Document 0NYX8ELNr69DaXvdXjM5X9Kb

3 GLP10-01-02 Interim Report 21: Analysis for PFOS, PFHS and PFBS in Decatur, AL Soils Collected from Well Location 610 in August, 2011 Study Title 3M Environmental Laboratory Analytical Protocol GLP10-01-01: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program Data Requirement Data Requirement EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 Study Director Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 Principal Analytical Investigator Cleston C. Lange, Ph.D. 3M Environmental Laboratory Interim Report Completion Date Upon Signing Performing Laboratory 3M Environmental Health and Safety Operations Environmental Laboratory 3M Center, Bldg 260-05-N-17 St. Paul, MN 55144 Project Identification GLP10-01-02-21 Total Number of Pages 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 This page has been reserved for specific country requirements. Page 2 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 ........ .. lGLP C o m p l ia n c e S t a te m e n t Report Title: GLP10-01-02 Interim Report 21: Analysis for PFOS, PFHS and PFBS in Soils Collected from Well Location 610 in August 2011. 3M Environmental Laboratory Analytical Protocol GLP-10-01-02: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: Exceptions to GLP compliance: The reference substances were not all characterized under GLPs. Because these are environmental samples and the study analytical in nature only, there was no specific test substance or control substance for this study. Page 3 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 HAUTY A ssurance Statement Report Title: GLP10-01-02 Interim Report 21: Analysis for PFOS, PFHS and PFBS in Soils Collected from Well Location 610 in August 2011. 3M Environmental Laboratory Analytical Protocol GLP-10-01-02: Analysis of Perfluorooctane Sulfonate (PFOS), Perfluorohexane Sulfonate (PFHS) and Perfluorobutane Sulfonate (PFBS) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 Site-Related Monitoring Program. This interim analytical report and the accompanying data were audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated below. The findings were reported to the principal investigator (P.I.), laboratory management and study director. Study Inspection Dates Nov. 14-15, 2011 Phase Interim Report and Data P.l. 11/25/2011 Date Reported to Study Director Management Study Director 1/13/2012 1/13/2012 ^ /y s r --- QAU Representative 1 -2 ^ X Date Page 4 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Ta b l e o f C o n t e n t s GLP Compliance Statement.................................................................................................................. 3 Quality Assurance Statement................................................................................................................ 4 Table of Contents...................................................................................................................................5 List of Tables.......................................................................................................................................... 6 1 Study Information............................................................................................................................7 2 Summary........................................................................................................................................ 8 3 Introduction......................................................................................................................................9 4 Test, Control and Reference Substances....................................................................................... 9 5 Test System...................................................................................................................................11 6 Method Summary.......................................................................................................................... 11 6.1 Methods............................................................................................................................ 11 6.2 Sample Receipt................................................................................................................ 11 6.3 Sample Preparation...........................................................................................................11 6.4 Percent Soil Moisture Determination................................................................................ 12 6.5 LC/MS/MS Analysis...........................................................................................................12 7 Analytical Results .......................................................................................................................... 14 7.1 Calibration......................................................................................................................... 14 7.2 Limits of Quantitation (LOQs)........................................................................................... 15 7.3 Continuing Calibration.......................................................................................................15 7.4 Blanks................................................................................................................................15 7.5 Laboratory Control Spikes (LCSs).................................................................................... 16 7.6 Laboratory Matrix Spikes (LMSs)..................................................................................... 17 7.7 Percent Moisture Determinations..................................................................................... 18 7.8 Individual Sample Results.................................................................................................18 Page 5 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 8 Conclusion.................................................................................................................................... 21 9 Data/Sample Retention................................................................................................................. 22 10 List of Attachments........................................................................................................................22 11 Signatures..................................................................................................................................... 22 L ist of Tables Table 1. Results for Decatur, AL Soils from Well Location 610........................................................... 8 Table 2. LMS Recovery for Decatur, AL Soils from Well Location 610............................................... 8 Table 4. Instrument Information..........................................................................................................13 Table 5. Gradient Liquid Chromatography Conditions (ETS-8-053).................................................. 13 Table 6. Mass Transitions................................................................................................................... 13 Table 7. PFOS Calibration Summary..................................................................................................14 Table 8. PFHS Calibration Summary..................................................................................................15 Table 9. PFBS Calibration Summary..................................................................................................15 Table 10. LCS Results (PFOS, linear + branched isomer).................................................................16 Table 11. LCS Results (PFHS, linear + branched isomer).................................................................16 Table 12. LCS Results (PFBS)........................................................................................................... 17 Table 13. Analytical Method Uncertainties......................................................................................... 17 Table 14. Percent Moistures for Decatur, AL Soils from Well Location 610......................................18 Table 15. Individual PFOS Results for Decatur, AL Soils from Well Location 610.....................18 Table 16. Individual PFHS Results for Decatur, AL Soils from Well Location 610.....................19 Table 17. Individual PFBS Results for Decatur, AL Soils from Well Location 610.....................20 Page 6 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 1 Study Information Sponsor 3M Company Sponsor Representative Gary A. Hohenstein Environmental Manager Special Projects, EHS Operations Bldg 224-5W-03 St. Paul, MN 55144 Phone: (651) 737-3570 gahohenstein@mmm.com Study Director Jaisimha Kesari, P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Study Analytical Testing Facility 3M EHS Operations Environmental Laboratory Building 260-5N-17 St. Paul, MN 55144 Study Personnel (3M Environmental Laboratory) Cleston C. Lange, Ph.D., Principal Analytical Investigator William K. Reagen, Ph.D., Laboratory Manager Patrick Kenney, Laboratory Technician (Pace Analytical, Professional Services) Marlene Heying, Laboratory Technician (Pace Analytical, Professional Services) Study Dates Study Initiation: March 08, 2010 Interim Analytical Initiation: September 12, 2011 Interim Analytical Completion: October 19, 2011 Interim Report Completion: Upon final Signatures Location of Archives All original raw data and analytical reports have been archived at the 3M Environmental Laboratory according to 40 CFR Part 792. The analytical reference standard reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 79 Page 7 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 2 Summary This interim report provides the PFOS, PFHS and PFBS concentration results for the four soils collected in August 2011 near well location 610, located near the 3M facility at Decatur, AL. One travel blank (trip blank), containing approximately 16 grams of control soil in a sample bottle, accompanied the sample bottles to and from the site and was also analyzed. Samples were logged into the 3M Environmental Laboratory information management system (LIMS) under project GLP10-01-01-21. Four aliquots of soil were removed from each sample bottle and accurately weighed for extraction. The first and second aliquot served as sample and duplicate sample. The third and fourth replicates were fortified with nominal 5.00 and 50.0 ng of PFOS (linear isomer), PFHS (linear isomer) and PFBS as a low and high laboratory matrix spike (LMS), respectively. A single LMS for the trip blank was fortified with nominal 1.00 ng of PFOS (linear isomer), PFHS (linear isomer) and PFBS. Sample were extracted and analyzed per method ETS-8-053 which employs analysis by liquid chromatography with triple quadrapole mass spectrometric detection (LC/MS/MS). The LMS recovery results provided a measure of data accuracy. The relative percent difference (RPD) of the duplicate sample results was used to assess the analytical precision of the sample results. The percent moisture of each soil was also determined as part of the study. The PFOS, PFHS and PFBS concentrations are summarized in Table 1. The PFOS, PFHS and PFBS recoveries from the LMS samples are summarized in Table 2. Table 1. Results for Decatur, AL Soils from Well Location 610 Analyte Concentration (ng/g; 3M LIMS ID [d] Sample ID dry) PFOS PFHS PFBS GLP10-01-01-21-001 DAL-SB-610S-0-0000 36.1 0.586 0.991 GLP10-01-01-21-002 DAL-SB-610S-0-0010 19.5 0.690 0.439 GLP 1 0 - 0 1 - 0 1 - 2 1 - 0 0 3 DAL-SB-610S-0-0040 3.00 1.11 0.572 GLP 1 0 - 0 1 - 0 1 - 2 1 - 0 0 4 DAL-SB-610S-0-0150 BLQ BLQ BLQ GLP 1 0 - 0 1 - 0 1 - 2 1 - 0 0 5 TRIP BLANK-1 BLQ BLQ BLQ LMS results were within acceptance criteria of 100 + 30% Concentration values are shown at 3 significant figures, but more precise data was used for data calculations. RPD values were less than 50% for all duplicate sample results unless otherwise indicated BLQ; analyte response was lower than the analyte response of the LLOQ which was nominal 0.200 ng/g low standard Table 2. LMS Recovery for Decatur, AL Soils from Well Location 610 3M LIMS ID [b] GLP10-01-01-21-001 Low Sample ID DAL-SB-610S-0-0000 Lab M a trix Spike Low LMS Recovery (%) PFOS [a] PFHS 91.3% PFBS 93.8% GLP10-01-01-21-001 High GLP10-01-01-21-002 Low DAL-SB-610S-0-0000 Lab M a trix Spike High DAL-SB-610S-0-0010 Lab M a trix Spike Low 97.8% [a] 102% 103% 109% 110% GLP 10-01-01-21-002 High DAL-SB-610S-0-0010 Lab M a trix Spike High 93.0% 95.0% 101% GLP10-01-01-21-003 Low DAL-SB-610S-0-0040 Lab M a trix Spike Low 112% 103% 112% GLP 10-01-01-21-003 High DAL-SB-610S-0-0040 Lab M a trix Spike High 111% 97.6% 109% GLP10-01-01-21-004 Low DAL-SB-610S-0-0150 Lab M a trix Spike Low 98.1% 92.3% 91.5% GLP 10-01-01-21-004 High DAL-SB-610S-0-0150 Lab M a trix Spike High 87.4% 91.6% 100% GLP 10-01-01-21-005 LMS Trip Blank-1 Lab M a trix Spike Low 97.4% 102% 115% LMSs were fortified with PFOS, PFHS and PFBS (linear isomers only) at nominal 5.0 ng (low) and 50.0 ng (high). The LMS for the trip blank was fortified at nominal 1.0 ng each of Pf Os , PFHS and PFBS Concentration values are shown at 3 significant figures, but more precise data was used for data calculations. [a] LMS fortification level was too low relative to the endogenous analyte level to make an accurate determination of recovery. Page 8 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 3 Introduction The soil analyses results reported herein were conducted as part of the Phase 3 Environmental Monitoring and Assessment Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain information regarding concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHS) and perfluorobutane sulfonate (PFBS) in various environmental media such as groundwater, soils and sediments that are associated with and near the Decatur facility. Reported herein are the results from analysis of soils from near well location 610, located near the 3M facility in Decatur, AL. The samples were collected by Weston Solutions, Inc. personnel in August 2011 and shipped to the 3M Environmental Laboratory for quantitative analysis of PFOS, PFHS and PFBS. One soil travel blank (trip blank) was also analyzed. This report describes the sample shipment, receipt, extraction and quantitative LC/MS/MS analysis procedures conducted for determination of PFOS, PFHS and PFBS in the soil samples received. Additionally included in this report are the assessment of the analytical precision and accuracy for the reported PFOS, PFHS and PFBS concentration results. 4 Test, Control and Reference Substances This study does not have a test substance in the classic sense of a GLP study because this study was purely analytical in nature. The reference and control substances are listed in Table 3. Table 3. Reference Substances Reference ID Chemical Name Chemical Formula Use Source Expiration Date Storage Conditions Chemical Lot Number TCR Number Physical Description Purity PFOS (linear) PFOS (linear + branched) PFHS (linear) n -P e rflu o ro o c ta n e -1 Sulfonate Potassium Salt Perfluorooctane Sulfonate Potassium Salt n -P e rflu o ro h e x a n e -1 -s u lfo n a te Sodium Salt n-CsF17SO3 K C8 F17SO 3 K n-C6F13SO3 Na Reference Standard for Calibration and LMSs Reference Standard for LCSs R eference S tandard for C alibration and LM Ss W ellington Laboratories 3M W ellington Laboratories 1 0 /1 8 /1 8 1 2 /1 4 /1 6 3/25/18 -20C -20C -20C LPFOSKBM06 171 LPFHxSAM08 T C R 0 8 -0 0 0 1 -1 /1 T C R -6 9 6 T C R 0 8 -0 0 1 8 -1 /1 C ry s ta llin e W h ite P ow der C ry s ta llin e 98% 8 6 .4 % >98% Page 9 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Table 3. Reference Substances Reference ID Chemical Name Chemical Formula Use Source PFHS (linear + branched) n -P e rflu o ro h e x a n e -1 sulfonate Potassium Salt n-C6Fi3S3 K Reference Standard for LCSs 3M PFBS (predominantly linear) P e rflu oro buta ne-1 -sulfo nate P otassium S alt n-C4F9S3 K R e fe re n ce S ta n d a rd fo r All PFBS 3M 13C4-PFOS [1 ,2 ,3 ,4 -13C 4 ]-P e rflu o ro o cta n e 1-Sulfonate Sodium Salt 13C412C4F17SO3 Na S u rro g a te W ellington Laboratories Expiration Date 2/12/17 1 /1 0 /1 7 9/8/2013 Storage Conditions -20C -20C -20C Chemical Lot Number NB 120067-69 101 MPFOS0910 TCR Number Physical Description Purity T C R -0 8 3 W hite Powder 98.6% T C R -1 21 W h ite P ow der 9 6 .7 % T C R 1 0 -0 0 4 4 -2 /9 M ethanol solution, sealed am poule > 9 8 % [a] Reference ID Chemical Name Chemical Formula Use Source 13C8-PFOS [13C s]-P e rflu o ro o cta n e -1 Sulfonate Sodium Salt 13C8F17S3 Na Internal Standard for PFOS W ellington Laboratories 13C3-PFHS [13C 3 ]-P e rflu o ro h e x a n e -1 S ulfo na te S odium Salt 13C 3 12C 3 F 1 3 S 3 N a Internal S tandard for PFHS W e llin g to n Laboratories 18O2-PFBS [18 2 ]-P e rflu o ro b u ta n e -1 S ulfonate A m m onium Salt C 4 FgS18 2 16 N H 4 Internal Standard for PFBS RTI International Expiration Date 9/28/2013 9 /2 8 /2 0 1 3 3/9/15 Storage Conditions -20C -20C -20C Chemical Lot Number 092310 092310 11546-107-2 TCR Number TCR10-0048-3/16, 4/16 T C R 10-0048-3/16, 4/16 T C R -1 0 4 2 Physical Description Purity M ixed IS m ethanol so lu tio n in se a le d am poule > 9 8 % [a] M ixed IS m e th a n o l so lu tio n in s e a le d a m p o u le > 9 8 % [a] M ethanol solution, sealed am poule > 9 9 % [a] [a] T he co m m e rcially provided m aterial w a s a m ethanol so lu tio n s and la be led w ith a w e ig h t/vo lu m e co n ce n tra tio n purity value. H ow ever, th e co n ce n tra tio n o f fu rth e r dilu tio n s w as based on the certifie d co n ce n tra tio n o f the sto ck m aterial. Page 10 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 5 Test System There was not a test system for this study in the classic sense of a GLP study. This study was conducted for analysis of off-site soils collected near well location 610, near the 3M facility in Decatur, AL. Samples for this study are "real world" environmental samples. 6 Method Summary 6.1 Methods Soil extractions and quantitative LC/MS/MS analysis were performed following validated method ETS-8-053.0. The analysis conducted for reporting results was performed on October 7, 2011 as analytical run s111007a. 6.2 Sample Receipt On August 23, 2011 four (4) empty 250-mL HDPE NalgeneTM sample bottles, and one travel blank (trip blank) containing approximately 16 grams of a control soil TCR-842, were sent from the 3M Environmental Laboratory to Weston Solutions, Inc. field personnel for collection of soils from well location 610. Following the soil sample collections by Weston Solutions, Inc. personnel, 4 soil-filled sample bottles and the trip blank were sent to the laboratory for analysis. The samples were received with sample chains of custody numbers 16926 on September 12, 2011. A discrepancy between the date of bottle order sent to Decatur (8/23/2011) and the listed date of collection of the soils (8/19/2011) indicated samples were collected prior to receiving the bottles and trip blank. Charles Young of Weston, Inc. who oversaw the soil collections at Decatur was notified and indicated that the trip blank likely did not accompany the samples during collection in Decatur since other bottles apparently were used than those sent on 8/23/2011. However, the trip blank did accompany the samples when shipped back to 3M. A protocol deviation regarding this was written and is maintained in the study folder for project GLP10-01-01-21. Soil samples from Decatur, AL are regulated and were appropriately shipped in accordance with USDA/APHIS soil permit number P330-09-00125. Sample nomenclature follows the form DAL-SB-610x-xx-xxxx where the first string defines the Decatur Alabama (DAL) project area, the second string defines the sample media (i.e., SB= soil boring), the third string defines the specific well identity (well 610). The fourth string defines the sample type (0 = primary sample, DB = field duplicate, RB = equipment rinseate blank). The fifth string indicates the sampling depth range (0040 indicates 4.0 ft to 4.5 ft interval soil sample). 6.3 Sample Preparation Sample preparation was conducted as a single batch on October 4-5, 2011. Each soil extraction involved removal of a 1 cubic centimeter (1 cc; 1 mL) soil aliquot (typically ~ 1 gram) from each sample bottle using a fixed volume 1 cc spoon, transferring it to a 15 mL conical centrifuge tube, followed by accurate weight determination of the aliquot on a 5-place balance. Then, nominal 3.0 ng of each stable isotope labeled internal standard (IS) was added to each soil aliquot. Internal standards 13C4-PFOS, 13C3-PFHS and 18O2-PFBS are described in Table 3. Each soil aliquot was extracted by addition of 8 mL of a 4:1 acetonitrile:water solution followed by sonication for 1 to 2 hours and then centrifugation to remove solids. The supernatant from each was then transferred to an autovial Page 11 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 for analysis. An accurately measured volume of each supernatant was analyzed by LC/MS/MS. For a few samples, the 1cc aliquot resulted in only ~0.65 gram of soil, therefore, extra soil was used in those extractions in order to be closer to 1 gram of sample. In those few instances the inclusion of extra sample ensured adequate sensitivity for target analytes was achieved for the final extract. During preparation, each sample received nominal 3.0 ng of a stable isotope labeled surrogate recovery standard (SRS) as 13C4-PFOS. Although not included as part of the data accuracy assessment for this study, SRS recovery determinations were included as part of an ongoing method validation aspect for SRS behavior in environmental soil samples for potential future applications. The SRS was quantified from a SRS calibration curve constructed from analysis of calibration standards prepared from the SRS in calibration standards. The SRS recovery was determined based on the calculated concentration of SRS from the analysis and recovery of SRS from each sample is included in Table 15, Table 16 and Table 17, but was not used for evaluation of data accuracy for this study and is otherwise excluded from the discussions in the report. Each analytical sample was prepared in duplicate for analysis of PFOS, PFHS and PFBS in the soil sample. Additionally, a third and fourth replicate was weighed out and used to prepare a low- LMS and high-LMS, fortified with PFOS (linear), PFHS (linear) and PFBS at nominal 5.0 ng and 50.0 ng each, respectively. LMS results were used for determination of data accuracy. RPD of duplicate samples results was used for determination of data precision. Calibration standards were prepared by spiking known quantities of PFOS (linear isomer), PFHS (linear isomer) and PFBS into 1-cubic centimeter (1 cc, 1 mL) aliquots of 3M Environmental Laboratory control soil TCR-842. The nominal mass of 1 cc of control soil TCR-842 is 1.0 gram (dry). The nominal calibration standard range prepared and analyzed was 0.200 ng/g to 500 ng/g. Laboratory control spike (LCS) samples were prepared with each sample preparation batch; prepared at three levels (nominal 3.0 ng/g, 30.0 ng/g and 300 ng/g) and each level in triplicate. The LCSs were prepared using control soil TCR-842, same as calibration standards, and were fortified with technical PFOS (mixed linear and branched isomer), technical PFHS (mixed linear and branched isomers) and PFBS. The LCS results were used to estimate the analytical method uncertainty. 6.4 Percent Soil Moisture Determination The percent moisture of soils was used to calculate the dry weight of the wet soils weighed during sample preparations for PFOS, PFHS and PFBS analysis, and was determined by gravimetric analysis. Dry weights were determined for separate weighings than the weighings used for extractions. To determine the percent moisture, duplicate aliquots of each soil sample were removed and the accurate "wet" weight determined for each. All aliquots were dried at > 100C until no further mass loss occurred from water evaporation, at which time the accurate dried weights were determined. The difference in mass, attributed to water evaporation, was used to calculate the percent moisture of the original soil. The averaged percent moisture result for each was then used to calculate the soil PFOS, PFHS and PFBS concentration on a dry weight basis. 6.5 LC/MS/MS Analysis The analysis of soil extracts for PFOS, PFHS and PFBS was performed by LC/MS/MS as described in method ETS-8-053.0. The relative percent difference (RPD) of duplicate prepared sample results was used as a measure of the analytical precision. The determined recovery of fortified PFOS, PFHS and PFBS from LMS samples was used as a measure of analytical accuracy. Surrogate recoveries are reported in Table 10, but were not used for evaluating analyte recovery for this study. The surrogate data was collected as part of an on-going evaluation of surrogate recovery from environmental field samples for supporting a method validation of ETS-8053. Page 12 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Details of the specific instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed are detailed in the raw data, and are briefly described below in Table 4, Table 5 and Table 6. Table 4. Instrument Information Instrum ent Nam e A n a ly tic a l M e th o d ID Liquid C h rom ato grap h G uard colum n E xtraction colum n A na lytica l colum n Injection V olum e M ass S pectrom eter Ion S ource P olarity S oftw are E T S -S ta n E T S -8 -0 5 3 .0 A g ile n t 1100 w ith B inary P um p P re -A u to sa m p le r; P rism RP (2.1 x 50 m m , 5 mm) O a s is H L B (3 x 2 0 m m , 2 5 m); 30C B e ta s il C 1 8 (2.1 x 1 0 0 m m , 5m) 2 5 mL API 4000 T urbo lo n Spray N egative A n a lyst 1.4.2 Table 5. Gradient Liquid Chromatography Conditions (ETS-8-053) Step Number Total Time [min] 1 0 .0 2 3.0 3 3.5 4 17.0 5 17.5 6 19.5 7 2 0 .0 8 23.0 Flow Rate [mL/min] 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 0 .4 0 0 Percent A [2 mm Aqueous Ammonium Acetate] 97.0 97.0 7 0 .0 4 0 .0 1 0 .0 1 0 .0 97.0 97.0 Percent B [ Acetonitrile] 3.0 3.0 3 0 .0 6 0 .0 9 0 .0 9 0 .0 3.0 3.0 Table 6. Mass Transitions Analyte Mass Transitions Monitored PFBS 299>99, 299>80 18O 2-P F B S (IS) 303>84 PFHS 399>99, 399>80 13C a-P FH S (IS) 402>80 PFOS 499>130, 499>99, 499>80 13C 8 -P F O S (IS ) 507>80 13C 4-P F O S (S u rro g a te ) 503>80 Note: Multiple m ass transitions are sum m ed to give the instrum ent response fo r that analyte. Page 13 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 7 Analytical Results Concentration results are rounded to three significant figures according to EPA rounding rules. Because of rounding some calculated values may vary slightly from those found in the raw data. Samples with RPDs for duplicate results of less than 50% and associated LMS results meeting the method acceptance criteria of 100 30% demonstrated that the method was appropriate for those samples and were reported without footnotes in results tables. The nominal 5.00 ng and 50.0 ng fortified quantities of PFOS, PFHS and PFBS into LMSs for field samples were at an appropriate level for evaluating sample-specific analyte recoveries, with respect to the endogenous levels measured in the samples. 7.1 Calibration A set of calibration standards were prepared by spiking varying known quantities of PFOS (linear), PFHS (linear), PFBS and surrogate (13C4-PFOS), and a fixed quantity of stable isotope labeled internal standards, into one cubic centimeter (1 cc, 1 mL) aliquots of 3M Environmental Laboratory control soil TCR-842 (nominal soil mass of 1.0 g/mL). A total of twelve (12) calibration standards were prepared as a set. The prepared standards were fortified from nominal 0.200 ng to 500 ng in 1 cubic centimeter of control soil TCR-842; equivalent to nominal 0.200 ng/g to 500 ng/g in soilTCR-842. Following analysis of the calibration standards, the concentration of each standard was plotted against the measured analyte /IS peak area ratio. A quadratic equation with 1/x weighting was used to fit the data for each analyte. Calibration curves were not forced through zero. Determining the standard concentration using the resultant calibration curve and comparing to the known concentration confirmed accuracy of each curve point at within 100 30% (+ 35% at the LLOQ). The correlation coefficient (r) was greater than 0.999 for all calibration curves, and the coefficient of determination (r2) was greater than 0.990. Calibration results for PFOS, PFHS and PFBS are summarized in Table 7, Table 8 and Table 9, respectively. Because soil weights can vary significantly for a 1 cc (1 mL) field sample, depending on soil type and moisture content, the instrument response was calibrated for the known concentrations of target analytes based on the mass quantity of reference substance added to a 1 cc soil (1 mL) calibration standard prior to extraction (e.g. calibrated in this study for a range of 0.200 ng/mL to 500 ng/mL PFOS, PFHS and PFBS). Because a 1cc aliquot of control soil TCR-842 weighs nominally 1.0 gram (dry weight) and has less than 5% moisture content, the nominal concentration range of the calibration was essentially 0.200 ng/g to 500 ng/g. However, because the sample soil aliquots typically weigh more than 1.0 gram and contain significant moisture, the determined concentrations during the analysis on an ng/mL basis from the calibration curve were adjusted for the accurate determined weight and percent moisture so they could be reported on a ng/g (dry weight) basis. Table 7. PFOS Calibration Summary Analytical Run Actual s111007a Recovery STD 1 0.200 STD 2 0.500 STD 3 0.750 STD 4 1.00 STD 5 2.50 PFOS (ng) STD 6 STD 7 STD 8 5.00 10.0 25.0 0.202 0.482 0.725 1.09 2.45 4.91 9.56 24.7 101% 96.4% 96.6% 109% 98.2% 98.2% 95.6% 98.8% STD 9 50.0 STD 10 100 STD 11 200 STD 12 500 r N/A 53.8 101 195 502 0.9997 108% 101% 97.5% 100% N/A Page 14 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Table 8. PFHS Calibration Summary Analytical Run Actual s111007a Recovery STD 1 0.200 STD 2 0.500 STD 3 0.750 STD 4 1.00 STD 5 2.50 PFHS (ng) STD 6 STD 7 STD 8 5.00 10.0 25.0 STD 9 50.0 STD 10 STD 11 STD 12 100 200 500 r N/A 0.234 0.491 0.746 0.96 2.37 4.84 9.9 24.6 49.8 99.9 202 499 1.000 117% 98.2% 99.4% 96.0% 95.0% 96.8% 99.0% 98.3% 99.6% 99.9% 101% 99.8% N/A Table 9. PFBS Calibration Summary Analytical Run Actual s111007a Recovery STD 1 0.200 STD 2 0.500 STD 3 0.750 STD 4 1.00 STD 5 2.50 PFBS(ng) STD 6 STD 7 5.00 10.0 STD 8 25.0 STD 9 STD 10 STD 11 50.0 100 200 STD 12 500 r N/A 0.199 0.47 0.802 0.989 2.41 5.00 9.96 26.1 50.3 102 195 502 0.9999 99.3% 94.1% 107% 98.9% 96.3% 99.9% 99.6% 105% 101% 102% 97.4% 100% N/A 7.2 Limits of Quantitation (LOQs) The lower limit of quantitation (LLOQ) was the lowest non-zero calibration standard in the curve that met the linearity and accuracy requirement for a low standard (100 + 35%) and for which the area counts were at least 2X that of the average response determined for the method blank injected just prior to the calibration standards . The LLOQ for this study was the nominal 0.200 ng calibration standard (nominal 0.200 ng/g in soil TCR-842), and was the lowest prepared calibration standard. All sample analyte responses less than the response of the 0.200 ng calibration standard were reported as BLQ (below the limits of quantitation). The upper limit of quantitation (ULOQ) was the nominal 500 ng calibration standard. 7.3 Continuing Calibration During the course of each analysis, continuing calibration verifications (CCVs) were performed by regular injection of a mid-level calibration standard after approximately every 15th sample injected in the analytical run. The back calculated concentration results were used to confirm that the instrument response and the initial calibration curve were still in control. All CCVs flanking reported data met the method criteria of 100% 30% accuracy. 7.4 Blanks Three types of blanks were analyzed during this analysis: method blanks were prepared with blank matrix soil TCR-842 and were spiked with IS and surrogate; travel blanks (trip blanks) prepared from aliquots of soil TCR-842 sealed in s ample bottle that accompanied the bottle order to and from the sampling site; and solvent blanks containing extraction solvent. The different blank results were reviewed to evaluate potential contamination during shipment, and to evaluate method performance parameters such as injector carry over and to establish the LLOQ. All blanks were below the LLOQ (BLQ) Page 15 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 7.5 Laboratory Control Spikes (LCSs) Laboratory control spikes were prepared by spiking know quantities of PFOS (linear + branched) and PFHS (linear + branched) into 1 cc aliquots of soil TCR-842, fortified with nominal 3.0 ng and 30 ng levels, with each level prepared in triplicate. The results of the LCS analyses and calculation of analyte measurement accuracies (percent recovery) for PFOS and PFHS are shown in Table 10, Table 11 and Table 12 respectively. The analytical method uncertainty determined from LCS results is shown in Table 13. (Determined Concentration o f LCS) _, LCS Recovery -------------------------------------------------- * 100% Spike Concentration Table 10. LCS Results (PFOS, linear + branched isomer) Sample ID PFOS Recovery 3.01 LCS 30.1 LCS 301 LCS LCSs (S111007a) 126% 125% 130% 127% 128% 134% [a] 139% [a] 118% 119% Average Recovery 130% 125% 127% Std Dev. 7.7% 6.4% 6.6% RSD 5.9% 5.1% 5.2% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFOS (linear + branched isomers), each prepared and analyzed in triplicate. [a] LCS result was outside of 100 + 30%, but included in statistical calculations______________________________________ Table 11. LCS Results (PFHS, linear + branched isomer) Sample ID PFHS Recovery 3.00 LCS 30.0 LCS 300 LCS 110% 103% 100% LCSs (S111007a) 108% 106% 112% 107% 104% 108% Average Recovery 108% 104% 107% Std Dev. 1.3% 1.3% 6.1% RSD 1.2% 1.3% 5.8% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFHS (linear + branched isomers), each prepared and analyzed in triplicate. Page 16 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Table 12. LCS Results (PFBS) Sample ID LCSs (S111007a) Average Recovery Std Dev. RSD 3.01LCS 101% 105% 105% 103% 2.1% 2.0% PFBS Recovery 30.1 LCS 97.3% 102% 96.0% 98.6% 3.3% 3.4% 301 LCS 88.4% 96.3% 92.7% 92.5% 4.0% 4.3% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFBS, each prepared and analyzed in triplicate. Table 13. Analytical Method Uncertainties Sample ID LCS Results PFOS PFHS PFBS 3.00 LCSs 126% 125% 139% 110% 108% 107% 101% 105% 105% 30.0 LCSs 130% 127% 103% 106% 97.3% 102% 118% 104% 96.0% 300 LCSs 128% 134% 119% 100% 112% 108% 88.4% 96.3% 92.7% Average Recovery Std Dev. RSD 127% 6.6% 5.2% 106% 3.6% 3.4% 98.2% 5.5% 5.6% Method Uncertainty (2 x Std. Dev.); 95% CI 13% 7.3% 11% Nominal LCS concentrations were 3.00 ng/g. 30.0 ng/g and 300 ng/g of PFOS (linear + branched isomers), PFHS (linear + branched isomers) and PFBS; each LCS level was prepared and analyzed in triplicate. 7.6 Laboratory Matrix Spikes (LMSs) Laboratory matrix spikes (LMSs) were generated by adding a known quantity of PFOS (linear), PFHS (linear) and PFBS to an aliquot of soil sample, and then preparing the sample the same as non-spiked samples. Spikes for this study, LMSs were spiked at levels that were appropriate for the endogenous analyte levels in the soils, determined from screening analysis and fortified with the target analytes from 0.5-times to 10-times the endogenous analyte levels determined in the soil/sediment samples during the range finding analysis. The LMS method acceptance criterion of within 100 30% were met for all LMS recoveries. The LMS recovery results are summarized in Table 2. The PFOS, PFHS and PFBS recovery calculations for LMSs used the following equation: T,, ,, ,, (Determine d Concentrat ion o f LMS - Determined Concentrat ion o f Field Sample) . , . LMS Recovery = --------------------------------------------------------------------------------------------------------------- ^ -- L *100% Spike Concentrat ion Page 17 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 7.7 Percent Moisture Determinations The percent moisture was determined for each soil sample. Duplicate aliquots of each were taken and accurately weighed to determine the "wet" weight. Then each aliquot was dried at > 100C until no further loss in mass occurred due to water evaporation, after which the dry weight was accurately determined. The average percent moisture and RPD of the duplicate determinations for each soil are reported in Table 14. The percent moisture was calculated by the following equation: ,, ,, , . (Original Soil Wet Mass - Dried Soil Mass) Percent Moisture = --- - --------------------------------------------------- - *100% Original Soil Wet Mass Table 14. Percent Moistures for Decatur, AL Soils from Well Location 610 LIMS ID Sample ID Average Percent Moisture (w/w) [a] GLP10-01-01-21-001 DAL-SB-610S-0-0000 13.0% GLP10-01-01-21-002 DAL-SB-610S-0-0010 9.46% GLP10-01-01-21-003 DAL-SB-610S-0-0040 12.8% GLP10-01-01-21-004 DAL-SB-610S-0-0150 19.4% G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 5 TRIP BLANK-1 1.97% [a] Percent moisture determined for duplicate samples of soil taken from each sample bottle Relative Percent Difference [a] 2.1% 0.53% 14% 0.32% 16% 7.8 Individual Sample Results The individual sample results for PFOS, PFHS and PFBS are shown in Table 15, Table 16 and Table 17, respectively. Table 15. Individual PFOS Results for Decatur, AL Soils from Well Location 610 Sam ple Description GLP10-01-01-21-001 GLP10-01-01-21-001 Dup GLP10-01-01-21-001 Low LMS GLP10-01-01-21-001 High LMS G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 2 GLP 10-01-01-21-002 Dup Surrogate (13C4-PFO S) Recovery 108% 105% 110% 102% 114% 106% LMS Spike Concentration (ng/g; dry w e ig h t) N/A 5.58 57.5 N/A Measured PFOS Concentration (ng/g; dry w e ig h t) 29.8 42.5 LMS Recovery N/A Average PFOS Concentration (ng/g; dry wt.) and RPD (%) 36.1 43.7 92.4 137% [a] 97.8% 35% 21.1 N /A 19.5 17.9 Page 18 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Table 15. Individual PFOS Results for Decatur, AL Soils from Well Location 610 Sam ple Description GLP10-01-01-21-002 Low LMS GLP10-01-01-21-002 High LMS Surrogate (13C4-PFO S) Recovery 103% 101% LMS Spike Concentration (ng/g; dry w e ig h t) 5.06 48.5 Measured PFOS Concentration (ng/g; dry w e ig h t) 30.9 64.6 LMS Recovery 226% [a] 93.0% Average PFOS Concentration (ng/g; dry wt.) and RPD (%) 17% G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 3 GLP10-01-01-21-003 Dup 100% 102% N/A 2.94 3.05 N/A 3.00 GLP10-01-01-21-003 Low LMS GLP10-01-01-21-003 High LMS 108% 120% 5.07 55.2 8.66 64.1 112% 111% 3.7% GLP10-01-01-21-004 GLP10-01-01-21-004 Dup 107% 116% N/A BLQ N /A BLQ BLQ GLP10-01-01-21-004 Low LMS GLP10-01-01-21-004 High LMS 118% 94% 4.66 59.7 4.58 52.2 98.1% 87.4% N/A G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 5 GLP10-01-01-21-005 Dup 108% 107% N/A BLQ N /A BLQ BLQ GLP10-01-01-21-005 LMS 105% 0.990 0.965 97.4% N/A N/A; not applicable BLQ; analyte response was lower than the analyte response of the LLOQ which was nominal 0.200 ng/g low standard. [a] LMS fortification level was too low relative to the endogenous analyte level to make an accurate determination of recovery. Table 16. Individual PFHS Results for Decatur, AL Soils from Well Location 610 Sam ple Description GLP10-01-01-21-001 GLP10-01-01-21-001 Dup GLP10-01-01-21-001 Low LMS GLP10-01-01-21-001 High LMS G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 2 GLP10-01-01-21-002 Dup GLP10-01-01-21-002 Low LMS GLP10-01-01-21-002 High LMS Surrogate (13C4-PFO S) Recovery 108% 105% 110% 102% 114% 106% 103% 101% LMS Spike Concentration (ng/g; dry w e ig h t) N/A 5.58 57.5 N/A 5.06 48.5 Measured PFHS Concentration (ng/g; dry w e ig h t) 0.449 0.723 LMS Recovery N/A Average PFHS Concentration (ng/g; dry wt.) and RPD (%) 0.586 5.68 59.3 91.3% 102% 47% 0.720 0.660 N/A 0.690 5.87 46.8 103% 95.0% 8.7% Page 19 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Table 16. Individual PFHS Results for Decatur, AL Soils from Well Location 610 Sample Description GLP10-01-01-21-003 GLP10-01-01-21-003 Dup GLP10-01-01-21-003 Low LMS GLP10-01-01-21-003 High LMS Surrogate (13C4-PFOS) Recovery 100% 102% 108% 120% LMS Spike Concentration (ng/g; dry weight) N/A 5.07 55.2 Measured PFHS Concentration (ng/g; dry weight) 1.070 1.152 LMS Recovery N/A Average PFHS Concentration (ng/g; dry wt.) and RPD (%) 1.11 6.33 54.9 103% 97.6% 7.3% GLP10-01-01-21-004 GLP10-01-01-21-004 Dup GLP10-01-01-21-004 Low LMS GLP10-01-01-21-004 High LMS 107% 116% 118% 94% N/A 4.66 59.7 BLQ BLQ 4.31 54.7 N/A 92.3% 91.6% BLQ N/A G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 5 GLP10-01-01-21-005 Dup GLP10-01-01-21-005 LMS 108% 107% 105% N/A 0.990 BLQ BLQ 1.01 N/A 102% BLQ N/A N/A; not applicable BLQ; analyte response was lower than the analyte response of the LLOQ which was nominal 0.200 ng/g low standard. Table 17. Individual PFBS Results for Decatur, AL Soils from Well Location 610 Sample Description GLP10-01-01-21-001 GLP10-01-01-21-001 Dup GLP10-01-01-21-001 Low LMS GLP10-01-01-21-001 High LMS G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 2 GLP10-01-01-21-002 Dup GLP10-01-01-21-002 Low LMS GLP10-01-01-21-002 High LMS G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 3 GLP10-01-01-21-003 Dup GLP10-01-01-21-003 Low LMS Surrogate (13C4-PFOS) Recovery 108% 105% 110% 102% 114% 106% 103% 101% 100% 102% 108% LMS Spike Concentration (ng/g; dry weight) N/A 5.58 57.5 N/A 5.06 48.5 N/A 5.07 Measured PFBS Concentration (ng/g; dry weight) 0.804 1.18 LMS Recovery N/A Average PFBS Concentration (ng/g; dry wt.) and RPD (%) 0.991 6.23 63.7 93.8% 109% 38% 0.470 0.408 6.02 49.7 N/A 110% 101% 0.439 14% 0.609 0.536 6.24 N/A 112% 0.572 13% Page 20 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Table 17. Individual PFBS Results for Decatur, AL Soils from Well Location 610 Sample Description GLP10-01-01-21-003 High LMS Surrogate (13C4-PFOS) Recovery 120% LMS Spike Concentration (ng/g; dry weight) 55.2 Measured PFBS Concentration (ng/g; dry weight) 60.8 LMS Recovery 109% Average PFBS Concentration (ng/g; dry wt.) and RPD (%) GLP10-01-01-21-004 GLP10-01-01-21-004 Dup 107% 116% N/A BLQ N /A BLQ BLQ GLP10-01-01-21-004 Low LMS GLP10-01-01-21-004 High LMS 118% 94% 4.66 59.7 4.27 59.5 91.5% 100% N/A G LP 1 0 -0 1 - 0 1 - 2 1 -0 0 5 GLP10-01-01-21-005 Dup 108% 107% N/A BLQ N /A BLQ BLQ GLP10-01-01-21-005 LMS 105% 0.990 1.14 115% N/A N/A; not applicable BLQ; analyte response was lower than the analyte response of the LLOQ which was nominal 0.200 ng/g low standard. 8 Conclusion Soils collected from near groundwater well location 610 in August 2011 were successfully analyzed for PFOS, PFHS and PFBS following 3M Environmental Laboratory method ETS-8-053.0 and conducted as 3M study GLP10-01-02-21. The average PFOS, PFHS and PFBS concentration results for the soil samples are summarized in Table 1 and the LMS recoveries are summarized in Table 2. The individual analytical sample results are shown in Table 15, Table 16, and Table 17 for PFOS, PFHS and PFBS, respectively. The soil trip blank that accompanied the sample bottles to the site and then accompanied samples back to the laboratory was sufficiently devoid of PFOS, PFHS and PFBS, indicating that no contamination of the samples occurred during sample shipment to the laboratory. The accuracy of the results based on LMS recoveries were within acceptance criteria of 100 + 30%; when the appropriate level of fortified LMS was evaluated relative the endogenous analyte level measured. The analytical method uncertainties were determined by statistical examination of the LCS results for PFOS, PFHS and PFBS and were determined to be + 13% for PFOS, + 7.3% for PFHS and + 11% for PFBS, respectively; determined at the 95% confidence interval (CI). Page 21 of 23 . Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 9 Data/Sample Retention All soil samples and associated project data (hardcopy and electronic) will be archived as project GLP1001-02-21 according to 3M Environmental Laboratory standard operating procedures. List of Attachments Attachment A: Preparation Forms, Raw Data and Chromatograms Signatures William K. Reagen, Ph.D., 3M Environmental Laboratory Management Date Page 22 of 23 Study: GLP10-01-02, Interim Report 21 Analysis for PFOS, PFHS & PFBS in Decatur, AL Soils Collected from Well Location 610 Attachment A Preparation Forms, Raw Data and Chromatograms Page 23 of 23