Document zdjgR9q0R95aXkKGBpNbaKNq6

P-1 ^ 3 6 . 2> 83 INTERIM REPORT # 23 - Analysis o f Sediment Sample STUDY TITLE Analysis o f Perfluorobutanesulfonste (PFBS), PeriluorohexanesuLfonate (PFHS), and Perfluorooctanesulfbnate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal liv er 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 May 2,2006 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 S i Paal,M N 55144 Phone: 651-733-6374 pro ject Protocol Number: P0001131 Exygen Study Number: P0001131 Total Pages: 110 P-2 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 QUALITY ASSURANCE STATEMENT Exygen Research's Quality Assurance Unit reviewed Exygen Study Number P0001131, entitled, "Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfhiorooctanesulfonate (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 phasesr 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 mid Management and to the Study Director. Phase 25. Final Raw Data Review and Interim Analytical Report Review Date Inspected Date Reported to Date Reported to Principal Exygen Date Reported to fay-SSjiffltfg Mmagsmcnt Study Director 05/02/06 05/02/06 05/02/06 05/02/06 Date 'Note: All in-lab inspections will be documented in the QA statement for the final analytical report at the conclusion o f the study. This QA statement involves only the review o f the interim report and associated raw data. Exygen Research Page 3 o f 110 P-3 . Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: POOO1131 CERTIFICATION OF AUTHENTICITY This interim-report, for Exygen Study Number P0001I31, is a true and complete representation o f the raw data. Submitted by: Exygen Research 3058 Research Drive State College, PA 16801 (814)272-1039 Principal Investigator, Exygen: Date Exygen Research Facility Management: Richard A. G President Exygen R< fa Study Director, Solutions, Inc. JaisimhaKt Weston Solutions, Inc Sponsor Representative, 3M Company: Michael Santoro Director Regulatory Affairs Exygen Research Date % 06 Date Page 4 of 110 P-4 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0Q01131 STUDY IDENTIFICATION Analysts o f 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 die 3M Decatur Monitoring Program . :. PROTOCOL NUMBER; P0001131 EXYGEN STUDY NUMBER: P0001131 TYPE OF STUDY: Residue SAMPLE MATRIX: Sediment . . .' . . TEST SUBSTANCE: Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) SPONSOR: 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 STUDY DIRECTOR: 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: 04/27/06 Intaim Analytical TerminationDate: 04/30/06 Interim ReportCompletion Date: 05/02/06 Exygen Research Page 5 o f l 10 P-5 Interim Report #23 - Analysis of Sediment 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 o f this interim portion o f the study: Name John Flaherty . Karen R is h a ............ Paul Connolly Christine Edwards Mark Ammerman Amy Sheehan Brittany Kravets , ,Scott Crain _ Frances Crespi Devon Ingram Christa Gallant Title Vice President Scientist Technical Lead-LC/MS Technician Sample Custodian - Associate Scientist Technician Technician Technician Technician Technician Exygen Research Page 6 of 110 P-6 TABLE OP 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........................................................................................................ 11 4.0 ANALYTICAL TEST SAMPLES............................................................................ 12 5.0 REFERENCE MATERIAL.........................................................................................12 6.0 DESCRIPTION OF ANALYTICAL METHOD.........................................................13 6.1. Extraction Procedure For Sediment........................................... 13 6.2 Direct Inject Extraction Procedure For Sediment......................................................14 6.3 Percent Solids Procedure For Sediment......................... 14 6.4 Preparation o f Standards and Fortification Solutions................................................14 6.5 Chromatography.... ................................................................................................... 15 6.6 Instrument Sensitivity................................................................................................15 6.7 Description o f LC7MS/MS Instrument and Operating Conditions........................... 15 6.8 Quantitation and Example Calculations.................................................................... 16 7.0 EXPERIMENTAL DESIGN.................................. 20 8.0 RESULTS.................................................................................................................... 20 9.0 CONCLUSIONS *............................................:.......;................................................ 20 10.0 RETENTION OF DATA AND SAMPLES............................................................. 21 Exygen Research Page 7 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 LIST OF TABLES Table I. P ig s Summary o f PFBS, PFHS and PFOS in Sediment Samples......................... 23 Table II. Summary o f PFOS in Direct Injection Sediment Samples.......... . 24 Table ID. Matrix Spike Recovery o f PFBS, PFHS and PFOS in Sediment Samples.....25 Table IV. Matrix Spike Recovery o f PFOS in Direct Injection Sediment Samples..... 26 Table V. Total Percent Solids in Sediment Samples........... .........................................27 Exygen Research Page 8 of 110 p.8 ------------------------------------------------ -- Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 1. LIST OF FIGURES Page Typical Calibration Curve for PFBS in M ethanol........... ..............................29 Figure 2. Non-Extraded Standards o f PFBS in Methanol, 0.2ng/mL and 0.5 ng/mL, Respectively................... ....................................................... ......30 Figure 3. PFBS in Reagent Blank, 0 4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively.........................................31 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID: C0172892, Data Set; Q42606F).................................................. 32 Figures. Typical Calibration Curve for PFHS in Methanol..........................................33 Figure 6. Non-Extracled Standards o f PFHS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively..................................................................................34 Figure 7. PFHS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively........................................ 35 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for PFHS (Exygen ID: C0172892, Data Set: 042606F).................................................. 36 Figure 9. Typical Calibration Curve for PFOS in Methanol..........................................37 Figure 10. Non-Extxacted Standards o f PFOS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively.................................................................................38 Figure 11. PFOS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively......................................... 39 Figure 12. Chromatogram Representing a Sediment Sample Analyzed for PFOS (Exygen ID: C0172892, Data Set042806B).................................................. 40 Exygen Research Page 9 of 110 P-9 intern Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 LIST OF APPENDICES Appendix A Study Protocol P0001131 (Exygen Study No. P0001131) with Analytical'Method V0001782: "Method o f Analysis for the Determination,ofPcrfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS", and Protocol Amendments.............................. Page .41 Exygen Research Page 10 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 r l.a SUMMARY Exygen Research extracted and analyzed sediment samples for die determination of perfhiorobutanesulfonate . (PFBS), pptJuorohexanesulfonate . (PFHS), and perfluorooctanesulfonate (PFOS) acconjmg td Exygen Method V0001782 (Appendix A). The limit o f quantitation for PFBS and PFHS jn sediment was 0.2 ng/g. The limit of quantitation for PFOS in sediment was 2.0 ng/g. The standard sediment method (V0001782) was originally used to extract all o f the samples. Use o f this method yielded poor recoveries fox PFOS. Because o f this, a direct injection method (Section 6.2) was used to analyze for PFOS. Analytical results for the analysis o f PFBS, PFHS and PFOS found in sediment samples extracted with the original method are summarized in Table I. Analytical results for the analysis o f PFOS found in sediment samples by direct injection are summarized in Table n. The average percent recoveries standard deviations for PFBS, PFHS, PFOS in sediment samples were 85 19%, 99 29%, and 93 6%, respectively. Fortification recoveries for the analysis o f PFBS, PFHS, and PFOS in sediment samples extracted with the original method are summarized in Table 111. Fortification recoveries for the analysis of PFOS in sediment samples by direct injection are summarized in T able IV. The total percent solids for sediment samples are detailed in Table V. 2.0 OBJECTIVE The objective of the analytical part o f this study was to determine levels of perfluorobutanesulfonate (PFBS), perfiuorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in sediment according to Protocol P0001131 (Appendix A). 3.0 INTRODUCTION This report details tire results o f the analysis for the determinatimi o f PFBS, PFHS, and PFOS in sediment using the analytical methods entitled, "V0001782: Method o f Analysis for the Determinatimi o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS." The study was initiated on November 05, 2004, when the study director signed protocol umber P0001131. The analytical start date for this interim report was April 27, 2006 and the analytical termination date for this interim report was April 30,2006. Exygen Research Page 11 of 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 4.0 ANALYTICAL TEST SAMPLES Three sediment samples (Exygen ID: CO172892-CO172894) were received on wet ice on April 22, 2006 from Tim Frinak at Weston Solutions, Inc. The samples were logged in by Exygen personnel and placed in refrigerated storage. 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 and PFHS, were supplied by 3M. PFBS 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 PFHS PFOS faYgcalBVCTfoiyypSP0005726 SP0002401 SP0002694 L ali 101 SE036 430180-1 Purity (%) 96.798.6 101.2 Expiration Pate 12/04/06 10/18/06 10/31/07 The molecular structures o f PFBS, PFHS and PFOS are given below: PFBS Chemical Name: Perfluorobutancsulfonate Molecular Weight: 338 supplied as the potassium salt (C4F9SO3IC*) Transitions Monitored: 299 -*99 , Structure: P F 1F F F IF ! FF PFHS Chemical ame: Periluorohexanesulfonate Molecular Weight: 438 supplied as the potassium salt (Q F^S O slC ) Transitions Monitored: 399 -* 80 Exygen Research Page 12 o f 110 Interim Report #23 - Analysis of Sediment Simples Exygen Study No.: PC001131 Structure: FFF F. F F F F F1 F FFF O3 PFOS Chemical Name: Perfluorooctanesulfonate . Molecular Weight: 538 supplied as the potassium salt (CgFnSOs'K*) Transitions Monitored: 499-> 80 Structure: ... o3 F 'F F F 6.0 DESCRIPTION OF ANALYTICAL METHOD The analytical method "V0001782: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" was used for the analysis of PFBS and PFHS in sediment samples. A direct injection method, detailed in Section 6.2, was used for the analysis o f PFOS in sediment samples. 6.1. Extraction Procedure For Sediment Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A 5 gram portion o f sediment was weighed into a fifty milliliter centrifuge tube for the extraction. After fortification o f appropriate samples, 35 mL of 1% acetic acid in water was added to the samples. The samples were vortexed and allowed to shake on a wrist action shaker for ~60 minutes. The samples were centriftiged for ~20 minutes at ~3000 rpm. The supernatant was then loaded onto a C n SPE cartridge conditioned with 10 mL of methanol and 20 mL o f water. The eluate was discarded. Twenty milliliters o f methanol was added to the sediment samples left in the centrifuge tube. The samples were vortexed and allowed to shake on a wrist action shaker for another 30 minutes. The samples were centrifuged again for ~2Qminutes at ~3000 rpm. The supernatant was then loaded onto the same C . SPE cartridge. The eluate was collected info a 500 mL Nalgene Bottle. The column was washed with 4 mL of methanol. The wash was collected in the same bottle as the eluate. Approximately two hundred milliliters o f water was added to the bottles. The samples were mixed by shaking and loaded onto another Cig SPE cartridge conditioned with 10 mL o f methanol Exygen Research Page 13 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 and 20 mL o f water. The eluate was discarded. Approximately five milliliters of methanol was added to the cartridge. Five milliliters o f eluate was collected into a graduated IS mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.2 Direct Inject Extraction Procedure For Sediment Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A one-gram portion o f sediment was weighed into a 15-milliliter centrifuge tube for the extraction. Ten milliliters o f 1% acetic acid in methanol was added to each sample. The samples were then shaken by hand, vortexed, and sonicated for thirty minutes. The samples were then centrifuged for -1 0 minutes at -3000 rpm. Each sample was analyzed by LC/MS/MS electrospray. 6.3 Percent Solids Procedure For Sediment . Percent solids were determined using the procedure indicated in Exygen method V0000427. Approximately 20 grams o f sample was weighed into a pan. The weight o f the sample plus the pan was recorded. The samples were then dried in an oven overnight at 104 2 C. Then the samples wore transferred to a dessicator and allowed to cool for -IS minutes. Each sample was then weighed again, including the weight o f the pan. The percent solid for each sample was then calculated. See Table V for percent solids results. 6.4 Preparation of Standards and Fortification Solutions A m ixed'stock standard solution o f PFBS, PFHS, and PFOS was prepared at a concentration o f 1000 pg/mL by dissolving 100 mg o f each ofthe standards (corrected for purity and salt content) in 100 mL o f methanol. From this solution, the following fortification standards were prepared: Cone, of Fort Stock or Fort. Volume Solution (mL) (pg/mL) 1 1000 10 100 10 10 10 1.0 10 0.1 10 1o f PFBS, PFHS, and PFOS Final Volume (mL) 100 100 100 100 100 Final Cone, o f Fortification Std. (pg/mL) 100 10 1.0 0.1 0.01 Exygen Research Page 14 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 A set o f non-extracted calibration standards containing PFBS, PFHS, and PFOS was prepared in methanol, as specified in Exygen method V0001782. The following concentrations were prepared: ' - Cone, o f Fort Fort or Calibration Volume Solution (mL) (ng/mL)1 100 L0 100 . 0.5 100 0.2 10 1.0 5.0 1.0 2.0 1.0 1ofPFBS, PFHS, and PFOS Final Volume (mL) 10 10 10 10 10 10 Final1Cone, o f Calibration Std. (ng/mL) 10 5.0 2.0 1.0 0.5 0.2 The stock standard solution and all fortification and calibration standard solutions were stored in a refrigerator (4 2C) when not in use. Documentation o f standard preparation is located in th raw data package associated with this interim report. 6.5 Chromatography ' Quantification o f PFBS, PFHS and PFOS was accomplished by LC/MS/MS electrospray. The retention times o f PFBS, PFHS and PFOS were ~0.56mins, -9 .4 mins, and ~11.4 mins, respectively. Peaks above the LOD were not detected in any o f the reagent blank samples corresponding to the analyte retention time. 6.6 Instrument Sensitivity The smallest standard amount injected during the chromatographic run had a concentration o f 0.2 ng/mL o f PFBS, PFHS and PFOS. 6.7 Description of LC/MS/MS Instrument and Operating Conditions In strum ent API 4000 Biomolecular Mass Analyzer Interface: Tuibo Ion Spray Liquid Introduction Interlace Computer: DELL OpfcPlex GX400 Software; Windows NT, Analyst 1.4.1 HPLC: Hewlett Packard (HP) Series 1100 HP Qua! Pump Exygen Research Page 15 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 HP Vacuum Degasser HP Autosampler HP Column Oven HPLC Column: Thermo Fluophase RPV50 mm x 2 1mm Column Temp.: -30 C Injection VoL: 15 pL - Mobile Phase (A): 2 mM Ammoniurn Acetate in water Mobile Phase (B): Methanol Time (mini 0.0 1.0 8.0 10.0 11.0 _ 18.0 Total run time: ~18min Flow Rate: 0.3raL/min *AA 65 65 25 25 65 65 %B 35 35 75 75 35 35 Ions monitored: PFBS PFHS PFOS Mode negative negative negative Transition Monitored 299 99 399 - 80 499 - 80 Approximate Retention Time (mini ~0.56 min. ~9.4 rain. ~11.4 min. 6.8 Quantitation and Example Calculations Fifteen microliters o f sample or calibration standard were injected into die 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 o f standards. The concentration was determined from the following equations. Equation 1 calculated the amount o f analyte found (in ng/mL, based on peak area) using the standard curve (linear regression parameters) generated by the Analyst software program. Please note that the equations in this section are presented in a different order than the equations in the method (V0001782), but this has no effect on the final calculations. Exygen Research Page 16 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Equation 1: Analyte found (ng/mL) = fFeak 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 o f PFBS'and PFHS prior to extraction, Equation 2 was used to convert thb amount o f PFBS arid PFHS found in ng/mL to ngfg (PPb). Eflaafipn.?; Analyte found (ppb) = rAnalvte found (ng/m lk x final volume (5 mLVl ; sample weight (5 g) Equation 3 was used to calculate the paren t recovery: Equation 3: Recovery (%) = (analyte found foobl - analyte in control (rob)) * 100% amount added (ppb) Equation 4 was then used to calculate the amount o f PFBS and PFHS found in ppb based on dry w eight Equation 4: . Analyte found (ppb) dry weight = Analyte found (ppb) x [100% / total solids(%)] An example o f a calculation using #n actual sample follows (calculation is for PFBS only): Sediment sample Exygen ID: C0172893 Spk F (Set: 042606F), fortified at 4 ng/mL with PFBS where: - ,. , peak area . _ 253819 intercept = -592 slope : .. 42300 dilution factor ^. 1 ng/g PFBS added (fort level) = 4 amt in corresponding sample (ng/g) ss 2.41 final volume (mL) , ^ . 5 sample weight (g) = ' S, :- total solids (%) = 54.37 Exygen Research Page 17 of 110 Inierim Report #23 - Analysis of Sediment Sample Exygen Study No.: POOO1131 From equation 1: Analyte found (ng/mL) = f2S3819- f-59217 x 1 42300 * 6.C1ng/mL From equation 2: Analyte found (ppb) = (6.01 ng/mL x S m D 5g = 6.01 ppb From equation 3: % Recovery = (6.01 ppb - 2.41 rrobl x 100% 4 ppb - 90% From equation 4: ' Analyte found (ppb) dry weight - 6.01 ppb x (100% 154.37%) = 11.1 ppb NOTE: This value may be slightly different than that of the raw data due to rounding. A slightly different set o f calculations was used for the direct irqectian samples analyzed for PFOS. Equation 1: Analyte found (ng/mL) = (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 ofPFOS prior to extraction, Equation 2 was used to convert the amount of PFOS found in ng/mL to ng/g (ppb). E flaato ?; Analyte fbund(ppb) - fAnalyte found (ny/mT.l x volume extracted (10 mLl] sample weight (1 g) Equation 3 was used to calculate the percent recovery. Exygen Research Page 18 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen -StudyNo.: P0001131 Equation 3: . Recoveiy(% )= . (analyte found (ne/gl - analyte in control (ng/eV) x l00% amount added (ng/g) Equation 4 was then used to calculate the amount o f PFOS found in ppb based on dry w eight Equation 4: ............ - Analyte found (ppb) dry weight = Analyte found (ppb) x [100% / total solids(%)] An example o f a calculation using an actual sample follows: Sediment sample Exygen ID: C0172892 Spk D (Set: 042806B), fortified at 400 ng/mL with PFOS where: peak area = 152371 intercept = 3720 slope = 22700 dilution factor = 100 ng/g PFOS added (fort level) = 4000 amt in corresponding sample {ng/g) = 2360 volume extracted (mL) = 10 sample weight (g) =1 total solids (%) * 66.54 From equation 1: Analyte found (ng/L) = flS2371-37201 x 100 22700 = 654 ng/mL From equation 2: Analyte found (ppb) .. " ' = (654 ng/mL x lQmLf \ 1-g . - 5540 ppb ' From equation 3: % Recovery ' = (6540 ne/g - 2360 ng/gf x 100% 4000 ng/g = 105% From equation 4: Analyte found (ppb) dry weight = 6540 ppb x (100% / 66.54%) = 9830 ppb Exygen Research Page 19 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PQ001131 NOTE: This value may be slightly different than that o f the raw data due to rounding. 7.0 EXPERIMENTAL DESIGN For sediment 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 fin'extraction. The sediment samples were extracted in one set. The set included one reagent blank and two reagent blanks fortified at known concentrations. The set contained three sediment samples. For each sample, two laboratory matrix spikes and a duplicate were extracted. Due to poor recoveries, the three sediment samples were extracted and analyzed using a direct injection method for PFOS. This method is detailed in Section 6.2. 8.0 RESULTS Analytical results for the analysis o f PFBS, PFHS and PFOS found in sediment samples extracted with the original method are summarized in Table I. Analytical results for the analysis o f PFOS found in sediment samples by direct injection are summarized in Table II The average percent recoveries standard deviations for PFBS, PFHS, PFOS in sediment samples were 85 19%, 99 29%, and 93 6%, respectively. Fortification recoveries for the analysis o f PFBS, PFHS, and PFOS in sediment samples extracted with the original method are summarized in Table III. Fortification recoveries for the analysis of PFOS in sediment samples by direct injection are summarized in Table IV. The total percent solids for sediment samples are detailed in Table V. 9.0 CONCLUSIONS The sediment samples were successfully extracted and analyzed for PFBS and PFHS according to analytical method V0001782. The sediment samples were successfully extracted and analyzed for PFOS using an alternative method, which yielded acceptable QC data. Exygen Research Page 20 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 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 studydirector. This does not include facility-specific raw data such as instrument or temperature logs.' Exact copies o f all raw data, as well as a signed copy o f the final analytical report and all original facility-specific raw data, will be retained in die Exygen Research archives for the period o f time specified in EPA TSCA Good Laboratory Practice Standards 40 TR 792. Exygen Research Page 21 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 TABLES Exygen Research Page 22 of 110 Interim Report #23 - Analysis of Sediment Sample Exygen Study No.: P0001131 Table L Summary of PFBS, PFHS and PFOS in Sediment Samples &YBnC C0172882 C0172882 Rap COI72883 C0172883 Rap C0172B9A C0172804 Rap CSant SamolaiD DAL-SO-BPPOVMIOOO QAL-St>aPF01-0^000- DAL-SO^PP02^0000 OAL-SD-aPPOZ^MlOOO* DAL-SO-aPPTO-(W00 dm. so n ffio s e jo a r C4 Sulfonate PFBS CSSuNanataPFHS CS SlAonsla PFOS -- -- Found Sp On M M 3.14 3.10 4AZ 4M 9A7 5.73 Accuracy (#-*) 40 40 30 30 X X M |h Fauna (pao.>8W DnrWa-- 84.3 50.1 74J3 64.7 t 123 Aaaaaaad Acaunaey W -*> JO 30 30 JO SO so Ana-- Found <W.noW Dty -- NR NR NR NR NR NR MiaaaU Aaouraoy (**> NR NR NR NR NR NR "UOurakay Owfcadt NR Not wportad dun tBat-- yeanBBli-- IM nw S-- Tbtllhm m iN w u h . Exygen Research Page 23 of llO Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P9001131 Tabie II. Summary of PFOS in Direct Injection Sediment Samples Exygen ID C O t7 2 8 9 2 C0172892 Rep C0172893 C0172893 Rep CO172894 C0172894 Rep Client Sample ID DAL-SD-BPP01-0-0000 DAL-SD-BPP01-0-0000* D A L -S D -B P P 0 2-0 -0 00 0 D A L -S D -B P P 0 2-0 -0 00 0* DAL-SD-BPPOO-O-OOOO D A L -S D -B P P 0 3-0 -0 00 0* Laboratory DjpScate C8 Sulfonate PFOS ~ -Psrtluoreoctsn--uMOnala Analyte Found (ppb.nflfo) Dry WelQht Assessed Accuracy 3560 3520 30 30 4160 3840 11900 12000 30 30 30 30 Exygen Research Page 24 of 110 Interim Report #23 - Analysis of SedimentSamples Exygen Study No.: P0001131 Table HI. Matrix Spike Recovery of PFBS, PFHS and PFOS in Sediment Samples ***** OMMOMOk Amami A rt Pound - Aoteuat * * F * d . AfMurt AM Famd A ura* 8p*w) m Sonado n n o o M mOanvm ftw w u w * tem pi. n u a w d Racotrty (NOtt) in a e) rt 4 ro o * ) * * V (AM lM tW l "ST DAL-OMRPQI'OOQOO (cm m aiopA c^****. QAL BO DPP01-00000 <cnnm m ^ m * * * * * 4 400 ZOO . - 4.47 zoo 202 0 0.1 464 so QAL4M FP01*0000 4000 zoo 2370 07. V , 8100 12 , rrt . HR NR OA|.-6DPMia<04000 **tnaS ph 9,4 0 * 1 M PAI 50 BRRg 00000 *rm m s * m * * M O + pm -o& oo PA10POPPO30.Q000 Cf?9flM lafel.AM *tM OAL<9O-8PP03^00Q0 jOUTR* A J.4-- tRNI QAL-$0-OPP0344000 4 400 4000 4 400 4000 Z41 Z41 A 4 30 4.30 4.30 3.02 00 .. 374 40.3 340 70 3020 SO 4M 6000 120 NR 7.71 33 4040 83 8 - 01.0 121 OU 203 4000 00 11t HR NR tifi NR NR t*w|MMon:i nM --NOW8IMRimal>: 1 ND IHWmariN--lnm!<>>ROCumamB|--mRH) IMkHwWi --wryBillMmi kImimia.n<wi| Rn mm, >NM*tow.H--Rittmmtmm. IniiNwNfAR'tmiNipii:: NNRR Exygen Research Page 25 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 T ablelV , Matrix Sfrike Recovery of PFOS in Direct Injection Sediment Samples S a n p te D aeatodon 0AL-SD-BPPO1-OOOOO teniam a sp aornee Ma *ptm DAL-St>8PP01-04>000 tcetnam a * e.oea m e (p*<i DAL-SO-BW12-0-0000 cat73M9 ifft a. aaae pcbadu) OAL-SD-BPPC2-0-0000 cairatM ak h. aoaaa m e 8p*aj DAL-SD-8PPC3-00000 (CWTM a J. COQPBpara) DAL-80-SPP03-0-0000 tCMTMat1* K.4MM * 6 (Int Amowt 4000 40000 4000 40000 4000 40000 c amfoMti p ro s Watweicht Amt Found in Sairto (noA i)w atw t Amount Recovered (no/M wetwt Recovery (%) 2360 2360 6540 40000 105 94 2260 2260 5960 38000 62 8 5260 5280 8770 41200 87 90 Average: Standard Devhrtkm: 93 8 Sarnpie leeidue m e e d i #>aipMng levd dgnMcandy (3k ^ k in g M ) : Iherafera, an eccurate lecovery value cmnot ba cakulatad ND NMdewrurt 1or tov fia UrnttofOuaneatien (LQQ)orC.2m rt (wet walr*). Note: Siace m e aummaiy tabla ahowa raunded nautto. recevez luaa may varyalgM y feoai (ha value* In tw raw data. Exygen Research Page 26 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Table V. Total Percent Solids in Sediment Samples Exygen IO CO172892 CO172893 C0172894 Sample Deecftotlon DAL-5D-BPP01-00000 DAL-SD-8PP02-0-0000 . DAL-SD-BPP03-0-0000 _. Total Sold (%) 1.54 " 54.37 44.46 Exygen Research Page 27 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 FIGURES Exygen Research Page 28 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 1. Typical Calibration Curve for PFBS in Methanol 04B808F & 4tfiM ntf4t (PFfl$ aU M JP RftfKMlon f t $ yr w e i g h t ! j 4J3*O 04x + -9X 2 (r 0 MOO) Area, couni Exygen Research Page 29 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PQ001131 Figure 2, Non-Extraeted Standards of PFBS in Methanol, 0.2 ng/mL and 0.5 ng/mL Respectively I SSPW6M -flW V * f f * * M tU V M ! Ai m j I W c m t M W ftta S M m N S ( K T t A S W atte Intens*, cps $S0O14SaS.prSS(M4O3MJIMAnu-*aml2taB**fn#W06F*te Ana:20M1 MWH 1.**009 Oft RT:OJSOml* totalst*, eps _ Exygen Research Page 30 of 110 .Interim Report #23 - Analysis of Sediraetat Samples Exygen Study No.:POOO1131 Figure 3. PFBS in Reagent Blank, 0,4 ngfatL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively intensity, cps mtsnslty, cps * M |M t I pHA - PTBS (D Q 2M JM B J) MM s i n , I t tlm OA20OSFMl* Ai m ; 10*7 i r t , H ilf h t '.0erX 33 HI: 0 0 0 7 Mf> 0.08 lU .A U t SpfcS. PFBS COC)2S8jO*8e n n s t n p l , 10 <* 4 *m MSBOSFjm* Am i : 100227 m i k M*IW; 1.11 Q04 m * R T:04S7 .in QOS Intensity, cps Exygen Research Page3l of HO Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID: C0172892, Data Set: 042606F) c m m a - p n a <ih i m ) m m e w -m * lx a m in m m m c * n * HHgtC XT: 1 S m 2800* *** 9V . ---- 1 ~--~~n ^T"~i ~. - - - r - . . V' 8 gr 10 f l 12 13 14 10 10 17 Tima, min Intensify, cpg Exygen Research Page 32 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: POOO1131 Figure 5. Typical Calibration Cuire for PFHS In Methanol omsOSF SadinuAiCk(PFHS>U n i I*R| w li>f i /* y> 70S*4004k4 -1.1x<QS<r 04005) Area, counts Exygen Research Page 33 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 6. No-Extracted Standards of FFHS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively I SSMMSK'AH*(RmMhM93taM*fMW.MWTr45ftMMXMF.mST A n * 72774a--m* MHfth TJSmMtf* 7/ t Intensiv, cp Intens*, cp I i me, n ttQO149O0 - PFM&(SUfuUri3 0 0 0 * 0 0 amu sample 2 * 49 te m O ttM O f M Ama: 3 3 Q eye* Height 1 7 3 * + 0 apt AT: 9 j40 rin *MT^ 1 i * * 7 -r '0 <) 11 12* 12 14 10 1 17 Time, mlo Exygen Research Page 34 of 110 Interim Report #23 - Analysis of Sedirtfent Samples Exygen Study No.: PQOO1131 Figure 7. PFHS in ReagentBlank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively I t m m c sa tn x -P fm pMtMtltelO s Km m m m -j* * * '* H U M T jw m hitensly, cps Intensity, cps A n x2 7 0 7 2 e o a n fe H e ight 1.flB >iO O l cp* R T :O JO iR ii QJO I R **g a Spk B . P fMS (O C )3 0 0 .0 *0 .0 amu - a m p la 10 a t45 fm O ttO O tF . * A ra 270070 aeond HaigM : 1.60a*004ga HT: 0.40 min 1Aa4- SOOOjO M'J---- ^---- --- I* 12 3 ---- ---------- r 4607 Tlroa. m b Intensity, tp s Exygen Research Page 35 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0G01131 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for PFHS (Exygen ID: C0172892, Data Set: 042606F) Atm; n A HUgt 2Zfc*03 AT;%4tm* 0.4* Intensify, cps 1000 1400 000 000 200- 0.42 1 2 0 4 - r 7t o 11 12 1 *4 18 10 17 Time, m * Exygen Research Page 36 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study N.: P00113I Figure 9. Typical Calibration Curve for PFOS InMethanol 8#d- 81 CPFOS^ -U fto ar Ro^rurton 0 * 1 hnoN H 0: y 2.27*004 * + 3.72**003 0 0.0046) Area, counts Exygen Research Page 37 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PD001131 Figure 10, Non-Extracted Standards o f PFOS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively A m ; S W f9 cw A i fk fg t M f u lt t c p t AT: tL 4 m im 11.49 Intensity, cpe Intensity, cps Area: 1222S m n l i H aight 7.72 %*0C2 opt R I: 11.4 Hilft 700 00000- 11.43 Time, mle Exygen Research Page 38 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 11. PFOS in Reagent Blank, 0.4 ng/m t Fortified Reagent Spk A, and 4.0 ng/m t Fortified Reagent Spk B, Respectively m t a c St*corn* HU gtb 2.**f**1cpr XT: ftjm /m ' e --A--m-:--1-0-0r0~0'eenat"o \ww/ ***** O il 000pa ftMT :ii1pli.4 m mia 000 " t*40 400' sS 200 Jil0 10^ I 1204S07SQ 10 Time, min RAare|a--: tOOTfOfci0m-mP$f0 9HQeiQghQt:46B.tOt7M*+O0O034me1*RcTam: 1p1le41m>in 46 font 042006 11 14 10 10 Exygen Research Page 39 of 110 Interim Report #23 -A nalysis of Sediment Samples Exygen Study No.: P0001131 Figure 12. Chromatogram Representing a Sediment Sample Analyzed for PFOS (Exygen ID: C0172892, Data Set:042806B) n**som um itwm A n a l SOT c m * flh*te-C M fr4M 2qpc XT: tiS m J r Exygen Research Page 40 of 110 p. 40 Interim Report #23-Analysis of Sediment Samples Exygen Study No.: P000113I APPENDIX A Study Protocol P0001131 (Exygen Study No. P0001131) with Analytical Methods and Protocol Amendments Exygen Research Page 41 of 110 p. 41 Interim Report #23 - Analysis of Sediment Samples .Exygen Study No.: P0001131 BxTim P re m o n ta te : POMI 13) STUDY PROTOCOL Study Title: Anajytb of Perfluorobutanaolfoaetc (PFBS), Perflnorohexaneaulfonate (PFHS), and Perfluorooctaoesnlfoiiate (PFOS) in Water, Soil, Sediment, Fish, Clam*, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program Exygen Protocol Number: P0001131 ExygnKMHRk 3058 Rem arci Drive State C ollege, PA 16801 Phone: (814) Z72-1039 M irtiael A . Sentono D irector o f R egulatory A ila in 3M B uildiiig 0236-01-B-10 S t Paul, MN 55144 Phone: (651) 733-6374 Pagr Ioj 6) Exygen Research Page 42 of 110 p. 42 Interim Report #23-Analysis of SediineBt Samples ` Exygen Study No.iPGOOl 131 Exytts PttftocoiNraofccr MOO! 131 DISTRIBUTION: 1) Jtinmho K atri, StudyDirector, Watoo Sotatioas 2) John M-Flataty, Principalbvntifttor, ExyjenResearch 3) Mirtwrl A. S atta o, Spom w Representative, 3M Company 4) ExypcnRcotHcb Quality Aoutanu Uat a . t P * tt2 a fi> Exygen Research Page 43 of 110 p. 43 Interra Report #23 -Analysis of Sediment Suuplcs \ Hxygen Study No.; P0001131 E*yico Protocol N arnberooom I PROTOCOL APPROVAL Study TMk A nlyni oOtefiotKobulanNultaate (PFBS), PaftwahauMMuIfeoue (PFHS),odPgatoroocfiwalfcnir (FTPS) in W wr, Soil, Swlimau. Pafa. C lw , Vipm inr. Sta*UMammal L m o wd Snail Manana! Sown IMngLC/MS/MS fcr U3MDecana MoonoringProgram Ejtygoc Protocol Number: P0001131 . .. . APPROV fa ip ir jj W eatoc Solution* Michael A 3M SpotMorRcpraeoucve Date & -acr-ta?t Date Q aettty A w n o c e U bK Poft}<J6S Exygen Research Page44oflI0 Interim Report #23 - Analysis of Sediment Sairtplcs Exygen Study No.: P0001131 fix y m Protocol Nunbtr PQ00U3I TABLE OF CONTENTS title pa g e _______ ;-- wsnuBLmoN_______ ------ --------- -------------------------2 PROTOCOL APPROVALTM TABLE O f CONTEXTS___ in t r o d u c t io n _________ TESTMATERIALS____________ O B JB C n V l___________________ TB87INO FACILITY__________ STUDY DIRSCTOK____________ SPONSOR ABHU8SNTATTVBTM ..-5 . ,5 ...6 ....6 ____7 --7 nUNdPAL INVESTIGATOR__ ,, -7 PROPOSED EXPERIMENTAL START ANDTERMMA1ICN DATES____________________ ._T IDENTIFICATION AND JUTOPtCATIONOFTHETB3T SYSTEM________ '!............ - ........... ........ SAMPLEPROCUREMENT, M O T T AND RETENTION................................................ ... SAMPLEIDENTIFICATION_____________________________________________________ . .9 ANALYTICALPROCEDURE 8UMMARY___________________________________ VERIFICATION OP ANALYTICAL PROCEDURE__________ METHOD FORCONTROL OPBIAS. STATISTICAL METHODS________ OLP STATEMENT______________ REPORT_____________. ________ SAFETY AND HEALTH______________________ AMENDMENTS TO PROTOCOL_______________ DATA RECORDKEEPING____________________ QUALITYASSURANCE_______ ___________ _ RETENTIONOPDATA AND ARCHIVING __ APPENDIX L ANALYTICAL METHODE_________ .It .11 .11 12 .13 .13 .14 . 14 IS hut 4ofa Exygen Research Page 45 of 110 Interim Report #23 - Analysis of Sediment Samples , Exygen Study No.: P0001131 Exyfm Protocol Nuntor POM113I INTRODUCTION The pwpoao o f flu* rindy i i to perform malyii fcr pcrflucrobuUnCTulfontte (PFBS), perfluorohexaranlfoiiate (PFHS) and periluorooctaneaulfonate (?FOS) in water, oil, aednaettt, fUb. claim, vegBUtion, rmaU nrnnmaJ liven and aaull national aeram Bring LGWS/MS for lbs 1M Decatur Monitoring P ro g ta n . The Bgy w ill be anditod for compliance w ilt EPA TSCA Oood Laboratory Practice Standarda 40 CPK 792 by the Duality Alamance Unit o f Exyien B anach. The teat material are parfluorabutanawlfimate (PFBS), petOuomhrotanrtnlfeitate (W HS) and petflnoiooetamauUbnat (PFOS) and ataalliig>pIicdby3M . PVB8 Chentcal Name: Pgfluoroboteatw lfem tc Molecular Weight: 338 aoppiied as tbe pocauiam ink (CrFeSOjK*) Lot Number. 101 Parity: 96.7% Tranailknu Monitored: 299 - 9 9 Structure: .F PPHS ' 438M olecalartaigh t: appliedaathepotaarium a a lt(C e F n S O jlO 6LotNbmber: 0 3 6 Parity: . % TramitioniMiaateroci: 399- 80 S tru ein re Pageleft! Exygen Research Page 46 of 110 p. 46 Interim Report #23 - Analysis ofSediment Samples ExygenStudy No.: P0001131 Exjfm P ro te c t Number; POOOi 131 PFOS C tanicai Name: FerfluorooctaneeaUbade MolacoJar Weight: 531 wppbed m the potassium n it (CsFirSOVlO LotNtanberr 21? -- Parity: 86.9% \ '*- " ' r'- Tnmritteai ia a aitored.- 4 9 9 - dutMUTK ' - OBJECTIVE The pmpoac ofAnt tody is to perfora mistyiii fbr perihiorabutBemHbiuto (Pf'bS), patflnoeobaxanasatfooate (FFHS) ad psruarooctanesiUfbaeiQ [PFOS) in wim, soil, mdinunt, dab, d w a w p ta iia small n-- m i liven ndn mammal ara* for e 3M Decatur Mentoring FRwim using the aonaa vtrsiaoa ofthe bfiowinf Exysi inilytics] method: V000I780: "Method of Analyst Ibr tbei Detamanotion of Poflnoraocuooic Add <FFOA)ia Wafer by LCMS/MS~ V00017I1: "M ated ofAnalysis (br tiie Dotendoatuxi of Perfluonxxunaic Add <PFOA)ia Sofl by LOM&MS" VOOOI782: "M eted ofAnalyst ftr the Ddenmnadco of Perfloorooctmoic Add<PFQA) ia Sadfanaatby IXM BfU T V0001783: I M a d of Analyaia ftr tha DetsaminatK ofPeriluoiooctanoic Add (FPQA) ia Fiahaid Clanis by IC tU SM F V0001784: 1 M U of Aaaty ftr tba Detenakatian ofPadluonoctanoic Add (PFQA) ia Vsgatation by LC/M5/MS" V00017S5: "Mdhod of Analyns ftr the Datmmiaatinn affo th o B W iewf Add (PfOA) is Santi MammalLiver by LC/MS/MS" V00017W: "M ated ofAnatyda fecteP atfeatiaation of Perihorooetanoic Add (HFOA)ia Small Manaad S e a t by LC/MS/MS" TESTING FACILITY Bxyfaa Kaaeaicb 1038 Pcaearch Drive r--- Stata CoUagst PA 16101 Phone: (814) 272-1039 ' Pa$etfc / Exygen Research Page 47 of 110 p. 47 in te rim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 B xypa PtMMOlNvnbcr. P0001131 STUDY DIRECTOR Jainaba Kenn PK-. DEE W etfan Solution!. Inc. 1400 Wernen Wy WeetCharter, PA 19310 Phooe: (610) 701-3761 Ftx: (610)701-7401 j.l[W i@ W t8THnlUtiOTH CBW SPONSOR REPRESENTATIVE Michael A. Sanoro 3M Company Director ofRegeiatory A fter* 3M Building 0236-01-B-l0 S t Pul,MN 53144 Phene: (661) 733-6374 PRINCIPAL INVESTIGATOR JotanM. Flaherty FxygenReeowch 3031 Remerch Drive Stete College, PA 16001 Phene: (814) 272-1039 jotm.fldierty@eKytBBXom . . PROPOSED EXFH&BHENTAL START A i TERMINATION DATES tt it h u m b I that Ihr analytical partisn o f On* Italy be conducted from October 01,2004 te December 31,2005, The duel experiment! nan and taonaatioB dam te taeM e4 fe tte ftml mport Pag*7qf6S Exygen Research Page 48 of 110 p. 48 Interim Report # 2 3 - Analysis of Sediment Samples Exygen Study No.: P&001131 BqrgnTiaoM l Nenten M001I31 IDBNTIFICAnOPfAPS)JUSTIFICATIONOFTHETEST SYSTEM The following m the test systems lor tin* study: Water (greandwater and m rfee water) Soil ' . Sediment PWi . C tn a Vegetation S a id Mammal Liver Small Mammal $m ns rae u m p itt wul be collected by wwtoQ Solution. Tba control samples wilt be p n rc W i and prepared by the [rating Aw&ty. Pmchasc and processing deoils far the eontrol samples w ia.be inetndod ip ibe final report with tbia Mady. The te a aynana went choeai to access the environmental impact o f PFBS PFHSaodPPOS in the Decatur, Alabama are*. SAMPLEPROCUREMENT, RECEIPTANDRETENTION Water, soil, sediment, fish, clam, vegetation, small -- i liver and small f " " *1 ^ g m o n p fc wifi be reestvod a t Exygen directly fio n Weston Sobhods. TbedeO flsofaainptepTocuraD eD tftrthaitady are outlined in tbe 3M woe* plan entitled "Phase 2 W edt Plan f ir Sampling Environmental M od Toe uUmber etd Opes o f aatnplea collected 'w ill very dcpoxluijf variability in 1bc field. The total nembar o f samples received and analyzed B reech " eorbt wiB be donm em td in the fiael report saaocuced with diii Water, eofl, and awHment mmplaa will be aaed es received without farther praew rtqcE xygen. Thcoe snplm win he stared refrigerated at 2*C-S*CFuh. clam , vegetation and small msmmal aver ramptes wifl bn processed aceontta* to the eppropriata analytical m hod (aee Appendix I). These " W h s will be stored t o m at t "10*C. s --*]> w m w , | whole blood ennpl* will bacw tiriiiged in the fidd at the tim e of collection and the lentm fiaetiaa wiU be used fa- the study. Small mammal scram will be swsed fiomsi st s -UPC. lb * receipt sod |n nrseeing o f the samples will be doemnented in the final report and rawdata asaocsstad with the study. \ flsfr S e fb S Exygen Research Page 49 of 110 p. 49 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 SAMPLE IDENTIFICATION E x y p s Protocol N n o tm : POOCI13I Prior to w uiysu, each sample w ill be uaigned laboratory sample reference number. The reference number will be unique and rill distinguish each labotatory sample that is processed throughout the analytical procedure. Cbrotnstographic data will b t identified by the laboratory sample reference number. Svnple storage eondhuos sod locatjou* will be documented throughout the study. ANALYTICAL p r o c e d u r e su m m a r y Returner. . VOGO17*0; "Method o f Aaalyais fcr the D etammatiop o f Pcrfiacrooctanoic Acid (PPOA) in W ater by LC/MS/ViS" V0001781: "Method o f Analysis fat the Detenninatioa o f Perfluorooctanoic Acid (PFOA) in Soil by LCMS/MS" V000I7S2: "Method of Analyiia for the Diernnination o f Perfluorooctanoic A dd (PFOA)in ScrSment by LOMS/MS* V00017S3: "Method of Analyeii fcr * e Deienmnation of Perfluorooctanoic Acid (PFOA) in Fish and Clam* by LC/MS/MS" V00017M: "Method of Analyaa Jbr the Detenrdiiatioa o f Perfluorooctanoic A dd (PFOA) in Vegetation by LGMS/MS" V0001785: `M ethod o f Analysis for (be Detenmastiop of Perfluorooctanoic A dd (PFOA) in Small Mammal Liver by LC/MS/MS" V00017*6: "Method o i Analyais 6 * the Determinatipn o f PerfluoroocUnox: A dd (WOA) in Small M anaaai.Senun by LC/MS/MS" The sh o rt meftaxle os analytical condition capable of separating the isesnen o f PFBS, PFHS and PFOS. The Anal report arili include (be isomen sosnmed into total PFBS, tool PFHS, end total PFS found. VEROTCATKINGF ANALYTICAL PROCEDUTO A labentocy to ta l sample will be used fcr the p n p e n tn n o f fortified eesttrol ample*. The tad balance will b e made to o solutions ss per tbe method, and added to the m eatiees via a R dcropipene. For welar ssmpHnfc &tygon will supply one boule per sample collected. The s'* b o ttte will be 500 a L pseeleened SeUSpec Prenier wide mouth HOPE botdon Them bottles have b e roatincly used for fluorochan ical sample Ptttiofii Exygen Research Page 50 of 110 Interim Report #23 - Analysis of SedimentSamples Exygen Study No.:- P0001131 E x Protocol N umber iOOOl I31 collection at fee tearing facility n d heve>ec row s to be free o f PFBS. PFHS andPFOS. Sampleewill be added to each container to volumetric fill tine at 200 mL. A field dapUcaleb * low field pike end e high field spike o f eacb aaople will be collected. The low and high field spike bottle will contain PFBS, VPHS end PPd8 ee w tflei perfhratnoctonoie ecid (PFOA) tod U -I3 C pcdbarodctaoott.aeid ('*C I*OAX PFOA eod 1JC PFOA are included to the aohrtionc ueed to pike,the ample*. th e retu lu (br PFOA end **C PFOA w ill net be raportod in this stndy. Exygen w ill eepply one field bleok (eonttoi wetor) end two field Weak y ik ee (contra) w ater fortified with PFBS, PFHS-end PPOS at.a low m d high ta d ) te -'every twenty samples collected. At the toeriag freifity, each water tem ple (enctodhrg field dapficeiee and field spikes) will be extracted ht digiWiwte eod w ill also be Unfilled at a leer end h i0 i ccncentreaon with PFBS. FFHS and PFOS and procaned through 8i described proowtar* tedeteenaie method accuracy and to cheek tor Mas. For toff, sediment, clams, and vegetation, Bxygeo anil supply one $00 mL preeJenaed Se#Spee Premier wide mouth HOPE bottle par a m p le collected or adp-acnlbag. All eoataacalbcgs need f c sample collection win be shipped to ihe am p le location. Samplce wilt be added to each container or bag in (be field. At the tearing freiSty, neb sunpte will be extracted in duplicate and will afro be fortified at a known coaceutradoe with 7RS&, PFHS end PFOS at ,#* both low end high level'and peoceeecd through the dcecribed procedure to (brCBrnme method ecenrecy end cdcheck fat bim. For meaB^mmtinai liver, Exygen win apply a SO mL polypropylene certrUbgetube. Fm nnaUmmtonateeiuni, Exygen will ngrply a collection kit ibr each sample omnajnrng eeram t epnratcc tnbee (red top), vacutaioers, M rik h o ld n i r i ftyxflst. m d polypfopylntt tube. At the teeing facility, each UVwand aenam sample will be extracted in riiyCjr/- snd wiU abo be ftitified at a known concantrabon with PFBS, FFHS and PFOS at both a low and high level and processed throoghltie described proccdnrc to detoriniDe method acccroeyaodto.eheck Ac bias. Low and high m iking levels for each aietnx are defined below: M taix Low Sotttoa Level H ta SoHon Level Water SOOrtfL 5000ta L Safi SadtiMnft A tari dO nifi 40 ruuV Fbfc CUene IH rti ^ ld W i lOOnfrg 100nc/ft VeerleHm Smell Mammal Liver tag M>_q^g lOOngfg lOOngfs Small MammalScram lOonhnL 100 ngfmL PftlOtfSS Exygen Research Page 51 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exypa Proacoi M i r 0 0 1 31 Reccvtrief are anticipated to be between TOH end 130% o f the fortified level* however, tba n e t p n d sio a end aocuncv ill be determined by the n u ty u o f the quality ooitro) u n i t e described above. A Malement of accuracy will be included m the foul report. METHOD FOR CONTROL OF MAS Control o f trial will be addranted by taking reprsentative aub-aaraplea from e homogeneous m ixtuie o f cacti matrix ftont untreated ooctrol samples, and by analyzing at kaat two torch o f (ortlfleadaw. STATISTICAL METBQIK3 Sttiacict win be boiled to tbaae specified in the wbrject methods and to the calralabon o f average recoveries, ae applicable. GLF STATEMENT All aspects o f this study shall be perfbaned and reported in eorapbance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The final roport or data package (auppbod to the Spooeor) A ab contain a ttalemem that die to d y was eondneted in eompHnw w in cunetn and applicable GLP standards and w ill oadma any deviations in the ftudy from those atandarda. This statement will be signed by the Shady Director end Sponsor R epneentatjva . RETORT A final report wflt be prapared by das principtl b tv en ip to r or ibeir designee at the coacinaioo o f tbe srdy. Tbc rvport will tucludc, hut will not be limited Io, tbe fbUuwing: e The Tarne and aridresa o f tbe Str-dy Diractor, Spccaor Reprcseximive. and o f tbe tasdag hehy. A laleearar o f GLP eompbanco (any related doeuannetation, weil as ebsm-of-oustody rococds, nuaat be in tbe ftndy reoord*). P *gw llefi) Exygen Research Page 52 of 110 p. 52 Interim Report #23 - Analysis of Sediment Samples ; Exygea Study No.: P0001131 E x n ProtocolM a ter. POOOU31 The aigned end diced temmert by the Exygea Reeeeich Quality Aeemanoa U n t m gariihg d a te o f M dy Mepccricrw and date* finding were reported to the Study D uceterand Mtoagemeet. A deacriptiea o f the exact m ly tical conditioae employed io the etudy. If the rubjecl method was fbOtnrad exactly, it ia aeeaaaeay to include only a copy o f die n a ly tiett method. Any tedM earioac to dad n o te d will be in coipetated ate t e report I f the m ete d it photo-reduced, the project number end page number m m be inehided on eachpage. e ' Doattlptuaiofthoinetninicntelion aeodandoperatingoonditiono. All teeatta io m all eeta enaijtmd. Central and fortified m aple* w ill be M uffled and the data table wM fadude eeepple naqher and fortification levaL Repeeneoadve c h n an a t^ n n e fcr eaeh analyte in each matrix, meluding chrotnatogroru o f a etoidard and a control (am ple, tod a chroincropim at a ftrttScadoo level The location o f the anaiyte peak* will be clearly wi fWd wM M te p m AB cimanatxnoea that may have ffbrunri the quality or integrity o f the data trill he documented ia te ie p o e t . . Loceeione where raw data end the final repent a n to be archived. mam AiMitxaa or m inrtiae to die i a l n p n t th all be in the tana o f an ' them* a tp a d by tha Stady Director- The i ntendment ehaB clearly identify that part o f the teport that ia being abend end the rcaaone for the a ta atio n t. The emanibnml will be eifsed and dated by (he Study Dunctorand A e Speneer Reproacntehvc. All epplicaMc laqnnemonri for lepm tini o f nudy r e n te p e r 40 CFR 792.15. SAFETY A N HEALTH e - Laboraaaypm nnael w aipcaottegaodaptelon and heahfa habit. Bvery reaaonable pracaatien t e l l be tahoi to paevaat inadvertent enpoauea o f pmeoaatel. ap d .t e environment ?o the teat or reference snbiQtaGfe(#X ' 1 1' Exygen Research Page 53 of 110 p. 53 Interim Report #23 -A nalysis of Sediment Samples . Exygen Study No.; P0001131 Extiki Fratte*! Number 0001131 AMENDMENTS TO PROTOCOL Alt tigpMeam chugs* to die (mtlytical protocol outlined here will be expreued in writing. signed and dated by the Study Director u d Sponsor Representative. Amendments oaualiy will be tuad prior to initiation of study phut ch u g s. However, when a dung* is requited w ithnutsufficim t tune for the sens o f a written amendment, that change may be effected verbally with supporting documentation .signed apd dated by die Study Director aad followed with a written amwrfmont a t aoan at ppciible. In tb it case, the effective date of the written amendment w ill be the dpte o f the documented change. Copica o f the agned neadmenb will be jpended to all dinributed etndy plan copeae. The original amendment will be maintained with the original atndy phut; Any deviation froradte study plan or from tire analytical method provided win be dnm mm nrl and reported promptly to the Sponior Representative. DATA RECORD KEEPING Record to be msmftincd include the following (aa appropriate): Sample tracking shmt(i} .. Sample receipt record* stooge hiitary, and chains o fcustody Hiitary m d preparation o fstu d u d a (Hock, fortificiinoo, calibration) Deacriptica o fm y modification to the mathod ' InH iu riw run sheets, bscch-shecta or ioga A natrim i trita tablet AO dwtmunogtaphic md mMnunental conditimi* Sam ple at traction and a a ly a it d a t a A complete lilting of atndy pom m el, aignahnea and irridali Chronological pr aaenrstion of all atudy conrepondancn Any other documentinoli neeeaury for the reconatmetion o f the atudy Chromatograms- All chromatogram will oontain the following: Sample idcnUfloation, itgeedan date, m ow or other indication o f the area ofinteri, e id Injection number eetreapending to the nm. AihHttramlly, fortification wtR includa the amount o f analyte added u d the sample number o fthe ample that war fortified. Analytic alandaid clauiuatograma win additionally include the uuncanlrstioo (e.g_ pgfmL). Pvttitfii Exygen Research Page 54 of 110 Interim Report #23 - Analysis of Sediment Samples Exygcn Study No.: P0001131 Exynea Protocol Ntaabcr: POOOU31 A span of t o docniiMotJtion die following sheets wiH bo included in each M lytkal act a ran sheet listing the nm piet to b e n in m th e e t, id * n ia n n n e u t cccdfcioos m eet describing the inurnment type end operating QUALITY ASSURANCE , 'n * Q A Unit OfB W n B w r th w ill'Inspect the toady 1 m tfn a h to uaura compliance with GLP's. end wffl report1the findings o f sudits to the Stndy Director. focygaa Management, tail the Sponsor Representative. RETENTION OP BATA AND ARCHIVING AUh a r d copy taw data, incladatg. bat not tunned to, the original chm uloyaaaa, worksheets, correspondence, and results shall be included with the data package submitted to fee Study Director. These will be archived with the original Body plan, mwedmem, final report, nod all pertinent iniortnatica from the Spoaeor. T)ie tetomg facility shall hasp all d sctraiic raw data and any instrument, aqupnMB, and Borage lege fbr tha period o r tim e specified in 40 CFR 792.193, An a u ct copy o f die m anaisls aobmitted to die study director will also be kept at Egtygen R e h e a t* . ' Baygen will obtain permiHian from the atedy director before discarding or returning sxmplea. '- Exygcn Research PateHof41 Page 55 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: POOO1131 1BqriuPnMomlNBiab: POOOIU APPENDIX I ANALYTICAL METHODS VOOO1780; -M*iod of A m lyw fcr the D eternanaion o f Perfljoroocnoic A dd (PFOA) a W aterby LC/MS/MS" VD0017SI: `'M ethodofA m lyii* Jbr (be Octennuialtoa ofPerfluoroocUnaic A dd (PFOA) in Soil by LC/MS/MS" V00017S2; "Mr&od o f An*lyiii far flie Dslenm njtion o f PsrfluoroocUnoic Acid (?TOA) in Sodbnent by LC/MSA1S" V0001783; "M tdiod o f A ndydt for the Petcxm tnuinn o f Pcrffoorooctino<c A dd (PFOA) in Puh and C l*ra by LC/MS/MS" V00017M: "M dhod of A oaiydt fcr Ac D dem nation o f Perfhiawooctanok A dd (P?OA) in VegeUlioc by LC/MS/MS" VWQ17S5: "Mefliod of Aalyi for the Dotom inatioc o f Perftporooctn>oic A dd (PFOA) in S cull Muwnai U totby LOMS/MS" V0001716: "M dbodof A n d y * bribeD ctonm aationofFerflam ooctuoic A dd (PFOA) in Small Mammal S a n a by LC/MS/MS" Exygen Research rt& IS c fii Page 56 of 110 Interim Report # 2 1 - Analysis of Sediment Samples Exygen Study No.: P0001131 E x r s n Protocol N u n b er POOOM)) M ul IM ANALYTICAL METHOD Ult>lwrtn: VQM17M JUM(WOA)PWir N H b w tlln Sm CUm FMMM TPlac*MKcfaclmia%iyhC' rCJ4A0,nk1.ip-: *<*** TMFipc 7 Exygen Research Page 57 of 110 Intcrim Rtport #23 - Analysis of Sedimcat Samples Exygen Study No.: P0001131 Exygao Protocol Nmbcx: PQ001I3I IqvahHM* IM M IM vV M I* i AfutyncALMiTwoo \ tfckoirfAffrkfem&wiwfcaorfyigi--tbbpi--kAciJOFOA)W-->y IJ S* IVc m M Ii to p v to ja i to * M d n m* I w i of jHftttaocaoofe U to Ejl M h m U p tf CtaMMPpavto * canto* M m fp iilw w irii It mm. is> U*t 13 Atot)<townedfcttoamwyfimkm. 12 CoMrtilNpFNpitekaDSMbiilMdfetisydMrtctlferpraNi taftry A C 1 t a p * Onto I t AHiw--nMi rp*ttoft4*iivnitloMIp1ttr1i1iMtHmiWvlWtkOUsMtMpIIMkII(lcDIpfltrMofpcMtoWtoftpaeTebpfhtask#*st-o02 12 Atok MtoirrMrtoktorjiali <n*pnton m i p*il*riiii U9.4 9 * l 9 N t o lljllll ifw H nnto i a f taMOOOl $. a to 'to ia te 19 15 i l jj , Tl^wpli (IT) Hflrf. 1W-WgT } 57 O M .U 9 Im h m I M l M 2ri.k*V bC iW tt. fV ttpattntototot 1J1Ji toMapiipWniMiflOtVtoMtOiONPOpla^iOlPI-fHflOwiivUUtoptoiiliritolitoa. y^.5r* P **J7 4 ** Exygen Research Page 58 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 E x y p a h o u c o i M o t o r MOOIIJ1 I . 1'............. ............. jtoU.niUM .M lTNOD GMVMS r*5raFB5STJ iMMOOip 41 PlnpknfQbjlmm l*aMkX3.11 (M kfinM ttllt) 4142 mTm3Trr>m(MAF>C: 1K >--r*hnttmmhW** 44 m w iw w i ; m m 4 N2QM12JJJ4 m %a U<JM4J1s uI77S55 nMm40000044444MlmI 44M74 ^ te V ik n ; ]*l.UhirniiHpi-- Bm TIBK B a M K aagr to t i m f i m oriv 7.i imii iniiT O M iprrririrfiiinr r r -r --f " . ^!>tobtol*-i1t1oWmiym- ktm m m g to to mtj M ihi |i ii to .I t I t o J >y to n IX t o l Exygen Research P o ftH o f* i Page 59 of 110 Interim Report #23 - Analysis of Sediment Samples. Exygen Study No.: P0001131 f e y p a Pnancei N n t a n P0001131 AiutyriSn o fT rtin ru i \*AM(PIOA}*Wmrky SllJ.Mltfv9iIiw+Mmttamltfi*MwiM*kM*MaItm-m9imi*T90A*t'memt lQg fr!3 ALllOe*eMliMgMmis.ftUamtSifmeltlflifMkiUMrtbMeM*.iffaffdOmAMiBmy'lwfamtffeCrAtriaM W * 'ALT" 1U t^aAAlLl-USoU1JfSUOiiipapmaLUaa1LLtt0H0m>M^MflcUlLMi.kaufltolHomM.lnai ra>a*lm0<oaafmaWdiOOnooAAhtaca>aMfo>iWronffyIa1Qio0n0f<ob>*ny>i*rtrb--ainamnnko~#aM>na-l1i0n f l j iAMl pupbd.h^iiH*Uinrim irtoHa afTTOA a pupait by Omaai . 1!A pantcoaMaalLMakoUkrfa*|lMrol4iMAat]aal Uan<0nmaIiaLtatMMma oakiatin>a a > fi*A n iiaaakol aaoBn|O a of aaof!iff<h loo aw aaMaotro.i Sl3" StoringCriftMlMifofeNtaM *11 to HTUC T* 111 ouy br ic 3a Si a tCi yraatow-i "Tow at ____ 1SS!_____ -fllll Iti 11 oaM aada M ioop d Oomf o0alaooxumacMtioUa<iSPC> Exygen Research fa ft W a fts Page60ofll0 Interim Report #23 --Analysis of SedimertfSamples fexygen Study No.: P0001131 Bxypa Fatocot Nwrtb*r F0001131 I . . AKUiVWCALMTroC ~ m - ua M M # {`R 'MtWilCS ' MM? a">Mi*oa M (M M U M M 10 W* a d q Q m wit h* ^ enfiwl 1U MC rtonHMd%n UyJCKm.mCiHwKr Ci lmi mlQ(-2* w iM 0a t la MmLmm ta r- k*m7d l1iUd ItatovM-SBLKWftMiMMl. CMm3Dta*^fJMitiaOa>iOlOitaied UaL M taanfla* a tttp ak a (fad fa 5* 14. UJ / 1iiiliiTgw ylC ft<H & - Kd Q M N f^T ` 134 113 134 IMpItMMtltt m i feUo U 13d A u rJtfc/tt Exygen Research Page 61 of 110 Interim Report #23 -Analysis o f Sediment Samples Exygen Study No.: POOO1131 Exypea Protocol Number: P0001131 m um i------------------ saasH Esnaiw " . . . l tcaoM US 10 111 QNNMpMiiivi|Nltfi*a|kiarMM NaipMi i f 41) n ll4M pM O Tpift*taaPfO AiM .M fci'dk< ( -- ) WJWI-- 4 1--MfawboliflKHa- US IIMMlMMlMFfOAaMiv*r4**^q- If* I t a M ta l*OA tontapm * t a ta * t a b ta mpfe IU ta w t a c T t a l i b i l i k t a -- fc ita lw a H W W 114 A* t a t a M ta t a i ! i MMtai t a * Ijr ta| B t a r It* a ir l u t a t a be * tr ita ta *f Mt c " ' rW m u rf Uhm I mOflHMd 3M te Mil a k v of i be Ik *an4iM%bttaam*tatatetataamgWMtaMtHatrail! airiristatali ICC Crinita *1 fW QAtari ln*L MUMIaU ... .......................................................................... Exygen Research Pcfcifofes Page 62 of 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exrt*Protocol Nuober POOO1131 iA | |a M . MMNalM*VMII7I0 | mvmmmin^niini,fiL Acjgydvjowa#ry . LO M iaa 144 1% w d k feriflai vtfc Im m i m a m * ofTPQA prior m e* m . a u iMWwi j CW)* rim w w Exygen Research HfUttfU Page 63 of 110 Interim Report #23 - Analysis of Sediment Sandies Exygen Study No.: P0001131 Bxyftfl PcDttcai N um ber WOO) 13! ANALYTICAL:MV9E0T0H1HO)D ***)T*** LCMMI lapetMc M N M tM n *m Q dk*.fA 14! AwweeMr. "~1^f-t---^l C J^ i.l TwMiw)iMm,L04IA fcqpe Itmm ****** tSm .jM M hr 1 Exygen Research Page 64 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study-No.: P0001131 Ex^ornM ocalNnlwr P400U3I |1 "p~-^QBSiEArSkTBDa> 1J -mihM k*to<*>*at*ii i l t a H W H Urid a I n n i in ' r ----- r ------ * T -- * ro amr u Atoomtai M Otmktmi mmXWfcwdloft--yrhwmiml I VUUI >111101)ftOf*** H AX ii p ta fe r MB 4.1 U44J.4 11 -KCXi MuOjmCMapCMMO* .origoeMft > 2 )M.? 20tdBLBiMtCBMO oMiMfit(M.MMMi,LlOO-MM.). MO IO.UOnH.1*liU*llH. VII W H fllk lla ( l|lC U M in M |l. via " " norJar* P9&24&6S Exygen Research Page65ofll0 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 E x y g n P lo tte d N m k e r POOOt 13] Aku,YnCALMgmOB | 90 wiLpatjfWfyttt* tab ai SKMtfm. 3.)HBX90BL> 11 a * w *A 1A M 09 J9 W tA * 0 J M 29 J9 0 J 2U> IS 75 0. 2 U U OJ U fc#m iw V *ew IJjiMMa t o t e m s * * a K*50kU u talM t-aU QmmM mb Own k m - i t i I * w itte *" mmatymm 7.1' mm 9k ill materii**13 IlMm m flltes w ttetorfm **4* aoia n 0tote* m *r ) .u n iibMMftafeLitferfc Exygen Research rat*nfv Page 6 6 of 110 Interim Report #23 - Analysis o f Sediment Samples fixygen Study No.: P6001131 Bxyfca Protocol Ntonber PD00U31 |T*' ' rtfailjMrtoitolrtowNriirfrun--rtt^nr^ ^ r VQDM7II I ^^ *0 ImbMPi III mt(imafoMlOOi tMa fptouLritryf)IPOdAdbktjarwIjQMOnL10with il-a I2SaL LDPefeott*. >13 aAA1.ofmtofrarJi.0A0ai*HlltaotLoiaakualtratwto aAfWnaOl *Aa*a;awtnaoaoayUafa >11 . i toituoL iM IM i. >1J afWOAto0aarMa)iana|B'>1.> * LaftoaMpfitaLtofeAaatoalaalvaJtoaaanoOwiihianiaaai >n 0.M ABU |IBt * iH iUaa kW i fHOA t^ n d ay b n ^ tg ia aaLlVafarnAt UU^naMLMAtolaa a tm aaitoaaaf100M m m * I U A M I aW .taA I aA aa toA naaflT O A a iiaada y jn n * i > 10 a t a f to ft) n M . a M a a to a Had ataaa o f 100 a ib M a a a lfc a ttta rf.L D n to a to & u TaitookaotoaHiatootoM UHaniakatotoaOtoantiitoator tototoO-- *tK aitoMatora Mariana ytotaOaf6 tooHta AaaitoOtoaa<oi|-- ! 1 933 UaMtoaatoaa^fWatotofia XC* P^r&vftS Exygen Research Page 67 of 110 interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Extern Prencslltgasbac MOOt 131 . ' *13 a m d m m tti H M n ( p WmMOM L feijaA iai * k li Atl'tCawliafMCttoVtaVpwtMO--Mwtal.tai--tifm15mhmLtpatamyyjrkatpt)ntmmWndMu IM IM MfcM i ofwM* m ai (t)*aafey30 Im) m IsM i taw MMa MM tan MMMMtaw0tat WBMl * 'wfy M M M W R ftrifttfeN tOJ l ^ ta M k t a W y M T M M t a ta v i ta e i li W p u N I IJ W ta l| fM M ta p 5 9 C y ta ) n w ita w iin s ita M f r r i f r tZIUJ TAtawi 4tai frMt i tuaM ital iwt anttoaafacwMfiM> iM l iint aiat atai Wta-iUtawr-wU awis.m m . I M ta f tar M v ta 40 a t itata natal ta t e L >otmr>Wn IIJ Cattarte-MMw-SO*. IM MW m Oa byi sSeCLttelH PwlCe tiawpei^(a1t1aw1MLI).SDy ryeaeaUoteaite1e0M1omrnwdtraynta JLT U ta M ta* *anpta w dta m t f M Cm S H c m l p Otawr IIJ lii BanwdyyMwiiftpfaci-pwSsw)LM ntiOiQfCM%rarttfwattpaawtayLbLwCCf/MfMlsWta35*.moiiw*StttatUwu <* pad* 110-CtaMT&fJTjgr ' l i LStOataHitMaraA taAtimtatkaaMatatads,toaptapiha matapMosaMteatpapiMo wowo ttaa*t M taitam a w toteM ta MM*r yMftiteftw tat ta s tat ta of s TiSTin PttftVofi Exygen Research Page 6 8 of 110 Interim Report #23 - Analysis of Sediment Semples Exygen Study N.: P001131 B x y p a Protocol N nnbcr: P0001131 telaImite . MaMNnteVnn^i e ........... luLrncAirdhraoo 1 . __ __ _____LOMate I aap te ti IM (to M M ftftr* ta n te fM M * l . . itetetenntenfcj-- tetta ten te Ite tear t n t o ti t e a n - U l Uh IH -r m M m r m fer ' a r t u t a . U h* m M o t h w t f e l l U ferfe.m*feti ri^p I lii n llllf laH *gfe*n fp*n i . 1U feH*fe *HW fea*r a l a n ^ a * M mtmmm. Aar ob*Hi Ha -- -- * -- *< HP-- H--MU frife* iIIhhiI M i ti ril i * . tergmternian.f.tptteetete4tttietweMep*wa|f--iaMtteettteataettetieatnteet anrrtMkteotatetetnmedtat).atnnt ett*attea ntat I U I h * * M a tta n a * a n a te la T O A * te tta a n * t t n t e LOQ if ll mfc h a t t e PWA t t t e t e j m A nf O te U tta a a * >l* > n Ate tetta U n te * feted te te a ttttfett atekar t e * * tta H um te a r ta te a w te n ateM tate tta a M M a i te tta tttttnttoo n m . "` rte n fe n a te a ttn im ntetet ttn cotekc t a* nate te * te tta late m ater te Afiftf1 Pttg*3f&$ Exygen Research Page 69 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Sxypui Protocol Sm eber P0001131 h -Mifcrttf iauTnaqia iiOB MjwofNcAwaxapotc LOMM4S 14* tM#pa*ON}W| Jtfrnotototom96mmnjwmim|uM n) 143 Ua*fl **. t atJTOA ton* jp apt. to HA UmwtiotaM*?M*ria*f .pada to ** to M M t r PfQA knmi m ppfc fWA fen* )*) *y *t*- m>* M C*ti * |IWHi Milw t*W ) Exygen Research Pa&Wofti Page 70 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.. P0001131 BzysnPiMoeol Nimbar. MOOIIM ANALYTICAL MSTSOD HO(W art MITO iAda<r*OA)la M ta rtM a Mi& *> . FAIM01 Ao*rir V -L f-lL M COab Tartriaal1Mrir LCMA Ptiqb M k .____ Dm Exygen Research A*f Page 71 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Exyym Protocol Number 10001131 I 5 AIUI.rnCU.MCTMO LONSMt 14 9m> n b aBMbta'aivrt*r*clMMmm4<mmiiKiODrp>tll>>Mca>Mc m i kr S U t a m in e U *nl Cloiw ip m b l1oeN* * " tfm m m S 0* m m O n a M it ii*uee U MV IMI . ,,d n alb u u n o U U XX13tI >h--N| I II- M fpoorapompmppvalo (LOMSMX 13 U * ii IM b 0 -IN il.lM -m u l4 . X_ I 'i_fm_ XL Uiy iM M H fc h u d o XI laXOaKlOXCiMkX X>.I) M- pamU--ii-f-c-a--M--.----- - XI) V i m l o M V a t u l t S i C l i m J.1I - Exygen Research Page 72 of 110 Interim Report #23-Analysis of Sediment-Samples ' Exygea-StudyNo.: P0001131 ExyfenProtocol Number POOOU31 I V . .... . .Mh u u w M mimSXL j u 3JJ U.S&* IXeLNlFWl--!*M86ve. 4.1 t r^fiumwnm u wSmmwf u i1p . %45A A33S 3Z0U0 25 41 uuor : 15pL o anr <KejwgeSd*U^2.l i w nm9m il 173955 75 05 000353 35 03 Am hL3 4My to basta* to m4*tn r ,,S S i] DipNtM n ttu M H ii 413- * * * fer O) TroaLtfwM )y aflnf 0154 | af Np>(7 HfUafiS Exygen Research Page 73 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exyg Protocol Number P0001131 U U.I A m L VH C 4LlBC TM 0P ] LCMMOrfy e a m w e w m Aod fFfO A) w J ib -- nib> r sa W ** M * acid to M M k ilS M U M M li. 1 U b e o e ^ t -- a f O A b | n 11 ib y h r i^ -g lO wL tt o m n*mL M m a teal M m ef 00 wife M tel2$m LlM loM b. U .1 ii1m ia r m iA iM iJ byfcnDpio a L rf* D M m L M m to a M v*lMMflOOiibmai'in U S iiL U H k A 9,1 / oAl0e.1ff--lwMlriJ.t^i MDMlpmy>w!oafaTdW^Oh*--lu *m10W0*d*01M--^# eIt* iQ IA IM k M k 1L1 A M I n a t iW e iH u W o f f f m i > ii|Miil tT r t f i e !9 l T to & ) M -- id M l --to m of IM rtfc %U TWO d to a w ftip n -- ac peM tflaoOi M It IQMMlfmMtoMl--ii--iwto--|fip--liBi--aoao*--40--* f|2 HMpbjOfkc)aifbMii,MM^iianliaimMltnoo.lfid--1iiiiiMimic--yb* M IOC 151 AvdJJ^U Exygen Research Page 74 of 110 Interim Report #23 - Analysis of Sediment Samples Exygcn Study No.: P0001131 Ex>rtCft Protocol Numbar P000113I - ... MMNMtaVtBMTB <yt*vnciifi5vi35 5S7 U iW A )^U h ix) S tjiiifciifii Aititi in;<>ure imib x* x-- i-- m u --i i r f -- dMiipiii)iiini 10D ******* 10.1 *3 l bafa at fatti Mrvytmftetermtptewteitteat >U HJ steri. jmIms B r i t e t e teQ . AriiJJaLaf HtMateafaisp, v*a*MMateMf Oorofy a lU IU te<H*aPB 0 fa * aL) far paafaac IDcbL hhomosI UJ- ^LaTOLC (t-tOteftlefapafateifCr u0VmBi efaatlseaidtepl.a mOmtderiyrt 1U UIUJ VS temtieSattetNliatwe4lMtaL^a^fp^fMaterLS G^aCtesaMteafaatete tMe a^dd t ri I'UMHO CAMatdteedmteittoaseapBitfeMfaftaaraaaafaaaaafLlattfeia~CMn)sPO1I1OtJatt,MteLffasarr^(i~a(lf2a*raas^MadiMjffaa)lr.dpaDMftaMteataflaaOaNottteiU.tettoatteMMtoMonyfMa 11U teas tell *5 wL MONaateasL Cates 5 ml oiMm* iato paten* ILI) t>elfWat,p--alnatiepjlMiagiiiwliMifcafpawMynLC{IMtelMi O............la d j. Exygen Research towtUtfS Page 75 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exyfca Protocol Number P0001131 AbitoLTnCAltO TWDto I s ucMttmfAmhtotorA t P a a ta --tfPtrfl--r-- flat Add (PPOA) i> 1 at ****** IlfwkiW iaiMOpbttiMM MpliiMtN 113 ta*ttaabafV--MIOi--fc to ta l ftrieraww 124 AmMb* ( rf a m iM ieieO aaiafiM oO ia. I ihc r bt b frta a <wta tta * of m ta u t *y a --tan r 5-10 w p taa ( a m o m to * a c t a mi i n I M m --e t a * MM to toe fi-- and l MMarolmaM1--mnH0toMOe--M---Aaa>t biNit--lMtNNittfoaiftpOaMtAooBIaBtlaoimVr0mM4atobi--orttouMtalu*taIadt*MoMlLOmIm> HIof* Mmtala e f--a r t j t a t a a -- t o a v to m i 70-130* to 1 i rtw l a i l to a r t * A t a -- *b Uato> to t f b a r f i a p l e b i i l l t o i M M t A sym ta* --to -- to. UOK --r t f ki -- a t by A t --toy a ta m e -- if a w - c t a A tyttiiabte - r t r t b o U W rtM ril rtto r by mm tto H--r ta r Tto, a bt b M tea At a to -ta of At tartan w n 4) Ito v t m d m r a w 2 M i or ir 9 ) tor r r ti r tm a m Exygen Research hqiHofiS Page 76 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 BxyfM frotocoJ Nwnbr P0001 J31 llaiU jUm-VBCALMSTBOP _____LOMMa im U M Om M M mmMM m t mmrn m m m i m s mm i .MMM .Iim. l a M B M M a M t a M a l *J M M dM M M liInw tM taM M . NMMM an (Nm mjmim prwn*rr t - M n NMm MMMM O M .IfMMMy. H i h<Ma.m|Im| Mili%Jbl^Mii^MniwMMMMioMw M--pMlMi ofMPTOiAfjp.nsr Mfxwcoo*. uc w m jN * IlMMtMM WM g w I*} UhtMilM ,*** ' noA hm dfm ki- ofmui J 144 UM * M U M mm M * W m m m t ) MM a iiM 0 m i m of rfO/i . M M M u t M o tto irr (*<. O*>Mp)MyMM-WO*fcMi|MHi[IWH/--IwUMS.) Exygen Research r*t*h ja Page 77 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 E x yfn Protocol NunbcnPOOOl 13! AHtMo i.VllDliCiAln1.tVCWIH01O7UO JSBaSHCmom*c*k'OA&MmI* ******* -Tiw*m\rt*mmiiMtrdm.IC-C.hypi t--itri Dom 'WMViirmmrrwnimotWmlmoi. OOoyoitOOn--Ml., reut Fjcygen Research M l i I P w fiJ c iU Page 78 of 110 Interim Report #23 - Analysis o f Sediriarf Samples Exygen SSy No.: P0001131 SxyteaProtocolNmabcr P000D31 'raodofA--h o l.ata o P -- LwtoofPwftwBW iiii AiiiW6A)iofrWw~ 1 ' OMOricMiMa 1 CH|jO . trtmmmmkrtmmm(LCmS!nEmi5Ei '"l"l<* ' 11,1 *'*" t MW ' XI AWw * H !!>-- m n t o ll. U 0MWaWFW*`OP** * " >M W 0| Hii l>pr00w>tr 3U3: AUmniPtfm _. _ avtt^ryiM Pta* mk iM-an^lB. tp* v npri0i au m a 9aU 4 jtaw 0 aaoptas b I n m i adM aeT JJ ta|feMtopMftni*fc*NiMb4aplfagpiMfartki 44.31 V N v-V L C prb tm M wih-tm jzm * 4 J G ab <12*400 44 k ft^ -B F lC p 49 Oh 444? *IM4*<iMLttCM*Af-tt-aRwj*nNylp*4 4 l-OsanJ-OKCp* 4* I I n a r t n i i i - l n ^ y l i 430 fifaN flyU M fem iw -taaiaaiin* 4JI T t h w - h i jW H i 44J2 yAwMflMMwtaacwAdna*Afat'A-ifMJ .iftn p a n * 14 inl m W JJ U 3J Omfp420U2 PpfpJt0*3 Exygen Research Page 79 of 110 Interim Report#23 --Analysis of Sediment Samples . . , Exygen Study No.: P0001131 EromcolNtaabrPOOOl131 ^EB3 _______ mi niAaOfPTOAjUF** CkMkr(CMMa uu SA &11l 1111IM1I11IMI13I * 8 {H IM . 1lMitLl {UMII.iLatf tO-lMMJ.'rtk * * ) <***MLm NM7IT7>. m MOi n 'U taiiiaoitB 13 JVC 13 k M tfta X A }: im kH m m m m >iii ww, 15 n+ m tfm m m 00 * u u mo 32J - *A 5 <* 25 0 05 rkm tm 1 1 JmLM > U 03 5 03 75 03 75 03 35 03 H IiiWm i :M ISpLtM fcte ^ i'M n la MM** MfaM5ftU --ifcii MliWini wmm. t a llw -U rOm piWavl m m 'mm**m p i* wt m , b x k w t . ate k> Exygen Research fttg550/ 6i Page 80 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 P0001131 Ua^rfA. tJfJafcfcfcatmeJ.Mmdowuar.MiiACrTtiQHte.lrAcMgTCAiitrtete I q -- ty ic u M g __________________ nt W M lia * | l f c l> W w > H ()lp l*n M tir> li nil- ;1| -1~ ITC*. ' * tat I M M t e Mp * * u U IMS liM* u Ii> Vr * h M 2 a f aaste l M m peapan* * t t n a t e t ' t>L a t e i t e s a s i U s u a t e Misi *1 w * "teM .I f i t e l H i l a s * - 1 teteL tfT T C A > r * * 0 r * - u M In llM U R M , * u * ij>--a. m m n u n rirc* ipanate * * . t e M te lM |i|M > s s M I l a t e i M i n i ofMO t e s a t e s i m a i t i i i> i i t u * 4 1 a p r ii fc ilte a ........ t y t nt t n ili t e a l t e l . * j t e t e t e o a l t e l saani s f ilo t e s a t e r i in -iW lM M t u * 4M a p r i i t e a asteria 10 t e af Ori 41 p p t e asteaa a t e i a a te a f 1 il* t e l i n ate. U n i ate t u Ih te tte W te te a la te a a a ta a a M ia iia tlia u ia taaateaiilT 4% t e ita M a t e a aa itea B paria* aT a a a te I-- te * a fi t e i p9f*4$6f6) Exygen Research Page 81 o fl 10 Intcriir. Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exncn Protocol Nombtt: P0001131 jjAXUULulllMr )U U ^A ^'*r~a.N--Lri, JK lAaU(FfOA)iafi*iDr O w IgpteM M MJ >X1 HHLOaCaMMIta aM*f aatoidaLoMM^ ftataaflaiB>* to* uiM*- LliJl'JCS.wLmmJH liW. 1LI Vai* i I at Myto M JL ( M l* m M . < K M a h * < ,1iUu rnh****ia*>**MaMirrufco-lwhH*r. nn*#*n i n* II.J I iLCJOU '* * *t o *<*.*I! , f --I f* lJ.* D W t o t H I D o 101 lilMXMMian* <U S a t o '* 1 " I M * * * * * *f "" '" * * * * MIkrIsMritHoHttMMmM a U HIk.yItBe--h* a t w to wl-- , ' ' M lM H fd M Npiiii Hgatl aft) Exygen Research Page 82 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: PC001131 ExyfnProtocolNmcrP0001131 ... . IvataM __. . MMNMtVtWD M iracAL arrapo 1 /V.' I '. I.te.Mlte.AMttetetePtew,iLaM--tobofoyrtihgMtyertmeniriA_i_H_ffP_O_A_S_iafi** il'.? QMkp M50 aL patypopjte*atei eaotetef api * zittito tpm U. .>aBpMMritteepetleMMEtl*lCoOomMte*teteWa aIot leM12i5tlaML iMImotet)tpeoMrttee*ir M I 1* aL mt Mtete I te MMpi te t e SO w L n te * te ILIO 111U.0I Mra i t o v Oite fcp t e te i t*ettelOert-Oei et-1et0"e 1M^ 51L iHtewiw MMttiMe tea teMtotet.e Mt enaMaaamM t a *2000*> SUOOMteteMMMCMteoml 11.14 P p l M i T i 11.15A4M aiplee,t--taemtiedribifataleatmeLe?nfa2%*aM*teotep(or*d4tdeP**CV!a at al tec ma ia SI.}? Tteotei ILI A *fc*l 110 ChLaiiii*iTly aaat k iateM a te bspouf od a teapOio. AOi mpilM. i Ite te n p o d t e a tory J-iO teote- te i ; of t Ml fciiw tJ by te t e tr t e tu te t t e aTh o i te t e Bm o d Imi k n t e in 114 U 1 rfa a te i|i r p io te tep Vt e t e t e #rpo o me* etepMioLfMi 12(eM*te) 0*4! Pogt42ef63 Exygcn Research Page 83 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: POOO1131 ExyfMProuMol N tantar POOO!131 ~" um unTiMBlTir^11"1"*' I - CMHtvLCMMU 5 y M adm uljiid .i* S5Z4*aIMi7BiWlHi4altfMiM|nififr|_0_*te_M_i_'epa_M*_2M#r*mtet*t 4kLm0Qt p'uI*Tm# em uterm i <ii mnt-ir "----- --r*~ 1U rf M 4 ite 4 i te a TM.anrW TO-\JO%* m. an stauam . AM*.l*thm* MtM DMthM M l uwdiDui rto g*m(M npMteenpmram) 142 HM MM- Exygcn Research Pngo 43 ofiS Page 84 of 110 Interim Report #23 - Analysis o f Sediment Samples J Exygen Study No.: P0001131 b y Protocol ) M r P0001131 rvcMtrt) -- AltoLYtMIU.WttO 1 M^da/AaMfcr*IMMMM0C7flM>wcwkAi(rrOA)BFt*id CLalyLCMSA* I ifPVOA f l i t to --*** M Exygen Research fepS'4 P f 44 o f61 Page 85 o f 110 Interim Report #23 - Analysis o f Sediment Samples. Exygen Study No.: P0001131 ExygeoProcoooi Number. P0001131 ANALYTICAL METHOD M iM IM ai; VWW7M MMbeiafAMfebb9m* Wh d b n H M k Actt(?FOa) m V ^M h aty iC M IM I Antrim! TMtagPMfltp ftojU iiw i mtXMaMhOMve MeCaO^FA ltfBI TeiifCaMMl^b r, IMS,bwil\niwb Oborin 534> ^ Exygen Research Page 8 6 of 110 Interim Report #23 - Analysis o f Sedimcn. Samples Exygcn Study No.: FCOOII31 Protocol Monbcr POOOlttl I AX*L>~nc*Lmxwao MSES7XSSiS<C3a05aBaa?F3BSSSSSr3npr3HiV bgrLCAOaa i vllT->u?lpIii * iamnilrri* 'mmO?******* * *mmimDM** 10 l* f X12I ifi i.i U jMMfcedtofaa pnariv CDb . 4. 41 VM-mCnii ' ' 41 Awl*fcfc-*LC9*fe 4 1 C f <1*1 44 MtfUM-VCr** 41 9 t o * i K - a a 0 f ) - f a f * * * 41 fM IW -llO R M k )-li^ 9 * 47 N IC >W| - l i < yiill U IO..... 1 - P L C f 4 t L A-- fii Ja t o tM*fa pta ftrdus ti . j * i 13 .(LOWm M>ofi^Mdii MW 13 Holm Pn>*itfts Exygen Research Page 87 of 110 *nteriir Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 ExypnMicol Nunbw: POQOU31 kpLBMSMS bA4 {PFOA)m vgmm 9i.lHl tmttkucwngniimtt^wnm+**>fr 19.11 Wrtmiliiimtmimi*ll*H*>r mkmtxVBOt^ t' *1 l-- Fl 7p9uCisTmM K-eJaC"C jlit f O ijUiiii f glwrti rXM -- >* i ) M Mv!ta(A): I --4>-- w fri fia+m b W o 1M5 MQlA<^--KCh3ip<9: HwImhI M 2XLl1U*0* &*22i59955A *27715S5 nttwU00c00.u933B9lft 11?4 QItfMlUtafiVr stfta' 19L(-- rtwriw-Tmwnr*tn390xn.U u m m r-D M Tte 4 m M n i I n M i ^ 4 4 Srte *>*ia w ftr ft 7.1* iMra*fnc;BWftM)llp rtfti m fftC<ftli*H <rail2 + * * * JW7 Pt*t47<jf6S Exygen Research Page 88 o f l 10 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exyaw Pnttcat Maribcr W0C1131 J4i^rMr63nrCBilaiMtwaff>ftMrniriM<iiiAe>dQVO)m . . . _ tyLOMttMi m f 0,154 j of U t i l KiwiHiaM bait^if>fM ikyiaaIm 2|afin(W B . MHkWaLWMtMl I H 38HTtiii)HifcliliiliBi k k W k p n --*ybttiMg3 L rm .1 ftl.l rt^*t**Mirf~IQItaLofffQAhykiatlOe mfBMAmjtHinmlMl2MM(cLUi*Mai4kfaekrp*Mift44iBtt140aLwi* t.U AU|i*f OAflwrtlt Itili rfFTOAfrf ^ --dfry i mLfAt UMn W . t U ii flati vote f 100v i* wmi h ilB o k U IV IM i *U. AdA.tlrfdlti.OOnntUarLkthlMa wt--hPHtfocfrFiwTOd--Aiipofl--OOflbitHyikMi^fiWcntilA UM iUNUM MA AM I &m1 l i H l n w liiit *f?OOA it pw pifl ylh > i 10 m L T A 4.1 m H . mM m k i M vite mi e f l M *h MA t1fc*rit k iW aU M M ft i ` a t tot boAm Ai p ttoo mitmmt i f ft saette U tll n14pftoLMintea r Aktien *gf 4S&6S Exygcn Research Page 89 of 110 In terim R e p o rt # 2 3 - A n aly sis o f S ed im en t Samples E x y g en S tu d y N o .: P 0 0 0 1 131 Exym Protocol Nhnrbti: POOD] 131 1 Mtiaoo """ iD5CT55^$rCE5353toiLe3CKMSu*n;BB157^RXrS u i i>a>nmiim i m y be *X* retre.** tm jr be f tepe n i m kbtU iai MX . I ftp e r f* TO m m m ) I i mmm Mlart UMiNayp**pi.k**m**tmwym! tron#bimnfki* IU tU tu (MOa5a1aoMr *napabMa Mf t<iaa>bm ml A1.W iiaiB*niaSaaiahliaiu fcrMSii MU eiiialM > mL mMiliM i nlia n l iBB B-ICOOnM *l1bL*4 tPaaa*aw*a awia*tuaimni* '--a*aa aa a--*<--rat*-ai--N-f-la^iiaall.t *t aa tau pt. 1 * M M a ltf a a a M a M art hi aBra. 0* *a O n a* aohawa * IlJ I M a* n s a l la M ta a by a a i a h - r aMaawhaia>*a**pa^al(ntiah*awaiaDiray**at.M u Mp**ay M in a*. , IVP ... HapaaMa,,**MaaaaeiaiiaSamaianihiltimt iaoDaaaijaMaaiaaMa ' P9p49f63 Exygen Research Page 90 of 110 Interim Report #23 - Analysis of Sedirijewt Samples Oxygen'Study No1.: P0OO1131 Exy(cx ho*cot N nrtn- NOOI ]31 - asaLvwcm. AmgTOAHV||aainc 1 At*IBH-- Mlsli<aaLin iftgiaic. HA te te te n n lc n a s te - lS te -- n c c r ta iiKm iliten - - -- - t M*C m<2000rpo iMtMK C d M l i U l i a t ; 1111..1111 lM Ml M |s ll.ie *++m * as*l Urn-- l.1 * a1apfac. aaaa k l.p i tec.l I ' 1IJ . - - 6facl>*telakataU aaM hn)n. - ............................................................... ' - r^liM 1 1 1 11.^1II Bln !l | J LOKWB. jjga*jMtescacMcfnclinBted.an?*as* IMUeasy* alain . te teaaas 0a haaataataaafsaafaaalnar ` ` '....... a te * m v M l M il b a t e cm. o n * c>M ha UJ. c* H M m 1 ,i i J J (arcsai lin g 1V1 rWanaatn .can Mar CMafa*a0accl a C M a t h c i cans iN ttrik 4atfte In <DMiaai)aa|ia3iiiaaaaaa ^toaaksthcattte7s IsUaifea t a . t k l c Np- PiftWofiS Exygen Research Page 91 of 110 Interim Report #23 -A nalysis o f Sediment Samples Exygen Study No.: P000U31 PMOOl Nooter: P000IU! 1 1 AKAivncALMnaSo .buiJiJw UMkmmmmf bfLCWnO IM 14kl K*aiOfe(<CUl>li MMMlfnULlMd(>I|*l. Mm*i m* kr HOAt t*m L> -a im um*>h--M(hiHiimmi*-- n*woAfcM*aiMLi. D- M ir tgr*H* IMM k B n a M , tf mmmbt MJ M a M M M illM M iM a ia fn U |iitrk M > M > .M kOM>k(MM*** mMMBeapaoM tM M yM " Exygen Research P a tt 31 c f6S Page 92 of 110 Interim Report #23 - Analysis of Sediment Sample Exygen Study No.: P0001131 E x y tn ftoucol Number POOOI131 ANALYTICAL METHOD A<w<rrc\i iXJmkyLGMMn A*TM**r- t ^ tmlQmSf G' U LI svmtw&m xhtoxM s A /t Exygen Research MHp 1 P filo ftS Page 93 of 110 p. 93 Interim Report #23 Analysis of Sediment Samples Exygen Study No.: P0001131 Pn 14 ExygciiProtocol Number P000113I AjaACAriqCtMOP MHMtUwyLCaaAtt M M M tiM ll U " `` ---- * ` ` rnfay i l ~Vamtrni*pmM mib**mmmaion. Mm fra faaa p ta fa' miil p M i-- wep a^fiaBtmi ^mi imtimf am m) lmwj.K m afte far ah ' , AMmtmky. tfdwi ItaiM BU wiaM trf * Hm* ifr>wpin>fiiii-- i tfaaitilaratta ad npt XI U ffa WwiM imiiini a fcqwfl1 faifa* ` 4i v*m-ancp*t ui l tM ta ftU V-mL Cep a ** 94 M AK4 mbmIvi* il i parti f )!>[ a 2 jM s r M p li W ii ji i'i g 5*340 r(LCMMa x i u ih M i m i- di m * ii fu ^ n a ia o o o t $. 94 i * lijb pl m a rtin i irti i 93 U nLtf^Mkfayiiyp^fHMdfk|fttlM. 54 n M M * M p lp a* (J aiL . I0O4BM9 XU? 2UaMLteUmMCmWi mULm Aqp5J^65 Exygen Research Page 94 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PC001131 C xypa Protocol N a b e r. POOOU3I |T-LU-'"^"'J ,!' ' i i . i mi j . MW-- _U^M_rA_a_S_N_^arMkUtanalMLiBrr(artiMrLMOXnaMHaleAcld<PP0A)ii$K3< 0 l M (0.m i M-IWu t i *t* m u . <*. *MVb (I()C U M c i.lS C e ftW C S O bfcof^tdfliB tU u L p o ftV O W iw a * >000tjw*. 0 Ob U (tmMatrnm * WC f* I >M4 >>2.1b m iM im , J* k l (idaU 31 03 3 tu 79 J 75 u 39 iM tb iiw d i w k iilio m u, 74 / 1k4*o Mboriqi 4 - 3 n* fa **>* Au$4oftS Exygen Research Page 95 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 BxytnrmocDl Nimbar MX1131 i ............ Axuvnongruoo . Mbbrfafina)aibraaei--imiaar*i*aaaiaaaAaMtrOA>itmll M Lbmbf LCMMM aytol lOObaLarwiM r. |.IM af 1. W.l 10a far M m tu n loo mL mi M fcB iK totttM .U PS to te A li^ litla a H te rffK lA liiifn d k y b n v iil 0, (* WO O L i M h m k dort af 100 wM t m u muLuanoMta. t l J A 01 p > L h illO lM ii a i f f f O A iiy o o d > y in ^ P | 10 t i s i i n w tL ffeo U>m ChL nfcM t >4m I total of 1001* M a W/4 th s e e * e f l S f l l l * l i * e e s o e O H e i e i i B i i m i e r ppMHMfty4*CMd MUAr MnM pwiedf0 oom M >IO<r|IBM IIII ntafnU J I m ruiIT i i M U n i W i w w M b>awfawol i ta ta , U 3 TI tahotap )Hped -- P*e Milfintal raw-- mim gay a f IM U IM IM 1M10J M*tMl UU>140 fCftfCooihi* J J ^jnotiltaltaiN taM M taii'L J2*-taL LDH m t-o ata k o k t a f Oadod ay ke psepand JJ c/45 Exygen Research Page 96 of 110 Interim Report #23 - Analysis of ScdimeritSamples ExygeriStudy No.: F0001131 13Ekt^ s Protocol NoobcrPOOOl } "iU m it , - >l .A im w y^1 m pm ifM kM bi M a in AoUfffOATi' M M H lU nrkrlCM M O it* MaiUlF' iti' **** I 30 or low) -- MiM i m Mm ' A M M M en m u n m f k i t e back. M qpAao Mill M m M lip4H M aiM aiN 4. 11UU1.T* OOMnj<MM(If.tM*i^u>*m"MMd-MkoOaMiOMiBMflic.io4-I1 i u cJrnlmmtCmin,---------------------------------------_ (I fr *mu pMMf N nl. MM.I.T* \ M>pMhrM.gWeCM<-IM|llll>DoM MtCOM--jMdry ft* tM )* .-M ec.n .lW --ilC ^ g i^ W V . D I M M . ILM I M M - I f l e T i i M l CMM 2 BL of MM> MB > irM uM tt.ll ' ` ` -------' ISM.oljt>opjMoMMi|oaio(teliMMff*u 11*, < hffVQApepto4ta|*)ii # * * * eettolMlaMta**!*. O * Ato e l rwMniioiiiMfctoB ! * * * * * * t o U fN u ifw d ft N J AriateM* tor ei nt eahm^*ama r*iwMme*rkfie\mwm i4K i --i r* p y m to ett al9awyS1eejjefeTaaNmoiMMfcrwnalMbMydMi0fsi O i \3m Exygen Research Page 97 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 ExyfcaProtocol Nomter P0001131 MMmuwirLQMM ' ' " ' ' `unM--mOrRM>O*MO*tmm.ram n W u M p a r t a i l i L O I l 14 llfQ A tfM ilM IB te < nowMm* u p h -- oOrOMnatmmmm u n i B. ` ~ -- < R R " O R * R R O M H k R * R H M 0 ,M M R .|W W m . Aw wmtm rU M0 io- 1MH Om M bo P ik H iO by M im tm t w> n u m m i i f i> 1JA Aw Tim, m f bo M M l* k iMi M Mh M. M_ momUf hOhfeMyatMiai Or m mHur * M l wmtm o f H M h fM O M o 6 m omM feo 0M 1MO M M w W O M jT te MOHH* TH M C <* AOlMOI g It li m A U ! >MlH. I OHHMMMlt lA H llb U M O g H i 0 M H O H m On* M R Or i O O kw O tte R H ltR lll M . V m M M o M o R ift acoododbo b o il nO lin R lllla O M tH O iiO M h aaJM UR Oh MR _ IR R O in tilto lO B fffOAMiHOpaooAoL R y illil O[HHHIHH) *-- n ^ i -rrt i i-- on *M nm i k t f MhofeyM M M *M M H HROnoHd. IfMMMry. 1*101 P*fS7tf6S Exygen Research Page 98 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Bityan fjotncol N aabar P0001131 M M IM vaunt I -- otnutncum craoB ....................................................................................................ill JUmwomhSnff* U nrtfLC M M ISI lU fa I f ffO A prtu io n n sio A . tue Exygen Research Ptftss^es Pagc99ofll0 Interim Report #?.3 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exycn tataeel Number WJOOl 131 ANALYTICALMVEttWTHIMOD C J L IM C M fe i 7*MKt.UK>r.U? M Dm Dm Exygen Research Page 100 of 110 p. 100 Interim Report #23-Analysis of Sediment Samples Exygen Study No.: P000113I B x y fn Psotocoi H u b e rt WOO3 J31 AMHVwr_Ai. " \ m, III. JkVrimciKMmMJnami. aMjH ftffV gi 1 ... ..t* U TimimtaibnUmfttM aontwikMiiiHi* by K 0 M h h Lh b * f t i m n H > j n u M M* ZUJ uw iftrHppmWr 1 JUJ lkHHI||lipMaHH k^|ltiHh HMHttaBHH)la H m o tiw m M HnHa^pHH--^HIaHHIeIlpHullH*1--HH>>>.1ynHj*riHiHhHW ylHHll>plinln*tHiIn U JmLttmHnCimi**. fjf p |p d |||h ||g , capaMt r f p m i n h b 2 i*OmC>MIMH *OIV| < >-3*0 hptun Pm* 40*f4S Exygen Research Page 101 of 110 p. 101 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 K >yaea Protocol N um ber 0 0 1 1 3 1 .......... .____________ I' Afcw-Vndu.MCTMOa ' iBB. I' ?553iiwI$M55tBeantBilHCSMi5l5I5ttSE,A3,p0S)T55r .I* OMHMlMMr. . 4 -CknuMiaaklilKM ` got m i) aaiMi u m m ire .. --Bam,y >4 M m ik M A : M _Q M M ? ^ 4 . hhaw . - 4 14 . ^ A., - t * -s *a 5 ts K 4 Itow kM u um i 04 15 0 J 75 04 7 0l) SS 05 4 4 hH>4aVataK U p i (mb to ta t m w i + M M k ja n L 3 w 2Z?i^n2ii fW m I I m i m ImboM m * pM m l m ay to JMgad roar to 74 iflimifMi IfQA.71 X w te B iiW in ijli il i M m w a>.BBiiii^4l3"36<a^far on) m U VamteWIM U lhMhHw - MwlMMMkItnalrtfaw. h|U1 Alftf 42 oj 65 Exygen Research Page 102 of 110 p. 102 Interim Report #23 - Analysis of SediiitehtSampleg 0 1 Exygen StudjiKo:: P0001131 Bxygm notocol Muofacr 9Q0Q\ 131 .. .__ ' : . ** .. MMUawkylOMa M l Pnpw iN klN N itf*M O l|lB llf?nA by|^ID B | mmmi[tommt i fcrywky)mi Om i l > .IJ A 14 p ta t M M M u if M A to > m w < Vy km *m | > L r f to IM u jM .N ta lin I Jm t tk M t f 100 w * M k tU S iL U H M k M J 4 HI p|M M kiM ia6tio>fffCU i ii pnpiai ky H apif u *' L t f -- l-0#| k l M in* a-- m i-- o n 0 0 i. i -- f a i mrnLLDNM. ipw rni* U Tta * * * -- * * * a n * totiopad to t JHotraiar at IA3 BfteJfMclMMfta|LtoIa 10 MtfeMUk ' 3 MA, aWtfefM k*mlapMMketiiofMc--rktmkiiemyMy*tkMkW*p-t ft oNmhkftmtflMs tottwotanl pyfertntotoi km will ka y w f io l ftp*? Exygen Research Page 103 of 110 p. 103 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Bxytea Franco* Noofecr P0001131 i ` ` 1MMXtittLMkimu* itrlCMM H.O IUI. kkmmm Ns* t Nmmi vahM Tm m wmtommt*******%tmm9b*mntfiiihim. 1U Ai*vm far**oiMMBf20iL C^t%Wy U1US 7m** i mLft $mmm*m******* pjpwmmI*mL w wdMrtMiiee**ir. t u CM * m C o t n aMj m yMM* mL Mt eM : II* Laarf*rMflMM4itMMdC*Dfwa^.dPinwhN4mihmi wy IL * tU* BHh*1.rift <4 1i*. UMmUMttimmpmLMfveCL(aCiumAlM*2MtmLawl* 2mmUm- k m 1 yiA .n.u t i t jari M M M f k Mftih* MU yilMl IM Ml* ifl 113 frMifrrih ifIVQA aiM i^ rih | m fc f o e r a 11? in if T nt -fnTintfTTi nm tm* ttm*rimiMm ikt*iiinilTMhHrfwrrmf rritk * m m iw y 510 m * tm A m **m*n> m m i* m at *Bm*m mm*** m y * 11 i f 1 M M m M toy M n w f tii mmM i ta M 9 0 iit w y 9 lO fl 9 ) e iM * M M frrftM riM rfa ia M & hi " ' ' ' b t t o a m i) M ( fri--tin OA Urn ] 17J MMd turvw arc I Wl MWlhrlHfpfpMtM-- aio* J J (r (fnnhM ) rfrJalTShnMrtiyMA Nr)<n Pt^a63^63 Exygen Research Page 104 of 110 p. 104 Interim Report #23 - Analysis of Sediment Samples 'Exygen StudyNo.: P0Q01131 E xrin Pnacol Niaobor: MOO1131 , , , , ^ mxLMKIwm 11 A* * 111- w< m k ..........4.4.1..--.......--. *a . a ia^B inaw u n il B m..uIIIau taifn . uk c 11 M aM U xtrolcM lcakaaiW Q A a im fcjm m rO m tW UX} IN J J J J M M l W M t l M a i ta k 1# aataL. H i m i h J >iwSy*m* j m \ is n ssL wm>* ' "'* * J'f * " " I n r^ iilli li. * * h i H A M Am t mmmh o m xn * * Maria* if wn x l o i k 11* -liu Mrih li. ! I I *m * kb* " ' lafa a a T M a a i r tM a M M t a B M ' i #tetotorabea mi btomM knuM M 111 mjh tifa iW u *** VPfMl Mpt MC to I i fcfl outoto ito* hiM*. Cm C ihr i M a l n t k l H i M*"kMM*M.*Ma****ltoil*i<*fc. ik|(M|- I (TFfOApur Idi -------------aC f^C fH t________ Pat**4eft} Exygen Research Page 105 of 110 p. 105 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P000U31 B a typ F M o e e l N u n POOOl131 jUUDfitca idttwoo TSBS3FXHSBnff5iB5SS35B3tfyiLHCEMMS i-o 'JmihI W I mnfrmLu> Exygen Research ft*toqfto Page 106 of 110 p. 106 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Ewgen 3058ResearchDrive Phene: 814-272-1039 StateCote**, PA18801 Fax: 814-231-1580 RESEARCH PROTOCOLAMENDMENT Amendment Number 1 g u cth m p esr oi/iam s Exypen Study Number. POOOUSt C lu d S tu d y Number N ana " Heft -- ..................... _ . 1) Anatyfcal Procedure Summmy V 0001780dac8on Oil 2) Vwflfcadon of Anetyical Pm eediee AMBRbBJTD -------- 1) Add to Secflon a ] : S e c to r S.1.8. A tem m welghta cVttandanjB mey b e u eed Id p repare a t o m * ooncantraStone o f rtro k s o to lo n s a a n e c a a e a N . A aam ate levete of fMdllcMion eoM tone may M m b e p re p e n d . y d .w0 , , P * >l 8 |* l , a * * a n a frfa far each matrix m ay b e a tte n d dapendtoo o n am ple fee ariajahle far fre ta o n a n d te r to om w ranalyteconcenbabone B isected ftATttllALg---------------------------------- fa tm prepared In ffler to piAefaesemofa 2) The emnpte d ie ewlahte far wnm mammal Kef and eurnwes imafcrthen ettpeeied. SpdfrQallh pm detannhad level In tte protocol putdmspdrad auw w U8milowerStanfaedefadtonfcnlt. Afacilie analyte level In ti groundwafer ^^ ^ " P y ^ f a .a ^ A ^ ^ te^etwnlnadaiiednpleyelB Metedh tie pratoooL When th e lewal In tie aampleagrea%aooeed tie pfldng level, an accurali mcwiery j^ cannot be nalndeledfar th e O C sample, Hgharsp8<faglovelBba>o hcMeet i w e the analytconcontndloni mmected In the waferample. CW)MUMHl ">* Cl e m J m e m m M a v e r an d le 1000 i ^ m L f a r a " * a * a n a * a t m om Q C recovery <fetn UBRARYD;Wa00122Mi ' jL A , M r* 1*1** Ewman QAU Remew I n s e titilr uaesTRATTyEFonu Exygen Research Page 107 of 110 p. 107 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 RESEARCH 3038 R n n re ti Oil Phone: 14-272-1039 S ta tt C ollate, fA 16801 F ee 814-231*1580 Amendm ent N um ber EffedvtDate: " Exygan Study Number PTOTOPOCAMENDMENT 2 "o&ftAx" * - P0001131 C teW 8 lu N u tn b tr Petal on N one 1) A l p o r t , 11 of V ~ 2) T a t Meterteto. papa 8 of B6: PFOS (ranaUcn m entored 48fl -> 8B. 1) I n te n d * o n e to a i report, Intartm re p o rt a b ieeued,' 2> PFOS trenatton monitored m ay to b e 400 -> BO. toi1Q N A I 1> O u t to tw aM c e a tw ita M a t h e data t te , intorire r e p o r t t o laaued to alow the J a n tto r e o tN td te ln tf m tN r r e -- n ****/ o iirfa r * tt 2> Tlw API 4000 L C M I8 M S a y tm td tK t Me 480 8 0 PFOS tran tao n M o m a tr aenaR M Iy>iartw 486->901raneM on. IMPACTON S fY ; 1) T h ed a r* b e a t* to r e a M t a t f M O i e d a m ore* * * . 9 T>re400->00 arewton aw be Otaelidth i ` b ittif chix*iwloflr*phy, ' gM ng o LanwnrikvooauaM- 5 S -------------- -***- w Exygen QAU Review . AOMtMTRATryt FORM Exygen Research Page 108 of 110 p. 108 Interim Report #23 --Analysis of Sedimentsamples Exygen Study No.: P0001131 n RESEARCH 3058 Research Drive Phone: 814-272-1039 State college, PA 16801 Fax: 814-231-1580 DEVIATION FORM G eneral: X Protect Specific Deviation _ _ FeciityD evialion P m iX 2 ' O sta of O ccurence: 04228106 E xygonP raiact#: P78CVP1131 D eviation#: s O en t P relect#: MA ' n M d l K I V 064)7$ R m M atorv D river DevlaMon Tup#: /Include V# for m ethods a n d SP) GMP X GLP ________ O tter ______ None Sam ple P s t/ta tf tg ; X Protocol VfcNA Notebook raforanca; MA M ethod - r- SOP L ogin#: L00061R1 C ontainer#.' NA LW #: p: * 1' , NA The three sedim ent sam ple* in 181*1 (C0172892-C 0172fl04)w #re ortginrfy extracted uelng h i eedW nentfnettiod\0iM 782. Poor recoveries w ere obtainad fa rP fO S , PROA end " c PFOA. B ecause o fftss, th e stady sponsor requested the uee of an tatem aliva e x tracto r for these compound*, a* (Ottawa: D irect Infection M ethod: Before the sam ples were weighed for th e extraction, they w ere mixed thoroughly by vtB oroutiyahM rg the container. A one-gram portion of sedim ent w as weighed info a IS -m lH arcan M u g e tube for the extraction. Ten m fM tarebM K acetic a c ta in mefowrol w as added b reach sam ple. The sam ple* w ere than shaken by hand, vortexad. end sanicaled for thirty minutee. The sam ptee w ere m en cenMfogM for--iO m inureslB t-3 0 0 0 rpm . Each sam ple w as rn ly z e d by LC/MS/MS eiectrosprey. Using this,m ethod acceptable data w as o tta ta a d iv P F O S . but.ths recoirertas forPFOA and c PFOA w ere sen poor. Another:aftsm abv* rrtethod w as H en used ta r PFOA and '*C PFOA, ** folow s A Jternadvs SPE M ethod: The sam ptaa that w are prepared In 1% acetic a d d for the direct injection m aiiod w u used for aila extradton. Alue'maM tars of each sam ple w as allquoied Into a 90-mL polypropytene cenirtfoge tube and the voluma w as tsx en to 40 reL w th w ater. The aam plea w ere then centrMUged for - t Ominutae a t -3 0 0 0 rpm The supernatant wea than kMdad onto a C ,, SPE catrtdga eonaoooed w th 10 m l of m stianol and 5 m l of w ater. The s t a l e w as bearded. Approximvtely th e m lH Ia rso f m e tte rd wee added to tha cartridge. Five m IM tere of eluata w as collected into a graduated 15 mL polypropylene centrifuge tube. Each sam ple w as analyzed by LCMS/MS eiectrosprey. Cause : Preparation Analysta Instrum ent Chant R equest x Other More usable d ata tr a i obtained. UBRARY IO: VD001MO-0 Exygen Research ADMINISTRATIVE FORM i*Bgc U W o l 1 1U Interim Report #23 - Analysis of Sediment Samples CKEH EH3* 236 1B 651 733 1958 iH i-a i :Mm trmwtm nurioB Exygen Study No.: P0001131 05/01 06 13:46 NO.106 03/03 MM M W H t M il Exygen Research Page llO o f 110 p. 110 Interim Report #23 - Analysis of Sediment Samples CHEN EHSR 236 1B n-twsii n:M 651 733 1956 tsurton Exygen Study No.: P0001131 0+5/01 06 13:46 NhO.u106r.m03n/a03 ww Exygen Research Page 110 of 110 V