050 %26625555A 65 %3733755555B Flow Rate (m.L00000.A....33333njn) 666...867 RIQnuujenacnTttiiiotmanteiV:ono-:lu2mP3eeam:kin1A5urtepeasL.-(ceaxntebrneailnsctraenadsearddtocaalsibmrauticohnacsu5rv0ep. L). TophteimabizoevethceoHndPiLtiConssysatreemin.tended as a guide and may be changed in order to 7.0 MS/MS System 7.1 MPFoOdAe:. Electrospray Negative MRM mode, monitoring 413 --> 369 m/z for TophteimabizoevethceoMndSitMioSnssyasrteemin.tended as a guide and may be changed in order to 8.0 Preparation of Solutions 8.1 Mobile Phase 8.1.1 a2mmmMonaiummmaocneituamte taoce1t0a0te0 imnLwoaftewraitserp.repared by adding 0.154 g of Alternate volumes may be prepared. Page 3 o f 7 Page 38 o f S7 Page 89 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygco Research Method Number V0001781 .________ ANALYTICAL METHOD Method of Analysis for the DeterminaLtiCon/MoSf P/MerSfluorooctanoic Acid (PFOA) in Soil by 9.0 Standard Preparation 9.1 999999S......t111111a......n363421darTammafAAAAmimaP1omdnrp0hrofe0LL11eLpSe0ate1m1a22t.hrptm.o1.h0no33ooo0sa01aaatftn1cxfLf2rpohmmnlplpokei5thytecgomgghlp/hLLtkeoFalfm/e/diigeammacnfoiLaLa/stL1naL1mr1ettnLLDaDt.lte0o00lhdiaLLycPfsfP10eofpfoiptDkfo12oEEc4agforgfp3r2ra0Pntop/srt/tgibbm5t.CiotmidErmrf1ifi/foo-etiolamfiiLmicutLptLccibafnrttactpiaaldalLnoLcsiteaesSLttrgoidtoa.ii.to(aotsoL/ooDniltlctlmonoeiualinnuoDoPuo.nolrttrLsunisetEnsPirfoiosootoeo.Ei-nosslnllcbosnu1otuulotaonbuttle0tttoilbtuoioitdoutoo0tiltltaoonteaientnifolnp.oeoffoafonosgi.nironfnff/faropamaiPPPrtnlulafoeFFFLarvvPOlimOtOootoaFoyvAAllaAOufu)boxfmmePliAiiaiiunsmssFnseemapdtppOiuloosorerrmAredeeffvpeopppiod1r1lpaaafbuel00rreruypit01e0eenerma0dddiwwwroat0eeobbbdeiidrttwyyyiehhog1ofibbb0hbfrtfmmyhir0rirgni6iiee1nnnbmegmtt0ghhmggrr0eiLaaaiii1nnotnnnnth0ogwgnoogwgarilltmninih1t11aitoihgnsnh0g00tl 9.2 Standard Calibration Solutions 9.2.1 9.2.2 TcpiLdarhCeeleinp/bMtarfircaoSeatldi/lloMotanwoSsissnntacgeamaenliddpisbealerdarasd.t.tsiyopanircesatlparneoxdcaaemrsdspseldea:rteahdrpodruietgpiohanreathdlecionenxHctreaPncLttriCaotniwonpasrtoemrc.eadyuTrbheee, F inal C oncentration Fortification Volum e o f C oncentration o f C alibration o f Fortification Vo lu m e Fortified Control C alibration Standard ID Solution (nob) (u L ) Sam ple (m L ) Standard (p o t)* (exam ple) 0 0 40 0 XC m m ddyy-0 10 100 4 0 25 XC m m ddyy-1 10 200 40 50 XCm m ddyy-2 10 4 0 0 40 100 XCm m ddyy-3 100 100 40 250 XCm m ddyy-4 100 200 40 500 XC m m ddyy-5 * The e1x0tr0acted concen40tr0ation of the c4a0libration standar1d00i0s equal to X8Cxmitms idnditwia-l6 cXoCnc=enetxrtartaioctne,ddcuaelitbortahtieocnosntacnendtarradt.ion of the standard during the extraction (SPE). Page 4 of 7 Page 39 o f 57 Page 90 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 Exygen Research Method Number V000178! _______________________ ANALYTICAL METHOD________________________ Method of Analysis for the DeterminaLtiCon/MoSf P/MerSfluorooctanoic Acid (PFOA) in Soil by 9.2.3 9.2.4 saSAettot2zroeeCfroasttloalsnte6adxnatCdrraa,dcrsudtpeedxstootcrlaautwcltiitboeordnwa.t(eiroeenkasgs.etanntdbalradnski)nm1u5s-mt bLepporleypparorepdylwenitehtuebacehs 9.2.5 Aneletedrenda.te volumes and concentrations of standards may be prepared as 10.0 Batch Set Up 10.1 10.2 pociREnornaeonetcqchthurereoiedrbqlauesagumrteaacfnellhointrtryetoctsciofafofisnseovstadruremorrfyalipaen(tlflcmeodeskreanpttenhholxadeowtnrdblnaaafcbobttclcreoahodrtn.hankt(icosteuyrpnsypritionrdcajgauetlipcl5otyln.imcs2aL0t(elsooarbfanmledcseostsnh)ptairmknooeulsls)tswapiniinlkdlcelbu)twedteosopraeetvcaielgferieaiefnsdytt 11.0 Sample Extraction 11.1 111111...342 1111..56 11.7 11.8 11.9 eEALcfBCCnTA1Wole5eolurnerodlunaeiealnaanmdntotdnidtltedrggeywresLi5iih.ffdztwf(eueitmedup,odhg5riegortsnLeetechbleahgypaytmotevfupnlh-ooafo5b5rtpterc)uofmlelumeeb-p.sCmte1mseyahlLtiis0mLlhsueedeoastnpmoSaisnf1uelnnaPoei0HapgmdncEln0Pueiea%pmtnnuLtolnclteetleioCadrtscxmrri4taftsao5rww0ruehstoni0tgodaaes-hmne3tlkgpmatleiheer0)ntLrca.Luse0oo(ybbl~0n(w.peca1Losott2aihCptlnC(ghywdm/fda,rMpoinrio.nwtrli6dilaspoSoeatl/p/mscnstMavoyeetecLonrlcdSet5)l)ii.nuc.ionCmaebmntDyneLecstohhepf=enSaooanktP5fsorr5es-iEtemf0ir1nullu5efLcggmotaa)emc.trrL1eot-tir01ulniuidb5punmmgoetteomeslLnsy.i.(pgnrfmurrouoDanetrdpettidhiusysfr.caalyyeanlenroaddels 12.0 Chromatography 12.1 12.2 12.3 abiALmSInnnetCntujagaees/nlircMtynedstzpnnbaSteteerihin/ddrrMeisgsensesScoadaasmlfmunebPspdtdeeyFletesowdOaatsfemt.eAimneeotnh.xacuentoenrArvtaareecoennrtscafyedpaldeyol5aoit-nbcic1fcdhra0aailanltsisibtgsoaasrenmnatato.mdtpiasoalprtentadlseln,.edsasstAaasaertmntsd.fdpaiavnlmreeEdauxasolstntretrdmmranpcufoatroseertrtiedctvieefcbdis,oeetenaadnnciansedeancnanmdltrutrdiapdrsftleeioeodmlsnlieonutawtlstoeotvftteahbhlleeesl Page 5 of 7 Page 40 o f 57 Page 91 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V001781 _______________________ ANALYTICAL METHOD________________________ Method of Analysis for the DeterminaLtiCon/MofSP/MerSfluorooctanoic Acid (PFOA) in Soil by extracted calibration standards may be injected at the beginning of a set (cftoaollliboacrwacetoiduonnbtystfaoenrxdtaraarscdetsceodmnucdasstliebbteroatthfioeenxftirrsastatcntaedndadrsdltasasntidninaterjderscsp)ti.eornsIenidneaietvhseearmrycpa5lse-e1s,0eet.sxatrmacptleeds 12.4 12.5 eSgvsUoxeeasfcrnmetseewupersladaliertnceeseatrdasaleiynrsfbospdrtsroaaetrttnmaihdsnoe.ednreaasssnrhptdaaoolnuyncdtlsudeaerrsvbdneysoschtlooinnefuoexcldraecrnebqetrereudagaftanrisoerttatisnthsnaeiudtorisaondirnndiu.lgusritMenesLgdpaisoan1snn/eLxsdayerwrsne.exsaitnga3Aahn.l3dtnyianyz(roegddsroa.ecmfquppurevliaeveksaslaethrnaeartae)t 13.0 Acceptance Criteria 13.1 13.2 13.3 13.4 13.5 TEHeiAwRteMdbmo1Cnhxnhlar3feoanjheaucreteue0rcwy4ioinrsltcrgrr%oouh1trkateehvccdmeokn3bvTotacdeednsteeesaloerr.deaeohrirtriodnsmbtb,oeewoitb.mtlrsgol,ouuaataantnhralin.ufottmadnieiivks(ofmonsst3Taasannectbyl6Pomhdonumme9tsFenoecapbtauuOstataloelen4rs.senmveoAd1ttnesdfael3xuufIsntlaxihaschfu)smorccahtepoeadaritlmobeietewlukeeecducenpfdundevooorltreadsten2eunpidolsbr(t0pntaaseabRrefyed%rnofinegeas)nrdelteonrkttsxroeohtsmPtmeftaotperofmF-chbtaaiefroeOekttcetuxahharrretsnctArileeetarxotdeaahdafsslbalacacstaissypuoelbnttactplsoaeotgsrlaritaldtcna5khfeleiloui.tds0-tetvcbiutloeesonsaiearnxrtcnAraultstmgtdasbiitoimroonil/deoauocLgnnytebntcosunerh,teteurraeeotmdtrmvhatsthdbiflteetPoaee.o3ieaistextnFnr6nfrhabrieiO9dcdextgeaebhcaeAtexaienwaycr.snftmdnpaepreeasualtwriureiantecksbahnbit-tietfborheneeleraeln7daxgodoatLt,0itmnulortsO-iwcakthmm1ntsoacaQeh3isutniudic0ipt.asdlelosHum%aedt,anrruI7rvptetfgdbbhh0oenlieeeseeesa.ft 13.6 sRat0paep.nt9erd9ona2ptrirodi(asnRtoe1trimtsht0eee.sp9rs8eb5leem)tv.wuasenletInfsbeecstatoaltifnabkdsraeaamnrtdiopstnloeasnraseddhsjuousluastlsmtdpfibnaleelslstrreuomamunutaesslnitydtzeneoodtpt.heedrsareitifotlnimm, oiatrsne,d thtehne than an4a%nalwytiitchainl raunnatnhaelnyttihcealserut nm.uIsft rbeeternetainoanlytizmede.drift exceeds this limit within Page 6 of 7 Page 41 o f 57 Page 92 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001781 | ANALYTICAL m e t h o d Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS 14.0 Calculations 14.1 UbgeasnseeedtrhaoetendfopblleyoawtkhienagrMeaea)qsusuasLtiiynongnxtthsooefctsawtlacanurdelaaptrerdotghcruearmavme: o(ulinnteaorf rPeFgOreAssifoonunpdar(aimn entge/rLs), PFOA found (ng/L) = (Peak area - intercept! x DF slope DF = factor by which the final volume was diluted, if necessary. 14.2 Fthoerfsoalmlopwliensgfeoqrtuiafiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp.rior to extraction, use Recovery (%) = [total analyte found (ng/L) - analyte found in control (ng/L)] ; analyte added (ng/L) 14.3 nUgs/eg t(hpepbf)o.llowing equation to convert the amount of PFOA found in ng/L to PFOA found (ppb) = (PFOA foundsafmnpgl/eLlwxeivgohltu(m5ege)xtracted /0.Q4L11 14.4 bUasseedthoen fdorlylowweinigghte.quation to calculate the amount of PFOA found in ppb PFOA found (ppb) dry weight = PFOA found (ppb) x [100%/total solids(%)] Page 7 of 7 Page 42 o f 57 Page 93 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 ANALYTICAL METHOD Method Number; V0001782 Method of Analysis for the SDeedteimrmenintabtyioLnCo7fMPeSr/fMluSorooctanoic A cid (PFOA) in Analytical Testing Facility: ES30txa5yt8egeCRnoeRslleeeagsreeca,hrPcDAhriv16e801 Approved By: PTaeuchl nCiocanlnLolelayLder, LCC-MSJ, ExLygIen Research Date lOT-fe/o-/ Voihc'ne PPFrlea7shiedretnytOpe/rati-ons, Exygen Research Date Total Pages: 7 Page 43 o f 57 Page 94 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 | ANALYTICAL METHOD | Method of Analysis for the DeterminatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 1.0 Scope TaScphieidsctmrboyemtheHotridgichisDtPeoetebrfceotoremrm(apLnlCocey/MedLSif/qMouriStdh)eiCnishsoreoldamitmiaoetnongta.rnadphqyuancotiutaptlieodn otof pearftlaunodroemoctaMnoasics 2.0 Safety 22..12 ApCrolewncsaauuyltstiootnhbses.earpvperosapfreialtaebMorSatDoSrybperfaocrteicheas.ndling any chemical for proper safety 3.0 Sample Requirement 333...312 33..34 pSASNtAeraalomotlmmjlspseeppaaceallmmtrsee.atspptc3ulloee0rselstplg.oemrrcooetucfidsoettesnssbreitpenfsrrgtoaihgmcioseerpdronalueuetreegefddhoselrydwsehmxiflootlirruxablscedeetdidosbibnpmee.efeconirafteilelsboadewmiinenpdglethssat.eomspaelmeqdupilfliionbrgreapxteltarantcotfioorrno.tohmis 4.0 Reagents and Standards 44444.....12343 PMAAWecmeraeftmthtlieuacoronn-AroHoilucoPim-cdLtHa-ACnPRcoLgeiecCtraaagAtdgeeecrn-aitddAge-r.CaSd.iSeg.mRae-aAglednritcGhrade 3.0 Instrument and Equipment 5.1 55..23 AAspAonLladvhlceyeiovgntniihtccnsaeelepctqobeteuracfdiloopatrnlpolmceeedacatntcwarcaaneipwtdahebldimalqaeutvMoaiadfrfaiorsaecrsbahplSdreeoipanmevkgcoatilttrnuoootmgem0gr.e0aerp0taient0hrij0oe(1ncLcatCagopn.r/aMdbclaqSepu/aMaobnSfltei)tp.aoutifmoinnp.jiencgtinugp 5t-o2002 555555555.........119187546120 SD2AW5D11P052imuias5EstmmtppLo-emoovpLLrcssasiLapladcdSebbeuiiLaessltluetrepDppemoHopsmPPssiPE(mapaai1ckLbbea0nrtllCnoVt0aeeeipr-afpvspr1ioc.ooipo0laweldl60lyyt.0-spkpcmicrr(ptoo5o.(Lpp0ulyyg-ta1hll)nee0dtbnn0Coeeu11tLcct08lee,-en1nSs1t0t.Pr0r0ii0Effu-up2cggL0aee)r0,ttturuuwiLbdbi)eegt.hsse..sd.isposa.ble tips. Page 2 of7 Page 44 o f 57 Page 95 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 Exygeo Research Method Number VOOO1782 I___________________________ ANALYTICAL METHOD | Method of Analysis for the DeterminatioLnCo/fMPSer/MiluSorooctanoic Acid (PFOA) in Sediment by 555...111435 VCWeornritstert-ixfaeucrgt.ieoncasphaabkleer.o' f spinning 50 mL polypropylene tubes at 3000 ipm. 6.0 Chromatographic System 6.1 Analytical Column: Fluophase RP (Keystone Scientific), 2.1 mm x 50 mm, 5p 6666....5234 GM(TMPero/oamNbbdp:iiilleeee8nr2aPPt5thhPu0aarr5eoss-e;eg0r((53aBA2m0)1):3C::0) M2 metMhanAoml monium Acetate in Water Tim2208120....0(.0050min) %6622655555A %3337755555B FimloLw00000/.....m33333Riantel 666...786 QRInuujeancnTttiiiotmanteiVo:no-:lu2Pm3eeam:kin1A5urtepeasL.-(ceaxntebrneailnsctraenadsaerddtocaalisbmrauticohnacsu5rv0ep. L). TophteimabizoevethceoHndPiLtiConssyastreemin.tended as a guide and may be changed in order to 7.0 MS/MS System 7.1 Mode: Electrospray Negative MRM mode, monitoring 413 - 369 m/z for PFOA. TophteimabizoevethceoMndSitMioSnssyasrteeimnt.ended as a guide and may be changed in order to 8.0 Preparation of Solutions 8.1 Mobile Phase 8.1.1 a2mmmMoniaummmaocneituamte taoce1t0a0te0 minLwoaftewraitserp. repared by adding 0.154 g of Page 3of7 Page 45 o f 57 Page 96 of 130 MPI Protocol P00003268; Intrim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 __________________________ ANALYTICAL METHOD__________________ j Method of Analysis for the DeterminatioLnCo/fMPSer/MfluSorooctanoic Acid (PFOA) in Sediment by 8.2 Extraction Solutions 8.2.1 11%000acmetLicoafcwidatienr.water is prepared by adding 10 mL of acetic acid to Alternate volumes may be prepared. ' 9.0 Standard Preparation 9.1 Standard Stock/FortiiicBtion Solution 9.1.1 9.1.2 9.1.3 9.1.4 9.1.5 9.1.6 TmAAaommaafAmmiAP1nrp0hrfoe1LLe1Lep00a1et1m2at2hp.r.hm.0oS1noo05oa0sa1ataft1nffxL2rpmhonmptpleo5itygthecogmghlhpLLt/koealm//eidmeigmamcnfiLLasa/tL1an1mL1tetLnLaDDt.l0oe00lhadLLycfsPP10efopfoptDko1f2oEEa4gfropfg52rrnP0tos/prttg/bib5m.CdioitEmmrfr1f/fioo-tielamifimiLcuttLcLpcbirfattactdaiplaLlaoLnicsteeastLtgoritdoia..i(ototaLson/oiDcltlltmooneiuanDnouioP.oonlrtrtLsuneisPsEinrfoosootoeE.i-olnsslnlcobsu1utoulotabontuttt0eltiolbooituitdouot0otilttlooanteatnienfilonp.oeofaoffoons.ginironfnfff/arpoPPamiaPrtnluflaFoeFFLaPrvvOOOlimtoFotaoovyAAAllaOufu)boxfmmPelAiiaiiiunssmsFnesemappdtpOiuloosorrermAeedreffvpeoppipo1dl1raapbafuel00rrreuyipte0e01enermadd0idwwworta0eeobbdbeiidrwttyiyyehhgo1obfibbbh0ftrmfmyhrrr0ii6ngiii1eennnmbmteg0thghggmrr0eaLiaaiii1ntnnnnonth0gowoggngowalirltmninih111taiotighns0nhg00tl 9.2 Standard Calibration Solutions 9.2.1 9.2.2 oTLfhCet/hMefoS0l/.l1MowpSignc/gmaliLisbrfaaottriytoipnfiiccsaatatlinoednxaasrmdoslpulateiro:enap.dredpitaiorendalincomnectehnatnraotliovnias dilution may be SooCflouFntoicorentnif(tirncagat/timioonnL) 100 too 100 10 5 2 V(omluLm)e 10 5 2 10 10 10 Dil(umteLd) to 100 too too 100 100 100 Con(ncFgei/nnmtarlLat)ion 10.0 5.0 21..00 0.5 0.2 Page 4 of7 Page 46 o f 57 Page 97 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 |_________;__________________ ANALYTICAL METHOD______________ | Method of Analysis for the DeterminatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 9.2.3 9.2.4 AnSaettloet2edrereCndaa.tltolec6vaolCilbu,rmuapteisotonanssditxacnmodnoacnrdethnsstir.nati1o2n5s-mofLstLaDndPaErdnsamrroaywb-me opurethpabroedttleass 10.0 Batch Set Up 10.1 10.2 oERcinonaenetcqhchueeiunbrqenaturmttaracetelhiianottytonesdsfafs(soslacaurmobrfanipcentlorlceodnesltarpeonlxaaldtnnsrdalpfaciobktretoewdtr)haoti(tosotyrvpupyerniorcdtijraufeeylcpaltyltp.iecrd2oa0tceecsodoruanrntlaerdolsslrss)epcimkofeovusresttriwyfiiineflldoclrbutedahetespbaektacnticlofehiwae.sdnt 11.0 Sample Extraction 11.1 11.2 1111..34 11.5 AnCCLffWooeoeodlreeanlndd-oidtdg6ewr3hiid0t5f(ei,udod5mrmgenecbegiLpanyttlnuhohao2tteecf)e0festsC1tum.alhi%ibmsdLeepsaaSoslncPaaefedmtEHti-imnpc3Pctl0iLoeaax0rcCtSoiw0rdOniwed,rlpgamclt)mtehae.Lsperf,((poc1v~orool-n2gry2dt,pde0ixrrt6iooomappmnn/iyensdLledue)cntse)hCeb.say.uckDeeponSaotPsnrnisEofiuatngcglweaetrr1tictr0suoitbdlmuaegmcseLt.in(ofmonrDuersttniihhsfdaacynkaryroeadsrl 11.6 cAeeludnadttrei2f.u0gemLtuboef. mCeatph,anvoolrtteoxthaendsesdhiamkeentonlefat iwnritshte abcotitotonmshoafkethrefo5r0 -m3L0 111111...879 11.10 11.11 11.12 11.13 ACDmEWAeSCf1ol5PeloenudiluannEclnaamdstouattledhrweyctLntiiehafsttwtecsiurehepodot.tigheortnslmibheelladceyaymemtgocp-htelts25prheeuee.o0altdmcetphnmuomsyainobnnLlnulLeedwosssntitoloC1ieenatof0phgit-csnH02-e4e%t13SPno0l1e0mPtL0.trc8m0EhiCLt.fe0mreucowotgsaLrhsapferapamtmmtornrteaiuoefdreybfltgwS(o.ehLe-rPsaaC-Etn(2C(e12f/ordoMic0lngrl.aalao,Srmenltp6C/cdriMv/itnosmdoleul5SgollcLtueea.e)c)mm.d.st.bLeCDotyhn=ooeopllat5fneehsolcemesuttliauLnsltteaheg)et.tceecao1eon0nilldnudumatmoactLedon.gdnmrrdaiueitdttnihutooadanntrteeyhoddel Page 5 of 7 Page 47 o f 57 Page 98 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygeo Research Method Number V0001782 | ANALYTICAL METHOD | Method of Analysis for the DeterminatioLnCo/fMPSerffMluSorooctanoic Add (PFOA) in Sediment by 12.0 Chromatography 12.1 12.2 SLaInntCajaen/lMcydtzaSetrh/ddMesssSoaamfmPspeyFlesOatsem.Amo.cuonArtreoscfpaeolainbcdrhaintsitgoanntod-asatrtadln,edasasartmdfpivlmeeuoasnrtdmpforoerrectiecfdioeendcaesannmdtraptflioeolnlionwlteovteahllesl 12.3 12.4 12.3 gvseSUbbsssimAnotttxeeeeaaaasnjufncrgtmeennntwsseeiwcdddutnpeerteaaalasaidnnblieorerrtrneitndcddenesinearsdtssrigaeas)neleii.nrynfsvmcibaonspdslearnsturaetoaareIetdydtystrtnanmrhidaenssomeaob3d.epdenrte-feeaiapi1tsrnsntsrlhie0hshpdetnaexeaaoeoljrssdntnyeuncreadectlacstuamedenat.ceanrevrdtsspbvaddeneelyelsdoero,yschayslttfotoic.icncnfuea5ataoeacxhll-lAidlare1cisebbrnsae0srbqrebmertaaertueaedts.atpignagiafotonlurimisneeonnarttiasntplnthstssnalieseietenudtortatrisa.sngaonnidnrandn(duoidtt.gaSliosaufvrtrirdMteaenadea,snsLgdscapdsaicmseo1naanmsotr/nneuLxudsdauefsynserowntsrntstltem.elxibsoarfitbeeougnaw3eArshan.testl3dhtnedyaiieanbtnyz(regecobsdofedlsyroiufaci.rnedcfmsoccqttuepnaaepudrelldraviliisaebvbnepkassrardseeatalarettttslrhiiantaooeehoratsadnnee)tft 13.0 Acceptance Criteria 13.1 Chromatogram must show a peak of a daughter ion at 369 amu from a parent 13.2 13.3 13.4 stRbewodMA1hanla3feaenametu0crin4iytgrrro%ph1kaehvlcok3neteadncstesrleameoorhiidmbtbenwoiu.lsortouausnaan.ntloftidinkv(bfos3Tssaeacnb6lmhouomPe9esnebpFtutsaatel4Ora.semvno1tisAdaln3uInlaefssu)oradphaadratmtioetakeccupunfelodoloredsdnenpuvstbttaanebaherynrldoineesendltnttserghostmPnetpreF-chteabiieokOeratexaerrtenitAlerxroaesrafaessalcassstyptltthtplsomeoasaitldntkfenuio.dsevtcsuotssaet0itcrAlsb.tmsbd2aoiendoleugyenttrnsorheetegretu-dmham/ebtimtPleoxaeeiixttFenLrrarbirOeia,cdtxechcbeAtttiwea.yhesfpnpdeeatunri.eantekshnbi-ieoaelnee7nxgoL0n,tulr-eOitwat1hmwscQ3ehiitd0iti.lsboHe%e,lnauI7ttfnghho0ikeeeasf 13.3 aseTHiEntpx0harojpcrenew9olrcduo9rteadcep2vrToderdeidr.e(rasrsR,etotmel,2tarhutmsteishot0teaent.pyo9nrst8eoacb5ltloeem)eve.nfueaxufsxnicmtccteIilebfsebuedenedctrteao2dolt0(fiaRbf%ksfrra)eeaomnxtomiftoproftanlroettchhstcreeeaesaddhslctijuoobaculutlratsaclastllduitbilfiobnarnanueatlsiltmotriroecnubouanmuenrortvasesfetlnioaysdttnfhzeedegeodaextp.rchntdeareeraslsaricebatttitrheoealdandittmi,oscimntatoasnnuu,cddsludtatrhrvtedhbbenseee. Page6of7 Page 48 o f 57 Page 99 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001782 | ANALYTICAL METHOD | Method of Analysis for the DeterminatioLnCo/fMPSer/fMluSorooctanoic Acid (PFOA) in Sediment by 13.6 Retention times between standards and samples must not drift more than an4a%nalwytiitchainl raunnatnhaelnyttihcealserutnm.uIsft rbeeternetainoanlytizmede.drift exceeds this limit within 14.0 Calculations 14.1 gUbeasnseeedrthaetoenfdopblleyoawtkhienagrMeeaaq)susuaLstiiyonnngxttoshoecfatswltcauanrldaeatperrdtohgceruaarmvme:ou(lnitneoafrPrFeOgrAesfsoiounndp(airnamnge/tmerLs), PFOA found (ng/mL) = fPeak arselaop-eintercept) x DF DF = factor by which the final volume was diluted, if necessary. 14.2 Fthoer fsoalmlopwliensgfeoqrtuiafiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOvAeryp.rior to extraction, use Recovery (%) = [ total analyte found (ng/mL) analyte found in control (ng/mL)1 analyte added (ng/mL) 14.3 Ungs/egt(hpepbfo).llowing equation to convert the amount of PFOA found in ng/mL to PFOA found (ppb) = fPFOA fousnadmCpnleg/wmeLiIgxhtf(in5agl)volume IS mUl 14.4 Ufosuendthien pfoplblobwaisnegd eoqnudartyiown e(iigfhnt.ecessary) to calculate the amount of PFOA PFOA found (ppb) dry weight = PFOA found (ppb) x [100% / total solids(%)] Page 7 of7 Page 49 o f 57 Page 100 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 ANALYTICAL METHOD Method Number; V0001783 Method of Analysis for the DeatnedrmCilnaamtisobnyoLf CPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish Analytical Testing Facility: S3E0txa5yt8egeRCnoeRslleeeagsreeca,hrPcDAhri1v6e801 Approved By: TPaeuchl nCiocanlnoLlelayder, LC-MS, Exygen Research DaHteli-fe/o rf Voihcne'PF/rl*ae>hsiedretynt, Operations, Exygen Research Date Total Pages: 8 Page 50 o f 57 Page 101 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001783 __________________________ ANALYTICAL m e t h o d __________________________ Method ofAnalysis for the DetermCilnamatisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and l .0 Scope TaScphieidsctmbroyemthHeotirdgichisDtPoeetebrfceotoermrm(apLnlCocye/MedLSif/qMouriStdh)eiCnihsforioslahmtiaaontnodgacrnlaadpmhqsyu.anctoiutaptlieodn otof pearftlaunodroemoctaMnoasics 2.0 Safety 22..12 CAolwnsauylst othbesearpvperosapfreialtaebMorSatDoSrybperfaocrteichesa.ndling any chemical for proper safety precautions. 3.0 Sample Requirement 33..12 3.3 pSasaSfAournnaaotobdammjlldleeyippmclaspleltsieer.aastos.tvc2iceoso0ehnlslogo.seoupcorletdfiSnaotenebnaisdenltpphsraaroofnormcmdocepzeodeplsguensleraeenfcdossieztrboeweertxhaifwlotgelrireatebhcseatoedimvxosrntepyprr.ealniecccisitgefi.ioheinntdP.tlfioanrPcolezatahelctlehneoewstshastmeaofmropfarrplgoilnezecgesanuripbnnslotaaicnlnmontpdfitoimlaeorixentiienhdoriessaf . 4.0 Reagents and Standards 4.1 Water-HPLC grade 444444444444............1331671482911203 TPFALCSMSADl-elui-oamicOoleArmprielfrtcbcmuehtliseaousotrecataoicnonhagnnlnnlirryeoee(to(oibrl6la1lu-lodiinR0(2-mlc-ci6e-c0eLt10aHah--HAacC0-4nlP2giPocH00od-L0ereLN0iPmo0tCnc-CaHLsmtemtARigCeljsggeacrehe-rrs-aniagasa)hddehgdrdRA-)ea)ee-e-e-.dnR-CaeSRtRge.RiSgeaegere.agnamaagetgRdganeegeee-ntnraAntatggtdlgrgedaegrnrrdaaritdaecdGdeheerade 5.0 Instrument and Equipment $.1 $5..23 AAAspoLnldvahecleioyvgnnithticnsceeaepltcqoetbuercafdiooplatrlponlmeeccadaetntwcarcaaneiwptdhaeldbimaqaleutvMaioadrfafiosarcrsebhpalSreedopaimvenkcogaitltnrutoootmgem0rgea.er0pati0enhtir0joe0(ncLc1atCaopgnr/a.MdbclaqSepu/aMaobnSfltei)tp.aoutifmoinnp.jiencgtinugp 5t-o2002 Page 2 of 8 Page 51 o f 57 Page 102 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygco Research Method Number VOM 783 _________________________ a n a l y t ic a l m e t h o d _________________________ Method of Analysis for the DetermCilnaamtisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and 5555555555555.............11111158914761352460 AW2DSCTD5R1110P52i2euiiomsrss5En5ttmimsppoaLstu-morottrpmLLmiuycssfaiLbpaaLludcdieezebbegtpiiLvaiessstlleeortaeepDprea(np.cooH2psmrPoass-0siP(Erpasapihm1achLbabeat0rnabltlLCokoete0aplere)pe-r.eprspv1ri(.d.oopooiS0aelwlfu0flyytls0ps-pakppmesirr(iptkloo5n.ocLspp0nou.yy-aitncl1lhneeag0dnnbt0.5eoeu1n0tLcct0olmee,-e.1nnsN1L0tt.rr000iip0ff5ouup-27lggLy01ee)p07,ttru7uuwoL)bb.pi)eety.hssl..edniesptousbaebsleatti2p0s0. 0 rpm. 6.0 Chromatographic System 6.1 A(Pn/Nal:yt8i2ca5l05C-o0l5u2m1n3:0F) luophase RP (Keystone Scientific), 2.1 mm x 50 mm, 5p 6666....2534 TGMMeroomabbdpiiilleeeenraPPtthhPuaarreosse:egr((a3ABm0)):C:: 2MmetMhanAoml monium Acetate in Water Time ("mini 2208120....0.0050 %6662255555A %3377355555B F(mloLw00000/.....m33333Riant)e 666...867 RQInuujenacnTttiiiotmanteiV:ono-:lu2mP3eeam:kin1A5urtepeasL.-(ceaxntebrneailnsctraenadsaerddtocaalsibmrauticohnacsu5rv0ep. L). TophteimabizoevethceoHndPiLtiConssyastreemin.tended as a guide and may be changed in order to Page 3of8 Page 52 o f 57 Page 103 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V000P83 _________________________ ANALYTICAL METHOD_____________.____________ Method of Analysis for the DetermCilnamatisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and 7.0 MS/MS System 7.1 MPFoOdAe:. Electrospray Negative MRM mode, monitoring 4 13 -> 369 m/z for TophteimabizoevethceoMndSitMioSnssyasrteemin.tended as a guide and may be changed in order to 8.0 Preparation of Solutions 8.1 Mobile Phase 8.1.1 a2mmmMonaiummmaocneituamte taoce1t0a0te0imnLwoaftewraitserp.repared by adding 0.IS4 g of 8.2 Extraction Solutions 8.2.1 8.2.2 o2a3c%0fi%ddiamisnDceoi1tmrh0bye0iltcdmhiyacLclhdiodliocfrihmnolsoemirtlohaesnathinelaaotnnlo.oelaiinfsintpoarlleuvpeoanrleuedmisbepyordfeip1sa0sroemldvLibnwygi2bthrgitnooglufineagnsce3o. rmbiLc Alternate volumes may be prepared. 9.0 Standard Preparation 9.1 Standard Stock/Fottification Solution 9.1.1 9.1.2 9.1.3 9.1.4 9.1.3 TPomaafmAmmiAA1nrphr0foeLeL1ep0e0atma1t2phr.m.hno.13o0osaa10aattfn1xfLr2omhnplepot3iytceohmglhpgLtkaolme/ideg/iamcnmfiLsaa/tnaL1m1tetnLaDlLt.oe0l0ahdLyLcsP01efofpktD1of2Eao4fogpf2r3Pn0rsoptrg/5bt.odiCEmtrmir1f/-oiftleamirfiiutLcbLpraifactctdpialoLLanaiceastLgorttd.(aitotiaLsn/ociDlotmltooeioanDuinoPo.nlorrtLunPseErnifsstooeEo.-iosscnlobs1ltoultuobaonue0tlttoblotuidtiu0totitloltootetaeniflniopn.eooafnofgs.nroionf/fafpromaiPrntuPlfaeoFLarFvPiltOmtOooaFoyvAlaOfA)uboxfPmelAiaiiunsmiFnsesmadOtpiluopsoermAdrrefvpeeoipoldr1pbafupel0aryuetip10erenrmae0dwiwrtdoa0eeoebdidrbwtiyehgo1yofib0hbfrtmfyh0biirng6ie1rnmmbegit0nhgmrr0eLaaigiltnnnoOtihognwwognamrglintiinh1ttoiaghhgn0stIl P8gc4of8 Page 53 o f 57 Page 104 of 130 MPI Protocol P00003268; Intrim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygcn Research Method Number V0001783 _________________________ ANALYTICAL METHOD_________________________ Method of Analysis for the DetermCilnamatisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and 9.2 Standard Calibration Solutions 9.2.1 9.2.2 pToLrfhCetep/hMaefroSe1ld/l.Mo0awpSsignncfgeameliidLbserdfaao.trtiyotipnfiiccsaatatlinoednxaasrmdoslpualteiro:enap.dredpitaiorendalincomnectehnatnraotliovnias dilution may be S99oo..C22lfuo..F34tnio00co0re..0nt1I100.ni.0.aAS..O120f0(0t3titn55rlcoa2taaetrt/ierinoConnianaLtlto)le V(omluLm) e Di(lmutLed) to Co(nUcFKeinn/mtarlLat)ion 25111...00500 calibrt1ao0tion 110000 standard1t111so0000o0000in 125-mL 0000.00..0.00.0.0000021251555 LDoP.oEo onsarrow-mouth bottles 6voClu, mupestoansdixcmonocnethnst.rations of standards may be prepared as needed. 10.0 Batch Set Up 10.1 10.2 iREocnonaentecqhchueeiunrbqentaurmttaarcetlehiianottytnoesdsaffs(soslaucarmobrfanipcnetlorlcedonesltarpeonlxaaldtnnsrdlapafciobktretoewdrt)haotit(osotyrpvuypreniordctijrauefeylcpaltyltp.iecrd2oa0cteecsodoruanrnltaerdolsslrss)epcimkofevousresttrwiyfiiinefllodclrbutedhaetespbaekatcnticlofehiwae.sdnt 11.0 Sample Extraction 11.1 11111111....3324 11.6 P(cdeStdfAPWPhfoaiiraialotdmeyllraechclarbdn.ciokkteengoeiwtr32ifhnahtzyt0b0hen,hyeydedaem5lamdsan2ctbLitLuingdcho0yrbeh-neooedel1omdmfodsfrfiayrgLeet1aioicidtnf2ocnhesLr,Se3nigotaalCoPrtznaoetofnE-henonrpmNrineeelitlwteratHLruSi(izcsilnitbPrleeeathe.hermEtrp.aloseifanedpClteouaDduilsnoarreebtti--snrninse'sm1eshddceisheaanaieaqmmhaktstrsipounodoeo)ieed.luoxnoudan3rfnstl.wc0tilDnihoelaeiawfenrtmllnrwywl.aao)ciLs.iszrgotkRtihheheslseiuepnttns2hmo.a.sfbelcelnygatyDpsitpsohefkrownleaosorrpinisrf-ntciylohshsasohltaiisemlank2ka,npge0lpel2ewroldmefiwcgwottfeeLhrlinlsatty~thithsoolreki1iflbcfs5uecua.mtehofmgnogeleeeuirtenhemlotu,a3untnun02ebcsos%eteel.ogs,,. Page 5 of 8 Page 54 o f 57 Page 105 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number; P0003268 Exygen Research Method Number V0001783 Method of Analysis for the ANALYTICAL METHOD DetermCilnaamtisobnyoLf CPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and ] 11.7 11.8 tDCfhoeeercn-pat1reni0atfurtm-ghseehinaetuphxteeetrdsa.5cf0ltamosknL. topCoaolylclpoercnotdptihytileoenneeelduatSutebPeBinscctoholenutma1i2nn5ifnimtgtebsdasmiinlapsnildeizeeadtth-ep2em0a0ro-0usthhrappomef 11.9 111111...111120 11.13 11.14 11.15 11.16 1111..1178 TeAetPMAtDHtfsSACPfhhhvxlaoarhldnaeeeoedemaaaatsrsadncradmcknps-pskaktaelte1eisaoey.creo2nsfi3mrat01ztsfg0tetiaph-tr0euuhorehe4t-emetmmgenesnhestapmhhe.taiierLdauisfnezeamz-itaLrbateusnpeeohomerrpehtaexrtee-pxefslahlodpstdwsestarphe5ri.lfuvsacnfeaiea0coctlofeucdaphareaatltftscosumeodgs-iekofdmznnaf1rt1tLpneliooiegaaef0-nrnttenlnorose,pHeazidkicfmsflsolbteoatsePetkrsalyrLhturicy.Lwnlaterfpt-ephaooCnroe1ihrordrlsdrfoo0tualsadvo-aupsspttmiicmoeiogncayrne1atolhegluhimsgteynmhtosetnhS2uuioahinLbxeenPstueisrCmie/itgEdonratnrseSu/imiLetgmaMlxsaboPcesttrpdoneEoorSioywilsrisalnfle/aseusccMveitpc.u2tmtoowvehoiom%Sl.annrtsnui.phinia.mtstzoeatabhtheri-nslettnaCraeechuticaoefbopontone5reilirgblrdlpo0.pue(ien-aescecct3matantsosmar0.<htmL-tchaspis4bhkdfele0crieeacnoerpeioenm.Cnalenuttd)trmda.hi-tsfte2eehufta0leeghani0leansud0kntiaonotrtuierilantpbtinhstmaiedoneel. 12.0 Chromatography 12.1 LInCje/MctSth/Me sSamsyesatemmo.unAt ocfaelaibchratsitoanndastradn,dsaarmdplmeuasntd pfroerctiefdieed asanmd pfleollionwto tahlel 12.2 12.3 12.4 egvUtsisiamSAhnnaaieenttsnetjmmuanraheeessnelreeceppuytsdrrtnnllslazpbeaeeitdteednicerscerddrs.aeoaedsiessanlesftaeirsf.coadbtA,eoalmrftusresacstPtpdovttahaahiFleaefnmloeeedinOrcdsnbyp.aaaiArblnalsrna5eiedlttbata-acgiel1sronnoyireac0nndrntttuare.niaasenorsritavbsndantiSmpaveylgtynossecaplttdn,oniailoncaednfdnaoaresifcdandnlraer(asgrsdntareoeqsdrttntmreuos.aatmgsaiuctamrernicsueetotttuossinlttssuseabfiteaunbtooetibsstelnotilefonnotfiuoh.nigwfisrnvetiececMeandarlfgLuossliapiredrisbs)nbceesm/treoryLxdasanoatyerwaindrdnoctedexnasstbictlhegaielo3tesbahnt.ntowrs3dtabcaitfnaeneet(rdisgnegioodntaintarnnojrrneadnecefdctqsivuiptsnaouierterogmvainrdavnyneksaaalds)enyl5.aaievdn-rrane1bdeIralt0neaaess)t software system. Page 6 of8 Page 55 o f 57 Page 106 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001783 ___________________ ANALYTICAL METHOD__________________________ Method of Analysis for the DetermCilnaamtisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and 12.5 eSxacmepedlesrtaenspdoarndseresshpoounlsdesnsohtouexldcebeedfusrtathnedradrdilurteesdpoanndserse.anAalynzyedsa.mples (hat 13.0 Acceptance Criteria 13.1 13.2 ModCafheu4rtgoh1hmo3tdeaartmboilgouanrn.ak(m3Ts6hmm9euua4ssm1tt 3usnh)oaortmewcpuoranepstpaaeerineantnkstPotFchfoOearAlroedssaasputooglnhfedvtcesearrltsboioogntnhreaedatitPo3exFr6iO9dtheAaa.mnaunthifoernoL,mOwaQhi.plearIetfhnaet 13.3 13.4 13.5 TEHmAebmRthnlhroenuuaetrecwyisnisorrottkerecvcnkbvaoTcseoneeelorretoiritronbs,eweeobttrsxl,atatnafhcaiottmnseieiivoafnoseaamnendctylPodoup2Ftsnecablat0Osetoalner%.sneodAndfsleufoIthaxihafsmrcofctpedaiutlbielhueklecenfdednevoortestebtunidoolr(entasteRrfadnofrgsl)redcleort-naoesetmmfluapxiommbbtaitrekrrttuebrahraesciceteaxttairthfobelaacsiosndelbtnaplaf.srlristcas0keitotuts.-aeai5utelonsniaxtcnddpstmtaiiarpaodlarurcbndecdsou,tsstuertothvdhbittfnleeh.eeijsetnaeahbrtcceagetbccete.enwoycdnpeua.eewutllreaidsabnbibtrnlebale7gdaet0inloti-ekhmm1nxe3suicct0alssHuum%t,rduvptebghoeldeeee.f 13.6 Rastp0eap.nt9erdo9na2ptrirdois(naRtoeJtrimtsht0eee.sp9rse8bl5eem)tv.wuaesntetInfsbeectsatoaltfinabsdkraaeamrntdipostlnoeasnrasedhdsoujusluastlsmtdpfibnaleelslstrreuomamunutaesslnitydtzeneoodtpt.heedrsareitfiotlnimm, oiatrsne,d thtehne than 4 % within an analytical run. If retention time drift exceeds this limit within an analytical run then the set must be reanalyzed. 14.0 Calculations 14.1 bUasseedtheonfoplleoawkinagreeaq)uuastiionng ttohecasltcaunldaaterdthceuarmveou(lnint eoafrPrFeOgrAesfsoiounndp(airnamnge/tmerLs), generated by the Mass Lynx software program: PFOA found (ng/mL) = /Peak aresalo-pientercept) 14.2 nUgs/egt(hpepbfo).llowing equation to convert the amount of PFOA found in ng/mL to PFOA found (ppb) * fPFOA founds(anmg/pmleLw) exigfihnta(lgv)olume (mL) x DF1 DF factor by which the final volume was diluted, if necessary. Page 7 of 8 Page 56 o f 57 Page 107 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ExyLIMS Protocol Number: P0003268 Exygen Research Method Number V0001783 I analytical m ethod Method of Analysis for the DetermCilnamatisobnyoLfCPe/MrflSu/oMroSoctanoic Acid (PFOA) in Fish and 14.3 tFhoerfsoallmopwliensgfeoqrtuiafiteiodnwtoithcaklcnuolwatne tahmeopuenrctsenotfrePcFoOveAryp. rior to extraction, use Recovery (%) = [total analyte found (ng/g) analyte found in control (ng/g)] ^ analyte added (ng/g) Page 8 of8 Page 57 o f 57 Page 108 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 Page 109 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Exygen Protocol P0003268 Amendment 1 "AnalysTishoisf Paemrileunodrombuetnatnemsuolfdoinfiaetse (tPhFeBfSo)l,loPwerifnlugorpoohertxiaonnesouflfopnroatteo(cPoFl:HS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, and Clams Using LC/MS/MS for the 3M Decatur Monitoring Program" P rotocol reads: Testing Facility M P I R esearch, 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 e a d : Testing Facility M P I R esearch, 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 2 6 0 -5 N -1 7 Maplewood, MN 55144-1000 Reason: Addlton of the 3M Environm ental Laboratory as a testing facility allows sam ples to be sent to the 3M Environm ental Laboratory for analysis. Th e initial sam ple analysis is outlined in the attached G eneral Project Outline (G P O ) authored by Michelle Malinsky, 3M Principal Analytical Investigator. Page 2 of 4 Page 110 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Exygen Protocol P0003268 Amendment 1 P rotocol reads: Analytical Procedure Summary References: E TS -8-12.0: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (PFPeA ), Perfluorohexanoic Acid (P FH A ), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (P FO A ), Perfluorononanoic Acid (PFN A ), Perfluorodecanoic Acid (PFD A ), Perfluoroundecanoic Acid (PFU nA ), Perfluorododecanoic Acid (PFD oA ), Perfluorobutanesulfonate (P F B S ), Perfluorohexanesulfonate (P F H S ), and Perfluorooctanesulfonate (P F O S ) in W ate r, Soil and Sediment by LC/M S/M S A m e n d to r e a d : Analytical Procedure Summary References: E TS -8-12: Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfluoropentanoic Acid (P FP eA ), Perfluorohexanoic Acid (PFH A ), Perfluoroheptanoic Acid (PFHpA), Perfluorooctanoic Acid (P FO A ), Perfluorononanoic Acid (PFN A ), Perfluorodecanoic Acid (PFDA), Perfluoroundecanoic Acid (PFU nA ), Perfluorododecanoic Acid (PFD oA ), Perfluorobutanesulfonate (P F B S ), Perfluorohexanesulfonate (P F H S ), and Perfluorooctanesulfonate (P F O S ) in W ate r, Soil and Sediment by LC/M S/M S E T S -8 -1 5 4 : Determ ination of Perfluorinated Acids, Alcohols, Am ides, and Sulfonates in W a te r by Solid P hase Extraction and High Perform ance Liquid C hrom atography/M ass Spectrom etry E T S -8 -0 4 4 : Method of Analysis for the Determ ination of Perfluorinated Com pounds in W a te r by LC /M S/M S ; Direct Injection Analysis Reason: These additional 3M Environmental Laboratory methods allow samples to be analyzed by other m ethods if deem ed appropriate by the 3M principal analytical investigator and 3M Environm ental Laboratory management. Page 3 of 4 Page 111 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Amendment Approval Exygen Protocol P0003268 Amendment 2 Michael A. Sanjdro, Sponsor Representative ' 'le. nDtatoe r ' . M icelle D. Malinsky,Jih.D.,Princi|ial A.na.lytical investig.ato:r ' . .' - nDuatetim s -r' ---------" " ' EHS Opns Environmental Lab Management ' ; ^ . . Date Jaisimha Kesari P.E., DEE, Study Director Date . Page 3 o f3 Page 112 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 ' ' ........... . Araertdmsrst Approval' Exygen Protocol P0O3268: . . . Amendment 2 . ..' " . ;^iicha^l-Avgaitorq,Sponsor.Reprcs^uative . . " P:,;,'-.; . :.^Date Micjiciic D. -: .'Ph.i),. P;v'c:;sa! /Vialyticai^nvisitgiitoti . ' *" ' . \ `Vliatfi Page T of 3 Page 113 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 3M 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 C asey Howell, QAI, 3M EHS&Opns; Environmental Lab Tim Frinak, Weston Solutions, Inc. Jai Kesari, W eston Solutions, Inc. Date: Subject: August 23,2007 Decatur Off-site Surface W ater and Sediment Sampling week of August 27, 2007 under G LP Protocol P3268 (3M Environmental Laboratory Request G LP07-003) Page 114 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 1 General Project Information P ro je c t C o o rd in a to r(s ) G L P S tu d y D irecto r G L P S p o n s o r R e p re s e n ta tiv e A n a ly tic a l F ac ility M a n a g e m e n t Lab Request Num ber S ix D ig it D e p a rtm e n t N u m b e r P ro je c t S c h e d u le /T e s t D ates 3M O verall P ro je c t C o o rd in a to r G ary H ohenstein 3M E H S O perationo 42-2E -27 6 5 1 -7 7 8 -5 1 5 0 gahohenstein@ m m m .com F ield S a m p lin g C o o rd in a to r Tim Frinak W esto n S o lutions, Inc. 3M A n a ly tic a l P ro je c t M a n a g e m e n t K e n t Lindstrom 3 M E H S O p n s, E n vironm ental Laboratory 260-5N -17 6 5 1 -7 3 3 -9 8 8 2 krlindstrom @ m m m .com P rin c ip a l A n a ly tic a l In v e s tig a to r M ichelle M alinsky 3 M E H S O p n s, E n vironm ental Laboratory 260-5N -17 6 5 1 -7 3 3 -9 8 5 9 m m alinskv@ m m m .com Jais im h a K esari W esto n S o lutions, Inc. 1400 W eston W ay W estchester, P A 19380 M ich ael A . S a n to ro 3M Com pany W illia m K. R e ag en 3M E n v iro n m e n ta l L a b o ra to ry M a n a g e r 3 M E H S O p n s, E n vironm ental Laboratory 260-5N -17 6 5 1 -7 3 3 -9 7 3 9 w kreag en @ m m m .co m G L P 07-0002 530711 S am pling to C o m m en ce on A u g u st 2 8 , 2 0 0 7 All verbal and written correspondence will be directed to Gary Hohenstein. Page 115 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 2 Background Information and Project Objective(s) On August 28, 2007, personnel from W eston Solutions, Inc. will collect sediment and surface w ater samples from an off-site location near the 3M Decatur facility. The EH S Operations Environmental Laboratory will analyze the w ater samples for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (P FH S ), and perfluorooctanesulfonate (P FO S) under G LP study G LP07-0003 (M PI Protocol #P 3268). The final report will be submitted to Gary Hohenstein upon completion. 3 Project Schedule Sam ple collection bottles will be prepared by 3M Environmental Laboratory professional services personnel for arrival in Decatur, A L no later than Monday August 27, 2007. Collection bottles will be sent to the W eston Solutions, Inc. office located at the 3M Decatur facility. 4 Test Parameters 4.1 Water Samples Estimated reporting limits will be 0.025n g/m L (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. T ab le 1. S am ple Locations and Spike Levels fo r S urface W a te r Sam ples. Sample Location *H(nCPisgFot/omnBreSLi.c)al h(insPCtgFoo/mnHreiSLc.)al h(insPCgtFoo/mnOreiLSc.)al L(onCwgo/SnmpeL.ik)e W e s t P o n d Location 1 N A N A NA 0.2 5 W e s t P o n d Location 2 N A N A N A 0.2 5 E ast P o n d Location 1 7.6 3 61 .8 437 10 E ast P o n d Location 2 7.6 3 61 .8 437 10 S w am p Location 1 (E m e rg e n t M arsh ) 7.6 3 61 .8 437 10 E q u ip m en t R in seate 1 NA NA NA **N A E q u ip m en t R in seate 2 NA NA NA -N A T rip B lank S e t 1 N A N A N A 0.2 5 Trip B lank S e t 2 N A N A N A 0.2 5 Trip B lank S e t 3 N A N A N A 0.2 5 M a x im u m s u r fa c e w a t e r c o n c e n tr a tio n s w ith in th e "E a s t P o n d " s a m p lin g a r e a . E q u ip m e n t R in s e a te s d o no t req u ire field m atrix spikes. M(niCdgo/SmnpeLi.k)e NA NA 100 100 100 -N A -N A 10 10 10 H(ignChgo/SmnepL.i)ke 5 .0 5 .0 500 500 500 -N A -N A 500 500 500 Page 116 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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 W ater samples will be extracted and analyzed by LC /M S/M S using procedures outlined in ETS 8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method 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 m ay be used if deem ed appropriate by the PAI and 3M laboratory m anagem ent include the following: ETS 8-44 "Method of Analysis for the Determination of Perfluorinated Compounds In W ater by LC/M S/MS; Direct Injection Analysis" E TS 8-12 "Method of Analysis for the Determination of PerfluorobutanoicAcid (PFBA), Perfiuoropentanoic Acid (PFPeA), PerfiuorohexanoicAcid (PFHA), PerfluoroheptanoicAcid (PFHpA), PerfluorooctanoicAcid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfbnate (PFBS), Perfluorohexanesulfonate (P FH S ), and Perfluorooctanesulfonate (P FO S) in W ater, Soil, and Sediment by LC/M S/M S. 5.2 Sediment Samples Sediment samples will be extracted and analyzed by LC /M S/M S using procedures outlined in E TS 8-12 "Method of Analysis for the Determination of Perfluorobutanoic Acid (PFBA), Perfiuoropentanoic Acid (PFPeA), PerfiuorohexanoicAcid (PFHA), PerfluoroheptanoicAcid (PFHpA), PerfluorooctanoicAcid (PFOA), Perfluorononanoic Acid (PFNA), Perfluorodecanoic Acid (PFDA), PerfluoroundecanoicAcid (PFUnA), Perfluorododecanoic Acid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (P FH S ), and Perfluorooctanesulfonate (P FO S) in W ater, Soil, and Sediment by LC /M S /M S ". 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 Page 117 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 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. G LP protocol is available upon request. Not attached due to file size limitations. 8 E-mail Communications Page 118 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 "Young, Charles T." Charles.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@WestonSolutions.com> "Frinak, Timothy R." <T.Frinak@WestonSolutions.com> bcc Subject P3267 / P3268 Decatur off-site SW/SD sampling Hlstory <P This message has been replied to: Kent and Michelle: T h e off-site sedim ent (S D ) and surface w ater (S W ) sam ples to be collected at D ecatur starting on T u esd ay 8 /2 8 and analyzed under the G L P Protocols P 3 2 6 7 and P 3 2 6 8 include the following: 39 primary sediment samples 4 field duplicate sedim ent sam ples Please add two spare bottles for the sediments 5 surface w ater samples 2 Equipment rinseate samples 3 Trip blank samples O f the S W sam ples, 2 are from a location upgradient of sources It is anticipated that only 0 .2 5 and 5 ng/mL spikes would be required for these "West Pond" samples. Based on earlier sampling, the m axim um S W concentrations within the "East Pond" sampling area were 526 ppb PFO A, 7.63 ppb PFBS, 61.8 ppb PFH S and 437 ppb PFO S. Current concentrations m ay 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 m ay be helpful in determining lab spiking levels for the sedim ents in a subsequent email. Thanks, Charlie Charles T. Young TWWf(1a6e41xeec00sshx0t)tn7oCW74nic00haeS11elso-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 Weston 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. Page 119 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Exygen Protocol P 0003268 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: Septem ber 5, 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 1o f3 Page 120 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Exygen Protocol P 0003268 Amendment 2 "AnalysTishoisf Paemrfelunodrombuetnatnemsuolfdoinfiaetse (tPhFeBfSo)l,loPwerifnlugorpoohretxioannesouflfponroatteoc(PoFl:HS), 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 P roject Identification G LP07-0003 A m en d to r ea d : Laboratory P roject Identification G L P 0 7 -0 2 Reason: W h en the original G L P project w as created using the 3M Environm ental Laboratory's Laboratory Information M anagem ent System (LIM S), the wrong project template w as used. With the correct tem plate, all sam ples collected under protocol P 0 0 0 3 2 6 8 and analyzed at the 3M Environm ental Lab will be logged in under G L P program num ber G L P 0 7-02 . S am ples from individual sampling events or different subcategories of sam ples (i.e. w ater vs. sedim ent) will be logged under separate projects under the sam e G LP program number. For example, the sediment samples collected on August 28-29, 2 0 0 7 will be logged under G L P project num ber G L P 0 7 -0 2 -0 1 . S am ples from the next event will be logged under project number G LP07-02-02. The new G LP program template allows for easier sample tracking and m anagem en t w hen numerous sam ples will be collected over an extended period of time. Page 2 of 3 Page 121 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Amendment Approval Exygen Protocol P 0003268 Amendment 2 Michael A. Santoro, Sponsor Representative 'A/i 'fi k ' ll / ' Si': ' Michelle D, Malinsky1,AF'h.jlc)l./.u .P/yrinsc-iApa' l Analytical lnvestigator Date 'Dmatei m - Page 3 of 3 Page 122 of 130 i MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Amendment Approval Exygeri Protocol P0003268 ! : Amendment 2 EHS Opns Environmental Lab Management Jaisimha Kesari P.E., DEE, Study Director ! Date Date Page 3 of3 Page 123 of 130 ; ,-.s: :: ... MPI Protocol P00003268; Intrim Report #5 3M Project G LP07-02-03 , Decatur Offsite 605 Sris Wells; April 2008 : ' ' " S-.1'- y% --^V - V i . - .-y; .; ;: Anrrtu2nd1m en't A* pproval y-` Amendment 2 . ' vy : y..: ,y -;` :-:!w'.il /* - I lY-" ;-.. *X ' ' =' . =:'=: ; -, ".il- = r "> ': : . ;=' . .. v ' ' ' ' ........ ' ' `V Michael A. Santoro; Sponsor Reprsenta.]' ------; . : : ...; . ; . ' ; ----- :--TT!-- v Date : ' :i.v ; y . i v - : ' y':yy--y-y::- , '--^-7-^-- t - :------ ;---------------- ------------------- :r . : - - i ; 1: ; "...i- -1 . ... ... . ' :: ;1 ^ i l ; ' ; ^ . V -- r v l l : ; ;llrh;l::i---:----.-------.-------.-------.-------le. L.'s- ' Ihte ' . : ' i _ . : ' ` ' . :r \ . .v - . .. -"i.- . . : : ' ' "" .i.; ' .'!. '7 ' ; .' ' : ' :i.'" : 'i" ' ' . ^ y y y ,:y ^ ' ' ' ' ' .' . :- < ;i,|: ; ' ' - : isimba:Ke$ari !\ElJ>E Stuy Director __________ W / fe? - . y.k'l:; K; .. :: . :"/> -vi:" ' : / 3 .i.:il''''i'i C^ ^,vl" ':':!fiSi^ . . .;.r .. ; . .. , . .. v r ..: " :' t1k v; v. * ......i...l -. -. Page 124 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Environmental Health & Safety Operations, Environmental Laboratory General Project Outline To: Gary Hohensteln, 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 C asey 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 60 0 series wells (M PI Protocol P3268; 3M GLP Program GLP07-02) Page 125 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 1 General Project Information P ro je c t C o o rd in a to rs ) G L P S tu d y D irecto r G U P S p o n s o r R ep re s e n ta tiv e F a c ility M a n a g e m e n t Lab Request Num ber S ix D ig it D e p a rtm e n t N u m b e r P ro je c t S c h e d u le /T e s t D ates 3M O verall P ro je c t G ary H ohenstein 3M E H S O perationo 42-2E -27 6 5 1 -7 7 8 -5 1 5 0 gahohenstein@ m m m .com F ield S a m p lin g C o o rd in a to r Tim F rinak W e s to n S o lutions, Inc. 3M A n a ly tic a l P ro je c t M a n a g e m e n t K en t Lindstrom 3 M E H S O pns, E n vironm ental Laboratory 260-5N -17 6 5 1 -7 3 3 -9 8 8 2 krtindstrom i m m m .com P rin c ip a l A n a ly tic a l In v e s tig a to r M ichelle M alinsky 3 M E H S O pns, E n vironm ental Laboratory 260-5N -17 6 5 1 -7 3 3 -9 8 5 9 m m allnskvfQ >m m m .com J a is im h a K esari W e s to n S o lu tio n s, Inc. 1 400 W eston W ay W estchester, P A 19380 M ich ael A . S a n to ro 3M Com pany W illiam K. R e ag en 3M E n v iro n m e n ta l L a b o ra to ry M a n a g e r 3M E H S O pns, E n vironm ental Laboratory 260-5N -17 6 5 1 -7 3 3 -9 7 3 9 w kreag en @ m m m .co m G L P 07-02-02 530711 S am pling to c o m m en ce th e w e e k o f S e p te m b e r 17, 2 0 0 7 All verbal and written correspondence will be directed to Gary Hohenstein. Page 126 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 2 Background Information and Project Objective(s) Personnel from Weston Solutions, Inc. will collect groundwater samples from off-site 6 00 series wells located near the 3M Decatur facility. The EHS Operations Environmental Laboratory will analyze the water samples for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (P FH S ), and perfluorooctanesulfonate (P FO S) under 3M GLP program number G LP07-02 (M PI Protocol # P 3268). Th e final report will be submitted to Gary Hohenstein upon completion. 3 Project Schedule Sam ple collection bottles will be prepared by 3M Environmental Laboratory professional services personnel for estimated arrival in Decatur, A L on Friday S eptem ber 1 4 ,2 0 0 7 . 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 0.025n g/m L (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 4 5 0 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 w ater to be used for equipment rinsing. Table 1. S am ple Locations and Spike Levels fo r S urface W a te r Sam ples. Sample Location/Well ID HCiostno(ncregicn/matrlLaP)tFioBnS HCiostno(ncregicn/matlrLaP)tFioHnS HCisotno(ncreigcn/matlrLaP)tFioOnS CoLn(oncwegn/SmtprLaik)tieon 601R NR 0.0 2 5 4 < 0.025 0.2 5 610S NR 0 .0 2 9 2 0 .0 3 4 4 0 .2 5 601L NR 2 0 .8 2 .5 4 0.2 5 602R 602S 602L 0 .2 2 1 0 .1 9 2 0 .1 1 5 0 .115 0 .137 0 .4 6 1 0 .193 0 .577 1 .7 7 0 .5 0 .5 0 .5 603R 603S 603L 0 .2 0 4 0.1 0 .0 4 4 1 0 .329 0 .106 0 .0 4 6 1 0 .120 0 .255 0 .182 0.2 5 0.2 5 0 .2 5 604R 604S 0 .119 0 .118/N R 0 .146 0 .2 1 3 /0 .1 5 9 0 .919 0.271 / 0 .0 5 4 8 0 .5 0.2 5 604L 0 .178/N R 0 .2 7 5 /0 .2 1 1 0 .9 4 5 / 0 .727 0 .2 5 605R 605L 0 .0 6 7 7 < 0.025 0 .0 4 1 8 < 0.025 0 .0 2 5 7 < 0.025 0 .2 5 0.2 5 CoHn(ignchegn/mStrpLai)ktieon 1 1 25 5 5 5 2 .5 2 .5 2 .5 2 .5 1.0 5 .0 1 1 Page 127 of 130 MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 "E q u ip m en t R in s e a te s do no t req u ire field m atrix spikes. T rip B la n k S e t 1: L o w spike: 0 .2 5 n g /m L ; M id spike: 0 .5 n g/m L; H ig h S pike: 1 .0 n g/m L T rip B la n k S e t 2 : L o w spike: 2 .5 n g /m L ; M id spike: 5 .0 n g /m L ; H ig h S pike: 2 5 n g /m L 5 Test Methods 5.1 Water Samples W ater samples will be extracted and analyzed by LC /M S/M S using procedures outlined In ETS 8-154 "Determination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In W ater By Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". This method 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 deem ed appropriate by the PAI and 3M laboratory m anagem ent include the following: E TS 8-44 "Method of Analysis for the Determination of Perfluorinated Compounds in W ater by LC/M S/MS; Direct Injection Analysis" E TS 8-12 "Method of Analysis for the Determination of Perfluorobutanolc Acid (PFBA), Perfluoropentanolc Acid (PFPeA ), PerfluorohexanoicAcid (PFHA), Perfluoroheptanolc Acid (PFHpA), Perfluorooctanoic Acid (PFOA), Perfluorononanoic Acid (PFNA), PerfluorodecanoicAcid (PFDA), Perfluoroundecanoic Acid (PFUnA), PerfluorododecanoicAcid (PFDoA), Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (P FH S ), and Perfluorooctanesulfonate (P FO S) in W ater, Soil, and Sediment by LC/M S/M S. 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 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. 7 Attachments None. G LP protocol is available upon request. Not attached due to file size limitations. 8 E-mail Communications Page 128 of 130 r MPI Protocol P00003268; Interim Report #5 3M Project G LP07-02-03 Decatur Offsite 605 Series Wells; April 2008 "Young, Charles T." <Charies.Young@WestonSol utions.com> 09/07/2007 02:07 PM To "Kent Undstrom" <krlindstrom@mmm.com> "Michelle Malinsky" <mmalinsky@mmm.com> cc "Frinak, Timothy R." <T.Frinak@WestonSolutlons.com> bcc Subject Last Sampling Round for Decatur 600 series wells prior to abandonment History. This message has been forwarded. Kent and Michelle: The fourteen 60 0 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 determ ine appropriate spiking ranges for P FB S , P F H S , P F O S and P FO A . A nalyses will be under the G L P protocols P 3 2 6 7 and P 2368. In addition to bottle sets for sam ples from each of the 14 wells, two equipm ent rinseate blank bottles and M illi-Q w ater and two trip blank bottle sets should be provided for the Q C samples. Sam pling will be perform ed by Tim Frinak during the w ee k of S eptem ber 17. C an the bottle sets be prepped and shipped later next week for Friday Septem ber 14 arrival at Decatur? Off-site 600 series wells Groundwater PFBS, PFHS, PFOS and PFOA Concentrations Decatur, Alabama Well ID 601R 601S 601L 602R 602S 602L 603R 603 S 603 L 604R 604S 604L 605R 605L Sample ID D A L -G W -6 01R -0 -0 6 0 4 13 D A L -G W -6 01S -0 -0 6 0 4 13 D A L -G W -6 01L -0-0 60413 D A L -G W -6 02R -0 -06 0413 D A L -G W -6 02S -0 -06 0413 D A L -G W -6 02L -0-0 60413 DAL-G W-603R-0-060413 DAL-GW-603 S-0-060412 D A L -G W -6 03L -0-0 60413 D A L -G W -6 04R -0 -06 0413 D A L -G W -6 04S -0 -06 0412 DAL-GWS-604S-0-061201 D A L -G W -6 04L -0-0 60412 D A L -G W S -6 04L -0-0 61201 D A L -G W -6 05R -0 -06 0412 DAL-G W -605L-0-060412 Sample Date 13-Apr-06 13-Apr-06 13-Apr-06 13-Apr-06 13-Apr-06 13-Apr-06 13-Apr-06 12-Apr-06 13-Apr-06 13-Apr-06 12-Apr-06 01-Dec-06 12-Apr-06 01-Dec-06 12-Apr-06 12-Apr-06 . Average PFBS (ppb, ng/mL) NR NR NR 0.221 0.192 0.115 0.204 0.1 0.0441 0.119 0.118 NR 0.178 NR 0.0677 ND Average PFHS (ppb, ng/mL) 0.0254 0.0292 20.8 0.115 0.137 0.461 0.329 0.106 0.0461 0.146 0.213 0.159 0.275 0.211 0.0418 ND ND = Not detected at or above Limit o f Quantitation (LOQ) o f 0.025 ng/mL Average PFOS (ppb, ng/mL) ND 0.0344 2.54 0.193 0.577 1.77 0.12 0.255 0.182 0.919 0.271 0.0548 0.945 0.727 0.0257 ND Thanks, Charlie Page 129 of 130 MPI Protocol P00003268; Interim Report #5 3M Project GLP07-02-03 Decatur Offsite 605 Series Wells; April 2008 Charles T. Young TWfW(1a6e4x1eec00sshx0t)tn7oCW74nic00haeS11elso-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 Weston 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. O ff-s ite GCx veils G W ail c o n s titu e n ts jd s Page 130 of 130