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p. 111 fiffi.ilA 6 _ 3 7 Z ? IN TER IM R E PO R T # 23 - Analysis o f Sedim ent Samples STUDY TITLE Analysis 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 the 3M Decatur Monitoring Program , DATA REQUIREM ENTS EPA TSCA Good Laboratory Practice Standards 40 CFR 792 STUDY DIRECTOR Jaisimha Kesari P.E.,D EE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 INTERIM REPORT COM PLETION DATE May 2,2006 PERFORM ING LABORATORY Exygen Research 3058 Research Drive State College, PA 16801 Phone: 814-272-1039 STUDY SPONSOR 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 Phone: 651-733-6374 P R O JE C T Protocol Number: P0001131 Exygen Study Number: P 0001131 Total Pages: 110 BEST COPY AVAILABLE 000134 Interim Report #23 - Analysis o f Sediment Samples . Exygen Study No.: P0Q01131 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT Exygen Study Num ber P0001131, entitled "Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexancsulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sedimept, Fish, Clams, Vegetation, Email Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M , Decatur Monitoring Program," conducted for 3M Company, is being performed in. compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by Exygen Research, with one exception. The laboratory control and control spikes for the direct injection method were not recorded promptly at the time o f extraction. ,: ?f Exygen Research Jaisim Study Directe: Weston Solutions, Inc. Exygen Research Date Da Date Page 2 of 110 000135 Interim Report #23 - Analysis o f Sediment Sample Exygen Study No.: P0001131 QUALITY ASSURANCE STATEMENT Exygen Research's Quality Assurance Unit reviewed Exygen Study N um ber P0001131, entitled, "Analysis o f Perfluorobutanesulfonate (PFS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Seram Using LC/MS/MS for the 3M Decatur Monitoring Program". All reviewed phases' were inspected for conduct according to Exygen Research's Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratory Practice Standards. All findings were reported to the Exygen Principal Investigator and Management and to the Study Director. Phase . Final Raw Data Review and Interim Analytical Report Review Date Inspected Date Reported to Date Repeated to Principal Exygen Date Reported to Investisator Manacement Studv Director 05/02/06 05/02/06 05/02/06 05/02/06 `Note: A ll 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 of 110 000136 p. 114 . Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PQOO1131 CERTIFICATION OF AUTHENTICITY This interim report, for Exygen: Study Humber P0001131, 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: ' M Date Exygen Research Facility Management: President Exygen Research ^ c i w r i Q tfr Study Director, W eston Solutions, Inc. Jaisim ha Kesfi'P.E., DEI W eston Solutions, Inc. Sponsor Representative, 3M Company: Michael A i Santoro Director o f Regulatory Affairs [ Exygen Research Date S k fO b Date % '06 Date Page 4 of 110 000137 p. 115 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 STUDY IDENTIFICATION Analysis 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 the 3M Decatur Monitoring Program . ;. PROTOCOL NUMBER: P0001131 ' EXYGEN STUDY NUMBER: P 0001131 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, M N 55144 . STUDY DIRECTOR: STUDY MONITOR: JaisimhaKesariP.E., DEE W eston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Michael A. Santoro 3M Company 3M Building 0236-01-B-10 St. Paul, M N 55144 PERFORMING LABORATORY: Exygen Research 3058 Research Drive State College, PA 16801 ANALYTICAL PHASE TIMETABLE: Study Initiation D ate: 11/05/04 Interim Analytical Start Date: 04/27/06 Interim Analytical Termination Date: 04/30/06 Interim Report Completion Date: 05/02/06 Exygen Research Page 5 of 110 000138 Interim Report #23 - Analysis of Sediment Samples. , p. 116 7s3------- j**--77-- Exygen Study No.: POOOl 131 PROJECT PERSONNEL The Study D irector for this project is Jaisimha Kesari at W eston Solutions, Inc. The following personnel from Exygen Research were associated w ith various phases o f this interim portion o f the study: Name John Flaherty Karen Risha Paul Connolly Christine Edwards M ark Ammemtan Amy Sheehan Brittany Krayets , (ScottC rain , 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 000139 p. 117 JL1_____ Si____________________ _____ _____________ __________;____________________ __ Interim Report #23-A nalysis of Sediment Samples Exygeh Study No.: P0001131 TABLE OF CONTENTS Page TITLE P A G E ......................................................................................................................................1 GOOD LABORATORY PRACTICE COM PLIANCE STA TEM EN T.................................2 QUALITY ASSURANCE ST A TEM EN T................... ....... .............................,........................ 3 CERTIFICATION OF A U TH EN TICITY ............................ ....... ....... ........ ............ ............... 4 STUDY IDENTIFICATION............................................................................................................5 PROJECT PERSO N N EL................................................................................................................. 6 TABLE OF CO N TEN TS....................................... .........................................................................7 LIST OF T A B L E S.............................................................................................................................8 LIST OF FIG U RES........................................................... 9 LIST OF A PPEN D IC ES................................................................................................................ 10 1.0 SU M M A RY ................................................ 11 2.0 O B JEC TIV E.............................................................. 11 3.0 INTRODUCTION....................................................................................................................11 4.0 ANALYTICAL TEST SA M PLES.................................................................................... 12 5.0 REFERENCE M A TE R IA L................................ 12 6.0 DESCRIPTION OF ANALYTICAL M ETH O D ............................................................... 13 6.1. Extraction Procedure For Sedim ent............................... 13 6.2 Direct Inject Extraction Procedure For Sedim ent............................................................14 6.3 Percent Solids Procedure For S edim ent............................. 14 6.4 Preparation o f Standards and Fortification Solutions.....................................................14 6.5 C hrom atography................................................................................................................... 15 6.6 Instrument Sensitivity..........................................................................................................15 6.7 Description o f LC/M S/M S Instrument and Operating Conditions.............................. 15 6.8 Quantitation and Exam ple C alculations........................................................................... 16 7.0 EXPERIM ENTAL D E S IG N .................................... ,.......................................................... 20 8.0 R E SU L T S.................................................................................................................................20 9.0 CO N C LU SIO N S..................................................:....... ;.............. .......................................20 10.0 RETENTION OF D A TA AND SA M PL E S.................................................................... 21 Exygen Research 1 Page 7 of 110 000140 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 LIST OF TABLES Page Table I. Sum mary o f PFBS, PFHS and PFOS in Sediment Sam ples......... ....................23 Table Q. Sum mary o f PROS in D irect Injection Sediment Sam ples, ............................. 24 Tabl m . M atrix Spike Recovery o f PFBS, PFHS and PFOS in Sediment Sam ples.....25 Table IV. M atrix Spike Recovery o f PFOS in Direct Injection Sediment S am p les...... 26 Table V, Total Percent Solids in Sediment Sam ples..............,........................................... 27 Exygen Research Page 8 of 110 000141 - aK-_______________ :________________________ Interim Report #23 - Analysis of Sediment Samples p. 119 -__________________________ _ Exygen Study No.: P0001131 Figure 1. LIST OF FIGURES Page Typical Calibration Crve for PFBS in M ethanol............ ................................. 29 Figure 2. Non-Extracted Standards o f PFBS iri M ethanol, 0.2 ng/m L and 0.5 ng/mL, R espectively.............................,...........................................................30 Figure 3. Figure 4. PFBS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/m L Fortified Reagent Spk B, R espectively............................................. 31 r' _( _ Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID: C0172892, D ata Set: 042606F).......................................................32 Figure 5. Typical Calibration Curve for PFHS in M ethanol.......................... ....................33 Figure 6. Non-Extracted Standards o f PFHS in Methanol, 0.2 ng/mL and 0.5 ng/mL, R espectively...........................................................................................34 Figure 7. PFHS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/m L Fortified Reagent Spk B, R espectively............................................. 35 Figure 8. Chrom atogram Representing a Sediment Sample A nalyzed for PFHS (Exygen ID: C0172892, Data Set: 042606F)........................................................36 Figure 9. Typical Calibration Curve for PFOS in M ethanol................. .............................37 Figure 10. Non-Extracted Standards o f PFOS in M ethanol, 0.2 ng/m L and 0.5 ng/mL, R espectively.......................................................................................... 38 Figure 11. PFO S in Reagent Blank, 0.4 ng/m L Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, R espectively.............................................39 Figure 12. Chrom atogram Representing a Sediment Sam ple Analyzed for PFOS (Exygen ED: CO172892, Data Set:042806B )........................................................40 000142 Interim Report #23 - Analysis of Sediment Samples p. 120 Exygen Study No.: 1*0001131 LIST OF APPENDICES Appendix A Study Protocol P000|i 131 (Exygen Study N o. P 0001131) with Analytical M ethod V0001782: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/M S/M S", and Protocol A m endm ents................................. Page ,41 Exygen Research Page 10 of 110 000X 43 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P001131 r 1.0 SUMMARY Exygen Research extracted and analyzed sediment samples for the determination o f perfluorobutanesulfonate (PFBS), pprfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) according to Exygen M ethod V0001782 (A ppendix A). The limit o f quantitation for PFBS andPFH S in sediment was 0.2 ng/g. The limit o f 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 m ethod yielded poor recoveries for 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 T able 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 ware 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 T able III. Fortification recoveries for the analysis o f PFOS in sediment samples by direct injection are summarized in T ab le IV. The total percent solids for sediment samples are detailed in T able V. 2.0 OBJECTIVE The objective o f the analytical part o f this study was to determine levels o f perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in sediment according to Protocol P0001131 (Appendix A). 3.0 INTRODUCTION This report details the results o f the analysis for the determination o f PFBS, PFHS, and PFOS in sediment using the analytical methods entitled, "V0001782: M ethod o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS." The study w as initiated on Novem ber 05, 2004, when the Btudy director signed protocol number 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 o f 110 000144 p. 122 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 w et ice on April 22, 2006 from Tim Frinak at W eston Solutions, Inc. The samples were logged in by Exygen personnel and placed in refrigerated storage. Sample log-in and chain o f 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 Exveen Inventory No. SP0005726 SP0002401 SP0002694 L o t# 101 SE036 430180-1 Purity (%) 96.7 98.6 101.2 Expiration Date 12/04/06 10/18/06 10/31/07 The molecular structures o f PFBS, PFHS and PFOS are given below: PFBS Chemical Name: Perfluorobutanesulfonate M olecular W eight: 338 supplied as th potassium salt (CaFgSOsTC^) Transitions Monitored: 299 > 99 , Structure: ' ... F F IF F F IF ! FF PFHS Chemical ame: Perfluorohexanesulfonate M olecular W eight: 438 supplied as the potassium salt (C6F )3S03'K +) Transitions M onitored: 399 --80 Exygen Research Page 12 o f 10 00014S Interim Report #23 --Analysis of Sediment Samples Structure: FF F. F F F F ' - F Exygen Study No.: PC001131 PFOS Chemical Name: Perfluorooctanesulfonate M olecular Weight: 538 supplied as the potassium salt (CsFnSOs'K*) Transitions M onitored: 499-- 80 . Structure: . '' 'F F ^ F ' F ` '' ' ` .. <V F F. F F . N ? <O n; 6.0 DESCRIPTION OF ANALYTICAL METHOD The analytical method "V0001782: Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" was used for the analysis o f 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. E xtraction P rocedure F o r Sedim ent 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 m illiliter centrifuge tube for the extraction. After fortification o f appropriate samples, 35 mL o f 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 centrifuged for ~20 m inutes at ~3000 rpm. The supernatant was then loaded onto a Cis SPE cartridge conditioned with 10 mL o f 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 m inutes. The samples w ere centrifuged again for ^2 0 m inutes at *-3000 rpm. The supernatant was then loaded onto th e same Cfg SPE cartridge. The eluate was collected into a 500 mL Nalgene Bottle. The column was washed with 4 mL o f 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 C i8 SPE cartridge conditioned with 10 mL o f methanol Exygen Research Page 13 o f 110 000146 p. 124 f ' ' Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: PQ001131 and 20 mL o f water. The eluate was discarded, Approximately five milliliters o f methanol was added to the cartridge, Five milliliters o f eluate was collected into a graduated 15 m L polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.2 D irect In ject E xtraction P rocedure F or Sedim ent 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-miIIiliter 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 ~10 minutes at -3000 rpm. Each sample was analyzed by LC/MS/MS electrospray. 6.3 Percent Solids P rocedure F o r Sedim ent 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 of the sample plus the pan was recorded. The samples were then dried in an oven overnight at 104 2 6C. Then the samples were transferred to a dessicator and allowed to cool for ~15 minutes. Each sample was then weighed again, including the weight o f the pan. The percent solid for each sample was then calculated. See T able V for percent solids results. 6.4 P reparation of S tandards an d Fortification Solutions A mixed stock standard solution o f PFBS, PFHS, and PFOS was prepared at a concentration o f 1000 pg/mL by dissolving 100 m g o f each o f the standards (corrected for purity and salt content) in 100 mL o f methanol. From this solution, the following fortification standards were prepared: Cone, o f Fort Stock or Fort. Volume Solution (mL) (pg/m L )1 1000 100 10 10 10 10 1.0 10 Oil 10 1 o f PFBS, PKHS, and PFOS Final Volume (mL) 100 100 100 100 100 Final Cone, of Fortification Std. (pg/mL) 100 10 1.0 0.1 0.01 Exygen Research Pge 14 o f 110 o o o i4 7 p. 125 Interim Report #23 - Analysis o f 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: r . - Cone, o f Fort Fort or Calibration Volume Solution (mL) (ng/m L )1 100 1,0 100 . 0.5 100 0.2 10 1.0 5.0 1.0 2.0 1.0 1of PFBS, PFHS, and PFOS Final Volume (mL) 10 ,, 10 10 10 10 10 Final Cone. 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 Instrument: API 4000 Biomolecular Mass Analyzer Interface: Turbo Ion Spray Liquid Introduction Interface Computer: DELL OptiPlex GX400 Software: Windows NT, Analyst 1.4.1 HPLC: Hewlett Packard (HP) Series 1100 HP Quat Pump Exygen Research Page 15 of 110 000148 p. 126 T*" Interim Repart #23 - Analysis of Sediment Samples Exygen Study No. : F0001131 HP Vacuum Degasser HP Autosampler HP Column Oven HPLC Column: Thermo Fluophase RP> 50 mm x 2 1 mm Column Temp.: -3 0 C Injection Voi.: 15 uL Mobile Phase (A): 2 mM Ammonium Acetate in water M obile Phase (B): Methanol Time fminl 0.0 1,0 8,0 10.0 1L 0.... 18.0 Total run time: ~ 18 min %A 65 65 25 25 65 65 %B 35 35 75 75 35 35 Flow Rate: Q.3mL/mm Ions monitored: Analvte PFBS PFHS PFOS Mode negative negative negative Transition M onitored 299 - 99 399 -> 80 499 -> 80 Approximate Retention Time (m ini ~0.56 min. -9 .4 min. ~ 1 1.4 min. 6.8 Quantitation and Example Calculations Fifteen microliters o f sample or calibration standard were injected into the LC/MS/MS. The peak area w as measured and the standard curve w as 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 0 0 0 1 ^9 e---------------- ~ "' ---------- p. 127 ' ' ' Interim Report # 2 3 -A nalysis of Sediment Samples - Exygen Study No.: P0001131 Equation 1: Analyte found (ng/mL) - iPeak area - intercept) x DF Slope Where: D F = Dilution Factor, factor by which the filial volarne was diluted, if necessary. For samples fortified w ith known amounts o f PFBS and PFHS prior to extraction, Equation 2 was used to convert th amount o f PFBS and PFHS found in ng/mL to ng/g (ppb). Equation 2: Analyte found (ppb) = fAnalyte found fng/m Ll x final volum e (5 mL)1 sample weight (5 g) Equation 3 was used to calculate the percent recovery. Equation 3: Recovery (%) = (analvte found (ppbl - analyte in control (ppb)) xlOO% amount added (ppb) Equation 4 was then used to calculate the amount o f PFBS and PFHS found in ppb based on dry weight. 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 (calculation is for PFBS only): Sediment sam ple Exygen ID: COl72893 Spk F (Set: 042606F), fortified at 4 ng/mL with PFBS where: v, peak area intercept slope *; : .. , ,, f. , . =: _ = 253819 -592 42300 dilution factor , , - ff- u 1 , ng/g PFBS added (fort level) = amt in corresponding sample (ng/g) =r 4 2.41 final volume (mL) ^ , sample weight (g) =? 5 = `5 total solids (%) = 54.37 Exygen Research Page 17 o f 110 000150 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: POOO1131 From equation 1: Analyte found (ng/mL) = T253819 --f-592>1 x 1 42300 = 6.01 ng/mL From equation 2: Analyte found (ppb) = (6.01 ng/mL x 5 mL) 5g = 6.01 ppb From equation 3i % Recovery . = (6.01 o n b - 2.41 opbl x 100% 4 ppb - 90% From equation 4: Analyte found (ppb) dry weight ~ 6.01 ppb x (100% / 54.37%) = 11.1 ppb NOTE: This value may be slightly different than that o f the raw data due to rounding. A slightly different set o f calculations was used for the direct injection 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 o f PFOS prior to extraction, Equation 2 was used to convert the amount o f PFOS found in ng/mL to ng/g (ppb). Equation 2: Analyte found (ppb) = (Analyte found (ng/mL) x volume extracted (10 mL)l sample weight (1 g) Equation 3 was used to calculate the percent recovery. Exygen Research Page 18 of 110 0 0 1 S 1 p. 129 Interim Report #23 - Analysis o f Sediment Samples - ' Exygen -StudyNo.: JP0001131 Equation 3: , Recovery (% )= , (analyte found (ng/g) - analyte in control fng/eVl x l0 0 % amount added (ng/g) Equation 4 was then used to calculate the amount o f PFOS found in ppb based on dry weight. Equation 4: ' .. ' Analyte found (ppb) dry weight = Analyte found (ppb) x [100% / total solids(%)J 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 slope dilution factor = 3720 = 22700 -- 100 ng/g PFOS added (fort level) = 4000 amt in corresponding sample(ng/g) = ' 2360 volume extracted (mL) sample weight (g) 10 =1 total solids (%) 66.54 From equation 1: Analyte found (ng/L) ................... = r152371 -37201 x 100 22700 = 654 ng/mL From equation 2: Analyte found (ppb) = (654 ng/mL x 10m L) ; ' ig - 6540 ppb From equation 3: % Recovery ' = (6540 n e /g - 2360 ne/e) 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 000152 p. 130 Interim Report #23 - Analysis o f Sediment Samples , Exygen Study No.: P0001131 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 for 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 m ethod are summarized in T able I. Analytical results for the analysis o f PFOS found in sediment samples by direct injection are summarized in Table IL The average perait 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 T able III. Fortification recoveries for the analysis o f PFOS in sediment samples by direct injection are summarized in T able IV. The total percent solids for sediment samples are detailed in T able 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 o o is 3 p. 131 Interim Report #23 - Analysis of Sediment Samples Exygen Study-No.: P0001131 10.0 RETENTION OF DATAAND SAMPLES W hen the final analytical report is complete, all original paper data generated by Exygen Research will be shipped to the study director. 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 the Exygen Research archives for the period of time specified in EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Exygen Research Page 21 o f 110 000154 Interim Report #23 --Analysis of Sediment Samples p. 132 Exygen Study No.: P0001131 TABLES Exygen Research Page 22 of 110 0 0 1 S 5 p. 133 Interim Report #23 -A nalysis of Sediment Samples Exygen Study No.: P0001131 Table I. Summary of PFBS, PFHS and PFOS in Sediment Samples Exynen ID CO172882 00172892 Rap C0172B93 C0172893 Rep C0172894 CQ172894 Rap Client Sample ID DAL-SD-BPP01-0-0000 DAL-SD-BPP01-0-0000' DAL-SD-BPP020-0000 DAL-SD-8PP02-0-0000'* DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0*0000# C4 Sulfonate PFBS CS SuHonsU PFHS C8 Sulfonate PFOS ParmiQfotximiMUloft11_____ Eertlniirchaaanaaulfonwe______ Parityorooctanaejltonai Analyte Found Aeeeeaed AnalyteFound Aaseeeed Analyte Found A ttttttd {ppb, ag/g> Dry Weight Accuracy < + /-*) (ppb.ngfo) DryW ant! Accuracy < *-*> (PPb.nO'B) Dry Weight Accuracy (/-%> 3.14 40 84.3 30 3.10 40 86.1 30 NR NR NR NR 4.43 30 74.5 30 4.64 30 64.7 30 NR NR NR NR 9.87 30 139 50 8.73 30 123 50 NR NR NR NR "LaboratoryOuplteata NR = Not reported due to qualitycontrol m ult failures. Sae Tibia II forre-ena|yele raeulta Exygen Research Page 23 of 110 000156 p. 134 Interim Report #23-A nalysis of Sediment Samples , . c Exygen Study No.: P0001131 Table II. Summary of PFOS in Direct Injection Sediment Samples Exygen ID C0172B92 C0172892 Rep C0172893 C0172893 Rep C0172894 C0172894 Rep C lie n t Sam ple ID DAL-SD-BPP01 -0-0 0 0 0 D A L-SD-BPP01-0-0000* D A L-SD -B PP02-0-0000 D A L-SD -B PP02-0-0000* D A L-SD -B PP03-0-0000 D A L-SD -B PP03-0-0000* Laboratory Duplicate C8 Sulfonate PFOS ' -Perfluorooctarw ulfonate Analyte Found (ppb, ng/g) Dry Weloht Assessed Accuracy (+/-% ) 3550 3 5 2 0 30 30 4160 3840 30 30 11900 12000 30 30 Exygen Research Page 24 of 110 0001S7 p. 135 A. Interim Report #23-A nalysis of Sediment Samples Exygen Study No.: P0001131 Table III. Matrix Spike Recovery of PFBS, PFHS and PFOS in Sediment Samples Sample oeecrioson C4 Sulfonate FTPSWetWeight C9 Sulfonate PfHSWelWelghl Amount Amt Found -Amount Arntpound . Amount 6pked In Sample RNOvtnd Recovery in tempi* Recovered Recovery (ntfel (natalwet wt <%> (ntfaiwehM. (*> CSStilfomdaPFQS WatWeight Amt Found - Amount In Sample Recovered Recovery (rata) wet wl <*> DAL*5 > 0 PF01*04)000 (Cttmes * * c,e pee DAL-5 I>*BPF014HXXK] fC*i?2H t dpRo, too pphape) DAL-SO-BPP0 1-0-0000 |Cei72M2Spk E.IDOOppkIplha) 4 400 4000 2.09 . 2.09 2.09 447 eo 262 66 66.1 454 80 _ 2670 7 56.1 , 5190 128 , nr .. NR NR DAt-SORPPOa-O-OOOO CeiTlMS 9pkF,4 ppbSpite) DAL-SD6 PPQZ-OOODO loeiTiiN apho, aeeppb spike) DAL-SD-BPPQ2-0-OQ0C icat72*ea m h, oaoppks^in$ 4 400 4000 2 2 41 ,2.41 6.02 SO .. . . . 374 S3 40.5 346 76 _ ` . . 2 0 96 40.5 5090 126 NR NR NR OAL-SD-8 PP03-0-0000 tcmTtaaa api>i, a Mb spiM) DAL-SD-SPP03-0-0000 {omater j. aae auk8p*> DAL-SO-BPPOSO-OOOO (C0172M4SpkK.M00ppk1^ 1) 4 400 4000 439 4.39 4.39 7.71 399 4840 93 . 89 - 61.8 121 01.6 263 4600 -_ 66 . _ 111 NR _ .. NR NR Average: aa Standard Deviation: i t 8ti Standard Deviation; 29 "Sample raeMueermeedetie epfchf feveitlgflllcantfy(3*iplWnglreiklher*fc*.ja accurate recoveryvutua cannot be calculated ND = Notdeieeied ator above lwLlmitDlQu*iltolloflp^ol0 2 fe*twmliwighb nr* noi reporteddue to owe* ooMRMresuiiiainm. Sea Taeie IVtorj*-aa*yeim4*Note: the* IhleaiMtfiiarylabte show* pounded iwuttt, recoveryvaluta mayveryatiahtirfromthe teNw Inthe m r dele. Average: NR Standard Deviation: NR Exygen Research *-rs `f* i Page 25 o f 110 000158 p. 136 Interim Report #23 - Analysis o f Sediment Sandies Exygen Study No.: P0001131 Table IV, Matrix Spike Recovery of PFOS in Direct Injection Sediment Samples S am pia Description D A L -S D -B P P 0 1 -0 -0 0 0 0 (CM72SD2 Bpk D.MOO ppb Spike) D A L -S D -B P P 01-0-00 00 (ceinsaa a t* e. m o m ppfc S p M DAL S D-BPF02-C-0000 (C6172SM Spk fi, M M ppbSpike) DAL-S D -8 P P02-0-0000 (C0172SM Spk H.MO00 ppb Spike) D A L -S O -B P P 03-0-0 000 (C01T2SM SpfeJ. MOOppb Spike) D A L -S D -B P P 03-0-00 00 tCOI72804 Spk K, MOtO P I* Spate) Amount Spiked (ppb) 4000 40000 4000 40000 4000 40000 CB S udonate PFOS W e i W eight Am t Found in Sam ple (no/u) wet wL Amount Recovered (ng/g) w et w t ............ Recovery (K > 2300 2360 6540 40000 105 94 2200 2260 5950 38000 92 89 6280 5280 8770 41200 87 90 A v a ra g e : S tandard D eviation: 93 0 ' Sample residue exceeds the spiking level significantly (3x spicing level); therefore, an accurate recovery vabe cannot be calculated ND = Not detected at or above the Lim it o f Quantitation (LOQ) o f 0.2 ng/g (wet weight). Note: Since this summary table shows rounded results, recovery values may vary slightly bom the values In the raw data. Exygen Research Page 26 of 110 000159 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Table V. Total Percent Solids in Sediment Samples Exygen ID C0172892 C0172893 C0172894 Sam ple 1 Description DA L-5D-BPPOi -0-QO DAL-SD-BPP02-0-0000 , DAL-SD-BPP03-0-0000 T otal S o ld a (%) 66.54 54.37 44.46 "Mi'l *I t .* Exygen Research Page 27 of 110 000160 Interim Report #23 - Analysis of Sediment Samples p. 138 Exygen Study No.: P0001131 FIGURES Exygen Research Page 28 of 110 00161 p. 139 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 1. Typical Calibration Curve for PFBS in Methanol 04S808F S iH IlM ritlib (P F B S ; "U lM Jf R tfll lion f 1 / m itM In g ): y 4 .2 3 * f0 0 4 x * 0B2 (r OJOSOO) A rea, counts Exygen Research Page 29 of 110 0O162 Interim Report #23 - Analysis o f Sediment Sampler* Exygn Study No.: P0001131 Figure 2, Non-Extraeted Standards ffPFBS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively I 0NMSM-Pnpunst}SMHMR9 -,%iirpl ff4$Jre MSitffF.wW A rtr: t W c n r i i H tig M ; KTs USS4m Exygen Research Page 30 of 110 000163 Interim Report #23 Analysis of Sediment Samples Exygen: Study No.P0OO1131 Figure 3. PFBS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively C otrtroi - p m C M M m r ; 9if f 45 from H H H F .m fF MtUmid) `' - Vl' * : ;^ `~ v~ 13.03 0. I R a ig m t SpfcS - PFBS C^C)200-0*0.0 amu - sample 10 of 4ff *om 042006F.rtf A m i : 10822? oeuftto Height: 1.1-1 *+004 *p* R T: 0.667 min 066 Exygen Research Page 31 o f 110 0001G4 p. 142 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID: C0172892, Data Set: 042606F) | CH72IR W M (IM n m iJ IM H M i m -tam p !* T *o fIS trom MXMKwflF A n a : r M c w i t t H U g tt 2M+M3<pt T: 1570 r*i 0.67 Intensity, cps H=4**-` er 7 Q 10 11 12 13 14 15 15 Time, min Exygen Research Page 32 of 110 000165 p. 143 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Figures. Typical Calibration Curve for PFHS in Methanol 042S06F StdimtnLtdb (PFHS): "U ntil* R t j w i o n f*1 / y - 7 0 S .* 0 0 4 * + .1.1 fr*0Q3 <r- 0.9005) Area, counts Exygen Research Page 33 o f 110 000166 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figur 6. Nam-Extracted Standards cf FFHS in Methanol, 0.2 ng/mL and 0.5 ng/mL. Respectively I SSMMSM m t (R K tt9 3 M .M a f MM umfiH to t45 *OM tOSOSF.wHf A n K 12774eo*a* BTi W w f * 0.40 Intensity, cps Arta: 33003 e*utr Haight 1,73*4033 ps RT: 0.40 min 0.40 Intensity, cps Exygen Research Page 34 of 110 00167 p. 145 Interim Report # 2 3 - Analysis o f Sediment Samples Exygen Study N o.: P0OO1131 Figure 7. PFHS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively I K tojont Control PfHS |IM w m ; M it W lM M -jumpl'* o*4S Item t tS H f.w tn fstrH ootftm w d) ............................................ 93 0.40 Exygen Research r * *s>^ Page 35 o f 110 000168 p. 146 4. Interim Report #23 --Analysis o f Sediment Samples- , Exygen Study No.; PQG01131 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for PFHS (Exygen ID: C0172892, Data Set: 042606F) I c tm m -P F H S 0 **M M ^ 3 M .ftW L 0 w v t cf4 S * o m M 2 IM F M ir A n *: fM fgit: 123+0U3ep# K T sM Im m 0.41 Intensity, cps Exygen Research Page 36 of 110 000169 Interim Report #23 - Analysis of Sediment Samples Exygen Study Nl: P001131 Figure 9. Typical Calibration Curve for PFOS in'Mthanoi 042800B S .d D liib (PFOS): " U n r Rraaiian C l t i e i m i g h i r n ^ y - 2 2 7 + 0 0 4 x + 3 72*+003 (f 0 .8 8 ) Area, counts Exygen Research Page 37 o f 110 000170 p. 148 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Figure 10, Non-Extracterf. Standards of PFOS in Methanol 0.2 ng/mL and 0.5 ng/mL, Respectively I S S M M 5W PFOS (Stam ford) 4 M L ftM * w - w io t* 1 o f 45 from M 2*M flLw ffr d m : f M 9 c M r t e N rigA t: U f i - 4 l 2 c f M RT: f t # 1 1 .4 3 Tima, min I S 5 0 0 1 4 6 0 $ P F O S ( 9 ta n d a id ) 4 0 0 - Q J 8 D .C j r r u i - O m p J 2 * f 4 $ front 0 4 2 9 0 0 B .Miff A f*j: 12226 o o u r* H aig h t 7.72 a+ 0 0 2 opt R T ;1 1 .4 m in 1 1 .4 3 Exygen Research Page 38 o f 110 000171 Interim Report #23 --Analysis o f Sediment Sampled Bxygen Study N.rPOOOl 131 Figure 11. PFOS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively K tagaat Centro! - PFOS -tam pH '9 oT4STn>m i f l I W M i r ' Ana: 339coaata H aight 2.4to*00f epa XT; tfS m l a ' ' ' 11. 2r I R t i t . i l Spk A - PFOS ( 0 0 4 0 0 0 * 0 .0 n a u in p li B ( f ro m >428086 A : 10080 ciMintF 0.21r*002 cp> RT:11.4 m i. | R ig .t 9p* B - PFOS (OQ OXUBOO i n t - u n .p l. 10 .f 46 ft.m 042B08B.Mitf A r t e 0 0 7 0 1 o r a n tt H .ig M : B 0 7 . .0 0 3 t p . RT: 11 4 m in Exygen Research Page 39 o f HO 000172 p. 150 v* . . ... Interim Report #23 - Analysis o f Sediment Samples . Exygen Study No.: P0001131 Figure 12. Chromatogram Representing a Sediment Sample Analyzed for PFOS (Exygen ID: C0172892, Data Set:042806B) I C IJ 7 2 M 2 - P F O S - t r m p l i 1 t r t -43from *42t06B.wiff A m : 5*91 c o u rtt AT; 113 m fr Intensity, tp s Exygen Research Page 40 of 110 000173 Interim Report #23 - Analysis o f Sedirhent Samples p. 151 Exygen Study No.: P0001131 APPENDIX A Study Protocol P0001131 (Exygen Study No. P0001131) with Analytical Methods and Protocol Amendments Exygen Research ^W' *$t 4 Page 41 o f 110 000174 p. 152 Interim Report #23 - Analysis of Sediment Samples , ,/Exygen Study No.: P0001131 ExygemProtocol Number P000113 > STUDY PROTOCOL Study Title: AnalyiU of Perfluorobutanesuifonate (PFBS), Perfluorohexanesuifonate (PFHSX and Perfluorooctaoesolfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program Exygen Protocol Number: P000113! P crfon nin g Laboratory: E xyg en Research 30 58 Research D riv e S tate C o lleg e , P A 16801 Phone: (8 1 4 )2 7 3 -1 0 3 9 Snonaor R epresentative: M ic h ae l A . Santoro D irecto r o f R eg u lato ry A ffa irs 3 M B u ild in g 0 2 3 6 -0 1 -B -1 0 S t P aul, M N 5 5 144 P h o n e:(651 )73 3-63 74 Atogr I aj 65 Exygen Research Page 42 of 110 0003.75 p. 153 Interim Report #23-- Analysis o f Sediment Samples : : - Exygen Study NoVrPOO1131 Eiysen Protocol Number: POOOI131 DISTRIBUTION: 1) Jaisimha Kesari, Study D irector, W eston Solutions 2) John M . Flaherty, Principal Investigator, Exygen Research 3 ) M ichael A . Santoro, Sponsor Representative, 3 M Company 4 ) Exygen Research Q uality Assurance U nit Exygen Research ? *-ft-f t Pag* 2 c f 63 Page 43 of 110 000176 p. 154 Interim Report #23 --Analysis of Sediment Samples , Exygen Study No.: P0001131 Exygen Protocol Number: POOOl l i I PROTOCOL APPROVAL Study T itle : Analysis ofPerfluorobulaneaul&nsle (PKBS), PerfluorohexaceauIfonBie (P FH S ), and Ferfboroocucesulfcnste (PFO S) in W ater, S oil, Sediment, Fish, Clams, Vegetation, Sm all M am m al Livers and Snudi M am m al Serum Using L O M S /M S tor die 3 M Decatur M onitoring Program Exygen Protocol Number: POOOl 1 3 1 ........................ Exygen Research Page 3 u j 65 Page 44 o f 110 000177 Interim Report #23 -A nalysis o f Sediment Saniples p. 155 Exygen Study No.: P0001131 Exygen Protocol Number P0001131 TABLE OF CONTENTS TITLE PA G E______ ..... ........ .......1 d i s t r i b u t i o n ___ ____ ..........................I PROTOCOL APPROVAL. TABLE OF CONTENTS ... ..........................3 .......... 4 INTRODUCTION............... TEST M ATERIALS..... ...... OBJBCTIVB....... ............... TBSTING FACILITY____ STUDY DIRECTOR...... .............. .................. S .......................... 5 ................6 ...... .................. 7 SPONSOR REPRESENTATIVE........... PRINCIPAL INVESTIGATOR__ __ _______________. 7 PROPOSED EXPERIMENTAL START AND TERMINATION D A T ES.................... ..................................7 IDENTIFICATION AND JUSTIFICATION OF THE TBST SY ST E M _______ .' ......................... S SAMPLE PROCUREMENT. RECEIPT AND RETENTION............. ............. .............. ................................ $ SAMPLE IDENTIFICATION............................................... ............................. ................................... .........,, 9 A N ALYTICA L PROCEDURE SUM M ARY________ ___ ____________ ______ _____ ______ 9 VERIFICATION OF A N ALYTICAL PROCEDURE......................................... ............. ................................9 METHOD FOR CONTROL OF B IA S ........................... .................................. ............ ....................... .... 1 1 STATISTICAL METHODS................................................................................................ ................................]) O IP STATEM ENT_______________ _________________ ;................................................... .........11 RE PO R T.,._______ __ ,,_________ __________________ __ _____________________ __ n SAFETY AND HEALTH........... ................................. .......................................... ................ ........................ . 12 AMENDMENTS T O P R O T O O L .................................................... ................. ...................... .................... . 13 DATA RECORD KEEPING............................... .... ............... ........................... ...................... ...................... 13 QUALITY ASSU RA N CE______ _____ ________ ____ * ................ ................... .................. ............14 RETENTION OF D ATA AND ARCHIVING .................................................... ............ ............14 APPENDIX I, ANALYTICAL METHODS........ ...............................................................................................15 Page 4 o f 65 Exygen Research Page 45 o f 110 000178 Interim Report # 2 3 -A nalysis o f Sediment Samples . p. 156 , Exygen Study No.: P0001131 E xygen P rotocol N iu n b e r POOOH3I INTRODUCTION The pwposo o f this study is to perform e&atysis fc r perfiuorobutanesulfonate (PFB S), perfluorohnrancsuUbnste (P FH S ) and perfiuorooctancsuIfonate (PFO S) in water, soil, sediment, fish, clams, vegetation, sm all m ammal liv e n and sm all mammal serum using L C /M S /M S fo r the 3M Decatur M onitoring Program . The study w ill be audited fo r compliance w ith E P A T S C A Good Laboratory Practice Staadanli 40 GFR 792 by the Q u ality Assurance U n it o f Exygen Research. . TEST MATERIALS The test m aterials are pertluorobutanesulfonate (PFB S). pcriluorahcxancsulfooatc (P FH S ) end perfluorooctaacaulibnate (PFO S) and aie a ll supplied by 3 M . PFBS Chemical Nam e: PeiUuorobutanesulfbOate M olecular W eight: 338 supplied as the potassium la k (C*FSOjTC*) Lot Num ber. 101 Purity: 96.7% Transitions M onitored: 2 9 9 - 9 9 Structure: F PFHS Chemical Nam e: PorEuwohexacesuifouate Molecuter^W eight: 438 supplied us the potassium salt (C s F n S O jT O Lot N um ber SS036 P urity: 98,694 Transitions Monitored: 3 9 9 - 80 . Structure: FFF P a te S o f 6S Exygen Research Page 46 of 110 000179 Interim Report #23-A nalysis o f Sediment Samples' p. 157 Exygen Study No.: PQOO1131 Exygen Protocol Number: P000 M3I PF06 Chemical Name; Perflunroactaaem lfboate M olecular W eight: 538 supplied a the potassium ealt (C sF itSOj'K *) Lo tN utnber: 217 - / ; Parity: 86.9% ' . i-*:- " ' ;' ' {' - Transition*M onitored: 499'^ 9 9 !l , Structure:' 'll' ' " r ' ` OBJECTIVE The puipoec o f tfiis study is to perform analysis fo r perfluorobutinesuHbiisto (PFBS), p eriluorohexinesulfonate (P FH S ) and perfluorooctanesulfonate (PFO S) In water, oil, sediment, fish, clama, vegetati, am ali m amm al livers and amali mammal sena for the 3 M Decatur M onitoring Program using the current versions o f the follow ing Exygen analytical methods: V0001780: "Method o f Analysis fo r the, Determ ination o f Perfluorooctanoic A cid (P F O A ) in W ater by L C /M S /M S " V 0 0 0 1 7 8 I: "M efood o f Analysis fo r the Determ ination o f Perfluorooctanoic A d d {P FO A ) in S oil by L C /M S /M S " V 0001782: "M ethod o f Analysis fo r the D e te m in a tk o f Perfluorooctinoic A dd <P F O A ) in Sediment by L O M S /M S " V0001783: "Method o f Analysis fo r the Determ ination o f Perfluorooctanoic A cid (P FO A ) m Fish and Clam s by L C /M S /M S " 0001V 784: "Method o f Analysis for the Detenm nation o f Perfluorooctanoic A cid (P FO A ) in Vegetation by L C /M S /M S " V0001785: "Method o f Analysis fo r the Determ ination o f Perfluorooctanoic A d d (P FO A ) in Sm all M am m al L iv e r by L C /M S /M S " V 0001786: "M ethod o f Analysis fo r the Determ ination o f Perfluorooctanoic A cid (P FO A ) in Small Mam m al Serum by L C /M S /M S " TESTING FACILITY Exygen Research 3058 Research D rive State College, PA 16801 Phone: (8 14) 272-1039 Pag* 6 o f 65 Exygen Research Mr Page 47 of 110 00Q180 Interim Report #23 - Analysis o f Sediment Samples p. 158 Exygen Study N o.: POOO1131 Exygta Protocol Number. P0001131 STUDY DIRECTOR Jaisimha Kesari P .E ., D E E W eaton Solutions, Inc. 1400 Weston W ay W art Chester, P A 19380 Phone: <610) 701-3761 Fax: (610)701-7401 j .kesari@ westoinolutioni.com SPONSOR REPRESENTATIVE M ichael A . Sanimo 3 M Company D irector o f Regulatory A ffaire 3 M B uikU n* 0236-01-B -10 S t Paul, M N 55144 Phone: (6 51) 733-6374 PRINCIPAL INVESTIGATOR John M . Flaherty Fxygen Research 3058 Research D rive State College, PA 16801 Phone: (8 14) 272-1039 john.lliheity@eKyeeR.com . . PROPOSED EXPERIMENTAL START AND TERMINATION DATES It w proponed that the analytical portion o f this study be conducted from October 01, 2004 te December 3 1 ,2 0 0 3 The actual experim ental n a n and term in atio n d ate* w U l be included la th e fin a l rep ort. Page lofts Exygen Research Page 48 o f 110 0 0 l8 i Interim Report #23 - Analysis of Sediment Samples p. 159 Exygen Study No.: P0001131 ExygtEPtowcol Number NOO1131 IDENTIFICATION AND JUSTIFICATION OF THE TEST SYSTEM The fo llow ing tic foe test systems fo r this Rudy: W ite r (groundwater and surface water} a S o il : . Sediment Fih a Clams a Vegetation : Sm all Mam m al Liver a Sm all M am m al Serum . - The aam plet w ill be collected by Wester) Solutions. The contra! samples w ill be purchased and prepared by tbc testing facility. Purchase and processing details for the control samples w ill be included in the fin al report associated w ith this study. The test system* were chosen to access the environmental im pact o f PFBS, PFHS and PFOS is the Decatur, Alabam a area. SAMPLE PROCUREMENT, RECEIPT AND RETENTION W ater, soil, sediment, fish, clam , vegetation, sm all mammal liv e r and small m ammal strum samples w ill be received a t Exygen directly bora Weston Solutions. The details o f sample procurement fo r this study are outlined in the 3 M w ork plan entitled "Phase 2 W ork Plan for Sam pling Environmental M edia," The number and types o f samples collected 'w ill vary depending availab ility in the field . The total number o f aamploa received and analyzed fo r each m atrix w ill be documented in the fin al report associated w ith this study. . . W ater, soil, and sediment samples w ill be used as received w ithout further processing at Exygen. These samples w ill be stoned refrigerated at 2C -8C . Fish, clam , vegetation and sm all m amm al liv e r sam ple! win be processed according to the appropriate analytical method (see Appendix I). These tiptoe w ill be a o n d frozen a t S - 10*C. Sm alt uuuninal w bok blood samples w ill be centrifuged in foe field at foe tune o f collection and the serum fraction w ill be used fo r the study. Sm all m amm al serum w ill be stored frozen at S -U P C . The receipt and processing o f the samples w ill be documented in the final report and raw data associated w ith the study. Page 8 o f 6$ Exygen Research Page 49 of 110 000182 Interini Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 E xyjtn Protocol Number: P00C1131 SAMPLE IDENTIFICATION P rio r to tru iy s il, each sample w iH be assigned a laboratory sample reference number. The reference number w ill be unique and w ill distinguish each laboratory sample that is processed throughout the analytical procedure. Chromatographic data w ill he identified by the laboratory sample reference number. Sample storage conditions and locations w ilt be documented throughout the study. ANALYTICAL PROCEDURE SUMMARY References: ., V 0001780: "Method o f Analysis fo r fee Determ ination o f Perfluorooclanoic A cid (P FO A ) in W ater by LC /M S /M S " V0001781: "Method o f Analysis for the Determ ination o f Perfluorooctanoic A cid (P FO A ) in Soil by L C /M S /M S " V0001782: "Method o f Analysis for the Determ ination o f Perfluorooctanoic A cid (P FO A ) in Sediment by L C /M S /M S " Y0001783: "Method o f Analysis fo r the Determ ination o f Perfluorooctanoic A cid (P FO A ) in Fish and Chuns by L C /M S /M S " V 0001784: "Method o f Analysis for the Determ ination o f Perfluorooctanoic A d d (P FO A ) in Vegetation by L C /M S /M S " `V0DD1785: "Method o f Analysts fo r fee Determ ination o f Perfluorooctanoic Acid (P FO A ) in Sm all Mam m al L iver by L C /M S /M S " V 0001786: "Method o f Analysis for the Determ ination o f Perfluorooctanoic A cid (P FO A ) in Sm all M am m al Serum by L C /M S /M S " The above methods use analytical conditions capable o f separating the isomers o f PFBS, FFHS and PPOS. The fin al report w ill include fee isomers summed into total PFBS, total PFHS, and total PFOS found. VERIFICATION OP ANALYTICAL PROCEDURE A laboratory osntnd sample w ill be used fo r fee preparation o f fortified oontrol sim ples. Toe test substance w ill be made into solutions as per the method, and added to fee matrices via a micropipene. For water sampling, Exygen w ill Supply one bottle per sample collected. The - bottles w in be 500 m L predeened Sci/Spec Prem ier w ide mouth H D PE bottles. These bottles have becu routinely used fo r fluoroehem ical sample P ngt9of6S Exygen Research Page 50 of 110 000183 Interim Report #23 - Analysis of Sediment Samples p. 161 Exygen Study N o .P 0 0 0 1131 i*" * Exyge* Protocol Number: POOOI1.31 collection at tbs to tin g fa cility and have been shown to be free o f PFBS, PFHS and PFOS. Sandies w ill be added to cadk container to a volum etric fill line at 200 m L. A fie ld duplicate, a low field spike and a high fie ld spike o f each sample w ill be collected. The low and high fie ld spike bottles w ill contain PFBS, PPHS and PFOS as w ell * * perfiuorooctanoic acid (P F O A ) and 1 .2 -13C perflueroOcUnoic acid ( l3C P FO A ). P FO A and ,JC PFO A are included in the solutions used to spike.the sample*. The results fo r P FO A and l3C FFO A w ill not be reported in this study. Exygen w in supply one field blank (control w ater) and two field blank spikes (control w ater fo rtified w ith PFBS, PFHS-and PFOS at>a low and high lev el) fo r every tw enty samples collected. A t the testing facility, each water Sample (excluding field duplicates and field apikea) w ill he extracted in duplicate and w ill also be fortified at a low and high concentration w ith PFBS, PFHS and FFOS and processed through the described procedure to determ ine m ethod accuracy and to check fo r bias. For soil, sediment, clams, and vegetation, Bxygen w ill supply one $00 m L precleaned Sci/Spec Prem ier w ide mouth H O PE bottle per sam ple collected or a zip-seal bag. A ll containem/bsgs used for sample collection w ill be shipped to the sample location. Samples w ill be added to each container o r bag in the fie ld . A t the testing facility, each sample w ill be extracted in duplicate and w ill also be fortified at a known concentration w ith PFBS, PFH S and PFOS at both a low and high level and processed through the described procedure to determine method accuracy and to check for b is . For sm all mammal liv er, Exygen w ill supply a SO m L polypropylene centrifuge tube. Fo r sm all mammal serum, Exygen w ill supply a collection kit fo r each sample containing serum separator tubes (red to p), vacutainers. needle holders and needles, transfer pipettes, and polypropylene tubes. A t the testing facility, each liv e r and return sample w ill be extracted in duplicate and w ill o be fo rtified at a (mown concentration w ith PFBS, PFHS and PFOS at both a lo w and high level and processed through the described procedure to determine method accuracy and tocheck fo r bias. Low and high spiking levels for each m atrix are defined below: M a trix W ster S oil S edim ent Low SpDdse Level SOOngfL tng/n A nati H le b S n lk in s Level SOOOntfL 40 na/a 40 mu's Fish lO ngfo 100 na/a Clam s Vegetation lO n g fx lO ngfg lO O n tt/R 1 0 0 n g /R Sm all M am m al liv e r lO ngfe lO O n g fg Sm all M am m al Serum 10 nghnL 100 ng/m L Pagt to efts Exygen Research Page 51 o f 110 000184 Interim Report #23 - Analysis o f Sediment Samples Exygen Study Ko.: P0OO1131 Exygen ProtocolNumber: POOOI131 Recoveries w e anticipated to be between 70% and 130% o f the fortified levels; bowevwytbe exact precision end accuracy w ill be doterniined by the enatyxii o f the quality control cample: described above. A statement o f accuracy w ill be included in the fin al report. METHOD FOR CONTROL OF !B5AS Control o f bias w ill be addressed by lik in g representative sub-samples from a homogeneous m ixture o f each m atrix from untreated control samples, and by analyzing at least two levels o f fortifications. S T A T IS T IC A L M E T H O D S Statistic w ifi be U nited to those specified in the subject methods and to the calculation o f avenge recoveries, aa applicable. GLF STATEMENT A ll aspects o f this study shall be performed and reported in compliance w ith E PA TS C A Good Laboratory Practice Standards 40 C FR 792. The final report or data package {supplied to the Sponsor) d u ll contain a statement that the study was conducted in compUanc w ith current and applicable GLP standards and w ill outline any deviations in the study from those standards. T h statement w ill be signed by the Study D irector and Sponsor Representative. REPORT A final report w ill be prepared by the principal investigator or th eir designee at the conclusion o f the study. The report w ill include, but v /ill not be lim ited to, the following: The name and addrem o f die S trdy D irector. Sponsor Representative, and o f the testing facility. A statement o f G LP compliance (any related documentation, such as chain-of-cuatody recorda, must be in the study records). Page U c f6 S Exygen Research Page 52 of 110 000185 Intrim Report #23 - Analysis of Sediment Samples p. 163 Exygen Study No.: P0001131 ' Exygwi Proiocol Number: POOOl 131 The signed tn d dued statement b y the Exygen Research Q uality Assurance U n it regarding diifcs o f study inspections and dates Endings war reported to the Study D irector Ad Managem ent. A description o f the exact analytical condition* em ployed in the study. I f the subject method was follow ed exactly, it is necesaaty to include only a copy o f die analytical m ethod. A ny m odifications to find method w ill be incorporated into the report. I f the method is photo-reduced, the project number and page number must be included on each page. ' Description o f the instrumentation used and operating conditions. A ll results from a ll sets analyzed. Control and fo rtified samples w ill be identified and the data table w ill include w n p le number and fortification level. Representative chromatograms fo r each analyte in each m atrix, including chromatograms o f a standard and a control sample, and a chromatogram at a fortification level. The location o f the analyte peaks w ill be clearly identified in a ll chromatograms. A lt circumstances that may have affected the qu ality or integrity o f the data w ill be documented in the report Locations where taw data and the fin al report are to be archived. Additions or corrections to the final report shall be m the form o f an amendment signed b y the Study D irector. The amendment shall clearly identify that part o f the report that is being altered and the reasons fo r the alterations. The amendment w ill be signed and dated by the Study D irector and the Sponsor Representative. A ll applicable requirements fo r reporting o f atudy results as per 40 CFR 7 9 2 .1 8 5 . SAFETY A N HEALTH Laboratory personnel w ill practice good sanitation and health hafcit. Bvery reasonable precaution shall be taken to prevent inadvertent exposure o f personnel and the environment to the lest or reference tubstance(s). ' Page >2 o f 65 Exygen Research Page 53 o f 110 000186 p. 164 Interim Report #23 - Analysis o f Sediment Samples ; ; , Exygen Study No,; POOO1131 E xyp o rro iacel Number: P000U3J AMEPfUMENlS TO PROTOCOL A lt significant change* in (be analytical protocol outlined here w ill be expressed in w riting, signed and dated by the Study D irector and Sponsor Representative. Amendments usually w ill be issued prio r to inltistion o f siudy plain change. However, when a change is required w ithout sufficient tim e for (be issue o f a w ritten amendment, that change m ay be effected verbally with supporting documentation .signed and dated by the Study D irector and follow ed w ith a w ritten amendment as soon a t possible. In this case, the effective date o f the written, amendment w ill hie d ie' date o f the documented ' change. Copies o f the signed amendments w ill bo ^pended to a ll distributed study plan copies. The original amendment w ill be m aintained w ith the original study plan; A ny deviations firom ihe study plan or from the analytical method a* provided w ill be documented and reported prom ptly to the Sponsor Representative. DATA RECORD KEEPING Records to be m aintained include the follow ing (as appropriate): Sample tracking sheetfs) . Sample receipt record*, atomge history, and chains o f custody History and preparation o f standards (stock, fbrtificetkm , calibration) Description o f any m odification to the method Instrum sxt run sheets, bench-sheets or logs A nalytical data tables AN chromatographic and instrumental condition* Sample extraction and analysis dates A complete listing o f siudy personnel, signature* and initials Chronological presentation o f a ll study correspondence Any other documentation necessary fo r the reconstruction o f the study C h rc m a to g ra m s - A ll chromatograms w ill contain the follow ing: S anp lc identification, injection date, arrow or other indication o f the area o f interest, and injection number corresponding to the run. A dditionally, fortifications w ill include the m o u n t o f analyte added and the sample number o f the sample that was fo rtified . **> A nalytical standard chromatograms w ill additionally include the concentration (e g.. p g taL ). Pag 3 o f65 Exygen Research Page 54 of 110 000187 Interim Report #23 -A nalysis o f Sediment Samples p. 165 Exygen StudyM o.: P0001131 RESEARCH 2056 R esearch Drive ! Phone: 814-272-1039 S tate College, PA 16801 Fax: 814-231-1580 D EVIA TIO N FO R M ssn e a !; X Prefect Specific Dviation ~ Facility Dviation Pan 1 of 2 Date of Occurrence: 04/28/06 Exygen Prefect # . P760/P1131 D ev iatio n # : s Client P roject#: NA R eference# : 06-076 Reoufatorv Driver: Dviation Tvoe: (Includo V# for methods and SPs GMP X GLP ________Other None Sam Dia d m eriatlon: X , Protocol , Method VKNA Notebook reference; NA.......... - SOP L o g in # : LQ0081& C ontain#: NA L b t# : NA Summary of Deviation: ^: The three sediment samples In L81&1 (C0172392 - C0172594) were originally extracted using Ihe sediment method V0001782. Poor recovertes were obtained forPFOS, N=OA end MC PFOA. Because of this, the study sponsor requested the use of an alternative extraction for these compounds, as follows: Direct Injection Method: Before the samples were weighed for the extraction, they ware mixed thoroughly feyvigorously shaking the container. A one-gram portion of sediment was weighed info a 15-mi*iter centrifuge tube for the extraction. Ten m illiters bf t % acetic acid in methanol was added breach sample. The samples were then shaken by hand, vortexed. and sonicated for thirty minutes. The samples Were then centrifuged for -1 0 minutes a t -3000 rpm. Each sam ple was analyzed by LG/MS/MS electrospray. Using this/nethod acceptable data was obtained-for PFOS, but the recoveries for PFOA and MC PFOA were .sea poor. Another alternative method was then used tor PFOA and " C PFOA as f o # o w s : Alternative SPE Method: The samples that were prepared In 1% Acetic acid for the direct injection method were used for tils extraction. 'FtveTTrfttWters of each sample, was HUquoted into a 50-mL polypropylene centrifuge tube and the volume was taken to 40 mLwith water. The samples were then centrifuged for -10 minute* at -3000 rpm. The supernatant was then loaded onto a Ou SPE cartridge conditioned with 10 mL of methanol and 5 m l of water. The ekiate was discarded. Approximately five mWllers of methanol was added to the cartridge. Five mWinters of etuata was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample waa analyzed by LC/MS/MS electrospray. ____Preparation____ A nalysis____ instrum ent____Client Request X other Impact: More usable data was obtained. W f1 LIBRARY ID : V0001MCM5 Exygen Research ADMINISTRATIVE FORM Rage iu y of 11U 000188 p. 166 Interim Report #23 - Analysis o f Sediment Samples CHEN EHSR 236 1B 651 733 1958 c-w-moi dmum rrMrtinwsomnoK Exygen Study No.: P0001131 05/01 '0 6 13:4 6 NO.106 03/03 mm r.in/ro m ii um utrnfciOPM M Exygen Research ***** . * / * *, * ,v . t I* :-r Page 110 of 110 000189 a-. Interim Report #23 - Analysis of Sediment Samples p. 167 Exygen Study No.: P0001131 n RtStARCH 3058 Research Drive Phone: 814-272-1039 State College, PA 18801 Fax: 814-231-1580 PROTOCOL AMENDMENT Amendment Number 1 gffecBv,Date: , 01/19TO5 Exypen Study Number P0QQ1131 Client Study Number Pegel of I DESCRIPTION OF AMENDED SECTON" 1) Analytical Procedure Summary V0001760:Secflon 9.1 2) Verification of Analytical Procedure None AMENDED TO 1) Add to Section 9.1: Section 9.1.8, Alternate weight* of standards may be used Id prepare alternate concentrations of stock solutions as necessary. Alternate levels of fortification soMion may also be prepared. 2) Low and tegf) sptdng levels o i foe analytes for each matrix may be altered depending on sample size available for extraction and/or to cover analyte concentrations expected in the samples. u RATIQNALE 1) HtQher concenlmUons of standards need to be prepared in order to spike the sample bottles et higher level*. 7) The sample ilze avalabie far small mammal Iver end serurn was *ma8erthan tpedad. Spiking at the pro-determined levels in the protocol puts the spiked concerttaion lower than the detection Bmll Also, h e analyte levels In the ground water samples are expected to greatly exceed the pre-determined spiking levels listed In the protocol. When the levels In h e samples greaty exceed h e spiking levela, an accurate recovery v ib e cannot be calculated for the QC sample. Higher spiring levels in the bottle* wiltcover the analyte concentration* expected Inthe water sam bas. IMPACT ON STUDY The LOQ Is 100 ngfe for a 0.1 g sample of sm al mammal Bver and Is 1000 notai. for a 0.01 mL sample ofsmafl mammal sarum. FBgherfevetsof spidng for foe water samples will ensure that more QC recovery data can be used. F LIBRARY ID; W 00Q 122- ExygenCWJ Review J L a L f iiliik _ ADMJNISTRAT1VE FORM Exygen Research 3 I ' A t' Page 107 of 110 OOO190 Interim Report #23 - Analysis of Sediment Samples p. 168 TT1 Exygen Study No.: PQ001131 RESEARCH 3058 Research Drive Phone: 814-272*1039 State College, PA 16801 Fax: 814-231-1580 Amendment Number Effective Date: Exygen Study Number PROTOCOL AMENDMENT '; 2 ' 03/07/06 ................................ P0001131 Cliehl Study N um ber P a g e lo H None DESCRIPTION OF AMENDED SECTION 11 Report, page 11 of 65 .................... - 2) Teat Materiata, page 8 of 85: PFOS transition monitored 480-> 99. AMENDEDTO 1) Instead of one linei report, h1itttmraparieM8.be tatuati. 2> PFOS transition monitored may eleo be 498-> 80. . ' " rationale ; 1> Due to the excessive ctees of the d atatela, Interim reports wMhe tsaued to enow the cfienl to receive data in a Umefler tern e'm'' eifa/*r *** 2} The API 4000 LCMS/MS systems d e te c t! 4 9 8 8 0 PF08transi8on with greater sensitivity than the 488 -> 80 transition. IMPACTON STUDY t) The d len tv be We to receive and rtvtoe me data more quicxly. 2) The 488 -> 80 taneMan can be dotactad wHh grimier eensMvlty; therefore, gMng better ctiromatography- Q uerwiriOcVDaDUBe-p Exygen Research ADMINISTRATIVE FORM Page 108 of 110 000191 Interim Report #23 - Analysis o f Sediment Samples p. 169 Exygen Study No.: P0001131 E xygcn P rotocol N um ber: P0001131 ______ ________________ H aOadtonka*vaaoi t o I ...................... A M A U f n C A L M r T H O P M o to d o f n i l y t o t o t o E a ta m io itii r. o r Par d o n e m m u A cid {PPOA) i . Small' M anual gam e by LO M SM S 13.0 A M u M u C w il ' ' 1 3.t C t e o c u ^ n a a m it durar > peek o f i u a j t a n K * ai 0 nmii In u n a parent ' ' o f d lito n . T te d L k w n m M d H a n w n u d tk j t o PPOA u ito , w h it t o ' fa e ^ l I-- p t t t o ) ........... H u t o a n f o n k e n d to id a . 133 todtodblrnfa mu rqWn PPOAat tombrw ar to n to LOQ ir* t W c o r n u a PPOA M louob p m tm d u n 10 M rinL, then a m w kiting ' 113 ' ' naU b m u tk d d to u o d M d teo H i M M io ik o ik -u tiK to d . t o c n a r t o o r control ipikao and matrix apkaa b u m ko k itw a n T O O * o f d w r t o o w l f liiir . If n m ro l m t o b i b c a b ide t o n n p U U i Lintm, the nrec Ml Og i f Irk ahoidd b e n * n a itia c to A n y tn o ria jpilcr outline 70- - I3 0 K M i t t o o n d u M kg t o in o ly it to t o r n a im i f i e - t n c t a b u trm iid/ ' I M `A q r eO K k n lb n a to d n rd t o o k k b ( t o riwin l nutU aaky w t o * t o H um ' B m r T to . m tr k* anfcidod to m t o calculation of t o cakkrattM t o n How ever t o M U number ofo o jlk n k o n xandarda t o t could b t u d x M M u r not n i n HWk o f t o M U m ot o r o f otondaida iujoaod. 13.3 T k o a w m lo d a o ooafll a a m 1) t o a t o n d o n o m w i f r o n t e d m in t be . hO.M2 fit1 hbM S ). I f cotibrodoe taaulla M oixaidd thoro lim iu. t o o W OOfob Of M M M U t bo t i l t o to adtiol H u m p m u p c n lio n , and the M M o o d o o rto Me0M M D fu n u lu A n d d ko w M ltn o d . 1 3 d S o n m iw t o k u w a to olondordl and a n p t o m a t aa drift a m t o n i + H w itbioaiiiootjticoIrM . Ifra tn lin i innidriftOM OOdodauKiM irklm i ton00 o m to to l m t o oat ow at ka m n aly z a d . left Ctlnlatloao l * I Voa t o fcUoariof m oatlait lu aafciiloto t o n c u a o f PPO A (band (in nob n lbam d a n poak mm) uaind t o atoodud c a m (b luer ragaoilon poranunfl) gan e n lod b y t o M am 1)011 aoflwaaa paogTaai: PPOA to n a l (apfmi.1 a O P a aliquot faccac D F <*b o o r ky winch t o tkaai vnhana waa A ln ia d i f aecaaaary Attune* t o t a l * 20 1A2 P er janaggao h W a i w ith know a to n m a ad PPO A fa in t o E xtn d io o . nac t o UUrwiao apuotoitrcaiciiiiaa to p a rc a a i lacovary. toaoaaayCH I* [ total n i n e F u n d (n ohnL) - roofanofaiiaidtnceoCHl<n^BU-)l . ,, P agt64of6i Exygen Research Page 105 o f 110 000192 Interim Report #23 - Analysis o f Sediment Samples p. 170 Exygen Study No.: P0001131 B xygn Protocol N m ix r P0001131 m w lW iO i Attlfrlil ', M vM Motel VMMW amalvtical m it k o p OfTofluoroogliiwtf Acid(PFOA| mSwl UkucimI SframbyLOMJ/MS U 5 !>M iMMo>wfaf qwbMancoBvcit MMKMMtorPPOA found nn^m Lu) ` **R)AfcM d(ppb) HOfrfavs to B c tn lj Exygen Research Far fan Page 6$ o f 65 Page 106 of 110 000193 interim Report #23 - Analysis o f Sedihieiit Samples ' p. 171 ExygenStudyN o.: P0001131 Sxygan Protocol Number: POO01131 M in i n m itv m c h h m rruoo' a x a l y t i c a i . "[ H U M ofAnelyele f tT fa rk litn iiiie iiia i T P erftioaiotiaante A cid f>FOA) in Smell '. M u tu a l S erna by LOM SIM S 9j0 S t u f a l i fn p ee e tfo n 9.1 *"* "* t h u M U NiUffafaii t a l t H u i .C.l to p a to e M o tk K d W a e f~ 1 0 0 ta L e fP F O A by weighing 10 m t e t ate i) ! riee l i i d (M ncied f c r p u r it y ) i n f d ilm e io lO O m L a itk s e d o t t i s i e 1 & U I .L D K borile, 9 . U A 1.0 M U L f a t i ll e a i e ii e e h riia e o i PFO A 1 prepared by bringing > a t o f f a tM iif ta L M tiilw a lD a One! voJu b k c f 100 wiiji nuilinivl k i llSMLLDPEloit. 5.1.S A 0.1 p y ta L fb riillc a tio o lc tlitfe a o T P K M .il prepeiod b y b m p a i 1 ' . o f f a 1.0 M t a L e e M u a i t i i a l eo k e p c o r 100 with m o an ! m a l u L L D H barila 9.1.4 The fin d : end feritflcariae w k v m i a n to b e n o ead In l l e f n e m io r m U b h i u I) f C a d w o ita b k far a n a period O f 6 rimnllw 9 J ffieadMd C a ifk k io a Salutam i 9.2,1 LQM UM SetUbnlinaatudeidia r a p n p a n d i n n a t f e u a l via Morion o f f a Oil p f M , fe n U e k ia a eeteileo. 1 12 T he A lleaS b i it a typical example: adtUNeiiAj eoecanliafiaee m ay be CfemViRlIlM VefcM JMtMalo Pinal Caiwmtratiaa M totfettod.) 1 m .. ID# M L) 1 U )<0 0i4.j 100 100 IDO CnofrnU 5.0 2.0 1.9 .U W 100 0.5 24 100 04 IJ^a1S4SiSSS>0a^ikfaS10r0iM^mri^BM0.1ow-inoulhbottim t ir e a re ,u p mat nrna*. 9.1.0 A h acn ili y p k o ie i a id cane u r i a l lari* o f ata n d a n k m ay h i p n y e ro r a* tao BatrbfaUp : . t o t le a k b a ta b a f B rifto a r tic le d (l>p*nH]' U at le a ) to o i w M r le t . eee i ta o a a tu c o a ro l end tw e la u n x M c o t t o n feriiHad known tca a u e iB c i i (M b a to n a l apifcea la verify p a ced recovery far f a bereh M l, RipuJuim o m f a BeM ta d labna a t y iKa Mreai Md arte wilt be ipcciliaJ in f a quality m e n c e p i u fc r Urie p n je e l. pic4r? P*gt 62 # 6 3 Exygen Research Page 103 of 110 000194 p. 172 Interim Report #23 ~ Analysis o f Sediment Samples ; Exygen Study No.: POOO1131 Bxygea Protocol Number: P0001131 o ip tn -rt mmm v o n in * I " ANALYTICAL M tra o a 3 t o 8 ^ i ^ Afllll i i X t t a l W Dtt tllilll l i lo f O n * i aiiUM t r A rid ( P F O A ) Small l i m a i Satani Oy LCVM3MS ] 11.0 S s a p le S m e t t o U .l U s a n t e l a l . o f m y f e in>o 3 0 m L y a ljvtn p j l r DE cem n O n ia f r a (fortify s a t a M n o t a t o t i a n i m a m lQ . Not ta li allentata n a to n e o f K n in a f t e t a r m im i riapaartiao e * u n ip la alani av a ala tln to eu a t- 31.2 * M ( * n l o t a a o ^ t a f c r f t a t ) o n t i n n o f i o L C aptljliU y 11.3 V e n e f a ~r stom a. t u TV oatte S mL o f tao m o to i m t * nifim ito p ip a in o a l i n L . diifinia>ln (o o W lip i n t U A d d i n i L tf aaataaaniaani li u t i f a - a o i a t o n a a m m m u tiwi l U cr , t u . d r i r |i i t a n f t a i a l 000 rp n f a - 3 n in n a i 1.7 ramini fin inum ani latri a 1Hwt toapamtli- rantrilhi lutar ami aiti! 13 mg, . I U Cttom.* C w I T I t t r t r i d f * (1 p. < a L ) Vy g u itt i >9 n L m ettano! S m d iy 5 s l f H ttC w w r ( ^ 2 * e p W . D oupilrteclw nn wndry ! ' ** U c d lV c is B ft* M g n d lta M d C > i STC cartxdit- D itcv d lu rtc - >L IO S hM itfl 4 L i f mA i m L C o lU tt 2 m l o T lu u c ina a in d u ite il . IV LGftWMS.H f w t p j f r f r a n rtp rtttriftgg wbo (Hmil 2 mL), i l i & B f ilk o > iisaM M K Q r ac m l 4 a a a ip la aiid fe rtifo d fifB p k imo tw UAoMb A cadbmiM Modard mu>( p m d e aid (Wtow all 112 Slidari ofTFCt* CwranoiitIimto * tati fiy q r ora caacammhm levate nuHbawledediaan aaaljrtiaai art. 1 2 J A* t ir e art o f calibratoli Standards m u ti t e rtelycM t t tba b # fin iM | end m f r rir* ~*ir im p ili i l i Stendardi m urt b t m lrtap en o d belwmfl vcry 5* io lim it a i. A M l l r t M U n , a * M id n a r t o f calibrati! riandante may be . teneteif * Ibi btlinibn l i I h i fbllmicd by aaJibndboi umliNlt ietenpamdmey 5-10 l^toaccani fcr l econd mi of Hinderte). In majoc*.rttfwr nuai calibratoli it w M f must bt (ha Arai n hit manna ia a 12.4 Ibv Bm v rtiadard n m b r Um v riandarti curvai are jaartilidfcflbaHim i bifli-- wy l M --ng is* wrcixMoi of peik area tonicalibiala rtMdwd eonccacrrtion arte MaaaLynx 3J (or oqwivalonii nfeTVMpateHL 174 MqrtHaa ittooJd ad cw d efenlerd mponiaa. Any sumpfet ihal m attd tnadasdimpanisi ttoold bc ftiiHwrdilatai d rnaMfriid. h y J lofi Page 63 # 65 Exygen Research Page 104 of 110 000195 Interim Report #23 - Analysis o f Sediment Samples p. 173 Exygen Study No.: P0001131 E x y g e n P ro to c o l N u m b e r: POOOI ) 31 iapiwl aaaail* - IkM HHtvVtMlitt I MALVnCALMCTIlOP ~ M *od afAjalpis t e On D i h i i M a ofPafluannctaiisk Acid CTFOA)in SmjT U n n i S m by LOM&MS 10 Step . ' 2.0 T b* s ta te d is isbsanpfcyadlbftlN M a d s* ssd lattiM ioasrperiluiK iocM oK s o d by Hi*h PsHbatnsacs Liquid C h m sa trip ip b y c c tp le d is ta s d s n U is t SpootracM tnc E taiM w ( tC M S M S ) vn a m U H w iu n il len m t Baft* 2.1 Afcraya oWen n n f t tab v n io iy pernice. 2 2 Ccp--il ft w c p r i K MSDfl bcibw lwndliQ i any c h a o ic tl for ptopv n fe iy pMMlMMtti 3J> SniTpla PaqaijsitM sd 3.1 Al !asal I islo flM H ^ lsfersu n c a co . M N s n a f t s m o m l i i f l i e t i t i lot oteom aas ig l ll , H ow avw . h a m s m s M s t a t u s alkaaitd 1 osasplataiy t e w is s o m M p a a s b r o S a b re use. 3 3 l aw plr B a ta te paw adsaas w ill b t apariflad i s t o aaaapto* p i far I b i r3* 4 0 Itregn a aa i U n i d i t ila 41 W abr-H PL C paSa 2 S tated !-H T L C p id t 4.1 A t a dirila - H W X p sd a 4.4 Amnsmsn Annata - AXIS. Urngm Onda 4.5 ParfhioaasetBasieAcid-9ipaAUnck SO Inatnm aadioU Ssaipoaaia 1.1 A hipb p a t t a t e n e * bqid d n a s a t o p i p f c capable o f p u n s i* * up i s 2 eetvas* epreppadw ilb a aa iia h ls volum e ia is e ts r capable a t iq s c t ii if S .2l>0 *L commcM ib a la r d * M a is S p a e n n s l t r O C M 3 M 5 1 3.2 A dairiesle sonasi aaw ala b e ( a d basan d o li and ipiaaiiisikre 3 3 A a aly licllHa laeie i rap al i * o f l a i l d ^ I s 00 0 0 0 1 g. SA 30 mL d iipou M e pslypaopylsire casarif a y nitoe. 5-5 11 m L drip eeeble polypropylene c e n s i t ip e tubas Id DlepoeeNeifcl<>pipell{50-H>0*L, IW-POOuL). 1.3 i a t t u r a aaam aoaoailbbsM aa. 5. 2 n d . cleat H P L C w alW . 3.3 Op asab la pip atasi. 3.10 Anlopip<iaaa(lQ0.1000 p L a d 10-100 |iLX w ife djapoaifela ripa. 3.11 Walcaa Bap Pa* Vac 6 ac ( ] | ) t C l l 3F E cartridges. 3.12 gB asaaiasnsasM bW . 3.13 van asar. P tgt tofS Exygen Research Page 101 o f 110 000196 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P00Q1131 Kxygm Protocol Number: POMI 131 m n n t i iiMrt , M aM N w tcrV H V I [' l i w TIC A 1 M ETH O D : T<rtm'<nfnnil)ilitlliHiilMlliw irn^inrmnHnnir ili it |T m n m'inill I 15.11)* . W II|M cttaiiM ir. Caraifat ippHtr f , ipiptet 1>1p>ly|<p)lli MM 1X *0ipra. 4 r C baw m fnfcH S yM a ' l l A iw ly lio l O l > m F l w p b m H P V x y a m S t i m i l e ) . 3.1 m m 50 w n . V . ( f lit I23&MH21341 . m iwttm tm arc 13; McM 1mm(): 2raM.Ain*ira Attirait W m M .M M A w O ) : MbQwotI i W G ndttctfnrm K f lo w JUae % A & B fPMlAMlrt 0.0 AS 55 0.3 1*0 65 55 0.3 25 T5 0.3 2 C J 25 7$ 0 3 t 65 35 0.3 .* bprtiea Vibra* I)yl(nabiiufiM M dlom Mu ch m 30ftL) 17 QttaBttkia: PHkAM -tzlMtlitiBtedeilibraliMtnim. .. I I RaflT ira r t-23abraha TteAonuntklMrraibiteiiM t i t gnidim l atybicliiniidm trier m . JipIPeiwIlBltoUCayibEi. 7. MSMSSymn 7.1 M pk B n m vi> rN vim M tN M d itiN M N i^ |4l3 ^ M 9n i/i(n m i.O Penn i n i 8i tiiiran 1.1 MofaikPfcm P.1.1 T r a i l i u m r a i r a u n i r *- ~ * * ~ " r ~ | ------1 v r " " " I " '** I * a a w n a e a lik lM illirv W . ..hiirajlmaraorayWc ifrali rra>>*f' Page 6 i o j 65 Exygen Research Page 102 of 110 000197 Interim Report #23-A nalysis of Sediment Samples p. 175 Exygen Study No.: P0001131 Exygoa Protocol Nwnber: P000] 131 EKyiM tw w rt. . v .,,V -I.V J* /' I .,- - A M A L.VIK 'AL>MCTKOD " ' I MwtwiofAjiliiiifccBitniiimilliiii/yeri>miiiollAellliPyOA)iiiSinM ' . . . MmNl Lmrby LCM3/MS !** f t i g m lw M M wMi tanw a a w M o f F K M prior to enmorion. w t * M o to i n j W M It w 10 cttleqUlo I h t p y c o u m a y o r / . Rmmt(K)- J< oM ibMi IM (iwiW - M fttfeM iiooaM O iiO iiL)] M Nl*00*MrivM<> w 14J Um dot iqaliM i 1CMVtnit* iraouai ofPFOA found m n^mL fe WOAtt.oJfml.t-rproAfanMIfMnrfdtnt<Ln'Ii(iiUf<uta)l r-l.tl Exygen Research M 7' Pe%t$&&/65 Page 99 o f 110 000138 Interim Report #73 - Analysis o f Sediment Samples p. 176 Exygen Study No.: P0001131 Exygen Protocol Number POOOl 13] /tNALYTlCAL METHOD M M M q k r; V00017W ~ ibyLOMMUSM rth o i t f A w l y * fa r f t * n i f iliiettM a y a j l i i m i m l c AriO (FFO a ) hi m i l AMlyfeilTMlBgFietttir BiMy fuRK w* *rcDhrive SmunnufAimi ApptttedBv: \-L ~ k , c _ J t L " iirw rin j \ TveteteclkweVr,IT M3,Bcypa E m * m liifo tt Date JiriFliba^r X r n e e d i D i . GocnJxm Bxys* RmmrIi Dew Exygen Research TetriFirm: 7 P*%t 59 o f 05 Page 100 of 110 000199 'V* ..V , l; Interim Rcport #23 - Analysis of Sediment Samples < p. 177 Exygeri Study No.: P0001131 G u y g ra P ro to c o l N u m b er; P 0 0 0 1 131 , wU' - t - ..... . , ._L. , MMNM>kKVOOOI?tI I ... .T.. . ^'^sALYTiCAiMgniop ^ I*M<ofArotyillWknPnNwntnilioiiofynrilmnoonlinoieAold(PFOA)inSimII -- . . M m c a l Liver by L C * C /M 5 10.0 BfacttaOp ' 10-1 ' Bilik M b o f l u n ik b U cM [ty p ierk y 2 0 o r k w ) miwl inclgdn t a w O X un w o l m M m i c m unm oM d a o n o li R x tilM u known 10. w n c a M k il ( l riil f i Vr)l<i y rifrproot<)(l w c t i v y f tr f tc b n c li. l2 h b n -- k h r W M --0 M ioiiln iy dnpiir i t M roO ip ik e i will 0 c ip n cillel . , . . tjn Bw witty i m u m r i ylnn l b . ukn project. , 1 1 .) W i^ k 1 j o f x f l M O o i O i n t . F o 1 r o p i* TM er o tnfii| n h b a Ifem fy i i 1 !Wjq. XMICO til m l mix wn). N o * b n nttnm au w n ttk b o f liver tn .y be H' J AiroXwwirwi ltInxOmwiiiar q^nookfOcnwiOtHiniyxliliMiMlijMvnebnobplioofLcr.m o. 1113 j h X iy nlm in x li minW um lwr W - l maud. ' * -`^IkmMcewkMbfMBbt.ll.< i t e e W I m L o f II ro m p k u w t ik x nnnlil plpnltn in 11 m l 11.5 Adi Sp C *f ttanifrite aod i h i h (far-<0muiulMon mwri*t*ctioo sinker. i l i tk* hike* tf^lOOO q*n A r - ) m inuter 13-? X gM M the B p w w I n t a L J fa jo rtM e QPKrtf&jc tub and 3d 33 !!* EM idai 9 0 Cm S n artridt [I f. b Bit) Vy puring W rat. mctfuael IbBpw d b y 5 tttL < fH F L C w a c f^ 2 < rQ ^ M C )i D o o i l * to te m n m * y ? fl.fr t b >4d iiw ip f r w r*iirtilinR*rfC ; |S f rB c ttid g e . D iacanleluate ll.H k E t a * 0 - 2 cpL o f m ttu tL CMtoet 2 m L o f d u a l* i o n a jreduw ed * mL p e fr p o p ytMC ccairi lWj i t u t i ( f a i l w t a r a c - 2 reL), U . U A ariyse mmptm i r a i i r iM hm pii y L O M 2/M 3. ' 12.1 Iqjcrt th* --Me nflail c f Mb tt--fart, -- p 4 t n d firtifiod tainplr irao dw - ~- 9 * a . A rilfwttinn tudard n u t pw i di and M lw >11 . , w lytcd 0i 1 1 2 t l m* + fP T O A cM Topcn f li n 1 t t < v * o r to w c o n m i t i n l*v>k m *be*tW ed IfljRwelytlcxJeeL 113 A A .B tinm ofilA ilim ttM dM diuittbcfc*hidcdatihcbc|m inftM K i * dw end o f i * t e ett. Standard m itt be M ttanpcrKd between r * r y M o n n v t n . A i * lttrm iiv * t i n sut o f cut f e m io n m n d ii r i i may he hfr*cd ftl lb* b c f t t n b i| Of * M l fettov*d b y c a lik m o R UB M inli . iiw p w c d w w y :H & < a m p in fro account to r a aecond a n o f u n w i n d s ,n - *Hnr c a w . aMb atkm w u * M m it t be th e f in t m d \m h^ ocHor in BttBpiCMt 1 2 4 Vhe lin a tt rt tm d a r i e m i t i r quawdlnJuu. U bcrt f m lin l cunrra n `gm m & d f c f h c -- ly tt b y f a c e r n j n mm m*% \ht w c isb iD f rp c o ltv a Peg* 56 o/65 Exygen Research Page 97 of 110 000200 interim Report #23 - Analysis o f Sediment Samples p. 178 Exygen Study No. : P0001131 E xygen P rotocol N um ber: F00Q U 3! B iw im iti_______ ____________________________ItotodHBefewViniiTtt amautooulwrmop ' ft Delen id n e f n cfFe>t)noroeciim lc A fld (P rP A )ii> Swell Ifiim iiU M tty L g lttW o4Hmiynw-m a n e go flb frica a im d ird a m u f c i n e h JdeeoLyw 3 ,J (o r e q u in i * ) 13. S m p k M K W aboul M n e n d i la o d i r i to e p ta m i. A ny a m p ie s ih d w iood i m il i d m p n --A o n b e f a t b w A hitad end rmn ilju m l 13.1 C h n m M ep W B m e t * a p e a k f a d i s f a t e Im i 361 m u h i i parm i etf*13 rml!, T b e 4 t> m i jm m cen apooda i fe FFO pin, while fe fewgklK ion (34* e m ) le p e m e * fe lee e u f a n n ido. U J M ethod h lfllk l MMt noi COnMO PTO A I levais p e a la r th in the LDQ. If limili i riHtm TTT*i ITI r i h |rrrtwlhm 1* rf'j. -*--------- u` -1 nmpk m l s QainaJ and fee mutin m t a m 1 m -exuacm d. l$j f t w w riw f u s i v i a p ik n w d m u t a m i l be betw een 70* 130% o f d m r know n vaJtMS. l i a t a m d y b i t o e m i d e I l i t w p i H t Im ita, ito m m a a f i l l i ehouM l e m a m e te d . Aay m f c u pile outside W- ]> 9 H ib o n l b* m lm C o d b y m snslyet co determine i f m ^xtraciicn >t 13.4 A ny n t o l w C a i r i f a m i lo b e a m ri k f c i l M illier by using the H u |c Error T e n m ey bo c h id e d fcema d ie c s k u b tio ii a f u eotifantion ourve However, fee m l w m b e r o f cetibntm n m s d v d i feei c o ild be etcluded a m t m s e e d W i o f 0w M m b n o f sfendaide b ecled 13J T he m n eh H w i eeefBem ot (R ) fee c t f b n l M curvee g i ieroied muet tw 1 4 1 2 (B? fe.M S ). I f afitam lion m i l l feu oulde feeor limile. e n e y opr i l e depe m m b e taken i adjust Iruam nu n i opw elw u. end the e m d a a d e c r fee rek v e l aot e f om p iw sh ould b e rie --ly r od 1J A lU i lt f i in fem e betw een M a d i d e wt e m p le o a n u t s e t d n i roorc b a n i 4 H w te lH 1 I y liM l MS. IfilfcU tiuu bene drill n c w d i c lim it within es m lydeal ran fern fee M tm M tba rem sJym d 14.0 Cslmlntkui 14 1 XJbe fee fe tto w b i e q u rte n m re lm lile U m o n t a o f F F O A feond (in o jfln L g m s o te d b y tk e M a a iL y software p ra g im i FFO A f e n d ( * f e l L ) {Cm Iu m J bU B . * W * e li4 * few er D F fe m e b y w fcicbfee fla ti votam e w eitfU uied. ITMoeeoery. A dorni feeler** 10 ipiin Pag 57 n /6 5 Exygen Research Page 98 of 110 000201 Interim Report #23-A nalysis o f Sediment Semples p. 179 Exygen Study No.: PC001131 E*y*a Protocol Number. P0001131 b n W ir t . . . . . . MgOoCNanbrYOU 1| ? I - .I . ... . AQjU-vnoo.urraon ' J t u f a OfA nM yro I b ii lu ' r irtm n iiH lim o < N i c u, mjmiioic A d d (PFO A ) S w ill _ ....................... M a n u a l l iv e r L C /M I/M * 9.9 r^ in n lri> pipm i 5.10 4rip ip i(ii(lO fr lO O O n L iV 10-100 >0 ,), whfc dUpOMb) tip. 5.11 W M t t S ^ M t V a f r i oe ( I f ) O S S 9 6 e n t r u ^ n . M2 , 8pB vtcmni iwmfcM 5.13 T ltM O llK . ` 5.14 Wriac*actiMibikar. 9.15 Crnibi& gf c q a b it tf i p ix i f l ta t 1* ttL p * ty P ttp y to n iu b o c * i 3000rp<Ti. (.0 Ctw nripipliir Byiun (.1 A n IjrtitA lC o lM K F t o p lU tt f t f ( K x y w > S e iu cife) 2.1 m m * 50 mm. $n CP/lt R2M S452I30) . 6f.i3. MT iopbp0i*a9lVinw; (WA)T- 2mMAmmoniumAnoturbWbIw S* UdHMtomQt): Mnfcmoi s .. 6.\ (Mioitapiw Floor J ti * %A & 2 , 65 35 0J 9 95 0.3 2$ 20.0 25 215 69 75 0,3 75 0.3 35 0.3 S i k j t t f c m V n f c i* 15 p L (cm V ta c tw u rt to -- Bauch m 50 pL ). 6.? flmnrHitfotr P*akAn*-mtmrt 0*Klv4c*Sfentoefi*4rrt. 5.1 fernTO*-23M0KM, fihduttiHiy tyntnT V tb tm mllttofc* ai* km O U m i p o t* m i m ay V c h im e d in M dcr * Til MSMSlpm . . 7,1 Mpdf c B h U i u f i j N o g itfo tM U M m ode, awmk>rfai| 413 - t 369 raft fur PPQA. opetaafet h&MSvtao. P a ft)o T ' Exygen Research ' " *%f \ f f Page 95 of 110 000202 Interim Report #23 Analysis o f Sediment Samples Exygen Study No.: P0001131 B x y i e n P ro to c o l N u m b e r P O M I 131 la p illi , MafedMaehrVIMI'n j am a lvu c a l m rrw op . M p fc iri rA ly l H eit D P W P iia d e e e fP w I l m a e e iw p itA d a (F F O A )ta Small ' " ------- - L i m b y L O M S /M S MM A a p a n fe o o fS d in lo iB fW-tMa-vn-iw- - K U 3 a M -- o d n m i t i -- M i iw p MOd b y o d d i a p f t lM y o f ' aroliiii reta ta 1000 m L orw iier. A ttaaialaehiB aaaaybepafM od. 9,0 S a n d d h e p M li e e I . M aariarl Tairlrll^illlIrMmin Bulinine fc l.l f o p e a t a a e k a o M a a i o f-lO O irp 'iB l.iifF F O A b y w eigh 10 j a f m ly tia a la m iM O (ponecie fea p e i l a d dituie la m e mL mill M a rita c i b l i i2$H W i.LD PI twade. 9.1JI A IO in feri. fcrtilie a lio a M M o o o fW O A la y p paied b y b rim in | I M l. a f f e t 10O u d d L m IMm b l e a I n a i v o h a e o f WO wiih mariaeel >*a 123 H. LDTE fcxtl. 9,1 J AHI pgfMLferiiliealinaMIcaiefrTOAia pepato by bringh| 10 . a L d d p t O p |f e i L a o h ilfa il Heel volum e o f lOOw ife raethMiel in * 1 a l L D H beule 9.M ttie aM k M lM U M Ie a lo M ie w B tB b ta lo n d iiiiM H im lo re i ppteidaaH ly *C aod ara atabla far a m txim w a period o f b montili fern fee dito e fp a n a rie . 92 f l i n d a d f iB b n tf a to h rio M 9.2.3 9 .2 2 L O M M K S rallla illo ii alandairia i p a c a to ti le m tlhaiw l ala d p i e r o ffe 0.1 p ( M . S e tiBoatio mbartoa TTk feltoiritfe a b p c e l u a p l r a d d u a a ) w w e iia ie iio n i m i r * lapale i d dl . rfM ilU fr VfaM* aakM mfmL\ frali Diluted wu Fiate CaneetM ien {mrtnW itT SJ I SO m 34 i n IO ito 14 HO - M IO HO V t IO 100 K IO H i O 0-5 03 0.1 M J I m o ilteallbaadoai n o t e d n 1 3 3 -a L L D H M m C a o u fe b o lile i e y c e fc , ufitotixnanfe. - V Ailw aa, h a m te d soneeatmipaM c f M u d a id i m ay Se pfrparcd M *<!< Page i i oJ6S Exygen Research Page 96 of 110 000203 Interim Report #23 - Analysis o f Sediment Samples p. 181 Exygen Study N o.: P0001131 Exyjen Protocol Number: P0001131 ANALYTICAL METHOD M4k4 M o to r V00017M Mltl U af A--l|ritil>f lw P m n llH ofPwSI--HQIIMmll A<M(PFOA) MS u fi ' H i m ll LNir>y LOW M U 70Anil oNTMtingFldtky: H yiM MSI IkMMRk Driv S o le Cnllajo, FA i M l Appm l By: 3 & X ....C J L _____ Pu iIC b a m II? | TadmcalLMdcr.IC'MS, fti?p> < iiw fc DM DM Exygen Research : t Total P i# * : 7 Pag* *2 o f65 Page 93 o f 110 0^9204 p. 182 'm......... Interin* Report #23 - Analysis of Sediment Sasnples , . Exygen Study No.: P0001131 P ro to c o l N u m b e r: POOQl 131 fc ip fim ri Y "' 1 hNMW wekf VVCtilTIS H ltiw r* frtta ^ iw r< in n i w tio ilP iw flu w > iC tiii k Aeif>FO A ) rnSretll M im riU vartyL C /M S M S 14 a w T a b tm e t* to be t f J e y h r Jto iiohliw i m q-- tH xiw i a f p p rfhiom cttfto* a iii by High f a f a i v w U gw d O n a m o g n p lQ r f W to a iw dcm M a s gprt r r >if t* D tto c h r (LCVM B M S ) a m a O i a ia i m i ll iv i t . 19 S**r ! 2.1 Ahwytown"*iafcli>>n>aiypunira U C m iK l b a i p i p i a i M D S baft** bawHiof a y d a r i c i l h r proper u f n y J ,0 Sungfe topfcsoM itt ) 4 A l l e t f ti I g |t a ( ia n p )f h r tatoGiioo 3.1 ' flapyTilaOniildtayritrimdt~rf|-n iulrt-liim rim **r *---------- r*- ' fc a g j i i i i im i md b n n m m iia i a r i * i > y k f . B w d a w w yte in rom iia m m a ,m e p ic I in te a m M o w a t a m l j k K> a lo w tor o a ito a d tetu a t w t eia i a a * . p eal m f l a w M a m p i n in U n a * n a m e a n a l nm# cm rnalyNi. A hanm aly. If P m a la aa (aw Blalanl am orni of m a fic (-k a i d a n 5 g . d a n n o p n r n ia aaaiaa n y and e a m p l e can be w a d aa tnptlH C 3.J Sam ple coHactioa fn m to m w i l ba apaaified in lice a m p ling plan for tin t PWjoet 4.0 Kaapimapd anadie* 4.1 Winr-aPLCpide 4.2 M a O P a a i- W lC in d a 4.3 A aakaieib-m C padc 4A AMMnaMa A cam a- A .C .|.lta a |n t C ode 4.5 n a fla m a o a m iie A c H -S v a e -A M ilc h 5.0 |aaBaaedlp*et 15.1 A Ifpb i n lam aaaa B i|tid i la m a Ummili n p aMa n f pum pinp ig> to i n h a i r r a p a p p a d n d * a vaalabla a d u a a e ajeelof na p ihl f a fin ja a tin a 5*200 liLinmiral am4MiiB8aicannimr(lc/MS/MPV 5J8 A d t r i c t t o laMecl r r t 5aea Ibr p e a t Iraaontflan and nnanriettinn. 5.3 Analytacal balance a p a k la a f i a a it tn i l a 0.00001 $. 1 4 30 a ti. dicqBaablt p a lj |i upyl-- Gsttnfiipa ttbaa. 5,5 15 a i l Piapnaabla palyiaa p y lm a CBftlriftjp r ttb a t5 4 D i g o a ib b irotroptpctt 13P-1<XM~ IW H O O uU 5.7 t S a a L U P B a a n a w - a in i l li M I l a a . 5.1 2m l dan IffLCnal Icit h a tin ''' Page 3 # 6 3 Exygen Research Page 94 of 110 000205 Interim Report #23 - Analysis of Sedimnt Samples ' ' 1 ' Exygen Study No- P0001131 1E x y i Protocol N unbcr: P000113 . B m i h w r t ____vDoo>7t< . * .. ' i - ~ - ----------- - A M lv fK M . M trrnop ' ....' J...X..r.th..o.d.o..fA..i.u.j.y.f.c.l.f.t.f.tt.i.a.r.'O WM_lim.klriCa aCfPMwSfMlilSiceor iuiojc A ft^ fP rO A ) k v . p tt f c o r ' , lU t n L c f n o m i n i ) . D 3 l i e , ic l t w U ' n . . ; i : r n i 8 mb. .......................... - I I . !U 1 - ....... , " br^mma.C M r if tf A * SC n L r e ts p r a n ta w * M U f c l* M n l r n -3 0 0 0 nan Om I 4 m M e t M M t o M M S I S MlUMO. C o l t a i l a U im a u ih M p n r A o 4 a u k sod bbhU m w ith th e eluent f e r n the imUal - ' 11.12 ft* a a tm p a 11 J f t i N f h li.1 i tp fe . 11.13 3-4 4 n p a o f M * M e i in llw y u p p i i fla * md I f y o n W it n d i r i rl prw i w o s n p M B l t y s o i p o i m (ot < 40*C). * ' l i . i * M i b O s floal v o lu m i, b y add& g 2 m L o f 2 % aacM btc a c to n a M h o t t 10 - , - - m jk m l h o 1 flash i p * tan ti ip nifcttaaslvo. ' 11,13 Tw os h i to t osttftets H P tC r it te miog toapoathl p ip iti. ' ' /" 1 : J f t o t f y n i r l i o s m i sUcBua p iay L C /M S M S , 12.0 Cl>09ll>9>fpliy 13.1 U^ect Hit U N O o f a c h M n d a d , aanqple aod S M Ila d u m p lc i n Mie * L C /M & M *7*iam A caUk m to a i k n J i r J u t praco sn 4 follow II ' - 1)1904ifHHplpB. : )1 2 S n o d a i * ofV PO A rnTTinnrilog to m Im m f tr s o r m oro o w c w w w w n levels w etbshklhidediheim lytieelieL ' 1 1 1 A i v e eat o f H tn M o d o IM m sttD dania mum h e tnrhidnl at ih* tn fto m a * m i at 0 m i o f a sampio sol. Extracted manfani qmh be n o m i n i s i t a fanami o * e fr S-I& tta ip U a . A i od a tu n m iv , mi m ire sot o f M i a d n N h 0 M B m o d * n a y to* injected th a t * ginning o f a m frlbw w d b y H r a r t ml r af t - d im H m d a d i iutm i pBim id o m y 3-10 a m ple (io tea w ad k r e m e a e d m t o f h r f a d i t --d a rd i), k a h h m a m ^ a x n e t a d caKkurnkm iO m te d im a a lb o dw fiim a u d last usoctkM e n p k am. 12A U so f a t a r m o d a n i rvas fbr p in H teiien . Lioosr fteadtod curvet me a - |a a ifa d Jfc to m a b b y faa a rfO |N ta o u aiftg lfrw |to tifi| rip o rta rc i : y r n w a ta U b ra d o m i n i a n nsafriticiB u f a f M a n ly n x 3.3 (o ro jm v a ltn ti ' . t oflofaas t u t e . - 1 2 J , flmopte .rim n a a should o si n u m i i f r ia o r i l u p a i . A ny samplct itui c o a i Qan d ird r a g u s eo should b o f l i r t a r < a m o d w A ncm itlyted. 13.0 dnrsplaojwOnhOta 13.1 CWnm aai^m a. to o m o a pooh o f a d m f o e r lo o 369 m oo h a m p a rt f i l l i n ; n e 4 13 odi p t m * e a c m p o o ia to the W O A . mod w M e the * daotfuor fa* ( 3 aow) leprenm too low o f carbon fccw ttt PeftOpf? Pttgf SOo f 65 Exygen Research M *U Page 91 o f 110 000206 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exygao Protocol Number- POMI 131 tMMNWORVaMITM I' ANA l 5T IC AL M ETHOD _______________ M * 4 rA a M ) fa t9 ta w D im o ilo l lt9n a f p u th c M io a a a e AaM tPTO A ) in Vh m i m bjrLDMSMS I3 MMMUeotemmanMioeiiiFFMalaacliiriamaaailieLOQ. Mente wpwlwc PPO A QlOTchpiurlfc-- P ^ ro b , <!>>c --w bl--lt Miopie n * obauad rod Ho --e ri u t m in br II n i n fali 13,3 Rnove l fa oCflamol lyifc-- md a rc i* qokgi am a be bftecco T0-I30tt of M i favvo h a i. If n * a * H p tta M b 9* 9*9 tbaaatiQMHe Molili. ite Min M ofaaeplao ikanldbo roaaacM i. 134 Axy lllibnlii n d r i fbimd a l a i a i l t e a ! eutlnr b) io n e ibc B*t Bnor TC o ay In f a d * Arca Ibo cakaM en o f Ito cCbrailon corre. H i a m , III* M i min* of id ifaaiiio O M a l ooM bo oiclodcd MMUal n m t 20% oflhM 1 a h r f Coloadonk LiyocHid. 13.5 ik e auntim M d a i (X) in eaUba*Mi a m leoanlod me* be 20.993 (R1 209*3). 3f caUfanliaa n a i a &H toarida th* Meato, iKcn Ijliaajtilal 999 M be M a to o^joa t i a n a l ofamion, ond ito oopili idi nr Ibi n f ir r u t nfreirp lr ...........li-- * !3LS ITaarlnn t i * M e * * M * ood empieo m a l m M fl n m no 4 % e iM m a H ) 9tK -Jna. tfm u lin i din*drig cxceedi lliia HallieHliw 99.IDRl3lt*llWM Iti m al (9999091)1*. 39.1 UicMiblleviegeqc(4oeioaicelaefaeim eaoioFPH M iiiaiid(iiiii|liaL M a* w peak * > * 1*9 Ha am ate* a m ( t * r naneeioe paremmo) poo* oa byfaba*elyo*iolhefaopKOiMo: PPOA 9o9<ah*L>-lE *k*aujlH W l) jlc^e I M Uee tfaDerle| 09001100lo eemeil the e r e e/pyOAfoaod eiiij'mL;# ort!n*> PPOA famd 0**) roFOA 0m 1fa^ml 3 Unti lum e ImL) , DPI empio wiljbtCj) UT- M a r ly wMckthe l a * votane a AMod, U m tam ty. 14j Fk e m p i* ta b le d w fatano arcu o * ofPTOA (*r le e n n n lw . re Da M lovilti matMO le retatole Ito p a o n i 1* 0*07. |fatllloalytelbBndttio>9> - reoltefecndmPMl{ni|)a)l [ffl. wielje*added ( n t) |) P agi 1 c f 6} Exygen Research Page 92 o f 110 000207 Interim Report #23 -A nalysis o f Sediment Samples Exygen Study No.: P0001131 Brygen Protocol N u o to : P0001131 - M fta rtN w * * VQWItt I ^ m ^ M lT H O D I M d h o d a f A n lly fit Ih r d a D lla j lC M td N rfls o ro o t*-- c Aoid (?F O A ) in V t--tation . - tyLCM O IM S T>-h----- -- ..........- . --` -- -*.--e- ^ ordei tn . . g a ta i i l A M S ld )a Bi M P raiaissr*daioa 4.1 M a M b f ta a 11.1 1 * M --is-aiiTO -- a m waw I pnpatd by Min; 0.IM ) of ta tn a a i a crt*H to 1000 b L a fw a a r. M B i n a i Solatoli 13.1 . *33 1% m i lit i! * i a wHIia o l p a g a i ! b y d i - d i v i n i 2 a o f m m iMc u k l f e 10D a u . t f B a d a m i. 3QH Tlio diy h tirb Iq aa illiBd b> hH w p p u p a b y b r ta g m 3 m L oditi--Wt y id lhloll-- l o * f a l l W i n p f IO p i i w ith n i n i A t a a --m b o -- a--? bo p n p u p d . r a H a d a d IM puatioa 4.1 H a d a d St--k'FortM M tioa lo iitio n 1 1 .1 P o p a n a Mode a s m a n o f - 1 0 0 jip A aL o ? PFQ A b y w a i b g 10 --g e l a a l j i a l h a d a d < e a a W d fc rF ri y ) a d d U e ta 100 mL wiih m r t i i h m l2S-mLLDFBbotfla. 13 A 1-B pidnl. H dtaafiodaolidtQ aofPF Q A ipopaiodb]rhviji|i]i| I a l q f d a 106 n o t a i a t a d a a a H a i volum a f 100 w d n-- aol . . lilD iL U in M l, 4.1.1 A 0 .1 p f ta L H n lla d lo i a b M k < ia f P F O A ia p c a p a a d b y lB ii|B ia 9 .A a L i d d 1.0 m W . a ld i l P t a l Y o h a m o f 100 w ith n c i h . l in I l i mLlXiPSbofU. A M I p ita iL A ttili--d a s a t a n a o f P F O A ia p a c p v td b y tam pina 10 a l . d f Ite a i llftall. H a t r a Olili volumi nf II wilh m i m a i io 111 m L LUPE b ona, 9 . 1 J T b i - x l a i d d a d flta tio a M in ti a t u u o to d ia n O i - m o r 1 id f --a ia --a l y a r a d a n iM kla tb r a m i n a n p a d d i a r a o s a tili fai-- fl--d a odp m --alia i . 3 Im ita d O d lh n iin tab u lo - 3.1 L & K M d q l ib t a id a d --d i r i -- r n p tn i in i-- tfuw oJ via diluirn oT llii LO M fa L brtiB eaO oo ip h H c ii r*ii4w Pat t4 o J 6 5 Exygen Research Page 89 of 110 000208 Interin) Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 E xygen P ro to co l N un& enPO O D l 131 bn HUM Nw* V0#17*4 I A.NAtYli^LMlEiliOO I M e ^ e f A a r i ^ t o t b a P e t i i n d B f K i a o f P e r f l a t m o n r o r A 4 (PFO A ) in V e |d a tm n brV&MVM pnpasdmnaedad.$ 2 2 T he frU ow tni is i t y p M e x so p h : Iditloeal c o n ta m n jo i* swty be rm tifim ifln SM Bifia b IA t* L i/ ' Cj 005 . .Al OjBM InLt 50 IS IO 10 10 10 1 D H inada alt I IN NO m 190 IM IN Pinal Cwawnretien (s# b U nos MU 001 0005 0A02J OjN I (LOOOS et 2*C to e*C, u p io six m aoA s, $34 A tam tav ela a o f M o t e j a m ay b e prepared a G.0 Batch 5 Up 1 0 1 o f a m p ie s e m m s d (typieelly 20 e r Jeae) m u st o w l * at least m ' M n M t e a m n d im M a d comtol fartiad ai known eanwn lii rto m Oabccw&td u n k e ) te amty ptcoaA -- i meow ry tot d a tatchfx rm tq ta m f i r Ald and lahon imy A c c e le s and i p i l w ill be specified In d a quality enarin n o e plan ftc W e p fq ja e u ILO Imripla Eafiagtite 1I.J 1 1.2 HU W& 5 i o f to a m i m p l e (alo SO n L p alypiO pylw r c a u r ifuge tabei (feafy es needed, n p tse e Ud und I x w elfc Add 30ttL feeelM te1)iM dflialM wriat sa fe n in k e r for -iS rm iw w * Caatrifapa d a 3 0 m i, p e ty p e w ) * * debe c e n a * aanpt et -2 0 0 0 tom IU IUl 11.6 r IIJ V Pack and m d itfea d a 8PB t n l n a u f a h n i t r tfaepcarihipadfim fcs. Pack te 3 0 m L SFB tube* in Bequeme i l 2 | AoriaiL, 2 | a ilk a | i l , 2 | arbow M 1 1 IC -N H * CondW en d a eo lu n o a wUh 20 m l o f ni nfam ol. O a a l n L o f acetate* } . Diecerd nC v eebce. O e d p i allow tbe eolinru a ** "Mn-1-- dm 125 m L m ir ahipnrl flaaki b y m a n s w i d the 30H O hntayU M ilseoeilins k> M e n a a e to fe c . R b m a fa e fla a k w iA ectucnc once, mfeiifhcmoepdpbiky^ndaoddaaoioml w(tiltvkiaeidnuiaaam).ofOniityinpdaaeieka e a u p to ely M o re am . P i eent d a c o m m a aepadfafem d IP B s o t a A tad b alda A n aw nA ot tbe p e a r-ta p e d Oadt. CfaUacl tba a l a * ta Ute 125 m L litm iaed p e v - t a p e hft **' P tg M lU C /t) Exygen Research Page 90 of 110 000209 Jki Interim Report #23 - Analysis ofSedirncn. Samples p. 187 Exygeu Study No.: rCOOl 131 E x y g m Protocol N um ber: P 0 0 0 1 U I I A i.A L H IC A L M ETHOD MMaTA^^tellHDMcndutbayBiocrmNn^Ha nSSiSrA c id (F F O A ) in V a ge utton 1j 1.0 * * * .^ ^ ' IlrdidnfnryMRiai^toMta M mp l^ toliqtemidiftClitiatcosBatoapa^dtiyo ^eeiu^pltMf^ ytoiu*oMoadcntonUHmcs Jpm uuiim iiii D i m (L C /M M fl) in yafiario. ZjO S d d y 3.1 A h n y ib a ww - f c h k w Iw y p n Bi i w . 2.2 O m au ll Ifag > y p * y ia fc MSD8 b e f t f h JttA J tn g y cfccmicil for proper w fety 1J .3i ^AptllttwttWilifetftUMdrlMeyfBaepwlacfdc rMfibiMr*tattr.tedoo. PUmtb*foamampleUI 6 o d jiu im c k a a t hn|in i |ii g T i w ilk f r y fe*. K ao * t h a m a p l in cc a frin e n nd bwrm P jm M 6 m m m m m r v a i j m R> attow fa r n f a a f rw id e wj iUmad cn. f m l and ptaec 6m u n p i n in fro r a m o | e otitil time n i --ptytf 3.1 S au th caliactfoc prxa4m i will b . >ojlM in tfcc louplin| plm for lJus 4.0 U njoin )Sued* 4.1 W a k r - H r i j C |n 4 * ' 4.1 A M n t i k - l d L C ^ g J CMmi0 3 0 4 mMi) - m* 4.4 M M unol-HFLCpi* 41 Sibe. p l (SOJOOBah) - Hu** *4 4 4 n W l< 0 -lM lP M k )-llM ta l|r> 4 . 4 .1 Ss h t c Im i LC -N H i - R a f a 1 4 J l cM M l-K rL C (n 4 t 4 * L -A -tiu n d -B n u u m 4.) D in M k jiM isM m iliM -S iafM ^ad 4.11 T i t * - > i i | . i j n d . 4.12 AmOKmkm A nN M -A .C .B .ltM |tG ndl 4.13 M honactB B K A cid-SvurA ttK k 3.<i banamuriBaiwnaat I.E A U |h iiiiH M iM A U411U i j B i w t a y j i i i Cf I k o f p u m p in j u p 10 2 *44i j a f r u i l M i ( n r i f b i f ytk m u 1^ l it e r O f iM c o f n j e n i n S*2M I i 4 m i m i 4 10 u l w i l n i M m t p i i t o i o i h i (LO'M S/M S l. 3.2 Aifytoilocoliict riwdMl fcrpMk tra ile r* 1,14taiodttoot 1.3 A flilp i n l I i It i rl | 4 i li u f i -- j u j 0.00001 ^ hpl3 Pag* 46 o j5 Exygen Research Page 87 of 110 000210 interim: Report #23 - Analysis o f Sediment Samples p. 188 Exygen Study No.: P0001131 Exygen Protocol Number: POOOU31 Meted N w tf f VQ001IV ATULYHCAL METWOl Aa2)M*fat e CtiesukUiwi eiPuflwraeeteeie Aetd {PFOA) inYcgetibon bylOMS/MS 14 JUfry m p y jy . 5.5 l U n L E M * * e d f l t e K ^ 9.7 1 14 9.1C 111 3.1!. ',U 114 3.1 19 ^ d ^ p ee iU n pelypH pjdH ie oiiMtiitafe tAe> P il|l3 r t1 l iin jf a -- (ffrW O uL, IKMOOeLX \&mL iU nm m w iwmhM Ite. 5 p t te*-H W JC vW lut Iftp o e tfrte p ip tfte A itartca (M M M O |* arfl0 .1 M |iL X * M .4 M p au M lii> i. f f t t b ( M U J (UH lM M l. > N0371T7X W ritaM tanifealM . C iM ktip< * iM rfip iiitafJO m I.lM l)fn n itaM M to u ?ao o iF v f ' W (K e y * ta n tS c I w d w I t Z .l ID (P/K: l2SQ3-0$3iX>) f.Z JC*C 6,1 M g M ta r ta w lA ) : t mM Ammom*m A s t e te W e e 64 > ! tiu K t W : M ftenei 43 c a tf m h v p W Flew lU ie r* T i n total HA a s Im U ttm l M OS 33 0.3 1.0 69 >5 0.3 1.0 23 73 0.3 M lO 7S 0.3 . 5 ( 3 35 0 3 6i,.V6 IHqijwMiliilaaiiVniitlmPKukX1 3mn-LK( atoaMte ilKitaMldHaiddlaeaMliibnnitiieDtiiMira30.|iU 6 1 I h u iT w :- 2 1 TM*w h . 7 fciowcMilrirai Ml tauiidati n i gaidc 6 mg? 6c dMTjtd in ondwto afriw A>Kne ijUtm. U MKMMjita 7.1 V4dl; B ltMMpcWivMUM wixta, mocliart4U - t 369 m/z fcr " IFOL F^. ) o/T Fage*7ef6S Exygen Research Page 88 o f 110 o o o zxi 4-- ' V p. 189 ` Interim Report #23- Analysis o f Sediment Samples ; ' ' Exygen Study No.: P0001131 Exygro ProtooolNumber: POOfll131 . . ____________ WHwdW--lfarVoeQITIJ J 1 ........ AK*bVMCU.MeTlK t i a b n j a tA n ily p i fcr * DNu m h lrim o f N rfbaTO urm w k M U (P fO A ) in f a > id . ... C tatyLC M S/M S | 1 1 3 f o r n ttp lM fcW M ri with know -- w e m e f W O a f r i e r lo atrtew M . m e *iM leiiiim M < lw ealnil> triliiiM noK iK en(]r. ecwny(%) > I***--IW*m*<NfP llWlb--laeeeB.itm'el Exygen Research t v* ftSaii p*e*44<4ti Page 85 of 110 000212 Interim Report #23 - Analysis o f Sediment Samples. ... p. 190 Vi" Exygen Study No.: P0001131 Exygen Protocol Number P000U31 ANALYTICAL METHOD MrtfcodH-- bn V00017M M U ed of d r i i M i r a l k B M i * f N r i l w r w i e w k A rid <FK>A> 1 V a p y u ty L C /M iA tt AMfetical TMtafPttttily: BxyiMJtMMMfe r o it ll w e r ti i Drive State C o tta * FA IttO I AppcwodBy: __ fcLjL__C-4?srt____ fcdlf i*HBMlli - I TedmiUl Laitar, UVK3, E k w eR M ad DM* JumFUurty ''V i c # N I M , O penriem , B x y | lUsaaick Exygen Research Total v : ? Pag* 45 o f63 Page 86 of 110 000213 Interim Report #23 - Analysis o f Sedinient Samples p. 191 Exygen Study No.: PC001131 R xygen P rotocol N im ie i: P0001131 ; ' 3- - t A W A L im C A L M rrB O O .*/ M tthod o t A iitty iii f a tira Di fwtiriwMiup ofFirftMirtOBXBOW AcM jfP O A ) in fia h and , , . ... ______ , C h n a b y L O M S /M I H :7 DHr i f t p tbc 5 9 m i. yeLypfepySitw tuba* cen U in iag i n o p ie m -20 00 rpm 11.t j D n n i Ih* e tn e i o a te a cao& iafled S fE co fa n o (hted incida the m outh o f ` iha p t t M b t p a l Naie. CoUeci toc t a t e in tb e 123 m L a h n tz e d p e a r* N p c - , flMk, I. 1.1 A d i l O o t a f nnM ootaile t e O t c o p te b d w S O n L o--triflu c lak t I ttP0d il M t t e a m te i p t a n a a t e p a fila n d a ie t e r - 3 0 racoad* eoa h a * i f t M iiiw r n l i 1 1 wf nrw alcalaila inni ttia tei i I I. 0 Sbaba d o aaaplc agate te r - 1 0 n a u t a a w ri * etiaii teakar. 11.11 n R a l i t a b i f i M B f c r * l h M r i N i 11.12 ra n lrifb p fba 50 m i jittypnpylapo tuba# a o n laiate| i m p l e n -2000 tptn fc r-l* rateata 11.1) D o ep l A a ra m a i e tto tra r a n a 9 tB whnnD. Colteci ih* a iu ta imo th n i piar c*d i n b l a i v id i d ia Iiw m f o r a th initiai LL.1I la iifr w C a fw ttiW flu a a h tt 3FE w l-- ni cota b i* Ha ctectc in ' d ia iM iM N ltti dttk. LLIS A id 3 4 d n p i o f t'OCtaatt lo 0 e ti e t ia A e p ta r ihipcO t u k a x t r a p e n t e m r a t e a i) p r e s o la m ia i a eotray r a p a te le * (et <*CTCy U .1C b i t t e A fiaal o b o e . by adduca 2 o L o f 2 % --cor t i c a d d in met a n i v> A a p e e ^ M H d a aniaw bJ la oM liaol?iL Jl.1 7 T\m b l k l t t a c a b l g t C i i l i i w m |( 1 i f i i i l > p i p t t . 11.11 mtfW a m p t a ttd m e te c tm p n y L C A Q /M S . 110 Cbrannopn*? 12.1 H e w t a -- l i m i o f a t h Mi dv i . cerag li an d fbrtii a d m a p l e im o 6 IX /M V M B l y ita n . A aU bntioa a taad ird m a t p an da n d te tto * aU atty n d in p ln I 2 J T O G A lin a ^ v illin i lo et b a it fiva or r a n wnM ntM lto* kvcis 03 12.4 - A dottive, e * e f e c l f t n t i o a t t n d a r d i i a u c t b c i D c t e M t t chi b a p n i o f i i t t al A i ad #2 a aattpl* rat. BlmflraJi m att ba hm aipaciad batwaew avery 3-iQ A> m alternativ an o t ta i t t o f calibration t e n d e r t i m y be _ * A b a p o u f o f a a n followed by abbnitirai fUadanl L ttu ttu ta iM ie y M O apliiiftecwouaL for a n co ro )era c fte c ttra d ix la te tta r caM w ttir irtnw a a t t r i a o v a i b e i b i f in i and laat tojcctten In ita g li Mt - Uaa b a ra r eteaiied canta* fi* q u a ttid o fl. U aaar u rta r* i m e re g a o n tfa i S a A c analyte by b a ia r r a p e n te * w w g 1/ ra c ifite ii o f peak irc i vm w ttl f t tt d t tt aH*Md taacantittion a ite f MaraLynx 3 3 (or cqatvakaQ Exygen Research *' . f *<>, Pag* 42 o f65 Page 83 of 110 000214 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 E x y g Protocol Number P0001131 M tM IW o V N W I I !WALrncAi.Mnno I U jtln d g f> nt> i ir < iIlf m iniSwfyrt>iOTlllln lc Atid(PPOA)inFiil>iiiit ClaabyLC/MSfMS J Mroiwq ii>ailrinarpi^w inMiyim]iMnbhmoiilmiitalteulahdtnKlithnm^diof.JarM. iuAJyaycMdmpk in 1U> t o y n O IW i : . U.l CbMauofnni m a l lUw pnk fi a t^h iir Hmm 363 mv /Voml piuCTrt ' <4U TU 4U n ynww s ia a youi w d a rFOA io, wM ih I M M iM (M MW* n f M M I i t e k m a r w l a i d l a c l . IM M i M wk*nw tM )w afciH D *a tomb u t a thwdLOQ. I f i H ak MdtUa FFOA UH a k p W Um U ftpk, # a i nw blank ample la M U c tnioWw iltn a ila w ia M t h i m n W 13.3 Hiw d a f earn! n<kw a4 mart* ip jk a m iu lU b a w ia 70-130Hf Weil k a m UklU. KarMUlmMlouulctotuKCMrtaklctautt. the akaaM rtanwlw dnnHUiwakaMd. 1 3 4 A n y eflH M to ii M a d a l <bve< e b e i M M lM e ile u d iirliy a i e * l i e Huge >na Tai. a n rU enMed A n da afciWiinii at da aKtntnn a m 1 3 J 1 k m n M M ruefflrlirt (X) fov hI M m a r a imttMed u l be Z& m 0t* 20JW). If K M NMl Ml waM* th.M Knut, ton i^pdurtifOwwlw a iicofwiMtiihwiMbTwiwlywd U toM iw i t i m t buw to MMtfwdi m i --p ploi auct not drift mon thon 14% w*hta i m yfctl nm. Ifrtotffeftttmtdnfl iccodvthii tun* v^bih I4.(i Chkvlatta* 14.1 U i i t J Miw h | n n < w fc Mi l l i f t B it H O r t t f PFQ A to n a l (in o f/m L . b -- d ob pook n ) h u ( d o to w h f d w r (iae*r rtgrrM km p*w n ek n f M n i a l by fei U m L y n w ftw iro profr-- PFOA fo-- d ( p |M 4 1 4 2 UM*fcOWk#(lUliflBlOCOBWW**IIBOOJlCf?POA f c u n d w ii i ^ L 0 Mmptewiljbtt*) PP (betrbywhichto flpslvolant w o diluted, ifhoc--iy, P age 43 o f 65 Exygen Research Page 84 o f 110 000^15 Interim Report # 2 3 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Exygen Protocol Number FOOD! 131 I ANALYTICAL HUTBOD 3 Huhal e fAeelyeieftr thelin n e lMrice ofFwthaweel-- fe Acid (PFOA1 i Firit Md -__ . - C taM byL O M M eS 7.0 M S M S S j m b 7.1 ' M ede: E lt -- pn y N e p b w M ftM m o d i. MICrMi^ i j - , j m it fo< FFOA. . 77>abavicM tltioiU il*intM iddu tu id iio d tu y b c lu n s ^ ji order to ap b o il Ib i M IM S lyM nv U rwpeieihim fMiniee L I M obil! P h M *1.1 2 mU e m c e i a e i m m * Ja m i i r ! y i ^ a r a d b y i d tb e i & I54 j o f u m a n a M W t IMO eiL o f w em . U ( U fitijig BotafaM ' 1.3.1 3% aauK b add j mrthtnol U pnyk id by dtcaotvini 2 Mcorbk mH m l n l. W M ta n a t l*3*2` 30Krn1Mrltorneil i inMmm prcporcdbybtwpn$ 3ml ofdimatfeyMirhlmviiitwmfi--l vphiroof1fimLw>&toluene A liam i voum B ayb o p n p an d . 9.1 S u i W l M U F a d i i i t t S o h i i i N 9.1.1 F n p * l M to k J lH ti M r - > m y iM f P P D i A b y t P M 9 h i r ^ l 0 in^ o f n t y t i a f i e t r i 4 (cow e K i fcr pm ky) m i g u te to 100 mL *n\h - a cd k n o H aB l2^ n l L O K b M l . 9 1 .2 A 1.0 n iftn L f tt ti f a m c n lelir t w o f P f O A i i y wptm d by b r ig f n ; n L f Ite IM p fta L w tatioa to fim i v o ta ta oflO O wbb bmIm oI m 123*L L I> rebotl* & U A A 1 |^ ta L J b ilU l itf M ie l) ttk Q f P P Q A itb n b b N d b f b rin im i 10 A ir o t t e 1.0 j l f t a L Rotation t o t f a l l vohUM oTL 60 wtthmrthMioUn ftm al LX>]*Bbenb. 9 .1 4 A B l jif ta L b f ita H s B K telio i o f FFQA a peejaial ly bnngiag 10 L f 0* Ol! p j f o L M b d t a k> fin ii volum e o f 10C m tb m f i m a l f a \2Sm L L D P H b o ^ e . 9.U Thommk wmhnilcitien arthnkw H ob eterei in a ntfogrttor n t r prwrii i H ly 4*C mA m rtebl fe r m o iia m i period o f 6 weexhe Exygen Research Ag< 40 0/ 6J Page 81 of 110 000216 .Ihterifn Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 E xygen P rotocol N u m b er P0001131 .. tM M N M tp v m m } I' - ........ A W A L \ln C j H * H T M O O I IIWadrtAiphriifctoiaMiupiiiaimrf^iaiieimciawipAcMtfPOiMwfiihti* O M U ty L C M M a M 3uufli)Cilllm li tnbtlruu P.?,,2 L C M S A ft c d h a tM i I t a t e d t m* y a p a r t in m cdw M l via dihitiaii atomi. t i f a i frntjff'm T it fc ie w ^ g t)p i ri m a p !* M M wa l tflWnWnoM m*y b t p n p m rtw M rtrt. Fatai ofF attiteli V ito M ufaafikataLt M J D tiuM li (LI C a tta n ti <M toU 1J` . t* Sj U 100 Ito 04$ 0.M5 1 14 100 041 U S IO 100 040$ IO m 04029 .1 IO m 0.001 OjBU 1 100 MW) 9.3J Wwa Ito mndml ID !. W t Mmm-maMli pollici " t i 2"C 6 *C.ttpXJ KK OMOfii. .2.4 AJUM* V W m oaM rt e o o t w n r t c i m r f o n d a li m *y De j w > u * d Bm SaU p ID.) lash Mk cfanplM m a r t (typically or lH> rrnat Muda kM c a t a a a r t m l and tw m i a u l M u n k k6B t a b m ..... n a b pill innlril ^tlniri in miH)rrrtrrfmil rtirr-rrr fVnl-l"!*-1- 10J Kaqoinmiit fer M i art H M a y duplica art ipHm wilt ba ipectfirt in da pirtky aaHDwpla fer H i ppbn. I t Sw upltEilm otiB 1M 13.2 11.) .1 1 4 11.) <14 VMrtb 5 1 e t *> a m p ia t o M n L polipcopytcM e m n h | c i b | M W y a n r t r t . n p a r t t r t n i i t arali). A r tM n a L r f a c a la iiiiito a riiim o o a w r rt a l i ita * lb r-1 5 m tui nart'^i>abiailM rA i-lliN r. 1 4 aa r t i lin a tba 3FH ruba d llala t l a y a r ib a p rc l t t l t f a H a 2 a t . B a r t i n p l wilfc p B orii. I p a r t a ( A 2 p aribmvari 11 LCJiHt CanCliM Dm Ib m ih 20 raL of mctanol. Hi w TT II ~ ............. . *** ' " -- *" " ---------" -- * " ~ 1------ --- *! Siftaonriitaij!riitiiiri 1i3--) a l . f a-n-r-t a-p-*r t-*-S-a l~a --b y*-r i a p-u-.l--h ,-1-1---M-I* M a n i by l a t t a r i ( k a r t r i a l . Day l a U r ta om apktcly bifore m e, tirtm iryitodrylB piT rtfoiibaiarfillapa. N ptS ai P a g e llo / tS Exygen Research Page 82 of 110 000217 Interim Report #23 - Analysis o f SedininfSamples p. 195 Exygen Study No.r PQOOl 131 *y|C(i Protocol N umber POOO) 13l M M uak*rV aci7H ANALYTICAL METHOD 1 M a& odof Am iyob fee fee PwifPnion ofP erflgow oittooio A d d (PEPA ) i Pah 4 * C lim i bp LOMSVM5 iM Setfe . , ,, ^ _ T h f e t o i f e i a l a t o a a i m l i y a d f e a l l i a i a o l a t e i t e q i a iaHMio a iifpariluoaoocniiwic aaH b r H t^ l fto fc i-- if Liquid O m u m w * e n p M I* a (Milani M al. SpwMOMBto D aM toa ( L C M M O ) in t e and alano. U l Safety ' '' 2.1 MnyietancHfeUniMiyyiMicH- 2 2 Coni l i lha appoggiale U S D S balena llaadling n y chem ical fcn piopee aafcly J O Sam ple l n -- l - 3.1 22 '` ' .. 32 A tq M i> r|M H B ffe fe r u n e tta il t i n 11 1 d (aM W pn e i n rtl ba lligli s a n c t i o n P laca I t o tisa n a m tip l HI a fcodpeacaaaacandiatoafaah wtlh dry i n ( t e a fea aainplai in ccnaiaen a n d lama* pan ie f t p u n n a n f a v a n d i to a t e * fe r oaiboa d n a id a anhDiaaboa, ' t e l and ytaaa (ha aamplaa In ftnnoa aiaraga M b I tone o f aaalyala la m pi* a n te d # pwaafew a w fl ba Ifacifiad In die M a te plan ie rth ii lai ' ` ' 4.1 4.2 44 4.1 4.5 4.6 4,T 4149 4.19 4.11 44.a12 W * r-H P L C * ifa C e * w <12fr409 m e ^ - I b e p e t p ad # M e^M l-H ?L C pd S O kl <6M 00 m * * > - R s m c p s d c A m i < K K M O th) - Rm*M p td o Sepedeie LC^tt - * e N end h O # m o -m jC w * D bncllofM w W m te - in d i T otM M -R M frtfnd Am m ortim i A ttttM - A .C .1 H m tm n te F m flo o rm --a k A p 4 -S > ^ A ld fk h $A fartn m r t r n r t Eowj owm m iv M ti p % < wife w ia W * w h a m tajw tD i C l f b l e o f rta etin f 4- 2X1 24 A^ LdortsMm Ma tafodQioiamtaima drfrlisMMimftrpS^piMllMMfMmltma riaaCo/tKqMm mS }tittfe* 5-3 A-- ly tin l b i l u c i c ^ t M o fr tm U n l f t.O M P l %, Aojf# J f of 65 Exygen Research Page 79 o f 110 000218 Interim Report # 2 3 Analysis o f Sediment Samples Exygen Study No.: P0001131 E x y f t t P ro to co l N u m b er: P 0 0 0 1 131 M M IM (rV l|7 0 "StoaplpfAmlji fcftL> AWALVTICALMETHOD oTHriluomnBHftfcAci4(WPOA)i*Fi*Htrd j ' ' O n ty tC M M I 1U4 Aft 1? II 1 5.10 I11I I3 5.11 51* 5.15 5.16 T|buu--mjirpfamr.wlw. ttS aL pO T ritefiiiM E fc f*yjrtfy\M r m ttr tfty tu b * . 15 mL f f tn M * pftyprrfyl-- rw rtrfc f t tab . D kfombi u to n p b f ( 5 W p L, 1010CmL). m - r t L D W o n w w MuiHC ortot. Dj nilodwa vrtHb(n9j4ClvNi<A l ld t . A>4 f p iya tte i ( IB U M B .iL a6 10-10* !), w h li dijy m M i tip a 5 P 8 tab* (2 6 n L ] {5^ 3*kw M l no N057177V Writ aelie duller. CwfcifMg" aipabla a t a p lm ta j $0 M L MfyyeopyleM tu ta a M 206C rpm. 6.6 OvwiiateiiaThieSyattra 6.i fTirT1"-1--- r*-----r - r --*'*'--'**>" -- c*-- *r (HN: 5 6 9 4 5 2 1 ) 4 .2 T iM iX n ttrK X>*C < 3 U abihM aM (A ): }M M A iniw m inA <tM iW aM r M a ie h ile P lw a t# ): M Kktaol 6 5 G n d isa t F n$ftM X tat& iiii a 1A 16 210 224 SfcA 5 5 2S 25 65 Flew Rate &B 35 a d 35 a s 73 a s 73 a s 33 a s 6 6 I n j e c t Vofcana: 15 fL (can be ac t t aaal lo aa m uch > 5 6 p i ) 67 O w ntitallen: F a tk A m *naw tm l w e * i d ealim io cun*, t . t f U o Thu: - 25 mmulea- The e k m ocM litlme w e Mended aa a *w da and majr 6* n h an |ed in d e l la epUmlnedw O T IC yaw. Exygen Research Page o f 63 Page 80 o f 110 000219 Interim Report #23 - Analysis o f Sediment Samples Exygen Study Mo.: P0001131 Exygen Protocol Number: P0001131 .... ............. laM H .u l v c w iin *1 " - ----- ANALYTICAL WtTBOD | M llN ) o fA eely k fc rlh iri im ;iriii o fT flu M O Q c tliu : A d d g T O A ) USadHQfiMby ' ............... _ .......... ... ............... _ L O M S ftU H A KIIMI ttmm b n i i a atuutodi u d -- pin muct m i dnfl more then ' 11111 im >fi -- Ijilinl um lrmfiiiimlinie iliifl gee--di M t limit umhin > Bwlytiml tm Iho--tmnMbe iwoelyed. I*J Ul* Ibfr&Uowt*faqtnlM01* catwUli 1)k w o u a to f f F O A IbuodGit atfntL. ImM ' ymk *> arttl *u W M n rw (New i**rtlm prawrert) p e M b r b i k b * l|a o l im |n |* B : ' >FO A > * * iM t e L l - rP e A IHM - jim te M I n F ilep* DP-fkaortywNel>lballnl*ol0 w u a ia a * ,lf n n w y . H I Pjm oftm fcitUUd wM b o m maenoti of PPOA prior cxUKtic*. uw ' Ihtfbiloti^yq--bo*tar*liilil*1li*y i Mli>lui'iij . R ew *y(H )- f tpl*llo*)ytfe<jftd(n*bnIJ - b *" ftmd in coonol(rn'mL)l *al>U adM (atli*L> * 14.1 (Wfcfel]*irla|*qrMouwnvtfitoi * o f PTOA b u n d in ny/ni. to W O A fem ulG ib)- tmipi* weiihi (31> H A U l* Aa Mlowin* o*u*ttc* O f w r n u rr) ki f i r t m On amount o f PFOA , k am dm pfblw id w d iy w ^ b L PF0|A ftwad &*& * y < n t|b t - W A found (ppk) n [ IM H / w r i **ttd*i*M) Fam ?>ri Page H t>f65 Exygen Research i'f Page 77 of 110 000220 p. 198 v ........ / ........... Interim Report# 2 3 -.Analysis o f Sediment Samples . t Exygen Study No.: P0001131 E x y g e n P ro to c o l N m f c c r : FOOOl 132 AHAtSmCAL METHOD H M o A H w i l r , VOOD17S3 H lliB i ef d d m lrliO M I/M AcM <PFOA)iFW> Analytical T tia g T tt& r. Eeysee lUwifch 3 0 J | naww c h P rhrt S i m Co8 *ft> P A 16101 A ppow dB y v t - l C L i L ________ F ulC araib' 1 TiusM J U * * f. CC-ftS, d y tn lU H U C li a /* > ___________ taP lrtany '*Viee PiaidM, Opririon* B*yr RmmcIi 1D e aM - DM TsU lPapa: I Exygen Research Page 78 o f 110 000221 Interim Report #23 - Analysis o f Sediment Sanities p. 199 Exygen Study No.: P0001131 Exygen Protocol Number: P0001131 r ....... A W A i.Y nC *L M tlH O P ...............1 M iytU f tf th < P t f m f M B eB Q fK rflM to a O ttB jc A M (P?Q A )"in Sodim a n y ......................... LCMSMI 3 -W S u n ell wfctoolio* a la a d iid i In 115-fuL L W E <erro->oyCi bollici P C e P & ^ riiin it> * 1 . Un i i M u o n oed rrninrawi l i n n n e m d o r t t ato y lic p n g tn d m IOjO f i e k k M U p ' 1IU b ob M ob * f o o cito M U M hpieoQy I t Io n ) n o e notula it In n * ) nin n a coaUol oed two raOraolod ooM nit farttffe at Inumi ro uMBUfauiOOboMW l nu n to m ie (muMuiolio conry fa rd i ton* . I t J Itowiiiwun ri f a JoM ou t U b c m a y p i t o n i ad i p la o wilt b o tp o rig e l n f t o w M i b r M WBn p lu i f c r t | iojM i. 11.0 S ^ t o B x b r a i i o e ' l l - l l o t I 0 o f M uwlo b o o m t. M lyeoopyOr a e n w r i h i o w b n (Jonify u boodod. n y l o n IM o M m b well). 113 A M 3 3 a L e f t1 t e m < i c o c i d l e ^ ,v a a m M o l i a k e e f i a w r t e f oetioeihoker . ftr* 4 0 m iaum 11.3 r -- lf>M toe o*oo e -3 0 0 0 [ y t f W - 2 0 a d o tn o . I IA f ioM M oo tbo C u 3 P E to ra idgoo (1 t 6 n i . ) b y p n i i o i 10 raL m othm al . M km M ly20aiL efB P L C 'V iM rt-3digyfee)i D o o alM m lu m o n m d ry 11.5 Load (decoal) tbo n u d e o e Ibo ecodiboind Cu SPB cirtridot. D im ed ' oHMe. U .4 A O d lO n L o f io H lu B o ii o ib o o o d l iD e a M l la U n b o a o e ) o f fee SO mL m U b p i Mm. C^j, r a n rad A b a ih o wriot oofion d o tt i for -30 11.3 C k e o tflfo Ito a t r a U -3 0 0 0 t p e to r - 2 0 e w e . 11.1 Docoot toe n o d M o l onto b o n o S M corafdie. CeHeel toe olone. 11. " 1" *~*- t *--------~ * ~ T - * n n to ra n l r u ll e - i ilii iliraio orni o lii ii m itn ' . A a t o t tf c ta n f l t a p 1 1 .&. 11.10 Conditlo a o n o o o d C t P E a e tr u t|D ( l I * m l ) b y p u t i i 10 m L im b u iti ' M J e e id by M aaLoTHPLC v to r( - 2 b e y ln e ) . D M t let oolutni imi dry 11.11 A id tbo meUunoi to ~ J00 raL c f wotor r a d load o r [ho lacocd eocsirioccd aranoirM io 1113 fihdo o l - 3 oaL H O b t u O n t Collect 3 mL o f ebano iato incuoim i 13 u t . p el||o iw y leio om ulb e n eibra (Hull t o m e - 3 mL). 11.13 A polyra ooe nilra rale o ln b o ipeoy LC1MB/M3. >ra>i ori Page U o fH Exygen Research Page 75 o f 110 000222 Interini Report #23 - Analysis of Sediment Samles Exygen Study No.: P0001131 E xygen P rotocol N um ber: P 000113) A K A U m C A LW nM P 1 u f A tonal f a a n a ia m to d aai a f PllflaarpecIH icie Acid (PPOA) ia Sedimela by LOMUMS 111 heA die a aamoai o f aac B u d in i. ia a ie la d Ratified empio imo ito E ^ I V U yem . A m H i--tw i itoadied n u n piac e d e and follow II u a lp u d M iglia. I l i 3ftnU vda fP T O A M en fO A d iag I M le a n five o r m ote concenti! wvols n u a t i s tKhkto I* ra a a y lM M . 113 Ab auto m a f a a a u ia d calibrado* Maadaida a n b t included ihc toftotonp ad fi tt end o f I mrf>! M . a u d a id i im m be imenpened hH wH w a y M O lampica. A a B u m tvc. m mire h i a f oBUM nm B u f a d ! a n y l a atoad at t o b i i naii n o f HI W lowwl by e#bnii> m a i n i iam aaaaad a * 5-10 o p ta i (io accollai fM t Hccmd I a i 1 1 4 U w l a w a M u m t o iiaindUBioii. L in f a to n d in i c u rv a aia f i m l i f f a t o aw lyl by t o u r la p a m na m in lA iw a i^ lim o f peto atea m u c a if a a im Mandato ccm u n tla n a n n i M iLyra 1.3 (or cq u iralem 1 1 5 m o f l o i n f u n i t o n a n o i caeeed a t u f a d a s m Any am pi ihai u c e a n d n 4 im p a n a i f a to d b a fluitar tolueni n d n a o a ly i ed. I l l Are m an fa em an a Ut H f a w a yade a f a f a i f a * ia o a l M I a m a f i r n a p a m * 14413 a o . I t o 413 aaa p u m i a a c n a fa a d i l a Iba F K 1A M io a. w M c Die h a 3 a u n ) la p n a a u a t o loa a f t a r t a n toeaida. Unta -- I am nutain TTlfi al Irrrli r -----**"1" T Ha Maak o a c h h a PflQA ai laaah p n a f b u 0 1 np faL , ito a a aaw M a * a a a f h a m a t o a b a n to a a l t o atab a aal m a i ba u a m a a ia d . lU a a M r iH a r a n iB o l f t o a a a d a m i U f a m aat b e b v i e l TO-I M S o f t o h t o a o a valaaa. I f a o f a i o l a p t o M ia m id a lh a a n o ts a b l t limito, ih udire f a f amiplii rtoaid b f iim cu t Any mania f a mide IO. I30K atom to smM M by t o aaalyat lo detonan if rt-am etm ia 11.4 A ny lalbaalliia a l a i f a t o m t o a a a tito iu l aalliar by iw iai tb Hage f a t o Tato, m ay b s H c t o m to rn t o lu la U a n a f Ito n U b n t m curie However, h e m a l aatobaa a f c U K to d oabbnaioa to n d n d a d m could bc al ani ucead 2 0 S o f t o M al atanbci a f tn e te d n u d a m i <3.1 Tb rroTilBjm annllinlui (K) t o f a h n d e n c a im a l u a m a d a u be IQ .W A * M J i n . I f cabto n ic a m a l i a h i t i o i d e i t o lim i. Caen appropria am pi am ai ba to tali la a d iv a M n u a a m operation. aad Ute m adam a ac Ito i to m a t ato o f lampla m ould b t n m aly m d . Pm7 Pagw3$ o f65 Exygen Research Page 76 of 110 000223 Jfc fi: p. 201 -Interim Report #23-A nalysis o f Sediment-Samples - - ' Exygen Study No.: P0001131 E x y g e n P ro to c o l N u m b er: POOCH 31 ..............Ma4a4Hi_6arV0l01W ' V .. ........................... AMALVT1CAL IM tT ffffg I V : M a te d W A a rtjB rttf O TW ii w r M n t W b u w i t A c * [PFOA) in SofcitTbv ............... ............. .... . LCMSIM S ' 1 4.W . W ri. codon iM ru, r . S J * O n n elflu t rapnhla a f a p k a ia e 50 n L , ,^ ' C.-*C 6 0 rinninalnyiplr Hj . i h y W n t a a M 3CCOipm . *.1 Anafrdeid Cnt-- nm>>ii i W (Kayi" " f c w f a ) . Z I mm W nm. In > ..< * > * M M -om joi 6 i T an ju rtto r M M 6.) M o U in u a i(A ): Au m c p Im Ac t h k Ic W m 6 4 M o M atlia a a p H M iO enil 6 3 O PadlauynynK S m b b ) 0.0 1.0 to 20.0 22,1 , %Jk 63 65 25 25 Plow Rat n a fmUrnfa) 35 0.3 33 0.3 75 0.3 75 a 3 35 0.3 6 6 l i j i d B X s t e l 6 p L ( o a n b a m c ia a u e to a in w c b a t 30 pL). 6.T Q n u j ir t i n . P n k A m - n l a c m l m a d o ri t b n d m m . 61 P Tioia * 33wiiiaaaa. Tkaakdvccaa4M anaafalaaaadadi4 ag iii(la i.iIn ia y b a c tiin c a d in o n tan o o p lU a * Ike HPLC a p a m . 1.0 M SM SSyMW PPO*.7.1 M o # : B ta c a w p n y Map r r a a H W m i ) d a .n u n it e r i m < l 3 - > 3 6 a r t f a . T ie a lm a aaaifliat aie W aadad a ia piid aaad n a y baah a |ad fo n d a rlo > 0 f t n o i alitai o f SohOooa 1.1.1 InKi aeam eio 1000m L o f m a t. 6y adito* 0.134 a o f Papal *17 Pag 2 o fa Exygen Research i i *t - y - Page 73 of 110 000224 p. 202 Interim Report #23 - Analysis o f Sediment Samples . Exygen Study No.: P0001131 Exygen Proloco! Number P000! 131 4 Masher VM0|7t2 1 AHALYimMfnP ........... 1 M e fe e d tf A w ly f e t e * 8 flirtm n W in u o f P s f lu o c p p t tw ic A cid fPFO A ) hi S e d i tt w b> l c /m s /u s 1,2 FirffrTWTtSthrrtnm 1 2 . 1 l % t M ti e ic id in w i b r i i p N p f l r a l t y adding lO d iL o rjie c tfe Mid to lO O O algfM tar. Afenmle v e l m mgr N p rq N n t 1 0 S t M ib i i Pw o t I w 1 1 S m d ir t I f c l f f wW fitM it S th ffy r . ? .i .i h e p ii t* o e f c tohrtiM o f~ M 0 e t FFOA by we*$htn# 10 it* e faM lytM ll i b M M d u n c U d h r purity) od d ilu ir to IOO mL witft lh ITW Ito lU f U A 11 m f n l fcttilfeelie* h M h b f PPO hi p i r p u d b y britip n g 10 a a L e f l w LOO p g ta L s f a t a to a f in d v d u ra c e f tOQ w ife m e ttav i b i iM u L L O raM b 1.1J1 >. 1J> M^b L ia c lif ic a lta w lB iicn t t i PFQ A i t prepared b y bringing 10 ttL u lh o M p g fa L idhitiM i I t t firu l v o h m o f 100 w ith n o t a t i In & m >LL D nboK to. f , 1 / A l l u ^ a d . fon U t a at e o ti d t a o fF F Q A i r prepared by btinfrAg 10 IfljifiiiT n t i d t a i f fin iiv ilu m ii f ~~ithmrftrnrlin * 123 b LLD PB b e ta . M i A 1 0 1 p ^ L firtifire ftio iitrh rk iio rT F O A l prepared by b r t a t a A t 0.) li^ ta L i o t a id * fia t! wliunD o f I N with c O M M i lU m L L D ra tonte. 5, I f T * te jg k a d J e r K it ll p p oD tlnotteD te * teoepd b t u p f t n s n l D f II - m n i n w l y *C < p d -- i WMd fo r m w jim iii p g x x l o f 6 m a i n i n IN M d a tf n p M l w . 92 HMfni' T1irhm*ni Trt-**-- I t L C M K M I i il l b M l n f lM irli i l i DIDp i t -- I i n m m l a o o l w d t o i f t 9.) ^ 2 T in f t t W t e t Id a typlcsl t e r t j l i : dM iduI m w o tn rtio n i rp*y >x C1MPenitUiSrwtliiaienB fa W aiW tU Ml IOC K1520 Vtknt (ff152L0> t11o00 DifatJto b1u00t) t1111o00o00 TimI O w in iiu if .....M 10i0l l. .. . J21O00 9.2 r v <or' Pag* i i o f i i Exygen Research Page 74 of 110 0 2 2 s ; interim Report #23 - Analysis of Sediment Samples Exygen Study No.. P0001131 E x y sroP rotocol N um ber P 0001IJI A M A LY T IC A L M B T H O D M M M N u n k : VDM I7M M rih a d a fA M lp ifc fc r t l D m n M k i i l l u l m U M i i A d d (W O A ) la . Id l u a l dy L C /m /M l A iulyucal T cstrai KBality: Ejtypw T i i S M I I I m m k Ii I M vc ftnaC M hfiL P A IH D I tW tv n iir- V - l C Jl, f o il Connolly | Tcohnletl L n d ii, LC-M& S x jb m K a m rd i a //f? _________ /f e te FIdm ty ' f Vipj foiidwl, Oycrtcft^Btyya Hwawdi __ LiWai Dm J& L Exygen Research i IiM th p i; 7 P a g e JO 0/ 6} Page 71 of 110 000226 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Exygea ProtocolNumber; POOOI331 i AHALynCAL M r r a o p I M w h q d ef M uyva f t c f t . B W t a . k a e f N rth w m w lm c ic A ta l (PFOA1 in SefeKtM by LOMSMS )> 3^ TbUcmfeJieieboimpbyedtofehotekwudqueotiimkmofperfoiaieocieooie *md Ir.- hflb fminimm 11 lq C ta m fe m k y evpM ufeam M tu frwaorertrir Detener(LOMSA<i)1<*liwttL 2.0 S o f t* . 2.1 i'JsiyiohmmefeUteiBWypnrtaae - t i pOrwaaeadti*oafc reprimeM5D5bft>bwirillMey idimiriTfr proper mftiy 3.0 StupiiSUcttfcinenl 1X2I ATiplbIeMrt f3I0t1pToTTlTiToIflTlTufy:Tf-c fciu lfm~~rItk mr .I til |*II 3 J Simple* u n d leMpiand tteutd be Hewed t quilibnie room tnbpiveim; 34 A l iMQpta mM btfe m fk ly mixed befecobans sampled Ibr extraction. 3.5 Semple eoHmimn peocefee wll bo pecifbd in 0 p h o t pfamfix this AO R e a * * * im i S t u f e * Al W an r-m C p * A3 M e S M o l-H P lC p ii A3 A e e tfe A ad -R e e p fe^ * A4 AmxwriumAceto-.CXR** Ore* XQ ImnimwumlEfflnxemg 5.1 A y f -- m i Uful ehm--lojrfrt capati ef pfepug i f e 1 e fe fe fe riteti t i * i fefcMe eohi fertitnr cr e i li of njaciinf 5*2CC nL Pii-- ilei le rttiem Urne Uperlinmiix (LC&tyMS) 5.2 AdcwootoooHeetro w dele fer peak late p itiw iu d y ia itfite tic* 5 3 A f e y t a r i i t i w i c t rupebtc T rc o rii* io 0.0000) %. 5 4 SO mLdbplbleFObp baeo*rtfteM ibeo5 5 15 ihL dteeo sM ep cly p raM to w co fe tR n nftoe. 5 J Diy w H i e im p ipi e (5 0-100aU 1D0-300h L). 5.7 '25-w L L D PS o o n o w -m o fe b a tth i. 5.1 Z m l.d f v J 9 l C v i * k t . 5 9 ntiM m bl* oleato*. iJO H L m i 10-100u U . i* Ifa p O M b I J.11 W < t a S v P t l [ V * K ( l t ) l C I I S F E a r t i d |m . Si 2 EPEMown* maiMd p1.; Pag 31 a f f i Exygen Research Page 72 of 110 000227 Interim Report #23 - Analysis of Sediment Samples p. 205 Exygeh Study No.: P001131 /"* E i y g e it P r o to c o l N u m b e r POOOl 131 . ii M ! . ________________ M e m o u m w i v w i ii n i I - -- - *WALyncu.Mmw> ..... f t ? A n i f r t o fc r the D m m i h i i im e f PcrfltKiiooetiitolc Aoid ( f f O A ) m S a l b y ' . ............ ............... .............. L O b lV M S " ' o tn e d c e la d o n lan d w ti may be o p e n d at tte t ^ a n | d i m " M f a n d b y m * m M o e S b M m iiie e M o M erq m M d e v y 1*16 m a k e 6 m w l l i r i i w l m l w d w d d o ) . leather cie e .n tn c m , P iH d u to y1i m iD un b e th e f i a t mod U n miocOoc 1b i m p k i ti , H * U w Ib m r -- ibid e n v o i k r qoi m ittiica L in w Mendaci a n a m ' b n n u d fc f fce a frn e b y h a n y a w i i m a 1/ w e o f a tm fo f p u t w n i -- a H W i t i M l d u d i M U t i t l an M i l l M a io ly im 3.3 (o r te i k a n I I S Sereyk la y c a w A a y noi a m i m M m p n u n Any am pk tk *'' e a a e d e t u b k d ic o p a m w M a M k a l b it ia d j li ii o d m d io i n e ly z e d - -13.0 > A r r g l w ce C o g ito l . 13 1 O oM oldp m ni d ie p o i n i lim a m i ic a M m u fieni > pereni o r 413 m a T W 4 J 3 n u y in M r w y o a W lo ibi f if iO n n wliilt dw beeetM r ie a C3^9 a lili) a y r e w u i d a lo ei o f c a rn a i tb e u < k 13 3 I t i l lr i* M u l a gnu* noi e m k i n PFOA a k r e k p e e le i O rai tb LOQ If . . b k l ll n U l t a r T O A a l i n k p o e ta r t k m 5 0 ItaTL, litro s MMr b l a M ntgk - m b e ehwIieHpud tln o l i i m m ia b i a im m illi. . ;- 13J - g u a n t a i e f a e u o l g i l l a i a o d a a b i K i i f e w m a i b e b u o n 7<M3<>% or d n a known w h m U i ornavi ^ A o O tti ovteido Ib i i m u m lilc kart. Ug M a e tei o f m * i thaeld be le m m a e A A ny B e a u pile W ide ft. 130H M o ti I aed u M d by th inilyK lo detenutile ir i n n c iim n mM. 1 M Any e r t a t e i M M o d feiad O b l i m i r i l i g a lli b y iu m | Ihc Huyc B i t I M r m y be w M m f in d a laln a liliiia o f tb e m N b n iien corvo, H o o a m r h o lo M a m b i r e f a g n e l l i cahOraitoft tu n d e id i h c a llo be a d a d m m n w a r a i 20% a f i l l o K M b i r o f e n n c le d m d irils 13.$ ' 13d n o iniiololiw i i h BIm m i (X> fee cilib n iloii o u tv et fen en teC m i be *0.992 (fi1 30.035). I f a e t t n t i o e m u l t i AU o u trid e t im e lim iti, then m e o g rio w Moya a n bo a i m to m b M inttrum eoi opom io n . m l the tm digdi ae Ib o n ilM cl w l of i ^ l w ihoiM koTW nilyiod. # M riiin dim e betw een ek a deida end eanipke n o n e t drH l w o n Dim * % w t N o a e u l y l i c i ] n w I f r a te u lo a dene drift ottceodedtio K n it w*un en w aly ciu l ten d m the aft nauet be reem lyied. iw ie ' P agi 18 e fiS Exygen Research + Page 69 of 110 00022 Interim Report #23 - Analysis o f Sediment Simples Exygen Study No.: P0001131 Exygen Protocol Number P0001131 EsyfN XmmvA M iM N to N w o n tt - - A .m m c * u T iO P ] Method efAmlytoi ferlto P to w ah ati of ierW pecntook Atod (PFOA> in SoJ by L0M M 4S 14.1 O m t o a f t B o ^ e p a i i e a t t e a f e i i l a t o t o o a m c w r t e r F P O A to m tit* o i / i . to ecd e e paaic ) m ix g to e trm fw d n r x ((M ar rapeM icm parameter) |M M d b y b i M w Lynx n f tw in pm qm i: -- ^ t i Hn r lope DF * Iw tor by lA id t * lo el r e to w wee dihiied, if iw w e e iy . M J Fot n m y tct N W M with tato*u am ow ti e ffF O A prior to eviction, m e (to Ibtiow fet equation to cakalattiJM percent recovery. JUeo*iey(% }- [to m ta n m -fc a n d frto U . -- iytobM X uio-- n K -0 .3 3 ^ adymtododtoJU H i U *t Ito feO m riof tauaftati i s a w l toe m u u p t o f PFO A f o n d in npfL to FtO A ItM i- r m u tom . i t m rL-iX v a liu m n i w a - t m eai.M ample w e i^ it (5 f ) H A Ua* to* fcttow bto equation to mJeuliae to* M o u n t o f PFO A Ibund in ppb bated on toy welsfe. PFOA to m d (ppb) to y v e W t - PFOA feund (ppb) i [100% i u t d eoW*(K)] Exygen Research P o u t TV o fM Page 70 of 110 000229 Jfc Interim Report #23 - Analysis o f Sediment Samples p. 207 Exygen Study No.: P0001131 Exygen Protocol Nomber P0Q0113! I .. ,, . IW h. d cf . , , AMjarncxL Mrrao 3 r f f u f l i m w i i r m n l r A cU (T FC W in Soil Oy LDM3/MS 94.1 h i | m f-K m i f FPfEA Vy ^ j h t n n 10 mg f t f i a i J y f o l r t M M ( c o m o t e d f t r purity) m d itth to 100 mL with ' ** ! fe];&aLLDKbaa]. ' . ' 9.1.2 A 19 pgtaL tori6bdice n o h itia p f f f O A it pwpw d by bringing li> > > 4 . i > r d it 1 0 D |t it a L M ) u b o i t i ftoa) v n lw n i lOOwiib nv>han(>> -* to iU Jra L U tffib o u te . 9.1.3 A I D p f t a L J b r t j f i o l i o n o f P P O A i > p f t p e r r i b y b r i n g i n g 1J ' m L a i t e ) 0 ) i f t a L B l u t k n U i Reel vchUM oClOO w ith methanol in 1 125 m LX X TE bottle. 9 .M A 0 4 p tftto L fttlH k o rio ilw lo tiO flttfF F O A iv p ^w n d by bringing M J ttL o f |b o U |^ L lW 1 0 B ie * f tM ltO t a o o f lOwittmeUnM Hia I m LLDFBbcttU. 9 1 .3 A ClOt p jfln L to r t ie n l io a aolutton o f PFO A in prepared by D rir^ o j v 10 wL o f d w Oil M f e L B a b u in to a Can! vo* k k o f I0Q w ilt m ri-- U n a 133 m i. L D M bottle. 94.6 H auadtad1b cttO ca(iM ao iu ti6 tti6 f i M iio n d iB irelr|K iio r i O ppradnstely **C m l m *W h r n ittMimuni period o f 6 arch ' ' f t w t f l w ^ l t o f p n f i i Miott. 9 2 ftn ndnid CBWw Bdo f ehttittiM 9X1 922 t O b O M S caHbrMlM M il f u d i u * prepared in m C w a w The r iH iilin a itaadbrdt m p i e c i n d t h m v h the rivetM ii procedure. Idatical towaplm. Tto fefewjnj in n typical mwnplr Bdfltloml concootmiioM moybe Find CtttOWMMP m M h im CoaMHTOlMOf CddntUM o f f f r i l l f i Vfchm* Fw tilled rwi GaUbaticn StMdMdlD M u t e (MU .H U m ic t a t i . Standard fcrtl4 faxend] 6 9 40 0 XCMnddyp-O 19 10 , M0 MB 40 40 23 X C an M y y -l SO XCnmddyy-2 19 409 40 140 XCmnaklyy*} m 100 40 m 200 40 m M i 40 230 M0 1000 XCmmddyy-4 X C M ori^-S X C an d d v v .4 Um iflaaojl BdMMWftiMioffe Mimii Board to oqun |x la hatial ' ooncdhfie iifra, OoctodW gr n rr n tra rirr o fIh o itn o d iid d u rin g th e ximciM a (8PE) Exygen Research - < i ** Page 26oJ65 Page 67 o f 110 000230 p. 208 Interim Report #23 - Analysis o f Sediment Samples ' ; Exygen Study No.: P0001131 E x y g e n P r o to c o l N u m b e r POOOl 131 z ]........... A i w - Y n c A L m n i o o ___________________________ M id m j r f Aabl fc r ttw P ii w i w i r n f W l i n r n n m icfc A d d (PFOA) in Swlfcy LCM SM S . } A aaro ta e itr i n tiitw * (i biaelO tmami >** p ^ p an to w e each 9 1 4 Stoner t ixtncMd u litatii fa) I$*m L p f tt y p n ^ y l m tebei n y C u ffC t^eB h w w iA i, 5 1 J AJm s M* v a lu to * apd aeM anfcatM ne o f M n d arcb m ay t o prepared u 10.0 B atebS atU e )& t MX2 . Soefa fcafeb f a s n p h a u n w e d (ty p ic a l? 3 0 o r tow ) m w include iewi c w # M m o o) (wtobad bleak v e la f 9 w L o fm cO an o l) ad two mapei* a to ll tor H ie d to know s case-- h i i m (Mb ccntvol epik) to verify p u n t o n i n o w a y tor (to Stock l e q e u -- M l tor A dd and h b o n lv ijf b f t o d M an d opUiico w ill b e pacified Ifafl quality -- nr f i n far Ihto p ip a iL 1 U w g b l | o f -- p to to w JO w L polypm pjil-- w fa fii> e ntoee (fe riifr ae needed, rtplac* lid n d m M fM l). !T Z Add 3 L o f m i r t i n i ta d toake e o e w r i t ectieo riiator tor 13 minute ! l i Tmanbrfatotobeiio nm toieoeto baft od mis rito b i -13 rommw. 1 1 4 Bring t o eolitoto vp to 49 a L vitb water in ton SO nL potypapylwe caefrujagitufcfl. C M t o y t to r-1 0 m aauaa to 3000 r p n C oadhtoa toe C a SPC n n r td g e e (1 g, 6 w L ) fay p la tin g 10 ta l m ettarol to&Mwed by J m t p f H P LC wtoer ( - 3 drop/fec). Do c o t let colum n run dry 11.7 Load (deeeaO tfat t o n il e m dee cooditkm ad C m SPB cartridge Diacard H J E bto w i t o - i a L 100% m ithm nl. Celiato 5 anL a t afe# iste pujuated 13 mLprifrfopyfene eertriA ga tube* ((into volum e S mL). U S . AmdyeovaqAmwing atortriapiay LC/MS/MS. 120 Q m t o p r ^ ' 12.1 faceto b e t t e * amount ofeaefa r i m t o d , sam ple and fertUled m a p le mio die LC A iiW dS >)to n . A m f t n t f m W Dderd mum precede end to to w all 12.2 Stoadmda o f HQA i iiii^iaifing to to lento t m a r ha inrbidad M n a lj t ir s l aai 1n s A it n u b e act o f i a b e tte d < ` wd to toe and of e i conw ntntion level be jeehided at toe > m iK to d e csuai be P ip iin Page 27 oj 6} Exygen Research Page 68 of 110 000231 Interim Report #23 - Analysis of Sediment Samples p. 209 Exygen StudyN o.:F0001131 E x y g e n P ro to c o l N i m b e r POOOl 131 I' ANALYTICAL M IT B O D ~ M e tb o d n f A uabete fee tfearta i rnu na i v e o f ra tg o o fc e c l u . c A d d (PFO A ) ja Sei *y " LOMSMS u) ... . _ , T bie m A o e ip b e n p lre4 b r i b e lanlaHaa t u i j -- ttatlim iefperfluoiB eem noic a n k r H tfk M b n m o m U g eid C k ra B a tD fn p b y e M p h d 10 n o d em M a e ' a y B M U kit Dem i (LCM SIM B)in i l \ '' ; . 'a : * / 2.0 SaM y X I A Jirty iifc air'in ftlih w ito iy p rtfrirK i, 2 4 Ccnsoh the apyacpr ii to MXD9 b e ftr t h a n d in g l a y ehamlc*] for proper lately pititaailtw - 3.4 Sample ftequlmnaM ' 3.1 .A t le a n I 5 t 0 l e i m p 4 e fa e m m c lio e , 3 1 H aeyeplepK ieeilin l nee4t4 beeeUaaiBplc*I l SempUa emcad r e i | * m eheeU b e ellowed to e q u ib b n ie to room 1 1 All a n p le e iiu a t be fcom <i|N ym iied b a b le beiea a m p ia d for extncM 3.5 Sample eoHaedan p i ro i n i iS be ap c eilM In dm aarnplmg p i n 1er lb 4.4 'RaapemaadStimdMda ' 4.1 Waar-HnCpreie 4 1 M edianil-K ? L C jra4 e A3 A aeononi A p e n e -A C S . Peep e t G n4a 4,4 PmftnmBQcammcAdd-Sane.AMcta e h e m eqvipptd wipe i variable volum e t a j e a n r ep afcle e rie je c ltitp J-3IJ0 p L n-- me d i o e m it m M a n Sp iuimaaeiiti (LCIMSA4S1, 31 A devicecollecta datafarpeakImaprareiMl Quamjiaae. 5.3 A iaty tirel balaeoa ta p a b la o f raataop Vo 0.40C411 . 5.4 H3 ntL d i^ ic ae b k p alyprtpylaaa c n C r if a y tobee. 51 13 nil.dintoariifa polyn a plnB m eriftifa lubor. 3.4 EtiapaaaUe atlcroplreta (34-lOOuL, lOO-MOet.). 3.7 la s -m L LDPB em jo e - n m ilb betalaa. 3.1 2 L clear HTLC viel U t 5.9 Q taptM ble p p -- 3.10 A M a p v a f lO fr lC O O p L o d 10*100 |iL J, w iA di^OMWe p*. M l W a le n 8p P i k V a c o s ( lg ) t C l f S t B earfiridg*5.12 S t t m w m i n i f t h l . 5.13 X flb w d c k flk PDfCifT Page 24 o f65 Exygen Research Page 65 o f 110 000232 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P000113l Exygen Protocol Number. POQOl 131 ____ _____________ ANALYTICALMITMOP C 7limi ut n w jitii\\I liniitiwnMiiiie iirrei'riwiiiiii uimii ~>i hi (tm ri) in ~ imT UOMMMM 344 SWb*m ice ilwVir. 5 4 S C t a U ilif i o f yiniM B t SO w i pd y p m p y lm i 5800 ipm. U ' Ck u u y ^ t ) M 44 6 0 21 3, Andyliee CeluFlwpheii*P(K*yiiBu$d Ptilk) . m uii Oiiro.)ii <pm; 30) U HPC 2 I M d PIMI i%> : 3 mM AaflPWikm AflUtu iaW tx r 4 4 V otaP hM i(B ): f t 4?U]iulFni|nai: I b H rU OjO li! 0 2Z5 5L 45 45 25 23 43 3L& 33 35 73 75 35 Plow Km tn tA rtt OJ OJ 0-3 OJ OJ .6 h g w th u V c h n w r U |t L { e u il f e M M * l S M f c S O f i L > . 4.7 ffru u ltaliu r M i Am - m a l f t a u M calibrato* n w . 4.1 HuhTIm ? -2 3 tau *. . T&* a te * c o s t a t a v t f e i a M d M t i M * o d m ay b a c h * 0*d io w d e rio TO M SM 3 B & m 7.1 4 M * B to tlC ip w N $ tiv M IU tf o 4 * . M M to (in ft4 lJ - 3 6 P 'z fQ r P P O ft. Tke ib o r untiti* e b e a d e d a su id < ii)d n y be 6h|ed ir orderte o p ttaizataU tU B iy**. li* rep u tata of S tM oni 8.1 U u W b P b a 1.1.1 I pM w u r m t a m u m to w r U y re p u a d b y a d d m | 0 -1 5 4 1 o f a n tts ta m aealM tdoo b L o f waur. A lM rM tvobB yta|N pai*4 Exygen Research P*gt2$*> f63 Page 66 o f 110 000233 interim Report #23 ~ Analysis o f Sediment Samples p. 211 Exygen Study No.: P0001131 Exy*nProtocol Number: POMI 131 1 ______ _ * m .y n c A .iii T n i ........ "| M m io ja tA iiily tttib fa w P m m iiM iionafP w llnotooeO iifc Acid {PPOAJm Wtw by . LC/MJ/MS I4 4 ft* M apln b r iM W kMWB m a m * e t PFQA p m to n irtelim . uir ih t M lo^ ipgtfJlIw e totttoiU te <fcapw n le to v y . Rewwt i j ( H ) - E m il-- friaftiu H fu tt) ifliM ihundaaiB rolC na/L )] Exygen Research Page 22 o f65 Page 63 o f 110 000234 Interim Report #23 - Analysis of Sediment Samples p. 212 Exygen Study No.: POOO1131 Bxygca Protocol Number: P0001131 AK ALTO CAL METHOD l U b g i H o b t c VOOOHM M M <TA u M h Mr (kt B ttt aml c m s t A M (PPO A ) lb BtH by A m lrU al T tufcg Fh Mq ; to p lM d i 3 M B i m w h Drtv S M M C olbth?A 1610] Approval C - J L _____ PbiO M M fly * TidMiMlLlK. LO-MEbSxypm m>rt> Dm Dan Exygen Research MM 1 Page 23 o f 63 Page 64 of 110 Interim Report #23 - Analysis o f Sediment Samples p. 213 fcxygen Study No.: P9001131 E x y |e s Protocol Nunfccr: POOOl131 k * feo d N h tf U0MI7I0 . jU U I Y T I C A L M E T H O Z) M rtto d o f A-- ly rta tn U * Oiiiiinrd--wtoa o ffrerd u o io o cirtirto Acid (PFO A ) in W anT >y ..................... ........................ L C M S M S 9X3 9 .1 4 W -5 A MR M n d M l M l-- SI (rW fM l M ttk J M O bm m wpanrt wilh e tc h rte fe --daidaaKiraclad. ib M # 0 acted caM ratonjiindiirda in l*`A L pofepM p)4r'bM elr c w6'C;iiwe weeks. AH-- a vel-- M i o 4 n e i w l i l i u f t i o f r ta a d a d i a > y be prepared n 10.0 B r t A S r tt * ' tObl fcrtfe brttfo o f m b tpfoi w ttw dn l to p a l lky 20 ey t e n ) w--i include al b a n CM r--rrd M M l (m rtto d blan k u r in f HPLC w r ttrj end two jm h o u en tro )i fo rtifirt know n copo-- n dowa {lab control np*kwi to ven ly { Fr a r id ier t moouar y farib ab atah . 102 Rnjaii--iinii far fld i and M w ito y diipfaalrt Hid a p tk d t wig be pacified ' io the qaafoy M m o so p in fof lbfa paojwL 11.0 8--phlJifrirtiOl 111 11.2 11.) 114 1 IJ Mo m m i 4 0 m l- o f a m p le w apart-- o f tH H iI n d U u to d m O n d l with w u tt bn o 90 m L p rty rw p y tan a crtMifl t u b rt C fectfr m --Pad, raplaca hd and dftwel). C codirim (be C BPB eactridgM (1 ( , 6 raLJ b y p -- * f 10 mL n--banol foUocrndby Jm L aT H P L C w a C rt (`<'2(fafriMC>. D o n e t l i t co b s-- run 1)17 to a d n a p le w e -- dibemedCi | S M cM tiidpa. D iac*drttirte. l b -- wtffc - 5 a L 100% n m w --rt. OoH ict 5 m L o f -- e into w id e n e d U a L p e tu p ie p y lin ie io lr ifle e e ik M (fie ri whim# 5 a L ) . A arty a m p le m i i f iilw to ip r iy LC/M S/M S, I l k faja rt iha m m -- uni a fa a o h m ii iw d , am ple --d fertided u m p ia k l e the I C A C M 0 lyttM. A < a ttn tiM i rtimlnl m u it p n c u d t and follow 11 Bwlyad aeaplM. ) 2 f t a l i r t i e f f f O A an-- p a l i n t to m la-- f l y or p m ponoantrmcwn b h -- tbataotodidia-- u afy ticilirt. I I P A n o-- r * a rt e l n ta e rte d ealiWatNin a u n d rtd t m u ll b e inckudrtl it ih t M p u n ii^ m d at Hie e n d o f wunpfo m i. E s t n r t a d a u n d v f o n w i he iUMin n i n I be-- n e v i y 5-IQ awuph a . A s -- i b a n --i v t, an b m h act o f a m e n d nalfcrarinn rtiw d lid t M ay b e iq je a e d u the b e jm e m f o f a irt followM by M tn rted c a tln r i-- r tin d v d i fattrap em d ovary s -io a a n p ia v ( b M a iled | , w i r t a rt a f a l t M i d n -- i r i i ) . In aitbar caaa, n n c u d eaJAertbm a rta d a id i-- b a tbo A n t --d Lwt -- actio n m i a m p l e art. I I # U#e f o u r rtewtanl c w rta far fianlHrticai Linear rtandird owvaa a t p a n im r d far & a m a frto b y kfartM rtpertkoe --to p t/x w d f t a i i if o f p k * ie a Par Page 2QoJ6S Exygen Research Page 61 o f 110 000236 JL ili Interim Report #23-Analysis o f Sediment Samples , , Exygen Study No.: PQOO1131 EnyfCft Protocol Number P0001131 AWALYTICAL M IT H O P U9M 3M S T u f i n lR tm irn itaaitanl m irriffirtm i ttfO gM aatLytix 3.3 (or oquvafao) lO&wiaetjM M . U S io p k r a p a v a ta r a li m i m o d m m ui ra p o i-- i. Any u o p i n trot t n J taia d ird r a p o p o a ahoaM b e fltnher m t w d rew elyeed, U . ) C T a w a tu p a ie rara ik o v a p--fc a f e d n i g h t r i r a * 360 h k fr-- > perwii o f4 1 3 mu> T h e4 1 J M tp arail Q fV M p o o d i to B o PTO A k m , v t o k l* la a flh ra i r a ( 3 m iu ) n p raa ra ta A l o o f c o b o e d i n Ml 33.2 M a t a l Waofc m * et c o n ta FOCA t o r t i p a r a r t r a i th U3QL i r a Matta pgntaneF F O A o tam ia p o t a r tban 50 n f/L , d o n a aw btankM mplc mhM beebteiM d rad ilis nira m i h m be r entritted. I 3 J R e e r * o f r e i pii* rad m tanx * m o rti betw eci 70-iJQ % of tbair knew n v a t e * * e m r t r o l p ik * f c H r a t d a tb c e c e e p ia b k t a r a th calile m i e f a - p l c a M d b e ic w tn t t i i Any o i n i i p&e oolda IO130% abpeU b e m In M bjr tb c eeay tt lo d a to m io c \t w m n d ia i ii 13.4 A ny eaUbnUoa M a M t a l io b e i s ra ta ita tl oatB ar by a c in i th H \* t E r ra ta lli tnoy b e e d a M f a n ihc Mfctiiatioe o f Kit calibrato fw *e J t o w m r , Dm m a l m a h * et t t n t t e d c a li b r a a r a t i t e l i thct w M be DMft t a l m a l 20% t f th lotat j n k r oC astraeteti iiandank 13.3 H o o a m M b i coef l d r a p t ) h r cattarcelo c o m i p M o a te d a m i be 2&JPQ (X3 3 A t t $ ) | f ftWgMM m i l l e y i o i d i t r a e b rain , the* f p i p r i M cu p e ram i h e tallii l a ta f u n n o u m c ojK nrion, and tbc M o d o d io e d o ra ta va M ailo fw o p t a f b AiM bTaacalyaad. U B rtw tira t t o hatwaea M aliardi ami aamptaa muta not drift m eri itun 1 4 M u ria te m i a n a t j M n n . f f m o n e t a t a r a I rfte x c e c d t O ta lim il within n o o lydcel n o then i m i m a b a ie a n i^yaed . 14j0 Ci IciiM o m 141 U* tee M b w ta f p a ta ta aleuta O c -- r a d efF PO A Jbund ( n ngH. b a ra i a a p eak a m ) i r a * tfca Mandarti o v e ( l u t a r r c p u c i o n p a la n d o ti) H M M al by tea M i n Lytuaoftvar propani: m A fco id { n p D alope aDP D F ta r a r by w hite tee finii *DhiawM lUM adJfQ eecNary. Exygen Research Pug* i t o f6$ Page 62 o f 110 0 0 Z 3 7 f Interim Report #23 - Analysis o f Sediment Samples p. 215 Exygen Study No.: P0001131 EuygenProtocol Number: POOOIUI ................. Mated Nutear V000I7M " 1 . : .................. . . , a .y n c *i.M g n io p t Mite U r f A ja frte IbtlhiT illiiiiM lIir iif> M ftiooow cfc teid(P F O A )ln W m rby lOHtS/M S 3.13 STB v o w a a M ali h H i-S-U W w tip rt)y fff y)w i ttttfX K U rp n 6 CtoQMtofnpfrfe A M 6.) i 6.2 62 64 65 AnMytkai O h m n ; Ftoephw r RP (Xcy m n a Bow tjflcX 7 .1 n w m j t a K ^ V (P M 129a w t n o 30TC MaMelWwi**: TwM fttuvnitim rtnffitrfnlTirrr m m nm w . m m C tiim ftpyuo; . OJ !J M 26.0 22J Plow R ile % A U imL/raial 45 35 0.3 45 35 0.3 25 75 0.3 25 75 0.3 65 >5 6 3 6 6 fejnrtinnY nhim r l } j i L ( n k e w i t lo o a n d t 50 |tL). 6 ? Q im ki w ; P w k A t ` iitlin 6 i(y W w lili w iflm . < J S n a T tB K <' 2 3 n i M K T bifcoV iW W dilfaiW iffiniw p6i6i|M <<idB iyU diin^m oidrip e y iU ttik ^ iiM n i. 7.0 M S W S ^ n 7.1 M c d e:B k Krapnty N p * f r f M R M mode, s w i f t r i n g * l 3 - 36 9 m/z. H w ibgrv* MA4WMI a r t town A d M a f o r t e n d n a y N ch an fad in order to oy W i d the M SU S ly tin n . t.0 - Pnpafiiioo offolutioos | J M uH iF han M l 2 n M n u w t n p M a t t e fei w a lir I prepared Vy W iny 0.164 g o f ubobki aoM o k> lOOOmL efwtUr. A ll-T in rnliim now jrlm prrpirfrt Exygen Research Page f i o j 6$ Page 59 of 110 000238 Interim Report #23 - Analysis o f Sediment SampJes p. 216 y ............ ; Exygen Study No.: P0001131 E x y g en P ro to c o l N u m b er: P 0 0 0 1 131 tpffMVMMMh M atoodftf A nalyte tot ite A H A im C A L METHOD XOUSA4S Mteto y*mbm VOOOI7JO A c id fP F O A ) f t w by 9.0 o n d a ti h r r n f e f l f.4 S tin to ti S n ifc fftitic itio i l o t e t e 9.1.1 T i i f o a a t e d e aotutioa oi-O OO p j t e L o f PTO A b y * * * * i o m g l T M t j t i r t i m a l a t i f t n m m d f n ty i a y ) and llm r in iriTmT ili n tiw isltit^ M lD P S b o ti . - V .12 A 1 0 hqW L htiiiM m abtadoo q fP E P A to p r a p n t i b y b n n g a i IO t a L o T t n >00 j t f t e t le te e r to a t o n i volum e o f 100 h imHn n ai * a!lS n L L D P fite to . M J A I J j U t e L fcs iffaartom a te to w o fy y Q A to pray m ad by brjnjjni m ' ' a l L o f t t e l O j i i M r a o t l l l t o a f e * fitto! r e t a n e o f 109 wtthm ttttftol in A 125 ML U V E te tto . . 9.1.4 A 0.1 |t|M aL dM Utoaden a s te to o tiP F O A toprepara* bybriafij io n L e f t e 2.0 |i^H L D to tto n k i A te ftiv o lu iM c rf 100 wrto mettono! in iltfa tu n to to 9 1 i 0.01 ) t |t o L A r tE c itiM aoluACfi oTTPOA i l p n p n d by tompLnu 910 w L t i to c 0.1 /m L a o h itM lo a final v o te n e o r 100 with R tiw M t te a l t o t I M beute. 9.1.0 Tito u s c ir a te f to iiff c a tta M h m o e a a n i b e a t e t i in a refliterato r ai ' ^ j m i -- to y 4 * C and are atibto fa r a n a n i i um p d o f 6 momK* 2j S tefani C attiate fittotela J .) U * t t w i J t M t i i 1 pnpt n i 1 u r i e a m a . T1k ^gjtofiitoo A n d t i i n peoeeeeed Oo a n n o io p pwc td m . . btonltei toam ptea. M Tb* M m m a ttum pto: itfdfcionl M K cnm tiaii* o uy b t ^ in l faawiBiiHne . FteJtelte Velane ef C w n iw tiflM f C astone of^rGeattoa V i t e P a r titi C a n ta Caltonten Standard 1D S ed ate fate) faLl Santi# OnU S m d m tu* teanptoj ,0 N IO IN N IO no 40 0 XCwtidyy-0 2$ X O e n tiy y .l XCtomtiyy-a IO m 1 XCtaratiyyO Mb IN 40 250 XCnmddyy-l m ito MA NO 40 40 900 1000 X C *uti*yy-J x d w te v a Tk*auaaai cancmbUam o T Ib a ciU b n tiai M n e it q u ii la I h i M t u a M a U I lM , i r t i * Hw c a a n a n t n a r f i t a a n d s r i n a i i h . m e t t a l i {SK% W .W M M iM a u M tifim i' P a g i 19 a fa Exygen Research Page 60 of 110 000239 Interim Report #231- Analysis o f Sediment Samples p. 217 Exygen Study N o.: P0001131 Euygeo Protocol Number POOOM31 ANALYTICAL METHOD M e*)M ahan V W dU tt MNhodaf Aaliyah Jhr BwBataoilMbm i f h r t N n t i t m h Add (TFOA) ta WMtr ' . byLCMMU A m lytiul Tatdiw fadW m '. Sxyfm 8 w irii M SI H a m ah priaa SthaC oU lft, PA ]6tC l A fpandB }; ' ' '. ___ t L - J h L i ____________________ fw K W e lly I T c d u rio l h m ife, LC-M S, Bi j ^ i R -- .ik ' _ _ jo to ft i Dt* /b k in k ty / . :. ' VicaFniidiat,OtMtiMi,>iWMfciMmfc Exygen Research * 4V * f *, P * $ t i t o f65 Page 57 of 110 000240 Interim Report #23 - Analysis o f Sediment Samples ,: . P-218 . : Exygen Study No,: P0001131 E xygen P rotocol N um ber: P 00 0 1 I3 I Ifa lM N a tte r VOMr a t ; AKLVHCALMKTBOP \ M alted of A arfrsfeftf ta c ii m ^ t t < Jr* to o n cm tic\6 iQ T Q A )m W tu rb y LGM 3/M S T fa m rtie * w fa b t in 4 > y id fe rd * ia o la t & > c d s in a a ia a u ttp f parflutapociiook: a d d by Higb f w l w n i n i liq u id O w n r p i p h p ' o w p M to a tandem M m M ft& im & k Bttaete?(LCVM yW 3 la a la r tO nsJWy i .s M arra safe bbofUoiy practice. 21 C o n ati ite ^propri-- USDS M n ta a d fe c a y eternit} ter prop u t a y f n e u d o o a . X t S a a ^lt JU qttbnaau 3.1 A i U a t t t t u d .O f t M M f t 9 t e Ik a c tio n . 02 H t tax ip ln p m o aai^ itaaadad inr warar a n p la a . J J S t e p ) its n d laP igented ta d d t e allowed cquititeaic to mom tep n tia . 3 4 .Jl t a s t a i B a x be feM M gM yiateadM br b a it* tu n p ted for attraction. 3.5 A&y u u p f e s w taitwa g p v t k k o shot t f b a c e m rtfu frt at `'3000 (pm for - 5 r " 1" * * `' T ' " " '"* 4 fc j,4 ` --1*--**" 3 4 SarapW adfaoticn pwcaf a aa win ba tptcifiad m Ike i --plinp ptan far Hiis ptyjaK. 4.9 R n ^ a a n . d lttg d iid c ^ 4.1 W dsr-H M U C ira te 4.3 M atlu m l-H P L C grad* 4.3 rtnanmhim lir n tiir f iH Tmi|t r ? ^ r * r 4.4 ftr0w M ertencA oid~ S ifnA ldric 5.0 ata v aaw acd Equip-- t 5.1 A h i # p t r t M M t t liquid rtfa m w a p a p li eapsble o f p a n p ta g up to 2 aatvaati aqufepad urite a uariaMa t o i q j a a a a p a U a o f ipaciint 0 0 pL teiteq tad ted W id iteM-- Sputiw id er ftC ftC ftQ ). 5.2 , A d f r ic s f a o o f l w t n w data fa r peak in fa m tio n a n d quat t i larion, 5 > A ra d y ik d Vatanri rapeM i o f iu a fta q la 0.00001 %. 5.4 50 mh S ep tetetagolyprapyltea aeotrttepe t a b 5.9 n m l liigw aakfaim ljjaaiiylnn f*ailTlf>igi andina 3.5 DfaposaWr mJMBffr i n { 4 t o U IttjQ O u L ). 3.7 ltf w L U V E te U 'viM noiitebrtda*. 5.1 2 n L c lc B H7LC d a l kit. p Dnpomfcto p ip a n te V I M a p ifam t< ia),to a |iL aii* I-n O |iU > w l* d Jap M ik lail| . $.11 W a i 9 a p N t V f c c ( * ( i e < C l l t t B a n r M |A T*r 2*t1 Pug* 7 *J 65 Exygen Research Page 58 of 110 000241 Interim Report #23 - Analysis o f Sediment Samples p. 219 Exygeri Study No.: P0001131 E x y g e n P n n u c o ) N u m b e r POOOl 131 A i part o f the documentation Ihe fo llow ing sheets w ill be included in each analytical set: a nm sheet listing the aamples to be run in the set, and an initrum ent cottditioos sheet describing the instrument type and operating conditioni. * QUALITY ASSURANCE The Q A U n it o f Exygcn Research t r ill1inspect th e stady at intervals adequate to assure compliance w ith G L i'a, and w fll report*the findings o f audits to the Study D irector, Oxygen Management, fend the Sponsor Representative. RETENTION OF DATA AND ARCHIVING A ll hard copy raw data, inclading. but not lim ited to , the original chromatograms, worksheets, correspondence, fend results shall be included w ith the data package aubmitted to the Study D irector. These w ill be archived w ith the original study plan, amendments, fin al report, and a ll pertinent inform ation from the Sponsor. The testing fa c ility shall keep a ll electronic raw data and any instrument, equipment, and storage logs for the period o f tim e specified in 40 CFR 792.195, An exact copy o f foe materials submitted to the study director w ill also be k q rt at Ejcygen Research. ' Bxygen w ill obtain permission from die study director before discarding or remm ing samples. "" Exygen Research * . * *-t 4 . < P age 14 o f i Page 55 o f 110 000242 Interim Report #23 7- Analysis o f Sediment Samples , Exygen Study No.: POOO1131 B x y g u Protocol Nomb: POOOU31 APPENDIX I ANALYTICAL METHODS V 0001780: "M ethod o f Analysis fo r the Determ ination o f Perfluorooctanoic A d d (P FO A ) in W ater by LC /M S /M S " V 00017 8 1: "Method c f Analysts fo r the Determ ination o f Perfluorooctanoic A d d (P FO A ) in Soil by L C /M S /M S " V 0001782: "Method o f Analysis for the Determ ination o f Perfluorooctanoic A d d (P FO A ) in Sediment by L C /M S /M S " V 0001783: "Method o f Analysis fo r the Determ ination o f Perfluorooctanoic A d d (P FO A ) m Fish and Clam s b y L C /M S /M S " V 0001784: "Method o f Analysis fo r die Determ ination o f Perfluorooctanoic A d d (P FO A ) in Vegetation by L C /M S /M S " V0001785: "M ethod o f Analysis fo r the Determ ination o f Perfluorooctanoic A d d (P FO A ) in Sm all Mam m al L iver b y L C /M S /M S " V 0001786: "Method o f Analysis fo r the Determ ination o f Perfluorooctanoic A cid (P FO A ) in Sm all M am m al Seram b y L C /M S /M S " Exygen Research Pag IS / S i Page 56 of 110 000243