Document ZJBnb1r39vkw3qGV488bq658V

INTERIM REPORT # 7-Analvsis of Soil Boring Samples STUDY TITLE Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program DATA REQUIREMENTS EPA TSCA Good Laboratory Practice Standards 40 CFR 792 STUDY DIRECTOR Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 INTERIM REPORT COMPLETION DATE October 27,2006 PERFORMING LABORATORY Exygen Research 3058 Research Drive State College, PA 16801 Phone: 814-272-1039 STUDY SPONSOR 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 Phone: 651-733-6374 PROJECT Protocol Number: P0001131 Exygen Study Number: P0001131 Total Pages: 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT Exygen Study Number P0001131, entitled "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program," conducted for 3M Company, is being performed in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by Exygen Research. /m fU M m Flaherty Principal Investigator Exygen Research Jaisimha Kesari P.E., DEE Study Director Weston Solutions, Inc. Mi Sponsor Kepresentauve 3M Company Exygen Research Date Page 2 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 QUALITY ASSURANCE STATEMENT Exygen Research's Quality Assurance Unit reviewed Exygen Study Number P0001131, entitled, "Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program". All reviewed phases1 were inspected for conduct according to Exygen Research's Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratory Practice Standards. All findings were reported to the Exygen Principal Investigator and Management and to the Study Director. Phase Date Inspected Date Reported to Date Reported to Principal Exygen Date Reported to Investi eator Management Studv Director 13. Raw Data Review and Interim 06/24,27-30/05 Analytical Report 07/01/05 Review 09/23/05 09/23/05 09/23/05 38. Raw Data Review and Interim Analytical Report Review 10/16-17/06 40. Final Report Review 10/27/06 10/26/06 10/27/06 10/26/06 10/27/06 10/27/06 10/27/06 Lydia Shaffer HtVia F latter- Technical Lead, Quality Assurance Unit Date C> 'Note: All in-lab inspections will be documented in the QA statement for the final analytical report at the conclusion of the study. This QA statement involves only the review of the interim report and associated raw data. Exygen Research Page 3 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 CERTIFICATION OF AUTHENTICITY This interim report, for Exygen Study Number P0001131, is a true and complete representation of the raw data. Submitted by: Exygen Research 3058 Research Drive State College, PA 16801 (814)272-1039 Principal Investigator, Exygen: Date Exygen Research Facility M:anagement: AJ Richard A. Grazzini President Exygen Research Study Director, Weston Solutions, Inc Jaisimha Kesari P.E., DEE Weston Solutions, Inc. Sponsor Representative, 3M Company: Ua m M U & Michael A. Santonzf Director of Regulatory Affairs Exygen Research Date Dace Page 4 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 STUDY IDENTIFICATION Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program PROTOCOL NUMBER: P0001131 EXYGEN STUDY NUMBER: TYPE OF STUDY: SAMPLE MATRIX: TEST SUBSTANCE: P0001131 Residue Soil and Water Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) SPONSOR: STUDY DIRECTOR: 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 STUDY MONITOR: Michael A. Santoro 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 PERFORMING LABORATORY: Exygen Research 3058 Research Drive State College, PA 16801 ANALYTICAL PHASE TIMETABLE: Study Initiation Date: 11/05/04 Interim Analytical Start Date: 04/06/05 Interim Analytical Termination Date: 06/27/06 Interim Report Completion Date: 10/27/06 Exygen Research Page 5 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 PROJECT PERSONNEL The Study Director for this project is Jaisimha Kesari at Weston Solutions, Inc. The following personnel from Exygen Research were associated with various phases of this interim portion of the study: Name John Flaherty Karen Risha Paul Connolly Chrissy Edwards Mark Ammerman Amy Sheehan Edward Kaiser Frances Crespi Mindy Cressley Cammy Graybill Ling Ling Liu Krista Gallant Kimberly Hall Ellen Dashem Brittany Kravets Title Vice President Scientist Technical Lead-LC/MS Technician Sample Custodian Associate Scientist Scientist Technician Technician Technician Technician Technician Technician Technician Technician Exygen Research Page 6 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 TABLE OF CONTENTS Page TITLE PAGE....................................................................................................................... 1 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT............................. 2 QUALITY ASSURANCE STATEMENT..........................................................................3 CERTIFICATION OF AUTHENTICITY...........................................................................4 STUDY IDENTIFICATION................................................................................................5 PROJECT PERSONNEL.....................................................................................................6 TABLE OF CONTENTS.....................................................................................................7 LIST OF TABLES...............................................................................................................8 LIST OF FIGURES..............................................................................................................9 LIST OF APPENDICES....................................................................................................10 1.0 SUMMARY................................................................................................................ 11 2.0 OBJECTIVE............................................................................................................... 11 3.0 INTRODUCTION....................................................................................................... 12 4.0 ANALYTICAL TEST SAMPLES.............................................................................. 12 5.0 REFERENCE MATERIAL........................................................................................13 6.0 DESCRIPTION OF ANALYTICAL METHOD........................................................ 14 6.1. Extraction Procedure For Soil................................................................................. 15 6.2 Extraction Procedure For Water.............................................................................. 15 6.3 Preparation of Standards and Fortification Solutions.............................................. 15 6.4 Chromatography...................................................................................................... 16 6.5 Instrument Sensitivity.............................................................................................. 17 6.6 Description of LC/MS/MS Instrument and Operating Conditions..........................17 6.7 Quantitation and Example Calculation.................................................................... 18 7.0 EXPERIMENTAL DESIGN......................................................................................20 8.0 RESULTS...................................................................................................................20 9.0 CONCLUSIONS.........................................................................................................21 10.0 RETENTION OF DATA AND SAMPLES.............................................................21 Exygen Research Page 7 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. LIST OF TABLES Page Summary of PFBS, PFHS and PFOS in Soil Samples................................... 23 Table II. Summary of PFBS, PFHS and PFOS in Re-extracted Soil Samples............. 30 Table HI. Summary of PFBS, PFHS and PFOS in Equipment Rinseate Blanks Samples.......................................................................................................... 33 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples............. 34 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS i n ................................... 49 Table VI. Total Percent Solids for Soil Boring Samples............................................... 57 Exygen Research Page 8 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Figure 1. LIST OF FIGURES Page Typical Calibration Curve for PFBS in Reagent Water................................. 63 Figure 2. Extracted Standards of PFBS in Reagent Water, 0 ng/L and 25 ng/L, Respectively.................................................................................... 64 Figure 3. PFBS in Reagent Blank, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively.......................................... 65 Figure 4. Chromatogram Representing a Soil Sample Analyzed for PFBS (Exygen ID: C0059098, Data Set: 040705B).................................................66 Figure 5. Typical Calibration Curve for PFHS in Reagent W ater................................ 67 Figure 6. Extracted Standards of PFHS in Reagent Water, 0 ng/L and 25 ng/L, Respectively....................................................................................................68 Figure 7. PFHS in Reagent Blank, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively.......................................... 69 Figure 8. Chromatogram Representing a Soil Sample Analyzed for PFHS (Exygen ID: C0053098, Data Set: 040705B).................................................70 Figure 9. Typical Calibration Curve for PFOS in Reagent Water................................ 71 Figure 10. Extracted Standards of PFOS in Reagent Water, 0 ng/L and 25 ng/L, Respectively....................................................................................................72 Figure 11. PFOS in Reagent Blank, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively...........................................73 Figure 12. Chromatogram Representing a Soil Sample Analyzed for PFOS (Exygen ID: C00053098, Data Set: 040705BR2)...........................................74 Exygen Research Page 9 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 LIST OF APPENDICES Page Appendix A Study Protocol P0001131 (Exygen Study No. P0001131) with Analytical Methods, Amendments and Deviation.................................... 75 Exygen Research Page 10 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 1.0 SUMMARY Exygen Research extracted and analyzed 146 subsurface soil samples for the determination of perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) according to Exygen Method V0001781 and analyzed 9 associate rinseate samples for the determination of perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) according to Exygen Method V0001780 (Appendix A). Not all soil sample results met data quality objectives and therefore only 106 of the soil sample results from initial analyses are reported. A total of 121 samples designated as not reported (NR) due to quality control failures were re-extracted and reanalyzed in an attempt to obtain quantitative results. The limit of quantitation for PFBS, PFHS and PFOS in soil was 0.2 ng/g (based on wet weight), and the limit of quantitation for PFBS, PFHS and PFOS in water was 25 ng/L. Analytical results and accessed accuracies for the analysis of PFBS, PFHS and PFOS found in soil samples are summarized in Table I. Analytical results and accessed accuracies for the analysis of PFBS, PFHS and PFOS found in re-extracted soil samples are summarized in Table II. Analytical results for the analysis of PFBS, PFHS and PFOS found in the equipment rinseate blank samples are summarized in Table III. Quantitative results were obtained for all samples and analytes except for PFBS in eleven samples, PFHS in one sample, and PFOS in five samples that are not reported due to quality control failures. The average percent recoveries standard deviations determined using wet weight for PFBS, PFHS, and PFOS in soil samples were 78% 16%, 89% 14%, and 91% 21%, respectively. The average percent recoveries standard deviations determined using wet weight for PFBS, PFHS, PFOS in re-extracted soil samples were 87% 27%, 92% + 23%, and 95% 24%, respectively. Percent solid results are detailed in Table VI. 2.0 OBJECTIVE The objective of the analytical part of this study was to determine levels of perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in soil and water according to Protocol P0001131 (Appendix A). Exygen Research Page 11 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 3.0 INTRODUCTION This report details the results of the analysis for the determination of PFBS, PFHS, and PFOS in water and soil using the analytical methods entitled, "V0001780: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS," and "V0001781: Method of Analysis for die Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS." The study was initiated on November 05, 2004, when the study director signed protocol number P0001131. The analytical start date for this interim report was April 6,2005, and the analytical termination date for this interim report was June 27,2006. 4.0 ANALYTICAL TEST SAMPLES Thirty soil samples (Exygen ID C0053083-C0053112) were received at ambient temperature on December 10, 2004, from Tim Frinak at Weston Solutions, Inc. Thirtyeight soil samples (Exygen ID C0054348, C0054349, C0054351-C0054353, C0054355C0054357, C0054359, C0054361-C0054389) and four rinse water samples (Exygen ID C0054350, C0054354, C0054358, and C0054360) were received on wet ice on December 17, 2004, from Tim Frinak at Weston Solutions, Inc. Sixty-two soil samples (Exygen ID C0056619-C0056626, C0056628, C0056629, C0056631, C0056632, C0056634C0056645, C0056647-C0056681, C0056683-C0056685) and three rinse water samples (Exygen ID C0056627, C0056646, and C0056682) were received on wet ice on January 14, 2005, from Tim Frinak at Weston Solutions, Inc. Sixteen soil samples (Exygen ID C0056817-C0056820, C0056822-C0056828, C0056830-C0056834) and two rinse water samples (Exygen ID C0056821 and C0056829) were received on wet ice on January 20, 2005, from Tim Frinak at Weston Solutions, Inc. The samples were logged in by Exygen personnel and placed in refrigerated storage. The soil sample identification (ID) codes for the soil samples analyzed and reported consisted of five sections or strings in the following format: Dxxx-xx-xxxxxx-x(x)-xxxx. For the soil samples, the first string begins with D for Decatur, Alabama and the xxx defines the sampling location within the study area where: DF06 = Field 6 DF8b = Field 8b DF09 = Field 9 DF14 = Field 14 (reference field) DBKG = Northwest comer reference area DLOI = LOI well The second string defines the type of sample where: SB = soil boring sample Exygen Research SBC = soil boring composite sample Page 12 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 The third string defines the soil boring location. The fourth string more specifically defines the sample type where: 0 = primary field sample 2 = equipment rinseate blank sample The fifth string defines the collection depth of the soil samples where: 0000 = 0 to 3 inches (SB samples); 0 to 5 ft. (SBC samples) 0005 = 0.5 to 1 foot (SB samples) 0010 = 1 to 1.5 ft. (SB samples) 0020 = 2 to 2.5 ft. (SB samples) 0050 = 5 to 5.5 ft. (SB samples); 5 to 6 ft. (LOI SB samples); 5 to 10 ft. (SBC samples) 0100 = 10 to 11 ft. (SB samples); 10 to 15 ft. (SBC samples) 0150 = 15 to 20 ft. (SBC samples) 0200 = 20 to 25 ft. (SBC samples) other Oxxx = interval from xxx ft. to 1 ft. below xxx ft. (SB samples) Sample log-in and chain of custody information is located in the raw data package associated with this interim report. Storage records will be kept at Exygen Research. 5.0 REFERENCE MATERIAL The analytical standards, PFBS (Exygen ID SP0000252 and SP0005726) and PFHS (Exygen ID SP0002401), were supplied by 3M. PFBS (SP0000252) was received from 3M at Exygen on July 06,2000. PFBS (SP0005726) was received from 3M at Exygen on May 13, 2005. PFHS was received from 3M at Exygen on January 20, 2003. PFOS was purchased from Fluka Corporation and was received at Exygen on April 23,2003. The available information for the reference materials is listed below. PFBS and PFHS were stored frozen and PFOS was stored refrigerated. Compound PFBS PFBS PFHS PFOS Exygen Inventory No. SP0000252 SP0005726 SP0002401 SP0002694 Lot# 101 101 SE036 430180-1 Purity (%) 96.7 96.7 98.6 101.2 Expiration Date 12/04/06 12/04/06 10/18/06 10/31/07 The molecular structures of PFBS, PFHS and PFOS are given on the following page. Exygen Research Page 13 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 PFBS Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt (C4F9S03`K+) Transitions Monitored: 299 -> 99 Structure: FF FF S03 FF FF PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (CeFoSOsTC*) Transitions Monitored: 399 - 80 Structure: FFF FF F FFF FFF 3 PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CsFnSOa'K^ Transitions Monitored: 499 -->80 Structure: FFFF FFFF F SO3 FFFF FFFF 6.0 DESCRIPTION OF ANALYTICAL METHOD The analytical method "V0001781: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS" was used for the soil samples in this study. The analytical method "V0001780: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS" was used for the water samples in this study. Exygen Research Page 14 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 6.1. Extraction Procedure For Soil The soil samples were extracted using the procedure indicated in Exygen method V0001781. Before the samples were weighed for the extraction, they were placed into a new, clean Ziploc bag and mixed thoroughly. The samples were then transferred back to the sampling container. A 5 gram portion of soil was weighed into a fifty milliliter centrifuge tube for the extraction. After fortification of appropriate samples, 5 mL of methanol was added to the samples. The samples were allowed to shake on a wrist action shaker for -15 minutes and were then sonicated in an ultrasonic bath for ~15 minutes. The volume was taken to 40 mL with water and the samples were then centrifuged for ~10 minutes at -3000 rpm. The supernatant was then loaded onto a Cjg SPE cartridge conditioned with 10 mL of methanol and 5 mL of water. The eluate was discarded. Approximately five milliliters of methanol was added to the cartridge. Five milliliters of eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.2 Percent Solids Procedure For Soil Percent solids were determined using the procedure indicated in Exygen method V0001658. Approximately 1- 10 grams of sample was weighed into a pan. The weight of the sample plus the pan was recorded. The samples were then dried in an oven overnight at 104 1 C. Then the samples were transferred to a dessicator and allowed to cool for -15 minutes. Each sample was then weighed again, including the weight of the pan. The percent solid for each sample was then calculated. 6.3 Extraction Procedure For Water The water samples were extracted using the procedure indicated in Exygen method V0001780. A 40 mL aliquot of the water sample was used for the extraction procedure. The samples were loaded onto a Cis SPE cartridge conditioned with 10 mL of methanol and 5 mL of water. The eluate was discarded. Approximately five milliliters of methanol was added to the cartridge. Five milliliters of eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.4 Preparation of Standards and Fortification Solutions Individual stock standard solutions of PFBS, PFHS and PFOS were prepared as specified in Exygen method V0001781. The stock standard solutions were prepared at a concentration of 100 pg/mL by dissolving 10 mg of each of the standards (corrected for purity and salt content) in methanol. From these solutions, mixed 1.0 pg/mL fortification standard solutions were prepared by taking 1 mL of each of the appropriate stock Exygen Research Page 15 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 solutions and bringing the volume up to 100 mL with methanol. By taking 10 mL of the mixed 1.0 pg/mL fortification standard and bringing the volume up to 100 mL with methanol, a mixed 0.1 pg/mL fortification standard was prepared. By taking 10 mL of the mixed 0.1 pg/mL fortification standard and bringing the volume up to 100 mL with methanol, a mixed 0.01 pg/mL fortification standard was prepared. A mixed stock standard solution of PFBS, PFHS, and PFOS was also prepared. The stock standard solution was prepared at a concentration of 1000 pg/mL by dissolving 100 mg of each of the standards (corrected for purity and salt content, if necessary) in methanol. From this solution, a 100 pg/mL fortification standard solution was prepared by taking 10 mL of the stock and bringing the volume up to 100 mL with methanol. By taking 10 mL of the 100 pg/mL fortification standard and bringing the volume up to 100 mL with methanol, a 10 pg/mL fortification standard was prepared. By taking 10 mL of the 10 pg/mL fortification standard and bringing the volume up to 100 mL with methanol, a 1.0 pg/mL fortification standard were prepared. By taking 10 mL of the 1.0 pg/mL fortification standard and bringing the volume up to 100 mL with methanol, a 0.1 pg/mL fortification standard was prepared. By taking 10 mL of the 0.1 pg/mL fortification standard and bringing the volume up to 100 mL with methanol, a 0.01 pg/mL fortification standard were prepared. A set of standards containing PFBS, PFHS and PFOS was prepared in water and processed through the extraction procedure, identical to samples. The following concentrations were prepared: Cone, of Fort Fort Solution Volume (ng/mL)1 (pL) 00 10 100 10 200 10 400 100 100 100 200 100 400 1of PFBS, PFHS and PFOS Volume of Fortified Sample (mL) 40 40 40 40 40 40 40 Final Cone, of Calibration Std. (ng/L) 0 25 50 100 250 500 1000 The stock standard solution and all fortification and calibration standard solutions were stored in a refrigerator (4 2C) when not in use. Documentation of standard preparation is located in the raw data package associated with this interim report. 6.5 Chromatography Quantification of PFBS, PFHS and PFOS was accomplished by LC/MS/MS electrospray. The retention times of PFBS, PFHS and PFOS were ~ 3.0 mins, ~ 10.0 mins, and ~ 13.2 mins, respectively. Peaks above the LOQ were not detected in any of the reagent blank samples corresponding to the analyte retention time. Exygen Research Page 16 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 6.6 Instrument Sensitivity The smallest standard amount injected during the chromatographic run had a concentration of 25 ng/L of PFBS, PFHS and PFOS. 6.7 Description of LC/MS/MS Instrument and Operating Conditions Instrument: Interface: Computer: Software: HPLC: API 4000 Biomolecular Mass Analyzer Turbo Ion Spray Liquid Introduction Interface DELL OptiPlex GX400 Windows NT, Analyst 1.4.1 Hewlett Packard (HP) Series 1100 HP Quat Pump HP Vacuum Degasser HP Autosampler HP Column Oven HPLC Column: Thermo Fluophase RP, 50 mm x 2.1 mm Column Temp.: 35 C Injection Voi.: 15 pL Mobile Phase (A): 2 mM Ammonium Acetate in water Mobile Phase (B): Methanol Time (miri) 0.0 1.0 8.0 10.0 11.0 18.0 Total run time: -18 min Flow Rate: 0.3 mL/min Ions monitored: %A 65 65 25 25 65 65 Analvte Mode PFBS PFHS PFOS negative negative negative %B 35 35 75 75 35 35 Transition Monitored 299 -> 99 399 80 499 -> 80 Approximate Retention Time (miri) ~3.0 min. -10.0 min. -13.2 min. Exygen Research Page 17 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 6.8 Quantitation and Example Calculation Fifteen microliters of sample or calibration standard were injected into the LC/MS/MS. The peak area was measured and the standard curve was generated (using 1/x fit weighted linear regression) by Analyst software using six concentrations of standards, except in a few cases of PFBS, where only five were used; as the 500 ng/L standard results were rejected as outliers. The concentration was determined from the following equations. Equation 1 calculated the amount of analyte found (in ng/L, based on peak area) using the standard curve (linear regression parameters) generated by the Analyst software program. Equation 1: Analyte found (ng/L) = (Peak area - intercept! x DF Slope Where: DF = Dilution Factor, factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of PFBS, PFHS and PFOS prior to extraction, Equation 2 was used to calculate the percent recovery. Equation 2: Recovery (%) = (analyte found (ng/L) - analyte in control (ng/LV) xl00% amount added (ng/L) Note: For the analyte recovery calculation, the "control" is the unspiked aliquot of the primary field sample. Equation 3 was used to convert the amount of PFBS, PFHS and PFOS found in ng/L to ng/g (ppb) on a wet weight basis. Equation 3: Analyte found (ppb) = [Analyte found (ng/L) x volume extracted (0.04D1 sample weight (5 g) Equation 4 was then used to calculate the amount of PFBS, PFHS and PFOS found in ppb based on dry weight. Equation 4: Analyte found (ppb) dry weight = Analyte found (ppb) x [100% / total solids(%)] NOTE: Total solids (%) = [wet weight (g) / dry weight (g)] x 100% Exygen Research Page 18 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 An example of a calculation using an actual sample follows (calculation is for PFBS only): Soil sample Exygen DD: C0053098 Spk C (Set: 040705B), fortified at 500 ng/L with where: peak area intercept = 97341 = 0.000947 slope = 120 dilution factor ng/L PFOA added (fort level) ng/L in corresponding sample volume extracted (L) = = = = 1 500 381 0.04 sample weight (g) =5 total solids (%) 83.29 = From equation 1: Analvte found (ng/Ll = [97341 - 0.0009471 x 1 120 = 811 ng/L From equation 2: % Recovery = (811 ng /L - 381 ng/L) x 100% 500 ng/L = 86% From equation 3: Analyte found (ppb) = (811ne/Lx 0.04L1 5g = 6.49 ppb From equation 4: Analyte found (ppb) dry weight = 6.49 ppb x (100% / 83.29%) = 7.79 ppb Note: Numbers may vary slightly due to rounding. Exygen Research Page 19 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 7.0 EXPERIMENTAL DESIGN For soil samples designated as laboratory matrix spikes, PFBS, PFHS, and PFOS were added at a known concentration to the samples in the laboratory after the samples were weighed for extraction. For the rinse water samples, empty bottles were shipped to the field, and filled. The samples were extracted in twenty-nine sets. Each set included one reagent blank and two reagent blanks, consisting of methanol, fortified at known concentrations of PFBS, PFHS and PFOS. Twenty-two sets contained five sample sites and six sets contained six sample sites. The nine rinse water samples were placed in their own set from nine sample sites. One soil sample was collected for each sample site. For each site (except rinse water sites), two laboratory matrix spikes and a duplicate were extracted. The samples were re-extracted in twenty sets. Each set included one reagent blank and two reagent blanks, consisting of methanol, fortified at known concentrations of PFBS, PFHS and PFOS. Six sets contained seven sample sites; six sets contained six samples sites; three sample sets contained eight samples sites; three sample sets contained five sample sites, one set contained four samples sites, and one set contained three sample sites. One soil sample was collected for each sample site. For each site variable matrix spikes of adequate concentration were extracted 8.0 RESULTS Analytical results and accessed accuracies for the analysis of PFBS, PFHS and PFOS found in soil samples are summarized in Table I. Analytical results and accessed accuracies for the analysis of PFBS, PFHS and PFOS found in re-extracted soil samples are summarized in Table II. Analytical results for the analysis of PFBS, PFHS and PFOS found in the equipment rinseate blank samples are summarized in T able III. Quantitative results were obtained for all samples and analytes except for PFBS in eleven samples, PFHS in one sample, and PFOS in five samples that are not reported due to quality control failures. Accuracies were assessed for each sample by reviewing the individual QC results obtained for each sample site. For the soil samples, there were two laboratory spike recovery results available for each sample site that were used to assess the accuracy. In instances of failed laboratory spike recoveries, the samples were not reported due to the quality control failure. The average percent recoveries standard deviations determined using wet weight for PFBS, PFHS, and PFOS in soil samples were 78% 16%, 89% 14%, and 91% 21%, respectively. The average percent recoveries standard deviations determined using wet Exygen Research Page 20 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 weight for PFBS, PFHS, PFOS in re-extracted soil samples were 87% 27%, 92% 23%, and 95% 24%, respectively. Percent solid results are detailed in Table VI. 9.0 CONCLUSIONS Except as noted above, the soil samples were extracted and analyzed for PFBS, PFHS and PFOS according to analytical method V0001781. Additional sample analysis was performed at the direction of the Study Director to obtain quantitative analytical results for the soil samples reported as re-extractions. The water samples were also successfully extracted and analyzed for PFBS, PFHS and PFOS according to analytical method V0001780. 10.0 RETENTION OF DATA AND SAMPLES When the final analytical report is complete, all original paper data generated by Exygen Research will be shipped to the sponsor. This does not include facility-specific raw data such as instrument or temperature logs. Exact copies of all raw data, as well as a signed copy of the final analytical report and all original facility-specific raw data, will be retained in the Exygen Research archives for the period of time specified in EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Exygen Research Page 21 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 TABLES Exygen Research Page 22 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Exvnen ID C0053083 C0053083 Rep C0053084 C0053084 Rep C0053085 C005308S Rep C0053086 C0053086 Rep C0053087 C0053087 Rep COO5 3 0 8 8 C0053088 Rep C0053089 C0053089 Rep C0053090 C00S3090 Rep C0053091 C0053091 Rep C00S3092 C0053092 Rep C0053093 C0053093 Rep C0053094 C0053094 Rep C0053095 C0053095Rep C0053096 C0053096 Rep C0053097 C0053097 Rep C0053098 C0053098 Rep C0053099 C0053099 Rep C0053100 C0053100 Rep C0053101 C0053101 Rep C0053102 C0053102 Rep C0053103 C0053103 Rep C0053104 C0053104 Rep C0053105 C0053105 Rep C lie n t S am ple ID DF06-SB-132R-0-0000 DF06-SB-132R-0-0000* DF06-SB-132R-0-0005 DF06-SB-132R-0-0005* DF06-SB-132R-0-0010 DF06-SB-132R-0-0010* DF06-SB-132R-0-0020 DF06-SB-132R-0-0020* D F 0 6-S B -132R -0-0050 DF06-SB-132R-0-0050* DF06-SB-132R-0-0445 DF06-SB-132R-0-0445* D F 0 6-S B -133R -0-0000 DF06-SB-133R-0-0000* D F06-SB-133R-0-0005 DF06-SB-133R-0-0005* DF06-SB-133R-0-0010 DF06-SB-133R-0-0010* D F 0 6-S B -133R -0-0020 DF06-SB-133R-0-0020* DF06-SB-133B-0-0000 DF06-SB-133B-0-0000* DF06-SB-133B-0-0005 DF06-SB-133B-0-0005* DF06-SB-133B-0-0010 DF06-SB-133B-0-0010* DF06-SB-133B-0-0020 DF06-SB-133B-0-0020* DF09-SB-131R-0-0000 D F 0 9-S B -1 3 1 R -0-0000* D F 0 9-S B -1 3 1 R -0-0005 D F 0 9-S B -1 3 1 R -0-0005* DF09-SB-131R-0-0010 DF09-SB-131R-0-0010* D F 0 9 -S B -1 3 1 R -0-0020 D F 0 9-S B -1 3 1 R -0-0020* D F 0 9 -S B -1 3 1 B -0-0000 D F09-S B -131 B-0-0000* D F 0 9-S B -1 31B -0-0005 DF09-SB-131B-0-0005* DF09-SB-131B-0-0010 DF09-SB-131B-0-0010* D F 0 9-S B -1 3 1 B -0-0020 DF09-SB-131B-0-0020* DF06-SBC-133R-0-0000 DF06-SBC-133R-0-0000* C4 Sulfonate PFBS C6 Sulfonate PFHS C8 Sulfonate PFOS Parfluofobutanftsulfonate______ PerfluorohexanatuHonata______ Parfluorooctanasulfonata Analyte Found (ra/n) drv wt. Assessed Accuracy (+/- %) Analyte Found (nfl/n) * v wt. Assessed Accuracy (/-% ) A n a ly te Found ino/o) dry wt. Assessed Accuracy (/-% ) 0.857 1.03 ND 30 30 30 10.3 10.3 1.06 40 NR 40 NR 30 NR - ND 0.275 0:245 1.02 0.995 0.874 0.951 NR NR 1.73 2.42 0.457 0.629 0.310 30 30 30 30 30 30 30 - 30 30 30 30 30 1.24 1.69 1.68 4.21 4.05 NR NR 2.34 1.86 15.3 28.3 8.03 10.0 2.54 30 NR - 30 NR - 30 NR - 30 NR - 30 NR - - NR - - NR - 30 24.6 40 30 19.4 40 30 NR - 30 NR - 30 NR - 30 NR - 30 NR - 0.271 0.640 0.633 2.12 1.97 0.818 0.708 0.784 0.821 2.19 2.68 3.53 2.88 3.66 4.23 0.924 1.04 1.30 1.39 3.78 3.67 3.52 3.17 1.05 30 30 30 30 30 30 30 30 30 40 40 30 30 30 30 30 30 30 30 50 50 30 30 30 2.47 5.70 5.57 29.6 27.9 15.4 12.2 6.88 6.94 20.0 24.3 54.6 54.5 NR NR 16.1 17.4 18.5 19.5 73.9 84.4 NR NR 59.7 30 NR 30 NR 30 NR 30 NR 30 NR 30 NR 30 NR 30 NR 30 NR 40 NR 40 NR 30 NR 30 NR - NR - NR 30 NR 30 NR 30 NR 30 NR 30 NR 30 NR - NR - NR 30 NR - 0.960 3.89 3.88 0.927 0.907 30 30 30 30 30 55.8 106 104 9.28 9.36 30 NR 30 NR 30 NR 50 NR 50 NR - ` Laboratory Duplicate ng/g.ND h Not detected at or above 0.2 N R = Not reported due to quality control failures, see Table II for re-extract data. Note: This summary table shows rounded results, therefore, results may vary slightly from the values in the raw data. Exygen Research Page 23 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Continued Exygen ID C0053106 C0053106 Rep C0053107 C0053107 Rep C0053108 C0053108 Rep C0053109 C0053109 Rep C0053110 C 0053110 Rep C0053111 C 00 5 3 1 11 Rep C0053112 C0053112 Rep C0054361 C0054361 Rep C0054362 COO543 6 2 Rep C0054363 C0054363 Rep C0054364 C00S4364 Rep C0054348 C0054348 Rep COO5 4 3 4 9 C0054349 Rep C0054365 C0054365 Rep C0054366 C0054366 Rep C0054367 C0054367 Rep C0054351 C0054351 Rep C0054368 C0054368 Rep C0054369 C0054369 Rep C0054370 C0054370 Rep C0054371 C0054371 Rep C0054352 C0054352 Rep C0054353 C0054353 Rep C lie n t S a m ple ID D F 0 6-S B -133R -0-0050 DF06-SB-133R-0-0050* DF06-SBC-133R-0-0050 DF06-SBC-133R-0-0050* DF06-SBC-133R-0-0100 D F 0 6 -S B C -1 3 3 R -0 -0 100* D F 0 6 -S B C -1 3 3 R -0 -0 1 50 D F0 6-S B C -1 3 3R -0 -0 150` DF06-SB-133R-0-0180 DF06-SB-133R-0-0180* D F 0 6-S B C -133R -0-0200 DF06-SBC-133R-0-0200* D F 0 6-S B C -133R -0-0250 DF06-SBC-133R-0-0250* DF8b-SB-135R-0-0000 DF8b-SB-135R-0-0000* DF8b-SB-135R-0-0005 DF8b-SB-135R-0-0005* DF8b-SB-135R-0-0010 DF8b-SB-135R-0-0010* DF8b-SB-135R-0-0020 DF8b-SB-135R-0-0020* DF09-SB-131B-0-0050 D F 0 9-S B -1 3 1 B -0-0050* DF09-SB-131B-0-0080 D F 0 9-S B -1 3 1 B -0-0080* DF8b-SB-135R-0-0050 DF8b-SB-135R-0-0050* DF8b-SB-135R-0-0190 DF8b-SB-135R-0-0190* DF14-SB-137R-0-0000 DF14-SB-137R-0-0000* DF14-SB-137R-0-0005 DF14-SB-137R-0-0005* DF14-SB-137R-0-0010 DF14-SB-137R-0-0010* DF14-SB-137R-0-0020 DF14-SB-137R-0-0020* DF14-SB-136R-0-0000 DF14-SB-136R-0-0000* DF14-SB-136R-0-0005 DF14-SB-136R-0-0005* DF14-SB-136R-0-0010 DF14-SB-136R-0-0010* D F 1 4-S B -136R -0-0020 DF14-SB-136R-0-0020* C4 S ulfonate PFBS Perfluorobutanesulfonata Analyte Found (ng/fl) dry wt. Assessed Accuracy </-%) 3.22 0.846 26.0 12.8 30 30 30 30 NR NR NR NR - NR NR NR NR NR NR 2.00 2.36 - 30 30 NR NR - NR NR NR NR 6.21 4.47 5.57 5.95 NR 50 50 40 40 - NR - NR - NR ND 50 ND 50 ND 50 ND 50 ND 30 ND 30 ND 30 ND 30 ND 30 ND 30 ND 50 ND 50 ND 40 ND 40 ND 50 ND 50 C6 S ulfonate PFHS Parfluorohexantsutfonats Analyte Found (ng/g) dry wt. Assessed Accuracy (+/-% ) NR NR NR NR NR NR 63.9 66.2 45.5 42.1 43.7 41.8 1.24 1.15 16.8 20.5 5.29 5.59 12.3 13.3 NR NR 56.1 41.7 55.0 55.3 50.4 39.6 85.1 87.1 1.43 1.36 ND ND ND ND ND ND ND ND ND ND ND ND ND ND - - - - - - 40 40 40 40 30 30 30 30 30 30 40 40 40 40 - - 40 40 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 C8 S ulfonate PFOS Perfluorooctanttutfonata A n a ly te Found (nfl/fl)drywt. Assessed Accuracy (+ /-% ) NR NR - NR NR NR - NR NR NR NR NR NR NR 4.28 4.24 NR NR NR NR NR NR NR NR NR NR - 30 30 - NR NR NR - NR NR NR - NR NR 43.3 41.1 24.4 23.0 4.48 6.23 39.1 39.4 118 - - 30 30 30 30 30 30 30 30 30 92.9 91.7 81.5 30 30 30 22.1 34.0 30 30 ` Laboratory Duplicate ND = Not detected at or above 0.2 ng/g. N R = Not reported due to quality control failures, see Table II for re-extract data. Note: This summary table shows rounded results, therefore, results may vary slightly from the values in the raw data. Exygen Research Page 24 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Continued E x y g e n ID C0054372 C0054372 Rep C0054373 C0054373 Rep C0054374 C0054374 Rep C0054355 C0054355 Rep C0054375 C0054375 Rep C0054376 C0054376 Rep C0054356 C0054356 Rep C0054377 C0054377 Rep C0054378 C0054378 Rep C0054379 C0054379 Rep C0054357 C0054357 Rep COO5 4 3 8 0 C0054380 Rep C0054381 C0054381 Rep C0054382 C0054382 Rep C0054383 C0054383 Rep COO5 4 3 8 4 C0054384 Rep C0054385 C0054385 Rep C0054386 C0054386 Rep C005437 C0054387 Rep C0054388 C0054388 Rep C0054389 C0054389 Rep C0054359 C0054359 Rep C0056619 C0056619 Rep C lie n t S am ple ID DF14-SB-136B-0-0000 DF14-SB-136B-0-0000* DF14-SB-136B-0-0005 DF14-SB-136B-0-0005* DF14-SB-136B-0-0010 DF14-SB-136B-0-0010* DF14-SB-136B-0-0020 DF14-SB-136B-0-0020* DF09-SBC-131R-0-0000 D F 0 9-S B C -1 3 1 R -0-0000* D F 0 9-S B -1 3 1 R -0-0050 DF09-SB-131R-0-0050* D F09-S B C -131 R -0-0050 D F09-SBC-131 R-0-0050* DF09-SBC-131R-0-0100 DF09-SBC-131R -0-0100* D F09-S B -131 R -0-0160 D F09-S B -131 R -0-0160* D F09-S B C -131 R -0-0150 DF09-SBC-131 R-0-0150* DF09-SBC-131R-0-0200 D F 0 9-S B C -1 3 1 R -0-0200* DF09-SBC-131R-0-0250 D F 0 9-S B C -1 3 1 R -0-0250* DF06-SB-133B-0-0050 DF06-SB-133B-0-0050* DF06-SB-133B-0-0160 DF06-SB-133B-0-0160* DF14-SB-137R-0-0050 DF14-SB-137R-0-0050* D F 1 4-S B C -137R -0-0000 DF14-SBC-137R-0-0000* DF14-SBC-137R-0-0050 DF14-SBC-137R-0-0050* D F 1 4-S B C -137R -0-0100 DF14-SBC-137R-0-0100* DF14-SBC-137R-0-0160 DF14-SBC-137R-0-0150* D F 1 4-S B -137R -0-0180 D F 1 4-S B -1 3 7 R -0 -0 180* DF14-SB-136R-0-0050 DF14-SB-136R-0-0050* DF14-SB-136R-0-0290 DF14-SB-136R-0-0290* DF14-SB-136B-0-0050 D F 1 4-S B -136B -0-0050* C 4 Sulfonate PFBS Perfluorobutanesutfonate Analyte Found (nfl/g)drywt. Assessed Accuracy (+/-% ) ND 30 ND 30 NR - NR ND 50 ND 50 ND 40 ND 2.38 2.03 6.84 6.56 19.7 16.4 33.5 34.2 40 30 30 30 30 30 30 30 30 35.7 29.2 35.7 33.7 33.8 28.8 5.69 8.66 30 30 40 40 30 30 30 30 20.7 22.3 NR 30 30 - NR ND ND ND 0.784 0.273 ND ND ND NO ND ND ND ND - 30 30 30 30 30 30 30 30 30 30 40 40 30 ND 30 NR NR ND 30 ND 30 C6 Sulfonate PFHS PerfluorohexanasuHonata A n a ly te Found (ng/g) dry wt. Assessed Accuracy (/-% ) ND 30 ND 30 ND 30 ND 30 ND 30 ND 30 ND 30 ND 30 44.8 30 34.9 30 53.0 30 48.8 30 NR - NR - 191 30 187 30 NR - NR NR - NR - NR - NR - 52.7 70.6 30 30 NR NR - 77.6 30 74.4 0.458 30 30 0.400 30 0.795 0.945 30 30 0.337 30 0.301 30 0.912 0.695 0.918 0.867 1.55 30 30 30 30 30 1.42 ND 30 30 ND 30 ND 30 ND 30 ND 30 ND 30 C8 Sulfonate PFOS Parfluorooctanasutfonata A n a ly te Found (ng/g) dry wt. 28.4 23.4 62.5 70.6 59.7 70.5 7.76 9.51 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR 59.2 78.0 0.959 1.12 34.2 19.1 NR NR 25.4 18.1 72.0 86.6 ND 0.238 0.952 0.887 Assessed Accuracy (+/-% ) 30 30 30 30 50 50 30 30 - - - - - - 40 40 30 30 50 50 - 30 30 30 30 30 30 30 30 ' Laboratory Duplicate N D = Not detected at or above 0.2 ng/g. N R = Not reported due to quality control bilures, see Table II for re-extract data. Note: This summary table shows rounded results, therefore, results may vary slightly from the values In the raw data. Exygen Research Page 25 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Continued Exvoen ID C0056620 C0056620 Rep C0056621 C0056621 Rep C0056622 C0056622 Rep C0056623 C0056623 Rep C0056624 C0056624 Rep C0056625 C005662S Rep C0056626 C0056626 Rep C0056628 C0056628 Rep C0056629 C0056629 Rep C0056631 C0056631 Rep C0056632 C0058632 Rep C0056634 C0056634 Rep C0056635 C005663S Rep C0056636 C0056636 Rep C0056637 C0056637 Rep C0056638 C0056638 Rep C0056639 C0056639 Rep C0056640 C0056640 Rep C0056641 C0056641 Rep C0056642 C0056642 Rep C0056643 C0056643 Rep C0056644 C0056644 Rep C0056645 C0056645 Rep C lie n t S a m ple ID DF14-SB-136B-0-0290 DF14-SB-136B-0-0290* D F 8 b-S B -134R -0-0000 DF8b-SB-134R-0-0000* DF8b-SB-134R-0-0005 DF8b-SB-134R-0-0005* DF8b-SB-134R-0-0010 DF8b-SB-134R-0-0010* D F 8 b-S B -134R -0-0020 DF8b-SB-134R-0-0020* D F 8 b-S B -134R -0-0050 DF8b-SB-134R-0-0050* DF8b-SBC-134R-0-0000 DF8b-SBC-134R-0-0000* DF8b-SBC-134R-0-0050 DF8b-SBC-134R-0-0050* DF8b-SBC-134R-0-0100 DF8b-SBC-134R-0-0100* DF8b-SBC-134R-0-0150 D F8b-S B C -134R -0-0150* DF8b-SBC-134R-0-0200 DF8b-SBC-134R-0-0200* D F 8 b-S B -134R -0-0270 DF8b-SB-134R-0-0270* DF8b-SBC-134R-0-0250 DF8b-SBC-134R-0-0250* DF8b-SB-134B-0-0000 DF8b-SB-134B-0-0000* DF8b-SB-134B-0-0005 DF8b-SB-134B-0-0005* DF8b-SB-134B-0-0010 DF8b-SB-134B-0-0010* DF8b-SB-134B-0-0020 DF8b-SB-134B-0-0020* D F 0 9-S B -130R -0-0000 DF09-SB-130R-0-0000* DF09-SB -130R -0-0005 DF09-SB-130R-0-0005* DF09-SB-130R-0-0010 DF09-SB-130R-0-0010* D F 0 9-S B -130R -0-0020 DF09-SB-130R-0-0020* DF8b-SB-134B-0-0050 DF8b-SB-134B-0-0050* DF8b-SB-134B-0-0090 DF8b-SB-134B-0-0090* C4 Sulfonate PFBS C6 Sulfonate PFHS C8 Sulfonate PFOS Parfluorobutanssulfonate______Parfluorohexanesulfonata______ PartluofooctanaauUonata Analyte Found (ng/g) dry wt. Assessed Accuracy </-%) Analyte Found (ng/g) dry wt. Assessed Accuracy (+/-% ) A n a ly te Found (ng/g) dry wt. Assessed Accuracy (+/-% ) NR NR - NR NR NR - NR - NR NR 1.30 0.701 0.763 0.730 2.21 2.26 30 30 30 30 30 30 141 145 NR NR 39.7 46.0 69.4 73.5 40 NR 40 NR - NR - NR 30 NR 30 NR 30 NR 30 NR - 2.19 2.30 2.01 3.44 NR NR NR NR 35.7 43.1 30 30 30 30 30 30 109 108 NR NR NR NR NR NR NR NR 30 NR 30 NR - NR - NR - NR - NR - NR - NR - NR - NR - 15.1 19.9 NR NR NR NR 9.27 16.6 50 50 - 30 30 NR NR NR NR NR NR NR NR - NR - NR - NR - NR - NR - NR - NR - NR - 4.57 33.8 0.255 0.311 0.490 0.440 1.80 1.77 0.259 30 30 30 30 30 30 30 30 30 NR NR 15.1 16.4 22.2 23.2 7.76 7.51 1.50 - NR * - NR 30 NR 30 NR * 30 NR 30 NR 30 NR 30 NR 30 NR - 0.238 0.569 30 40 1.50 2.06 30 NR 30 NR - 0.488 0.662 0.628 NR NR NR NR 40 40 40 1.35 1.76 2.22 96.6 101 NR NR 30 NR 30 NR 30 NR 30 NR 30 NR - NR - NR Laboratory Duplicate ND = Not detected at or above 0.2 ng/g. N R = Not reported due to quality control failures, see Table II for reextract data. Note: This summary table shows rounded results, therefore, results may vary slightly from the values in the raw data. Exygen Research Page 26 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Continued E xyg e n ID C0056647 C0056647 Rep C0056648 C0056648 Rep C0056649 C0056649 Rep C0056650 C0056650 Rep C0056651 C0056651 Rep C0056652 C0056652 Rep COO5 6 6 5 3 C0056653 Rep C0056654 C0056654 Rep C0056655 C0056655 Rep C0056656 C0056656 Rep C0056657 C0056657 Rep C0056658 C0056658 Rep C0056659 C0056659 Rep C0056660 C0056660 Rep C0056661 C0056661 Rep C0056662 C0056662 Rep C0056663 C0056663 Rep COO5 6 6 6 4 C0056664 Rep C0056665 C0056665 Rep C0056666 C0056666 Rep C0056667 C0056667 Rep C0056668 C0056668 Rep C0056669 C0056669 Rep C lie n t S a m ple ID DF09-SB-130R-0-0050 DF09-SB-130R-0-0050* DF09-SB-130R-0-0150 DF09-SB-130R-0-0150* DLCJI-SB-220R-0-0000 D LO I-S B -2 2 0R -0 -00 0 0 * D LO I-S B -2 2 0 R -0 -0 0 0 5 D LO I-S B -2 2 0R -0 -00 0 5 * D LO I-S B -2 2 0 R -0 -0 0 2 0 D LO I-S B -2 2 0R -0 -00 2 0 * D LO I-S B -2 2 0 R -0 -0 0 5 0 D LO I-S B -2 2 0R -0 -00 5 0 * D LO I-S B -2 2 0R -0 -01 70 D LO I-S B -2 2 0R -0 -01 70* D LO I-S B -220L-0-0000 D LO I-S B -2 2 0L -0 -00 0 0 * D LO I-S B -2 2 0L -0 -00 0 5 D LO I-S B -2 2 0L -0 -00 0 5 * D LO I-S B -220L-0-0020 D LO I-S B -2 2 0L -0 -00 2 0 * D LO I-S B -220L-0-0050 D LO I-S B -2 2 0L -0 -00 5 0 * D LO I-S B -2 2 0L -0 -00 7 0 D LO I-S B -2 2 0L -0 -00 7 0 * D L O I-S B -2 2 6 R -0 -0 0 0 0 D LO I-S B -2 2 6R -0 -00 0 0 * D LO I-S B -2 2 6 R -0 -0 0 0 5 D LO I-S B -2 2 6R -0 -00 0 5 * D L O I-S B -2 2 6 R -0 -0 0 2 0 D LO I-S B -2 2 6R -0 -00 2 0 * D LO I-S B -2 2 6 R -0 -0 0 5 0 D LO I-S B -2 2 6R -0 -00 5 0 * D LO I-S B -2 2 6R -0 -01 80 D LO I-S B -2 2 6R -0 -01 80* D LO I-S B -2 2 6L -0 -00 0 0 D LO I-S B -2 2 6L -0 -00 0 0 * D LO I-SB -226L-0-0005 D LO I-S B -226L-0-0005* D LO I-S B -226L-0-0020 D LO I-S B -226L-0-0020* D LO I-S B -2 2 6L -0 -00 5 0 D LO I-S B -226L-0-0050* D L O I-S B -2 2 6 L -0 -0 1 70 D L O I-S B -2 2 6 L -0 -0 1 70* D B K G -S B C -00 1 B -0 -01 50 DBKG-SBC-001 B-0-0150* C4 Sulfonate PFBS Parfluorobutanasulfonata Analyte Assessed Found Accuracy (ng/g) dry wt. (+/-% ) 5.24 30 5.79 30 5.38 30 7.23 30 2.05 2.26 40 40 0.437 40 0.402 1.22 40 40 1.13 NR NR NR NR 40 - 0.938 30 0.995 30 0.316 30 0.318 30 1.03 40 1.16 NR NR NR NR 40 - 0.983 50 1.11 50 0.680 50 0.592 50 0.753 40 0.789 1.35 1.76 0.441 0.488 40 30 30 30 30 2.33 50 2.35 0.483 50 50 0.460 NR NR NR NR NR NR NR NR 50 - * C6 Sulfonate PFHS Pnrfluorolw xM M utfonate A n a ly te Assessed Found (ng/g) dry wt. Accuracy <+/- %) 42.6 30 47.8 55.7 71.0 30 30 30 1.07 0.894 30 30 0.337 30 0.323 1.15 30 30 1.27 0.750 0.852 30 30 30 5.22 7.32 0.879 0.910 30 30 30 30 0.331 30 0.321 30 2.23 2.37 30 30 3.48 30 3.68 30 1.93 30 1.80 30 0.561 30 0.571 30 0.446 30 0.497 30 0.317 30 0.318 ND 30 30 0.241 0.689 0.632 30 30 30 1.29 1.34 0.472 30 30 30 0.429 0.522 30 30 0.567 30 0.308 30 0.301 0.762 30 30 0.589 30 ND 30 ND 30 C8 Sulfonate PFOS PtrfluorooctanM ulfonata Analyte Assessed Found Accuracy (ng/g) dry wt. (+ /- %) NR - NR - NR - NR 123 40 138 40 NR - NR - 96.2 40 139 16.7 40 30 19.5 30 6.75 6.44 30 30 NR - NR NR - NR - NR - NR - 25.9 30 28.6 30 NR * NR - 108 30 149 30 NR NR - NR - NR 27.4 30 31.1 NR 30 - NR NR NR 136 30 142 86.5 30 30 96.9 7.43 30 40 6.52 40 NR - NR 0.716 30 0.613 30 'Laboratory Duplicate ND = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table II for re-extract data. Note: This summary table shows rounded results, therefore, results may vary slightly from the values in the raw data. Exygen Research Page 27 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Continued Exvoen ID COO5 6 6 7 0 C0056670 Rep C0056671 C0056671 Rep C0056672 C0056672 Rep COO5 6 6 7 3 C0056673 Rep COO5 6 6 7 4 C0056674 Rep C0056675 C0056675 Rep C0056676 C0056676 Rep C0056677 C0056677 Rep C0056678 C0056678 Rep C0056679 C0056679 Rep C0056680 C0056680 Rep C0056681 C0056681 Rep C0056683 C0056683 Rep COO5 6 6 8 4 C0056684 Rep C0056685 C0056685 Rep C0056817 C0056817 Rep C0056818 C0056818 Rep C0056819 C0056819 Rep COO5 6 8 2 0 C0056820 Rep COO5 6 8 2 2 C0056822 Rep COO5 6 8 2 3 C0056823 Rep C0056824 C0056824 Rep C0056825 C0056825 Rep C lie n t S a m ple ID D B K G -S B C -001B -0-0200 DBKG-SBC-001 B-0-0200* D LO I-S B -310R -0-0000 DLOI-SB-31OR-O-OOOO* DLOI-SB-31 OR-0-0005 DLOI-SB-31 OR-0-0005* DLOI-SB-31 OR-0-0020 D LO I-S B -3 1 0R -0 -00 2 0 * D LO I-S B -3 1 0 R -0 -0 0 5 0 DLOI-SB-31 OR-0-0050* D LO I-S B -310R -0-0370 D LO I-S B -3 1 0R -0 -03 7 0 * D B K G -S B -001B -0-0000 DBKG-SB-001 B-0-0000* DBKG-SB-001 B-0-0005 DBKG-SB-001 B-0-0005* DBKG-SB-001 B-0-0010 DBKG-SB-001 B-0-0010* DBKG-SB-001 B-0-0020 DBKG-SB-001 B-0-0020* DBKG-SB-001 B-0-0050 DBKG-SB-001 B-0-0050* DBKG-SB-001 B-0-0230 DBKG-SB-001 B-0-0230* DBKG-SBC-001 B-0-0000 DBKG-SBC-001 B-0-0000* DBKG-SBC-001 B-0-0050 DBKG-SBC-001 B-0-0050* DBKG-SBC-001 B-0-0100 DBKG-SBC-001 B-0-0100* D LO I-S B -3 1 7L -0 -00 0 0 D LO I-S B -3 1 7L -0 -00 0 0 * D LO I-S B -3 1 7L -0 -00 0 5 D LO I-S B -3 1 7L -0 -00 0 5 * D LO I-S B -3 1 7L -0 -00 2 0 D L O I-S B -3 1 7 L -0 -0 0 2 0 * D LO I-S B -3 1 7L -0 -00 5 0 D LO I-S B -3 1 7L -0 -00 5 0 * D LO I-S B -3 1 7L -0 -02 9 0 D LO I-S B -317L-0-0290* D LO I-S B -320L-0-0000 D LO I-S B -320L-0-0000* D LO I-S B -320L-0-0005 D LO I-S B -320L-0-0005* D LO I-S B -320L-0-0020 D LO I-S B -320L-0-0020* C4 S ulfonate PFBS ParfluorobutanMulfonate Analyte Assessed Found Accuracy (no/fi) dry wt. </-% ) NR NR - 4.62 5.08 NR NR 0.639 30 30 40 0.535 40 0.474 0.549 NR NR 30 30 - 0.663 50 0.602 NR NR NR 50 - NR - NR - NR 0.290 40 0.323 40 NR - NR - ND 40 0.241 40 NR - NR NR - NR - 3.77 4.53 30 30 0.897 0.953 30 30 2.24 30 2.57 4.31 30 50 3.60 NR 50 - NR 2.76 30 2.60 30 2.12 30 2.27 30 8.59 8.48 40 40 C6 S ulfonate PFHS PttrfluorohaxanMutfonata A n a ly te Found Assessed A ccu racy (ng/a) dry wt. </-% ) ND 30 ND 30 1.70 1.39 ND 30 30 30 0.286 30 ND 30 ND 0.875 1.01 30 30 30 10.6 11.0 0.273 30 30 30 0.286 ND 30 30 ND 30 ND 30 ND 30 0.255 0.271 0.231 30 30 30 0.253 30 0.262 30 ND 30 0.290 ND 30 30 0.991 30 0.760 0.401 30 30 0.317 30 NR - NR 0.716 0.509 30 30 2.00 30 2.03 16.3 30 30 9.39 0.324 30 30 0.425 4.55 30 40 4.07 2.32 2.50 4.92 5.23 40 30 30 40 40 C8 S ulfonate PFOS ParfluorooctanMUlfonate Analyte Found Assessed Accuracy (nfl/fl)drywt. (/-% ) 1.48 30 1.06 30 NR NR NR NR 71.7 40 74.5 NR NR 27.4 26.1 31.1 40 40 40 30 34.1 96.5 30 30 95.6 31.0 30.5 30 30 30 16.5 16.9 2.06 30 30 30 2.13 0.930 30 30 0.939 30 29.8 32.4 2.49 2.91 1.60 1.38 NR NR NR NR 30 30 30 30 30 30 - NR - NR NR - NR 7.89 30 8.54 NR NR NR NR NR NR 30 * * - 'Laboratory Duplicate ND = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table II for re-extract data. Note: This summary table shows rounded results, therefore, results may vary slightly from the values in the raw data. Exygen Research Page 28 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Soil Samples Continued Exygen ID C0056826 C0056826 Rep C0056827 C0056827 Rep C0056828 C0056828Rep C0056830 C0056830 Rep C0056831 C0056831 Rep C0056832 C0056832 Rep C0056833 C0056833 Rep C0056834 C0056834 Rep C lie n t S a m ple ID D LO I-S B -3 2 0L -0 -00 5 0 D LO I-S B -320L-0-0050* D LO I-S B -3 2 0L -0 -01 70 D L O I-S B -3 2 0 L -0 -0 1 70* D LO I-S B -3 2 0L -0 -02 9 0 D L O I-S B -3 2 0 L -0 -0 2 9 0 * D LO I-S B -327R -0-0000 D LO I-S B -3 2 7R -0 -00 0 0 * D LO I-S B -3 2 7 R -0 -0 0 0 5 D LO I-S B -3 2 7R -0 -00 0 5 * D LO I-S B -3 2 7 R -0 -0 0 2 0 D LO I-S B -3 2 7R -0 -00 2 0 * D LO I-S B -3 2 7 R -0 -0 0 5 0 D L O I-S B -3 2 7 R -0 -0 0 5 0 * D LO I-S B -3 2 7 R -0 -0 1 5 0 D LO I-S B -3 2 7R -0 -01 50* C4 Sulfonate PFBS C6 Sulfonate PFHS C8 Sulfonate PFOS ParftuorobutanesuHbnate______PerftuorohexanesuHonata______ PartluorooctanaiuHonaf A n a ly te Found (ng/g) dry wt. Assessed Accuracy (/-% ) A n a ly te Found (ng/g) dry wt. Assessed Accuracy (/-% ) A n a ly te Found (ng/g) dry wt. Assessed Accuracy (+ /-% ) NR NR 0.575 0.610 NR NR 27.8 35.0 58.0 58.0 15.3 15.0 NR NR NR NR 40 40 30 30 30 30 30 30 * NR NR 0.781 ND 18.3 8.97 71.0 84.3 NR NR 21.8 21.9 NR NR NR NR NR - NR 30 NR 30 NR 30 NR 30 NR 30 NR 30 NR - NR - NR 30 NR 30 NR * NR - NR - NR - NR ` Laboratory Duplicate N D = Not detected at or above 0.2 ng/g. N R = Not reported due to quality control failures, see Table II for re-extract data. Note: This summary table shows rounded results, therefore, results m ay vary slightly from the values in the raw data. Exygen Research Page 29 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table II. Summary of PFBS, PFHS and PFOS in Re-extracted Soil Samples Exygen ID C0053083 C0053084 COO5 3 0 8 5 C0053086 C0053087 C0053088 C0053089 C0053090 C0053091 COO5 3 0 9 2 C0053093 C0053094 C0053095 C0053096 C0053097 C0053098 C0053099 C0053100 C0053101 C0053102 C0053103 C0053104 C0053105 C0053106 C0053107 C0053108 C0053109 C0053110 C0053111 C0053112 COO54361 COO5 4 3 6 2 C0054363 COO5 4 3 6 4 COO5 4 3 4 8 C0054349 COO5 4 3 6 5 C0054366 COO5 4 3 6 7 C0054373 C0054375 COO5 4 3 7 6 C0054356 C0054377 C0054378 C0054379 COO5 4 3 5 7 C0054380 C0054381 C0054382 C0054383 C0054387 C0054359 C lie n t S am ple ID DF06-SB-132R-0-0000 DF06-SB-132R-0-0005 D F 06-S B -132R -0-0010 DF06-SB-132R-0-0020 DF06-SB-132R-0-0050 DF06-SB-132R-0-0445 DF06-SB-133R-0-0000 DF06-SB-133R-0-0005 DF06-SB-133R-0-0010 DF06-SB-133R-0-0020 DF06-SB-133B-0-0000 DF06-SB-133B-0-0005 DF06-SB-133B-0-0010 DF06-SB-133B-0-0020 D F 0 9-S B -1 3 1 R -0-0000 DF09-SB-131R-0-0005 D F 0 9-S B -1 3 1 R -0-0010 DF09-SB-131R-0-0020 D F 0 9 -S B -1 3 1 B -0 -00 0 0 D F 0 9 -S B -1 3 1 B -0 -00 0 5 DF09-SB-131B-0-0010 D F09-S B -131 B-0-0020 DF06-SBC-133R-0-0000 DF06-SB-133R-0-0050 DF06-SBC-133R-0-0050 D F 0 6-S B C -1 3 3R -0 -01 00 D F 0 6-S B C -1 3 3R -0 -01 50 D F 06-S B -133R -0-0180 DF06-SBC-133R-0-0200 DF06-SBC-133R-0-0250 DF8b-SB-135R-0-0000 D F8b-S B -135R -0-0005 DF8b-SB-135R-0-0010 DF8b-SB-135R-0-0020 D F 0 9-S B -1 3 1 B -0-0050 D F 0 9-S B -1 3 1 B -0-0080 DF8b-SB-135R-0-0050 DF8b-SB-135R-0-0190 DF14-SB-137R-0-0000 DF14-SB-136B-0-0005 D F09-S B C -131 R-0-0000 D F 0 9-S B -1 3 1 R -0-0050 D F 0 9 -S B C -1 3 1 R -0-0050 D F 0 9-S B C -1 3 1 R -0-0100 D F 0 9-S B -1 3 1 R -0-0160 D F09-S B C -131 R -0-0150 D F 0 9-S B C -1 3 1 R -0-0200 D F 0 9-S B C -1 3 1 R -0-0250 DF06-SB-133B-0-0050 DF06-SB-133B-0-0160 D F 1 4-S B -137R -0-0050 DF14-SBC-137R-0-0150 DF14-SB-136R-0-0290 C4 Sulfonate PFBS Partluorobutanasulfonata A n a ly te Found (no/fl) dry wt. Assessed Accuracy (+/-%> -- --- -- - NR - - --- -- ------- --- --- -- - --- - - 42.1 13.0 3.78 6.23 NR - 0.739 2.33 5.05 - - - 30 30 50 50 - - 30 40 30 - - NR 3.65 - ND - - - 30 - 30 - --- - 6.84 - - 30 - -- ND 50 C6 Sulfonate PFHS P arilM orohaxanasulfbnate A n a ly te Found (ng/g) dry wt. Assessed Accuracy <+/-%) --- - 7.20 - - 30 - -- -- -- -- -- --- -- - 96.0 - 30 -- -- - 249 - 30 -- -- - 12.6 156 173 - 30 30 30 -- -- -- -- -- -- - 19.1 - 50 -- -- -- -- -- -- -* -- 101 30 -- 221 50 168 40 250 30 - 314 - 30 -- -- -- *- C8 Sulfonate PFOS ParfluorooctanM ulfonata A n a ly te Found (ng/g) dry wt. Assessed Accuracy (/-% ) 2830 1120 934 943 3422 4090 5950 2970 12800 17100 18000 5800 NR 25600 101000 7690 3390 73200 158000 16900 7820 4350 1740 NR 2310 478 200 228 30 50 30 30 40 30 40 40 30 30 40 30 NR 30 30 30 30 30 30 30 50 40 30 30 40 30 30 - 3250 1860 1510 590 3100 2020 635 83.7 96.3 - 50 30 50 30 30 50 40 30 40 - 16300 3230 19600 2540 1130 1470 999 424 1940 2370 8.84 9.78 - 40 30 30 50 50 50 30 30 30 50 30 30 - 'Laboratory Duplicate ND = Not detected at or above 0.2 ng/g. NR - Not reported due to quality control failures. Note: This summary table shows rounded results, therefore, results m ay vary slightly from the values in the raw data. Exygen Research Page 30 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table II. Summary of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued E x y g e n ID C0056620 C0056621 C0056622 C0056623 COO5 6 6 2 4 C0056625 COO5 6 6 2 6 COO5 6 6 2 8 C0056629 COO56631 COO5 6 6 3 2 COO5 6 6 3 4 COO5 6 6 3 5 COO5 6 6 3 6 C0056637 C0056638 C0056639 C0056640 COO56641 C0056642 COO5 6 6 4 3 COO5 6 6 4 4 C0056645 COO5 6 6 4 7 C0056648 COO5 6 6 5 0 C0056652 COO5 6 6 5 3 C0056654 C0056655 COO5 6 6 5 6 C0056657 COO5 6 6 5 8 C0056660 COO56661 COO5 6 6 6 3 C0056664 C0056666 C0056667 COO5 6 6 6 8 COO5 6 6 6 9 C0056670 C0056671 COO5 6 6 7 2 C0056674 C0056675 C0056677 C0056678 COO5 6 6 7 9 C0056681 COO5 6 6 8 4 C0056685 C0056817 C0056818 C lie n t S am ple ID DF14-SB-136B-0-0290 DF8b-SB-134R-0-0000 DF8b-SB-134R-0-0005 DF8b-SB-134R-0-0010 DF8b-SB-134R-0-0020 DF8b-SB-134R-0-0050 DF8b-SBC-134R-0-0000 DF8b-SBC-134R-0-0050 DF8b-SBC-134R-0-0100 DF8b-SBC-134R-0-0150 DF8b-SBC-134R-0-0200 D F8b-S B -134R -0-0270 DF8b-SBC-134R-0-0250 DF8b-SB-134B-0-0000 DF8b-SB-134B-0-0005 DF8b-SB-134B-0-0010 DF8b-SB-134B-0-0020 DF09-SB-130R-0-0000 DF09-SB-130R-0-0005 D F 09-S B -130R -0-0010 DF09-SB-130R-0-0020 DF8b-SB-134B-0-0050 DF8b-SB-134B-0-0090 DF09-SB-130R-0-0050 D F 09-S B -130R -0-0150 D LO I-S B -2 2 0 R -0 -0 0 0 5 D LO I-S B -2 2 0 R -0 -0 0 5 0 D LO I-S B -2 2 0R -0 -01 70 D LO I-S B -2 2 0L -0 4)000 D LO I-S B -2 2 0L -0 4)0 0 5 D LO I-S B -2 2 0L -0 4)0 2 0 D LO I-S B -2 2 0L 4 )4)0 5 0 D LO I-S B -2 2 0L 4 )4)0 7 0 D LO I-S B -2 2 6 R 4 )4 )0 0 5 D LO I-S B -2 2 6 R 4 )4 )0 2 0 D LO I-S B -226R -04J180 D LO I-S B -2 2 6L 4 )4)0 0 0 D LO I-S B -2 2 6 L -0 4 5 0 2 0 D LO I-S B -226L4)4)050 D LO I-S B -2 2 6L 4 )4)1 70 DBKG-SBC4J01B-0-0150 DBKG-SBC4J01B-0-0200 DLOI-SB-31OR-O-OOOO D LO I-S B -310R -04)005 D LO I-S B -3 1 0 R 4 )4 )0 5 0 D LO I-S B -310R -0-0370 D B K G -S B -001B -0-0005 D B K G -S B -0 0 1B -0 -0 01 0 DBKG-SB-001 B-0-0020 DBKG-SB-001 B-0-0230 D B K G -S B C -001B -0-0050 DBKG-SBC-001 B-0-0100 D LO I-S B -317L-0-0000 D LO I-S B -3 1 7L -0 -00 0 5 C4 Sulfonate PFBS P e rfluo ro b utan ssu lfo na ts A n a ly te Found (ng/fl) dry wl. Assessed Accuracy (+/- %) ND 17.5 - 30 30 - - - - 19.7 45.6 30 40 20.4 14.0 10.5 20.4 - 0.701 0.655 NR 1.48 30 30 - - 50 40 30 50 - 50 0.589 3.73 0.401 ND NR 1.07 3.38 0.455 ND ND NR 0.359 NR - * 30 30 30 40 50 30 30 30 30 30 - - - C6 Sulfonate PFHS Perfluorohaxanssulfonata A n a ly te Found (ng/g) dry wl. Assessed Accuracy < + /-% ) 1.22 30 - 62.3 30 - - 137 340 745 437 332 145 74.7 642 72.9 - 50 30 30 30 30 30 30 30 40 - - - - - 184 30 --- -- - - - 6.54 - - 30 - CS Sulfonate PFOS Psrtluorooctanesulfonat A n a ly te Assessed Found (ng/g) dry wl. Accuracy (+/- %) 80.6 30 125000 212000 30 30 33700 30 18700 798000 30 30 128000 2600 1660 30 30 30 637 1230 165 64.9 143000 NR 23000 50 30 30 30 30 - 30 16500 40 1290 303 259 30 30 30 293 5110 3900 30 30 30 1130 455 83.0 - 30 30 30 - 530 30 286 30 483 30 -- 50.7 244 30 30 134 15.3 75.3 - 40 30 30 - -- 5.41 - 40 - -- 260 30 158 30 386 30 -- -- - * -* -- -507 30 241 30 ` Laboratory Duplicate ND = Not detected at or above 0.2 ng/g. NR - Not reported due to quality control failures. Note: This summary table shows rounded results, therefore, results may vary slightly from the values In the raw data. Exygen Research Page 31 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table II. Summary of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued Exygen ID C0056819 C0056820 C0056822 C0056823 C0056824 C0056825 C0056826 C0056827 C0056828 C0056830 C0056831 C0056832 C0056833 C0056834 C lie n t Sam ple ID D LO I-S B -3 1 7L -0 -00 2 0 D LO I-S B -3 1 7L -0 -00 5 0 D LO I-S B -3 1 7L -0 -02 9 0 D LO I-S B -3 2 0L -0 -00 0 0 D LO I-S B -3 2 0L -0 -00 0 5 D LO I-S B -3 2 0L -0 -00 2 0 D LO I-S B -3 2 0L -0 -00 5 0 D LO I-S B -3 2 0L -0 -01 70 D LO I-S B -3 2 0L -0 -02 9 0 D L O I-S B -3 2 7 R -0 -0 0 0 0 D LO I-S B -3 2 7 R -0 -0 0 0 5 D L O I-S B -3 2 7 R -0 -0 0 2 0 D LO I-S B -3 2 7 R -0 -0 0 5 0 D LO I-S B -3 2 7 R -0 -0 1 5 0 C4 Sulfonate PFBS Parfluorobutanasulfonate A n a ly te Found (ng/g) dry wt. Assessed Accuracy (+/-% ) -- - NR - 12.1 - NR - NR NR 30 - - C6 Sulfonate PFHS P erfluorohexanesulfO nate Analyte Assessed Found Accuracy (ng/g) dry wt. (/-% ) -- --- - - 11.8 - - 225 - 10.7 NR - 30 - - 30 40 - C8 Sulfonate PFOS Parfluorooctanasulfonata Analyte Assessed Found A ccu racy (ng/g) dry wt. (+/-% ) 231 30 157 40 -- 873 396 NR 467 8.35 114 15400 12700 3660 50 30 30 30 30 30 30 30 NR 843 30 ` Laboratory Duplicate ND - Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures. Note: Tills summary table shows rounded results, therefore, results may vary slightly from the values In the raw data. Exygen Research Page 32 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Table III. Summary of PFBS, PFHS and PFOS in Equipment Rinseate Blanks Samples Exygen ID C0054350 C0054354 C0054358 C0054360 C0056627 C0056646 C0056682 C0056821 C0056829 Client Sample ID DF8b-SB-135R-2-0190 DF14-SB-136B-2-0020 DF 14-SB-137R-2-0100 DF14-SB-136R-2-0290 DF8b-SBC-134R-2-0100 DF8b-SB-134B-2-0090 DBKG-SBC-001B-2-0000 DL01-SB-317L-2-0050 D L 0 1-SB-320L-2-0020 C4 Sulfonate PFBS Perfluorobutanasulfonate ND ND ND ND ND ND ND ND ND Analyte Found (ppt, ng/L) C6 Sulfonate PFHS Perfluorolraxanttsuffonate ND ND ND ND ND ND ND ND ND C8 Sulfonate PFOS Perfluorooctanesulfonate 71.5 ND ND ND ND 324 128 ND 85.1 ND = Not detected at or above 25 ng/L. Exygen Research Page 33 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples S am ple Description D F 0 6 -S B -1 3 2 R -0 -0 0 0 0 (C0053083 Spk C, 4 ppb Spike) D F 0 6 -S B -1 3 2 R -0 -0 0 0 0 (C0053083 Spk 0,40 ppb Spike) Amount Spiked (naiS) C4 Sulfonate PFBS W e W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (%> C 6 Sulfonate PFHS W ei W eight Amt Found Amount In Sample Recovered Recovery (ng/g) (ng/g) (% ) C 8 Sulfonate PFOS W et W eight Amt Found Amount in Sam ple Recovered Recovery _C (ns/B) (% ) 4 0.666 4.66 99 8.24 13.6 134 NR NR NR 40 0.686 38.6 95 8.24 4 6 .5 96 NR NR NR D F 0 6 -S B -1 3 2 R -0 -0 0 0 5 (C00530S4 Spk E, 4 ppbSpike) 4 0.100 3 .9 5 96 0.936 4.79 96 D F 0 6 -S B -1 3 2 R -0 -0 0 0 5 (C0053064 Spk P, 40 ppbSpike) 40 0.100 37.2 93 0 .9 3 6 38.5 94 NR NR NR NR NR NR D F 0 6 -S B -1 3 2 R -0 -0 0 1 0 (C0053085 SpkG, 4 ppbSpace) D F 0 6 -S B -1 3 2 R -0 -0 0 1 0 (C005308S Spk H, 40 ppb Spike) 4 40 0.232 0 .2 3 2 3.68 3 0 .8 86 76 1.42 1.42 5.38 38.7 99 93 NR NR NR NR NR NR D F 0 6 -S B -1 3 2 R -0 -0 0 2 0 (C00530B6 Spk 1,4 ppb Spike) D F 0 6 -S B -1 3 2 R -0 -0 0 2 0 (C0053086 Spk J. 40 ppb Space) 4 40 0.848 0.848 4.45 3 4 .3 90 84 3.49 3.49 7 .0 9 39.7 90 91 NR NR NR NR NR NR D F06-SB -132R -0-0050 (C0053087 Spk K, 4 ppbSpike) 4 0.750 4 .3 9 91 NR NR NR NR D F06-SB-132R-0-0050 (C0053087 Spk L. 40 ppbSpike) 40 0.750 36.2 89 NR NR NR NR NR NR NR NR D F 0 6 -S B -1 3 2 R -0 -0 4 4 5 (C0053088 Spk C, 4 ppb Spike) D F 0 6 -S B -1 3 2 R -0 -0 4 4 5 (C0053068 Spk D, 40 ppb Spike) 4 40 NR NR NR NR 1.86 5.50 91 NR NR 1.86 40.8 97 19.6 19.6 18.6 4 7 .0 69 D F06-SB-133R-0-0000 (C0053088 Spk E, 4 ppbSpike) D F 0 6 -S B -1 3 3 R -0 -0 0 0 0 (C0053089 Spk F, 40 ppb Space) 4 40 1.42 1.42 5.62 37.5 105 90 12.5 12.5 26.1 53.9 * 104 NR NR NR NR NR NR D F 0 6 -S B -1 3 3 R -0 -0 0 0 5 (C0053000 Spk G. 4 ppbSpike) D F 0 6 -S B -1 3 3 R -0 -0 0 0 5 (C0053090 Spk H. 40 ppbSpace) 4 40 0.457 0.457 4.20 36.6 94 90 6.77 6.77 11.0 4 3 .6 106 92 NR NR NR NR NR NR D F 0 6 -S B -1 3 3 R -0 -0 0 1 0 (C0093001 Spk 1,4 ppb Spike) D F 0 6 -S B -1 3 3 R -0 -0 0 1 0 (C0053091 Spk J, 40 ppb Spike) 4 40 0 .2 6 5 0.265 3 .8 3 34.4 89 85 2 .1 8 2.18 5.78 41.7 90 99 NR NR NR NR NR NR D F06-SB-133R-0-0020 (C0053092 Spk K, 4 ppbSpike) D F06-SB-133R-0-0020 (C0053082 Spk L, 40 ppb Spike) 4 40 0.540 0.540 4.02 3 0 .6 87 75 4.81 4.81 8.56 39.7 94 87 NR NR NR NR NR NR 'Sam ple residue exceeds the spiking level significantly: therefore, an accurate recovery value cannot be calculated ND s Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 34 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued Sam ple Description D F06-SB-133B-0-0000 (C0053093 Spk C. 4 ppb Spike) D F06-SB-133B-0-0000 (C0053093 Spk 0 , 40 ppb Spike) Amount Spiked (ng/g) C^ujfgjatePFB^WetWejghtCeSuJfbnat^FHSWetWgflh^^^^ceSujfonat^PFOSWetWelgM Amt Found Amount Amt Found Amount Amt Found <%)in Sample Recovered Recovery in Sample Recovered Recovery in Sample (ng/g) (ng/g) (n q /fl) (%> (n g /g ) Amount Recovered (ng/g) Recovery 4 1.73 6.07 109 24.1 26.5 NR NR NR 40 1.73 36.7 87 24.1 57.6 84 NR NR NR D F06-SB-133B-0-0005 (C0053084 Spk E. 4 ppb Spike) D F06-SB-133B-0-0005 (C0053004 Spk F, 40 ppb Spike) 4 40 0.684 0.684 4 .2 4 38.6 89 95 12.9 12.9 13.4 47.9 68 NR NR NR NR NR NR D F06-SB-133B-0-0010 (C0093095 Spk G. 4 ppb Spike) D F06-SB-133B-0-0010 (C0053065 Spk H, 40 ppb Spike) 4 40 0.650 0.650 4.18 32.3 88 79 5.70 5.70 9.84 36.7 104 76 NR NR NR NR NR NR D F06-SB-133B-0-0020 (C0053096 Spk 1.4 ppb Spike) D F06-SB-133B-0-0020 (C0053099 Spk J, 40 ppb Spike) 4 40 1.82 1.82 4.45 27.4 66 64 16.6 16.6 18.6 43.2 67 NR NR NR NR NR NR D F09-SB -131R -0-0000 (C0053097 Spk K, 4 ppb Spike) DF09-SB-131 R-0-0000 (C0053097 Spk L, 40 ppb Spike) 4 40 2.74 2.74 5.64 37.4 73 87 4 2 .5 4 2 .5 4 5 .8 70.6 70 NR NR NR NR NR NR DF09-SB-131R -0-0005 (C0053098 Spk C. 4 ppb Spike) 4 3.05 6 .4 6 65 NR NR NR NR DF09-SB-131 R-0-0005 (C0053098 Spk D, 40 ppb Spike) 40 3.05 37.5 86 NR NR NR NR NR NR NR NR DF09-SB-131R -0-0010 (C0093099 Spk E, 4 ppb Spike) DF09-SB-131 R -0-0010 (C0053099 Spk F, 40 ppb Spike) 4 40 0.769 0.769 4.62 37.0 96 91 13.4 13.4 16.7 52.3 97 NR NR NR NR NR NR D F 09-S B -13 1 R -0 -0 0 2 0 (C0053100 Spk G, 4 ppb Spike) DF09-SB-131 R-0-0020 (C0053100 Spk H, 40 ppb Spike) 4 40 1.08 1.08 4 .7 9 33.7 93 82 15.4 15.4 18.9 47.8 * 81 NR NR NR NR NR NR D F 0 9 -S B -1 3 1 B-0 -0 0 0 0 (C0093101 Spk 1,4 ppb Spike) D F 0 9 -S B -1 3 1 B -0-0 0 00 (C0053101 Spk J, 40 ppb Spike) 4 40 2.99 2.99 7.72 118 58.6 41.0 95 58.6 82.4 110 129 NR NR NR NR NR NR D F09-SB-131B-0-0005 (C0053102 Spk K, 4 ppb Spike) 4 3.02 5.65 66 NR NR NR NR DF09-SB-131 B-0-0005 (C0053102 Spk L, 40 ppb Spike) 40 3.02 34.2 78 NR NR NR NR NR NR NR NR 'Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 35 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued Sample OescriDtion D F 09-S B -13 1 B -0-0010 (C0053103 SpkC, 4 ppbSpike) DF09-SB'131 B-0-0010 (C0053103 Spk D, 40 ppb Spike) Amount Spiked (na/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (n g /fl) (ng/g) C6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (%> C 8 Sulfonate PFOS W et Weight Amt Found in Sample (ng/g) Amount Recovered Recovery (% ) 4 0.880 4.46 90 50.2 49.4 NR NR NR 40 0.880 37.8 92 50.2 86.4 91 NR NR NR D F 09-S B -13 1 B -0-0020 (C0053104 Spk E. 4 ppb Spike) DF09-SB-131 B-0-0020 (C0053104 Spk F, 40 ppbSpice) 4 40 3.20 3.20 5.80 39.0 65 90 87.2 87.2 77.4 134 117 NR NR NR NR NR NR DF06-SBC-133R -0-0000 (C0053105 SpkG, 4 ppb Spice) DF06-SBC-133R -0-0000 (C0053105 Spk H. 40 ppb Spike) 4 40 0.774 0.774 4.53 38.5 94 94 7.74 7.74 15.2 41.1 187 83 NR NR NR NR NR NR DF06-SB-133R -0-0050 (C0063106 Spk 1,4 ppb Spike) 4 2.70 4.75 51 NR NR NR NR DF06-SB-133R -0-0050 (C0053106 SpkJ. 40 ppbSpike) 40 2.70 36.8 90 NR NR NR NR NR NR NR NR DF06-SBC-133R -0-0050 (C0053107 Spk K, 4 ppb Spike) 4 21.3 19.2 NR NR NR NR DF06-SBC-133R -0-0050 (C0053107 SpkL, 40 ppbSpike) 40 21.3 44.9 59 NR NR NR NR NR NR NR NR DF06-SBC-133R -0-0100 (C0053108 Spk C, 4 ppbSpike) D F 06-S B C -1 33R -0-0100 (C0053106 Spk D. 40 ppbSpice) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR DF06-SBC-133R -0-0150 (C0053109 SpkE. 4 ppbSpike) DF06-SBC-133R -0-0150 (C0053109 SpkF, 40 ppbSpike) 4 40 NR NR NR NR 54.3 51.8 * NR NR 54.3 78.9 62 NR NR NR NR NR NR D F 06 -S B -1 3 3 R -0 -0 1 80 (C0053110 Spk G. 4 ppbSpike) D F 06 -S B -1 3 3 R -0 -0 1 80 (C0053110 Spk H, 40 ppbSpike) 4 40 NR NR NR NR 38.9 44.5 . NR NR 38.9 63.8 62 NR NR NR NR NR NR DF06-SBC-133R -0-0200 (C0053111 Spk 1.4 ppb Spike) D F 06-S B C -1 33R -0-0200 (COOS3111 Spk J, 40 ppb Spike) 4 40 NR NR N R N R 34.6 35.9 NR NR 34.6 72.9 96 NR NR NR NR N R NR D F 06-S B C -1 33R -0-0250 (C0053112 SpkK, 4 ppb Spike) D F 06-S B C -1 33R -0-0250 (C0053112 Spk L, 40 ppbSpike) 4 40 NR NR NR NR 1.01 4.94 98 3.47 NR NR 1.01 32.6 79 3.47 7.11 31.8 91 71 DF8b-SB- 135R-0-0000 (C0054361 Spk C, 4 ppbSpice) 4 1.63 5.39 94 DFBb-SB-135R -0-0000 (C0054361 Spk D, 40 ppbSpice) 40 1.63 34.7 83 13.7 19.0 . 13.7 42.2 71 NR NR NR NR NR NR ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated NO = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V ter re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 36 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description DF8b-SB>135R -0-0005 (C0054362 Spk E, 4 ppbSpike) DF8b-SB-135R -0-0005 (00054302 Spk P, 40 ppbSpike) Amount Spiked (n fl/fl) C4 Sulfonate PFBS W et W eight Amt Found Amount (ng/g)in Sample Recovered Recovery (n g /fl) (% ) C6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C 8 Sulfonate PFOS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (% ) 4 NR NR NR 4.33 7.01 67 NR NR NR 40 NR NR NR 4.33 32.6 71 NR NR NR D F 8b -S B -135 R -Q -0010 (C0054363 SpkG. 4 ppbSpike) D F8b-SB-135R-0-0010 (C0054363 Spk H, 40 ppb Spike) 4 40 NR NR NR NR 10.0 12.4 60 NR NR 10.0 33.0 58 NR NR NR NR NR NR D F8b-$B -135R -0-0020 (C0054364 Spk 1,4 ppbSpike) D F 8b -S B -135 R -0-0 020 (C0054364 Spk J, 40 ppbSpike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR D F 09-S B -13 1 B -0-0050 (C0054348 Spk K, 4 ppb Spike) DF09-SB-131 B-0-0050 <00054346 Spk L, 40 ppb Spike) 4 40 5.14 5.14 7.50 37.1 59 80 46.5 46.5 4 2 .6 7 1 .8 . 63 NR NR NR NR NR NR D F 0 9 -S B -1 3 1 B -0 -0 0 8 0 (C0054349 Spk C, 4 ppb Spike) DF09-SB-131 B-0-0080 (C0054349 Spk D, 40 ppb Spike) 4 40 4.60 4.60 10.2 140 45.4 3 8 .5 85 45.4 49.4 8 8 .0 107 NR NR NR NR NR NR D F 8 b -S B -1 3 5 R -0 -0 0 5 0 (C0054365 Spk E. 4 ppb Spike) D F 8 b -S B -1 3 5 R -0 -0 0 5 0 (C0054365 Spk F, 40 ppb Spike) 4 40 NR NR NR NR 41.2 35.9 . NR NR 41.2 76.1 87 NR NR NR NR NR NR D F 8 b -S B -1 3 5 R -0 -0 1 9 0 (C0054366 Spk G, 4 ppb Spfce) D F 8 b -S B -1 3 5 R -0 -0 1 9 0 (00054366 Spk H, 40 ppb Spike) 4 40 NR NR NR NR 71.1 82.4 . NR NR NR 71.1 120 122 NR NR NR NR NR D F 1 4 -S B -1 3 7 R -0 -0 0 0 0 (C0054367 Spk 1,4 ppb Spike) 4 ND 2 .2 6 57 1.22 4 .6 5 86 D F14-SB-137R-0-0000 (C0054367 SpkJ. 40 ppbSpike) 40 ND 2 1 .5 54 1.22 36.8 89 NR NR D F 1 4 -S B -1 3 7 R -0 -0 0 0 5 (C0054351 Spk K. 4 ppbSpike) 4 ND 2.24 56 ND 3.58 90 42.2 D F 1 4 -S B -1 3 7 R -0 -0 0 0 5 (C0054351 Spk L, 40 ppbSpike) 40 ND 2 1 .4 54 ND 34.4 86 42.2 NR NR 48.0 74.7 NR NR 81 D F14-SB-137R-0-0010 (C0054368 Spk C, 4 ppbSpike) 4 ND 3.15 79 ND 3.58 90 19.4 19.4 . D F14-SB -137R -0-0010 (C0054368 Spk D, 40 ppb Spike) 40 ND 25.4 64 ND 34.0 85 19.4 50.9 79 `Sample residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated NO = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 37 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description D F 1 4 -S B -1 3 7 R -0 -0 0 2 0 (C0054369 Spk E, 4 ppb Spike) OF 14-SB -137R -0-0020 (C0054369 Spk P, 40 ppb Spike) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C 6 Sulfonate PFHS W et W eight Am t Found in Sample (ng/g) Amount Recovered Recovery (ng/g) (% ) C8 Sulfonate PFOS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (%> 4 ND 3.60 90 NO 3.65 91 3.60 7.40 95 40 ND 33.4 64 ND 35.4 89 3.60 39.4 90 D F 1 4 -S B -1 3 6 R -0 -0 0 0 0 (C0054370 Spk G, 4 ppb Spike) 4 ND 3.04 76 ND 3.74 94 31.8 30.6 * D F14-SB -136R -0-0000 (C0054370 Spk H, 40 ppb Spike) 40 ND 2 8 .6 72 ND 37.6 94 3 1 .8 6 0 .9 73 D F14-SB -136R -0-0005 (C0054371 Spk 1,4 ppb Spike) 4 ND 2 .1 7 54 ND 3.46 87 9 6 .8 D F 1 4 -S B -1 3 6 R -0 -0 0 0 5 (C0054371 Spk J, 40 ppbSpike) 40 ND 22.1 55 ND 35.4 89 9 6 .8 106 . 131 86 D F14-SB-136R-0-0010 (C00S4352 Spk K, 4 ppbSpike) 4 ND 2.42 61 DF 14-SB -136R -0-0010 (C0054352 Spk L, 40 ppb Spike) 40 ND 20.1 50 ND 3.48 87 75.4 ND 34.6 87 75.4 6 1 .2 122 117 D F14-SB-136R-0-0020 (C0054353 Spk M, 4 ppbSpike) 4 NO 2 .3 5 59 D F 1 4 -S B -1 3 6 R -0 -0 0 2 0 (C0054353 Spk N. 40 ppb Spike) 40 ND 2 2 .6 57 ND 3.42 86 18.3 ND 33.0 83 18.3 30.4 54.0 89 D F14-SB-136B-0-0000 (C0054372 Spk C, 4 ppb Spike) 4 ND 3.33 83 ND 3.16 79 2 3 .4 DF 14-SB -136B-0-0000 (C0094372 Spk D. 40 ppbSpike) 40 ND 40.0 100 ND 40.9 102 2 3 .4 2 5 .8 6 4 .5 . 103 D F14-SB-136B-0-0005 (C0054373 Spk E, 4 ppbSpfce) D F14-SB-136B-0-0005 (C0054373 Spk F. 40 ppb Spike) 4 40 NR NR NR NR ND 3.22 81 52.7 NR NR ND 32.5 81 52.7 4 8 .3 84.0 * 78 D F14-SB-136B-0-0010 (C0054374 Spk G, 4 ppbSpike) 4 ND 2.34 59 ND D F 1 4-S B -136 B -0-0 010 (C0054374 Spk H, 40 ppbSpike) 40 NO 4 9 .8 125 ND 3.42 86 4 6 .5 51.4 129 48.5 62.4 105 141 D F14-SB-136B-0-0020 (C00943S5 Spk l, 4 ppb Spike) 4 ND 2.60 65 ND 3.32 83 6 .3 5 11.1 119 O F14-SB -136B-0-0020 (C0054355 Spk J, 40 ppbSpike) 40 ND 23.4 59 ND 33.2 83 6 .3 5 4 1 .9 69 D F 09-S B C -13 1 R -0 -0 0 0 0 (C005437S Spk K, 4 ppbSpike) DF09-SBC-131 R -0-0000 (C0054375 Spk L, 40 ppb Spike) 4 40 1.96 1.96 5.55 44.9 89 107 37.2 37.2 29.0 80.0 * 107 NR NR NR NR NR NR = Not detected at or above 0.2 ng/g.Sample residue exceeds the spiking level significantly', therefore, an accurate recovery value cannot be calculated ND NR s Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 38 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued Sam ple Description D F09-SB-131R-0-0050 (C0054376 Spk C, 4 ppb Spike) DF09-SB-131 R-0-0050 (C0054376 Spk D, 40 ppb Spike) Amount Spiked (n g /fl) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/a) (ng/g) i% ) C6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C 8 Sulfonate PFOS W et W eight Amt Found in Sam ple (ng/g) Amount Recovered (ng/g) Recovery (%> 4 5.55 10.2 116 43.0 4 2 .7 * NR NR NR 40 5.55 4 0 .6 88 43.0 7 3 .4 76 NR NR NR DF09-SBC -131 R -0-0050 (C0054356 Spk E, 4 ppb Spike) 4 15.4 19.6 . NR NR NR NR DF09-SB C -131 R -0-0050 (C0054356 Spk F, 40 ppb Spke) 40 15.4 43.2 70 NR NR NR NR NR NR NR NR D F09-SBC -131R-0-0100 (C0054377 Spk 0 ,4 ppb Spke) 4 2 6 .6 28.7 * 152 143 . NR D F09-SBC -131R-0-0100 (C0054377 Spk H, 40 ppb Spke) 40 2 6 .6 59.0 81 152 188 90 NR NR NR NR NR D F09-SB -131R -0-0160 (C0054378 Spk 1,4 ppb Spke) 4 2 8 .6 33.4 NR NR NR NR D F 0 9 -S B -1 3 1 R -0 -0 1 6 0 (C0054378 Spk J. 40 ppb Spke) 40 2 8 .6 59.0 76 NR NR NR NR NR NR NR NR DF09-SBC -131 R -0-0150 (C0054379 Spk K, 4 ppb Spke) 4 2 8 .3 2 8 .8 * NR NR NR NR DF09-SBC-131R -0-0150 (C0054379 Spk L, 40 ppb Spike) 40 2 8 .3 55.4 68 NR NR NR NR NR NR NR NR DF09-SBC -131R -0-0200 (C0054357 Spk M, 4 ppb Spike) 4 2 5 .8 24.2 * NR NR NR NR DF09-SBC-131 R -0-0200 (C0054357 Spk N, 40 ppb Spke) 40 2 5 .8 54.2 71 NR NR NR NR NR NR NR NR DF09-SBC-131R -0-0250 (C0054380 Spk C, 4 ppb Spke) DF09-SBC-131 R-0-0250 (C0054380 Spk 0 .4 0 ppb Spke) 4 40 4 .7 0 4 .7 0 9.68 125 43.4 25.2 51 43.4 58.6 84.8 * 104 NR NR NR NR NR NR D F06-SB-133B-0-0050 (C0054381 Spk E, 4 ppb Spke) 4 16.9 20.1 * NR NR NR NR D F 0 6 -S B -1 3 3 B -0 -0 0 5 0 (C0054381 Spk F. 40 ppb Spke) 40 16.9 48.2 78 NR NR NR NR NR NR NR NR D F 0 6 -S B -1 33 B -0 -0 1 60 (C0054382 Spk 6 . 4 ppb Spke) D F 0 6 -S B -1 33 B -0 -0 1 60 (C0054382 Spk H, 40 ppb Spke) 4 40 NR NR NR NR 65.0 88.8 NR NR 65.0 96.0 78 NR NR NR NR NR NR D F 1 4 -S B -1 3 7 R -0 -0 0 5 0 (C0054383 Spk 1,4 ppb Spke) 4 ND 3.25 81 0.364 3.70 83 D F14-SB-137R-0-0050 (C0054383 Spk J. 40 ppb Spike) 40 ND 31.0 78 0.364 34.1 84 NR NR NR NR NR NR `Sample residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND * Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in die raw data. Exygen Research Page 39 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description DF14-SBC -137R-0-0000 <C0054384 Spk K, 4 ppb Spike) DF14-SBC -137R-0-0000 (C0054384 Spk L. 40 ppb Spice) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Am t Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (*> C 6 Sulfonate PFHS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery <*> CB Sulfonate PFOS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (%> 4 ND 3.59 90 0 .6 5 9 4 .3 0 91 49.1 71.0 40 ND 31.7 79 0 .6 5 9 36.6 90 49.1 104 137 DF14-SBC -137R-0-0050 <00054385 Spk M 4 ppbSpice) 4 0.212 3.17 74 0.262 3.23 74 0 .7 4 3 OF14-SB C -137R -0-0050 (C0054385 Spk N. 40 ppb Spike) 40 0.212 25.5 63 0.262 2 9 .3 73 0 .7 4 3 3.57 2 7 .3 71 66 D F14-SB C -137R -0-0100 (C0054386 Spk C, 4 ppb Spice) DF14-SBC -137R-0-0100 (C0054386 Spk D. 40 ppb Spike) 4 40 ND ND 3.10 78 0 .6 9 8 3.93 81 24.9 62 0 .6 9 8 29.1 71 2 6 .2 2 6 .2 29.0 4 7 .3 * 53 D F14-SBC -137R-0-0150 <00054387 Spk E, 4 ppb Spike) 4 ND 3.23 81 0 .6 3 5 3.94 83 D F14-SBC -137R-0-0150 (C0054387 Spk F. 40 ppb Spike) 40 ND 24.9 62 0 .6 3 5 32.6 80 NR NR NR NR NR NR D F14-SB -137R -0-0180 <00054388 Spk6 ,4 ppbSpice) D F14-SB -137R -0-0180 (C0054368 Spk H, 40 ppb Spike) 4 40 ND ND 2.44 30.7 61 77 1.14 1.14 3.92 35.4 70 86 18.6 18.6 11.2 48.7 . 75 DF 14-SB -136R-0-0050 (00054388 Spk 1,4 ppb Spike) 4 ND 2.94 74 D F 1 4 -S B -1 3 6 R -0 -0 0 5 0 (C0054388 Spk J, 40 ppb Spike) 40 ND 27.4 69 ND 3.70 93 6 0 .0 ND 35.3 88 60.0 7 0 .8 92.8 . 82 DF 14-SB -136R -0-0290 (C0054359 Spk K, 4 ppb Spike) DF 14-SB -136R -0-0290 (00054359 Spk L, 40 ppbSpike) 4 40 NR NR NR NR NR NR ND ND 3.52 35.4 66 89 ND ND 3.70 35.5 93 69 DF 14-SB -136B-0-0050 (C0056619 Spk C, 4 ppb Spike) 4 ND 3.17 79 ND 3.66 92 0.760 4.21 86 D F14-SB-136B-0-0050 (C0056619 Spk 0.40 ppb Spike) 40 ND 4 6 .6 117 ND 52.2 131 0.760 52.2 129 DF 14-SB -136B-0-0290 (00056820 Spk E. 4 ppbSpike) D F14-SB-136B-0-0290 <00056620 Spk F, 40 ppb Spike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR D F 8 b -S B -1 3 4 R -0 -0 0 0 0 (C0056621 Spk6 .4 ppbSpike) D F 8 b -S B -1 3 4 R -0 -0 0 0 0 <00056621 Spk H, 40 ppb Spike) 4 40 NR NR NR NR 106 92.8 * NR NR 106 129 58 NR NR NR NR NR NR ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND = Not detected at or above 0.2 ng/g. NR * Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 40 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description D F8b-SB-134R-0-0005 (C0056622 Spk 1.4 ppb Spike) D F8b-SB-134R-0-0005 (C0056622 Spk J. 40 ppb Spike) Amount Spiked (ng/g) C ^ & jl^ a te P F B ^ ^ ^ e ig h t^ ^ ^ ^ ^ u tfo n a t^ F H ^ W ^ W e ^ j^ ^ ^ C ^ ijfo n a ^ ^ F O ^ W e n ftje ig h ^ Am t Found Amount Amt Found Amount Amt Found (ng/g) (ng/g) (ng/g)in Sample Recovered Recovery in Sample Recovered Recovery in Sample (% ) ("0'S ) (%> (n fl/g ) Amount Recovered (ng/g) Recovery (% ) 4 1.10 4.74 91 NR NR NR NR NR NR 40 1.10 35.5 86 NR NR NR NR NR NR D F8b-SB-134R-0-0010 (C0056823 Spk K, 4 ppb Spike) D F 8b -S B -134 R -0-0 010 (C0056623 Spk L, 40 ppb Spike) 4 40 0.636 0.636 3 .7 9 34.6 79 85 33.1 33.1 4 3 .0 68.8 89 NR NR NR NR NR NR D F8b-SB-134R-0-0020 (C0056624 Spk C, 4 ppb Spike) D F8b-SB-134R-0-0020 (C0056624 Spk 0 ,4 0 ppb Spike) 4 40 1.84 1.64 5.30 3 8 .6 87 92 5 7 .8 57.8 62.6 97.6 . 100 NR NR NR NR NR NR D F 8b -S B -134R -0-0050 (C0056625 Spk E. 4 ppb Spike) D F 8b -S B -134 R -0-0 050 (C005662S Spk F, 40 ppb Spike) 4 40 1.82 1.82 5.21 85 35.1 83 91.2 91.2 94.4 126 * 87 NR NR NR NR NR NR DF8-SBC-134R -0-0000 (C0056626 Spk 6 .4 ppb Spike) 4 1.66 5.19 88 NR NR NR NR D F8b-SBC -134R-0-0000 (C0056828 Spk H, 40 ppb Spike) 40 1.66 37.7 90 NR NR NR NR NR NR NR NR DF8b-SBC -134R-0-0050 (C0056628 Spk 1,4 ppb Spike) DF8b-SBC-13 4 R -0 -0 0 5 0 (C0050628 Spk J, 40 ppb Spike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR D F 8b -S B C -134R -0-0100 (C0056829 Spk K, 4 ppb Spike) D F8b-SBC -134R-0-0100 (C0056629 Spk L, 40 ppb Spike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR D F S b -S B C -134R -0-0150 (C0058631 Spk C, 4 ppb Spike) 4 29.0 40.4 NR NR NR NR D F8b-SBC -134R-0-0150 (C0056631 Spk D. 40 ppb Spike) 40 29.0 6 8 .1 98 NR NR NR NR D F 8 b -S B C -13 4 R -0 -0 20 0 (C0066632 Spk E, 4 ppb Spike) 4 11.2 13.3 53 NR NR NR NR D F 8 b -S B C -13 4 R -0 -0 20 0 (C0056632 Spk F, 40 ppb Spike) 40 11.2 36.5 63 NR NR NR NR NR NR NR NR NR NR NR NR D F 8 b -S B -1 3 4 R -0 -0 2 7 0 (C0056634 Spk 6 .4 ppb Spike) D F 8b-S B -1 3 4 R *0 -0 2 7 0 (C0056634 Spk H, 40 ppb Spike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR ` Sample residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND * Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 41 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description D F8b-S B C -134R -Q -0250 (C0056635 Spk 1. 4 ppbSpike) D F 8b -S B C -134R -0-0250 (C0056635 Spk J. 40 ppbSpike) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) <%> C6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C8 Sulfonate PFOS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery <%> 4 NR NR NR NR NR NR NR NR NR 40 NR NR NR NR NR NR NR NR NR D F 8b -S B -134 B -0-0 000 (C0056636 SpkK. 4 ppbSpite) 4 6.78 10.6 96 NR NR NR NR D F 8b -S B -134 B -0-0 000 (C0056636 Spk L. 40 ppbSpike) 40 6.78 39.2 81 NR NR NR NR NR NR NR NR D F 8b -S B -134 B -0-0 005 (C0056637 Spk M, 4 ppbSpike) D F 8b -S B -134 B -0-0 005 (C0056637 SpkN. 40 ppbSpike) 4 40 0.504 0.504 4.57 33.8 102 83 NR NR NR NR NR NR NR NR NR NR NR NR D F 8b -S B -134 B -0-0 010 (C0056636 SpkC. 4 ppbSpite) D F 8 b -S B -134 B -0-0 010 (C0056638 Spk0.40 ppbSpike) 4 40 0.255 0.255 3.48 33.3 81 83 12.7 17.8 12.7 48.5 90 NR NR NR NR NR NR D F 8b -S B -134 B -0-0 020 (C0056639 SpkE, 4 ppbSpite) D F 8b -S B -134 B -0-0 020 (C0056639 SpkF. 40 ppbSpike) 4 40 0.409 0.409 3.48 33.4 77 82 18.6 23.3 . 18.6 53.1 86 NR NR NR NR NR NR D F 09-S B -1 3 0 R -0 -0 0 0 0 (C0056640 Spk G. 4 ppbSpike) D F 0 9 -S B -13 0R -0 -0 0 0 0 (C0056640 Spk H, 40 ppbSpite) 4 40 1.13 1.13 4.65 35.2 88 65 4.87 4.87 9.92 39.6 126 87 NR NR NR NR NR NR DF09-SB-130R -0-0005 (C0056641 Spk 1,4 ppbSpite) D F 09-S B -1 3 0 R -0 -0 0 0 5 (C0056641 SpkJ. 40 ppbSpike) 4 40 0.220 0.220 2.79 29.0 64 72 1.27 1.27 4.67 36.6 85 88 NR NR NR NR NR NR D F 09-S B -1 3 0 R -0 -0 0 1 0 (C0056642 SpkK, 4 ppb Spite) 1DF09-SB- 30R -0-0010 (C0056642 Spk L, 40 ppbSpite) 4 40 0.466 0.466 3.11 24.1 66 59 1.69 1.69 4.67 35.9 75 86 NR NR NR NR NR NR DF09-SB-130R -0-0020 (C0096643 Spk C, 4 ppbSpike) DF09-SB-130R -0-0020 (00056643 S pk D, 40 ppb Spike) 4 40 0.543 0.543 3.03 23.9 62 58 1.45 4.97 68 1.45 32.9 79 NR NR NR NR NR NR D F 8b -S B -134 B -0-0 050 (C0056644 Spk E. 4 ppbSpike) D F 8 b -S B -1 3 4 B -0 0 0 5 0 (C0056644 Spk F. 40 ppb Spike) 4 40 NR NR NR NR 78.1 NR NR 78.1 71.4 125 . 117 NR NR NR NR NR NR Sample residue exceeds the spiking level significantly: therefore, an accurate recovery value cannot be calculated ND = Not detected at or above 0.2 ng/g. NR Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 42 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description D F 8b -S B -1 3 4 B -0 -0 0 9 0 (C0056645 Spk 6 ,4 ppb Spike) D F 8b -S B -1 3 4 B -0 -0 0 9 0 (C0056645 Spk H. 40 ppb Spike) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (% > C 6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% > C 8 Sulfonate PFOS W et W eight Amt Found in Sam ple (ng/g) Amount Recovered (ng/g) Recovery (% ) 4 NR NR NR NR NR NR NR NR NR 40 NR NR NR NR NR NR NR NR NR D F 0 9 -S B -1 3 0 R -0 -0 0 5 0 (C0056647 Spk I, 4 ppbSpike) D F 0 9 -S B -1 3 0 R -0 -0 0 5 0 (C00S6647 Spk J, 40 ppb Spike) 4 40 4.44 4.44 8.64 105 36.1 32.6 70 36.1 46.9 64.4 . 71 NR NR NR NR NR NR DF09-SB-130R-0*01 SO (COOS6648 Spk K, 4 ppb Spike) D F09-SB -130R -0-0150 (C0056646 Spk L, 40 ppb Spike) 4 40 4.22 4 .2 2 7.45 29.0 81 62 43.7 4 3 .7 54.0 80.6 93 NR NR NR NR NR NR D LO I-SB-220R -0-0000 (C0056649 Spk C, 4 ppb Spfce) 4 1.65 4.22 64 0.856 3.98 78 D LO I-SB-220R -0-0000 (C0056649 Spk D, 40 ppb Spike) 40 1.65 2 8 .9 68 0 .8 5 6 34.2 83 98.4 98.4 105 * 152 134 DLO I-SB-220R -0-0005 (C0066650 Spk E, 4 ppb Spike) 4 0.378 2.57 55 0.291 3.73 86 DLO I-SB-220R -0-0005 (C0056650 Spk F, 40 ppb Spike) 40 0.378 25.5 63 0.291 33.2 82 NR NR NR NR NR NR DLO I-SB-220R -0-0020 (C0096651 Spk G, 4 ppb Spike) 4 0.992 3.58 65 0.936 4.68 94 DLO I-SB-220R -0-0020 (C0056651 Spk H, 40 ppb Spate) 40 0.992 20.7 49 0.936 35.6 87 78.1 78.1 114 . 132 135 D LO I-SB-220R -0-0050 (C0056652 Spk 1,4 ppb Spike) D LO I-SB-220R -0-0050 (C0056692 Spk J, 40 ppb Spike) 4 40 NR NR NR NR 0.610 4.26 91 NR NR 0.610 33.5 82 13.6 13.6 2 5 .0 4 4 .6 * 78 D LO I-SB-220R -0-0170 (C0056653 Spk K. 4 ppb Spike) D LO I-SB-220R -0-0170 (C00S6653 Spk L, 40 ppb Spite) 4 40 NR NR NR NR NR NR 4.27 4.27 7.74 38.2 87 85 5 .5 3 5.53 9.68 38.4 104 82 D L O I-S B -2 2 0 L -0 -0 0 0 0 (C0056654 Spk C, 4 ppb Spfce) 4 0.742 4.35 90 0 .6 9 5 4.20 88 D L O I-S B -2 2 0L -0-00 00 (C0056654 Spk D. 40 ppb Spike) 40 0.742 35.5 87 0 .6 9 5 35.8 88 NR NR NR NR NR NR DLO I-S 8-220L-0-0005 (C00566S5 Spk E, 4 ppb Spike) DLO I-SB-220L-0-0005 (C0056655 Spk F, 40 ppb Spike) 4 40 0.278 0 .2 7 8 3.72 27.0 , 86 67 0 .2 9 0 0 .2 9 0 3.99 3 2 .6 93 81 NR NR NR NR NR NR Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated NO * Not detected at or above 0.2 ng/g. NR * Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. \ Exygen Research Page 43 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description DLO I-SB-220L-0-0020 (C0056656 Spk G. 4 ppbSpike) DLO I-SB-220L-0-0020 (C005665fi Spk H, 40 ppb Spike) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) <%> C6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g)_____ C8 Sulfonate PFOS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (% ) 4 0.872 3.51 66 1.89 5.96 102 NR NR NR 40 0.872 2 7 .2 66 1.89 38.8 92 NR NR NR DLO I-SB-220L-0-0050 (C0056657 Spk 1,4 ppbSpfce) DLO I-SB-220L-0-0050 (C0056657 Spk J, 40 ppb Spike) 4 40 NR NR NR NR 2.77 NR NR 2.77 5.56 37.2 70 86 2 0 .6 2 0 .6 24.2 6 6 .6 * 115 DLQ I-SB-220L-0-0070 (C0056656 Spk K, 4 ppb Spfce) DLO I-SB-220L-0-0070 (C0056658 Spk L, 40 ppbSpike) 4 40 NR NR NR NR 1.58 5.04 87 NR NR 1.58 34.6 83 NR NR NR NR NR NR DLO I-SB-226R -0-0000 (C0056659 Spk C, 4 ppb Spike) 4 0.816 3.16 59 0 .4 6 6 3.86 65 DLO I-SB-226R -0-0000 (C0056659 Spk D. 40 ppbSpike) 40 0.816 24.6 59 0 .4 6 6 35.8 86 8 9 .6 8 9 .6 95.2 123 . 84 DLO I-SB-226R -0-0005 (C0056660 Spk E, 4 ppbSpike) 4 0.571 2.72 54 0 .3 7 4 3.94 89 D LO I-SB-226R -0-0005 (C0056660 Spk F, 40 ppb Spike) 40 0.571 2 5 .5 62 0 .3 7 4 32.5 80 NR NR NR NR NR NR D LO I-SB-226R -0-0020 (C0056661 Spk G. 4 ppb Spike) 4 0.601 3.27 67 0.253 3.70 86 D LO I-SB-226R -0-0020 (00056661 Spk H, 40 ppb Spike) 40 0.601 26.2 64 0.253 40.2 100 NR NR NR NR NR NR D LO I-SB-226R -0-0050 (C0056662 Spk 1.4 ppbSpfce) 4 1.07 4.07 75 ND 3.86 97 2 1 .8 19.4 . D LO I-SB-226R -0-0050 (C0056662 Spk J, 40 ppbSpfce) 40 1.07 25.2 60 ND 36.0 90 2 1 .8 50.4 72 DLO I-SB-226R -0-0180 (C0056663 Spk K, 4 ppbSpike) 4 0.332 2 .8 9 64 0.519 4.70 105 D LO I-SB-226R -0-0180 (C0056663 Spk L. 40 ppb Spfce) 40 0.332 2 6 .9 66 0 .5 1 9 39.3 97 D L O I-S B -226L -0 -0 0 0 0 (C0056664 SpkC, 4 ppb Spfce) 4 1.82 4 .0 0 55 1.01 4 .0 2 75 DLO I-SB-226L-0-0000 (COO56664 Spk D, 40 ppb Spike) 40 1.82 27.8 65 1.01 35.1 85 NR NR NR NR NR NR NR NR NR NR NR NR D L 01 -S B -2 2 6 L -0 -0 0 0 5 (C0056665 Spk E, 4 ppbSpike) 4 0.404 2.60 55 0 .3 9 5 3.70 83 DLO I-SB-226L-0-0005 (C0056665 Spk F, 40 ppb Spike) 40 0.404 2 2 .3 55 0.395 34.6 86 114 114 111 144 75 ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated NO = Not detected at or above 0.2 ng/g. NR * Not reported due to quality control failures, see Table V for re-extract data. Note; Since this summary table shows rounded results, recovery values may vary slightly from foe values in foe raw data. Exygen Research Page 44 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description D L O I-S B -2 2 6 L -0 -0 0 2 0 (00050606 SpfcG, 4ppb Spike) DLO I-SB-226L-0-0020 (C0056666 Spk H, 40 ppb Spike) Amount Spiked ..(n g /g ) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (%> C 8 Sulfonate PFOS W et W eight Amt Found Amount in Sam ple Recovered Recovery (ng/g) (ng/g) (% ) 4 NR NR NR 0.419 3.89 87 69.4 101 40 NR NR NR 0.419 33.7 63 69.4 110 102 DLO I-SB-226L-0-0050 (COO56067 Spk 1, 4 ppb Spike) DLO I-SB-226L-0-0050 (C00S6667 Spk J, 40 ppbSpice) 4 40 NR NR NR NR 0.247 3.59 84 NR NR 0.247 33.0 82 5.97 5.97 11.4 37.6 136 79 D LO I-SB-226L-0-0170 (C0056668 Spk K, 4 ppbSpike) D LO I-SB-226L-0-0170 (C0056666 Spk L, 40 ppbSpike) 4 40 NR NR NR NR 0.614 3.83 80 NR NR 0.614 33.8 83 NR NR NR NR NR NR DBKG -SBC-001B-0-0150 (C0056666 Spk M, 4 ppb Spike) DBKG-SBC-001 B-0-0150 (C0056669 Spk N, 40 ppbSpike) 4 40 NR NR NR NR ND 3.20 60 0.590 3.60 75 NR NR ND 31.6 80 0.590 32.3 79 DBKG-SBC-001 B-0-0200 (C0056670 Spk C, 4 ppbSpike) DBKG-SBC-001 B-0-0200 (C0056670 spk D. 40 ppb Spike) 4 40 NR NR NR NR ND 3 .7 6 94 1.25 NR NR ND 35.0 88 1.25 4.31 31.8 77 76 D LO I-SB-310R -0-0000 (C0056671 Spk E. 4 ppb Spike) DLO I-SB-310R -0-0000 (COO50071 Spk F, 40 ppb Spike) 4 40 4.44 4.44 6.00 38.7 69 66 1.63 1.63 4.82 35.8 80 85 NR NR NR NR NR NR D L O I-S B -31O R -0-0005 (C0056672 SpkG, 4 ppbSpice) D LO I-SB-310R -0-0005 (C0056672 Spk H, 40 ppbSpike) 4 40 NR NR NR NR ND 3.99 100 NR NR NR ND 35.4 89 NR NR NR NR NR DLO I-SB-310R -0-0020 (C0056673 Spk 1,4 ppb Spice) D LO I-SB-310R -0-0020 (COO50673 Spk J, 40 ppb Spice) 4 40 0.546 0.546 3.26 29.7 68 73 ND 3.86 97 61.4 ND 3 7 .3 93 61.4 65.4 117 139 D L O I-S B -3 1 0 R -0 -0 0 5 0 (C0056674 Spk K, 4 ppb Spice) 4 0.408 3.34 73 0.753 4 .4 0 91 DLOI-SB-31 OR-0-0050 (C0056674 Spk L, 40 ppb Spike) 40 0.406 2 4 ,2 59 0.753 36.0 88 NR NR NR NR NR NR DLO I-SB-310R -0-0370 (C0056675 Spk C. 4 ppbSpike) DLO I-SB-310R -0-0370 (C0056675 Spk D, 40 ppb Spike) 4 40 NR NR NR NR 8.72 NR NR 8.72 11.6 39.6 72 77 2 2 .6 22.6 20.5 4 9 .8 68 ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated NO = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 45 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued Sam ple Description D B K G -S B -001B -0-0000 (C0066676 Spk E, 4 ppb Spke) DBKG-SB-001 B-0-0000 (C0056676 Spk F. 40 ppb Spke) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C 6 Sulfonate PFHS W ei W eight Amt Found in Sample (ng/g) Amount Recovered Recovery (ng/g) (% ) C 8 Sulfonate PFOS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (*) 4 0.526 2.60 57 0.217 3.77 89 2 4 .6 2 9 .0 40 0.526 24.0 59 0.217 35.8 89 24.6 6 0 .2 89 DBKG-SB-001 B-0-0005 (C0056677 SpkG, 4 ppb Spke) DBKG-SB-001 B-0-0005 (C0056677 Spk H, 40 ppb Spike) 4 40 NR NR NR NR ND 3.71 93 80.0 NR NR ND 34.9 87 80.0 88.8 119 98 DBKG-SB-001 B-0-0010 (C0056678 Spk 1,4 ppb Spike) DBKG-SB-001 B-0-0010 (C0056676 Spk J, 40 ppb Spke) 4 40 NR NR NR NR ND 3.87 97 2 7 .0 NR NR ND 35.8 90 2 7 .0 3 6 .0 66.2 98 DBKG-SB-001 B-0-0020 (C0066679 Spk K. 4 ppbSpke) DBKG-SB-001 B-0-0020 (C0056679 Spk L, 40 ppb Spke) 4 40 NR NR NR NR 0.255 3.90 91 NR NR 0.255 37.0 92 13.9 13.9 12.8 4 6 .0 80 DBKG-SB-001 B-0-0050 (C005S680 Spk C, 4 ppb Spke) 4 0.257 2.43 54 0.205 4.00 95 DBKG-SB-001 B-0-0050 (C0056680 Spk D. 40 ppb Spke) 40 0.257 2 3 .6 59 0.205 34.8 86 1.82 1.82 5 .5 3 3 6 .6 93 87 DBKG-SB-001 B-0-0230 (C0056681 Spk E. 4 ppbSpke) DBKG-SB-001 B-0-0230 (C0056661 Spk F, 40 ppb Spke) 4 40 NR NR NR NR 0.210 3.62 65 0.747 NR NR 0.210 34.3 65 0.747 4 .4 8 3 5 .4 93 87 DBKG-SBC-001 B-0-0000 (C0056683 SpkG. 4 ppbSpke) DBKG -SBC-001B-0-0000 (C0056683 Spk H, 40 ppbSpike) D B K G -S B C -001B-0-0050 (00050604 Spk 1,4 ppb Spke) DBKG-SBC-001 B-0-0050 (C0056664 Spk J, 40 ppbSpke) DBKG-SBC-001 B-0-0100 (G00S6665 Spk K. 4 ppb Spke) DBKG-SBC-001 B-0-0100 (C0056685 Spk L, 40 ppb Spke) 4 40 4 40 4 40 ND ND NR NR NR NR 2.76 69 0.249 3.69 24.1 60 0.249 36.1 NR NR 0.840 4.45 NR NR 0.840 37.4 NR NR 0.326 3.79 NR NR 0.326 36.8 91 90 90 91 87 91 2 5 .6 2 5 .6 2.11 2.11 1.30 1.30 2 6 .8 57.8 6.06 36.7 4 .3 3 35.8 81 99 86 76 86 DLO I-SB-317L-0-0000 (C0056017 Spk C. 4 ppbSpke) DLO I-SB-317L-0-0000 (C0056617 Spk D, 40 ppbSpke) 4 40 3.44 3.44 7.46 4 0 .8 101 93 NR NR NR NR NR NR NR NR NR NR NR NR Not detected at or above 0.2 ng/g.`Sample residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND = NR h Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from foe values in foe raw data. Exygen Research Page 46 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued Sam ple Description DLO I-SB-317L-0-0005 (C0056818 Spk E, 4 ppbSpike) DLO I-SB-317L-0-0005 (C0056818 Spk F, 40 ppbSpike) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C 6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C8 Sulfonate PFOS W et W eight Amt Found Amount in Sam ple Recovered Recovery (ng/g) (ng/g) (% ) 4 0.798 4.42 91 0.637 4 .2 6 91 NR NR NR 40 0.798 34.2 84 0.637 35.2 86 NR NR NR DLO I-SB-317L-0-0020 (C0056819 Spk6 .4 ppbSpike) DLO I-SB-317L-0-0020 (C0056819 Spk H. 40 ppb Spike) 4 40 1.94 1.94 6.08 37.2 104 88 1.74 1.74 5.94 37.9 105 90 NR NR NR NR NR NR DLO I-SB-317L-0-0050 (C0056620 Spk 1,4 ppb Spike) DLO I-SB-317L-0-0050 (C0056820 Spk J, 40 ppb Spike) 4 40 3.71 3.71 5 .8 9 30.3 55 66 14.0 14.0 12.0 48.1 . 85 NR NR NR NR NR NR DLO I-SB-317L-0-0290 (C0056S22 Spk K, 4 ppbSpike) DLO I-SB-317L-0-0290 (C0056822 Spk L, 40 ppbSpike) 4 40 NR NR NR NR 0.324 4.21 97 6.58 NR NR 0.324 34.1 84 6.58 11.0 3 7 .0 111 76 DLO I-SB-320L-0-0000 (C0096823 SpkC. 4 ppb Spike) 4 2.19 5.63 86 3.61 623 66 DLO I-SB-320L-0-0000 (C0056823 Spk D, 40 ppb Spike) 40 2.19 36.9 87 3.61 38.1 86 NR NR NR NR NR NR DLO I-SB-320L-0-0005 (C0056824 Spk E, 4 ppbSpace) 4 1.72 5.67 99 O LOI-SB-320L-0-0005 (C0056824 Spk F, 40 ppb Spike) 40 1.72 38.7 92 1.88 1.88 6.21 4 3 .0 108 103 NR NR NR NR NR NR DLO I-SB-320L-0-0020 (C0056825 Spk G, 4 ppb Spice) DLO I-SB-320L-0-0020 (C009862S Spk H, 40 ppbSpike) 4 40 7.26 7.26 9.92 37.0 67 74 4 .1 6 4 .1 6 6.70 38.1 64 65 NR NR NR NR NR NR DLO I-SB-320L-0-0050 (C0056826 Spk 1,4 ppbSpike) DLO I-SB-320L-0-0050 (C0056826 Spk J, 40 ppbSpike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR DLO I-SB-320L-0-0170 (C00S6827 spk K. 4 ppb Spike) 4 0.503 3.22 68 0 .6 8 4 3 .5 8 72 DLO I-SB-320L-0-0170 (C0056827 Spk L, 40 ppb Spice) 40 0.503 33.5 82 0.684 37.8 93 NR NR NR NR NR NR NR NR NR NR NR NR DLO I-SB-320L-0-0290 (C0056828 Spk M. 4 ppbSpice) DLO I-SB-320L-0-0290 (C00S6828 Spk N 40 ppb Spike) 4 40 NR NR NR NR 15.8 11.6 . NR NR 15.8 44.0 71 NR NR NR NR NR NR Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated NO * Not detected at or above 0,2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 47 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table IV. Matrix Spike Recovery of PFBS, PFHS and PFOS in Soil Samples Continued S am ple Description D LO I-SB-327R -0-0000 (C0056830 Spk C, 4 ppb Spike) D LO I-SB-327R -0-0000 (C0056830 Spk D. 40 ppb Spike) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C 6 Sulfonate PFHS W et W eight Amt Found In Sample (ng/g) Amount Recovered Recovery (ng/g) <%> C 8 Sulfonate PFOS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) 4 26.1 42.1 66.6 78.2 NR NR NR 40 26.1 62.2 90 66.6 113 116 NR NR NR D LO I-SB-327R -0-0005 (C0056631 Spk E, 4 ppb Spike) 4 52.4 50.2 * NR NR NR NR DLO I-SB-327R -0-0005 (C0056831 Spk F, 40 ppb Spike) 40 52.4 83.2 77 NR NR NR NR NR NR NR NR D LO I-SB-327R -0-0020 (C0056832 Spk G, 4 ppb Spike) D LO I-SB-327R -0-0020 (00056032 Spk H, 40 ppb Spke) DLO I-SB-327R -0-0050 (C0056833 Spk i, 4 ppb Spike) DLO I-SB-327R -0-0050 (C0056633 Spk J, 40 ppb Spike) 4 40 4 40 12.2 12.2 NR NR 15.4 47.2 NR NR 88 NR NR 17.4 17.4 NR NR 22.9 60.3 NR NR * 107 NR NR NR NR NR NR NR NR NR NR NR NR NR NR D LO I-SB-327R -0-0150 (C0066834 Spk K, 4 ppb Spike) DLO l-S B -327R -0-0150 (C0056634 Spk L, 40 ppb Spike) 4 40 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Average: Standard Deviation: 78 16 Average: Standard Deviation: 89 14 ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND * Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures, see Table V for re-extract data. Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Average: Standard Deviation: 91 21 Exygen Research Page 48 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Sam ple Description D F 0 6 -S B -1 3 2 R -0 -0 0 0 0 (C0053083 Spk E, 4000 ppb Spfce) Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (% ) C6 Sulfonate PFHS W et W eight Amt Found in Sample (ng/g) Amount Recovered (no/g) Recovery (%> 4000 . C8 Sulfonate PFOS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) 2260 6070 95 D F 0 6 -S B -1 3 2 R -0 -0 0 0 5 (COOS3084 Spk G. 2000 ppb Spike) 2000 - - 984 3870 144 D F 0 6 -S B -1 3 2 R -0 -0 0 1 0 (C0053085 Spk 1,2000 ppb Spike) 2000 - - 788 2500 86 D F 0 6 -S B -1 3 2 R -0 -0 0 2 0 (C0053086 Spk K, 2000 ppb Spfce) 2000 . - 781 3130 117 D F 0 6 -S B -1 3 2 R -0 -0 0 5 0 (C0053087 Spk M, 4 ppb Spike) D F 0 6 -S B -1 3 2 R -0 -0 0 5 0 (C00530S7 Spk N, 4000 ppb Spfce) 4 4000 6.18 9.84 92 .. - - 2940 5530 65 D F 0 6 -S B -1 3 2 R -0 -0 4 4 5 (00053088 Spk E, 4 ppb Spfce) 4 NR NR NR D F06-SB-132R-0-0445 (C0053068 Spk F 40 ppb Spike) 40 NR NR NR . -- .-- D F 0 6 -S B -1 3 3 R -0 -0 0 0 0 (C0053086 Spk G, 4000 ppb Spfce) 4000 - - - 3340 7070 93 D F06-SB-133R-0-0005 (C0053090 Spk 1,8000 ppb Spite) 6000 D F 0 6-S B -133 R -0-0 010 (C0053091 Spk K, 4000 ppb Spfce) 4000 D F 0 6-S B -133 R -0-0 020 (COOS3092 Spk M, 20000 ppb Spike) 20000 D F 06 -S B -1 3 3 B -0 -0 0 0 0 (C0053093 Spk E, 20000 ppb Spite) 20000 D F 06-S B -133 B -0-0 005 (C0053094 Spk G. 20000 ppb Spike) 20000 D F 06-S B -1 3 3 B -0 -0 0 1 0 (C005309S Spk 1,8000 ppb Spike) 6000 DF06-SB-133B -0-0020 (C00S3096 Spk K, 8000 ppb Spike) 8000 .. . . . - - - 5020 15800 135 - 2540 5050 63 - 10800 30600 99 - 13900 33900 100 - 15000 27700 64 - 4800 14500 121 - NR NR NR D F 0 9 -S B -1 3 1 R -0 -0 0 0 0 (C0053097 Spk M, 40000 ppb Spike) 4 00 00 - - 19900 56900 93 D F 09-S B -13 1 R -0 -0 0 0 5 (C0053098 Spk E, 200 ppb Spike) 200 DF09-SB-131 R-0-0005 (C0053098 Spk F, 200000 ppb Spike) 200000 D F 0 9 -S B -1 3 1 R -0 -0 0 1 0 (C0053099 Spk G, 8000 ppb Spike) 6000 D F 09-S B -13 1 R -0 -0 0 2 0 (C0053100 Spk 1,8000 ppb Spike) 8000 D F 0 9-S B -131 B -0-0 000 (C0053101 Spk K. 80000 ppb Spfce) 80000 D F 09-S B -13 1 B -0-0005 (C0053102 Spk M, 400 ppb Spfce) 400 DF09-SB-131 B-0-0005 (C0053102 Spk N. 200000 ppb Spike) 200000 D F 09-S B -13 1 B -0-0010 (C0053103 Spk E, 20000 ppb Spike) 20000 . 79.9 277 99 - -- - - - 84200 327000 121 .- . - 6400 13000 83 .- - - 2820 11800 112 .- - - 58000 116000 73 . . 214 546 83 . -- -- - - 136000 371000 118 -- - - 14200 33500 97 *Sam ple residue exceeds the spikin g level sign fcantiy, therefore, an accurate recovery value cannot be calculated ND * Not detected at or above 0.2 ng/g. NR 3 Not reported due to quality control failures Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 49 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued Sam ple Description Amount Spiked (n fl/g ) C4 Sulfonate PFBS W et Werpht Amt Found Amount in Sample Recovered (nq/Ql (ng/g) Recovery (%> C 6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) C8 Sulfonate PFOS Wet Weight Amt Found in Sample (n o /fl) Amount Recovered (nfl/g) Recovery (%> D F 09-S B -13 1 B -0-0020 (C0053104 Spk 6,8000 ppb Spike) 8000 . 6430 10500 51 D F 06-S B C -1 33R -0-0000 (C0053105 Spk 1,8000 ppbSpike) 8000 - . 3630 9120 69 D F 0 6 -S B -1 3 3 R -0 -0 0 5 0 (C0053106 Spk K. 40 ppb Spike) D F 0 6 -S B -1 3 3 R -0 -0 0 5 0 (C0053106 Spk M, 8000 ppb Spike) DF06-SBC -133R-0-0050 (C0063107 Spk M, 400 ppb Spike) D F 06-S B C -1 33R -0-0050 (C0053107 spk N, 2000 ppb Spike) 40 8000 400 2000 . . . - 10.6 52.1 104 . .. - - 1460 10400 112 128 448 80 . .. - - NR NR NR D F06-SBC -133R-0-0100 (C0053108 Spk E. 40 ppb Spike) 40 34.9 80.8 115 . . . . D F 06-S B C -1 33R -0-0100 (C0053108 Spk F, 400 ppb Spike) 400 . . 143 426 71 . . D F 06-S B C -1 33R -0-0100 (C0053108 Spk G. 2000 ppbSpike) 2000 -- - . 1920 3610 85 D F 06-S B C -1 33R -0-0150 (C0063109 SpkG, 20 ppb Spike) D F 06-S B C -1 33R -0-0150 (C00S3109 Spk H. 600 ppb Spike) 20 800 10.4 10.4 2 8 .9 751 93 93 .. . - - - 383 872 61 DF06-SB*133R -0-0180 (C0053110 Spk 1,4 ppbSpike) D F 0 6 -S B -1 3 3 R -0 -0 1 8 0 (C0053110 Spk J, 40 ppbSpike) D F 06-S B -133 R -0-0 180 (C0053110 Spk K. 200 ppb Spike) 4 40 200 3.23 3.23 5.50 20.8 - 57 44 - .. . . .. . - - - 171 304 67 D F 06-S B C -1 33R -0-0200 (C0053111 Spk K. 4 ppbSpite) DF06-SB C-133R -0-0200 (C0053111 SpkL, 400 ppbSpike) 4 400 4 .9 3 7.04 - 53 - .. . . - - 180 522 86 D F 06-S B C -1 33R -0-0250 (C0053112 Spk M, 4 ppbSpike) 4 NR NR NR . . . . DF06-SBC -133R-0-0250 (C0083112 Spk N, 40 ppbSpike) 40 NR NR NR - - - D F 8b-S B -1 3 5 R -0 -0 0 0 0 (C0054361 Spk E, 4000 ppbSpike) 4000 -.. - 2650 4850 55 D F 8b -S B -1 3 5 R -0 -0 0 0 5 (C0054362 Spk G, 40 ppb Spike) D F 8b -S B -135 R -0-0 005 (C0054362 Spk H, 20000 ppbSpike) 40 20000 0.605 40.4 - 99 - . . . - . 1520 22500 . 105 D F 8b -S B -135 R -0-0 010 (C0054363 Spk 1,4 ppbSpike) D F 8b -S B *13 5R -0-0010 (C0054363 SpkJ, 40 ppbSpike) D F 8b -S B -135 R -0-0 010 (C0054363 Spk K. 4000 ppbSpike) 4 40 4000 2.05 2.05 4.58 27.0 - 63 62 . . . - . . - 1330 3690 . . 59 DF8b-SB-135R -0-0020 (C0084364 Spk K, 4 ppbSpite) 4 4.18 7.06 72 . . DF8b-SB-135R -0-0020 (C0054364 Spk L, 40 ppb Spike) 40 4 .1 8 36.6 81 15.5 37.0 54 D F 8b-S B -1 3 5 R -0 -0 0 2 0 (C0054364 Spk M, 800 ppbSpike) 800 - -- - - - 498 1150 82 ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated Exygen Research Page 50 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued Sam ple Description Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found in Sample (na/g> Amount Recovered fn a /a ) Recovery C6 Sulfonate PFHS W et W eight ^ ^ _ C 8 S y jfg n a te _ P F O S ^ y g t^ e i^ Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (%> Amt Found in Sample (ng/g) Amount Recovered Recovery (% ) D F 09-S B -13 1 B -0-0050 (C0054348 Spk M, 4000 ppbSpike) 4000 .. 2570 6740 104 D F 0 9 -S B -131 B -0-0 080 (C0054349 Spk E, 4000 ppbSpice) 4000 -- 1670 3980 58 D F 8b -S B -135 R -0-0 050 (C0054365 Spk G, 4 ppbSpike) D F 8b -S B -135 R -0-0 050 (C0054365 Spk H. 40 ppbSpike) D F 8b -S B -135 R -0-0 050 (C00S43S9Spk 1,2000 ppb Spike) D F 8b -S B -135 R -0-0 19 0 (C0054366 Spk 1.4 ppb Spike) D F 8b -S B -135 R -0-0 190 (C0054366 SpkJ, 40 ppbSpice) D F 1 4 -S B -1 3 7 R -0 -0 0 0 0 (C0054367 SpkK, 400 ppb Spike) 4 40 2000 4 40 400 NR NR 3.05 3.05 NR NR 6.30 34.1 - NR NR - 81 78 - 526 . 70.0 1770 105 - 62 88 - 82.4 358 69 D F 1 4-S B -136 B -0-0 005 (C0054373 Spk 6 ,4 ppbSpike) D F 1 4-S B -136 B -0-0 005 (C0054373 Spk H. 40 ppbSpike) 4 40 ND ND 3.43 48.3 86 121 - D F 09-S B C -131R -0 -0 0 0 0 (C0054375 Spk M, 40000 ppb Spike) 40000 .- - D F 09-S B -13 1 R -0 -0 0 5 0 (C0054376 Spk E. 8000 ppbSpike) 8000 -- - DF09-SBC-131 R-0-0050 (C0054356 Spk 6,400 ppbSpike) DF09-SBC-131 R-0-0050 (C0054356 Spk H. 20000 ppbSpike) 400 20000 .. 79.3 374 -- - - -- - -- 13500 67400 135 2770 13000 128 74 . .. - 15400 40200 124 DF09-SBC-131R -0-0100 (C0054377 Spk 1. 4000 ppbSpike) 4000 -- - - 2020 4180 54 DF09-SB-131 R -0-0160 (C0054378 Spk K, 4000 ppbSpice) 4000 . - 177 5920 144 904 3140 56 D F 09-S B C -1 31R -0-0150 (C0054379 Spk M. 400 ppbSpike) D F 09-S B C -1 31R -0-0150 (C0054379 Spk N, 4000 ppbSpike) D F 09-S B C -13 1 R -0 -0 2 0 0 (C00543S7 Spk 0,400 ppbSpike) DF09-SBC-131 R-0-0200 (C0054357 Spk P, 2000 ppbSpike) D F 09-S B C -13 1 R -0 -0 2 5 0 (C0054380 Spk E, 400 ppbSpike) D F 0 6 -S B -133 B -0-0 050 (C0054361 SpkG, 400 ppbSpice) D F 0 6 -S B -133 B -0-0 050 (C0054381 Spk H, 2000 ppb Spike) 400 4000 400 2000 400 400 2000 . . 133 406 68 . . . -- - - 1170 3410 56 . . 191 527 84 . .. -- - - 763 2660 95 -. - - 350 797 112 . . 257 542 71 . .. -- - - 1580 3220 82 D F 06-S B -133 B -0-0 160 (COOS4382 Spk 1,4 ppb Spike) 4 5.73 9.60 97 .. . -- D F 06-S B -133 B -0-0 160 (C0054362 SpkJ, 40 ppbSpike) 40 5.73 53.0 118 -- - -- D F 06-S B -133 B -0-0 160 (C0054382 Spk K, 4000 ppbSpike) 4000 - - - - - 1980 4220 56 ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND = Not detected at or above 0.2 ng/g. Exygen Research Page 51 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued Sam ple Description Amount Spiked (n a ta l C 4 Sulfonate PFBS W et W eight Amt Found in Sample (n a ta l Amount Recovered (n a ta l Recovery (% ) C 6 Sulfonate PFHS W et W eight Amt Found Amount in Sample Recovered Recovery (n a ta l (n a ta l <%1 C8 Sulfonate PFOS W et W eight Amt Found Amount in Sample Recovered Recovery (n a ta l (n a ta l (% ) D F 1 4 -S B -1 3 7 R -0 -0 0 5 0 (C0054383 Spk K. 20 ppb Spike) 20 7.03 27.4 102 DF14-SB C-137R -0-0150 (C0054387 SpkG. 4 ppbSpike) 4 . . 6.77 10.1 83 DF 14-SB -136R-0-0290 (C0054359 Spk M, 40 ppbSpike) DF 14-SB -136R -0-0290 (C00S4359 Spk N, 40 ppb Spike) 4 40 ND ND 2.19 25.6 55 64 ,,. -- . - D F 1 4-S B -136 B -0-0 290 (C0056620 Spk G. 4 ppbSpke) 4 ND 3.37 84 0.928 4 .1 9 82 . D F 14-S B -136 B -0-0 290 (C0056620 Spk H. 40 ppb Spike) 40 ND 40.2 101 - 61.1 104 107 D F 8b -S B -1 3 4 R -0 -0 0 0 0 (C00S6621 Spk 1, 4 ppb Spike) 4 D F 8 b -S B *13 4R -0-0000 (C0056621 SpkJ, 40 ppbSpke) 40 D F 8b-S B -1 3 4 R -0 -0 0 0 0 (C0056621 SpkK, 200000 ppbSpike) 200000 13.2 13.2 19.0 62.2 . 123 .. . .. . - - 94400 355000 130 D F 8b -S B -1 3 4 R -0 -0 0 0 5 (C0056622 Spk K, 200 ppbSpke) 200 D F 8b-S B -1 3 4 R -0 -0 0 0 5 (C0056622 Spk L. 400000 ppbSpike) 400000 52.5 291 119 .. - - 178000 650000 118 D F 8 b -S B -1 3 4 R -0 -0 0 1 0 (C0056623 Spk M. 40000 ppbSpke) 40000 . . 28100 74000 115 D F 8b-S B -1 3 4 R -0 -0 0 2 0 (C0056624 Spk E, 20000 ppb Spke) 20000 . . 15500 34700 96 D F 8b -S B -1 3 4 R -0 -0 0 5 0 (C0056625 SpkG, 800000 ppb Spike) 800000 D F 8b -S B C -134R -0-0000 (C0058626 Spk l. 200 ppbSpke) 200 DF8b-SBC-134R -0-0000 (C0056626 Spk J, 400000 ppbSpke) 400000 . .. 114 222 - . 666000 1460000 99 54 . . - 106000 590000 121 D F 8b -S B C -134R -0-0050 (C0056628 Spk K, 40 ppbSpke) D F 8b -S B C -134R -0-0050 (C0056628 Spk L, 400 ppbSpike) D F 8b -S B C -134R -0-0050 (C0056628 Spk M. 4000 ppbSpke) 40 400 4000 15.4 - 51.2 . - 90 . - .. 266 611 -- _ 86 - - 2030 5560 . - 88 D F 8b -S B C -134R -0-0100 (C0056629 Spk M, 80 ppb Spike) DF8b-SBC-134R -0-0100 (C0056629 Spk N. 800 ppb Spike) D F 8b -S B C -134R -0-0100 (C0056626 Spk 0,2000 ppb Spike) 80 800 2000 35.8 86.0 . - 65 . - . .. 584 1310 91 - -- . 1300 . . 3530 . . 112 DF8b-SBC-134R -0-0150 (COOS6631 Spk E, 40 ppbSpike) 400 . - 355 775 105 518 724 52 D F 86-S B C -1 34R -0-0200 (C0056632 Spk H, 40000 ppb Spke) D F 8b -S B C -134R -0-0200 (C0056632 Spk 1,400 ppb Spke) 40000 400 - . . .. . 912 50400 124 - - 247 686 110 - -- ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 52 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued Sam ple Description Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery <%) C6 Sulfonate PFHS W et W eight Amt Found in Sample (ng/g) Amount Recovered (ng/g) Recovery (% ) Cfl Sulfonate PFOS W et W eight Amt Found Amount in Sample Recovered Recovery (ng/g) (ng/g) (% ) D F 8b-S B -1 3 4 R -0 -0 2 7 0 (C005M34 Spk 1,4 ppb Spike) 4 16.6 12.8 . D F 8b-S B -1 3 4 R -0 -0 2 7 0 (C0056634 SpkJ. 40 ppbSpike) 40 16.6 48.6 80 . - D F 8b-S B -1 3 4 R -0 -0 2 7 0 (C0056634 Spk K. 400 ppb Spike) 400 . 118 470 .88 134 554 105 D F 8b -S B -1 3 4 R -0 -0 2 7 0 (C0056634 Spk L. 20000 ppb Spike) 20000 - - 134 24500 122 D F 8b-S B C -134R -0-0250 (C00S6635 Spk L. 40 ppbSpike) 40 11.0 62.6 129 . . D FS b-S B C -134R -0-025 0 (C005663S Spk M, 800 ppbSpike) 800 .. 58.3 912 107 50.6 1050 125 D F 8b -S B C -134R -0-0250 (C0056635 Spk N, 20000 ppbSpike) 20000 -- - 50.6 26700 133 D F 8b -$B -134B -0 -00 00 (C0056636 Spk M. 40000 ppbSpike) 40000 D F 6b -S B -134 B -0-0 000 (C0056636 Spk N, 200000 ppbSpike) 200000 . . 470 41800 103 - -- - - 105000 279000 87 D F 8b -S B -134 B -0-0 005 (C0056637 Spk P, 80000 ppb Spice) D F 8b -S B -134 B -0-0 005 (C0056637 Spk R. 40 ppbSpike) 80000 40 . . NR NR NR - 61.4 117 139 D F 8b -S B -134 B -0-0 010 (C0056638 $pk E, 20000 ppbSpike) D F 8b -S B -134 B -0-0 020 (C0056639 Spk6.40000 ppb Spike) 20000 40000 ' - - - 19400 34600 76 - - 13800 67200 134 D F 0 9 -S B -1 3 0 R -0 -0 0 0 0 (C0056640 Spk 1,2000 ppb Spfce) 2000 - - - 808 3300 125 D F 0 9-S B -130 R -0-0 005 (C0056641 Spk K. 400 ppbSpike) 400 - - - 257 566 77 D F 09-S B -130 R -0-0 010 (C0056642 Spk M, 400 ppb Spike) 400 - - - 212 531 80 D F 0 9 -S B -1 3 0 R -0 -0 0 2 0 (C0056643 Spk E. 400 ppbSpike) 400 .. D F 8b -S B -134 B -0-0 050 (C0056644 Spk 6. 4 ppb Spike) DF8t>-SB-134B-0-0050 (C0056644 Spk H. 4000 ppbSpike) 4 4000 8.48 10.7 . 56 - . . 241 571 83 .. .. - - 4130 7300 79 D F 8b -S B -134 B -0-0 090 (C0056649 Spk 1,40 ppb Spike) DFBb-SB-134B-0-0090 (C0056645 Spk J. 800 ppbSpike) D F 8 6 -S B -134 B -0-0 090 (C0058645 Spk K, 8000 ppbSpike) 40 800 8000 16.9 41.2 . - 61 - .. .- 152 1010 107 -- - - 3220 10600 92 D F 0 9 -S B -1 3 0 R -0 -0 0 5 0 (C0056647 Spk K. 2000 ppb Spike) 2000 - - - - - - 960 2390 72 ` Sample residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND * Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in tee raw data. Exygen Research Page 53 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued Sam ple Description Amount Spiked (ng/g) C4 Sulfonate PFBS W et W eight Amt Found Amount in Sample Recovered (ng/g) (ng/g) Recovery (% ) C 6 Sulfonate PFHS W et W eight Amt Found in Sample (ng/g) Amount Recovered Recovery (% ) C 8 Sulfonate PFOS W et W eight Amt Found in Sample in o /a ) Amount Recovered Recovery (% ) D F 0 9 -S B -1 3 0 R -0 -0 1 5 0 (C0056648 Spk M. 600 ppb Spike) 600 . 357 1180 103 D L O I-S B -220R -0 -00 05 (C0056650 SpkG, 200 ppbSpike) 200 - 71.7 250 89 D L O I-S B -220R -0 -00 50 (C0056652 Spk K, 4 ppbSpike) D L O I-S B -220R -0 -00 50 (C0056652 S pk L, 40 ppb Spike) 4 40 0.570 0.570 3.47 26.20 73 69 - D L O I-S B -220R -0 -0170 (C00S6653 Spk M, 4 ppbSpite) D L O I-S B -220R -0 -0170 (C00S6693 Spk N, 40 ppbSpike) 4 40 0265 0265 6.17 59.1 148 147 . - . -- D L O I-S B -220L -0-0000 (C0056654 Spk E, 800 ppbSpite) 800 - - 419 1130 69 DLO I-SB-220L-0-0005 (C0056655 Spk 6.400 ppbSpike) 400 -- - 251 619 92 DLO I-SB-220L-0-0020 (C0056656 Spk 1.600 ppbSpike) 800 -- - 410 1290 110 DLO I-SB-220L-0-0050 (C0056657 Spk K, 4 ppb Spike) DLO I-SB-220L-0-0050 (C0066657 Spk L. 40 ppb Spike) 4 40 NR NR NR NR NR NR . - .. -- DLO I-SB-220L-0-0070 (C0056656 Spk M , 4 ppb Spite) D L O I-S B -220L -0-0070 (C0056656 Spk N, 40 ppbSpike) DLO I-SB-220L-0-0070 (C0056666 Spk0 ,400 ppbSpike) 4 40 400 121 1.21 1.21 3.34 24.3 323 53 58 80 . .. . 41.4 77.7 91 - 41.4 450 102 D L O I-S B -226R -0 -00 05 (C0056660 Spk G. 400 ppbSpike) 400 .- - - 205 542 64 D L O I-S B -226R -0 -00 20 (C0056661 Spk 1,200 ppbSpike) 200 -- - - 107 228 61 D L O I-S B -226R -0 -0180 (C0056663 Spk M. 20 ppbSpite) DLO I-SB-226L-0-0000 (C0056664 SpkE, 200 ppb Spite) 20 200 . -- - . 11.5 31.4 100 - - 58.7 236 89 D L O I-S B -226L -0-0020 (C00S6666 Spk 1,4 ppb Spike) 4 0.473 4.23 94 -- -- DLO I-SB-226L-0-0050 (C0056667 Spk K. 4 ppbSpike) 4 2.99 5.43 61 -- -- D L O I-S B -226L -0-0170 (C0056668 Spk M, 4 ppb Spite) D B K G -S B C -001B -0-0150 (C0056669 Spk 0 .4 ppbSpike) DBKG-SBC-001 B-0-0150 (00056669 Spk P, 40 ppbSpike) 4 4 40 0.323 ND ND 4.66 2.52 15.1 108 63 38 - - 4 .3 6 6 .7 9 61 .. .- -- - -- DBKG-SBC-001 B-0-0200 (C0056670 Spk E, 4 ppbSpike) 4 NR NR NR .. DBKG-SBC-001 B-0-0200 (C0056670 Spk F, 40 ppbSpike) 40 NR NR NR - - - --- ` Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND = Not detected at or above 0.2 ng/g. NR * Not reported due to quality control failures Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 54 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued S am ple Description DLOI-SB-31OR-O-OOOO (C0056671 Spk 6,400 ppbSpike) Amount Spiked (ng/g) C ^ u lfo o a te P F B S W d W g g W ^ ^ ^ C ^ u lfg g a te P F H S W e tW e jg h ^ ^ ^ ^ Q & jlg S a te P F O S W e tW e ji Amt Found Amount Amt Found Amount Amt Found Amount in Sample Recovered Recovery in Sample Recovered Recovery in Sample Recovered Recovery (naia) (ng/g) <%) (ng/g) (ng/g) (%) (ng/g) (ng/g) f%) 400 . 250 542 73 D L O I-S B -310R -0 -00 05 (C0056672 Spk 1.4 ppbSpike) DLO I-SB-310R-0-00Q5 (C0056872 SpkJ. 40 ppbSpike) DLOI-SB-31 OR-0-0005 (C0056672 Spk K, 200 ppb Spike) 4 40 200 0.944 0.944 5.93 60.2 125 148 - - .. . - - 139 342 102 DLOI-SB-31 OR-O-OOSO (COO50674 Spk M, 400 ppbSpike) 400 . - 332 750 105 DLOI-SB-31 OR-0-0370 (C0056675 Spk E. 4 ppbSpke) DLOI-SB-31 OR-0-0370 (C0056675 Spk P. 40 ppbSpike) 4 40 2.78 2.78 5.81 35.3 76 81 .. -- . - D B K G -S B -001B -0-0005 (C0056677 Spk 1,4 ppbSpike) DBKG-SB-001 B-0-0005 (C0056677 SpkJ. 40 ppbSpike) 4 40 0.377 0.377 4.27 45.7 97 113 .. -- DBKG-SB-001B -0-0010 (C0056678 Spk K, 4 ppbSpke) 4 ND 4.11 103 DBKG-SB-001 B-0-0010 (C0056878 Spk L. 40 ppbSpike) 40 ND 38.5 96 D B K G -S B -001B -0 -0 0 20 (C0056679 Spk M. 4 ppbSpike) DBKG-SB-001 B-0-0020 (C0056679 Spk N, 40 ppbSpike) 4 40 NO ND 3.90 4 0 .9 96 102 . - . - DBKG-SB-001 B-0-0230 (C0056681 Spk 6 ,4 ppbSpike) DBKG-SB-001 B-0-0230 (C0056681 Spk H, 40 ppbSpike) 4 40 NR NR NR NR NR NR . - D B K G -S B C -001B -0-0050 (C0056884 Spk K, 4 ppbSpke) D B K G -S B C -001B -0-0050 (C0056684 Spk L, 40 ppb Spike) D B K G -S B C -001B -0-0100 (00056685 SpkM, 4 ppbSpike) DBKG-SBC-001 B-0-0100 (C0056685 Spk N, 40 ppbSpike) 4 40 4 40 0.304 0.304 NR NR 4 .1 3 39.6 NR NR 96 98 NR NR . - D L O I-S B -317L -0-0000 (C0056817 Spk E, 20 ppbSpike) DLO I-SB-317L-0-0000 (C0056817 Spk F, 600 ppbSpike) 20 800 .. 5.96 28.2 111 -. - - 462 1060 75 D L O I-S B -3 1 7 L -0 -0 0 0 5 (C0056818 Spk G, 400 ppb Spike) 400 ... - - 214 558 86 D L O I-S B -317L -0-0020 (C0056619 Spkl, 400 ppb Spike) DLO l-S B -317L-0-0050 (C0056620 Spk K, 200 ppbSpike) 400 200 -- - - 201 578 94 - - - - - 135 406 136 DLO l-S B -317L-0-0290 (C0056822 Spk M, 4 ppbSpike) 4 NR NR NR .. -- D L O I-S B -317L -0-0290 (C0056822 Spk N, 40 ppbSpke) 40 NR NR NR - - - - -- ' Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND * Not detected at or above 0.2 ng/g. NR * Not reported due to quality control failures Exygen Research Page 55 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table V. Matrix Spike Recovery of PFBS, PFHS and PFOS in Re-extracted Soil Samples Continued S am ple Description DLO I-SB-320L-0-0000 (C0056823 Spk E. 2000 ppbSpike) Amount Spiked (n a /fl) C4 Sulfonate PFBS W el W eight Amt Found in Sample (n a /9 ) Amount Recovered (ng/g) Recovery (% ) C6 Sulfonate PFHS W et W eight M it Found in Sample (ng/9) Amount Recovered (na/o) Recovery (%> C 8 Sulfonate PFOS W et Weight Amt Found in Sample Amount Recovered (no/a) Recovery (% ) 2000 693 3590 145 D L O I-S B -3 2 0 L -0 -0 0 0 5 (C0056824 Spk0.800 ppbSpike) 800 - 321 1220 112 DLO I-SB-320L-0-0020 (C0056825 Spk 1. 2000 ppbSpike) 2000 - - - NR NR NR DLO I-SB-320L-0-0050 (C0056826 Spk K. 4 ppbSpice) 4 10.3 13.7 85 .. . .. DLO I-SB-320L-0-0050 (C0056826 Spk L, 2000 ppbSpike) 2000 . 10.1 2430 121 396 2850 123 DLO I-SB-320L-0-0170 (C0056827 Spk M, 20 ppbSpike) 20 . . . 7.31 26.2 94 DLO I-SB-320L-0-0290 (C0056828 Spk 0 ,4 ppbSpike) 4 NR NR NR DLO I-SB-320L-0-0290 (C0056S20 Spk P 40 ppbSpike) 40 NR NR NR DLO I-SB-320L-0-0290 (C0056828 Spk Q 200 ppbSpike) 200 -- .. . .. .. . .. - - 98.4 239 70 D L O I-S B -327R -0 -00 00 (C0056830 Spk E, 20000 ppbSpice) 20000 .. . . 14400 37200 114 D L O I-S B -327R -0 -00 05 (C0056831 Spk G. 400 ppbSpike) D L O I-S B -327R -0 -00 05 (C0056631 Spk H. 20000 ppbSpice) 400 20000 . 203 528 81 . .. .. - - 11500 34600 116 D L O I-S B -327R -0 -00 20 (C0056832 SpkJ, 4000 ppbSpike) 4000 -- - - 2910 7380 112 DLO I-SB-327R-0-0050 (C0056833 Spk K. 4 ppbSpice) D L O I-S B -327R -0 -00 50 (C0056833 Spk L. 20 ppbSpike) D L O I-S B -327R -0 -00 50 (COOS6833 Spk M. 40 ppb Spike) D L O I-S B -327R -0 -00 50 (C00S6833 Spk N, 4000 ppb Spice) D LO J-S B -327R -0-015 0 (C0056634 Spk M, 4 ppbSpike) D L O I-S B -327R -0 -0150 (C0056834 Spk N. 40 ppb Spike) D L O I-S B -327R -0 -01 50 (C0056834 Spk 0,2000 ppb Spike) 4 20 40 4000 4 40 2000 NR NR NR NR NR NR 8.64 i i . i .. . 62 . . . ,,. .. NR NR 8.64 44.6 90 . .. .. - - NR NR NR NR NR NR NR NR . ... NR NR .. - ..- . - 757 3340 129 A v erag e: Standard D eviation: 87 27 A v e ra g e : Standard Deviation: 92 23 A v e ra g e : Standard Deviation: 95 24 'Sam ple residue exceeds the spiking level significantly; therefore, an accurate recovery value cannot be calculated ND = Not detected at or above 0.2 ng/g. NR = Not reported due to quality control failures Note: Since this summary table shows rounded results, recovery values may vary slightly from the values in the raw data. Exygen Research Page 56 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table VT. Total Percent Solids for Soil Boring Samples Exygen ID C0053083 C0053084 C0053085 C0053086 C0053087 C0053088 C0053089 C0053090 C0053091 C0053092 C0053093 C0053094 C0053095 C0053096 C0053097 C0053098 C0053099 C0053100 C0053101 C0053102 C0053103 C0053104 C0053105 C0053106 C0053107 C0053108 C0053109 C0053110 C0053111 C0053112 C0054361 C0054362 Client Sample ID DF06-SB-132R-0-0000 DF06-SB-132R-0-0005 DF06-SB-132R-0-0010 DF06-SB-132R-0-0020 DF06-SB-132R-0-0050 D F06-SB-132R-0-0445 DF06-SB-133R-0-0000 DF06-SB-133R-0-0005 DF06-SB-133R-0-0010 DF06-SB-133R-0-0020 DF06-SB-133B-0-0000 DF06-SB-133B-0-0005 DF06-SB-133B-0-0010 DF06-SB-133B-0-0020 DF09-SB-131R-0-0000 DF09-SB-131R-0-0005 DF09-SB-131R-0-0010 DF09-SB-131R-0-0020 DF09-SB-131B-0-0000 DF09-SB-131B-0-0005 DF09-SB-131B-0-0010 DF09-SB-131B-0-0020 DF06-SBC-133R-0-0000 DF06-SB-133R-0-0050 DF06-SBC-133R-0-0050 DF06-SBC-133R-0-0100 DF06-SBC-133R-0-0150 DF06-SB-133R-0-0180 DF06-SBC-133R-0-0200 DF06-SBC-133R-0-0250 DF8b-SB-135R-0-0000 DF8b-SB-135R-0-0005 Total Percent Solids (% ) 80.10 87.91 84.41 82.83 85.81 79.59 81.62 84.30 85.53 84.36 81.41 83.60 82.82 83.25 77.79 83.29 83.20 83.07 79.24 85.79 84.15 82.18 83.48 83.67 81.88 82.95 85.07 85.40 79.07 81.05 81.49 81.79 Exygen Research Page 57 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table VI. Total Percent Solids for Soil Boring Samples Continued Exygen ID C0054363 C0054364 C0054348 C0054349 C0054365 C0054366 C0054367 C0054351 C0054368 C0054369 C0054370 C0054371 C0054352 C0054353 C0054372 C0054373 C0054374 C0054355 C0054375 C0054376 C0054356 C0054377 C0054378 C0054379 C0054357 C0054380 C0054381 C0054382 C0054383 C0054384 C0054385 C0054386 Client Sample ID DF8b-SB-135R-0-0010 DF8b-SB-135R-0-0020 DF09-SB-131B-0-0050 DF09-SB-131B-0-0080 DF8b-SB-135R-0-0050 DF8b-SB-135R-0-0190 DF14-SB-137R-0-0000 DF14-SB-137R-0-0005 DF14-SB-137R-0-0010 DF14-SB-137R-0-0020 DF14-SB-136R-0-0000 D F 14-SB-136R-0-0005 DF14-SB-136R-0-0010 DF14-SB-136R-0-0020 DF14-SB-136B-0-0000 DF14-SB-136B-0-0005 DF14-SB-136B-0-0010 D F 14-S B -136B-0-0020 DF09-SBC-131R-0-0000 DF09-SB-131R-0-0050 DF09-SBC-131R-0-0050 DF09-SBC-131R-0-0100 DF09-SB-131R-0-0160 DF09-SBC-131 R-0-0150 DF09-SBC-131R-0-0200 D F 09-S B C -13 1 R-0-0250 DF06-SB-133B-0-0050 DF06-SB-133B-0-0160 DF14-SB-137R-0-0050 DF14-SBC-137R-0-0000 DF14-SBC-137R-0-0050 DF14-SBC-137R-0-0100 Total Percent Solids (% ) 81.14 81.40 82.89 82.63 81.72 83.62 85.57 97.32 79.19 80.34 81.40 82.12 82.25 82.71 82.48 84.34 81.25 81.83 83.06 81.15 78.35 79.53 80.09 79.24 76.43 82.50 81.70 83.71 79.51 82.93 77.52 76.45 Exygen Research Page 58 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table VI. Total Percent Solids for Soil Boring Samples Continued Exygen ID CO0 5 4 3 8 7 C0054388 C0054389 C0054359 C0056619 C0056620 C0056621 C0056622 C0056623 C0056624 C0056625 C0056626 C0056628 C0056629 C0056631 C0056632 C0056634 C0056635 C0056636 C0056637 C0056638 C0056639 C0056640 C0056641 C0056642 C0056643 C0056644 C0056645 C0056647 C0056648 C0056649 C0056650 Client Sample ID DF14-SBC-137R-0-0150 DF14-SB-137R-0-0180 DF14-SB-136R-0-0050 DF14-SB-136R-0-0290 D F14-SB-136B-0-0050 DF14-SB-136B-0-0290 DF8b-SB-134R-0-0000 DF8b-SB-134R-0-0005 DF8b-SB-134R-0-0010 DF8b-SB-134R-0-0020 DF8b-SB-134R-0-0050 DF8b-SBC-134R-0-0000 DF8b-SBC-134R-0-0050 DF8b-SBC-134R-0-0100 DF8b-SBC-134R-0-0150 DF8b-SBC-134R-0-0200 DF8b-SB-134R-0-0270 DF8b-SBC-134R-0-0250 D F 8 b -S B -13 4 B -0 -0 0 0 0 DF8b-SB-134B-0-0005 DF8b-SB-134B-0-0010 DF8b-SB-134B-0-0020 DF09-SB-130R-0-0000 DF09-SB-130R-0-0005 DF09-SB-130R-0-0010 DF09-SB-130R-0-0020 DF8b-SB-134B-0-0050 DF8b-SB-134B-0-0090 DF09-SB-130R-0-0050 DF09-SB-130R-0-0150 DLOI-SB-220R-0-0000 DLOI-SB-220R-0-0005 Total Percent Solids (% ) 69.19 73.13 83.29 73.49 79.87 75.82 75.25 84.27 83.35 83.19 83.36 82.67 78.25 78.38 81.20 74.35 81.51 78.06 73.13 84.26 84.20 83.45 62.76 84.89 82.00 82.05 80.82 82.67 84.75 78.39 80.29 86.33 Exygen Research Page 59 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Table VI. Total Percent Solids for Soil Boring Samples Continued Exygen ID C0056651 C0056652 C0056653 C0056654 C0056655 C0056656 C0056657 C0056658 C0056659 C0056660 C0056661 C0056662 C0056663 C0056664 C0056665 C0056666 C0056667 C0056668 C0056669 C0056670 C0056671 C0056672 C0056673 C0056674 C0056675 C0056676 C0056677 C0056678 C0056679 C0056680 C0056681 C0056683 Client Sample ID DLOI-SB-220R-0-0020 DLOI-SB-220R-0-0050 DLOI-SB-220R-0-0170 DLOI-SB-220L-0-0000 DLOI-SB-220L-0-0005 DLOI-SB-220L-0-0020 DLOI-SB-220L-0-0050 DLOI-SB-220L-0-0070 DLOI-SB-226R-0-0000 DLOI-SB-226R-0-0005 DLOI-SB-226R-0-0020 DLOI-SB-226R-0-0050 DLOI-SB-226R-0-0180 DLOI-SB-226L-0-0000 DLOI-SB-226L-0-0005 DLOI-SB-226L-0-0020 DLOI-SB-226L-0-0050 DLOI-SB-226L-0-0170 DBKG-SBC-001B-0-0150 DBKG-SBC-001B-0-0200 D L O I-S B -3 10 R -0 -0 0 0 0 DLOI-SB-310R-0-0005 DLOI-SB-310R-0-0020 DLOI-SB-310R-0-0050 DLOI-SB-310R-0-0370 DBKG-SB-001B-0-0000 DBKG-SB-001B-0-0005 DBKG-SB-001 B-0-0010 DBKG-SB-001 B-0-0020 DBKG-SB-001 B-0-0050 DBKG-SB-001 B-0-0230 DBKG-SBC-001 B-0-0000 Total Percent Solids (% ) 81.15 81.28 81.89 79.13 87.78 84.76 79.43 81.63 83.01 84.01 79.84 79.59 75.36 77.94 83.72 80.30 80.27 80.64 82.40 84.16 96.15 87.89 85.57 86.05 82.36 79.31 82.86 87.12 84.15 88.55 80.37 85.80 Exygen Research Page 60 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Table VI. Total Percent Solids for Soil Boring Samples Continued Exygen ID C0056684 C0056685 C0056817 C0056818 C0056819 C0056820 C0056822 C0056823 C0056824 C0056825 C0056826 C0056827 C0056828 C0056830 C0056831 C0056832 C0056833 C0056834 Client Sample ID DBKG-SBC-001B-0-0050 DBKG-SBC-001B-0-0100 DLOI-SB-317L-0-0000 DLOI-SB-317L-0-0005 DLOI-SB-317L-0-0020 DLOI-SB-317L-0-0050 DLOI-SB-317L-0-0290 DLOI-SB-320L-0-0000 DLOI-SB-320L-0-0005 DLOI-SB-320L-0-0020 DLOI-SB-320L-0-0050 DLOI-SB-320L-0-0170 DLOI-SB-320L-0-0290 DLOI-SB-327R-0-0000 DLOI-SB-327R-0-0005 DLOI-SB-327R-0-0020 DLOI-SB-327R-0-0050 DLOI-SB-327R-0-0150 Total Percent Solids (% ) 84.76 81.11 91.17 88.98 86.94 86.08 83.36 79.35 81.04 84.48 85.20 87.54 86.33 93.74 90.37 79.54 80.50 89.77 Exygen Research Page 61 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 FIGURES Exygen Research Page 62 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Figure 1. Typical Calibration Curve for PFBS in Reagent Water 040705B Boil Boring.rdb (PFBS): " U n o a f Rogtession ("1 / y wwifhtine); y * 120 x + 0.000047 (r - 0.0087) Area, counts Exygen Research Page 63 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 2. Extracted Standards of PFBS in Reagent Water, 0 ng/L and 25 ng/L, Respectively XC942945-4 - PFBS (StMMdwrd) pmmk not found) amu - n m p lt 1 o f 49 from M tftSB .w iff Intensity, cps Intensity, cps A iti: 3742 counti Hight: 58.7 cp* RT: 3.03 min 3.03 SO- 8.98 8.86s. 88Ck'1< 4 2 g 4.84 5.46 8-81V 8.25s. 27A f \ t " 1 1 . 13.01 14.18 I W /N s A 10 ^17.09 Exygen Research Page 64 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Figure 3. PFBS in Reagent Blank, 0 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively I Roagomt C ontrol . PFBS fU kam m ) 2 M IM L 0 n r -taarpt* 9 o f 4$ from M f7 t3 B .w flf pom* not H and) Tim, min I R tjg c n t S p kA - PFBS(QC)200.0/00,0 jm u - u m p lt 10 of 48 from 040706B .wiff A r t* : 6717 counts H o ig h t1 1 7 .e p s RT: 3.04 min 3.04 T im *, min I R o ig tn t Spk B PFBS (QC) 2 9 0 .0 *8 .0 <mu u m p l 11 of 46 from 040709B.wiff Atoj: 62669 counts Hoighfc1070.eps RT: 3.04 min 3.04 Tim, min Exygen Research Page 65 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 4. Chromatogram Representing a Soil Sample Analyzed for PFBS (Exygen ID: C0059098, Data Set: 040705B) I C M 53099-PFBS (UHtaowa) 29SL * & * * -M w p lt 17o f 4$ from MW705B .w iff At m : 45S11 com nts H tig t 77d cps RT: 3lM m in 3.09 Intensity, cps 8 9 10 Time, min - 9 --T - 12 13 I" * 19 17 Exygen Research Page 66 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 5. Typical Calibration Curve for PFHS in Reagent Water 0407008 Soli Boring.rdb (PFHS): " U n t a f Rtgroision ?1 / x " lig h t in g ) : y - 271 x + 0.00146 (r - 0.9076) Area, counts Exygen Research Page 67 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 6. Extracted Standards of PFHS in Reagent Water, 0 ng/L and 25 ng/L, Respectively X C M 2M 5-# - PFHS (Staadard) 399. * f M am * - aamp/a 1 o f 49 tram 940793B.wifT p a a k a o t foaad) 10.05 Intensity, cps Intensity, cps Aita: 7411 counts Hight:304. cps RT: 10.0 min 10.02 Time, min Exygen Research Page 68 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Figure 7. PFHS in Reagent Blank, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively I ffa a g u n t C ontrol-P F H S (Unknown) 3 ML<VM.0 n m n ra m p fa $ o f 49 from M97Q5B.wiff faoak n o t found) Intensity, cps Tint, min R tagant Spk A - PFHS (QC) 388.0/B0.0 amu - sample 10 of 48 from 040705B.w|ff A rt a: 15831 counts H aight 687. ops RT: 10.0 min Intensity, cps | R ta g tn t SpkB - PFHS (00)388.0/80.0 am u-sam ple 11 of 48 from 04070SB.wtff Art: 147615 counts Height: 8100. cps RT: 10.0 min 10.04 Intensity, cps Exygen Research Page 69 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Figure 8. Chromatogram Representing a Soil Sample Analyzed for PFHS (Exygen ID: C0053098, Data Set: 040705B) Intensity, cps I C9053990 PFHS - p it 17o f 49 from 946705B.wiff A r m 2570251 coont* Hoigkt: 147000.cp* RT: 19.0 m itt 1.4*5 10.02 1.3*0 1.2*5- 1.1*5- 1.0*5- 8.0*4- 8.0*4- 7.0*4- 0.0*4- 5.0*4- 4.0*4- 3.0*4- 2.0*4- 1.0*4- 0.0 -L 1 2 3 4 5 0 7 8 8 10 11 12 13 14 15 10 17 T im *, min Exygen Research Page 70 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 9. Typical Calibration Curve for PFOS in Reagent Water 040705BR2 Soil Boring.rdt. (PFOS): "Linoi f R o g ra s io n fl I * ' IgMing): y - 180 x + 2.38-005 (i * 0.0002) Area, counts Exygen Research Page 71 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 10. Extracted Standards of PFOS in Reagent Water, 0 ng/L and 25 ng/L, Respectively I XCSS040S-0 PFOS (Standard) 4 9 S ir M ama -tam pI* l o t SI from M m O iB R lw iff p o t* aotfoaad) Intensity, cps XC0S040S-1 - PFOS (St*ndlld)409.0/B0.0 im il sim p lt 2 of 57 from 040705BR2.wiff Afa: 4313 oounts H aight 175. ops RT: 13.2 min 14.40 Intensity, cps Exygen Research Page 72 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 11. PFOS in Reagent Blank, 50 ng/L Fortified Reagent Spk A, and 500 ng/L Fortified Reagent Spk B, Respectively Am gont Control - PFOS (Unknown) 499.W99.9amn -aampla 9 o f ST from $49795BPZwiff S>*nk n o t found) 14.30 13.18 13.17 3000 "J2000 1000 0 ,M . . 8 0 10 12 13 14 15 16 17 Tim , min Exygen Research Page 73 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Figure 12. Chromatogram Representing a Soil Sample Analyzed for PFOS (Exygen ID: C00053098, Data Set: 040705BR2) I C N S 3 M I PFOS (U tftiro w jfJ 499.9/94.9 mm* 17 o f 57 from A n * : 1*7939conots Haigkt: 9999. cp* RT: 13.2 m in 13.18 Intensity, cps Exygen Research Page 74 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 APPENDIX A Study Protocol P0001131 (Exygen Study No. P0001131) with Analytical Methods, Amendments and Deviations Exygen Research Page 75 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 STUDY PROTOCOL Study Title: Analysis of Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program Exygen Protocol Number: P0001131 Performing Laboratory: Exygen Research 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 Sponsor Representative: M ichael A . Santoro Director o f Regulatory Affairs 3M Building 0236-01-B -10 St. Paul, M N 55144 Phone: (65 1) 733-6374 Page I oj 65 Exygen Research Page 76 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 DISTRIBUTIONS 1) Jaisimha Kesari, Study Director, Weston Solutions 2) John M . Flaherty, Principal Investigator, Exygen Research 3) Michael A . Santoro, Sponsor Representative, 3M Company 4) Exygen Research Quality Assurance Unit Exygen Research Page 2 o f 65 Page 77 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: POOO1131 PROTOCOL APPROVAL Study T itle: Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Livers and Small Mammal Serum Using LC/M S/M S for the 3M Decatur Monitoring Program Exygen Protocol Number: P0001131 APPROVALS JaisimhatKesan, S' Weston Solutions Michael A Santoro, Sponsor Representative 3M Comparfy Date Quality Assurance Unit Date -M Page J o j 65 Exygen Research Page 78 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 TABLE OF CONTENTS TITLE P A G E .....................................................................................................................................................................1 D IS T R IB U T IO N ............................................................................................................................................................... 2 PROTOCOL APPROVAL.............................................................................................................................................. 3 TABLE OF CONTENTS................................................................................................................................................ 4 I N T R O D U C T IO N ............................................................................................................................................................. 5 TEST M ATERIA LS........................................................................................................................................................ 5 O B JECTIV E..................................................................................................................................................................... 6 TESTING FACILITY......................................................................................................................................................6 STUDY DIRECTOR........................................................................................................................................................ 7 SPONSOR REPRESENTATIVE................................................................................................................................... 7 PRINCIPAL INVESTIGATOR..................................................................................................................................... 7 PROPOSED EXPERIMENTAL START AND TERMINATION D A TE S............................................................7 IDENTIFICATION AND JUSTIFICATION OF THE TEST SY ST EM ................................................................8 SAMPLE PROCUREMENT, RECEIPT AND RETENTION..................................................................................8 SAMPLE IDENTIFICATION........................................................................................................................................9 ANALYTICAL PROCEDURE SUMMARY.............................................................................................................. 9 VERIFICATION OF ANALYTICAL PROCEDURE................................................................................................9 METHOD FO R CONTROL OF B IA S..........................................................................................................................11 STATISTICAL M ETH O D S............................................................ 11 GLP STA TEM ENT..........................................................................................................................................................11 R EPO R T.............................................................................................................................................................................11 SAFETY AND H EA LTH ................................................................................................................................................12 AMENDMENTS TO PR O TO CO L............................................................................................................................... 13 DATA RECORD K EE PIN G .......................................................................................................................................... 13 QUALITY A SSURANCE...............................................................................................................................................14 RETENTION OF DATA AND A RCHIVING.............................................................................................................14 APPENDIX I, ANALYTICAL M ETHODS................................................................................................................. 15 Page 4 o f 65 Exygen Research Page 79 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 INTRODUCTION The purpose o f this study is to perform analysis for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) in water, soil, sediment, fish, clams, vegetation, small mammal livers and small mammal serum using LC/MS/MS for the 3M Decatur Monitoring Program. The study w ill be audited for compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by the Quality Assurance Unit o f Exygen Research. TEST MATERIALS The test materials are perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) and are all supplied by 3M. PFBS Chemical Name: Perfluorobutanesulfonate Molecular Weight: 338 supplied as the potassium salt (C FSO T O Lot Number: 101 Purity: 96.7% Transitions Monitored: 299 - > 99 Structure: PFHS Chemical Name: Perfluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (C6F13SO3X * ) Lot Number: SE036 Purity: 98.6% Transitions Monitored: 399 - 80 Structure: F S03 Page 5 o f 65 Exygen Research Page 80 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 PFOS Chemical Name: Perfluorooctanesulfonate Molecular Weight: 538 supplied as the potassium salt (CgF^SOjTC*) Lot Number 217 Purity: 86.9% Transitions Monitored: 499 - 99 Structure: FFFF FFFF F S03 F OBJECTIVE The puipose o f this study is to perform analysis for perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS) and perfluorooctanesulfonate (PFOS) in water, soil, sediment, fish, clams, vegetation, small mammal livers and small mammal serum for the 3M Decatur Monitoring Program using the current versions o f the following Exygen analytical methods: V0001780: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Water by LC/M S/M S" V0001781: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Soil by LC/M S/M S" V0001782: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/M S/M S" V0001783: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/M S/M S" V0001784: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Vegetation by LC/M S/M S" V0001785: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Small Mammal Liver by LC/M S/M S" V0001786: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LC/M S/M S" TESTING FACILITY Exygen Research 3058 Research Drive State College, PA 16801 Phone:(814)272-1039 Page 6 o f 65 Exygen Research Page 81 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 STUDY DIRECTOR Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: (610) 701-3761 Fax: (610) 701-7401 j.kesari@westonsolutions.com SPONSOR REPRESENTATIVE Michael A . Santoro 3M Company Director o f Regulatory Affairs 3M Building 0236-01-B-10 St. Paul, M N 55144 Phone: (651) 733-6374 PRINCIPAL INVESTIGATOR John M . Flaherty Exygen Research 3058 Research Drive State College, PA 16801 Phone: (814) 272-1039 j ohn.flaherty@exygen.com PROPOSED EXPERIMENTAL START AND TERMINATION DATES It is proposed that the analytical portion o f this study be conducted from October 01, 2004 to December 31, 2005. The actual experimental start and termination dates w ill be included in the final report. Page 7o f 65 Exygen Research Page 82 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 roENTIFlCATiON AND JUSTIFICATION OF THE TEST SYSTEM The following are the test systems for this study: Water (groundwater and surface water) Soil Sediment Fish Clams Vegetation Small Mammal Liver Small Mammal Serum The samples w ill be collected by Weston Solutions. The control samples w ill be purchased and prepared by the testing facility. Purchase and processing details for the control samples w ill be included in the final rep o rt associated with this study. The test systems were chosen to access the environmental impact o f PFBS, PFHS and PFOS in the Decatur, Alabama area. SAMPLE PROCUREMENT, RECEIPT AND RETENTION Water, soil, sediment, fish, clam, vegetation, small mammal liver and small mammal serum samples w ill be received at Exygen directly from Weston Solutions. The details o f sample procurement for this study are outlined in the 3M work plan entitled "Phase 2 Work Plan for Sampling Environmental Media." The number and types o f samples collected w ill vary depending availability in the field. The total number o f samples received and analyzed for each matrix w ill be documented in the final report associated with this study. Water, soil, and sediment samples w ill be used as received without further processing at Exygen. These samples w ill be stored refrigerated at 2C-8C. Fish, clam, vegetation and small mammal liver samples w ill be processed according to the appropriate analytical method (see Appendix I). These samples w ill be stored frozen at -10C. Sm all mammal w hole blood samples w ill be centrifuged in the field at the time o f collection and the serum fraction w ill be used for the study. Small mammal serum w ill be stored frozen at -10"C. The receipt and processing o f the samples w ill be documented in the final report and raw data associated with the study. PageS o f65 Exygen Research Page 83 o f 144 Interim Report #7-AnaIysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 SAMPLE IDENTIFICATION Prior to analysis, each sample w ill be assigned a laboratory sample reference number. The reference number w ill be unique and w ill distinguish each laboratory sample that is processed throughout the analytical procedure. Chromatographic data w ill be identified by the laboratory sample reference number. Sample storage conditions and locations w ill be documented throughout the study. ANALYTICAL PROCEDURE SUMMARY References: V0001780: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Water by LC/M S/M S" V0001781: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Soil by LC/M S/M S" V0001782: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/M S/M S" V0001783: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/M S/M S" V0001784: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Vegetation by LC/M S/M S" V0001785: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Small Mammal Liver by LC/M S/M S" V0001786: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LC/M S/M S" The above methods use analytical conditions capable o f separating the isomers o f PFBS, PFHS and PFOS. The final report w ill include the isomers summed into total PFBS, total PFHS, and total PFOS found. VERIFICATION OF ANALYTICAL PROCEDURE A laboratory control sample w ill be used for the preparation o f fortified control samples. The test substance w ill be made into solutions as per the method, and added to the matrices via a micropipette. For water sampling, Exygen w ill supply one bottle per sample collected. The bottles w ill be 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottles. These bottles have been routinely used for fluorochemical sample Page 9 of65 Exygen Research Page 84 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol Number: P0001131 collection at the testing facility and have been shown to be free o f PFBS, PFHS and PFOS. Samples w ill be added to each container to a volumetric fill line at 200 mL. A field duplicate, a low field spike and a high field spike of each sample w ill be collected. The low and high field spike bottles w ill contain PFBS, PFHS and PFOS as well as perfluorooctanoic acid (PFOA) and 1.2-13C perfluorooctanoic acid (l3C PFOA). PFOA and l3C PFOA are included in the solutions used to spike the samples. The results for PFOA and l3C PFOA w ill not be reported in this study. Exygen w ill supply one field blank (control water) and two field blank spikes (control water fortified with PFBS, PFHS and PFOS at a low and high level) for every twenty samples collected. A t the testing facility, each water sample (excluding field duplicates and field spikes) w ill be extracted in duplicate and w ill also be fortified at a low and high concentration with PFBS, PFHS and PFOS and processed through the described procedure to determine method accuracy and to check for bias. For soil, sediment, clams, and vegetation, Exygen w ill supply one S00 mL precleaned Sci/Spec Premier wide mouth HDPE bottle per sample collected or a zip-seal bag. A ll containers/bags used for sample collection w ill be shipped to the sample location. Samples w ill be added to each container or bag in the field. At the testing facility, each sample w ill be extracted in duplicate and w ill also be fortified at a known concentration with PFBS, PFHS and PFOS at both a low and high level and processed through the described procedure to determine method accuracy and to check for bias. For small mammal liver, Exygen w ill supply a SO mL polypropylene centrifuge tube. For small mammal serum, Exygen w ill supply a collection kit for each sample containing serum separator tubes (red top), vacutainers, needle holders and needles, transfer pipettes, and polypropylene tubes. At the testing facility, each liver and serum sample w ill be extracted in duplicate and w ill also be fortified at a known concentration with PFBS, PFHS and PFOS at both a low and high level and processed through the described procedure to determine method accuracy and to check for bias. Low and high spiking levels for each matrix are defined below: M atrix Low Spiking Level High Spiking Level Water 500 ng/L 5000 ng/L Soil Sediment 4 ng/g 4 ng/g 40ng/g 40 ng/g Fish 1 0 ng/g lOOng/g Clams 1 0 ng/g 1 0 0 ng/g Vegetation 1 0 ng/g 1 0 0 ng/g Small Mammal Liver 1 0 ng/g 1 0 0 ng/g Small Mammal Serum 10 ng/mL 100 ng/mL Page 10 of65 Exygen Research Page 85 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Recoveries are anticipated to be between 70% and 130% o f the fortified levels; however, the exact precision and accuracy w ill be determined by the analysis o f the quality control samples described above. A statement o f accuracy w ill be included in the final report. METHOD FOR CONTROL OF BIAS Control o f bias w ill be addressed by talcing representative sub-samples from a homogeneous mixture o f each matrix from untreated control samples, and by analyzing at least two levels o f fortifications. STATISTICAL METHODS Statistics w ill be limited to those specified in the subject methods and to the calculation o f average recoveries, as applicable. GLP STATEMENT A ll aspects o f this study shall be performed and reported in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The final report or data package (supplied to the Sponsor) shall contain a statement that the study was conducted in compliance with current and applicable GLP standards and w ill outline any deviations in the study from those standards. This statement w ill be signed by the Study Director and Sponsor Representative. REPORT A final report w ill be prepared by file principal investigator or their designee at the conclusion o f the study. The report w ill include, but w ill not be limited to, the following: The name and address o f the Study Director, Sponsor Representative, and o f the testing facility. A statement o f GLP compliance (any related documentation, such as chain-of-custody records, must be in the study records). Page l l o f 65 Exygen Research Page 86 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 The signed and dated statement by the Exygen Research Quality Assurance Unit regarding dates o f study inspections and dates findings were reported to the Study Director and Management. A description o f the exact analytical conditions employed in the study. If the subject method was followed exactly, it is necessary to include only a copy o f the analytical method. Any modifications to this method w ill be incorporated into the report. I f the method is photo-reduced, the project number and page number must be included on each page. Description o fthe instrumentation used and operating conditions. A ll results from all sets analyzed. Control and fortified samples w ill be identified and the data table w ill include sample number and fortification level. Representative chromatograms for each analyte in each matrix, including chromatograms o f a standard and a control sample, and a chromatogram at a fortification level. The location o f the analyte peaks w ill be clearly identified in all chromatograms. A ll circumstances that may have affected the quality or integrity o f the data w ill be documented in the report. Locations where raw data and the final report are to be archived. Additions or corrections to the final report shall be in the form o f an amendment signed by the Study Director. The amendment shall clearly identify that part o f the report that is being altered and the reasons for the alterations. The amendment w ill be signed and dated by the Study Director and the Sponsor Representative. A ll applicable requirements for reporting o f study results as per 40 CFR 792.185. SAFETY AND HEALTH laboratory personnel w ill practice good sanitation and health habits. Every reasonable precaution shall be taken to prevent inadvertent exposure o f personnel and the environment to the test or reference Page 12 o f 65 Exygen Research Page 87 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: POOOl 131 AMENDMENTS TO PROTOCOL A ll significant changes to the analytical protocol outlined here w ill be expressed in writing, signed and dated by the Study Director and Sponsor Representative. Amendments usually w ill be issued prior to initiation o f study plt change. However, when a change is required without sufficient time for the issue o f a written amendment, that change may be effected verbally with supporting documentation signed and dated by the Study Director and followed with a written amendment as soon as possible. In this case, the effective date o f the written amendment w ill be the date o f the documented change. Copies o f the signed amendments w ill be appended to all distributed study plan copies. The original amendment w ill be maintained with the original study plan. Any deviations from the study plan or from the analytical method as provided w ill be documented and reported promptly to the Sponsor Representative. DATA RECORD KEEPING Records to be maintained include the following (as appropriate): Sample tracking sheet(s) Sample receipt records, storage history, and chains o f custody History and preparation o f standards (stock, fortification, calibration) Description o f any modifications to the method Instrument run sheets, bench-sheets or logs Analytical data tables A ll chromatographic and instrumental conditions Sample extraction and analysis dates A complete listing o f study personnel, signatures and initials Chronological presentation o f all study correspondence Any other documentation necessary for the reconstruction o f the study Chromatograms- A ll chromatograms w ill contain the following: Sample identification, injection date, arrow or other indication o f the area o f interest, and injection number corresponding to the run. Additionally, fortifications w ill include the amount o f analyte added and the sample number o fthe sample that was fortified. Analytical standard chromatograms w ill additionally include the concentration (e.g., pg/mL). Page IS of 65 Exygen Research Page 88 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P 0001131 As pat o f the documentation the following sheets w ill be included in each analytical set: a run sheet listing the samples to be run in the set, and an instrument conditions sheet describing the instrument type and operating conditions. QUALITY ASSURANCE The QA Unit o f Exygen Research w ill inspect the study at intervals adequate to assure compliance with GLP's, and w ill report the findings o f audits to the Study Director, Exygen Management, and the Sponsor Representative. RETENTION OF DATA AND ARCHIVING A ll hard copy raw data, including, but not limited to, the original chromatograms, worksheets, correspondence, and results shall be included with the data package submitted to the Study Director. These w ill be archived with the original study plan, amendments, final report, and all pertinent information from the Sponsor. The testing facility shall keep all electronic raw data and any instrument, equipment, and storage logs for the period o f tim e specified in 40 CFR 792.195. An exact copy o f the materials submitted to the study director w ill also be kept at Exygen Research. Exygen w ill obtain permission from the study director before discarding or returning samples. Exygen Research Page 4 o f 65 Page 89 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 APPENDIX I ANALYTICAL METHODS V0001780 V0001781 V0001782 V0001783 V0001784 V0001785 V0001786 "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Water by LC/M S/M S" "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Soil by LC/M S/M S" "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/M S/M S" "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Fish and Clams by LC/M S/M S" "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Vegetation by LC/M S/M S" "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Small Mammal Liver by LC/M S/M S" "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LC/M S/M S" Exygen Research Page 15 o f 65 Page 90 o f 144 Interim Report #7-Analysis of Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: POOO1131 ANALYTICAL METHOD Method Number V0001780 Method of AaalyiU for the Decenniotie of Perflnrooctnolc Acid (PFOA) to Water byLC/MS/MS Analytical TootingFacility: Exygen Reoeerch 3058 Research Drive StateColtole, PA 16801 Approved By: r v u c-ik PPaauull PCaomnnuolllvy Technical Leader, LC-MS, ExygenRaaeareb <o|n/d*f Date /JroJohhnnFlahberty / ' VViicme PPwrsiidait, Operations, Exygen Research Exygen Research Total Pages: 7 Page 6 o f 65 Page 91 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 BaygaaRaseaGli Mttbod Number VOOOino ANALYTICAL m e t h o d Method ofAnalysis for the Determination o fPerfluorooctanoic Acid (PFOA) in Water by LC/MS/MS 1.0 Scope Thu Tf|ad>nd Uto be employed for the eolation and quantitation ofperfluorooctanoic add by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector(LC/MS/MS) in water. 2.0 Safety 2.1 Always observeaafelaboratorypractices. 2.2 Consultdie appropriateMSDS beforehandling anychemical for proper safely precautions. 3.0 SampleRequirement 3.1 At least 40mL o ftestsamplefor extraction. 3.2 No sampleprocessingis needed for watersamples. 3.3 Samples stored refrigerated should be allowed to equilibrate to room temperature. 3.4 AU samplesmustbe thoroughlymixed before being sampled for extraction 3.5 Any samples containing particles should be centrifuged at ~3000 rpm for -5 minutesandthe supernatantused for the extraction. 3.6 Sample collection procedures w ill be specified in the sampling plan for this project 4.0 ReagantaandStandards 4.1 Water- HPLC grade 42 Methanol-HPLC grade 4.3 AmmoniumAcetate- A.C.S. ReagentGrade 4.4 Perfluorooctanoic Acid - Sigma-Aldrich 5.0 Instrument andEquipment 5.1 A high performance liquid chromatograph capable o f pumping up to 2 solvents equipped with s variable volume injector capable of injecting 5-200 pL connectedto a tandemMaaeSpectrometer (LC/MS/MS). 5.2 A deviceto collectcawdataforpeak integration andquantitation. 5.3 Analyticalbalancecapableofrawtingto 0.00001 g. 5.4 50mL disposablepolypropylenecentrifoge tubes. 5.5 15mL disposablepolypropylenecentrifoge tubes. 5.6 Diqiosable micropipets(SO-IOOuL, 100-200uL). 5.7 125-oL LDPE nsrrow-mouth bottle. 5.8 2 mLclew HPLCvial kit. 5.9 Disposablepipettes. 5.10 Autopipettes (100-1000 pL and 10-100pL), with disposable tips. 5.11 Water* SepPskVac6 cc(lg)t&8SPE cartridges. Page 2 of? Page 17 o f 65 Exygen Research Page 92 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Bxyfnlamicb MtfbodNumbV00017SO L ANALYTICAL m e th o d MethodofAnalysis for the Determination ofPerfhioroocUnoic Acid (PFOA) in Waterby LC/MS/MS 5.12 SPEvacuummanifold. 5.13 Centrifogecapableofgrinning 50 mL polypropylene tubes at 3000rpm. 6.0 Chromatographic System 6.1 Analytical Column: Floophue RP(Keystone Scientific), 2.1 mm x 50 mm.5^ (P/N: 82505452130) 6.2 Temperature: 30"C 6.3 Mobile Phase(A) : 2 mM Ammonium Acetate in Water Mobile Phase(B ): Methanol Gradient Program: Tpmafminl 0.0 1.0 8.0 20.0 22.5 &A 65 65 25 25 65 Flow Rate &J3 (mLftninl 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3 6.6 Injection Volume: 15pL (cm beincreasedto asmuch as50 pL). 6.7 Quantitation: PeakArea- external standardcalibration curve. 6.8 RunTime: -2 3 minutes. Theaboveconditionsareintendedasaguide and maybe changed in orderto optimize theHPLC system. 7.0 MS/MS System 7.1 Mode: EiectroepcayNegativeMRM mode,monitoring 413- 369 m/z. The above conditions are intended as a guide and may be changed in order to optimize the MSMS system. 8.0 PreparationofSolutions 8.1 MobilePhase 8.1.1 2 mM ammonium acetate in water is prepared by adding 0.154 g of ammonium acetateto 1000mL ofwater. Alternate volumeamaybeprepared. Exygen Research Page 18 o f65 Page 93 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExyinftMCMdi Method Number V0001780 | ANALYTICAL METHOD j MethodofAnalysis for theDeteraunation ofPerfhiorooctanoic Add (PFOA) in Waterby LC/MS/MS 9.0 StandardPreparation 9.1 StandardStock/Fortification Solution 9.1.1 Prepare a dock solution o f100 ^g/mL of PFOA by weighing 10 mg ofanalytical standard (corrected for purity) and dilute to 100 mL with methanol in a 123-mL LDPE bottle. 9.12 A 10 pg/mL fortification solution o fPFOA is prepared by bringing 10 mL ofthe 100 pg/mL solution to a final volume of 100 with methanol in a 125mL LDPBbottle. 9.1.3 A 1.0pg/mL fortification solution ofPFOA is prepared by bringing 10 mLofthe 10pg/mL solution to a final volume of 100 with methanol in a 12$mL LOPEbottle. 9.1.4 A0.1 pg/mL fortification solution ofPFOA it prepared by bringing 10 mL ofthe 1.0pg/raL solution to afinal volume o f 100with methanol in a 12SmL LOPEbottle. 9.1.5 A 0.01 pg/raL fortification solution o f PFOA it prepared by bringing 10 mL o f the 0.1 pgtaL solution to a final volume of 100 with methanolin a 125mL LDPE bottle. 9.1.6 Thestock andfortification solutions are to bestored in a refrigerator at approximately 4C and are able for a maximum period of 6 months from thedateo fpreparation. 92 StandardCalibration Solutions 92.1 LC/MS/MS calibration standards are prepared in KPLC water. The calibration standards are processed through the extraction procedure, identical lo samples. 922 Tbs following is a typical example: additional concentrations may be F in a l C oncentration Fortification V olum e o f Concentration o f C alibration o f Fortification Volum e Fortified C om m i C alib ratio n Standard ID Solution fo o t) (UL) S im la fm L Standard foot)* (exam olO 0 0 40 10 too 40 to 200 40 to 400 40 too too 40 too 200 40 too 400 40 0 25 50 100 250 500 1000 XCmmddyy<0 X C m n)ddyy*] X C m m ddyy-2 X C m m ddyy-3 X C m m ddyy-4 X C m m ddyy-5 XCm m ddw -6 * Theextracted concentration ofthecalibration standard is equal to 8k its initial concentration, dueto theconcentration o fthe standardduring the extraction (SPE). XC - extractedcalibration standard. Page 4 of ^ Page 19 o f 65 Exygen Research Page 94 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol Number: P0001131 ExypaJUsNicfa M ethedNwnb VOOOI7SO | ANALYTICAL METHOD | Method o fAnalysis forthe Determinationo fPerfluorooctanoic Acid (PFOA) in Waterby LC/MS/MS 9.2.3 A zero standard solution (reagent blank) mint be prepared with each setofstandards extracted. 9.2.4 Store all extracted calibration etandarda in 15-mL polypropylene tubes at2*C to 6*C, upto two wedca. 9.2.3 Alternate volumes andconcentration* o fatandaida maybe prepared as needed. 10.0 Batch SetUp 10.1 Each batch of eunplce extracted (typically 20 or leas) must include at least one reagent control (method blank using HPLC water) and two reagent controls fortified at known concentrations (lab control spike! to verify procedural reooveryfor thebatch. 10.2 Requirements for field and laboratory duplicates and spikes w ill be specified mthequality assuranceplan for this project 11.0 SampleExtraction 11.1 Measure 40 mL of sampleor aportion o fsample diluted to 40 mL with water into 30 mL polypropylene centriftige tubes (fortify as needed, replace lid and mix well). 11.2 Condition the Cu SPE cartridges (1 g. 6 mL) by passing 10 mL methanol followedby 3mLo fHPLC water(~ 2 drop/sec). Do not let column run dry 11.3 Loadsampleonconditioned Cu SPEcartridge. Discard eluate. 11.4 Elute with -5 mL 100% methanol Collect 5 mL of eluate into graduated 1SmL polypropylene centriftige tubes(final volume * 3 mL). 11.5 Analyze sanqile*using electnupray LC/MS/MS. 12.0 Chromatography 12.1 Inject the aTMamounto feachstandard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzed samples. 12.2 StandardsofPFOAcorre^onding to at least five or more concentration levels mustbe includedin ananalytical aet 12.3 An entire set of extracted calibration standards must be included at the Kagiwning and at the end of a sample set. Extracted standards must be interspersed between every 3-10 samples. As an alternative, an entire set of extracted calibration standards may be injected at the beginning of a set followed by extracted calibration standards interspersed every 3-10 samples (to account for a second set of extracted standards). In either case, extracted calibration standardsmustbethe first and last injection in asample set. 12.4 Use linear standard curves for quantitation. Linear standard curves are for the analyteby linearregressionusing 1/x weighting ofpeakarea PagJ of7 Page 20 o f 65 Exygen Research Page 95 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol Number: P0001131 Exygra Rm m k Ii Method Number V00017M ANALYTICAL METHOD Methodo fAnalysis fortheDetsrauoationo fFerfluorooctanoic Acid (PFOA) in Waterby LC/MS/MS venue calibration standard concentration using MasaLynx 3.3 (or quivalem) software system. 12.5 Sample response should not exceed standard responses. Any samples that exceedstandardresponses shouldbe Antherdiluted and reanalyzed. 13.0 AcceptanceCriteria 13.1 Chromatogram must show a peak o f a daughter ion at 369 amu from a parent o f413 amu. The 413 amuparent corresponds to the PFOA anion, while the rf<..ghtiy ion (369 amu)representsthe lossofcarbondioxide. 13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank contains PFOA at levels greater than 50 ng/L, then a new blank sample must beobtainedandthe entire setmustbere-extracted. 13.3 Recoveries of control spikes and matrix spikes must be between 70-130% of their known values. I f a control spike Arils outside the acceptable limits, the entire set of samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by die analyst to determine if re-extraction is warranted. 13.4 Any calibration standard found to bo a statistical outlier by using the Huge Error Test may bo excluded from the calculation of the calibration curve. However, the total number of extracted calibration standards that could be eluded must not exceed 20% o f the total number o f extracted standards iqjected. 13.5 The correlation coefficient (R) Aar calibration curves generated must be 20.992 (R* 20.985). If calibration reaults foil outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standards ortherelevant setofsamples Shouldbe reanalyzed. 13.6 Retention times between standards and samples must not drift more than 14 %within ananalytical nm. I f retention time drift exceeds this lim it within ananalytical run thenthesetmustbe reanalyzed. 14.0 Calculations 14.1 Use foe following equation to calculate foe amount of PFOA found (in ng/L, baaed on peak area) using foe standard curve (linear regression parameters) generatedby foeMaasLynx softwareprogram: l>POA found Ing/U - fPwk im - intercept) x PF slope DF - Actorby which the final volumewasdiluted, if necessary. Page 6 o f7 Page 21 o f 65 Exygen Research Page 96 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExypeR M atreb MMbod Number VOOO1780 I ..................... A N A L m C A t M1THOD | Method ofAnalyiii for the Determination of Porflaorooetanoic Acid (PFOA) in Water by LC/MS/MS 142 For aamplea fortified with known amount! o f PFOA prior to extraction, use foefollowing equationto calculate foe percentrecovery. Recovery(%) - f totalanalytefound(ng/L) - analytefound in control(nfl^L)] ---------- -----------w ly te ^ ld c d W )---------------------'" 00 Exygen Research P lj. 7 of- Page 22 o f 65 Page 97 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ANALYTICAL METHOD MethodNumber V0001781 Method ofAnalysis for the Determination ofPerfluorooctanolc Add (PFOA) la Soil by LC/MS/MS Analytical Tailing Facility: Exygen Research 3058 Research Drive StateCollege, PA 16801 Approved By: T U . CJL PaulConnolly ' Technical Leader, LC-MS, ExygenResearch Date John Flaherty x / Vice President, Operations,ExygenResearch Date Exygen Research Total Pages: 7 Page 23 o f 65 Page 98 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol N um ber P0001131 Beygea Reamrck M *dd Number V000P8I ANALYTICAL METHOD Methodo fAnalyst* fortheDetermination o fPerfiuorooctanoic Acid (PFOA) in Soil by LC/MS/MS 1.0 Scope Thu methodis to beemployed for the isolation andquantitation o fperfiuorooctanoic acid by High Performance liquid Chromatography coupled to a tandem Maw SpectrometricDetector(LC/MS/MS) in soil 2.0 Safety 2.1 Alwaysobservesafe laboratorypractices. 2.2 Consult the appropriate MSDS before handling any chemical for proper safety precautions. 3.0 SampleRequirement 3.1 At least 15g ofteatsamplefor extraction. 3.2 Nosampleprocessingis neededfor soilsamples. 3.3 Samples stored refrigerated should be allowed to equilibrate to room temperature. 3.4 A ll samplesmustbethoroughlymixed before being sampled for extraction. 3.5 Simple collection procedures w ill be specified in the sampling plan for this project. 4.0 ReagentsandStandards 4.1 Water-HPLC grade 4.2 Methanol- HPLCgrade 4J AmmoniumAcetate-A.C.S. Reagent Grade 4.4 Perfiuorooctanoic Acid - Sigma-Aldrich 5.0 InstrumentandEquipment 5.1 A high performance liquid chromatograph capable of pumping up to 2 solvents equipped with a variable volume injector capable o f injecting 5-200 pL connectedto atandemMass Spectrometer(LC/MS/MS). 5.2 A device to collectraw datafor peak integration andquantitation. 5.3 Analytical balancecapableofreading to 0.00001 g. 5.4 50raL disposablepolypropylene centrifUge tubes. 5.5 IS mL disposablepolypropylene centrifoge tubes. 5.6 Disposablemicropipets (50-lOOuL, 100-200uL). 5.7 125-mLLDPB narrow-mouthbottles. 5.8 2 mL clearHPLC vial kit. 5.9 Disposablepipettes. 5.10 Autopipetles(100-1000 pL and 10-100 pL), with disposable tips. 5.11 WatersSepPakVac6 cc(lg)tC18SPE cartridges. 5.12 SPE vacuummanifold. 5.13 Ultrasonic bath. Pag2 o f? Page 24 o f 65 Exygen Research Page 99 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number. P0001131 ExygmRanareh MMtod Nweabw VOOO1781 ANALYTICAL METHOD Method ofAnalysis for tbs Determinationo fPerftuorooctanoic Acid (PFOA) in Soil by LC/MS/MS 3.14 Wrist-action shaker. 5.15 Centrifuge capableofspinning 50 mL polypropylene tubes at 5000rpm. 6.0 Chromatographic System 6.1 Analytical Column: FhiophaieRP(Keystone Scientific), 2.1 mmx 50 mm. 3m (P/N: 82305-032130) 62 Temperature: 30*C 6.3 Mobile Phase(A ): 2mM Ammonium Acetate in Water 6.4 Mobile Hu n (B ): Methanol 6.S GradientPropam: Flow Rate & A & fmL/min) 0.0 63 35 0.3 1.0 65 35 0.3 8.0 23 75 0.3 20.0 25 75 0.3 22.S 65 35 0.3 6.6 InjectionVolume: IS pL (canbeincreasedto asmuch asSOjiL). 6.7 Quantitation: PeakArea- external standardcalibration curve. 6.S RunTime: ~ 23minutes. Theaboveconditionsareintendedass guide andmaybechangedin order to optimize theHPLC system. 7.0 MS/MS System 7.1 Mode: Blectrospray Negative MRM mode, monitoring 413- 369 m/z for PFOA. Theaboveconditions areintendedasaguide and maybechanged in order to optimizefoe MSMS system. 8.0 PreperationofSolutione 8.1 Mobile Phase 8.1.1 2 mM mmonium acetate in water is prepared by adding 0.154 g of ammonium acetateto 1000mL o fwater. Alternate volumes may be prepared. Page 3 of 7 Page 25 o f 65 Exygen Research Page 100 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Exygc R m w h Method Number V000I 711 ANALYTICAL METHOD MethodofAnalysis fordie Determinationo fPerfluocooctanoic Acid (PFOA) in Soil by LC/MS/MS 9.0 StandardPreparation 9.1 StandardStock/Foitificatton Solution 9.1.1 Preps* astock solution of~100 pg/mL o f PFOA by weighing 10 mg of analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125-mLLDPEbottle. 9.1.2 A 10pg/mL fortification solution o fPFOA is prepared by bringing 10 mL ofthe 100 pg/mL solution to s final volume of 100 with methanol in a 12SmL LOPEbottle. 91.3 A 1.0 p g /m L f o rtific a tio n s o lu tio n o f P F O A i s p re p a re d by bringing 10 ml. o fth e 10 p g f a iL s o lu tio n t o a fin a l v o lu m e o f 100 with methanol in a 123 m L L D P E bottle. 9.1.4 A 0.1 p^mL fortification solution o fPFOA is prepared by bringing 10 mL of|he 1.0 pg/mLsolutionto a final volume o f 100with methanol in a 125mL LDPE bottle. 9.1.3 A 0.01 pg/mL fortification solution of PFOA is prepared by bringing 10 mL o f tiie 0.1 p^mL solution to a final volume of 100 with methanolin a 123mL LDPBbottle. 9.1.6 The stock and fortification solutions areto bestored in a refrigerator at approximately 4*C and no stable for a maximum period of 6 months ftom thedateofpreparation. 9.2 StandardCalibration Solutions 9.2.1 LC/MS/MS calibration standards are prepared in HPLC water The calibration standards are processed through the extraction procedure, identical to samples. 9.2.2 The following is a typical example: additional concentrations may be prepared asneeded. F in a l Fortification V olum e o f Concentration o f C alibration o f Fortification Volum e Fortified C ontrol C alib ratio n S tandard ID Solution (nob) (u L ) Sam olefm L ) Standard foot)4 (exim ole) 0 0 40 10 100 40 0 XCmmddyy-0 23 XCmmddyy-1 10 20 0 4 0 30 XCmmddyy-2 10 400 40 100 XCmmddyy-3 100 100 40 230 XCmmddyy-4 100 200 40 500 XCmmddyy-5 100 400 40 1000 XCm raddw -6 * Theextractedconcentrationofthecalibration standardis equal to 8x it* initial concentration, dueto theconcentrationo fthestandard during the extraction (SPE). XC extractedcalibration standard. Pag4 of7 Page 26 o f 65 Exygen Research Page 101 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: POO1131 ExygM lU m rek M eth o d N n b e rV 0 0 0 l? 8 I I .... ANALYTICAL METHOD ~~| Method o fAnalysis for theDeterminationo fPerfluorooetanoic Acid (PFOA) in Soil by LC/MS/MS 92 3 A zero standard solution (reagent blank) must be prepared with each seto fstandardsextracted. 9.2.4 Store all extracted calibration standards in 15-mL polypropylene tubes at 2*C to 6*C, upto two weeks. 9.2.5 Alternate volumes andconcentration* o fstandards msy be prepared as needed. 10.0 Batch SetUp 10.1 Each batch o f samples extracted (typically 20 or less) must include at least one reagnt control (method blank using 5 mL o f methanol) and two reagent controls fortified at known concentrations (lab control spike) to verify procedural reooveryforthebatch. 10.2 Requirements for field and laboratory duplicates and spikes w ill be specified in thequality assuranceplan for this project. 11.0 SampleExtraction 11.1 Weigh 5 g o f sample into SOmL polypropylene centrifuge tubes (fortify as needed,replacelid andmix well). 1\2 Add5 mL o fmethanol andshakeooa wrist action shakerfor-15 minutes. I I 3 Transferthetubesto anultrasonic bathandsonicate for -IS minutes. 11.4 Bring the volume up to 40 mL with water in the SO mL polypropylene ceotrifofo tube. 11.5 Centrifoge for-10 minuteat-3000 rpm. 11.6 Condition the Cis SPB cartridges (1 g, 6 mL) by passing 10 mL methanol followedby SmL ofHPLC water(- 2 drop/sec). Do not let column run dry 11.7 Load (decant) the sample on the conditioned Cu SPE cartridge. Discard eluate. 11.8 Elute with -S mL 100% methanol. Collect S mL o f eluate into graduated 1SmLpolypropylenecentrifogetubes(final volume - SmL). 11.9 Analyzesamplesusingelectrospray LC/MS/MS. 12.0 Chromstognpby 12.1 Iqject the sameamountofeach standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzed sample. 12.2 StandardsofPFOAcorrespondingto at least five or more concentration levels mustbeincluded in ananalyticalact 12.3 An entire set o f extracted calibration standards must be included at the beginning and at the end of a sample set Extracted standards must be interspersedbetweenevery S10samples. As an alternative, in entire setof Page 3 o f 7 Page 27 oj 65 Exygen Research Page 102 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 E xyinlM H ick MMbod Number V00017SI ANALYTICAL METHOD MethodofAnalysis for theDeterminationofperfluofooctanoic Acid (PFOA) in Soil by LC/MS/MS extracted calibration standard may be injected at the beginning of a set followed by extracted calibration standards Interspersed every 5*10 samples (to account for a second seto fextracted standards). In either case, extracted calibration standardsmustbethefirst id last injection in a sampleset. 12.4 Use Unear standard curves for quantitation. Linear standard curves arc generatedforthe analyteby line regression using 1/x weightingofpeak area versus calibration standard concentration using MassLynx 3.3 (or equivalent} software system. 12.5 Sample response should not exceed standard responses. Any samples that exceedstandardresponsesshould be furtherdiluted andreanalyzed. 13.0 AcceptanceCriteria 13.1 Chromatogram mustshow apeako f a daughter ion at 369 amu from aparent of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the daughterion (369 amu)representsthe Ion o fcarbondioxide. 13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank w lH PFOA at levels greater then 50 ng/L, then enew blank sample mustbeobtainedandthe entire setmustbere-extracted. 13J Recoveries of control spikes and matrix spikes must be between 70-130% of their known values. If a control spike falls outside the acceptable limits, the entire set o f samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by foe analyst to determine if re-extraction is 13.4 Any calibration standard found lo be a statistical outlier by using the Huge Enor Test, may be excluded from the calculation o f the calibration curve. However, the total number of extracted calibration standards that could be excluded must not exceed 20% o f the total number o f extracted standards injected. 13.5 The correlation coefficient (R) for calibration curves generated must be 20.992 (R* 20.985). I f calibration remits fall outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standards or therelevant setofsamplesshould bereanalyzed. 13.6 Retention times between standards id samples must not drift more than 4 %within ananalytical run. I f retention time drift exceeds this lim it within in analytical runthendie setimiatbereanalyzed. Pte6on Page 28 of 65 Exygen Research Page 103 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol N um ber P0001131 ExytcaRaMHch Mathod N u a b w V0001781 ANALYTICAL METHOD Method ofAnalysis forthe Determination ofPerfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS 14.0 Calculations 14.1 Use the following equation to calculate foe amount o f PFOA found (to ng/L, baaed on peak area) using foe standard curve (linear regression parameters) generatedby theMass Lynx softwareprogram: PFOA found (ngO,) - (PMklTCI-HKgKBll x DF slope DF - factorbywhichfoe final volumewasdiluted if necessary. 14.2 For sample* fortified with known amounts of PFOA prior to extraction, use foefollowing equationto calculate foe percentrecovery. Recovery(% ) [ totalanalytefound(ng/L) - analytefoundin control(ng/L)] ^ analyteadded(n^L) 14.3 Use the following equation to convert the amount o f PFOA found in ng/L to ng/g(ppb). PFOAfound (ppb) - (PFOAfound fna/D x volume extracted (0.04D1 sampleweight (5 g) 14.4 Uae foe following equation to calculate the amount of PFOA found in ppb baaedondry weight PFOAfound (ppb) dry weight **PFOA found (ppb) x [ 100%/ total solids(%)] Ptg*7of7 Page 29 o f65 Exygen Research Page 104 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number; P0001131 ANALYTICAL METHOD MethodNumber V0001782 Method of Amalyiii for the Determinano of Perfleorooctuok Add (PFOA) io Sediment by LC/MS/M8 Analytical Testing Facility: ExygenResearch 3038 ResearchDrive StateCollege, PA 16801 Approved By: C J .____ Paul Connolly I Technical Leader,LC-MS, ExygenResearch a /w r f U / ----------- /John Flaherty f VicePresident,Operations,ExygenResearch ___ LS kfaM . Date j>M fr_ Date Exygen Research Total Page: 7 Page 30 o f 65 Page 105 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Exypn Roewefa Matfeod Number V00017B2 1 ANALYTICAL METHOD | Methodo fAnalyiii for the Detennination ofPerfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS 1.0 Scope U til method is to be employedfor the iaolatioa andquantitation ofperfluorooctanoic add by High Perfbnnance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector(LC/MS/MS) in sediment 2.0 Safety 2.1 Alwaysobserveaafolaboratorypractices. 22 Consult theappropriate MSDSbeforehandling anychemical for propersafety precautions. 3.0 SampleRequirement 3.1 At least30gofteet sample for extraction. 3.2 No sampleproctnms is neededfor sediment samples. 3.3 Samples stored refrigerated should be allowed to equilibrate to room temperature. 3.4 A ll samplesmustbethoroughlymixed before bring sampled for extraction. 3.5 Sample collection procedures w ill be specified in the sampling plan for this project 4.0 ReagentsandStandards 4.1 Water-HPLC grade 4.2 Methanol- HPLC grads 4.3 Acetic Arid - Reagentgrade 4.4 AmmoniumAcetate-A.C.S. ReagentGrade 4.5 Perfluorooctanoic Arid - Signu-Aldrich 5.0 Instrument andEquipment 5.1 A high performance liquid chromatograph capable of pumping up to 2 solvents equippedwith a variable volume iqjector capable of injecting 5-200 pL connectedto atandemMassSpectrometer(LC/MS/MS). 5.2 A deviceto collectraw dataforpeakintegration andquantitation. 5.3 Analytical balancecapableofreading to 0.00001 g. 5.4 50mL disposablepolypropylene centrifrige tubes. 5.3 IS mL diqxMablopolypropylenecentrifuge tubes. 5.6 Disposablemicropipets (50100uL, 100-200uL). 5.7 125-mLLDPBnarrow-mouth bottles. 5.8 2 mL clearHPLC viatkit. 5.9 Disposablepipettes. 5.10 Autopipcttos (100-1000 pL and 10-100pL), with disposabletips. 3.11 WatersSepPakVac6 cc (Ig) tC18 SPEcartridges. $.12 SPEvacuum manifold. Page 2 u f7 Page 3/ of 65 Exygen Research Page 106 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Nuniber: P0001131 Exyge* Rem reh Method Number V0001782 | ANALYTICAL METHOD | MethodofAnalyst for theDetermination ofPerfluorooctanoic Acid (P70A) in Sediment by LC/MS/MS 5.13 Vortexer. 5.14 WiieMctioa abiksr. 5.15 CcntriAigecapableofspinning 50mL polypropylene tuba it 3000rpm. 6.0 ChromatographicSyetem 6.1 Analytical Column: FluophueRP(Keystone Scientific), 2.1 mm x 50mm, 5p (P/N: 82505*052130) 6.2 Temperature: 30*C 6.3 Mobile Pbaee(A ): 2 mM AmmoniumAcetate in Water Mobile Phaae(Bj : Methanol Gradient Program: Tim a fm inl 0.0 1.0 8.0 20.0 22.5 2 iA 65 65 25 25 65 Flow Rate 2fc fm L /m in) 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3 6.6 bgectioa Volume: 15pL(canbeincreaedtoasmttchae50pL). 6.7 Quantitation: PeekAwe-external itandard calibration curve. 6.8 RunTime: - 23minutes. Theabovecoodjtkmaare intendedat aguide andmaybechangedin order to optimisetheHPLC system. 7.0 MS/MS System 7.1 Mode: Blectrdapriy Negative MRM mode,monitoring 413 - 369 m/s for PFOA. Theaboveconditions areIntended at aguide andmay bechanged in order to optimize die MSMSayatem. 8.0 Preparationo fSolution 8.1 Mobile Phaae 8.1.1 2 mM ammonium acetate In water it prepared by adding 0.154 g of ammonium acetateto 1000mL ofwater. Page 3 o f7 Page 32 o f 65 Exygen Research Page 107 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P000U31 ExyfMRMMrafa Mtlfaod Number V0001782 I ANALYTICAL METHOD 1 Methodo fAnalysis for theDetermination ofPerfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS 8.2 Extraction Solutions 8.2.1 IS acetic acid in water i i prepared by dding 10 mL of acetic acid to 1000mL o fwater. Alternate volumes maybeprepared. 9.0 StandardPreparation 9.1 StandardStock/FbrtificatianSolution 9.1.1 Prepare a etock solution of-100 pg/raL o f PFOA by weighing 10 mg of analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125*mLLDPB bottle. 9.1.2 A 10 fortification solution o f PFOA ia prepared by bringing 10 mL o f the 100 pgtaL solution to a final volume of 100 with methanol in a 12SmL LDPEbottle. 9.1.3 A 1.0 pgfaiL fortification solution o fPFOA is prepared by bringing 10 mL ofthe 10pg/mL solution to a final volume o f 100 with methanol in a 125mL LDPEbottle. 9.1.4 A0.1 gg/mL fortification solution o fPFOA ia prepared by bringing 10 mLofthe 1.0pg/mL solution to a final volume of 100with methanol in a 125mL LDPEbottle. 9.1.5 A 0.01 pgfaiL fortification rotation o f PFOA it prepared by bringing 10 mL of the 0.1 pg/mL solution to a final volume of 100 with methanolin a 125mL LDPEbottle. 9.1.6 Theetockandfortification solutions areto be stored in arefrigerator at approximately 4*C and are stable for a maximum period o f 6 months from tbadateofpreparation. 9.2 StandardCatibtationSolutions 9.2.1 LG/MSAdS calibration standard areprepared in methanol via dilution oftbeO.l pgfaL fortification solution. 9.2.2 The following ie a typical example: additional concentrations may be Concentration ofFortification Solution (nafaiL) too 100 too 10 5 2 Volume (mL) 10 5 2 10 10 10 Dilutedto (mL) 100 100 100 100 100 100 Final Concentration (na/mL) 10.0 5.0 2.0 1.0 O.S 0.2 Pag 4 of 7 Page 33 o f65 Exygen Research Page 108 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol Number: P0001131 B nypnA am rek Mffhod Number V00017 | ANALYTICAL METHOD | Methodo fAnalyst fortheDeterminationo fPerfluorooctanok Acid (PFOA) in Sediment by LOMS/MS 9.2.3 Storeall calibration standards in 125-mL LDPE narrow-mouth bottles at2*C lo 6C, upto six months. 9.2.4 Altemate volumes snd concentrations o f standards may be prepared as 10.0 Batch SetUp 10.1 Each befch of ample* axtracted (typically 20 or lea) must include at least one untreated control and two untreated controls fortified at known concentrations(lab control spike) to verify procedural recovery for the batch. 10.2 Requirements for field and laboratory duplicates snd spikes w ill be specified in die quality assuranceplan forthis project 11.0 SampleExtraction 11.1 Weigh S g o f sample into 50 mL polypropylene centrifuge tubes (fortify * needed,replacelid andmix well). 112 Add 35 mL o f 1H acetic acid, cap, vortex and shake on a wrist action shaker for-60 minutes. 11.3 Centriftige thetubesat~3000rpm for -20 minutes. 11.4 Condition the Ct| SPE cartridges (1 g, 6 mL) by passing 10 mL methanol followedby 20mL o fHPLCwstsr( 2 drop/sec). Do not let column run dry 11.5 Load (decent) foe sample on foe conditioned Cis SPE cartridge. Discard 11.6 Add 20 mL o f methanol to the sediment left in the bottom of foe 50 mL centrifuge tube. Cap, vortex and shake on a wrist action shaker for -30 minute. 11.7 Centrifligefoetubes it 3000 rpm for->20minutes. 11.8 Decantfoemethanol ontothesameSPEcartridge. Collect the eluate. 11.9 Washfoe column with 4 mL o fmethanol Collect the eluate and add it to the eluatecollected in step 11.8. 11.10 Condition*secondC SPEcartridge (lg , 6 mL) by passing 10mLmethanol followedby 20mLofHPLC water(2 drop/sec). Do not let column run dry 11.11 Add the methanol to 200 mL o f water and load on foe second conditioned SPEcartridge. 11.12 Elute with 5 mL 100% methanol. Collect 5 mL of eluate into graduated 15mLpolypropyleneccntriftige tubes(final volume 5 mL). 11.13 Analyse samples usingeleetroeprayLC/MS/MS. P apJof? Page 34 o f 65 Exygen Research Page 109 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 Bsygroksitwcb M tfte d Nuntter V0001782 ANALYTICAL METHOD | Methodo fAnalyris for theDetermination ofPcrfluorooctanoic Acid (PFOA) in Sedimentby LC/MS/MS 12.0 Chromatography 12.1 Inject the eameamount o feach standard, temple and fortified sample into ihe LC/MS/MS system. A calibration standard must precede and follow all analysed samples. 12.2 Standardso fPFOAcorrespondingto at least five or more concentration levels mustbeincluded in ananalytical set. 12.3 An entire set o f extracted calibration standards must be included at the beginning and it tbe end of a sample set. Standards must be interspersed between every 5-10 samples. As an alternative, an entire set of calibration standards may be injected at the beginning of a set followed by calibration standards interspersed every 5-10 samples (to account for a second set of standard!). In either case, calibration standards must be die first and last iryection in asampleset. 12.4 Use linear standwd curves for quantitation. Linear standard curves arc genaratedfortbeanalyteby Sneerregressionusing 1/x weighting o f peak area venue calibration standard concentration using MassLynx 3.3 (or equivalent) soft** system. 12.5 Sample response should not exceed standard responses. Any samples that exceedstandardresponsesshouldbe Anther diluted endreanalyzed. 13.0 AcceptanceCriteria 13.1 Chromatogrammust show apeak o fa daughter ion at 369 amu from aparent of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the daughterkm(369 amu)representsthe losso fcarbondioxide. 13.2 Method ^ must not contain PFOA at levels greeter than the LOQ. If a blank contains PFOA at levels greater than 0.2 ng/mL, then a new blank samplemustbeobtainedandthe entire setmust bere-extracted. 133 Recoveries o f control spikes and matrix spikes must be between 70-130% of their known values. I f a control spike foils outside foe acceptable limits, the entile set o f samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by the analyst to determine if re-extraction is warranted. 13.4 Any calibration standard found to be a statistical outlier by using the Huge Error Test, may be excluded from foe calculation o f foe calibration curve. However, foe total number of extracted calibration standards that could be excluded must not exceed 20% o f the total number of extracted standards iqjected. 13.5 The correlation coefficient (R) for calibration curves generated must be 0.992 (R1 20.985). If calibration remits foil outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standardsor foe relevant setofsamplesshould be reanalyzed. Page6of 7 Page 35 o f 65 Exygen Research Page 110 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol N um ber P0001131 Baygsafcmawh Method Number VOOOlItt I ANALYTICAL METHOD | Methodo fAnalysis for theDetanunation o fPerfluoroocunoic Acid (PFOA) in Sediment by LC/MS/MS 13.6 Retention times between standards end samples muit not drift more then 4 % within ananalytical ran. I f retention time drift exceedsthis limit within enanalyticalrun thenthesetmustbereanalyzed. 14.0 Calculation* 14.1 Uaethefollowing equationto calculatethe amount of PFOA found (in ng/rnL. based on peek area) using the standard curve (linear regression parameters) generatedby theMies Lynx softwareprogram: PFOA found fng/mL) - (Peakarea- intercept) xDF slope DF " factorby which the final volume wasdiluted, if necessary. 14.2 For samples fortified with known amounts of PFOA prior to extraction, use the following equationto calculatethepercentrecovery. Recovery(S )* f totalanalytefound(ng/mL) analytefoundin oontrol(ng/mL)l analyteadded(ng/mL) 14.3 Usethe following equation to convert the amountofPFOA found in ngfaiL to ngfg(ppb). OTHA fanM - rPFflA found fng/mL) x final volume fS mLH sampleweight(3 g) 14.4 Uee foe following equation (if necessary) to calculate the amount of PFOA found in ppbbasedon dry weight. P F O A fo u n d (p p b ) d ry w e ig h t" P F O A fo u n d (p p b ) x [ 100% / to tal soltds(% >] F ife 7 of 7 Page 36 o f6S Exygen Research Page 111 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ANALYTICAL METHOD MethodNumber V00017S3 Method of Analysis for the Determination of Perfinorooctanoic Acid (PFOA) in Flsb and Clama by LC/MS/MS Analytical Tectiag Facility: Exygen Research 305$ ResearchDrive StateCollege, PA 16801 Approved By. y U , C _ J L ____________ Paul Connolly I Technieal Leader,LC-MS, ExygenReeeerch iM vtM Dale John Flaherty ' VicePresdiadteantit, Operations, ExygenResearch Date Exygen Research Total Pages: 8 Page 37 o f 65 Page 112 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 BxygtaXsm sfeb MethodNumberV00017S3 ANALYTICAL m e t h o d MethodofAnalysis fortheDetermination ofPerfluorooctanoio Acid (PFOA) in Fish and Clamaby LC/MS/MS 1.0 Scope This method is to beemployed for the isolation and quantitation ofperfluorooctanoic acid by High Performance Liquid Chromatography coupled to a tandem M ass Spectrometric Detector(LC/MS/MS) in fish andclaims. 2.0 Safety 2.1 Always obeervesafelaboratorypractices. 2.2 Consulttheappropriate MSDS beforehandling anychemical for proper safely precautions. 3.0 SampleRequirement 3.1 At least20g ofteet samplefor extraction. 3.2 Samples should be processed before extraction. Place the frozen sample in a food processorendhomogenizewith dry ice. Place the samples in containers and leave open in frozen storage overnight to allow for carbon dioxide sublimation. Seal and place the samples in frozen storage until time of analysis. 3.3 Sample collection procedures w ill be specified in foe sampling plan for this project. 4.0 Reagenti andStandards 4.1 Water-HPLC grade 4.2 Acetonitrile - HPLC grade 4.3 Carbon(120-400mesh)- Reagent grade 4.4 Methanol-HPLC grade 4.5 Silicagel (60-200mesh)- Reagentgrade 4.6 Florisit(60-100mesh)- Reagent grade 4.7 SupercleanLC-NHj - Reagentpads 4.8 1-Octanol- HPLC grade 4.9 L-Aecorfoic acid- Reagentgrade 4.10 Dimefoytdkhloroailane- Reagentgrade 4.11 Toluene- Reagentgrade 4.12 Ammonium Acetate- A.C.S. ReagentGrade 4.13 Perfluorooctanoic Add - Sigma-Aldrich 5.0 Instrument endEquipment 5.1 A high performance liquid chromatograph capable o f pumping up to 2 solvents equippedwith a variable volume injector capable of injecting 5-200 pL connectedto atandemMaasSpectrometer(LC/MS/MS). 52 A deviceto collect rawdatafor peak integration andquantitation. 5.3 Analytical balancecapableofreading to 0.00001 g. F ie 2 of8 Page 38 of 65 Exygen Research Page 113 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 E sy y eRemish Method Number VOOO1783 ANALYTICAL METHOD Method ofAnalysis forthe Determination o fPerfluorooctanoic Add (PFOA) in Fish and Clarasby LC/MS/MS 5.4 Rotmyevaporator. 5.5 Tissumizer. 5.6 125mL pear-shaped flasks. 5.7 50mL disposablepolypropylene centrifUge tubes. 5.8 15mL disposablepolypropylene centrifuge tubes. 5 .9 Disposablemicropipets (5 0 -1 0 0 u L , 1 0 0 -2 0 0 u L ). 5.10 125-mL LDPBnarrow-mouthbottles. 5.11 2 mL clearHPLCvial Id l 5.12 Disposablepipettes. 5.13 Autopipettes (100*1000pL and 10-100pL), with disposabletips. 5.14 SPEtubes(20tnL) (Supeleocat no.N057177). 5.15 Wristactionshaker. 5 .1 6 Centrifugecapableo fspuming5 0 mL polypropylene tubes at 2 0 0 0 rpm. 6.0 Chromatographic System 6.1 Analytical Column: FluopbaseRP(Keystone Scientific). 2.1 mmx 50 nun. $m (P/N: 82505-052130) 6.2 Temperature: 30*C 6.3 Mobile Phase(A ): 2 mM Ammonium Acetate in Water 6.4 MobilePhase(B): Methanol 6.5 GradientProgram: Flow Rate A fmlTrain^ 0.0 65 35 0.3 1.0 65 35 0.3 8.0 25 75 0.3 20.0 25 75 0.3 22.5 65 35 0.3 6.6 Injection Volume: 15 pL (canbe increased to as much as50 pL). 6.7 Quantitation: PeakArea- external standardcalibration curve. 6.8 RunTime: - 23minutes. Theaboveconditions are intended asaguide tnd maybechanged in order to optimize theHPLC system. P tge3of8 Page 39 o f 65 Exygen Research Page 114 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExygmXMMfCfc . Method Number V000]783 I ANALYTICAL METHOD | Methodo fA ndy fortheDetermination ofPerfluorooctanoic Acid (PFOA) in Fish and Clamsby LOMS/MS 7.0 MS/MS System 7.1 Mode: Electrocpray Negative MRM mode,monitoring 413 - 369 m/z for PFOA. Theaboveconditions areintendedaaaguide and maybe dunged in order to optimize the MSMSsystem. 8.0 Preparationo fSolutiona 8.1 Mobile Phase 8.1.1 2 mM ammonium acetate in water ia prepared by adding 0.1$4 g of ammomumacetateto 1000mL o fwater 82 Extraction Solution 8.2.1 2% ascorbic add in methanol ia prepared by dissolving 2 g o fascorbic add in 100mL ofmethanol. 8.2.2 30%Dimethyidiehlorositane in toluene is prepared by bringing 3 mL ofdimethyldichloroeilaneto afinal volume o fl 0 mL with toluene. Alternate volumesmaybeprepared. 9.0 StandardPreparation 9.1 StandardStodc/Fortificatkm Solution 9.1.1 Preparegslo6kaolutionof~100)i^mLofPFOAby weighing 10 mg o f analytical standard (corrected for purity) and dilute to 100 mL with methanolin a 12S-mL LOPEbottle. 9.1.2 A 1.0 ng/mL fortification solution o f PFOA is prepared by bringing 1 mL o f die 100 pgfrnL solution to a final volume of 100 with methanol in a 123mL LDPEbottle. 9.1.3 A 0.1 pgfaiL fortification solution ofPFOA is prepared by bringing 10 mLoftbe 1.0MgfaL solution to a final volume of 100with methanol in a 123mL LDPEbottle. 9.1.4 A 0.01 ng/mL fortification solution o f PFOA is prepared by bringing 10 mL of the 0.1 |igfaL solution to a final volume of 100 with methanolin a 125mL LDPE bottle. 9.1.5 Thestock andfortification solutions areto be stored in a refrigerator at approximately 4*C and are stable for maximum period of 6 months from thedateofpreparation. Page 4 of8 Page 40 o f 65 Exygen Research Page 115 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol N um ber P0001131 Exyfca Km nrch M ethod N um ber V0001783 ANALYTICAL METHOD Method ofAnalytic for foeDetermination o fPerfhiorooetanoie Acid (PFOA) in Fish and Gamaby LC/MS/MS 9.2 StandardCalibration Solutiooc 9.2.1 LC/MS/MS calibration standards are prepared in methanol via dilution ofdie 1.0pg/mL fortification solution. 9.2.2 The following ii a typical example: additional concentrations may be prepared at needed. C o n esiU ra tio n Fowl o f Fortification Volum e D iluted to C on cen trati ) Solution fu a/m L ) (nL) (m L ) (u t/a iL ) IX) 5.0 100 0 .0 5 l JO 2.5 100 0.025 Ub 1.0 100 0.01 0.05 10 100 0.005 0.025 10 100 0.0025 0.1 10 100 0.001 0.005 10 100 0.0005 9.2.3 Store all calibration standards in 125-mL LDPE narrow-mouth bottles at 2*C to 6*C, up to six months. 9.2.4 Alternate volume* andconcentrations ofstandards may beprepared as needed. 10.0 BatchSetUp 10.1 Bach batch of samples extracted (typically 20 or leas) must include at least one untreated control and two untreated controls fortified at known concentrations(labcontrolspike)to verityprocedural recovery for thebatch. 10.2 Requirements for field and laboratory duplicates and spikes w ill be specified in foequality awuanceplan for this project. 11.0 SampleExtraction 11.1 Weigh 5 g of frozen sample into SO mL polypropylene centrifuge tubes (fortify asneeded, replaceUdandmix well). 11.2 Add 30 mL ofacetonitrile andshakemi awrist action shakerfor -15 minutes 11.3 Placethetubesin afreezer for -1 hour. 11.4 PackandconditionfoeSPEtubesandsihurize the pear-shaped flasks. 11.5 Pack the 20 mL SPE tubes in sequence with 2 g florisil, 2 g silica gel, 2 g carbon, and I $ LC-NHj. Condition the columns with 20 mL o f methanol, then 20 mL of acetonitrile. Discard all washes. Do not allow the column to dry. 11.6 Silmise the 125 mL pew-shaped flasks by rinsing with the 30% diiiicthyidichLoroailane in toluenesolution. Rinse the flask with toluene once, followed by methanol (three times). Dry the flasks completely before use, eitherbysir-drying or with s streamo fnitrogen. Page 5 oiS Page 41 of65 Exygen Research Page 116 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExypaRaMaKh Mrtbod Number VOOOI7 ANALYTICAL METHOD MethodofAnalysis for theDetennination ofPerfluorooctanoic Acid (PFOA) in Fish and Clamsby LC/MS/MS 11.7 Centrifiige the 50 mL polypropylene tubes containing sample at ->2000 rpm fo r'1 0 minutes. 11.8 Decant the extract on to aconditioned SPE column fitted inside the mouth o f the pear-shaped flask. Collect the eluate in the 125 mL silanized pear-shape flask. 11.9 Add 10 mL o f acetonitrile to the sample in the 50 mL centrifuge tube. Homogenize the frozen fid phaaeuamga tissumizer for -30 seconds and nnse thetiaaumfearwith-JOmL o facetonitrile into thetube. 11.10 Shakethesampleagain for-10 minuteson a wrist-action shaker. 11.11 Placethetubesin afreezerfor -1 hourmore. 11.12 CentrifUge the 50 mL polypropylene tubes containing sample at '2000 rpm for'1 0 minutes. 11.13 Decant the extract onto the same SPB column. Collect the eluate into the same pear-shaped flask and combine with the eluent from the initial extraction. 11.14 Pass20 mL ofacetonitrile through the SPE column and combine the eluate in the samepear-shaped flask. 11.15 Add 3-4 drop* of 1-octanol to the extract in the pear-shaped flask and evaporateatreduoedpressureusingarotary evaporator(at < 40SC). 11.16 Make the final volume, by adding 2 mL o f 2% ascorbic arid in methanol to diepear-ihaped flask andswirl to mix/diisolve. 11.17 Transfertheextracts to HPLC vials usingdisposable pipets. 11.18 Analyze samples using electroeprayLC/MS/MS. 12.0 Chromatography 12.1 Iqject dm sameamounto feach standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzed samples. 12.2 Standards ofPFOA eoae^iondnig to at least five or more concentration levels mustbeincluded in analytical set 12.3 An entire seto fcalibration standardsmust be included at the beginning and at the endo ft sample set Standards must be interspersed between every 5-10 samples. As an alternative, an entire set o f calibration standards may be injected at the beginning of a set followed by calibration standards interspersed every 5-10 samples(to account for a secondset o f standards). In cither case, calibration standwdt must be the first and last injection in u sample set 12.4 Use linear standard curves for quantitation. Linear riandard curves are generatedfor theanalyteby linear regression using 1/x weighting ofpeak area versus calibration standard concentration uamg MaasLynx 3.3 (or equivalent) software system. P tg e 6 o fS Page 42 o f 65 Exygen Research Page 117 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExyfnXM M idi M ethod N im b er V0001713 ANALYTICAL m e t h o d Method ofAnaiyiU for theDetermination o fPerfluorooctanoic Acid (PFOA) in Fish and Claras by LC/MS/MS 12.3 Stable response should not exceed standard responses. Any samples that exceedstandardresponsesshouldbe further diluted andreanalyzed. 13.0 AcceptanceCriteria 13.1 Chromatogram must show apeak of a daughter ion it 369 amu from a parent of 413 amu. The 413 amuparent corresponds to the PFOA anion, while the ion (369 amu)representsthe loeso fcarbondioxide. 13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank contains PFOA at levels great' than 0J ppb, then a new blank sample mustbeobtainedandfoe entire eetmustbe "extracted. 13.3 Recoveries of oontrol spikes and matrix spikes must be between 70*130% of their known values. I f a oootrol spike Mis outside foe acceptable limits, the entire setofsamplesshouldbere-extreeted. 13.4 Any calibration standard found to be a statistical outlier by using the Huge Enm Test, may be excluded from the calculation of foe calibration curve. However, the total number of calibration standards that could be excluded mustnotexceed20%o ffoetotal numbero fstandardsinjected. 13.5 The correlation coefficient (R) for calibration curves generated must be 20.992 (R1 20.983). I f calibration results foil outside these limits, then appropriate steps must bo taken to adjust instrument operation, and the standardsor the relevant seto fsampleshouldbereanalyzed. 13.6 Retention time between standards and samples must not drift more than 4 % within ananalyticalrun. If retention time drift exceeds this lim it within ananalytical run thenfoe setmustbereanalyzed. 14.0 Calculations 14.1 Usefoe following equationto calculate the amountofPFOA found (in ng/mL. based on peak ana) using foe standard curve (linear regression parameters) generatedby foeMassLynx software program: PFOA found (ng/mL) (Peakarea intercept) slope 14.2 Ueefoe following equationto convert the amount ofPFOA found in ng/mL to ng/g(ppb). PFOA found (ppb) - [PFOA found fng/mL) x final volume (mL) x DFI sampleweight (g) DP* factorby which foe final volumewas diluted, if necessary. Pace 7 o fs Page 43 o f63 Exygen Research Page 118 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Esygeo Ruem di Mmbod N umber V000J ?83 ANALYTICAL m e t h o d MethodofAnalysis for theDetermination ofPerfluorooctanoic Acid (PFOA) in Fish and Clams by LC/MS/MS 14.3 For samples fortified with known amounts of PFOA prior to extraction, use die following equation to calculate thepercent recovery. Recovery (% ) [ totalanslytefound(ngfr) analytefoundin control(ng/g)] tlQQ analyteadded(ny'g) Exygen Research Peg S o fS Page 44 o f 65 Page 119 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ANALYTICAL METHOD MethodNumber V0001784 Method ofAnalysis for the Determination of Perfiaorooctanolc Acid (PFOA) in Vegetation by LC/MS/MS Analytical TeetingFacility: ExygenResearch 3058 Research Drive StateCollege, PA 16801 Approved By: Paul CooooUy Technical Leider. LC-MS. ExygenResearch n,//r> f /U /________ .John Flaherty ' v i c e President.Operations, Exygen Research __ l a j j i M Date Date Exygen Research Total Pages: 7 Page 45 o f 65 Page 120 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 BxygeeRewsieh Method Number V00017M ANALVTICAL METHOD MethodofAnalyst* fix the Determination o fPcrfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS 1.0 Scope H ot method is to be ployed for foe isolation andquantitation o fperfluorooctanoic add by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometnc Detector(LC/MS/MS) in vegetation. 2.0 Safety 2.1 Alwaysobeervesafe laboratorypractices. 2.2 Consulttheappropriate MSDS before handling anychemical for proper safety precautions. 3.0 SampleRequirement 3.1 At least20g o ften samplefor extract. 3.2 Sample* should beprocessed before extraction. Piece the frozen sample in a food processorand homogenizewith dry ice. Place the samples in containers and leave open in frozen storage overnight to allow for carbon dioxide sublimation. Seal and place the samples in frozen storage until time of analysis. 3J Sample collection procedures w ill be spedfied in the sampling plan for this project 4.0 ReagentsandStandards 4.1 Water-HPLC grade 4.2 Acetonitrile - HPLC grade 4.3 Carbon(120-400meah)- Reagent grade 4.4 Methanol~ HPLC grade 4.3 Silica gel (60-200mesh)- Reagentgrade 4.6 F loriiil (60-100mesh)- Reagent grade 4.7 SupercleanLC-NHj - Reagentgrade 4.8 1-Octanol-HPLC grade 4.9 L-Aacorbic add- Reagentgrade 4.10 Diinethyklichlorosilane- Reagentgrade 4.11 Toluene- Reagentgrade 4.12 AmmoniumAcetate~A.CS. ReagentQnde 4.13 Perfluorooctanoic Acid - Sigma-Aklrich 5.0 Instnueot andEquipment S.t A high performance liquid chromatograph capable o f pumping up to 2 solvents equipped with a variable volume injector capable of injecting 5-200 pL connectedto atandemMassSpectrometer(LC/MS/MS). 52 A deviceto collectrawdataforpeak integration andquantitation. 5.3 Analyticalbalancecapableo freading to 0.00001 g. Page 2 of 7 Page 46 o f 65 Exygen Research Page 121 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: POOO1131 BsygeelUieawh Method Number V00017M ANALYTICAL METHOD | MethodofAnalysis for theDctenmnttkn ofPerfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS 14 Rotaryevaporator. 5.5 125mLpear4hapedflaiki. 5.6 50mL dispoeablepolypropylene oesUrifiigetubes. 5.7 15mL diipoMble polypropyleneceotriftige tubes. 5.S Disposablemicropipet(50-100uL, 100-20taL). 5.9 125-mLLDPEnarrow-mouth bottle*. 5.10 2 mL clearHPLCvial kit. 5.11 Diapoeiblepipettes. 5.12 Autopipettes (100-1000 pL and 10-100pL), with disposable tips. 5.13 SPBtubes(20mL) (Supelcocat. no.N057177). 5.14 Wrist action shaker. 5.15 Centriftigecapableofspinning 50mLpolypropylene tubesat 2000 rpm. 6.0 ChromatographicSystem 6.1 Analytical Column: FhiophaaeRP(Keystone Scientific), 2.1 nun x SOmm. 5p (P/N: 82505-052130) 6.2 Temperature: 30*C 6.3 Mobile Phase(A): 2mM Ammonium Acetate in Water Mobile Phase(B): Methanol Gradient Program: Flow Rate LA fmlAnin) 0.0 65 35 0.3 1.0 65 35 0.3 8.0 25 75 0.3 20.0 25 75 0.3 22.5 65 35 0.3 6.6 Injection Volume: 15pL (canbeincreasedto asmuch as 50 pL). 6.7 Quantitation: PeakArea- external standardcalibration curve. 6.8 RunTime: -2 3 minutes. Theaboveconditions areintendedasaguide andmaybechanged in order to optimize theHPLC system. 7.0 MS/MS System 7.1 Mode: Blectroepray NegativeMRM mode,monitoring 413 -369m/z for PFOA. Page 3 o f 7 Page 47 o f 65 Exygen Research Page 122 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 Exy|di Rmaich Method Number VOOOI784 ANALYTICAL METHOD MethodofAnalysia for die Determination ofPerfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS Theaboveconditions areintended u a guideandmaybe changed in order to optimize die MSMSsystem. 8.0 PreparationofSohitions 8.1 Mobile Phase 8.1.1 2 mM ammonium acetate in water is prepared by adding 0.154 g of ammoniumacetateto 1000mL ofwater. 8.2 Extraction Solutions 8.2.1 2% ascoltateadd in methanol is preparedby dissolving 2 g ofascorbic addin 100mL o fmethanol. 82 2 3OS Dimediyldichlorosilane in toluene is prepared by bringing 3 mL o fdimethyldicUorosilaiieto a final volumeo f 10mL with toluene. Alternate volumesmaybeprepared. 9.0 StandardPreparation 9.1 StandardStocfcTortificationSolution 9.1.1 Prepare astock solution o f-100 pg/mL o f PFOA by weighing 10 mg ofanalytics! standard(corrected for purity) and dilute to 100 mL with methanol in a 125-mL LDPEbottle. 9.1.2 A 1.0 pg/mL fortification solution o f PFOA is prepared by bringing 1 mL o f the 100 (igAnL solution to a final volume of 100 with methanol in a 125a L LDPEbottle. 9.1.3 A0.1 pg/mL fortification solution ofPFOA is preparedby bringing 10 mLofthe 1.0 pg/mL solutionto a final volume o f 100with methanol in a 125mL LDPEbottle. 9.1.4 A 0.01 pg/taL fortification solution of PFOA is prepared by bringing 10 mL o f die 0.1 pg/mL solution to a final volume of 100 with methanolin a 125mL LDPE bottle. 9.1.5 Thestockand fortification solutions areto be stored in arefrigeratorai approximately 4*C and are amble for a maximum period of 6 months from die dateofpreparation. 9.2 StandardCalibration Solutions 9.2.1 LC/MS/MS calibration standards are prepared in methanol via dilution ofdie 1.0pg/mL fortification solution. Pi*c 4 ul ' Page 48 o f 65 Exygen Research Page 123 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P 0001131 Btyi m lw ich M ethod Number VOOOl 714 A Na LY TIC A L m e t h o d Method ofAnalysis for theDetennination ofPerfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS 92.2 The following is a typical example: additional concentrations may be prepared asneeded. Coocrotrstian Final ofFoctificetian Volume Diluted to Concentration Solution (unfaL) (mL) (m L) (MSfalL) 1.0 3.0 100 0.05 1.0 2J 100 0.023 1.0 1.0 100 0.01 0.03 10 100 0.003 0.02$ 10 100 0.002$ 0.1 10 100 0.001 0.003 10 100 0.0005 92.3 Store all calibration standards in 125-mL LDPE narrow-mouth bottles at2C to 6*C, up to six months. 92.4 Alternate volumes andconcentrations o fstandards may be prepared as needed. 10.0 BatchSetUp 10.1 Each batch of sample extracted (typically 20 or less) must include at least one untreated control end two untreated controls fortified si known concentrations (labcontrol spike) to verity procedural recovery for thebatch- 102 Requirements for field and laboratory duplicates and spikes w ill be specified in the quality assuranceplan for this project. It.O SampleExtraction 11.1 Weigh 5 g of frozen sample into 30 mL polypropylene centrifuge tubes (fortity asneeded,replacelid andmix well). 11.2 Add 30mL ofacetonitrile and shakeon s wrist action shaker for - 15 minutes. 11.3 Centrifuge the 30 mL polypropylene tube containing sample at -2000 rpm for ~10 minute*. 11.4 Packandcondition theSPBtubesandailanize thepear-shaped flasks. 11.5 Pack the 20 mL SPE tubes in sequence with 2 g floruit, 2 g silica gel. 2 g carbon, and 1 g LC-NHr- Condition die columna with 20 mL of methanol, then 20 mL o f acetonitrile. Discard alt washes. Do not allow the column to dry. 11.6 Silanizc die 123 mL pear-shaped flasks by nosing with the 30% dimefltyldldilorosUstte in toluenesolution. Rinsethe flask with toluene once, followed by methanol (three times). Dry the flasks completely before use. eitherby air-drying orwith sstreamo fnitrogen. 11.7 Decant die extract on to a conditioned SPE column fitted inside the mouth of the pear-shaped flask. Collect the eluate in the 125 mL silanized pear-shape Page $ o f ' Page 49 o f 65 Exygen Research Page 124 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study N o.: P0001131 Exygen Protocol Number: P0001131 Bxygaa Rw-- ch Method Number V0001784 ANALYTICAL m s t h o p 1 Method ofAnalysis for foeDeterminationo fPerfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS 11.1 Add20mL ofacetonitrile to theamplein foe 50 mL centrifuge tube. 11.9 Shaketheample again for **10" in111** on awrist-action ahaker. 11.10 Centrifoge foe SOmL polypropylene tubes containing sample at ->2000 rpm for~5 minutes. 11.11 Decant the extract onto the same SPE column. Collect the cluate into the wine pear*ehapod flask and combine with foe eluent from foe initial extraction. 11.12 Repeatsteps 11.8 through 11.11 again. 11.13 Add 3*4 drops of 1-octanol to the extract in foe pear-shaped flask and evaporateatreducedpressure usingarotaryevaporator (at < 40C). 11.14 Make the final volume, by adding 2 mL o f 2% ascorbic acid in methanol to thepear-shapedflask andswirl to mix/dissolve. 11.15 Transfertheextract to HPLC vials usingdisposablepipeta. 11.16 Analyze samplesusingelectroepray LC/MS/MS. 12.0 Chromatography 12.1 Inject tbs aamemount o feach standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow 11 analyzedsamples. 12.2 Standardso fPFOA correspondingto at least five or more concentration levels mustbeincluded man analytical set. 12.3 An entire set of extracted calibration standards must be included at the and at the cod of a sample set. Extracted standards must be interspersed betweenevery 3-10 samples. As an alternative, an entire ret of extracted calibration standards may be injected at the beginning of a set followed by extracted cstibntion standards interspersed every 5-10 samples (to account fix a second set o fextracted standards), hi either case, extracted standardsmustbethe first and last injection in a sampleset. 12.4 Use linear standard curves for quantitation. Linear standard curves are generated for foe analyte by linearregression using l/x weighting o fpeak area versus calibration standard concentration using MassLynx 3.3 (or equivalent) softwaresystem. 12.5 Sample response should not exceed standard responses. Any samples that exceedstandardresponau shouldbe further diluted andreanalyzed. 13.0 AcceptanceCriteria 13.1 Chromatogram mustshow apeak o fa daughter ion at 369 amu from a parent o f 413 amu. The 413 amuparent corresponds to foe PFOA anion, while the daughterion(369 amu)representsfoe ton o fcarbondioxide. p*s*6on Page 50 o f65 Exygen Research Page 125 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 Bnyy faMgch M ethod N um ber V0OI7S4 ANALYTICAL m e t h o d Method ofAnalysis for theDeterminationo fPerfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS 13.2 Method blanks must not contain PFOA at levels greater titan the LOQ. If a blank coataiM PFOA at levels greater than 0.9 ppb, then a new blank sample mastbeobtainedandfoe entire aetmustbeie-extracted. 13.3 Recoveries ofcontrol spikes mid matrix spikes must be between 70*130% of their known values. If a control spike foils outside the acceptable limits, the entire seto fsamplesshouldbere-extracted. 13.4 Any calibration standard found to be a statistical outlier by using the Huge Error Teat, may be excluded from the calculation o f the calibration curve. However, foe total number of calibration standards that could be excluded mustnot exceed20H ofthetotal numbero fstandards injected. 13.5 The correlation coefficient (R) for calibration curves generated must be *0.992 (R* 20.985). I f calibration results foil outside these limits, then appropriate step must be taken to adjust instrument operation, and the standardsor therelevant seto fsamplesshould bereanalyzed. 13.6 Retention times between standards and samples must not drift more than 4% within ananalytical run. If retention time drift exceeds this lim it within ananalytical runthenthe setmustbereanalyzed. 14.0 Calculations 14.1 Usethe following equationto calculatethe amounto f PFOA found (in ng/mL, baaed on peek nee) using foe standard curve (linear regression parameters) generatedbytheMam Lynx softwareprogram; PFOA found (ng/mL) - /Peak area- intercept) slope 14.2 Usethefollowing equationto convertthe amounto fPFOA found in ng/mL to O/* (ppb). PFOAfound (nnM - fPFOA found fna/mLl x fla il volume (mU x DF1 sampleweight (g) DF- factorby whichthe final vohtmewas diluted, if necessary. 14.3 For samplae fortified with known amounts o f PFOA prior to extraction, use foe following equationto calculate thepercent reoovery, Reoovery(H) [ totalanalytefound(ng/g) analytefound in control (ng/g)] analyteadded(ng/g) Page 7 ol' 7 Page 51 o f 65 Exygen Research Page 126 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: POOO1131 ANALYTICAL METHOD MethodNumber V0001785 Method of Analysis Her the Determination of Perfborooetaook Acid (PFOA) Hi Small Mammal Liver by LG/MS/MS Analytical Toting Facility: ExygenResearch 3058 Research Drive StateCollege, PA 16801 Approved By: . ___C - r r l L j _______ Paul Connolly I Technical Leader,LC-MS, ExygenReward} ________ John Flaherty ' Vice President,Operatiooa,ExygenResearch Date M r Dite Exygen Research TotalPaces: 7 Page 52 o f 65 Page 127 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 ExygM M M aick Method Number V00017IS I ANALYTICAL METHOD Method ofAnalyris ibr (beDetermination ofPerfluorooctanoic Acid (PFOA) in Small Mammal Liverby LC/MS/MS 1.0 Scope This method is to be employed Ibr die isolation andquantitation o fperfluorooctanoic acid by High Performance Liquid Chromatography coupled to a tandem Mass Spectromtrie Detector (LC/MS/MS) in smallmammal liver. 2.0 Safety 2.1 Alwaysobaarveaafelaboratorypractice#. 2.2 Consul! die appropriate MSDSbefore handling any chemical for proper safety 3.0 SempleRequirement 3.1 At least Sg oftest samplefor extraction. 3.2 Samples should be processedbefore extraction. Place the frozen sample in a food proceator endhomogenize with dry ice. Place the samples in containers and leave open in frozen storage overnight to allow lor carbon dioxide sublimation. Seal and place die samples in frozen storage until time of analysis. Alternately, if there ii an neuiSicknt amount o f sample (-less than Sg),thenno processingis necessaryandthe samplecanbe used assupplied. 3.3 Sample collection procedures w ill be specified in the sampling plan for this project 4.1 Water-HPLC grade 4.2 Methanol- HPLC grade 4.3 Acetonitrile - HPLC grade 4.4 Ammonium Acetate- A.C.S. ReagentGrade 4.5 Perfhtorooctmoic Acid- Sigma-Aldrich S.0 Inatnxnent andEquipment 5.1 A Ugh performance liquid chromatograph capable o f pumping up to 2 solvents equipped with a variable volume iqjector capable of injecting 5-200 jiL connectedto atandemMasaSpectrometer(LC/MS/MS). 5.2 A deviceto collect rawdatafor peakintegration andquantitation. 5.3 Analytical balancecapableo freading to 0.00001 g. 5.4 50mL disposablepolypropylenecentrifoge tubes. 5.5 15mLdisposablepolypropylenecentrifoge tubes. 5.6 Disposablemicropipets (50-100uL, 100-200uL). 5.7 l25*mL LDPEnanowmouthbottles. 5.8 2 mL clearHPLC vial IdL Pta2on Page 53 o f 65 Exygen Research Page 128 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 E m u a lh m wh Method Num b VOOOI7I5 I ANALYTICAL MBTHOD Method ofAoalyiis fbrthe Determination o fPerftaorooctanoic Acid (PFOA) in Small Mammal Liverby LC/MS/MS 5.9 Disposablepipettoa. 5.10 Autopipettes(100-1000 pL and 10-100pL), with disposable tipi. 5.11 WatersSepPakVac6 oc (If) tC18 SPEcartridge. 5.12 SPEvacuummanifold 5.13 Tiaaoemizer. 5.14 Wriat-actioD ahaker. 5.15 Centrifuge capableofgrinning 15mL polypropylene tubes at 3000rpm. 6.0 Chromatographic System 6.1 AnalyticalColumn: FluophasaRP(Keystone Scientific), 2.1 mm x 50 mm. 5m (P/N: 82505-052130) 6.2 Temperature: 30*C 6.3 Mobile Phase(A ): 2 mM Ammonium Acetate in Water Mobile Phase(B): Methanol GradientProgram: Tima (mini 0.0 1.0 8.0 20.0 22.5 2U 65 65 25 25 65 Flow Rate 3LB fml/m in) 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3 6.6 Injection Volume: 15 pL (canbe increasedto as much as 50 pL). 6.7 Quantitation: PeakAna - external standardcalibration curve. 6.8 RunTime: -2 3 minutes. Theaboveoonditionasreintended si aguide and maybechanged in order to optimize theHPLC system. 7.0 MS/MS System 7.1 Mode: EloctroaprayNegativeMRM mode,monitoring 413 -369 m/z for PFOA. The above conditions an intended as guide and may be changed in order to optimize theMSMSsystem. Page 3 of? Page 54 o f65 Exygen Research Page 129 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 Exygen Protocol Number: P0001131 Exyfaa RNMrck MethodNumber VOOQ17 I ....................... a n a l y t ic a l armop Method ofAnalysis for foeDetermination ofPerfluorooctanoic Acid (PFOA) in Small Mammal Liverby LC/MS/MS 8.0 PreparationofSolutions 8.1 Mobile Phase 8.1.1 2 mM ammonium acetate in water is prepared by adding 0 154 g of ammoniumacetateto 1000mL o fwater. Alternate volumes maybe prepared. 9.0 StandardPreparation 9.1 Standard Stock/FoctificationSolution 9.1.1 Prapara a flock solution of-100ng/mL o f PFOA by weighing lOmg ofanalytical atandard (oonected for purity) and dilute to 100 mL with methanolin a l23*mL LDPEbottle. 9.1.2 A 1.0 pg/mL fortification eolution of PFOA is prepared by bringing I mL o f foe 100 p^mL solution to a final volume of 100 with methanol in a 125 mL LOPEbottle. 9.1.3 A 0.1 pg/mL fortification solution o fPFOA ie prepared by bringing 10 mLofthe 1.0 pg/mL solution to a final volume o f 100with methanol in a 125mL LDPE bottle. 9.1.4 Tbestock andfortification solutions areto be stored in a refrigerator a( approximately 4*C and am stable for a maximum period of 6 months from thedateofpreparation. 9.2 StandardCalibration Solutions 9.2.1 LC/MS/MS calibration standards amprepared in methanol via dilution ofthe0.1 Mg/mLfortification solution. 9 2 2 The following if a typical example: additional concentration! may be Concentration Final ofFortification Volume Solutionfn^mL) (mL) Diluted to (mL) Concentration (na/mL) 100 5.0 100 100 2.0 100 100 IX) 100 5.0 2.0 1.0 5.0 10 100 2.0 10 100 1.0 10 100 0.5 0.2 0.1 9X3 Store all calibration standards in 125-mL LDPE narrow-mouth bottles at 2*C to 6"C, up to six months. 9.2.4 Alternate volumes and concentrations of standards may be prepared as needed. P*ge4f? Page 55 o f 65 Exygen Research Page 130 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen P rotocol N um ber: P0001131 E xytaB M M rch Method Niunber VOOO1783 I ANALYTICAL METHOD Method ofAnalysis forthe Determination of Perfluoiooctinoic A c id (PFOA) in Smell Minimal Liver by LC/MS/MS 10.0 Bitch SetUp 10.1 Each bitch of cimples extracted (typically 20 or leci) mu*t include at least one untreated control and two untreated controls fortified at known conccntntiona (lab control ipike) to verify procedural recovery for the batch. 10.2 Requirements for field and laboratory duplicates and spikes w ill be specified in thequality assuranceplan forthis project. 11.0 Simple Extraction 11.1 Weigh 1g ofiam pleintot 50 raL polypropylene centrifuge tubes (fortify as needed,replacelid andmix well). Note that alternate weights of liver may be measureddependingondie sample size available for use. 11.2 Addwaterto the samplefor afinal volume of 10mL. 1U Homogenizesampleuaingatiasuemirer for -1 minute. 11.4 TYmsfor 1 mL o f the sample uaing a disposable pipette into a IS mL disposable oentrifog* tube. 11.5 Add SmLo facetonitrile andshakefor-20 minuteson awrist-action shaker. 11.6 Centrifugethetubes at-3000 xpmfor-5 minutes. 11.7 Decant the supernatant into a $0 mL disposable centrifoge tube and add 35 mL ofwater. U.ft Condition the Cis SPE cartridge* (1 g, 6 mL) by passing 10 mL methanol followed by 5 mLo fHPLCwater 2 drop/sec). Do not let column run dry 11.9 Loadthe sampleon conditionedCu SPEcartridge. Discard eluate. 11.10 Elute with -2 mL of methanol. Collect 2 mL of eluate into a graduated IS mL polypropylene oentrifogttube (final volume 2mL). 11.11 Analyze samplesusingeloctrospray LC/MS/MS. 12.0 Chromatography 12.1 Iryect the sameamounto feach standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzedsamples. 12.2 StandardsofPFOA correspondingto at least five or more concentration levels mustbeincluded in ananalytical set 12.3 An entire eato fcalibration standardsmust be included at the beginning and at foe end o f a sample set Standards must be interspersed between every 5-IU samples. As an alternative, an entire set o f calibration standards may be injected at the beginning o f a set followed by calibration standards interspersed every 5-10 samples(to account for a second set o f standards). In either case, calibration standards must be the first and last injection in a sampleset 12.4 Use linear standard curves for quantitation. Linear standard curves are generatedfor theanalyteby linearregroaaionusing 1/x weighting o fpeakarea Page 3 of? Page 56 of65 Exygen Research Page 131 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 E x y |M l id i M aiiod Number V00017I5 I a n a l y t ic a l m e t h o d Method ofAnalysis fortheDeterminationofPerfluorooctanoic Add (PFOA) in Small MammalLiverby LG/MS/MS versus calibntioa standard concentration uaing MacaLynx 3.3 (or equivalent! software system. 12.5 Sample rcapoose should not exceed itandaid reaponses. Any samples that exceedstandardresponsesihould be Antherdiluted andreanalyzed. 13.0 AcceptanceCriteria 13.1 Chromatogrammust show a peak of adaughter ion at 369 amu from a parent of413 amu. The 413 amu parent corresponds to the PFOA anion, while the os(369 amu)representsdie loss ofcarbondioxide. 13.2 Method blanks must not contain PFOA at levels greater than the LOQ. If a blank **'"**" PFOA at levels greaterthan 10 ng/g, then a new blank sample mustbaobtainedand theentire setmustbere-extracted. 133 Recoveries o f control apikes and matrix spikes must be between 70-130% of their known values. If a control spike foils outside the acceptable limits, the entire act o f samples ihould ba re-extracted. Any matrix spike outside 70 130% ihould be evaluated by the analyst to determine if re-extraction is warranted. 13.4 Any calibration standard found to be a statistical outlier by uaing the Huge Error Teat, may be excluded from die calculation o f the calibration curve However, die local number of calibration standards that could be excluded mustnotexceed20%ofthetotal numbero fstandards injected. 13.3 The correlation coefficient (R) for calibration curves generated must be 20.992 (R1 20.985). I f calibration results foil outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standards ortherelevantaatofsamplesshouldbe reanalyzed. 13.6 Retention tunes between standards and samples must not drift more than 4 % within ananalytical ran. I f retention time drift exceeds this limit within ananalyticalran then theactmustbereanalyzed. 14.0 Calculations 14.1 Usethe following equation to calculate the amounto f PFOA found (in ng/mL. based on peek area) uaing the standard curve (linear regression parameters) generatedby dieMassLynx softwareprogram: PFOA found(ng/mL) - (Peakarea- intercept! x DP x aliquot factor slope DF factorby winch die final volumewasdiluted, if necessary. Aliquot factor-10 Pag*6 of 7 Page 7 o f 65 Exygen Research Page 132 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Exygen U m w eh Motbod Nurabor V00017B 1 ANALYTICAL METHOD Method ofAnalysis forthe Determinationo fPerfluorooctiooic Acid (PFOA) in Small Mammal Liverby LC/MS/MS 14.2 For sample fortified with known amounts o f PFOA prior to extraction, use die following equationto calculate thepercent recovery. Recovery(H) - [ totalanalytefound(ngfaiL) - analytefoundin control(ng/mL)] ^ ^ analyteadded(ng/mL) 14.3 Um the following equationto convert the amountof PFOA found in ng/mL io ng^g(ppb). P F O A found(p p b ) - f f f Q A found f p g t o U X fin al v o lu m t ( m U l ampleweight (g) Exygen Research Page 7 o f 7 Page SS o f 6S Page 133 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ANALYTICAL METHOD Method Number V00017M Method of Aaalyals for the Petsnalaathm of Porfluorooctoooic Add (PFOA) la Small Mammal Serum by LC/MS/MS Analytical TeatingFacility: Exygen Research 3058 Research Drive State College, PA 16801 Approved By: ' v - s - ' X ___c -- l A v j Paul Connolly I Tactaioal Letter, LC-MS, BxyganReaaarch a / /!? ________ Jbhn Flaherty / Vice President,Operations, BxyganResearch ___ U\U>t'l Date Due Exygen Research Tout Faga: 7 Page 59 o f65 Page 134 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Z " *' Exygen Protocol Number: P0001131 E x y im lU ie iie h M ethod N u u to r VOOOI7SS 1 ANALYTICAL MKTMOP .... MethodofAnalysis for theDaterainstion ofPerfluorooctanoic Acid (PFOA) in Small MammalSeramby LC/MS/MS 1.0 Scope Thie method is to be employed for ttw isolation andquantitation of perfluorooctanoic acid by High Performance Liquid Chromatography coupled to a tandem Mass Spectrometric Detector(LC/MS/MS) in emailmammal serum. 2.0 Safety 2.1 Always obeervesafelaboratorypractices. 2.2 Consultthe appropriateMSDS beforehandling any chemical for propersafety precautions. 3.0 SampleRequirement 3.1 At leest 1mL o fteatsamplefor extraction. 3.2 No sampleprocessing is needed for serum samples. However, frozen serum samplesmustto allowed to completelythaw to room temperaturebefore use. 3.3 Sample collection procedures w ill be specified in the sampling plan for this project 4.0 Reagentssod Standards 4.1 Water-HPLC grade 4.2 Methanol - HPLC grade 4J Acetonitrile - HPLCgrade 4.4 Ammonium Acetate- A.C.S. ReagentGrade 4.5 PerfluorooctanoicAcid - Sigma-Aldrich 5.0 InstrumentandEquipment S.l A high performance liquid chromatograph capable o f pumping up to 2 solvents equipped with a variable volume iqjeetor capable of injecting 5-200 pL connectedto atandem Mass Spectrometer(LC/MS/MS). $2 A deviceto collectrawdata forpeakintegration end quantitation. 5.3 Analytical balancecapableofreadingto 0.00001 g. 5.4 50mL duposablepolypropyleneceotrifoge tubes. 5.5 15mL disposablepolypropyleneceotrifoge tubes. 5.6 Disposablemicropipets(SO-lOOuL, 100-200uL). 5.7 125-raLLDPBnarrow-mouthbottles. 5.8 2 mL clearHPLC vial kit. 5.9 Disposablepipettes. 5.10 Autopipettes (100-1000 pL and 10-100 pL), with disposable tips. 5.11 Wstcrs SepPtk Vac6 cc (1g) tC18 SPEcsrtridges. 5.12 SPEvacuummanifold. 5.13 Vortexer. Page 2 o f1 Page 60 o f65 Exygen Research Page 135 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExyfnX cM V di Method Number V000I7S6 I a n a l y t ic a l m e t h o d Method ofAnalysis for theDetermination o fPerfluorooctanoic Acid (PFOA) in Small MammalScrum by LC^MS/MS $.14 Wrist-actionshaker. $.15 Cmtri&ge capableofqrinnuig 15 mL polypropylene tubes at 3000 rpm. 6.0 Chromatographic System 6.1 Analytical Column: FluophaeoRP(Keystone Scientific), 2.1 mm x 50 mm. 5p (P/N: 82505-052130) 6.2 Temperature: 30*C 6.3 Mobile Phase(A ): 2 mM Ammonium Acetate in Water Mobile Phase(B): Methanol GradientProgram: Time (mini 0.0 1.0 8.0 20.0 22.5 2 iA 65 65 25 25 65 Flow Rate % B (mL/min> 35 0.3 35 0.3 75 0.3 75 0.3 35 0.3 6.6 Injection Volume: 15pL (canbemenacedto as muchas 50 pL). 6.7 Quantitation: PeakArea- external standardcalibration curve. 6.8 RunTime: ~ 23minutes. Theaboveconditions aremtmdedasaguide andmay bechanged in order to optimizedie HPLC system. 7.0 MS/MS System 7.1 Mode: ElectrosprayNegative MRM mode, monitoring 413- 369 m/z for PFOA. The above condition* are intended as a guide and may be changed in order to optimize the MSMS system. 8.0 Preparationo fSolutions 8.1 Mobile Phase 8.1.1 2 mM ammonium acetate in water is prepared by adding 0.154 g of wnwiium acetateto 1000mL ofwater. Alternate volumes maybe prepared. Pas 3 of 7 Page 6/ o f 65 Exygen Research Page 136 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 ExygM Research Method Number V00017&6 I ANALYTICAL M ETHOD MethodofAnalysis fin theDetermination o fPerfluorooctanoic Acid (PFOA) in Small MammalSerumby LC/MS/MS 9.0 StandardPreparation 9.1 StandardStock/Fortificaiion Solution 9.1.1 Prepare a stock solution o f -100 pgftnLof PFOA by weighing 10 mg of analytical standard (corrected for purity) and dilute to 100 mL with methanol in a 125-mL LDPE bottle. 9.1.2 A 1.0ngfaiL fortification solution o f PFOA it prepared by bringing I mL o fthe 100 pg/mL solution to a final volume of 100 with methanol in a 125mL LDPEbottle. 9.1.3 A0.1 gg/mLibitificatioo solution o fPFOA is preparedby bringing 10 mLo fthe 1.0jigtaiL solution to a final volume of 100with methanol in a 125mL LDPEbottle. 9.1.4 Thestock andfortification aolutions areto be stored in a refrigerator at approximately 4*C and are stable for a maximum period of 6 months from thedateofpreparation. 9.2 StandardCalibration Solutions 9.2.1 LC/MS/MS calibrationstandards arepropped in methanol via dilution ofthe0.1 pg/mL fortification solution. 9.2.2 The following is a typical example: additional concentrations may be prepared asneeded. ofFortification Volume Solutionfai/mL) (mL) IMIutodto (mL) Final Concentration (nc/ml) 100 5.0 100 100 2.0 100 100 1.0 100 5.0 2.0 1.0 5.0 10 100 O.S 2.0 10 100 1.0 10 100 0.2 0.1 9.2.3 Store alt calibration standards in 125-mL LDPE narrow-mouth bottles at2*C to 6*C, up to six months. 9.2.4 Alternate volumes andconcentrations o f standards may beprepared as needed. 10.0 BatchSetUp 10.1 Each batch o f samples extracted (typically 20 or leas) must include at least one untreated control and two untreated controls fortified at known ooneentrationa(lab control spike) to verify procedural recovery for thebatch. 10.2 Requirements for field and laboratory duplicates and spikes w ill be specified in thequality refinanceplan for this project. Pe*e4of7 Page 62 o f 65 Exygen Research Page 137 of 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Nurriber: P0001131 ExytnK M M C b M tdwd Nwnbw V0001786 I ANALYTICAL METHOD Methodo fAnalysis fortheDeterminationo fPerfluorooctanoie Add (PFOA) in Small Mammal Seramby LC/MS/MS 11.0 SampleExtraction 11.1 Measure 1mL o fample into a 50 mL polypropylene centrifuge tubes (fortify as needed, replace lid and mix well). Note that alternate volumes of serum maybemeasureddependingondie sample size available for use. 11.2 Add waterto thesamplefor afinal volume o f20 mL. Captightly 11.3 Vortex fbr-1 minute. 11.4 Transfer 1 mL of the sample using a disposable pipette into a IS mL disposable oentriflige tube. 11.5 Add SmLo facetonitrile andshake for-20 minutes on awrist-action shaker. 11.6 Centrifogedie tubesat-3000 ipm for -5 minutes. 11.7 Decant the supernatant into a 50 mL disposable centrifuge tube and add 35 mLo fwater. 11.S Condition the Cts SPE cartridges (1 g, 6 mL) by passing 10 mL methanol followed by 5 mL ofHPLC water(~ 2 drop/sec). Do not let column run dry 11.9 Loadthe sampleonconditioned Cu SPEcartridge. Discard elualc. 11.10 Elute with -2 mL of methanol. Collect 2 mL of eluate into a graduated 15mL polypropylene centrifbge tube(final volume - 2 mL). 11.11 Analyze samplesusing electroapray LC/MS/MS. 12.0 Chromatognphy 12.1 Inject the sameamounto feach standard, sample and fortified sample into the LC/MS/MS system. A calibration standard must precede and follow all analyzed samples. 12.2 Stadards ofPFOA corresponding to at least five or more concentration levels mustbe included in ananalytical act. 12.3 An entire seto fcalibration standardsmust be included at the beginning and at fire end of a sample set. Standards must be interspersed between every 5-1o samples. A t a alternative, a entire act of calibration standards may be iqjected at the beginning of a set followed by calibration standards interspersed every 5-10 samples (to account for a second set o f standards). In either ease, calibration standards must be the first a d last injection in a sampleset. 12.4 Use line standard curves for quantitation. Line standard curves are generatedforthe analyteby line regressionusing 1/x weighting ofpeak area versus calibration standard concentration using MassLynx 3.3 (or equivalent) softwaresystem. 12.5 Sample response should not exceed standard responses. Any samples that exceedstandardresponsesshouldbe fbrtberdiluted and reanalyzed. Page 3 uf ? Page 63 o j 65 Exygen Research Page 138 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 Exygen fcuearek Method Number V0001786 I ANALYnCALMETHOD ..... Method ofAnalysis for theDetermination ofPerfluorooctanoic Acid (PFOA) in Small MammalScrumby LC/MS/MS 13.0 AcceptanceCriteria 13.1 Chromatogram mast show apeak of adaughter ion at 369 amu from a parent of 413 amu. The 413 amu parent corresponds to the PFOA anion, while the daughterion (369 amu) representsdie loss o fcarbon dioxide. 13.2 Method blanks must not contain PFOA at levels greater than the LOQ. if a blank contains PFOA at levels greater than 10 ng/mL, then a new blank samplemustbeobtainedandtheentire setmustbere-extracted. 13.3 Recoveries of control spikes and matrix spikes must be between 70-130% of their known values. If a control spike falls outside the acceptable limits, the entire set o f samples should be re-extracted. Any matrix spike outside 70 130% should be evaluated by foe analyst to determine if re-extraction is warranted. 13.4 Any calibration standard found to be a statistical outlier by using the Huge Error Test, may be excluded from foe calculation of the calibration curve However, foe total number o f calibration standards that could be excluded mustnot exceed20%o fthe total numberofstandards injected. 13.5 The correlation coefficient (R) for calibration curves generated must be 20.992 (R* 20.985). I f calibration results (alt outside these limits, then appropriate steps must be taken to adjust instrument operation, and the standardsorfoerelevant setofsamplesshould be reanalyzed. 13.6 Retention times between standards and samples must not drift more than 4 % within ananalytical run. If retention time drift exceedsthis limit within ananalytical tun then the setmustbereanalyzed. 14.0 Calculations 14.1 Usethe following equationto calculate the amountof PFOA found (in ng/mL. based on peak area) using foe standard curve (linear regression parameters) generatedby theMass Lynx software program: PFOA found(ng/mL) - (Pent m - intercept) x DF x aliquot factor slope DF ftetorby whichfoe final volume wasdiluted, if necessary. Aliquot factor"20 14.2 For lampi fortified with known amounts of PFOA prior to extraction, use foe folk)wing equationto calettiatethepercent recovery. Recovery (% )- [ totalanalytefound(ngflnL) - analytefound inoontrol(ng/mL)] ^ analyteadded(ng/mL) Page 6 of 7 Page 64 o f 65 Exygen Research Page 139 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 B w t o -- dl __________________________ M etbodN uat, V00CI7le I ANAjLyriCAL MgTHOD Methodo fAnalyeia for the Determination o fPerfluomocunoic Acid (PFOA) in Small Mamma! Seramby LC/MS/MS Id.3 the the following equation to convert the amounto f PFOA found in n*imL to PPb- PFOA fcund (ppb>- fPFOA found fnnhnl.l final wihima tmt t] uniple volume (mL) Exygen Research Pat 7of7 Page 65 o f 65 Page 140 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No.: P0001131 3058 Research Drive Phone: 814-272-1039 State College, PA 16801 Fax: 814-231-1580 PROTOCOL AMENDMENT Amendment Number 1 Effective Date: 01/18/05 Exygen Study Number P0001131 Client Study Number P ag elo M DESCRIPTION OF AMENDED SECTION 1) Analytical Procedure Summary V0001780:Section 9.1 2) Verification of Analytical Procedure None AMEN PEP TO 1) Add to Section 9.1: Section 9.1.6, Alternate weights of standards may be used to prepare alternato concentrations of stock solutions as necessary. Alternate levels of fortification solutions may also be prepared. 2 ) Low and high spiking levels of the analytes for each matrix may be altered depending on sample size available for extraction and/or to cover analyte concentrations expected in the samples. RATIONALE 1) Higher concentrations of standards need to be prepared in order to spike the sample bottles at higher levels. 2) The sample size avalable for small mammal iver and serum was smaller than expected. Spiking at the pre-determined levels in the protocol puts the spiked concentration lower than the detection lim it Also, the analyte levels in the ground water samples are expected to greatly exceed the pre-determined spiking levels listed in the protocol. When the levels in the samples greatly exceed the striking levels, an accurate recovery value cannot be calculated for the QC sample. Higher spiking levels in the bottles will cover the analyte concentrations expected in the water samples. IMPACT ON STUDY The LOQ is 100 ng/g for a 0.1 g sample of small mammal liver and is 1000 ng/mL for a 0.01 mL sample of small mammal serum. Higher levels of spiking for the water samples will ensure that mote Q C recovery data can be used. LIBRARY ID: W 0001226*` . .. '' ADMINISTRATIVE FORM Exygen Research Page 141 o f 144 Interim Report #7-Analysis o f Soil Boring Samples Exygen Study No. : P0001131 3058 Research Drive Phone: 814-272-1039 State College, PA 16801 Fax: 814-231 -1580 Amendment Num ber Effective D ate: Exygen Study Num ber PROTOCOL AMENDMENT 2 03 /07/05 P0001131 C lient Study N u m b er **0 1 of 1 None DESCRIPTION OF AMENDED SECTION 1) Report, page 11 of 65 2 ) Test Materials, page 6 of 65: PFOS transition monitored 499 -> 99. AMENP6P TO 1) Instead of one final report, interim nsports will be issued. 2) PFOS transition monitored may also be 499 -> 80. RATIONALE 1) Due to the excessive sizes of the data sets, interim reports w il be issued to allow the cfient to receive data in a timelierreaneFi o ib ttr 4 ** 2) The API 4000 LG/MS/MS systems (M eet the 499 > 80 PFOS transition with greater sensitivity than the 499 > 99 transition. IMPACT.Q N STMPY 1) The d e n t will be able to receive and review the data more quickly. 2 ) The 499 -> 80 transition can be detected with greater sensitivity; therefore, giving better chromatography. LIBRARY IO: VD00122S-S- Exygen QAU Review LJJ QjJe&llS ADMIN1STRATTVE FORM Exygen Research Page 142 o f 144 Interim Report #7-Analysis of Soil Boring Samples Exygen Study No.: P0001131 JUL.2S.2005 8:56AM EXYGEN RESEARCH NO. 774 P .3 E^ygeI T RESEARCH 3058 Research Drive Phone: 814*272-1039 State College, PA 16801 Fax: 814*231*1580 Amendment Number E ffective D ate: Exygen Study Number PROTOCOL AMENDMENT _____ 3 07/18/06 P1131 Client Study Number: Paget on NA DESCRIPTIO N O F AM ENDED SECTIO N Verification o f Analytical Procedure, page 10 of protocol. AM EN M E The field duplicate can be used for the laboratory spikes and replicate when the primary sam ple volum e is limited. Bfi The sample size for a w ater sample Is 200 m l- If a sam ple site requires re-extraction for any reason, there would not be enough of die primary sam ple to repeat two laboratory spikes and a replicate. The field duplicate hr technically fire sam e samp* as the primary sam ple and therefore, can be used for laboratory spikes and replicates as needed. JM EAgLO H STU PV No negative Impact on the study. Using the duplicate sam ple allows for the fuB QC of the sam ple site to be completed. A JL. Study Djretktf Signatura GA /Wnc^aai Irwesflgelor S ig n a l^ il Director Exygen Maqrfei 1 ________ Sponsor Signature^ required) Data U - m i - as Date .7/ " M Date Exygen QAU Review 7)., f t / LIBRARY ID: V000122SB ADMINISTRATIVE FORM Exygen Research Page 143 of 144 Interim Report #7-Analysis of Soil Boring Samples Exygen Study No.: P0001131 09-20-2005 02:34pr Fros-IESTON SOLUTIONS Ewgen RESEARCH T-394 P .002/004 F-437 3058 Research Drive Phone: 814-272-1039 State College, PA 16801 Fax: 814`231'1580 fisaiQU X Project Specific Deviation DEVIATION FORM Page 1 cf 1 Facility Deviation Date o f Occurrence: 03/1S/05 Exygen P ro jec t#: P760/P1131 D eviatio n#: 1/1 Client Project # : NA Reference # : 05-122 Regulatory Driver: Deviation Type: (Include Vfi formethods and SOPs) GMP GLP O th er None Sam ple D eacrintien: ______Protocol _______M ethod V#: 0001658-3 Notebook reference: NA X SOP L o g in # : _______ NA C ontainer#: NA Lot#: NA Sum m ary o f D eviation: Thle deviation pertains to all soil and sediment samples analyzed fo r percent solids before 07/07/05. a. No blanks or duplicates were run as required by section 8.3. b. Some sample weights exceed the allowable range (> 10g). Cause: Preparation Analysis Instrument Client Request X Other There has been no negative impact on the study. All of the percent solid values that w ere determined during the tim e period in question are considered valid, although the SO P was not followed. In the newly revised version of the SO P blanks and duplicates are no longer required. Also, in fee new SO P, fee allowable amount of sample to be used is < 20 g. All of fee samples in question in this deviation weighed less than 20 g. The technician analyzing fee samples for percent solids was following the new procedure before it was formally approved. Coiracttv Actions: A new version of the SOP has been Issued and approved (V0000427-S). ^qA lality Assurance /o g ~ Date Sponsor Management Date Exygen Research Page 144 o f 144