Document M499dZeJgzQzabZNdaJ4pJdRV

P-1 R aaG - 362Z IN TERIM REPORT # 23 - Analysis o f Sedim ent Samples STUDY TITLE Analysis o f Perfluorobutanesulfonate (PFBS), Periluorohexanesulfonate (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., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 INTERIM REPORT COM PLETION DATE May 2,2006 PERFORMING LABORATORY Exygen Research 3058 Research Drive State College, PA 16801 Phone: 814-272-1039 STUDY SPONSOR 3M Company 3M Building 0236-01-B-10 St. Pani, MN 55144 Phone:651-733-6374 ' Mg Protocol Number: P0001131 Exygen Study Number: PG001131 Total Pages: 110 P- 2 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT Exygen Study Number P0001131, entitled "Analysis o f Perfluorobutanesujfonate (PFBS), PerfluorohexanesuIfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sedimept, Fish, Clams, Vegetation, Sm all -Mammal Liver and Small Mammal Serum U singLC/M S/M S for the 3M , Decatur Monitoring, Program," conducted for 3M Company, is being performed incom pliance 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. . ; . Weston Solutions, Inc. Michael Ar. Santoro Sponsor Representative 3M Company Jf Exygen Research Date Date Page 2 of 110 P-3 Interim Report #23 - Analysis of Sediment Samples Exygen Study Nb.; P0001131 QUALITY ASSURANCE STATEMENT Exygen Research's Quality Assurance Unit reviewed Exygen Study N um b P0001131, entitled, "Analysis o f Perfluorobutanesulfonate (PFBS), Perfluorohexwiesulfonate (PFHS), and Perfluorooctanesulfonatc (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program". All reviewed phasesf were inspected for conduct according to Exygen Research's Standard Operating Procedures, foe Study Protocol, and all applicable Good Laboratory Practice Standards. A ll findings were reported to the Exygen Principal Investigator and Management and to the Study Director. Phase 25. Final Raw Data Review and Merini Analytical Repent Review Date Inspected Date Reported to Date Repeated to Principal Exygen Date Reported to foyss&a&r Mmsienaml Study. Director 05/02/0$ 05/02/06 05/02/06 05/02/06 a sm jo i Date 'Note; All in*lab inspections will be documented in the QA statement for the final analytical report at the conclusion o f the study. This QA statement involves only die review o f the interim report and associated raw data. Exygen Research Page 3 of 110 P-4 . Interim Report #23 - Analysis of Sediment Sample? Exygen Study No.: PQOO1131 CERTIFICATION OF AUTHENTICITY This interim- report, for Exygen Study Number POOOH31, is a true Mid complete representation o f the raw data. Submitted by: Exygen Research 3058 Research Drive State College, PA 16801 (814) 272-1039 Principal Investigator, Exygen: D ate Exygen Research Facility Management: Richard A President Exygen R< 6, Study Director, Weston Solutions, Inc Jaisimha K esariT.E., DE Weston Solutions, Inc. Sponsor Representative, 3M Company: Michael Santoro Director Regulatory Affairs ( Exygen Research Date % 06 Date Page 4 of 110 P-5 Interim Report #23 - Analysis of Sediment Samples Exygen StudyNo,: P0001131 STUDY IDENTIFICATION Analysis o f Perfluorobutanesulfonate (PFBS), Pcrfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for A e 3M Decatur Monitoring Program ^ : PROTOCOL NUMBER: P0001131 EXYGEN STUDY NUMBER: P0001131 TYPE OF STUDY: Residue SAMPLE MATRIX: Sediment `_ . TEST SUBSTANCE: Perfluorobutanesulfonate (PFBS), Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS) SPONSOR: 3M Company . 3M Building 0236-01-B-10 St. Paul, MN 55144 STUDY DIRECTOR: Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 STUDY MONITOR: Michael A. Santoro 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 PERFORMING LABORATORY: Exygen Research 3058 Research Drive State College, PA 16801 ANALYTICAL PHASE TIMETABLE: Study Initiation Date: 1 1/05/04 Interim Analytical Shut Date: 04/27/06 - Interim Analytical Termination Date: 04/30/06 Interim Report'Completion Date: 05/02/06 'i ' . -' Exygen Research Page 5 of 110 P-6 Interim Report #23 - Analysis of Sediment Samples. . Exygen Study No.: P0001131 PROJECT PERSONNEL The Study Director for this project is Jaisimha Kesari at Weston Solutions, Inc. The following personnel from Exygen Research were associated w ith various phases o f this interim portion o f the study: Name John Flaherty Karen Risha . Paul Connolly , ....... Christine Edwards Mark Ammerman Amy Sheehan Brittany Kravets . , Scott Crain v Frances Crespi Devon Ingram Christa Gallant Title Vice President Scientist . Technical Lead-LC/MS Technician r Sample Custodian Associate Scientist Technician Technician Technician Technician > Technician , , Exygen Research P ageof 110 P-7 Interim Report 023 - Analysis of Sediment Samples Exygeh Study No.: P0001131 table of contents Page TITLE PA G E..................... 1 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT...............................2 QUALITY ASSURANCE STATEMENT....................................................:...................... 3 CERTIFICATION OF AUTHENTICITY................... 4 STUDY IDENTIFICATION................................................................................................... 5 PROJECT PERSONNEL........................................................................................................ 6 TABLE OF CONTENTS........................................................................................................ 7 LIST OF TABLES.................................. 8 LIST OF FIGURES....................................................... 9 LIST OF APPENDICES............... 10 1.0 SUMMARY.............................................................. II 2.0 OBJECTIVE............................................... 11 3.0 INTRODUCTION................................................... II 4.0 ANALYTICAL TEST SAMPLES..............................................................................12 5.0 REFERENCE MATERIAL................................................... 12 6.0 DESCRIPTION OF ANALYTICAL METHOD.................... 13 6.1. Extraction Procedure For Sediment.......................:.......... ........................................ 13 6.2 Direct Inject Extraction Procedure For Sediment....................................................... 14 6.3 Percent Solids Procedure For Sedim ent.......................... 14 6.4 Preparation o f Standards and Fortification Solutions.................................................14 6.5 Chromatography............................................. 15 6.6 Instrument Sensitivity............................ 15 6.7 Description o f LC/MS/MS Instrument and Operating Conditions............................ 15 6.8 Quantitation and Example Calculations..................................................................... 16 7.0 EXPERIMENTAL DESIGN................................. 20 8.0 RESULTS.......................................................................................................................20 9.0 CONCLUSIONS *........................................... :........:..................................................20 10.0 RETENTION OF DATA AND SAMPLES............................................................... 21 Exygen Research Page 7 of 110 p .8 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: POOOl131 Table I. LIST OF TABLES Page Summary o f FFBS, P.FHS and PFOS in Sediment Samples........ ................. 23 Table II. Summary ofPFOS inD irect Injection Sediment Sam ples............................. 24 Table ID. Matrix Spike Recovery o f PFBS, PFHS and PFOS in Sediment Samples....25 Table TV. Matrix Spike Recovery o f PFOS in Direct Injection Sediment Sam ples...... 26 Table V , Total Percent Solids in Sediment Samples............ .............. 27 Exygen Research Page 8 of 110 ...-* ........... - .........-- .......- - foterim Report #23-Analysis of Sediment Samples P-9 .- - Exygen Study No.: P0001131 Figure l. LIST OF FIGURES Page Typical Calibration Curve for PFBS in M ethanol............,..............................29 Figure 2. Non-Extracted Standards o f PFBS id Methanol, 0.2/ng/mL and 0.5 ng/mL, R e s p e c t i v e l y ........................................................................30 Figure 3. PFBS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively..........................................31 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID: C0172892, Data Set: 042606F)...................................................32 Figure 5. Typical Calibration Curve fox PFHS in M ethanol...........................................33 Figure 6. Non-Extracted Standards o f PFHS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively....................... .34 Figure 7. PFHS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively..........................................35 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for PFHS (Exygen ID: C0172892, Data Set: 042606F)...................................................36 Figure 9. Typical Calibration Curve for PFOS in M ethanol...........................................37 Figure 10. Non-Extracted Standards o f PFOS in Methanol, 0.2 ng/mL and 0.5 ng/mL, Respectively..................................................... 38 Figure 11. PFOS in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively......................................... 39 Figure 12. Chromatogram Representing a Sediment Sample Analyzed for PFOS (Exygen ID: C0172892, Data Sfc042806B)................................................... 40 Exygen Research Page 9 o f 110 Interim Report W21- Analysis o f Sediment Samples Exygen Study No.: P0001131 LIST OF APPENDICES A ppendix A Study Protocol PGOOl 131 (Exygen Study No. P0001131) with Analytical Method V0001782: "Method o f Analysis for the D eterm inationof Pcrfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS", and Protocol Amendments............................... Paye .41 Exygen Research Page 10 of 110 Interim Report #23 - Analysis of Sediment Sample Exygen Study No.: P0001131 1.0- SUMMARY Exygen Research extracted and analyzed sediment samples for die determination o f perfhiorobutanesulfonate . (PFBS), . pp^uorohexanesulfonatc (PFHS), and perfluorooctanesulfocate (PFOS) according to ExygeoM ethod V0001782 (Appendix A). The lim it o f quantitation for PFBS and PFHS m sediment was 0.2 ng/g. The limit o f quantitation for PFOS in sediment was 2.0 ng/g. The standard sediment method (V000J782) was originally used to extract all o f die samples. Use o f this method yielded poor recoveries for PFOS. Because o f this, a direct injection method (Section 62) 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 foT the analysis o f PFOS found in sediment samples by direct injection are summarized in Table n. The average percent recoveries standard deviations for PFBS, PFHS, PFOS in sediment samples were 85 19%, 99 29%, and 93 6%, respectively. Fortification recoveries for the analysis o f PFBS, PFHS, and PFOS in sediment samples extracted with the original method are summarized in Table 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. 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 (A ppendix 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, "V0Q01782; Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/M S/M S" The study was initiated on November 05, 2004, when the study director signed protocol number P0001131. The analytical start date for this interim report was April 27, 2006 and the analytical termination date for this interim report was April 30,2006. Exygen Research Page l l o f l l O Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 4.0 ANALYTICAL TEST SAMPLES Three sediment samples (Exygen ID: C0172892-C0172894) were received on wet ice on April 22, 2006 from Tim Frinak at Weston Solutions, Inc. The samples w o e 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 w ill 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 ExmaiInventoryNo- SP0005726 SP0002401 SP0002694 tatJ 101 SE036 430180-1 Eiateflft BamtfaiLBiite 96.7- 12/04/06 98.6 10/18/06 101.2 10/31/07 The molecular structures o f PFBS, PFHS and PFOS are given below: PFBS Chemical Name: Perfluorobutanesulfonate M olecular Weight: 338 supplied as the potassium salt (GtFsSOaTC*) Transitions Monitored: 299 ,-/.* 99*,.} . _ .f,; . Structure: ' , PFBS Chemical ame: Periluorohcxanesulfonate M olecular Weight: 438 supplied as the potassium salt (Q F iaS O jlC ) Transitions Monitored: 399 -* 80 Exygen Research Page 12 o f 110 Interim Report #23 - Analysis o f Sediment Samples Structure: F F F F .F Exygen Study No.: PC001131 PFOS Chemical Name: Perfluorooctanesulfonate . ' Molecular Weight: S38 supplied as (he potassium salt (CgFnSOj'K*) Transitions Monitored: 4 9 9 '- 8 0 . Structure: . ./I > FF FF F F F FF 6.0 DESCRIPTION OF ANALYTICAL METHOD The analytical method "V0001782: Method o f Analysis for die Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" was used for the analysis of PFBS and PFHS in sediment samples. A direct injection method, detailed in Section 6.2, was used for the analysis o f PFOS in sediment samples. 6.1. E xtraction Proc.edur' e For'Sedim e-nt , . ' x' ' 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 die 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 centrifoged for ~20 minutes at -3000 rpm. The supernatant was then loaded onto a C u SPE cartridge conditioned with 10 mL of methanol and 20 mL o f water. The eluate was discarded. Twenty m illiliters o f methanol was added to the sediment samples left in die centrifuge tube. The samples were vortexed and allowed to shake on a wrist action shaker for another 30 minutes. The samples were centrifuged again for ~2Q minutes at -3000 rpm, The supernatant was then loaded onto the same Cta .SPF cartridge. The eluate was collected into a 500 mL Nalgene Bottle. The column was washed with 4 mL o f methanol. The wash urns collected in the same bottle as the eluate. Approximately two hundred m illiliters o f water was added to the bottles. The samples were mixed by shaking and loaded onto another Cig SPE cartridge conditioned with 10 mL o f methanol Exygen Research Page 13 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 and 20 mL o f water. The eluate was discarded. Approximately five m illiliters o f methanol was added to the cartridge, Five milliliters o f eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.2 D irect Inject Extraction Procedure For Sediment Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A one-gram portion o f sediment was weighed into a 15-miIIiliter centrifuge tube for the extraction. Ten m illiliters o f 1% acetic acid in methanol was added to each sample. The samples were then shaken by hand, vortexed, and sonicated for thirty minutes. The samples were then centrifuged for -1 0 minutes at -3000 ipm. Each sample was analyzed by LC/MS/MS electrospray. 6.3 Percent Solids Procedure F or Sedim ent -1 Percent solids were determined using die procedure indicated in Exygen method V0000427. Approximately 20 grams o f sample was weighed into a pan. The weight o f the sample plus the pain was recorded. The samples wore then dried in an oven overnight at 104 2 C. Then the samples were transferred to a dessieator and allowed to cool for -1 5 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 o f S tandards and 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 mg o f each o fth e standards (corrected for purity and salt content) in 100 mL o f methanol. From this solution, die following fortification standards were prepared: Cone, o f Fort Stock or Fort. Volume Solution (mL) (uB/mL)1 1000 10 100 10 10 10 1.0 10 0.1 10 1o f PFBS, PFHS, and PFOS Final Volume (mL) 100 100 100 100 100 Final Cone, o f Fortification Std. (pg/mL) 100 10 1.0 0.1 0.01 Exygen Research Page 14 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 A set o f non-extractcd calibration standards containing PFBS, PFHS, and PFOS was prepared in methanol, as specified in Exygen method V000I782. The following concentrations were prepared: ' "^ * 1- 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 1o fPFBS, 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 2Q 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 LQD w ere 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 die 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 OptiFlex <3X400 Software: Windows NT, Analyst 1.4.1 HPLC: Hewlett Packard (HP) Series 1100 HP Quat Pump Exygen Research Page 15 of 10 Interim Repent #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 HP Vacuum Degasser HP Autosampler HP Column Oven HPLC Column: ThermoFluophase RP, 50 nun x 2 1 mm Column Temp.: -30 C Injection V oi: 15 pL ~ Mobile Phase (A); 2 mM Ammonium Acetate in water Mobile Phase (B): Methanol 0.0 1,0 8.0 10.0 11.0........ 18.0 Total run time: -18 min AA 65 65 25 25 65 65 24B 35 35 75 75 35 35 Flow Rate; 0.3mL/inin Ions monitored: Analyte Mode PFBS PFHS PFOS negative negative negative 6.8 Quantitation and Example Calculations Transition M onitored 299 -> 99 399 80 499 80 Approximate Retention Time Crain) ~0.56 min. ~9.4 rain. -11.4 min. Fifteen microliters o f sample or calibration standard were injected into the LC/MS/MS, The peak area was measured and the standard curve was generated (using 1/x fit weighted linear regression) by Analyst software using six concentrations 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 die method (V001782), but this has no effect on the final calculations. Exygen Research Page 16 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: F0001131 Equation 1: Analyte found (ng/mL) = fPeak area - intercept) x DF Slope Where: DF * Dilution Factor, factor by which the finalvolum e 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 this amount o f PFBS add PFHS found in ng/mL to ng/g (ppb). Eqiqirinn 2: _' Analyte found (ppb) = fAnalyte found (ng/mLVx final volume (5 mLVI sample weight (5 g) Equation 3 was used to calculate the percent recovery: Equation 3: Recovery (%) = fanalvte found (nob) - analyte in control (nob)) xlOO% amount added (ppb) Equation 4 was then used to calculate the amount o f PFBS and PFHS found in ppb based on dry w eight Equation 4: .. Analyte found (ppb) dry weight = Analyte found (ppb) x [100% / total solids(%)] An example o f a calculation using an.actual,sam ple follows (calculation is for PFBS only): Sediment sample Exygen DO: COl72893 Spjc F (Set: 042606F), fortified at 4 ng/mL with PFBS where: ; - peak area , ;v ^ 253819 intercept - -592 . slope , : .4 2 3 0 0 , . dilution factor , , ~ 1 ng/g PFBS added (fort level) = 4 amt in corresponding sample (ng/g) = 2.41 final volume (mL) , q , ^ 5 sample weight (g) - total solids (%) " 54.37 Exygen Research Page 17 of 110 Interim Report #33 - Analysis of Sediment Samples Exygen Study No.: P00Q1131 From equation 1: Analyte found (ng/mL) -- f253819- (-59211 x 1 42300 * 6.CI ng/teL Front equation 2: Analyte found (ppb) - (6.01 ng/mL x 5 mL) 5g = 6.01 ppb Front equation 3: % Recovery _ . = (6.01 p p b - 2.41 ppb) 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 forP FO S . . Equation 1: Analyte found (ng/mL) * (Peak area - intercept! x DF Slope Where: DF **Dilution Factor, factor by which the final volume was diluted, if necessary. For samples fortified with known amounts ofPFOS prior to extraction, Equation 2 was used to convert the amount ofPFOS found in ng/mL to ng/g (ppb). Equation 2; Analyte found(ppb) (Analyte found fng/mLl x volume extracted (10 mLH sample weight (1 g) Equation 3 was used to calculate the percent recovery. Exygen Research Page 18 of 110 Interim Report #23 - Analysis of Sediment Sample Exygen Study No.: PO001131 E au a tio n 3 : Recovery (%) = . (analvte found (iuz/el - analvte in control fag/el) xl00% 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: CO172892 Spk D (Set: 042806B), fortified at 400 ng/mL with PFOS where: 1 .' peak area se 152371 intercept ss 3720 slope '- 22700 dilution factor 100 ng/g PFOS added (fort level) 4000 amt in corresponding sample^ng/g) =s ' 2360 volume extracted (mL) 8= 10 sample weight (g) -= 1 total solids (%) ar 66.54 From equation 1: Analyte found (ng/L) = ri52371 - 37201 x 100 22700 = 654 ng/mL From equation 2: Analyte found (ppb) ; = (654 ne/mL x 10 rriLl ig . * 6540 ppb * . ' From equation 3: % Recovery j- = (6540 n g /p - 2360na/gl 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 o f 110 interim Report #23 - Analysis of 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 said a duplicate were extracted. Due to poor recoveries, the three sediment samples w o e extracted and analyzed using a direct injection method for PFOS. This method is detailed in Section 6.2. 8.0 RESULTS Analytical results for the analysis o f PFBS, PFHS and PFOS found in sediment samples extracted with the original method are summarized in T able L Analytical results for the analysis o f PFOS found in sediment samples by direct injection are summarized in Table IL The average percent recoveries standard deviations for PFBS, PFHS, PFOS in sediment samples were 85 19%, 99 29%, and 93 6%, respectively. Fortification recoveries for the analysis o f PFBS, PFHS, and PFOS in sediment samples extracted with the original method are summarized in 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 COfSCLy$IO N S The sediment samples were successfully extracted and analyzed for PFBS and PFHS according to analytical method V0001782. The sediment samples were successfully extracted and analyzed for PFOS using an alternative method, which yielded acceptable QC data. Exygen Research Page 20 of 110 Interim Report #23 - Analysis of Sediment Samples Exygeo Study-No.: P0001131 10.0 RETENTION OF DATA AND SAMPLES When the final analytical report is complete, all original paper data generated by Exygen Research will be shipped to the study director. This does not include facility-specific raw data such as instrument or temperature logs. Exact copies o f ail 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 fo r the period o f tim e specified in EPA TSCA Good Laboratory Practice Standards 40 C FR 792. Exygen Research Page 21 of 110 InterimReport #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 TABLES Exygen Research Page 22 of 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Table 1. Summary of PFBS, PFHS and PFOS in Sediment Samples Exvaen D C0172882 C0172*02 Rop COI72003 00172003 a* COI72804 C 0172004 Rap Otont Sam pN lO dal^ o b p p o i^ ocioo CA L-ao-appoi4M ooo* DAL-SO^mM-O-OOOQ OAL^O-8PR02^HXX' 0AL4M PP034M W O A i-S O Ja p p a u iJxxxy C S S u n m iteP T B S C SSolfeM teP FH S C s Sotfonato P F 05 An*** Found (UF*FT*inm.a-*l-w4-l A nwm Accuracy A m * found F * .n * W DnfWrtioi a i4 40 4.3 1 1 0 40 0.1 4.43 30 74.5 4 8 4 30 64.7 9.87 30 130 8,73 30 123 Atm m m t Aoouiuoy <**> 30 30 30 30 50 so Andy!* Found 1PF4.no*) DryWoM AttitM d Aoouraey (FM tt NR NR NR NR NR NR NR NR NR NR NR NR *U ta o to y ( to ta l* NR *N(Xr*porMHu*to W(RvcentralmMIMunM. Sm TM m IIterm onofrN, rwute. Exygen Research P age23of 110 Interim Report #23 - Analysis of Sediment Samples . Exygen Study No.: P0001131 Table II. Summary of PFOS in Direct Injection Sediment Samples -- ExygenlD C0172892 C0172892Rep C0172893 C0172893Rep CO172894 C0172894 Rep Client SampleID DAL-SD-BPP01-0-0000 DAL-SD-BPP01-0-0000* DAL-SD4BPP02-0-0000 DAL-SD-SPP02-0-0000* DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000* "Laboratofy Duplcata CS Sulfonate PFOS -P*rfUiorooctnwMitfonte AnalyteFound Aaaesaed (PPb,ng/0) Accuracy (+/-%) 3550 30 3520 30 4160 30 3640 30 11900 12000 30 30 Exygen Research Page 24 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Table III. M atrix Spike Recovery o f PFBS, PFHS and PFOS in Sediment Samples sam p* OMCrtotoa CtlMtteaafr PfMWnWiflR C iX i> f PPHtWXWaiaN Ar ic u iI in S a n M (A M I (k m im im -A m m o M /a u m . Amount FtocoMwed Saccwery m S nn^i* RpCOVOty m ta im u t ( ) (AM )tMM W i fnaB lvstn . m CMM vnw **fQ * * * * * * * m sm M . mmo. rm c n w ii Raoouary (*> DAl'O D-RPPQ 'M H XW ecim aiapc*dfpaaflm i 4 . ZOO . . 447 m QAL'SD-BPD<-M0Q < f i* m m * m * * * m * * * 40Q . lo o 2 06 60.1 4M to tU l 8&8PP0t-Q^00C c m a m * * m m o i * * * * 000 100 2670 SOV . , 6190 1 * NR . NR NR O A t-oc^P w e-M iooci 1MJ D A l-aM m W K W O O 0 H n m ***m m *** Q M .-S D S P *K 4<X m v *n m *+ *> *m m *+ * 4 400 4000 I4 t 141 .2 - l 102 90 - 3T4 ** * ' 3020 06 a 4 t * - 340 404 0090 , m '` m. NR . m OAL-80-8PPO3-0-OOOO p s e ffiw eptu. * * spa QAL-SO-APPOMM&OO % *} 4 400 4000 4.30 4 430 7,71 5 4040 S3 w '-014 121 01J an 4000 w % . in HR NR . ,, NR Av-- gar m St t ^ a rdP -laOan: 1* * M |it M IWwUnl D idrtw ; JO tNNTDRQHw.no.in.Ki.p.X>..na.Kn.i.cf.al>.i<.tt.iit.aio.T.M.a.*.MM..n.a>.fo.c.>.o.Mt.ii.|Pr.M.n.i.fco.r.%ym(3nMm.S^oaciTi^ale*M>>?vttworfe>ffcw^win.jMitwiQi<t>.agaO.T>ii.-aweryv#gBWwoteo^<ul^3 M o*a:ttw >>aeim w ?ylabia ahoaai i minda4 iaiOla. inaowiy *Nnia i^ m ylohgif irm t tfca %oiaIn R o --M Sia. .to rn 1. M l Ml Exygen Research Page 25 of 110 Interim Report #23 -r Analysis o f Sediment Samples Exygen Study No.: P0001131 Table lV , M atrix Spike Recovery ofPFO S io Direct Injection Sediment Samples Sam p* D sacriotion DAL-SO-SPP01-0-0000 m in iK B p k a a H H tiiM ) DAL-SJ>8 P P 01-<MXXX) KM IM H d * f , 4MM m* D A L-SD-BPP0 2 -0 -0 0 0 0 (C M m w a* a . 4MDM d d * ) OAL-SD-8 PP03-0-0000 caintM pk M.moto * * i d i OAL-SO-8 PP03-WM00 pk j , m m ppe d a ) DAL-SO -B PP0 3 -0 -0 0 0 0 C M m M d * K. 40M M* tp ftd S p fta d (tM Amt Found In Sam ple 4000 40000 , .. 2300 2360 4000 40000 4000 40000 2260 2260 5260 5280 Amount R acouarad (no/o)w otw t 6640 40000 3960 38000 8770 41200 A varapa: S tan d ard D eviation: R aeom y (H i 106 94 92 89 87 90 93 6 . M i e wmnwy ta t* mow. rounds raauH, (coiwt * * m mayvuy sSpMy Iran d n l i . k. m um dato. Exygen Research Page 26 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Table V. Total Percent Solids in Sediment Samples ID C0 172892 CO172893 C0172894 ampta -- ...... ...Deecrtptton DAL-SD-BPP01-0-0000 DAL-SD-BPP02-G-0000 DAL-SD-BPP03-0-0000 , Total Sods <%1 68.54 " 54.37 44.45 Exygen Research Page 27 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 FIGURES Exygen Research Page 28 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 1. Typical Calibration Curve for PFBS in M ethanol a i oatnosr S4 <irxnL>t (pcbsj:"Un*^ ^^4*004x*-oa2cr*oaooo) Area,counts Exygen Research Page 29 of 110 Interim Report #23 - Analysis o f Sediment Semples Exygen Study No.: P0001131 Figure 2. Non-Extratfted Standards o f PFBS in M ethanol, 0.2 ng/mL and 0,5 ng/mL, Respectively I tS f*U S M -P fm MwMIHQ 40mmfCreMMrto H*it4t n m fU i * 14U r*m M Ht&.wm XT: t.lS4 mt* 3SMM4MS. f S M m: 200*1 m M unu *an<. 2 * tm *wm 04t6M T m 1.4Mr>8 tv * RT: 0.580 min IntenaJV. cps Wwisi*, eps Exygen Research Page 30 of HO .totcrim Report #23 - Analysis of Sedimetat Samples ' Exygen Study No.: P0OOll31 Figure 3. PFBS in Reagent Blank, 9,4 ng/mL Fortifled Reagent Spk A, and 4.0 ngftnL Fortifled R eagent Spk B, Respectively tin 0.00 * 1 29*90780 10 --r 11 r...* ...* 12 13 Time, mtm I fu,9.,tspke. prs;oc)2aea*o mw*awapio10of40fcsw043000?mW Am: 100227 Matr HatgM? 1.11**004pa RT:O087 min 0 ' r ....T- .i--.| 14 1* 16 17 TIm*. ad* Exygen Research Page 31 of 110 Interim Report #23 - Analysis ofSediment Samples Exygen Study No.: PQ001I31 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID: C0172892, Data Set: 042606F) m k matcw* m 0 t ztm+mcf* tm *.* OM7 r* y # 9 10 11 wCrtm ia 13 14 1 10 17 time, mtn Exygen Research Page 32 of llO Interim Report #23 - Analysis of Sediment Samples Exygen Study No.. P0001131 Figure 5. Typical Caiibration C u m for PFHS in M ethanol CM290SF S .* * r i r d k <PFH9>*Uc>*r R| W i t 5 f i S i t y - 7 JO # * * * -1.1**009(r* C M i ) A ru , couni Exygen Research Page 33 o f llO Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 6. Non-Extracted Standards o f PFHS in M ethanol, 0,2 ng/mL and 0.5 ng/mL. Respectively I SSMMJM. m m <Wn TX774asm* fT4SRwuxtf.w m t-BM iW v* KTt Intensity, cps SSOCTMaea-rfHS0UrjUi)aOBOlSOE m y um,I* 2 WHSam 0020001 : 33003 NWS Haiti t.73aM03 a** RT;0.40min intensity, cpe Exygen Research Page 34 of 110 interim Report #23 - Analysis of Sedimerit Simples Exygen Study No.: P0001131 Figure 7. PFHS inReagentBIank, 0.4 ngftnL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk E, Respectively I HwtufwfttMCmrfMftwt>oPfm fUtfmm) .MmpHiot'iftrtH ' .Ot'iKftteir tntensgy.cps Intensity, c u t An*: 27073 OMDtt 1SO<e003 of* *T :0J8 AK 1000 iooo> 300 9-30 <l S 0 10 11 12 12 14 Tlnia,nd | - PfHS(;)3Q0jCUS0i) m u . n n p l. 10 .145 tni*CM2S0SF^M 4***270070 eeunli H*igMMJOnHXMe# NTr 0.40 mitt 8.40 1.0*4 wo&o s jL 4 10 11 12 rim a , mfa 1 17 Intensity, cp* Exygen Research Page 35 o f 110 Interim Report #23 - Analysts o f Sediment Samples- - Exygen Study No.: POGOl 131 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for PFHS (Exygen 10: C0172892, Data Set: 042606F) C9tnm * MMmijaMtMJMw .np rtet4Utom a * : m f w w * W a t t i z k + m t p t rti m * h <* 2200 0,41 2000 1000 1000 1400 1200 1000 0.43 1 2 0 4 -0 0 7 *0 0 ....... 11 1 p T"' i i 11 12 1 44 15 16 17 T in * , in te Msnstty. tp s Exygen Research Page 36 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Figure 9. Typical Calibration Curve for PFOS in Methanol <a*ow 8,<- l rt (PFOB):"URr l i e y ? . 2 7 * K 4 x + 3 71*003<f00046) Area, counts Exygen Research Page 37 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Figure 10. Nois-Extracted Standards o f PFGS in M ethanol, 0*2 ng/mL and 0.5 ng/mL, Respectively I S5 3 3 M5M PfOSfStaextrrO) -tampf* lolISftwm MSMBMIT *nm n W c M it O t y lt m uW l iiii KT: t4mtm 11. Mentfty, cp* Atm: R222S M.nfc H .iiht 7.m *0C 2 m RT; 11.4 min 11.43 Intensity, cps Exygen Research Page 38 o f 110 Interim Report #23 - Analysis o f Sediment Samples Bxygen Study N.rPOOOl 131 Figure 11. PFOS in Reagent Wank, 0.4 n g/m t Fortified Reagent Spk A, and 4.0 ng/mE FortifledReagent SpkB , Respectively t ss*cvmmt HtfgMrZm'(ept 15tMula ' . 11.4* IU4r t A . pro 00408.0000 JA MAPI <Ammm042M M jM 4: 100(0 omi* HttaM: OJtlrHX <pt lT: 11.4 ml 9000 11.44 Tim, min Exygcn Research Page 39 o f 110 p. 40 Iniemn Report *23 - Analysis of Sediment Samples . JBxygpn Study No.: P0001131 Figure 12. Chromatogram Representing a Sediment Sample Analyzed for PFOS (Exygeu ID; C0172892, Data Set:042806B) TMI AMgr4*%*+*M**2.'|N,mr fif.fmi tmLpSAm/Ui rtjSfnm Htmurn* Exygen Research Page 40 o f llO p. 41 Interim Report #23 - Analysis ofSediment Samples Exygen Study No.: P0Q01131 APPENDIX A Study Protocol P0001131 (Exygen Study No. P0001131) with Analytical Methods and Protocol Amendments Exygen Research Page 41 of 110 p. 42 interim Report #23 - Analysis of Sediment Samples , .'Exygen Study No.: P0001131 ExTfsaFnKoedl NvEb*r POCO] 13) STUDY PROTOCOL Study Title: AnalyiU of Perfluorobutanesulfomate (PFBS), Perfluerohexaneeulibnate (PFHS), and Perfluorooctaneaalfonate (PFOS) in Water, Soil, Sediment, Fish, Clan, Vegetation, Small Mammal Liver and Small Mammal Seram Using LC/MS/MS for the 3M Decatur Moaltoring Program Exygen Protocol Number: P000113J Exygen KaMareft 305$ Research IXnive State College, PA 16801 Phone; (814)273-1039 S m a lm m sa t ssi Michael A . Santoro Director o f Regulatory A ffiiin 3M Building 0236-O1-B-1O S t Paul, MN $5144 Phone; (6S1) 735-6374 Magr / oj OS Exygen Research Page 42 of 110 p. 43 Interim Report #23 - Ajnalysis of Sediment Samples ' ;; 1 - Exygen StuSy No.VPOOOl131 E xytu Proweol H a tte r. MOO! 131 DISTRIBUTION: 1) JauunbaK sttti. Study Director, W*ton Sohtiamt 1) John M. Fltaty, Piiwap! Inve!j*1or, Exygto Xjatetrcb 3) MuAd A. Santoro, Spoor RopnacatKive, 3M Company 4>Exy^IUMwdi(^M%AMunm^]^BA . . 'bu - V.* ' ' ' '. ` ` .ci Exygen Research P a t* 2 o f 65 Page 43 of HO Interina Report #23 - Analysis of Sediment Samples Exygen Study No.: POOOl 131 ProltxotNumber FOOOllSI PROTOCOL APPROVAL Study TW: AmfynaofPetfluortAuunwuHbn* (PFBSX Pfluorohe*oeraifooete (PFHS),*ndPeiftaotoocoo**alfca*t(PFOS)m W*wr, Soil, Scdnott, Fh, O hm, VtgsttM.Smtll Munmii t i n a ni Swill Mammal Sun UingJLOMS/MS fltbs3MDciurM<mitorii^rognun Exygcn Protocol Number. POOOl1 1 1 ................... Exygen Research Pofv 3<jftS Page 44 o f 110 Interim Report #23--Analysis o f Sediment Sairiplcs Exygcn StadyNo.: P0001131 B q v m Protocol N ta b tr. POOOU31 TABLE OF CONTENTS Trim page______ ______________ _ h d is t r ib u t io n ___ ___ ___________ _____ ___ PROTOCOL A P P R O V A L TM ,..!.._______ ____ ort a b l e c o n t e n t s __________________. .. .. in t r o d u c t io n ________ __ ______________ _ TESTMATERIALS_______________________ oareenvg___________ TESTINGFACnJTy______________ STUDYDIRECTOR___________________ SPONSOR HBPRBSEHTATIVB___________ PRINCIPAL INVESTIGATOR__ PROPOSED EXPERIMENTAL START ANDTERMINATION DATES IDENTinCATJON AND JUSTUTCATIONOP THE TBST SYSTEM____ SAMPLE PROCUREMENT. RECEIPT AND RETENTION__________ _ sa m pl e [d e n t if t c a h o n __________________________ _________ ANALYTICAL PROCEDURE SUMMARY______________ ;__________ VERIFICATION OP ANALYTICAL PROCEDURE___ .______ 1______ METHOD FOR CONTROL QT BIAS_______________ STATISTICAL METHODS_____ __________________ OLP STATEMENT_____________________________ REPORT,;___________ l_________ - ____ _______ SAFETY AND HEALTH________________________1 AMENDMENTS TO PROTOCOL______________ _ DATA RECORD KEEPINO____ . _________________ QUALITY ASSURANCE_______ ___________........... RBTENtlM I OP DATA AND AtCWVTNO ,_ TM __ ;____ APPENDIX L ANALYTICAL METHODS_____________ ............. 6 ............ i ........ 7 .7 7 Pm ttftfi! Exygen Research Page 45 of 110 p. 46 InterimReport #23 - Analysis of Sediment Samples , . , Exygen StudtyNo.: P0001131 Eyjen Protocol V w rter pooaiui INTRODUCTION The pwpcto o f thia *ady ie to perfotm auriynt fcr prihicn>buiwiulfon*te (THE). pwflucfohraneaulfonate (PFHS) and perfluoroocttneaulfonaie (PFOS) in water, mil. aediment, fi* . cUme, vegeuno^ M il mmnmai l,v mammal eerum Being IOMSACS for the 3M Decatur Monitoring P ro p s . The qdy will be eudited fix cotBplienw! with EPA TSCA Good Laboruory Practice Staaderdi 40 GFR 792 by the Qaahfy Aaaueenee Unit o f Exygen TEST MATERIALS The teat mmeriala a n perfluorobutanaeuKboite CEFBSX pqfluomhcarrocwit&oetg (PFHS) end pecfloorooettneeuiibnat (PFOS) and are ail tgipbed by 3M. ; PFB8 Chemical Name: PerfluototmtanmMboete ' Molecntar Weight: 33* euppHed aa die jxxtarium eak (CFSO,TC`) Lot Number 101 Parity: 96.7% Tiaoaitkm Momtonat 299 -->99 - Sttucttne: ` ' - SOj' PFHS ! Chemical Meae: PerEauobcxaeeaaifcute "W iled u die potaerium aait (CiFnSQjX*) Parity: 9*6% T rxantiau M anured 399->80 Struemre: - - S0}* A*lefts Exygen Research Page 46 o f 110 p. 47 hiterm Report #23'-Analysis of Sediment Samples ExygenStudy Ko.:POOO1131 E xjfn ProtoctfNumber: PQOO1131 tvos Chemical Nane; Paflaatoocfwnfow tfe Molecular Weitfii: 5S tap p ati a* the patateum alt (CjF itSOj C ) Number-21? ' ' ` \ ......r-- TriM$tfonMqntaKd: 499V ,- Sm ettaxtf r ' O B JEC TIV E Thojpwpoec ofth itudy i> lo perform ubnl for perfluonobutaocmlionato (PFBS), p*rflno>ohrxinwmlfomM (PFHS) ad parfiutsoodweaidfoaaae (PFOS) in water, toil, aedneot, Adi, d aim vegetation, mali mammal Uve and m all mammal m um for tfte 3M Decatur Monitoring Program uring the coneat verrions offl feflowmg Exym analytical method*: V00017W: "Method at Analyaia for the Determination o f Perfluorootaanoic Add<PFQA) in Waterby LC/MSACT V00017I1-. "Mafood of Analyaia for the Detenmnatuxi of Perfluaroocunoie Add<PFOA) ia Soil by LMS4S" V000I7S2: "Mothod ofAnaiyaia for the Detetnaratfinri o f Perftoorooctanoic Add<proA)mS<rfinml>ylX^MSAiSr V0001783: "Method of Analyaia ftr a Determination ofParfluorooctanoie Add(FFOA) FiahaaidCtamaby LOMS/MS" V00017S4: "M attai o f Analyaia fiar tb t Detam lnat o f Parfhtoroactanoic Add (PFOA) ie Vegetation by LC/MS/MS" V00017S5: "Matood of Anatyna for the Patarmiaation o f Perfluoroocunoic A dd (PIPOA) is Small Mammal Liver by LC/MS/MS" V0001786: "Method of Analyaia fttr cb* Dawrmiaatioo o f Porooroocuooic Add (PFOA) in fonali a te s a d Sanan by LOMS/MS" TESTIN G FA C ILITY Hxygao Ramarci 30$BReaaarchDrive ! Stata Cottele, PA 1 6 *0 1 Phot; (814) 272-1039 P a* S u ffi Exygen Research Page 47 of 110 p. 48 InterimReport #23 - Analysis of SedimentSamples Exygen Study No.: JP00Q1131 Bxypa PnxocslNmstw: WOOmi STUDY DIRECTOR JaifOBh* Keeari P A , DEB Weatna Sotatkau, Inc. 1400 Weaaoc Way Wart Cheater, PA 19310 Phono: (610) 701-376) Fax: (610) 701-7401 j.keariwcton>olution.coin SPONSOR REPRESENTATIVE Michnei A. SaofiMO 3M Coaaptoy Directoro fRegulatory Affiun 326 Building 0236-01-&-10 S t Paul,M N5J144 Phone: (651) 733-6374 PRINCIPAL CWISTIGATOR JohnM . Flaherty ExygeoRcaoaith MSI Research Drive State Collcg* PA 16K Phoor (814) 273-1039 johaftaharty@ erygee.cnin . , PROPOSED EXPERIMENTAL START AND TERMINATION DATES A k prepared Ant the analytical pcatkn o f this itudy be conducted &om October 01,2604 tc Deeambar 31, 2005, The actual experimental aunt and tomunatioo date w illbe tocledod in the final report Pngr lo ftS Exygen Research Page48 o f 110 p. 49 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P001131 ExygraProtocol Number reOCl 131 IDENTIFICATION AN JUSTIFICATION OF THE TEST SYSTEM The following are toe tad eyetome for tW*etudy: Water (grocndwttCT and ariace water) Soil Sediment h* :' Chmt - . Vegetation Small Mammal liver Saudi MammalSena - - The aanplea will be collected by Weatoo Solution. The control ample* will be pmehaaed end prepared by the teabag toMbty Pmchaac and proccsaing deoil for the control ample wilt.be (netnded to toe final report utociared w itt tide atady. . The teal (yuan were cboeon to ecceaa toe environmental impact of PFBS, PFHS and PPOS in the Decatur, Alabona are*. SAMPLE PROCUREMENT, RECEIPT AND RETENTION Water, oll, m tsent, Oah, dam , vegetation, amafi mammal liver and email mammal aerum aamplea will be w aived to Bxygaa directly fiwn Weaton Solution* The detaib o faanfotoprocurement fo rth tudy *re ostiined in ihc 3M work plm etoitied "Pbaae 2 Work Plan for Sampling Environmental Media.'' The somber sod type o f ample* collected -will vary depending availability in toe field. The total number o f latnpio* received and analyzed tor each matrto witt be docaaented to (ha final repeat aoctatcd with toil ' etody. - ' -- *' Wtocr, aoQ, and edbnant aaraptea will be tued aa received without ftntocr proceeito* at Exygea Theae mreple will be itored reftigerated at 2*C-$'C. Hah, elate, vagwtttoa and mail mammal fiver aamplea witt be proceeaed according to toe approptiaa anelytical metood (tee Appendix rj. Them vamp!* will be atom! 'fiheca et S -10'C. Small mammal wik> bluod ttol will be ceatritoged in the field Mthe time of collection and die aentm faction will be u ed tor the tody. Smell mammal aerran will be awed b o n a at i -IO*G Tbe receipt end proceaeing o f toe aamplee will be doemnented in die find report andtaw data aaaodated with the tatty. Pfiofti Exygen Research Page 49 o f 110 Interim Report #23 - Analysis o f Sediment Samples ... Exygen Study No.: P001131 SAMPLE BESTJFiCATION E x Protocol Nnnb*r: FOTO!131 Prior to n aiyiis, each sample will bo assigned a laboratory sample reference ownher. The reference Dumber will be unique end will distinguish each H n*ory sample that is procoeaed throutfrout the analytical procedure. CbroRMopeplue d m will be idem!Bad by die laboratory sample reference number. Semple storage conAticos rod bcebcnc win be documented throughout the study. ANALYTICAL PROCEDURE SUMMARY RcArbcm: . V00017W: "Method of Anaiyaii for the Detoininetioo o f PerfijcroocUncic Acid (PPOA)m Water by 1X/MSAIS" V00017J: `Method of Analyiit (or the Determination of Perfluorooctwoic Add(PFOA) in Soil by LC M SA iy V000172: "Method of Anelyiie for the Determination o f Perflaorooctenoic Add (PFOA) in Sedboent by LC/MS/M5" V00017S3: "Method ofAnslysu for the Determination of Perfhrorooctanotc Acid (PPOA) in Fids end Ctanu by LC/MS/MS" VOOI7S4: "Method of Analysis for the DetmndnttKM of Perfluorooctanoic Add (PFQA) in Vegetation by LC/MSlMS" V00017S: 'Method of Analysis Har the Detenniaatiftti of PerBuorooctanoic Add (PPOA) in Small Mammal Uver by IXVMS/MS" V0001786: "Method of A nalyst fix the Determination o f Perirorooctinoro Acid (PFOA) in'Small MamtudSerum by JLC/MS/MS" Tbe above method oat analytical conditions capable of separating the isomere o f PFBS, FFHS tndPFOS. The final report will include the saner* nmmod into total PFBS, total PFHS, and total PFOS found. VERIFICATION O f ANALYTICAL PROCEDURE lafcemory erotnd cample will be u*d fiar the preparation o f fortified control ample. The teat aahatroce will he made nte ohitrot per tiro nunhod, rod added to the matrice* via a mJcropipetie. Fot wah r sampn* Bxygro will supply one bottle per tample collected. The f*" 1 will be 500 mL praclaroed Sd/Spee Prem ia wide mouth HOPE bottle Theae botde* have baro routinely used for Quoroebeanical sample P utt 9oftS Exygen Research Page 50 of 110 Interim Report #23 - Analysis of SedimentSamples Exygen Study No.: P0001131 Exypa Pnnocel Nwsbtr MOOi 1.11 collection at foe taring beiUty end hevrlw an tbown to be free of PFBS, PFHS and PPOS. Sample! will be added to each container to a volumetric GU hoe at 200 mL. A Odd dedicate, < low Odd pike end a high field pike oT each aampto inO be collected. The low tad h ig h fid d spike botllea will contain PPBS, PFHS ndPFO S tow eBtopcrfhiaeoctanoie acid (PFOA) and 1.2-13C petflnarooeUnoioacjd ('iC PfOA). PFOA and " C PFOA an faetaded in the lohaieoiuaed to spike.tbe ewnpJe*. H ie rw uia for PFOA and C PFOA will net be imported in fob study, EeygnB win n pp iy one field blank (control water) and two field blank spike (control water fortified with PFBS, FFHS and PPOS But lew and high level) foe every twenty samples colleoted. At the tsatfag foeflity, aaafc wtrtar am ple (unhidm g field doplicatea and field apikea) win be extracted In dupih'q rtc and will alao be fortified at a low and high mmentntkm with PFBS, FFHS and PFOS and pmcaaaad through the described ptoeadare tad eMrmin method accuracy and to check forties. For toil, sediment, dame, and vegetation, Bxygeo will supply one $00 mL preeleaned Sci% ac Premierwida month HOPEbottle per sample eollected or a zip-eeal bag All ocotahiaa/baga oaed (br sample collection will be shipped to the sample location. Samples witt be added to each container c* bag intbe field. At toe hating facility, each tampk will heextiseted in duplicate and wiBelro be fortified at known eoocontnrtioc with PFBS, PFHS end PFOSet ^ both a low and Ugh level and paoceaaed through the dcacribed procedure to determine method accatacy and to check for biw. For aasiB 'aaam nal Hver, Exygeo win supply a JO mL polypropylene centrUUgetnbe. TbramtOl mananal aenim, Exy^en will anpply a collection kit for each aampSe oontaintiig sam e aaparator tube* (rod topX vacutainen, needle liden sod needles, tr*n*&rpipcttee,*nd po]ypropyieie tubes. At foe testing lacahy, each Itvar and eenrtn temple wiil b e eacttected in duptlcate and w M tlrobe& rtifiri si a Imowa concentration with PFBS, PFHS tod PFOSst both a lew and Ugh level and proocaeed through the dcecnbod proeednre to . detw m i method atOTicyaod to tieck feb iae. Low and high oikiiig levrte fbi each matrix are defined below: Matrix Law8oikhMLevel HlfbStrtkiai Level Water - 300a 5000luPL S<nl SaBMHt Adu*Tfca 40 ns/a 40 ng/* Hat . n a t 100ng% rr! ..... . lOOnglg Veflatioe W nai 100 M/B Small Mammalliver lOaaifi lOOngig SmallMamma!Sana' lOiWmL 100 mt/mL fifr/O s fiS Exygen Research Page 51 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001 ]31 Sxyiaa honest NaatocNOOtUt Recovtrie* are anticipated to be between 70H end 130M o f !ho fortified levels; however, tbs exact ptecinoe end accuracy mS be determined by the uudyiU of the quality ooMrni sanplet described above. A statement of accuracy wiU be included in tbe final report. METHOD FOR CONTROL OF BIAS Controlo f Was will be addressed by taking reprsentative aub-aamplet from a bcmogeooou* mnctuie o f each matrix from untreated control tem plet, end by aatlyxiag at lea* two levels o ffbrtflcadcm. STATISTICAL METHQtM Statistics wiO be touted to those specified in dm subject methods and to the cabedatHm ofaven^m covtadee, applicable. GLF STATEMENT Ail aspects o f tbit Body shat be performed aod reported io compliance with EPA TSCA Good Laboratory Practice Standard* 40 CFR 793. Tbe final report or data package (auppKed to tbe Spooaor) hall contain a statement that tbe rody wee eendaeted In somplieoce with current and applicable GLP standard* and will oatbse toy deviations in the rtudy from (bate standards. This statement anil be signed by tbe Study Director and Sponsor Rcpteacntative. . RETORT A final report wOt be prepared by the principal investigator or their designee at the coocioakro o f the atody. The report will elude, but rrti} not be limited to, the following: a The naiae and addieea o f dm StnfylHraetor, Sponsor Representative, and oftbouonj facility. * A itsteraras o f <3LP ooapfience {any related documastation, nwh as chain-of-custodyrecords. taitat be in tbs tady records). P m t'tlo f& i Exygen Research Page 52 of 110 Interim Report #23 - Analysis of Sediment Samples ' Exygen Study No.: POOO1131 Exjuw frotocot Mth>w POOOlUt The c u d and dated w anest by the Exygen Research Quality AMuranu Unit regarding d a t t i todyo f ir m pe c t x r m and date finding wer* reported to the Staaly Director ad Minagenienl. A doeertptioa of the axact analytical condition* employed in the study. If the mhject method wet foflowod cauctly, it ia necen ary to include only a copy of f lic analytical mediod Any m&toation to find medaod will be incorporated iato the report If the method ie photo-reduced, the project number id page um ber too be included on cecb page. a ' Deeeription ofthe inatwheenlationaeod and operating condition. All remit hoc# ali aet* analyzed. Control and tonified ample w>.Dbe Mutant adthedata table ton hwlttdf feaph.inete and fortification level a Rapreeerxjtivc chromatogram for each analyte in eoob matrix. including chrom atoputu of* etandard sod a cootrol amtple, and a dhrcanatograni at fortification level, th e location o f the analyte peaks will be clearly identified ia all ebroeutocreota. , AB cimButancee that may beve aflbetod die quality or integrity o f toe data wiObe documented in toeteporL . a . Locadbne where w data and the nel reportare to be drived. Additions or eearadfane to (he find (apart fall be in toe tona o f an ' w eidm ent aigeod by toe Stody Director. th e amandnient ahafi eleeriy identify tort port o ftoe report that ia befog abend and toe reeeona tor toe alteration. The ttneodment will be afgaed end dated by toe Study Directorand toe SpenaorRapreaetilative. All qjplicabto raqnimmenli far reporting o f tady remit aep er 0 CTR 792.185. SA FETY A N X 5H IA LTH V' . ' 9 ~ Tihoiiirtijf p f i w i i l wKt p u n irti y j**n s i M i o i Bvwy meotuM e p ts c ttric o iiu U b * talus to p rm e t butovorunt . t ootpoiMWj o f psraoaoil. apd Ib i to v a o p n i the test cop nfintoca 1ntoatttto6(a).': ' 1 ' Pt*l79f6S Interim Report #23 - Analysis o f Sediment Samples . , Exygen Study No.: P0001131 ExnpnhMMtlNMter. 7000113) AMUNDMENIS TO PROTOCOL AU significant change* to the analytical protocol outlined hens will be tpreaaed in writing, ugnai and dated by die Study Director and Sponsor Representative. Amendments otnally will be inwad prior to UUtalK of study plan change. However, when * change ii required withoutauffirient time for the ieeoe of a written amendment, that change may be effected verbally with supporting documentation rijned. M)d dated by die Study Director u d followed wUh t written m m /ham t a t aoon a* ppeaible. in due cu e, the effective date o f the wriBeo MneodBifinl wifi be the dpte of rbe documented ' ' dmnge. Co|dm o f the ripeed am endinariiw illbe eppended ro alt diembuied etudy plan eopiee, The originai amendment will be maintained with the original cttdy pine Any deviations fioro.# study pian a t b o ta the analytical method aa provided wil] be documented and reported promptly to tbc Sponsor Representative. DATA RECORD KEEPING .. Reeotda to be mttnfiincd include the following (aa appropriate): * SaropletracloBg alm t(i) . * Sample receipt record* atomge history, and chain o f curtody History and preparation o f etaodarda (atodt, fortification, calibration) * Descripixmtrfany modifleatiom to the method ` * IrutnnpcMnm sheets, beccfc-aheets or log* < Aaalytical data table* * AHchromatographic and inrinunental condition* * Sample odnenoo and analyrii date* * A complete Hating ofetndy poananel, ugruming and initials * Chronologicalpresectation ofafl study correapoodenco Any other documentation noceaaery for the reconstruction of the study C hrom atogram *- All chromatograms will contain the foUowring; Sample identification, infection date, aero* or other iodicatkut o f the area ef internal, and injection number corresponding to the ran. * Arirtitlonrily. fcttiSctdoca will iaduda the roouirt o f analyte added and the ample numbero fthe sample that was fortified. * Analytical ataadard chromatogiama will addjrionaHy include the eoneeeitmlion<e.g. pgfatL). P o fH e fS S Exygen Research Page 54 of 110 p. 55 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.; P0001131 Exygea Prancol Nuotar POOOU31 Aspart ofttredocwnenutita ita folloaringsheett will beinehtded in each analytical act: a ro n itad t taring 8 m a fia to be run in the set, and iaabaoKnt corditiena taeat describing the imtrunwot type and optaatinj COOditipna.. ' QUALITY ASSURANCE The QA Unit o f Exygw Research wilikispect the tidy at intervia adequate to aaattrccnpU**wilGIi,,a .a j^ wmrBpo^.the finding of audit* io the Study Director, Bxygen Management, tad the Sponsor Reproatatiatve. RETENTION OF BATA ANB ARCHIVING All b ad copy tear dab, inctading. b it not Hmited lo, the original ehnHnatogmm, worksheet*, correapoadence, and resulti shall be included with the data package auhmitted to the Study Director. Theta will be archived with the originai tody p ta , atnandmatna, final report, and afi pertinent infcrmstioa boat die Spooaor. The toting facility shall keep all electronic raw data and any inatrameni, p ip ne, and storage log fin (he period of tune specified in 40 CFR W2.M5. An eaact copy o f die vm aabt msaiti to the taidy director will also be kept at Bxygen Research. ' Bxygen will obtain penmaaian fined th e study director belbre discarding or returning amptea. Exygen Research P a gr H o f 61 Page 55 o f 110 Interim Report #23 --Analysis of Sediment Samples Exygen Study N-: P0001131 SxnaahfMMolNM*-. POOOIU) APPENDIX I ANALYTICAL METHODS V0001780: -Mrt&Qd of An*iy*il for th Determinotion o f Prrfluoroocunoic Acati (PFOA)u>W *w by LC/MS/MS" V0001781: "Metiod of A m lvm iar tbe DdermlnMioa o f Pcrfluoroocunoic Add (pfo a ) in sonby lc /m s/m s** V0001782: "Mcud a l A m tyt fi ftw DMcmMlfon of PerfluorooeUnoic Ad (PFOA) in Sodboett by LC/MS/MS" VOGO1783: "Mcthod of A n d y for th Dwenrnnirion ot Perfluorooctinoic A dd (PFOA) m Fidi nd C hn by LC/MS/MS" V0001784; "Metbod of Antlyd* for Ibe D etenrioiiko of Perfluarooctanok Add (PFOA) in Vegetttioo by LC/MS/MS** V000178J: "Melhod o f Analynt for th Detenran*tioa o f Pertfooroocanoic Add (PFOA) in S o d i M utanti LiTcrby LC/MS/MS" V0001786: "Mclbod of Anolyd* fot tbe Detemnctk o f PerfluooocU*o)c Acid (PFOA) in Smtll Mimmi] Sara Iry LC/MS/MS" Exygen Research f m t**f& Page 56 o f 110 Interim Report # 2 1 - Analysis of Sediment Samples Exygen Study Mo.:P0001131 E xytta Pnm cai Nwnber W00I131 ANALYTICAL METHOD Mi M M k VOMITM - . h rLC M M W WUmir t fti Aw m y . 1* -- G j--w ll- v . . * Ifliip v IO M 9 , f tijf a i iM a m V)MlnBdMlQp&*rtltiM^SltJt|al^MNNtt iStotl jvhdi- Exygen Research rmn^m tofittfis Page 57 of 110 Interim Report #23 - Analysis of Sediment Samples Exygctt Study No.: P0001131 r n m Prfrnrrt Hmrrr P001131 y.........." 1 AWALmCALMITBOO LCM SM I N M trVQ M n ........... t^ S S S S l& S i mW I an** Mio MT 22S2 CAaat*w*m<4mBt 0w*iaMuWnmO**pw*alf m tw kiltr tram ai i MaplilU Mlatf4a l KW aa*l *** tp n W a a a M a a -MHO t|M t>r >5 aw dB e< w *A w - *w a n hmiwii a a **r" a i t a 4J 4.a1 4.1 4. MI w a v 'B K r tn u IM a a t- H U C ia * AwwlaiAaua - A ti. iw eai Oa* e e w a w W ie Aa< - AW A , M k I rru r f ^ t < t# 1 anSi 'm m * * ra** ***ttfa u *** rlata* w Mi l ,1M > a * -a a aiftryak U h> i *--" AariytelMaMMtaMMranflafaWOOM * S aH ^ 1 il si . 2r aaL- aiauaaimt tacuaak ka .anMwn* u t Sm ypApIzIrMa -I^II .. .a * *..*.* . US w n la M tV a ta O e iC U m a n M ia . P * # it f*S Exygen Research Page 58 of 110 Interini Report #23 - Analysis o f Sediment Samples Kxygen Study No.: P0001131 E xyjm fra n c a i N im bo; POOOllJl - -*? . - " l - - ' ' ............. ' ...... .............. . ' `."'I- .^ y T iC M . a fT H o o vaiata S.U i n n M l * l l iruninon vwom > t i r i l i MpwMi m I mMnoMSoat - 12 YlMBMfeMI WG U m M b lN W ! mwiTinOB; marniu m I -- ir t i iM tm h W * 4 $ O m m h g mr , OJ 14 II M* 23J %A a 3 33 34 *1 fa ld M l 35 03 33 03 73 03 03 M 03 M kMaVMai >}^f<MtoiiM<laaaaMkiaStM-l 4 ! QmmImImb tniliAm -mcmmI ilMlMlnnSbMtiMi cima u . a n n * -U m k A** ' TXMWMim|niiMaainMun<lM|ftl>lnlliawlnp ' l|W I H M l| m ta ta tfO m . 7.1 t inti- Ite-- pnyWip H ni mXwit, mnmrirtu-3<rt- U HI IftlX * i Exygen Research P a flto jU Page 59 of 110 Interim Report #23 - Analysis of Sediment Samples. . s Exygen Study No.: P0001131 xygM PtoocoJ Number WOO! 131 V............. . ' ....... jk'itJLi.irtflP AlTl lt t C T fltt icnttim .... ~ .. i t i inni>iriiiiiniwiWM ~ _ ....... i i . i . i ^ *** (< - iw m - * r r c * r 10" - iiruimir'- *-- "- * -- - * *~ i--`~* " * "* . w ta a lh l]M U )n tM lft ...... f.J 2 I) lO in iw Hu l l iillw i ilniT Ml ifT ~ ~ ` *-| I .... ......... m L a rta M m W . n M b K * * '* * f IW * * illia U IM M It . . .u A1 0 ,1 * luiHitM r t l u f W C * i iy r * l l-< tl i V) , ]2j mlu sn b aft. .1.4 A ftJ * H I .* . H ffO A 'a 3is t U N K M A *. f.tU A10f*t.<****1. (*.I*M **rt-Mh M M * rf 100h .........1-- h 'V C * M A H d m * * -- * r fta a n to ft* --iriC iH u rtu ll)* '-- *3.1 _________ < H HTIC mm. Tin JJl HWhrtiihW*t i m*> b t _______ aONrthm-- JSSL tot Vimm* V-ia--- M*UC*M> **+<** 100 XycmCMmiTfc'H3 ..j*______ MirOrr xcmmUn 1 "XiDwmmimMrhi* Exygen Research P o fW e fM Page 60 o f 110 Interim Report #23 - Analysis of SedimentSamples Exygen Study No.: P0001131 8 * y |n J w tm l >taBbr. WOO1131 Ui M M m VM IHO iu tiv n ru u im o i | i m | BW|J <wr m a t .o fM a * a * } W M M 1 1 t<W M M M l Wrt MWiilMto0>uMMb mm m m m mM fraM M M M t M a t W CC (O r) M l t~o * * hmM M M a M m iummrtii IM cwK MM u w * ' fc M a M b ir....... ' J IJ m H M n i M M f M < m m o * m m w m o M iM O -IIJ iCMm WlmiM* iCan--C.MiMU mM( lMi. <M- U iOOjaiwm k nMM> iM*! 1imIJ SMiwSM.P<li.Mft,--moMiMMna.i.c..i.i..MM.....p..M....*... ' ' U M -M m M jI-- m- Wm m j* M M 5 1 4 - 11 111 h jM lB M IC M M M A m ill lnilIIII M M M M * M M M 1U HiilMiMHOAiinm>mMpMMMXM OMMnianImk H ia lM M ta M |M < I2 J A* to to .to W w toitof t o jM ^ . * * lto to o f to Mwtol (to to m*y*i**i * *>botMtm4 f itiM MiMi towy J-tO -- ' ' e m m m m mmimh**) ttoe mtotmormn h+ ,munto* dM iK ftM toM % 1 to ........... " " ""*`ImMT MtoMl *** * * if t w toJtoH ffta k mm Jof* fim g*M o/6S Exygen Research Page 61 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: PQ0O1131 Exyfn PiotwdKonter: nOOl 131 w m tak te a 9 o j^ w l> -- ite k a ir t e t e aafTaA --aw iaa ilU -- ii^ A Iia W --rk y ,, --aaa-- t e --a--te d --w--an------kma.)-- lJ<oroai*k--> HL ' i-- a Ute-- tern MI mxmt atedu o w n Aar--Kaunas Hte Xitel fum ili teaMtalaatariWai--t e i --aaftaail *30 A----a--*C t*-- 0.1 Cli-- it e -- ten a--a*r*atH tei--ai--t a t * -- - -- aTAMaaaa. h m M i M K i t e t e o t i m M i t e t e i H : -- a)ta(M te - a ta a - teteaafiate--te i Ha. IM -- --ite -- te tatet WO* Inte patte te te LOS tkteateateHOAait--taja--nteaJAaiiliii-- aa-- M te--apfe lO te te a te te ia a n U n -- 1 IM lat--a--ta f atta a-- --n a tt e -- --kt-- a TO-Uteaf t e tta m i t e -- > am te --t e t e --i*ta t e can a te -- atte tat o< i--ate t e t e k i anrnte . Aa* i----i --ita --t e r KL 19m -- M W wate t e kr t e --al-- a> te--tea it -- ate -- u U4 IAM--V'eaT--SVaaaBl--BpafaepttMaMfefeMfeWarfieMwiafea MMmIMalMMI9trlllVtrMaMtdebtCitedeNWt--IMar n ar. te m l --tear aftteM aft e t t e -- aia-- tei --te kt i%$ Ikt w h i W0MM CK) fe* eMfcmta* w w ywasad mm b* StfUD Jfe* Jf irifeaff tw le fed M b few tinrifc. fee ppnp*fefe* Mp mW b hin b Mfeefe Immhmm epeneiee Md etc IM tea-- teaa Mm----aatei --t tat--te w--aei teil a n aus t a -- - attu ati--. tfm -- telateSaacateMtlteivMa -- attuate ti -- te a te tta tt--t t it i mUaitl Mt M ate* tatet -- t e a >ateteSkrteXtaam ia atte --an y --' JKMfc--KarU t il--OUkte --tiaa^L. ' il W te--tytete t e * te alt--wtt teaa. Itra u m ;. >--11 fltflH *(6S Exygen Research Page 62 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P00Q1131 BtyiwhotocetNunber 1*0001HI r ...... ............................................. ........ ........... ~i IO M IM tU 4m44WMM^*flM4*Mi44Mit*mhmaMwbIbii4m--fmmatfsWnoOwAvyp.mx oyiaia. uu lliwij (W>- Exygen Research HfUafti Page 63 o f 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Bxy(i ProtocolNuraberWOQlUt ANALYTICAL METHOD IfiaiflTfcmhir YWMJM AuUyUwJTmlNjFx) . LOM M M Iqpilmm b MM tMCMMMhfmAkMM 1mM0 I A tm M tfS in " R j ; C - lL _____ PTairgliwOMi*M1o,i^dr w,lC4 f t fcq*jo Hui--h OW M 4 L -. JthkkM. a Exygen Research Pfl3a/U Page 64 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen StodyNo.VPOOOl 131 ExTtnhMocaiNntwr POOOUJI .. m i l l K l I W 1 l i lt) 'Wi^a^Aiiiipi4pAtt--ilp<fartwi--anj--AAdOgK)*>S^llp !- % . i mm n* Oemer<LOIH>tiiiea 2,0 II 24 Ca-- **qmrt*OlTTW>ferahnd** wyrh--<wl fcrprapimfay -Z 2l Z ? 7Z i r i*'~si otwrh (w w v m -V- v* aw.. ..f .-.-* hpm b Un a ..p.twuKLm- V.. RJUHl M AllMiiyll w tlw fc --T|llV 34 S*aft niHriM j m * r a util to a p ttttf 1fl* MR9nf pm ftr m t 4* 4i wttm-mtcm* 4t 444 "iM` nlMi li H*ill -"AX"U,Ibn.p.a..i.(3n4a li l i A K|k pr lm MM -- -- a-- * n e w t t f p m *** m 2 in -- aptpi i w-- >-ariatti -- fcj--at -- h af aparti n o 5J Ajit------nToi--m --i----toiktrr--iiii----p----iafufrnUdWoaAaIaIuP--. -- JJ ia ^ W M -- -- M afaii<>tlM I o 1* ad.-- -- patppnppaaa n --tiif i --a ) j Jla iiii> p il1pnii|lau iifli|i ml n ja n i^ n n ii tn n iiia o t-w o ^ , ioo4ooat> J.7 nO aaLUM a-- MO-- . 1-0 l a L --arHKCaMMt, 5J Sap-- pi----. 1-1 AaMpp--a <100-1000(. aailO-100L). **<i-- li Up. VII M tV (n )ia O P i--ri-- StJ U *w aM b Atft14efti Exygen Research Page 65 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 E xygn Protocol in k e r. PQOOIDI 1 ...... aiulyticai, r o g n a 'i ~ kita*fte<)thlfc8rofriteteLirCoMfTMrtIlCTroiroMliitaMffPOAt)t<ll>y 5-14 IWiirtwiWwi M l C-- l i n i t * tk b qfipatag 99m l m m * m 0 gam. U> thmMMiyiyfcli Vfm m , fJ . *u4 * eT--mpei--iw*r.mM3*C6| M iH b M M W i ? flCijra-- W H U q t i mm jwMAmIHIHIBH^HMSaIarotifaIte 30 w a . f r l i l l T tw ( l) : ** O tatatefragn--c SMMwlAURI * * V 3z0u at&5 <225555 ?)& u 25 <u <U35 04 n 25n 04 04 ,. uJ I(fMMtMViteMijMNMiltijyhJiH,(i--*<lN*VF*|li<ttileldwhp*?6**iIeBeWaeIwI8mglWei, U ta a llM t-B a ta tt . - - Tfc* * * * t a s ta i tp iiiM tM jr to iiM iffttin ite r natala A sH T lC ja m -.o UMOevM ? .l iia te H m m f N| ta --M* M -- 4, --ta rmi 4 m .- - ' llwriwtfajHnitafanatalaaMlittaytaclliaHt"** tip P j wlmit fiatai--i M tWiftiii M .J I M -- fa-- a-- te ta le H pm i-- l by --M-- O lM > * f M M M -- I iO K L f M t* . ' Ali--ntapmwtftotata>*t n a )*' J> *t*2 3 o {6 S Exygen Research Page 66 o f 110 interim Report #23 - Analysis of Sediment Samples Exygeri Study No.: P6001131 S x y je n P rotocol N w n b e r P000113I M <toOM vraint ---- ---- *"A1r'Vri6j. mBbo UM eWn A iwW i t r AtU(PPOAt m r t ~ ,1,1 Pn-- <11111 mtiHi t-WOHfM- IWTOA*, iototl 1 m, S m moM (MMlal * r m i 4 M I it ** ' MtMlh>ISLUVebgK. ' * i a : ' a m h a n i m n i m u Mo *f w o a w O t >* *'" . 4.of M100.I K > W-- H> IWn> W W * " O.U< !tAotKlMrtolotUUMtilMwlk.*'< tm>AhtMttntii}*impnf,u, b in * LDP*Peek. . 0,o i0 o M i*W .* B l t * * * i t * ** "** *< a * | 4 A W M M L a u ! H l n i o f ITO A a i( w it x * m * t - 10 b L W * 0.1 h ML k W 10 < Em I x t a m of IW ib .u T it m il lio n ln m tm iim -------- --------- *-------" r * * * ^pnodOEHfr j*C wml-- fh li fcr BMfcwwi yri0 ofAawO* -- wOnotiiinmlo l i t Tim m. Wh* n a l K W w l u w-- In" --y -fSS~ YUtat mVriaMlMCKatirtol WkMrii CMOntwi nrintiri_^a.-- iiwMrf> twifc^wr .jjpiffjy- If HI HI * mnm*o XxCr,mmmitttrryv>2 xXCoWm*MTt>hs im XFmmni m * to P * * * tn * < * rt* m & * * * * * * * Exygen Research Page 67 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygcn Study No.: P0001131 E x y fc a P rotocolNyrabwn M 0 0 1 13 i VW8I71I I- " " ""'""" ' .......... "" '' Til^afAa#4fcMbaiMda#rtai4iwiaiiniiiiAM(rfaA)isi*7 . 9 X i a m b n M n itfta k ta a ) L fe u a e ia i w h 9X4 StaynCdiauftMffiiNylNiMt&nw6awmtoMtartfil&}5'tLpo4jfrp>4c0*tb* m *m k$ #V r - 1ILI SiA h ^ ^ C M *tean a4 (tjfkaly 9rlW)iBaK fextekat kkM 3 4pl4*4m|frlNirnritMMmi*ftcalpttiomfttiit4m^4Mfiapa&arrft*lJ+rrtiNM* *N*f*rct*M* *7%J^iii*ajMlaispo{tpbaNi mtlii.tWw *ipne*p*m* . ie iM fia iilj M inirii|fci II, m Wd||i11a^nsfiiImpJ9mL|M^)pM^iM4wj|^pt*towtbrtfir aaatM>ate4<Maa*4fr !U M H n tlt l* lll a l Mi atariaaaaataM ahc-U iniM ai SIA TwaaHflalaHtaMlaQa*l>M H i'ia a - mmmm. Ifc * M ag M a M a * a a ta ri. * t t a M * is * a aaL irty a a r^ a * a i> n > . Uf~J* ^rmM*w0 >cawwupi(i tom. k id M a rtI* J l fra n c C m M ta n n *) !L7 L a f (4m 4 * t w all m Dm loaliliwui Cx SW catridp Otoont n j * s* -4 * to rn aaM a i. o r t a a t j a i a f < * * < < * * m t>iyiwf|lwi Min ^ n aibatHailwIaM-Smt-) U S . Aa fr i f f hi m ot ilirw ifu r tXVMV. m M M | M naaa r a a* < 111111 n,I, -- I* w t fe rtfc d W fiftf a a tC M C M i i)M<a A a M * M M a awaafr a* M ow * 1U MaMabafMttA-- MS***M HwiaiBiiiiaMiiwIfflfiM M k ta U if e n M M t U Am m tm M a f W * M a H a d a M a A a a * a --t iit u a m* M U w a rf * 4 a t a f tM M * m . U M M M M A fc a a f^ M M aa h / 1*-13-- y W A a a a la a a fe a t a a if*a > a f K a lS ? n tg r!7 o ft i Exygen Research Page 68 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygeh Study NS.: P0001131 fixygMnoMMl tM w . rooomi .. I- . . . A K u.m cu.> qinoo 1*1l 1 . l W te H I - . ____________ _____ UVMSM " ; `m m mmmrn m m m * te i m * * t iM- m < * tm ' tl'.' (MnMVRMflMtfftetffftiINlNkNfMtNlMMClfitffttMt*AllfMtaItMt6M)mMmM3IftffaWitfNtftBC^MIfSt.MfWl,atMft * " U.< M I h mmM r m ft* fMailalto Ubo t a d a n a r IrfMMMiftrfcft-- jjftHyfcMrwip--if t f tiif ^mmm^Kkmm M Nawanttaa ai* i U f y i i 31 far % - 113 AaaM Ml hm Um M MpftiM. Aay HHylM t* - ., om--ImmMMmp-- * --MIwtkifti ftlhmd--dno^ilyxad. IXOs'AateteMQSMh 1/. H I VO M M p M IM I l* W > M t M M aD a) M I t e -- ftHlfbMIiift TMM<Ba^--MfMi tmMlmddMMIMMIftMfiftfMIMIMdblftKiftUii IMO, tll I . 1X2 WAMtieuiiMImMMi,WmOAmalpnMli|Mi VMISr2MAal20lmak^vp*umteMMwWt ewLltOMQ.nifl** f t e t e i te M l w H t e t e t e t e -- l t e ri M IMI . >}J l l l l i M i C M M i < l M f M M t M i I W I t ( . v . te mM --) t e * te iniii tny -- n M M i TttlWH M M p M ii< y Mi t e M M in n lm if o m o , a I l a M < M l a M M M W l u l M M t i r l r H i <l>Ual ` ' M T te wm te -- 1 I o t e M M * f te u te te i o r * . B-- ! t e IMI flteter f MMMt attm te JM tete te i coad kc u iiM t e M M O t M M a t e i f i n M n i M 111 " I te M a t e a 9 ) t e MteMka m tm m m nm -- w - a m (X1 to.mst. r a M n M U > t e M U i , i H H te M ite UM te Wh M M te -- t u m l n . od t e a te te te aiiiMMt^RRMMlteMUkTMl]tea 1M b t e t e t e * team t e t e i ani m i t e a t e ** w * w> xdKteM tedM Utelnai S a t e l t e W M M M > t e teiin P a frlS a ftS Exygcn Research Page 69 o f 110 InterimReport#23 - Analysis of Sediment Samples Exygen Study No.: P0001131 S x n m m aocol Nwrber: POOOi 131 M a iw > w n i! t - -........Ajtu.mcAi.MKnK... ~~ ...... .....I icna*aUUitA4|nii4mbDM^p|iit<if^ r l MneiBl8 A o Jo te A iin fa Jt, ______________________ _______________ 4 * CdWMtfMM -- M.I >kM MMtUUMWBaOMrffQAIMtanirt. Mw4w * aw) w ru (Smm m^m ini [u n a m n) - - .rm _____ B w w b O S _ " ' ' 'l*----MW 143 Uat ri ncuM w t ofIW34 Bw4 4f4. 144 On f c Mw>ln HMrtw 1ulu lwi w -- 1 <4ffOA 'M a M a fty M ftL i. ^4 *m*OM)*y-*m-f*04M Or)>JlMInnlfcM*)) Exygen Research P a & M a ftl Page 70 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.. P0001131 GtjinfiMHalliMkir 1*0001131 A>X<AnLynn>CAnLr MvtEoTtHmOaD 1MhmdMk HM(MH*I* m m h ic h m M * * * M a t 710* ill r.fc p i FAIMOt C Jl M C m n I^ Ti > i< r tl r ,lC 4 4 t n p f a iw l /v,_vqi_w/FimWiiiwiiViri i,nU>i*./n.. no m*-- .iiW aL Dm jb kk- Exygen Research W ho 1 Pag* 30 of61 Page 71 of 110 Interim Report #23 - Analysis o f Sediment Samples ,,Exygen Study No.: P0001131 Exytm Protocol Number. P0001 13t Esr LGM*M>o t MotlM M M th blOb'lllllOt / Ib fh b lMt1hll.il.Amt # 0 A ) in i I. hm ' IN-- Olot>ooilorithrMlinM rotodvpophotlin f)rf> . arwnit mul bf MjbJN I .... mil Clwuni Hotr oooiood t noth kam 10 Mt . . 11 iltim ih m m>k m m hMih imitnhoil i Coenibhooti-oibeilOOtluftitbitWmtoy*i"lpltbc|KMbiy 1* t'boioil 11 Al holt JO| pitto hwyli im f illio. 11 Wwmli|oonMhhoMNhrii4bonilniiNM. XI tehtjMol ubili ion Ohott Io m um m t wm m XX4I A10lt0o0oNtMtltalotlaMtoIbOOOCBOOOO|UIyiHne>u0OOlothinBhlOoao|iObDOOW>IQMIMhrnpttMKMtoo.M X1 Vtar-mCm* M b o M 'K b tC p N o 41 A o O hA O d-M oM p oO t Aenm-ACl 45 iHMtHMK w t I qh^ hmhK XI A pttm m m fd t b i n b m l r* f c rf poopiof * 2 ' w>ob nobi li um t m u Mhoo Woon mibh of POMO*H W oLtboooMto oboioat Mohl|MbomOB(M9WMA|. U A*obomobMliooMi>o|iMkbOi p OlioooOoo<oiihim *1, AiofeMMImeooiiMoflMNfaaomMf. 11 nU^mw.0otW0MtMioMoMp^af^lhioitaMtfo,bloHt-0m|tt>c0oauo. x lohthoim ctioiW L x i nooN iiboM XI .*tn Hhi (IW-IOM t tob 10-100HU wMfooooMo dp. XII o o o l M V b l * | l s e i l R i o i b p > XU VI wette atotMd MW ! /><*S to ff* Exygen Research Page 72 of 110 Interim Report #23 - Analysis of SedimentSampkS ; : , Exygei Study No : POOOU31 ExyjcB PrMDcat N u n *r ?0001131 . . . awalyuco. m r r u p SSmwwn iiim i 1 IMCOivm. 4.0 C fe u n rtB p ^ ife ty M i r.flmSMHntn(.1 AMl i t i Culai H nOiiKK>in w W --HrX tH -- 1 0 -- . li . T i n ...H r XPC U m m m -- CAj: M IM w l U w ft 1 i IT 1 - Ml 4 2M %A l$ , 43 13 U M PlowIt 311 IH ygH 04 33 03 03 75 03 03 '(1.1r QIjmr mltdt m.iH:tUk| Jm. ( faHtllrMni tHoi4n41nr>i.ii rl rot 4 fcl Mull TkikMlaMtaHwMbMm< adlayktgkMli>(Mtar p M v ife SMC D *ta. 1.0 MHHIW 7.1 ' . HO*. _ H>p*l HTH 1,I1MInnil}- >44/.fee ' T te 4 U ^ tt4 M tt M M M i lfa *tlM B H *b 4 ta 4 C > d i r< fc 'lo 1.1.1 tliwrlp>-- H >y0ltnM 44| it W G O a l-rfM iB . hmw Exygen Research Page 73 of 110 Interim Report #23 - Analysis of Sediment Samples . Exygen Study No.: PQ001131 E*y$a Protocol Nuwixr POOCI131 I ___ LOHMa * Adi 1 inU tm m b> 'tJ-1 It<m--**.**. tn * t a M. 9.1>a 9hR td(S liM i4N nM E iilM ftilM faB i ' .i.I vfMpm*Mtt mM h t l ~ m m fr t t t t r CMAjr*HDnt li) mt ' ` ' - .fOHirmiWifc>uno>.muiwHumrtmlb.pmltr) m i O a t H B a H i* t l J I A K mtmi. tiMiiUnn nWIm afTfOA It pnym nil>? 19 a t f< lt HWt w>iwi lt a a l>wr f>W*ittii* n i htiH M iunvxu^ 1.1...' >.t1fJfwcWM .i*|U*aW*tMalMi>aaMcfPfOhAMitirfnW<n<*rM*>MiiWi >1/ Aa.lMfcU >wHn*w n rr>OAir'M 'd > y > T 'i^ iu tL! A *UMI^wUMK.bImiMlwa AtuKm<HWUt>n)MH>ilnii| S m I tn ta m o riM *> rcaatffca m a t . U>ntank. 3 <*>UN M W M m JM MU 7 b M m I | > 4 ( p N i M flyw ------K 3 ----* *- Ofctti* mm MB 1 J 2 -- wmm -- 1*9 19 29 t* S 1 19 109 19 li 1 __ a ___ __ -IB________ a ____ P tq p S io ft} Exygen Research Page 74 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exyten Protocol Number P0001131 fc - - __________________________ H iO nlH tictirV W .. ..... IC M M I m hnntiiimii" - -- -**- ^ ijim lll Oil 14.1 Iiil iiim H iluP y or la) to lu rid t o i - -a.m.--M* toW-.t..o-a..K.aM.)--a--a-a--t-o---m--M-i--M----M----*---H- *n- UJ IU H3 ** m *ji3Ii*M$rrmkft--tMM*flMil*Hfaati*.ii*Q">*M>| ibWMBWMMf iP--lwifcM >M*dObariifyta*f tu IU iij CfimMWa aMMCMiMiSW-HaaUMiaOto-JO M M . 10mLtotooi )toto>yMnLCMaMtotort D alm aa*j Umt ( M t o a # a t o m JMn. a C ,, HI o a t o * . D ia to H J to J Iia L tr fa M to a to a to a a M b to la M a tr to X la L . a to p to . C p , a a a t o to la a t o * to o to fe t to - 11,1 IU 1U .V to to * k a * to M *L (a . C M * t o ha * a rt t o i a * 51Jo D M C M W atM M M C .in alto a(l|i aL |b r ato t< )al. to to ' WtoanerWaliOBnCwtort-Itoptoy. towWietowairtiy tUT t o t o a ia a o l a - 0 ai. ofoar t o I to a to w oto MotoonoJ H M W t o - > a t. WO H ill* C b la l J a t o f t o * la o a to a u d i m l a i) | l i la a rit o i a la (to i l 1to w t * L ) U.I) rtto y a -- f t a * rta M a a r i r a t o i t a la '1 PWHpfW Exygen Research Page 75 o f 110 Interim Report #23 - Analysis of Sediment Sammies Exygen Study No.: P0001131 E ty f a Protocol Nuoaben P0001I31 111 UtAfam Ml itm k -- M , -- to m i M U M m a rk km to . uamam < . A m UbaHkm tm im m m pmoacl* m M am *il 111 M*3*lMlNltlltaiMlytoiM 1 1 1 * > a-- m a f -- m l n i lm ta * * m m to 'n rtu lu l m IK >M -- W wyM OM BU A a a i t MIHM . -- a a a f a l t o i M . M ) >-1 MBplM < I-- lM MB Ml *t Dj***)*. 0 C a t tt i liM 0 4 UW l M M t o <\wdMtoa- U-- Wt frr b i w - la *U>BigliaBipiana tor ktoaLpt 13 (or-- ) 111 tto m-- to w >p to li ta s ta r l a 14-- to ft n i K l a p M a a f K * i t r Q * . warn u 111 M i l i t a t o m m m m a tm n o i taw mb to * t i w q . ( f t M ak a a -- K * ai to * -- to M a W . -- a mm I ta a m a l i ibiil1niVrhTf nf*~--^ ......... . to a n to t f a a a l to* a t -- *toa -- a ton-- 7WH af tosatati vtoa. I i ia mi la Mi a r t* to -- 11limito to ta fia to M a * * Il -- I ****<**-- INK toa m -- p to a to n ia t m m im a t u n * * ' IU t o t o D t o a M tato stotaalalMl auto pr M* ita Ha toM ta. torto Miltot *ato itaia e l to atoalwn ww Ba n, to UBI atot I nini ultoil tiatoto tot * to il i ttamaaMa in a PO to untotli m a t a ri -- t aami*?aMU). I tto to M to U i................ MMUtla -- -- I M a # * l -- a * to * m m a M ato t o t * a maliria. P atti! eftS Exygen Research Page 76 of 110 Interim Repent #23 - Analysis o f Sediirient Samples Exygen Study No.: P0001131 Sxyfta *hxooo1Norntwr: POOOi 131 ' I 1:1.'............. . _ _ ... 4 ju j,y n c x i.u n B 0 0 >n muniinvmtm "1 LCM VM I 13* ,. .tIMMMii f*a.*Waafci lil* ***** aaMia*lMaw--* .aM*aftfl*m1--kKaKa. 14* ij kHM'drfifWNH*kfi*uWm"liiw^IwM1i`**--n**M~~JI* hm m w i i if i m i pam t t n t 1 ft^a** U M w M itaa^ > rflTOApri a Wei. i H m -irT W - . 14J iWfcfcflmmputoio--aw* a an ro* Ina* IMLa ' **<** "' RM ta*W --na 0g) 144 U*><Mlwl*notaiQtmmmfi wmialm0I-- f>f04 . *aa|ki*kt>M *M *rl*l W *4 #*< M| *y **! - 1W4 * a ^ * * ) i [106* / wal wW HfJ npiai Part H a fts Exygen Research Page 77 of 110 InterimReport,#23-.Analysis of Sediment Samples . .. , Exygen Study No.: P0001131 Exy|M friXocol N w ter K001I3) ANALYTICAL SKTHOD I(On lu ll it VW017IJ Aariynnl'MNirMiMr krb C M M U A < M 9 K M )ia lM i Kx jim iRim m A 3 M M M W k P rtw jMHCtMfkfA IUOI ****** _ V ^-k C-JtL1------- i W tltM K !C W ,> N > lM A >*h*M----- Dm Exygen Research YataUftpc; I 7 ef6S Page 78 of 110 Interim Report #23 - Analysis of Sedin^fSamples Exygen StiSdy No.: P0001131 Sxyfeo Protocol Nnabcr POtO) U t I ............... *-* j ~AtoLYIlCAL IHUD a * m * r u a m iM M rtw O w rttl vm iT O ..... t**m4 14 sv m .* , 2MtSllHMllstS4S4Mpi9ysdtoiHsiMSll4iMI M4|pMNSltMMNI9fpSfflWQSBMMBMC W k r M * M i-- U qtM n f n l ) ' m p M > m tm Mu> Itin n iioit i p .m>. ftOMMWi. t M W ` 22 VO At4pK36iaf|MMKfi*fel ^ b44V^dpasesaadk a lM iO M k t f l w i l l i M i 9itifti tMatUWhHBal l i ladatya||Ma nOal niini^tftt &toMNtUMnMrGtMor0SsW*tndtif4eWntWof }J I^MiSvdhi4*SNGpiiBgplMifertktt 44.41 AWM*M-HiPrtsL-CH#KsjiCs prt 44 C iiN e (l M 0 0 e w fc -l |* l|w l 44 M M o H -m C in d * 49 -- P* 44 4 f*M W M *> )ttc M ft> -fts M ip s d s 4I4 I .............Ul " "4 J * W n d M irW n 444132 MAaBMMriRMMiA0i^rtAap~i-AaiC|>a.*AaIi4|NdtdabNd* 14 JJ A MJi pafcmbm ip H d m a s* * * * pM* s i * * * * * * *p \ ................................................................. s f i ir iii *>ifc> . 12 A M n a s a in t mmdtfs t 3-3 <lyinllilw i afrm* + >OMPI | Exygen Research Page 79 of 110 Interim Report #23 -Analysis of Sediment Sample* . Exygen Study No.: P0001131 Exrpmtn*Dc6i nmbttt P0001131 P a i itu n n d I ' ....... . AtM.vnc*Lwnuoo M * m i9 N u ^ L fc r* P .r f \wKtm mm Cm rtyfcCW M S Ik M M M v tlllW Auu5 IIl11*fIU 5*1uli11.03t*r n19ipPmi piitinipp nm m ia>w(oM.buM. m H U M M M M W ilM . O*nhpw|MXbflffcttpHpfac>.d.*10-1 tip* tn a k M < M L ) ( v * a t m WJ7177V W H U M aM **. OXHfti MWII 30ml oftpwpr<". m m X30M ipn 6i> ->C&nm ifffNQliPSlHttM l . 1 A(H4K>*tUcXat.UCiS^lxim:n pt x y flti3il-- Hr). 3. 46JJ lkia*wManinttwnc(A30):C tuMMaMMnkMM nirtill IfcP I Q ): M W taPl rh w ip ifp g n M r 1! %A 5 L u 10 M 3*4 V n* a SkM u 75 75 35 01 03 03 03 03 M IS |d .(B a l> >< * M k a > l.> tlx:47 QxwjMtx -- 1-- i4 i< ritiWxim MX I J Has - D a tiM * JltMAdMkjftH t tMti HB)TI#dpBpMlAOdktM 3 hJ*l Hgw)9e/to Exygcn Research Page 80 o f 110 Interim Report #23'- Analysis of Sediment Samples Exygen Study No.: P0001131 hoMcol M a h r . P000! U l r .. . C taM kyLC M S A ja i&mamm *J M tim !>-- prty> * M IM m A , uwwiiM <13+ H *wt * * < w*OA. . U . llih t t i W nn K tl >1 9^ l fc mtv jn p v * by Mb fcl$4f *T fctM O & ? **!*. ' l l ) *> M ih ; o U C T d y rtM oM M iM f lK r t k M il liO*I.afiMat , M 4' 39* w -- y f t f c n -- I W * p n fm l 9 f tn y m f 3 wt 9* 1 fM lytK i-- lK<(WKm t r >))--<4gnM<p la r n t nt -- M taM tha U h IJ>Mt IUMmI m M m P>OA i i hy kinM i ; > K t e ia t iu M , K m m ip t iT o > -- o fm o w a tM > io i . . ittajaL U M C M k. M J ~ A * I .............................. .. LTMIa 3990.B t t a OK Mkau of 110<*MKMin M U alU M W ki *M XW MM*nUtoulKKKaaiarmUKaHK><lkyMKH( ad. 9 41 U h l M m < M tcIk m MM -ii m im u ii i n r I rrrn > . i M 3 TI * Mi iMMllMwIlilMi ! -- iiaiM nn> M lwlihr W Mi m u Mfcr k 4 mm p i f6 Exygen Research f*V 4 0 c f6 i Page 81 of 110 Iritcriir*Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Exyyni Protocol Numb: nOOl 131 'I `m vfM jiM iiB ar >toto*ftoi?ktotopiatoii<totoi C toltyL C 'U M a j f j. n il v&mMiJMMwmmtm*mpmpmim HQm i4 n M t m tm m . I l l TM tMMMMMMM >HM>iMrtwi --qr be m it m o.ow to8-- 1.atotffu <urt lii^ uS$L ` <2*rk4*C.vplo<ats<M k*. A4 -- mtmmto Knicwnlm i o fw to rt h >jhhi>i ;M toaktat* 1W t o t it o l c f a ^ t o t o to ( to to y 3 1 t o ) ra w to lto to t ou t M M M l iw M M l t&$ V M M M M tM l I m M M m M m m m m M v 0M m m m I MMM M im w M prI jw w iiy M M i M M . t&l tout-- Itfar to! 1 ikumorj Niimi to ip ltm wtH>>iin iv Mb tpMhy MMMMiMM tar M i im Im 114 9MIffctafeMfcM li.1 W iM > * f t o * " I1* t o 3 a ir f olifw p f to I t o lt o to lU M JtaLrfm W tibtotototntw toaitoitotote-IJauM IU I h ip t lt o k iiM t h - lt o .114, to k t o M ttt o tokk lntoi tok k t o i to r a it o iiJtoto 114 M h . a t l i n t o t -- n v k l( B to a ,tf rito |ii2 . to , t o 1 jU M O * C totoa to t o to It t*L f a to to . t o M i ^ a t a t o t o k . mrnrntitlwmtm. t e n t o * t o t o n to . . - < M M to to t o 139 1 j -- t o n lto > ky to r a f to k t o X M ta M JvM H fca tfta ttta M lM M a a lta M i N m iA s fttak v MhqIm m m m M M M i i r M -- I Wm M >. Q fy tm Am M iw u rfin fr M fcv mm vMn p Mf H v M vahvM svfvtavML Mliu Pag* of IS Exygen Research Page 82 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: PC001131 EjcyjmPwmcol N am ier NOOI131 N il ----------- . . . . . miioimi i vamnt t - ............ -- *M .m c A L w n a o o ...." " ..................| Htao<o<Amtymitota tVtwInli.1,ifPirflw--u--akAM|WM|mfit w* .........................................Q w ty tx a a a a __________________ HT , a h Otww 1 n w i lln m mfU m ^tooa - . H J jO w i fg i m n i< S n < i W t f H X iM d im t M h iif ' - H a f in la M M L C o O M ta ta w n tk t IUml4lMz>pc<r<tn< . lIlt.#ltta'taMtattanaaMftitoKarttaaiMltalat'Mafala-BltaIaOUMitiaaaMMta*anl*aiikeM*ftaalpalnl{tn>MaaBntiotanfaMIttbtoaafec'W*5t.0initMatLatgoaMa.artiifMcpriaiMt i II1U.U1 tCaWwKlht apt aa*n n**i nS l--I<apf aii-yl tlma Ita--n.Iiniiiiiin i--lu-M0rya ta-ltatam . 11.0 Mdwtm* tan tkmiri &M dB ffcMMm i U i AM*4 4np af t-c itopa*#* 1 IU mMip>taliMmO<tnoatiodiim,^mimliflaaL**r>frKnmmwrn*r(tii*to4d0*Cto).--OMMW U.rt tro*amp aMnMtoM)*ta9muk*VtHf t o*hawMma+o+tv n .1 1 wMMMIX ! ifc ftft p * ndufeM tonl 4 * tooM M am ple fa GU d ta ta d u fffO A -- y d u n n l n i l *rm ....nim iim W . ` n m ta -S tliO id a n Mi i j d iil n t 1X3 t a n ta in t * n lta lm --ita * n f ta jnWd tta Inamii ad n ndOnwflttarfaMaamdHttm*m.irHm.imMmwmImh lNfwwiawttafwl M--taanmr1yMj-IOn I--MHmnannatirM340lMa Mnta(iMiBatiniktanmlonntawImnftnaMemnnn)Xn IM - t a 'l m t a t a l o n e > f t a t a n I t a n M a n i n )-- * t a t a D n t y ll i i ri|ii m lia l/ fndt tn t - wwn n O n ta a da t a ! n immlui |1 H M m L p a H {.qvkM) h a *a i P a tfO a fM Exygen Research Page 83 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 E iy f Protocol Nimber P000113I I5 ....jMrncja.mimSr bfuamna A i*P Q A)r*fca Mi feMetoMM--MfehMtot|MfmMi--. My N--jM--BM tSJ AMpMGAarii . . 1M P -- W |p M > 1X3 5H3M?tfMImatOoMmMmH*--MP--M--MiiliPPtVfesQIBAMtfbMnfktCpKa4-BKofKlM0^titoLQQ- If MMfe--MriMWO* Kla--Igp--Mr&MW Jpfc. --* MVbMt n--yte MMWMMM*--4fl-MdMMlMMtelMMBMMt 1X9 X----*->f--MMlffc-- ! W- HaM*WMMt MK--70-1*W IMvMi m vMmx Ifi tnyrtf if*1* t**"*^^ wtfyiiHf i&Hfn. ft irivillfM piNAHM W iHrtM i 1X4 My--MMtai --<! ft--t --Ma--MM--i --tfwrfrya--BfwNay tm r Ta-- M t a M M I -- ti--m M M m i M ito --M a tta i t w t Hm w , JmMl MritarWHflMn aMM ft* mmU ta utaM 1X9 Tta --mMm --Imi (H) tar ctaVtaoa mm tm m t --i ta J tM t 9? M M O . r I M M iMWfriaa aap M I* at * HmnMmmM ot*nwMcmU. mto* a th. IM I mmMmi dot katMM nmS S mimI MaptaMWMMM Mit nan Hum X * W * ttfc * M iiX iM ta a . Ifn w tfM O iM d n ftM K M b U i (b * Im M MyllcMMt M im tHau* buiMMtgwd 141 Um* IMairtu np l i m I ihImhI--1 *nii ffWPA faaa*;i tmiL. tMl M )Mk m ) lag 4a mmM un (loaar n^MMM) mmmdmih PPO A fctf*M Ll-l>MfcMa-i*Mail 142 !* * * * * * a *m* 4 inaM*crm}Atad * * . DP- M mtr-oM* O*M * a a n M . 4MtMHy. ft ta ft Ayr 43$ iS Exygen Research Page 84 of 110 Interim Report #23- Analysis of Sediment Samples ' Exygea Study No.: POO01131 BxygnProtocolNoaher P0001131 H 'M N m I v V M i W rT ~ " A K A ir ir ic .u . u r ta S .............................. 0W rto d * * * > * to toP rto o d M tto rO te d m a w ii A r id ( m W a r iir S r *t)>LOMSMt 143 fa t MPflMI IbM tfttf lOW S I --T Exygen Research I W 1 Pup 44 O f Page 85 o f 110 Interim Report #23 - Analysis of Sedimenl Samples. . , Exygen Study No.: POOOl 131 E xftea ftotoooi Number P0001 J3\ AMKiAMLYTMICAiiL; MVQE0T0H17O4D * YiHithatyLCPMf.il> M M P P O A }ii A m i^ TmmmPwaKr - ilW fl-- w hO W v M aCaD atFA IttDt AypmOy: C -IL T iX itU i U H r , W riB , to H p i Im w h .... i& lM a lH Out ^ ______ OfaMXW i Bayjaa lU cuK k sS ^- Exygen Research ToAdVapK 7 Pof4Se/*S Page 86 o f 110 Interini Report #23 - Analysis of Sedimene Samples Exygcij Study No.: PC001131 Jbcy&a Protocol N onben PO0O1131 fc iP *<iMin - ( ii-- m w ifw t ................ A8Mt.nQU.>acoo........... Xlpf*l>l>nliP-- hplnfhrmitni!Hl1AddCTTO)SI?! ttrLCMHMS .1 *di fcjr H d~twtmmm(LmOmKlWinOa i)!Ck ' '' ZO U *y Z I A fcn P ' to w 'V M fatriN alM yjnN iM A 22 C dM *tifpwpriilii fcOMtaftn b a t t e i nty cfc--ari! fcrprofwr wfcty U finalitipfcw - 1.1 A ilM B ltt < a iiis a n H *to M O n k . 12-. tapi M ImmmmitoteMate Ptawttw*mmmm*u f e d ^ M i t t i l i i i p ^ i d i i i * ) i k K n *tt H ip |n iji n M d te n a p t e r n u p m a id * in far n te n d a i* d M W d H * * m k ) h M a M |M a ilu H W M dpd. U 3W | 1 te te te l p o n te w in to gM t t U fa t e d far ito 4 41 T t a - m c p p 42 AoMdate-HKCMfe 4) Q *w (l*M eJ6-N 4 * M ite M i~ tf? L C |ra 4 4a1 nSwaWiaMp Uil-WioTfwlwfad)-jR-- 47 Ipiid--iIC4WI - tw p ii 9*Ai 444M1t *l`M H"i-V"L C" l* 4H 412 A M m lM A a d N C A R ** O o d 413 " ` .................... ........ pt ' " i i A p ta tt ddpdoitieodi-,d--<,--pw. ouifpimdfk$i%fi sI**m2 S2 A ofrteltote .......... d ia t e 400001 PvMtfiS Exygeu Research Page 87 of 110 ^iterili! Repcrt #23 - Analysis of Sediment Sampies Exygen Study No.: P0001131 Exy^aPlCtacolNuotar HX1 31 tata*-- * ! AfM .m cAi.Km io s i ^LOMSACS e fm i (3TOM' Vtputm i* . . l i )3fMl.|taMfe*lifcta. l11i5i? HHtia - lt.a ll|t a _f_l>_lf_11 ' _ Ouptian.iyliawii n'ii... >miIiIMPOri ltl> CcLtarMMCiWI*. U t ta ta tta H W -ta O > l.ta )0 -W |J .X tl> t a n ta *. 1113 noti tata tata.a Ita C itai ) (! it a ita .W B fflT B . U l C-- r ttp t a t a t r o l t a * t a . i t a yita il-- ta n HOOOf u C ta ta M ta tta ly M lutaiirl MiC. ............ 1f i li-- tat a -- I(M jta ta 3.1 50 it a . 3 (M 6 H 4 flim f T ttr.M ta M M M altalA I: |t a t a t a i t a b W t a M > & > !t o * MMmwI 4$ M i ) M l& 18 20 au *A <3 6 25 25 <5 F1*w0 3UI t t M 0,3 55 03 7* 03 03 3S 03 U lu ta ta V ita ta I I U t t a l ta ta n M ta M IM M I M )iU 4,? O M tatatac ta ta A ita - t a l M ultaita a n ta ita r x . 1 8 rn m im * T ta ta m c ta ta a m ta ta ta a n ta a tn q r 3 * * ) ta ti M >italta itari>piwiiwita i iiita<i)^iiitaibt - noi. ta llo * /a fU T tfS i Exygen Research Page 88 of 110 Interim Report #23 - Analysis of SedimentSamples Exygeto Study No.: P0001131 Exyam ProxxMl Namber W001131 .mHmXmmk,------ . - . '^1IfiUUtotifemitlHoJmoaiidmoi^t^MaM^ Amd(HFOA)a * .. . .... . ^ riO M /m 4 1 M M liV laa 4i.i MMHila UMaL otwwur. 43 IM M tfw i JfJ iio B i ai9ir 141 !<--. >y totfliriaxtitfagw afe . . M ttfc l< B M .tfa M M M i. t-1 3 ic * a m m m ik w o iix w a w . i . im u i w a m a m a m . 1 tfBaaBoMMmaaMaiftMlvMaMtflOaOLviiiiafc' M m tm m tm m m D W p m ^ M M X Tmlt*i>HinXn inhxin. *1.1 id tfm 0 }B ia l> k a *tf< M B W Itffe r|a riq ! a a l4 0 iii M lW is l. i* a W ll a i l& a L lB H M k . 4 1 4 a u tffA i iaO B axiw M W m t f w *o a a m x d feyfctapm f a d .tf* m m tal W m n < w li'p lm i 'll i i> iM a w i . - to .U 3 a i* u iv iftW B . 1 1 3 A 0 1 |ia ti M a M lM M w tfH ,0 A il|a |x a m b ? M a ffa f i t . L lld ilU N m - lM lH B lM 'n m iillM 'M ia tM . llllliU H M H m # wA .ma.t*iimrBi.a.aiHmhwm*.,naot imii. ^w *o m* i mmmammt >tfytieaM.uv.i 4<C a l a M lr > M (M aBO M nlia MWam 4.1. UM M lm BM tw IfaOtf tflaaaU a tB & n B *i haf Plfttieji} Exygen Research Page 89 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 S xytn Pmloeol Muaber PCIOOI IM N IM i t ' -......... ' ' *Na.rTtu*t.titwe MLh<Aml)^4r*abtimaiiaMbriataoaumsiwfCs M i 0TOA) in' AM Hm Uams rn M l -- It: tKIrtmtl rnmmit aUtmMy be . iif*e : . la . MMMB* i19t . *J*^LiBmltotfmmmm*" US^uj^L- . .. w2*Crc.iail>am aifc. S himi it mmm i . nri mit ili111 fattitamia mayta p-- I ICW*oO as m hm> n * a tu sa a k m * M l w--ah im ita m Ins ! . i(h*wHiil ^l>i)li l^ inii>--I ) n i muh t m lM M h r H M M im i miy f iat i m i! m t a h v ll h> m tn fim m m i<inaihrn r w ii tu _>tmami. M _ afina l n i ala **% l .2 ShhWthtafanawhrnaMihahtahamiialtn iw ia *a h l) n HJ CfriM aaM awrhha uhm m tihha * t -asso mm IU M m M m a < in a h i.< a M ih ) m M M a t u f a tti mi. M i*aa ia n -- w 1 a fttiiai. 1 aMm pi. 1 - - MihBlataealaaMhL D M t i h m OaaatrifcwSmaaltiatie t u M M * tas ml. imihiipiS amia * mm mm tht w*. MMWMmaaMalalaMHaahMm. huthmMh-Martaam aa. hOwwi ayitmm l (Damham Day m dmu iimaMit/ MWa m. . ,, altehralHlqha*rUiaammiarMaaa. , IW Omamfwm w t i t am<rtal W ajama DM a a ocua. w . . ha anhaS Hath. CMM M Mhi flmias mLiMMaam-hM Exygen Research Page 90 of 110 Interim Report #23 - Analysis of Sediriiint Samples1' -' ' ^xygenSttidy No.: P0OO1131 1 1B xytt* P m * * N a t o r POOOI 3 - A.A U T K A t. U C TtH " a_m_pa M. .p.i_r__fa_niii>i.iin..titirilOfMmManimmiiahijSKtk wpacSr JJ4 ii.m-e **p H 4 I B fto .1 * -3000 tpm N>toO OthoMrn* tot*o amMm. tmo Ull..Mtl tAtooMppeyteo*p**pMl*MMmPlelp-p<tnoMMMUMItapp|*htmm.mtmafmmom/oatmomp(pn*i*pC*pCt UM BMjBBMk *1JBl* Mi JUi MMBfltMSMQiM .. ,, BMIMPMIm m I JfcMfcm i MHMIpd^U faH lM L f t i* w fi0 m tw p t v c n tu fm . it _ . 1*1 Mm . A w ttnataR MaMari m m jm m lb m ti ftMWw 11 - - ` m iy m itm jk * . IU IP ^ P ilifT fO A llilipilWl h l P M l--pftMWfllOHUOlWBiaWlPMP - ' M to iM p M W P m to jiM M . . "(13 AaaabwMft at om m d o Um Im i aoaitata r a bo nefcaa at tht * t o P * m i it m m or t a a * m . i w M m m m u Pw iiiiiiiM i H h i I l p ) n a mpn At a t ilaoaoht, m main m at to p mat P p p m * a a lip r ip f I m M to O g r to i " " ` ` ` '......... a ta m j M l i a P a k p m p p m ik ia fa iM M P M M ta tM fk u . atamkamB A U w (P a r m m aattm P r p M M a . I P * am P M tanm m i m a pn irPpptpPpM PM raw M am*M m ppp* Bm P p I P lI lM I J (or a ** i* B uj, 11.0 1J.1 totoPto* PMPa*yakaft *ppto p*a ]* r * t > * f c n 4 l i a * i |a M m a i i U P H HO U a p M il jg # iiiP H P -- > a M P ta r a tn iP iP PottSOofis Exygen Research Page 91 o f 110 Interim Repent #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 ExyywPfotocol Number POOoi U1 ' OttM-XTUM.MlriiSo"................ I >4attMafail)attttttPittattMiMir* a t i iliiaiiilii AttffTOA)ia Var n a to L C M V M 113 iirntitMtom i iam m ieTfO iam bimmnMnmiXlQ. j ' W!pfc t t a OJ f f j , m tm m bua tm rft B 3 ta M M e a iii) y fe a riM fa A i> a M l(W ( y a iR tb lmetmmbm. V tm t n lmOmbm m tlib o m rnmUt Hadti. da ee 0 tt t etum petattnl& M rM Q M N t* 13 A toy aaftaatta awtttt ftaat kma attim i aia* kj>aaa* itt Kat fewt t a t ttw t vWtt h tt * ttttdtttt r tta ttUntta nm. HWttttMI tt ttfc e i*h a * * *1 ewWWMttttl aalaalaMidmtafttalaM MattarafaaattafclajaaaM. IM ttt at tilla Mid i W tta n itattn dama amala urne w a W (k* M W * ttudiii a t t a M atta. M a h a iban ttyaafdltt alatt * la atta la a#tt I m a m-rica, aad tm aaattatt> ahat t aBd'attuila MaMOaa n ly n l !U Battila ttt t ttttaaa ttattM aaal aaaaptta aatt aaa Ad* atta ttaa *4attamaaal*n>iaB. tfiaaaai. daii Miaaaattttadadiatti aa:aaalaittn4-amattbaiaanatyrad I4A OttaMatt' ' Md U=tta Stottn * > laailatti da aaaaal offro*, f a n Qom < - ttaa* t t f a * --a) atta tmtmmmt aarw (llaaar lataaaiaa pannai) aaattally ttattaa liaatta'*aart*lu : 142 UM ttenaafcin ttlttaain iaitttiaiittlMWOMiiattttaattLia **< *> HO* lattaifrtt) - t g g j t lt tl flu iti >Itti tttn t.fnjXtM] Dii lisi te) AatthrM * a Maia m a a n Matt ttawaqrW2 daraaaaatti Mattai 4tt kaava aaaatt oflfOA pr la anra>t>on. aa> attttlwlaga|aariMHiattalittaaaBaiaiaaaaanr. t aawaayftw |ttttlMltttt*W - !* fatti*aoaM(*,>l Mal) adaaaMD P u y e ii o ft i Exygcn Research Page 92 of 110 Interim Repart #21 - Analysis of Sediment Samples Exygen Study No.; P0001131 E*yeo ftm e o i Number POOOi HI A.N..A..L.Y..TICALMvoEoTeHimOO M M * to r toa M n s M to i # frn m m m ^ (^ ' n-- m u n ttfvo m m (M tC eiep,n uM *i .^ A ..C j L m irm n W f I Tiim1id l n i t , 1C4C1I r y f I i (Wq y X vVMj0m0* fFrMRmMWBMmylQpHR|toHfcfcjpXHA itllA fotf M hp T Exygen Research Page 93 o f 110 Interim Report #23 Analysis o f Sediment Samples Exygen Study No.: P0001131 Exygca Piwocol Nun*: P000113I wiiiini wim " *A A L T ic A t trre o o A W tW O A liu M . M m m tU m tH O m N * U t tapi - T n M H > l ip M rf * > * !* * i d h-- iIih im n iilw m a K u ' ** tt+ fm tm m m UpW ^ inmlni milu1m W n m tm Mw ! ? ><l l n H C H a W ) ! M l i w d l n u M ir il - . 0 > iw iiit^ t*p *p i*I T O ta ^ ta rfB p g ^ i B i5 ilfc rp w p riW ta y 3.9 t U 'i&MmM-Uprnimibmnwnmton. H--ftt6--n*i mm ***** ***- ftw ljp iin ii awlli-- p i^ ii l i t i Ayl. t t -- fe n -- p h n k nowUn in kr wfca*d t* "d*"jd"fc ttM* il*ifr**ifik*wt h* Mtods tketinl w1mtmwniraffnwap* hf8(-Hoimtfcr' X3 y w i ti MdB! y iM w w fl| i t q t j fltd k dw wwiydig p iifc rU M 4.9 m w m w tS m d e ii 4.1 W tr-U M L C p * ttt- m C p a * U filn td l -H H X p a * k A f f t A t t - 4 r f IflO n d U *m l i ww f Im,fc W- Hj w> Ak Wafc XI ***** iMpnMioT|Miptaj| npi 2 SM ui3jk SUsu.1J I m W i l l l l l u r I H U li r w n .O B I M miltpmMiM>ii|||i|iJii|. pip>ji\MmmiiiiiihUh.uilimni. lUaLMMoHuRCnMi mllik. ' - hr* P ^ S J o f } Exygen Research Page 94 o f 110 O il JO qa&ssdlg usSXvg ^V<"Cl>tnrwipw>ywnnHIP< 'm %awi ' *' W ^itai<Ai|>i|pliaM M |iM )i||ww*iu *wp- r* n*ttmiwiw>ninnnlT<ti iina'>'i<iii n r# n# re re <W !*) ayitau ft U 1L it St I* t* ft TTOO tz vn% < w n ! iOM. 3pEhnt . Vrnr*t rtf'* iTW iii w * a a n i^ taicwiriwrowiwtitM>wfv) "* 00K n o -- ) ti Bug!JOi | fr |--J 5U rt ___ .... _ j mtre xb ' " 'I'111BI >01*1) x m*oot-tx -- t <0001-wo * <(>.v irt re i____ - . w w i Mni-- i i ..................-7. . 8W W TOIHCTT ---- -- . ; | ICIIOOM J^fiaM lxcw uin^Cua ICl 1003d "ON jiptUS o^X xa S9|du*8s |U3UttpdSjo sisXpmv - 7M uocbtf uuiui Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 S*y*on rmtocol N unbor POM1131 V o tU io ro o * * f e a P n n iin m iiL i n i w n iii ii'tr i tU ) 'g S T * 1 H n l Uno? UCMM0 Sjfi ItOIOMIOOOfSilttlOM U MoMotHm HU 1 m m ION aLoTwoMr. <* H) .' tMMM.IMh^MoliOMMmMfcMODdMMItoHBMolfK-IOOtiyolofffOAkyMiiioolo., iraM M ttM |M iM k iM i)w *iaiiiiee iiiaw a M ta M th l -o * . U M In * H U * U ctM . * M m In Wim o f W O * l W i l ky m jm l L fal*)l|M . * * in ) sknoaftOO Mi ama * t USaL U>mU >.1J A Ol n --L u r l i nOWniitfFOA.il >npm Hin" 10 MtW oUllMm WM ** * qif w w of 1 et* * * ! i - iJA 1tm **tfM M o*M Sfcn k *on a>*M |on oo rii S*wSs * * l'fC*oiiOOM*r. oioii-- r portal a f t m orn 93 StoadM C a tta ti* M a ta M* 11ttMpjmLiirOtipMtaiiiwwmM^fmtddik^ *****>{,rar mi* iUO- -wu1t*t -- w- nSr M U * -U o m o o ik m la m o O a i^ IJ J -a L L D rf >-**' iMIriciiO#"Hei;nn--(DiOiaxoio*ion. lfiMfnirtMitinwrhifim.it V `-'1 /a * j j y s .5 Exygen Research Page 96 of 110 faterim Report #23 -Analysis of Sedimertt Samples ExygenStudy No,:P0001131 GxjnanFratoool Number P0001131 ___ ____ nuaiiMi U r tll W t VWOI7M ...... ^ ` ----tUmkfbCM..U..a--liMMiTfOA)mh5r fak'ftlUtr ' ' ' - I I I ' t i tkfcMtot oiMvtoi Pn>ia*7 >Im) m m iw M t Uni l i M M M a k ) MriQr)NMtoni m m t f tor to tto e l fcrid * lle lE y erf ^ e * 811. <ftotfto k r w m m m jlm torMUpnlw . *d# 1 Mt a JOa l p d Mn n mHiMl I Ii.ivM..h...wifrcmmajryb*c Jfj3 A#wv1BM9ftiftrtaMlwaMMPif]ML "1iiruU"j .'ApimlpMaUtaliatFkadlTaa.*imNia_aL_#blt_ittNH_mta^_.t_a_N_aa_adHvJto'-l-^i t n QMi<iaMBiNu-Maoi|Nb~tBiMn t i t D in i n i i i i m i - " t w n....j..&.....i nb>Cvi. nm- ii mn im nmfc. n mj ju>rir sm m t c l. m Oiiiih 'I11t.- Mtto*tMt atof -hifiLMTimi WaltmCLuMMMM3 i 1^ a..t.*..........i..n....t ptdUMff ` HM-HItMT*-- Iltlgi1 | (All ii> M i-tm U tt.ll M p a a f h iliiliila ia y t O I I M B . tu . ll*ftV0ANaNfwb(Oall*Nwa a;JMNMfcaMfr*Hlm i R af ftf(Ma mmiaHM uatmaliiNkrulMlMiiNiiiNu to IM UMttoptJotMoH. I MM to to t Sm m A tot iwiMto in _ ,,____ ___________ ---tobtoaM>1itoTito|i'ili nilI Ilk ft**' H&iitfts Exygra Research Page 97 of 110 Interim Report #23 - Analysis o f Sediment Samples . Exygen Study No.: P0001131 Protocol Numbor F000113! _____ MMaWUwtyLCMtMS ____ mi n M'iit | * ) J (m mi--i 11 MWMfWI B WM MMiM*aaiMM. iMA ui,ni O* ill . >X M Tl*I#M 'Im * MI MM h a * * * !> tX 41t*W X P X IMM* * MdA ITOAlMIO. HIM im fm (MOWMM*** M>lHtrMrtlMMl. M W IM )M in eaM m M b M iM M tM illaU IQ . If. MM MMht l*CA IM * MM Mm Ift A Mt *Mt MM iMUfM MM^m M M M M M mM m -- M m n l M t * " M M #Mm mb x M m TdlMK of IT1 M M mi. bmMA . MMIWIIi iMi. A. . .. ----------- X n ir t im l. Aw *M M X MM* Id IM I < M M i MlIlt by At M*iyM M liliniiini if r 114 AW M M M M M M X i M M m Um by a* At Hu* M l TAaw WAM bM At I M i if At nHiiii.. mm l Am im M X m iu M W ilTAlMMl af Mnnlnili I * ciiA IM IX < i IBi m i (H At *XM*M m i (MMMtf nuM X a * w (*? a eu tsi it X AO M X * Aim Imjk. am I m X iAii m w i <mm>Im iX riiX w iM ^iiT - *1 *x> X ti-- iii lu ll Md m m nm m i m M m h X 14wMfeMM M >M lim VaMMMI IMI AH m m M.AU bait wiihin m aMAMMm i Am Oa m am iX m m Dw A 1*1 ! H * M M i M a i < X a a n a i f IMOAkuM (ia I ( * u aM krIX IM M liaiM fcnnxofna: i*x*^eixq-aaa*xjmeeioriiNwAeir A0*b*uAtBMMmXM-]MMAi AM Mm. am MM. Hm cm trr. Exygen Research Pa&S7*f6S Page 98 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0001131 Exyam Protocol Nonbar. POOOI131 *4*- la taw m m m rflP ftft prtor aaoaaton. tat . . . . ... , **J " *I"IM.11*"***1-- h i -- m m *;. rnfmmr^Om ^ . to m ti !>! - 'N tfS p b ^ no*faoiaow-ima aoCPtOA.feunikm*M. -"--iim Exygen Research haa'W' Ptttsatfts P age99ofll0 p. 100 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Bxygsa PbbcacoI Number POOOH31 /lNUAMLYMTaKh^rM. VFOTMHOIIO mm*/**** i WHinMfocytfLriOnlnPaaO^ui.yiafo^h nm Ai^kittMiMIr m--lwwfc . . B W IU w A P 'T.irtfrvi--nt\i*t*AfLr*rt 1:.CM3>JBl|LpaIf.c.w..w.r* J W rn R ; S /h e P M l 0.-.ahafru Dm/t*Jr Exygen Research irnfm* * P *l*S 9 a f*i Page 100 of 110 p. 101 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P000113] BxrpmAnacolHaabtr.K0Q1U1 : J* Mm , , <Mm.yncM.)iiMC(t ............. **<* N a M J M ik r U M ia m M W K # rw h m rn m U p M C lw m p p > ) c a * M m m 4m > u a u h tm a M D m O M IM n iia ia lJa n a lm M MHr t*t AJVNQpisfeMFniPb MMfpMJFpMMMMk u c a * !** <*<* im p (iir 14) IJ M t-- t I -- pH ____ ___ 3*2 N tootp^tffMfMtifjiii MtOfO ifcf w n MHptak flOtwvn iM to NMK * IMPlHlMHlfMtMtlOtiBflSfNIBNMtitiHOHOMIiHOBplNtsfeflf^pMttHtfItMOVliOtOBttMMMHpHMtlMklPtl|OPkPRflWttBtMlUttt *j> ........ .1 vm-musfm'- ' - U4J NAmMm*M*-I-KinrCn|b* M M M in i* m in - i. C t c q n iii j/i iMirwMiatMriBtNPBMl 11 (AisiMIMOBM#lfBfMOp>Mip--pVMalmlvOM^iM%vMiflllOM^fMvtlMsHlOt V(lCOtfOplgIUffitpkbs(wmyksiefdMqrf3*2020 u 14 II11U3ff? 1I51.1l1f10 Mi: llWlMllKfIfilllJfrWOL. ICO-MMJ. filin'(kp-iob>l<io-ioomU W m HIN t v t . 8 ( l i a i nm n rKf . n*t*n Pi Exygen Research Page 101 o f 110 p. 102 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No,: P0001131 te y g a i PTMOCO) Number: f*000l 131 .... - .... ' ..i - M m ite ia itg rL O M M It J ltiM jtM fe a ie tta r. , i l l Cw#ei<<W*ef*iie*sl$d>lfF*ri*wii*wii)<Wipm. 4* ' i x ,U M )CM-- WI)>1I| QCvpmmmIrit U tXi.1 urn n . V (MMi<. (mrphtUmMMkSjtrlMc I 1 M W---W--l-lh*<Sl: ... * w J. . . a* ^ 2U X4 IS 41 25 25 IS flaw tea* IS 03 IS 03 n 03 n is 03 l* ktm m V ttm K H MM >DimThHnfb-faEm* ( I --c>t t >1 n*irinmnan. TIsaOpMiMAStottMBirtCMMftipUtmlAltyIwdffgMfMWteM 74 M lW Iy iw ' T.I K w te B w iw w n ;W ^ o ii M i w i *> i ri | 4 il- l6 * fc r /n afto** toumm m W M * aatf oaap to rt--p i fa onto M I toMfaPto . - 4 %u w fa m we pm m i y " ' - aaatoH*MM to*10tttoLfv**ar. m h # Exygen Research * *c 4 /o /4 J Page 102 of 110 p. 103 Interim Report #23 - Analysis o f Sedioit'Samples ' 1 ExygenStudyKo:: P0001131 Ebcyt Pm oeai Nunibar: P0001131 ' * ** * " ' ' 7'~r. . ttUfribi-wmiiB.. .... 1 .. M--illniiibyWMW *wl(ipjv>iWa M. aaahmtrmm* ' ' ,1 lw*i<ii1nNiilllrii(iiii^i>iir ,' M .l tPtwn*paMfy*m>*Oa*aKm$kaM*ml*Htt.aitMaemrere-alm<a01mMatw|Mm'trr)nmrO*Adttbuaycxibi(ItOiiOni( lIdii*( ' .1.3 'A t.9pfM. MUmHhi w,a iWOA Wftfm ti Vyimuin, . ' > -' - iiLUfJ*altU0 HinMM.wtl.^inia of too wMi mlwngi - ' *.U l.liIn<>.arW O *.u^ii.ilV ? >pmt i aLmcfldiUl.QHinMriL ni>Mim tM(lf 1001Mi m i ' "1-*' qTpkpMHH>nMkMi^*^f*bCMmMItM**MataiUM*teianoiMkd*nmMiMifwMMdt*ti**M|in**r*it p j ShnAMIGMAn^miSMmmh M il IC IM tH M n n -- w h > w p iM >1mOmml * * *BBH f W tfW L M > M ia a M o a . U U lb H w ijn a m l m m 0m t m tM l n w ru a r tim am) M iw> wamtmitr . , I V l p ln M f -- >l iiW m l f t --! 30 m I t ) m m m k + Iurn tmniwi--arMntam* tmbiantM* Wm*iaatamitnWwilOMmiMiKwMrtk!m>u]m'fcnaNtxamrn M3, laptpM>B{k>Mti*iM*aiy4i^MMMl>itewUllHrpKiM a * a tr* * fm m m m rm h r* ln a fr* . awl fatadafts Exygen Research Page 103 of 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 Bxyten Protocol Naraber P00GU31 I------ MatotWtttorYOtolTI ...^'JSSSBUtlXiMmBM.. .............. umili iMtotobylCfrOWg u.O U to li Im ir tto .. . t u . dII--totairttami, MfoaMa foutoi--stod0al.NlotHtofllu|i)1i--Mhmi miiint a)mi mMtwifmcnifitr 1U Aida-- **aaplftraaladM dfX *L 0tl|M y .. tVuU nVma--arfa-l *--rl a --*t ahi **--mi-- -- *u t . ILA. C-- (ifaMfaa*-MII>ifalB-4aiaiiM. IIJ6 O-- Ih-- tfam i g a C d i p -- l a i -- rillp ial -- -- M W lB 1M C-- d C n W w ald-- (1 1.1 mLt faf m > r i - MU-- it . -M *M lfairJaU rm M art>ldap*M fa 0 M M |-- Mi* il 1--lte a # l m -- IMaiiilC tilM ia iiHd n ia i *um . !U d -- Afe-4 a l . f a -- . n a ia 1. Ttu-- 1-- )n * nnn *---- 7H a ty j> w m ]lw i u-- llfap i a i t >d a i m .- l L > . . I ti ' A afca-- * la a k LOMMIA e . i> . ' i k i fadaiil-- MMMimafadiiMaiadaaajMdlMdddMmai-- -- IVM BW A-- a . a a ttu ila -- I m i p-- -- (fan-- a 1 S m S S -- |m * a M l n i i -- a n * > lm k . m rt W M mM li i Marmai aL I?-' ^ iiH w m iiri i a im -- m ii -- b iiir a -- m i m a -- I -- t a m i I i m r k m . la utiifa a -- fai Ina -- i l a m a m y n> a. A* M a -- a h * m ala a l f aafibmfm am a-- my 1 . , fa-- . -- a # -- t t m t i i w l fay a l l -- u -- mi famnam i m m > l) a In (a ni-- i m a i-- m f -- dai). li m am . a R m -- -- dadi m fa da &m a i -- ai---- . -- pfcm U.A Ih fama -- ria l ---- far ia-- l u U rna -- I u n a m --aad a-- -- faa fa-- i iiy a iin.....n u -- a a P i p a i a a -- a -- a -- I rnua -- ti n fan l-- l .jm D t r a a n tm a d'.'i'j i-- -- .. . .1 U *a li iv-- -- a a a d a -- am-- --r -- Ma -- a l -- dad ma lia Mu li a l -- llfania ita a d ili. hpiin fogrt! ajts Exygen Research Page 104 o f 110 p. 105 Interim Report #23 - Analysis of Sedimcnt Sampled 'Exygen StudyNo.:P0001131 P w m l Numben y W l 131 S3ESm S m w 'I-- . A N 4 ^ y n c A L M x fa o 9 Ar(Mwmwia#Virnai--UM A h f t m S T 13.Q tu - I ' ' kpafcvf m j m *m a m lk ) a i) M D l M p r ill ir r a A l m . JH- iV. -ffM-BM f-lMt IBM- i*tj4PHNV W---J 4w ^ O T p W .V- W--V M *V* WvM W- ? _- ,--. *^ Hotttt%fMWRHpfchtItflsmMlfH1minii^mAMveMmMh m MAM&pf<wM>^dwMIfatsiihd^f4^h4v . IJ M k W ( r M k M t f In w W n M a n i ( f i w Tw m n h ' lOllH--fcnl14KlWwlOif>]rHai Ha w m Twt --r n i m a m -- a m u ih u m nin t u . H n f ndWimi a i 1 m m u M N iW U J T b M W n M a P ) H Hi p m rm p n m n l m m <*t . a m a & a u a n . lf a t t o r i a* M m * mm a i *m mMfMtW M|N HMtf IMtlfcflft A lllMMMk Md ihc 1)4 UmaMi Umb^IwimiNttitfldi todvMRdct mmmrdriftm*ctwu -141 bl*mmftmMipMivfca$RnfiaA*<dMoBilMhtnofM*(KiOiwVriQvp4fttPitMM4pftinaMiiM*MtwL) p M W Q y iiM w ty w w N i jw p -- i -0 4 +m Of i d q n (k ar P F * M W fcy W * ^ n il ' ni -- MImmI. tfiun-- ny. 14.} NA*riMM^I*|MIMMAMM*MitafucMl*MAIMtoJHMMNMiMrrfMOlAjr|.narheDona. ,,^m-i.i--Iw--Ilap ^-P...a|P|LPabWttM-alMaMiMit^eLf)c ^ ...... - - ^ ,,,w --- Exygen Research Page 105 of 110 p. 106 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P000U31 B xyft*ftotoc^N iunbtr P00113J ;. - VO .; - `-- UaonriWmiylCMSMf A n P F O l A |M 4 ttfl(/W.W . . - . ^rr-T-rrmnlKflwWitimiinf mit Exygen Research rmr> /'a i a ia Page IQ ofllQ p. 107 Interim Report #23 - Analysts of Sediment Samples Exygen Study No,: P0001131 S30ta5teRCeoseiea*rech,PDAriv1e01 PhFontae:: 1144--227321-1-10519 w t k c t iih fw anctr t 'm iiim fim ,. .w a rn & m * n * / H * * * L m m O bet Study Humber None ., - - Po1 oft 1)MagicalProcedureS>Tu=m>->m;aruyVlXOO*fO:I3T7M?A~s5c7B'oan>f1tl =Yk*!i 2)VerffcadonofAnafyicalPraoncitn ...... ..rnll.M..jTri~l-l--..I..... "Ti "" ' " ......... ... tpfo)ntraApcadardtettoaonlSeeemcodaMoletnoon9o.n;m:cSaaenydtraotBonoe9o6.1ea.op,fArHepoacrrkTerdMo.MmtwonaeigatatenoerctteaanadaBryr.dAaXrnaemyabtaelueaved*loor 2oimn)hLeaoemwapmalnepdalafheaat.tiaavpaMianbfgalefavraeiaKboafctdieonaannatdyfteeretfoocroevaecrhamnaaltyrtixacmoanyobaentaaMtfoarnaededxeppeecntdedno 'J.' 1 ) Hl^oo^lradon6rfstandBrdsnaadlobep<aoamdlnadartopike8*aampie bottna at Mphar towti. 2)ThaampleahaamiableforanmammalMrandaerunwaacmdterthan tpactad. Spitingalthepi^daleirahedlevelIntheprotocolputaOwepked canaMtaionlowertanttedatectonMl Atao,theenatylelevataInthegroundwalar aamplaeanexpectedtogreat*exceedtieprwdatemtinedapklnotern*WedIntar ProtocoLWhenthetevetehtteMrryMgreatyexceedtieapSdnglavale,anaccurate breoctotleverwyvecotovecratnhneoatnbae^ctceeloonucteetMordafHcrotntwaQexCpieacratepdteIn.tHhetawhaatrearpaMamnpglieeev.etebitte _c01n-a.i0Qn1hb~aImOerlQnieeev~elaeedml1.0pa~0tteMncrdraTntmgaatrloemrtaim.e1m0waalaItMtemarPrpetAaleeCnron.TpfOMtaeNiia*gmTaUawmlafumiraaltOrevtemraonrteilQaC1CtCac0orwtfmayLdtaetara ExypenC*U Review L f l l l f t J l l i r , uaruKvKKwtooiSBMi .... v': " ' ' ' MMaeamunyEranM E. Exygen Research Page 107 of 110 p. 108 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0001131 3098 Reward Drtw Phonr H4-Z7M039 Stew College, FA 1M01 Fc I14-2J1-1580 RESEARCH Amendment Number Elfedh*# Deter Exygen Study Number PROTOCOL AMENDMENT 2 P0001I 31 C fc W S to N um ber p *e *i of i Nona f^ gp g fttp iQ io f85 ......... - 2} T w tMatoneH .p a y flo f 86: PfOStnwtXon mon>or8d488-> aft 1 ) Irato ed to n e fin alrpporl, W atm report e ttb a fa a u a d .' 2> PTOS tranatton monfcxvd may too b * 400 SO. . Ratio nale ' 1) CXm to tweaoeeataitian of tw dale wfe, interim report be laaued to alow the ciam to receivedata inefirneiter *'*< < '' n M r 'W 3$ Trie API 4000 LCMSiMSiyatoma dated t*4 S 6 *> 80 PFOBtnaneilonMrNh greater eenrtMtyMnto496->eoiraMNon. __ ^A gr,aiatvoY : : t) Ttwdtontw*tabtetoicaNe andnMaw dateman 2) The 480 - 00 te neMan can be detactod wh greater m o M to i wretaa, giving bettorrtewnatograptiy. ' o wamutrnevoaBUtod- ExvnonQAURavtow T J u Itih AOMMaTRATIVE FORM Exygen Research Page 108 of 110 Exygen Research Kagc UWol 1iU InterimReport #23 - Analysis of SedimenfSamples ExygeaStudyNo.:P0001131 (o0 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0Q01131 CHH EHSit 236 IB 651 733 1956 W f W : * JrWtfWTW MUffi 05/01 '06 13:46 NO.106 03/03 + t-m r.m uva m h . . *" V * * . / . **V *iv s s s i " % '^ s SlA lC K . -, \ < V w * ' ^ ' 'n , , * * flftflwTtflWPOWM;. . * * i s S l . , '^,7 -t .. ,v: SgjW -.,, >' J o h b L J " CWlP^V|Nt* mam*. ` ' V. ' . 'a ' , > 1*, , ' ;' * * . >. v* * * & & hd*F UWMRTJftVtBMW '& * '* . I , m i" f* '. v ,_ . i nn V ' ' . * * t \ 1'.'* V };, , '. . \ ' .y < 4 * > . * .',V '. * , * * ';\ v' . : ; ' : . . >'?.' vi*'7V.i i'XV V . ` i* j * .` ' . /* JJ* ?,, * * ' * . ; 3a *' ' -T ' v V : . . *,V * * . *' 4 r.*.t . .*14i*,'A*'*',,><**;***r** '. `- ;; *. * * -**'* " * Exygen Research Page U O o f 110