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P-1 A -fL A . $ 6 2 7 INTERIM REPORT #23 Aaaivsis of Sediment Samples STUDY TITLE Analysis o f Perfluorooctanoic Acid (PFOA) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program DATA REQUIREMENTS EPA TSCA Good Laboratory Practice Standards 40 CFR 792 STUDY DIRECTOR Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 Phone: 610-701-3761 INTERIM REPORT COMPLETION DATE 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. Paul, MN 55144 Phone:651-733-6374 PROJECT Protocol Number: P0000760 Exygen Study Number: P0000760 Total Pages: 110 P-2 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0OOO76O GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT Exygen Study Number P0000760, entitled "Analysis o f Perfluorooctanoic Acid (PFOA) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program," conducted for 3M Company, is being performed in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by Exygen Research, with one exception. The laboratory control and control spikes for the direct injection and alternate SPE methods and the spiking procedures for the surrogate were not recorded promptly at the time o f extraction. ohn Flaherty Principal Investigator Exygen Research Study Director Weston Solutions, Inc. Michael A.. Santoro Sponson Representative 3M Company Exygen Research Date 6 Date Page 2 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 QUALITY ASSURANCE STATEMENT Exygen Research's Quality Assurance Unit reviewed Exygen Study Number P0000760, entitled, "Analysis o f Perfluorooctanoic Arid (PFOA) 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 phases* were inspected for conduct according to Exygen Research's Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratory Practice Standards. All findings were reported to the Exygen Principal Investigator and Management and to the Study Director. Phase 31. Final Raw Data Review and Interim Analytical Report Review Date Inspected 5/2/06 Date Reported to Date Reported to Principal Exygen Date Reported to Investigator Management Study Director 5/2/06 5/2/06 5/2/06 affer y / j Lead, Quality Assurance Unit j/fc / C Date 'Note: All in-lab inspections will be documented in the QA statement for the final analytical report at the conclusion of the study. This QA statement involves only the review o f the interim report and associated raw data. Exygen Research Page 3 of 110 P- Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0OOO76O CERTIFICATION OF AUTHENTICITY This interim report, for Exygen Study Number P0000760, is a true and complete representation of the raw data. Submitted by: Exygen Research 3058 Research Drive State College, PA 16801 (814) 272*1039 Principa] Investigator, Exygen: Exygen Research Exygen Research Facility Management: 7 /7 7 Richard j<yi izzdni President Exygen Ri - ra*n.-ij Study Director, Weston Solutions, Inc. Date Date JaisimhaTiesari P.E., DEE Weston Solutions, Inc. Sponsor Representative, 3M Company: Michael M. Santoro Director offRegulatory Affairs Date Exygen Research Page 4 of 110 P-5 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 STUDY IDENTIFICATION Analysis o f Perfluorooctanoic Acid (PFOA) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program PROTOCOL NUMBER: P0000760 EXYGEN STUDY NUMBER: P0000760 TYPE OF STUDY: Residue SAMPLE MATRIX: Sediment TEST SUBSTANCE: Perfluorooctanoic add (PFOA) SPONSOR: 3M Company 3M Building 0236-01-B-10 S t Paul, MN 55144 STUDY DIRECTOR: Jaisimha Kesari P.E., DEE Weston Solutions, Lie. 1400 Weston Way West Chester, PA 19380 STUDY MONITOR: Michael A. Santoro 3M Company 3M Building 0236-01-B-10 St. Paul, MN 55144 PERFORMING LABORATORY: Exygen Research 3058 Research Drive State College, PA 16801 ANALYTICAL PHASE TIMETABLE: Study Initiation Date: 11/05/04 Interim Analytical Start Date: 04/27/06 Interim Analytical Termination Date: 04/30/06 Interim Report Completion Date: 05/02/06 Exygen Research Page 5 of 110 P-6 interim Report #23 - Analysts of Sediment Samples Exygen Study No.: P0000760 PROJECT PERSONNEL The Study Director for this project is Jaisimha Kesari at Weston Solutions, Inc. The following personnel from Exygen Research were associated with various phases o f this interim portion o f the study: Name John Flaherty Karen Risha Paul Connolly Christine Edwards Mark Ammerman Amy Sheehan Brittany Kravets Scott Crain Frances Crespi Devon Ingram Christa Gallant Title Vice President Scientist Technical Lead-LC/MS Technician Sample Custodian Associate Scientist Technician Technician Technician Technician Technician Exygen Research Page 6 of 110 P-7 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 TABLE OF CONTENTS Page TITLE PAG 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.................................................................................................................... 11 2.0 OBJECTIVE................................................................................................................... 11 3.0 INTRODUCTION......................................... 12 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 Additional SPE Extraction Procedure For Sediment..................................................14 6.4 Percent Solids Procedure For Sediment..................................................................... 14 6.5 Preparation of Standards and Fortification Solutions.................................................14 6.6 Chromatography.............................................................................. 16 6.7 Instrument Sensitivity............................................................. 16 6.8 Description of LC/MS/MS Instrument and Operating Conditions............................16 6.9 Quantitation and Example Calculation........................................................................17 7.0 EXPERIMENTAL DESIGN......................................................................................... 19 8.0 RESULTS....................................................................................................................... 19 9.0 CONCLUSIONS.........................................................................................................20 10.0 RETENTION OF DATA AND SAMPLES...............................................................20 Exygen Research Page 7 o f 110 p.8 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Table I. LIST OF TABLES Page Summary o f PFOA in Sediment Samples......................................................... 22 Table H. Summary of PFOA in Direct Injection Sediment Samples............................. 23 Table HI. Summary o f PFOA in SPE Extracted Sediment Samples............................... 24 Table IV. Matrix Spike Recovery of PFOA in Sediment Samples.................................. 25 Table V. Matrix Spike Recovery of PFOA in Direct Injection Sediment Samples....... 26 Table VI, Matrix Spike Recovery of PFOA in SPE Extracted Sediment Samples......... 27 Table VH. Surrogate Spike Recovery of UC PFOA in Sediment Samples..................... 28 Table VIEL Surrogate Spike Recovery of ,3C PFOA in Direct Injection Sediment Samples.......................................... ................................................................. .29 Table IX. Surrogate Spike Recovery of ,3C PFOA in SPE Extracted Sediment Samples..............................................................................................................30 Table X. Total Percent Solids in Sediment Samples................................ ..................... 31 Exygen Research Page 8 o f 110 P-9 In te rim Report #23-Analysis of Sediment Samples Exygen Study No.: P0000760 Figure 1. LIST OF FIGURES Page Typical Calibration Curve for PFOA in Methanol.......................................... 33 Figure 2. Extracted Standards o f PFOA in Methanol, 25 ng/L and 50 ng/L, Respectively.... .................................... 34 Figure 3. PFOA in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively....................................35 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFOA (Exygen ID: CO172892, DataSet: 042806D).................................................. 36 Figure 5. Typical Calibration Curve for 13C PFOA in Methanol....................................37 Figure 6. Extracted Standards o f 13C PFOA in Methanol, 25 ng/L and 50 ng/L, Respectively....................................................................................................... 38 Figure 7. ,3C PFOA in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively....................................39 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for l3C PFOA (Exygen ID: C0172892, Data Set: 042806D)............................... 40 Exygen Research Page 9 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 LIST OF APPENDICES Appendix A Study Protocol P0000760 (Exygen Study No. P0000760) with Analytical Method V0001782: "Method o f Analysis for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS", and Protocol Amendments............................. gg .41 Exygen Research Page 10 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 1-0 SUMMARY Exygen Research extracted and analyzed sediment samples for the determination of pcrfluorooctanoic acid (PFOA) according to Exygen Method V0001782 (Appendix A). The limit o f quantitation for PFOA in sediment was 2.0 ng/g. The standard sediment method (V0001782) was originally used to extract all of the samples. Use o f this method yielded poor spiking recoveries for PFO A Because o f this, a direct injection method (Section 6.2) was used, which also yielded poor recoveries. Finally, an alternative SPE column extraction (Section 6J ) was used to analyze for PFOA and UC PFOA. Analytical results for the analysis o f PFOA in sediment samples extracted according to the method based on dry weight are summarized in Table I. Analytical results for the analysis o f PFOA in sediment samples by direct injection, based on dry weight, are summarized in Table II. Analytical results for the analysis o f PFOA in sediment samples by alternative SPE extraction, based on dry weight, are summarized in Table III. The overall average percent recovery standard deviation for PFOA in sediment samples based on wet weight was 73 16%. Fortification recoveries for the analysis o f PFOA in sediment samples are summarized in Table IV. Fortification recoveries for the analysis o f PFOA in direct injection sediment samples are summarized in Table V. Fortification recoveries for the analysis o f PFOA in SPE extracted sediment samples are summarized in Table VI. The average percent recovery standard deviation for n C PFOA in sediment samples based on wet weight was 97 27%. Fortification recoveries for ,3C PFOA in sediment samples based on wet weight are summarized in Table VII. Fortification recoveries for ,3C PFOA in direct injection sediment samples based on wet weight are summarized in Table VIH. Fortification recoveries for 13C PFOA in SPE extracted sediment samples based on wet weight are summarized in Table IX. The total percent solids for sediment samples are detailed in Table X. 2.0 OBJECTIVE The objective o f the analytical part o f this study was to determine levels of perfluorooctanoic acid (PFOA) in sediment according to Protocol P0000760 (Appendix A). Exygen Research Page 11 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 3.0 INTRODUCTION This report details the results of the analysis for the determination o f PFOA in sediment using the analytical methods entitled, "V0001782: Method o f Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS." The study was initiated on November 05, 2004, when the study director signed protocol number P000076Q. 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. 4.0 ANALYTICAL TEST SAMPLES Three sediment samples (Exygen ID: CO172892-0)172894) were received on wet ice on April 22, 2006 from Tim Frinak at Weston Solutions, Inc. The samples were logged in by Exygen personnel and placed in refrigerated storage. Sample login and chain of custody information is located in the raw data package associated with this interim report. Storage records will be kept at Exygen Research. 5.0 REFERENCE MATERIAL The analytical standard, PFOA, was purchased from Oakwood Products, Inc. and was received at Exygen on March 17, 2005. The surrogate spiking standard, I3C labeled perfluorooctanoic acid (I3C PFOA SP0004184), was received at Exygen on April 15, 2004 from the 3M Company. The available information for the reference materials is listed below. PFOA was stored ambient and ,3C PFOA was stored frozen. Compound PFOA ,3CPFOA Exveen Inventory No. Lot# SP0005444 203 SP0004184 3507-195 Purity (%) Expiration Date 99 03/31/07 97 C3/29/09 The molecular structure o f PFOA is given below PFOA Chemical Name: Perfluorooctanoic acid Molecular Weight: 414 Transitions Monitored: 413 369 (for quantification) and 413 -> 219 (for confirmation) Structure: Exygen Research Page 12 of 110 Interini Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 ,3C PFOA Chemical Name: 1,2-!3C perfluoiooctanoic acid Molecular Weight: 416 Transition Monitored: 415 --370 Structure: 6 0 DESCRIPTION OF ANALYTICAL METHOD The analytical method "V0001782: Method of Analysis for the Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" was used for the sediment samples in this study. 6.1 Extraction Procedure Far Sediment Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A 5 gram portion o f sediment was weighed into a fifty milliliter centrifuge tube for the extraction. After fortification o f appropriate samples, 35 mL of 1% acetic acid in water was added to the samples. The samples were vortexed and allowed to shake on a wrist action shaker for -6 0 minutes. The samples were centrifuged for ~20 minutes at -3000 rpm. The supernatant was then loaded onto a Cu SPE cartridge conditioned with 10 mL o f methanol and 20 mL of water. The eluate was discarded. Twenty milliliters of methanol was added to the sediment samples left in the centrifuge tube. The samples were vortexed and allowed to shake on a wrist action shaker for another 30 minutes. The samples were centrifuged again for -2 0 minutes at -3000 rpm. The supernatant was then loaded onto the same Qg SPE cartridge. The eluate was collected into a 500 mL Nalgene Bottle. The column was washed with 4 mL of methanol. The wash was collected in the same bottle as the eluate. Approximately two Exygen Research Page 13 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 hundred milliliters of water was added to the bottles. The samples were mixed by shaking and loaded onto another C u SPE cartridge conditioned with 10 mL of methanol and 20 mL of water. The eluate was discarded. Approximately five milliliters of methanol was added to the cartridge. Five milliliters o f eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.2 Direct Inject Extraction Procedure For Sediment Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A one-gram portion of sediment was weighed into a 15-milliliter centrifuge tube for the extraction. Ten milliliters o f 1% acetic acid in methanol was added to each sample. The samples were then shaken by hand, vortexed, and sonicated for thirty minutes. The samples were then centrifuged for ~10 minutes at -3000 rpm. Each sample was analyzed by LC/MS/MS electrospray. 6.3 Additional SPE Extraction Procedure For Sediment The samples that were prepared in 1% acetic acid for the direct injection method were used for this extraction. Five milliliters o f each sample was aliquoted into a 50-mL polypropylene centrifuge tube and the volume was taken to 40 mL with water. The samples were then centrifuged for -1 0 minutes at -3000 rpm. The supernatant was then loaded onto a Ct SPE cartridge conditioned with 10 mL o f methanol and 5 mL of water. The eluate was discarded. Approximately five milliliters o f methanol was added to the cartridge. Five milliliters of eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.4 Percent Solids Procedure For Sediment Percent solids were determined using the procedure indicated in Exygen method V0000427. Approximately 20 grams of sample was weighed into a pan. The weight of the sample plus the pan was recorded. The samples were then dried in an oven overnight at 104 2 C. Then the samples were transferred to a dessicator 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 Table X for percent solids results. 6.5 Preparation of Standards and Fortification Solations A mixed stock standard solution of PFOA and !3C PFOA was prepared at a concentration of 1000 jig/mL by dissolving 100 mg of each o f the standards (corrected for purity and Exygen Research Page 14 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 salt content) in 100 mL o f methanol. From this solution, the following fortification standards were prepared: Cone, o f Fort Stock or Fort. Volume Solution (mL) (ug/mL)1 1000 10 100 10 10 10 1.0 10 0.1 10 1o f PFOA and 13C PFOA Final Volume (mL) 100 100 100 100 100 Final Cone, o f Fortification Std. (pg/mL) 100 10 1.0 0.1 0.01 A stock solution o f only ,3C PFOA was also prepared at a concentration o f 100 pg/mL by dissolving 10 mg the standard (corrected for purity and salt content) in 100 mL o f methanol. From this solution, the following fortification standards were prepared: Cone, o f Stock or Fort. Solution (MgfaL)1 100 10 1.0 1o f 13C PFOA Fort Volume (mL) 10 10 10 Final Volume (mL) 100 100 100 Final Cone, of Fortification Std. (pg/mL) 10 1.0 0.1 A set o f non-extractcd calibration standards containing PFOA and ,3C PFOA was prepared in methanol, as specified in Exygen method V0001782. The following concentrations were prepared Cone, o f Fort or Calibration Solution Fort Volume (mL) - M g L ) 1. 100 1.0 100 0.5 100 0.2 10 1.0 5.0 1.0 2.0 1.0 o f PFOA and 13C PFOA Final Volume (mL) 10 10 10 10 10 10 Final Cane, o f Calibration Std. (ug/mL) 10 5.0 2.0 1.0 0.5 0.2 Exygen Research Page 15 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 The standards at final concentrations of 10, 5.0,2.0,1.0, 0.5 and 0.2 ng/mL were used for calibration. Extracted calibration standards were prepared following method V0001780. The stock standard solution and all fortification and calibration standard solutions were stored in a refrigerator (4 2C) when not in use. Documentation of standard preparation is located in the raw data package associated with this interim report. 6.6 Chromatography Quantification of PFOA was accomplished by LC/MS/MS electrospray. The retention time o f PFOA was -11.1 min. Peaks above the LOD were not detected in any of the reagent btank samples corresponding to the analyte retention time. 6.7 Instrument Sensitivity The smallest standard amount injected during the chromatographic run had a concentration of 0.2 ng/mL o f PFOA. 6.8 Description of LC/MS/MS Instrument and Operating Conditions Instrument: API 4000 Biomolecular Mass Analyser Interface: Turbo Ion Spray Liquid Introduction Interface Computer. DELL OptiPlcx GX400 Software: Windows NT, Analyst 1.4.1 HPLC: Hewlett Packard (HP) Series 1i 00 HP Quat Pump HP Vacuum Degasser HP Autosampler HP Column Oven HPLC Column: Thermo Fluophase RP, 50 mm x 2.1mm Column Temp. : -30 C Injection Voi.: 15 pL Mobile Phase (A): 2 raM Ammonium Acetate in water Mobile Phase (B): Methanol Exygen Research Time iminl 0.0 1.0 8.0 10.0 11.0 18.0 %A 65 65 25 25 65 65 %B 35 35 75 75 35 35 Page 16 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Total run time: ~18 min Flow Rate: 0.3 mL/min Ions monitored: Analvte PFOA PFOA Confirm Ion 13C PFOA Mode negative negative negative Transition Monitored 413 -> 369 413->219 415 -> 370 Approximate Retention Time (min) -11.1 min. -11.1 min. -11.1 min. 6.9 Quantitation and Example Calculation PFOA concentrations are quantitated in nanogram o f PFOA per milliliter o f extract and then converted to nanogram per gram. The PFOA concentrations were quantitated in nanogram o f PFOA per liter for Set #3 (Set 042806D). 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 seven concentrations of standards. The concentration was determined from the equations below. Please note that the equations in this section are presented in a different order than the equations in the method (V0001782), but this has no effect on the final calculations. Equation 1 calculated the amount of analyte found (in ng/L, based on peak area) using the standard curve (linear regression parameters) generated by the Analyst software program. Equation I: Analyte found (ng/L) = fPeak area - intercept! x DF Slope Where: DF = Dilution Factor, factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of PFOA and 13C PFOA prior to extraction, Equation 2 was used to convert the amount o f PFOA found in ng/L to ng/g (ppb). Equation 2: PFOA found (ppb) ** fPFOA found (ng/L) x SPE volume extracted! [sample aliquot volume x (sample weight / direct inject sample volume)] Exygen Research Page 17 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Equation 3 was used to calculate the percent recovery. Equation 3: Recovery (%) = . (analvte found (ng/g, wet weight) - analyte in control fng/g, wet weight)! xl00% amount added (ng/g, wet weight) Note: For the PFOA recovery calculation, the "control" is the unspiked aliquot of the primary field sample. Equation 4 was then used to calculate the amount o f PFOA found in ppb based on dry weight. Equation 4: PFOA found (ppb) dry weight = PFOA found (ppb) x [100% i total solids(%)] An example of a calculation using an actual sample follows: Sediment sample Exygen ID C0172892 Spk D (Set: 042806D), fortified at 4 ng/mL with PFOA where: peak area = 236588 intercept = 4630 slope = 420 dilution factor = 100 ng/g PFOA added (fort level) = 4000 amt in corresponding sample (ng/g) = 586 SPE volume extracted (L) = 0.04 sample aliquot volume (mL) =5 sample weight (g) direct inject sample volume (mL) total solids (%) =' 1 - 10 = 66.54 From equation 1: Analyte found (ng/L) From equation 3: PFOA found (ppb) = r236588 - 46301 x 100 420 * 55200 ng/L = (55200 ne/Lx 0.04 LI [5mLx(l g/10m L)] = 4420 ppb From equation 3: % Recovery = 0 4 2 0 ng/g - 586 ng/g) x 100% 4000 ng/g = 96% Exygen Research Page 18 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 From equation 4: PFOA found (ppb) dry weight = 4416 ppb x (100% / 66.54%) = 6640 ppb NOTE: This value may be slightly different than that o f the raw data due to rounding. 7.0 EXPERIMENTAL DESIGN 13C PFOA was used as a surrogate for all the samples. UC PFOA was added to the sediment samples in the laboratoty after the samples were weighed for extraction. For sediment samples designated as laboratory matrix spikes, PFOA was also added at a known concentration to the samples in the laboratory after the samples were weighed for extraction. The sediment samples were extracted in one set. The set included one reagent blank and two reagent blanks fortified at known concentrations. The set contained three sediment samples. For each sample, two laboratory matrix spikes and a duplicate were extracted. 8.0 RESULTS Analytical results for the analysis o f PFOA in sediment samples based on dry weight are summarized in Table I. Analytical results for the analysis of PFOA in sediment samples by direct injection, based on dry weight, are summarized in Table II. Analytical results for the analysis o f PFOA in sediment samples by alternative SPE extraction, based on dry weight, are summarized in Table III. The overall average percent recovery standard deviation for PFOA in sediment samples based on wet weight was 73 16%. Fortification recoveries for the analysis o f PFOA in sediment samples are summarized in Table IV. Fortification recoveries for the analysis o f PFOA in direct injection sediment samples are summarized in Table V. Fortification recoveries for the analysis of PFOA in SPE extracted sediment samples ate summarized in Table VI. The average percent recovery standard deviation for l3C PFOA in sediment samples based on wet weight was 97 27%. Fortification recoveries for ,3C PFOA in sediment samples based on wet weight are summarized in Table VII. Fortification recoveries for I3C PFOA in direct injection sediment samples based on wet weight are summarized in Table VIII. Fortification recoveries for 13C PFOA in SPE extracted sediment samples based on wet weight are summarized in Table IX. The total percent solids for sediment samples are detailed in Table X. Exygen Research Page 19 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 9.0 CONCLUSIONS The sediment samples were successfully extracted and analyzed for PFOA using an alternative SPE method, which yielded acceptable QC data. 10.0 RETENTION OF DATA AND SAMPLES All original paper data generated by Exygen Research that pertains to this interim report will be shipped to the study director. This does not include facility-specific raw data such as instrument or temperature logs. Exact copies of all raw data, as well as a signed copy of the interim analytical report and all original facility-specific raw data, will be retained in the Exygen Research archives for the period o f time specified in EPA TSCA Good Laboratory Practice Standards 40 CFR 792. Exygen Research Page 20 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No,: P0000760 TABLES Exygen Research Page 21 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Table I. Summary o f PFOA in Sediment Samples Exyqen ID C 0172892 C0172892 Rap C017283 CQ172893 Rap C 0172864 C 0172894 Rep Client Sample ID DAL-SO-BPPOVO-OOOO DAL-SD-BPP01-0-0000* DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000* DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000* Analyte Found (ppb, ng/g) Dry Weight C 8 Acid PFOA Perfluorooctanoic Acid NR NR NR NR NR NR Laboratory Duplicate N R = Not reported due to quality control result futures. Sea Table It for re-analysis results. A sse sse d Accuracy (+ /-% ) NR NR NR NR NR NR Exygen Research Page 22 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Table II. Summary o f PFOA In Direct Injection Sediment Samples Exygen ID C0172892 C 0172802 Rep C 01728B3 C 0172893 Rep C 0172894 COt72894 Rep Client Sample ID DAL-SD-BPP01-0-0000 DAL-SD-BPP01-0-0000' O AL-SO -BP P02-0-0000 DAL-SD-BPP02-0-0000' DAL-SD-BPPQ3-0-0000 D A L -S D -B P P 03-0-0000* Analyte Found (ppb, ng/g) Dry Weight CAddPFOA Perfluorooctanolc A dd NR NR NR NR NR NR 'Laboratory Duplicate N R * Not reported due to quality control result failures. See Table III for re-analysis results Assessed Accuracy W -%1 NR NR NR NR NR NR Exygen Research Page 23 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Table III. Summary o f PFOA in SPE Extracted Sediment Samples E nyuanlO C0172882 C0172882 Rap COI 72883 C O I72883 Rflp C0172894 C0172894 Rap Taborakwy Duplicato CBant Analyta Found (ppb, ng/g) D ry W aight CB Acid PFO A D AL-SD -BPP01-0-0000 DAL-SD-ePP0 1-0-0000* D A L -SD -B P P 0 2 -0 -0 0 0 0 D A L-SO -B P P C 2 -0 -0 0 0 0 * DAL-SO -BPP03-04000 DAL-SD-BPP03-0-0000- 881 943 627 823 2380 2380 AMM$d A ccu ra cy - .. 30 30 30 30 3D 30 Exygen Research Page 24 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Table IV. M atrix Spike Recovery o f PFOA in Sediment Samples Sample Description OAL-SD-BPP01-0-0000 cornasi spa o,eoo ppbaprite) DAL-SO-BPP01-0-0000 fCatTU Sl Spk E, 4000 ppt>Spite) DAL-SD-RPP02-0-0000 (comas* Spkg, stoppe spike) DAL-SD-OPP02-0-0000 (Cornaas spk h,4m ppe spike) DAL-SD-BPP03-0-0000 (catnaps Spk J, 4MppbSpike) DAL-SD-BPP03-D-0000 (C0171to4 Spk K, 4000 ppb Spike) Amount Spiked W s) 400 4000 400 4000 400 4000 Amt Found in Sample Inert wst weight C91,A1dd P".F.OA- Amount Recovered (nfl/g)wetweigtit NR NR NR NR NR NR NR NR NR NR NR NR Recovery (%) NR NR NR NR NR NR Average: Standard Deviation: NR NR Sample residua exceeds Hie spiking level significantly (3< spiking level); mentore, an accurate recovery value cannot be calculated. NR* Not reported due to quality control result failures. See Table Vtor re-analysie resulta. Note: Sin ce th is sum m ary table sh o w * rounded resulta, recovery values may vary sligh tly from the vetoes In the raw data. Exygen Research Page 25 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Table V. Matrix Spike Recovery of PFOA in Direct Injection Sediment Samples Sample Description DAL-SD-8PP01-0-0000 (CC1T7SB2 Spk 0, X ppb Splk) DAL-SO-BPP01-0-0000 <172882 Spk C,<0000 ppb Spike) DAI-SD-BPP02-0-0000 (com ae* Spk o, <ooo ppb Spfcei DAi.-SD-BPP02-0-0000 |cot72aajspk h.<ooooppnspnw) DAL-SD-BPPQ3-0-OOOQ IC0172SMspk J, 4000ppbSpa) DAL-SD-BPP03-0-0000 (C0172004 Spk K, 40000 ppb Spite) Amount Spiked ._(nsft) ... Amt Found in Sample (ng/o) we* weight C B A rid P F O A Amount Recovered (nafolwet weight Recovery . _. (%) 4000 40000 NR NR NR NR NR NR 4000 40000 NR NR NR NR NR NR 4000 40000 NR NR NR NR NR NR Average; Standard Deviation: NR NR "Sample residue exceeds the spiking level significantly (3x spiking level); therefore, on accurate recovery value cannot be C a la istad. N R Not reported due to quality oonfeol result failure See Table VI for re-analysis results. Not: Sin ce this sum m ary table sh o w s rounded results, recovery values m ay vary sligh tly from the value In the raw data. Exygen Research Page 26 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Table VI. M atrix Spike Recovery of PFOA in SPE Extracted Sediment Samples Sample Description DAL-SD-BPP01-0-0000 (C017MM*pk D.4M0n/* Iplk.) DAL-SD-9PP01-0-0000 (CO iruutpk E. 400Mngfc *p#c) DAL-SD-3PP02-0-0000 (C017MMCpfca . 4MPn*/pSplk.;. DAL-SD-BPP02-0-0000 (C01mS Spk M,nos n et Spttal DAL-SD-BPP03-0-0000 |CH7a.*4 apt J, 400Smyp Splk*| DAL-SD-BPP03-0-0000 ICO-173*SpVK. 400*0 ng/g Sptkt) Amount Spiked 4000 40000 4000 40000 4000 40000 Amt Found n Sample 589 589 504 504 1060 1060 ca Aod PFOA Amount Recovered (ng/g) wot weight 4420 25600 3860 25100 4140 23200 A v *rij : SU n d a rt Deviation: Recover 96 83 84 61 77 55 7j is N o t.: S in e thl. aum m ary tabl* .h o w * round* r**u lts. m cov.ry v .lu m ay vary .ligh tly from th* v a lu *. In th* orw data. Exygen Research Page 27 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Table VII. Surrogate Spike Recovery o f ,3C PFOA in Sediment Samples Exygen ID Sample Description C0172892 COt72892 Rep C0172892 Spk C C 0172892 Spk D C0172892 Spk E C0172893 CQ172893 Rap C0172893 Spk F CO I72893 Spk G C O I72893 Spk H C0172894 C0172894 Rep C 0172894 Spk 1 CQ172894 Spk J C 0 172894 Spk K DAL-SD-BPP01 -0-0000 D A L-SD -B P P O 1-0-0000 DAL-SD-BPP01-0-0000 DAL-SD-BPP01-0-0000 DAL-SD-BPP01 -0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-8PP02-0-0000 DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000 Amount Spiked (ng/g) 4 4 4 400 4000 4 4 4' 400' 4000 4 4 4 400 4000 1lC -P F O A Amount Recovered Wet Weight (no/oi NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Average: Standard Deviation: NR = Not reported due to quality control result failure*. See Table VIII for re-analysf* results. Note: Since this summary labia shows rounded results, recovery values may vary slightly tom the value* in the raw data. 7 Recovery (%) NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Exygen Research Page 28 of HO Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Table VIH. Surrogate Spike Recovery o f C PFOA in Direct Injection Sediment Samples Exv s en ID ------- CO172892 COI 72892 Rep C O I72892 Spk C C 0172892 Sp k D C0172892 Spk E C0172693 CO172893 Rep C0172893 Spk F C0172893 Sp kG C0172893 Spk H C0172894 C0172894 Rep C 0172894 Spk 1 C0172894 Spk J CO172864 Spk K Sample Description - ..... - DAL-SD-BPP01-0-0000 D A L -S D -B P P 0 1 -0-0000 D A L -S D -B P P 0 1 -0-0000 D A L -S D -B P P 0 1 -0-0000 D A L -SD -B P P 0 1 -0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP02-0-0000 DAL-SD-BPP03-0-0000 DAt-SD-B PP03-0-0000 DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000 DAL-SD-BPP03-0-0000 Amount Spiked (09/9) 40 40 40 4000 40000 40 40 40 4000 40000 40 40 40 4000 40000 wC-PFOA Amount Recovered Wet Weight t^g) NR NR NR NR NR NR NR NR NR . nr NR NR NR NR NR Average: Standard Deviation; NR = Not reported due to quality control result failure. See Table IXfor re-analyjis result*. Note: Since M s summary table shows rounded results, recovery values may vary slightly from the values In the raw data. Recovery <%) NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Exygen Research Page 29 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Table IX. Surrogate Spike Recovery o f ,3C PFOA in SPE Extracted Sediment Samples Exyoan ID C O '72662 C0172892 Rap C O I72892 S p h D C0172892 Spk E C O t72893 C 0172893 Rap C 0 172883 Spk G COI 72893 Spk H C01728M C0172894 Rap C O I72894 Spit J COI 72894 Spk K Sample Datcriplion DAL-SD-BPP01-0-0000 OAL-SD-BPPOI -0-0000 0AL-SO -8PP01-0-0000 DAL-SD-8PP01 -0-0000 DAL-SD-BPP02-0-0000 DAL-SD-B PP02-0-0000 PAI.-5D-8 PP02-0-0000 DAL-SD-BPP02-0-0000 D A L-SO -BP P0 3-0 -0 000 DAL-SD-BPP03-Q-OQOO D A L-SD -0 P P O 3 -0-0000 DAL-SD-BPP03-0-0000 Amount Spiked (OB'S) 40 40 4000 40000 40 40 4000 40000 40 40 4000 40000 " C-PFO A Amount Recovered W ei Weight <n*9> 52.0 51.0 3750 26800 47.8 51.8 3500 25200 45.2 40.3 3060 22100 Not. Sine#thttaumrrarytablethan roundedreaulte,recoveryvetoes(rayvarygMly fromthevalueIntherawdata Average: Standard Oevlatlen; Raoovary (%> 130 128 94 85 120 129 86 63 113 101 7? 55 97 27 Exygen Research Page 30 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No,: P0000760 Table X. Total Percent Solids in Sediment Samples Exygen ID C0172892 C0172893 CQ172894 S am ple D escrip tio n D A L -SD -B P P C 1-0-0000 D AL-SD-BPP02-0-0000 D A L-SD -BPP03-0-0000 T o tal S o lid (% ) 6 6 .5 4 5 4 .3 7 4 4 .4 6 Exygen Research Page 31 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 FIGURES Exygen Research Page 32 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Figure 1. Typical Calibration Curve for PFOA in Methanol i 0439000 Sad. SPE.rd* (PFO*> "Una a f p 7 * MMi|Mt*g y 420 v + 4 63*0Q3 0 - O.QOQ9) Area, counts Exygen Research Page 33 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygtn Study No.: P0000760 Figure 2 . Extracted Standards of PFOA in Methanol, 25 ng/L and 50 ng/L, Respectively I jVCM ZIN*f-PNM ( R W d l^ ^ U N M llM r MMpJff 2 ofM tr*m M N ia w iT T Art#.* n z M w f f i m fgm s f .? 6 t+ M 3 q PT? 11.01 I XjC042609-2 PFOA CStr4Jd) 4134X063X1 *m<j - u n p l i 3 t 48 Item 0428090.** Area: 26169 eeunb H*iiht2.14**<J03 M RT:11.1 min 11J06 Exygen Research Page 34 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Figure 3. PFO in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively I ftM fM t Cortiv! -PFOA fUM mm)4txeaa.M amt -tsrnflU t a f jf f t vm HltM Omm >'**4mmm0 1TOO Exygen Research Page 35 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Figure 4. Chromatogram Representing a Sediment Sample Analyzed for PFOA (Exygen ID: C0172892, Data Set: 042806D) I cAirnru: 3n342p*feoeaw(tur*HJt*riefvUn:)4iTnf.cia.Ont.ttcspm*aR7i n.*mittu rrom um tosum 11XM intansty, cps Exygen Research Page 36 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Figure 5. Typical Calibration Curve for ,3C PFOA in Methanol 042006b SihL S P E .d f c C ^ PrCAfc fUgj&alerts^t JVMriQhUpg): ym 4 0 8 x 0.0 0 1 0 (r 0.0000) Afea, tourte Exygen Research Page 37 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Figure 6. Extracted Standards of 13C PFOA in Methanol, 25 ng/L and 50 ng/L, Respectively XC U H $*1 tiC P fO {5 tsm fs* )4 1 lP 3 7 * .9 * m * Am: 1T901****** m igAt: R 7:11.$min l* f4 tm m 042tMttwfflr 11.0Q intensiv, cpe intensiv, cpe A**: 26803 2000 1500. 1000 50- H%ijM:2.^e+CC3 9f *7:11.1 min 11.00 7 7# # ^ o S ! L 9 10 Tin*, min i Exygen Research Page 38 of 110 interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Figure 7. ,3C PFOA in Reagent Blank, 0.4 ng/mL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent Spk B, Respectively I t>*t* !**</)ftM fM t Cettrol - rSCPfOA fM ttttm ) 4Ti.V3Tt.ttm -ttm ph tv ftffr rm te fM O w tff .a . 1 2 4 4 S 0 7 0 10 H Tim*, min I ft9rrt$-pfcA- 13C PFOA (O C )419.0/370 0 im u - Mfttpl 10 of 40 from O42BQO0 Mlir Am: 2720Q oountr H eigh t2,021+083 <%rt *T : 11JD ml 12 13 W 13 IS 17 1101 11SST Exygen Research Page 39 of HO p. 40 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for 13C PFOA (Exygen ID: C0172892, Data Set: 042806D) I C H T H 92 *3C P F Q A raw MMpfe 2T o f 4SfhM i A rt*; 3 M H 7 cra/rbr HtfgMtzZ9U+094*p9 XT; 11,1mis 2 8*4 11JD7 2.0*4. 2.4*4. 2.2*4 2.0*4. 10*4- 1.6*4 1.4*4- 1.2*4- 1.0*4- 6000.0 60000 40000 2000.0 0.0 J-------- --- ---- 1--------1--- --------------- ---- '-- ---- --------- 1-------- ----------1 1 1 2 3 4 6 6 7 8 9 10 11 Tim*. ml* " -------- --------- .-------- 1-------- J-------- r12 13 14 13 16 17 Intensity, cps Exygen Research Page 40 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 APPENDIX A Study Protocol P0000760 (Exygen Study No. P0000760) with Analytical Method and Protocol Amendments Exygen Research Page 41 of 110 p. 42 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exygro Protocol Num ber POOOQ7IO STUDY PROTOCOL Study Title: Analysis of Perfluorooctanoic Acid (PFOA) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program Exygen Protocol Number: P0000760 Parfotmina Laboratory: Exygen Research 3058 Research Drive Stale College, PA 16801 Phone: (814)272-1039 Sepbioc Representative: Michael A. Santoro Director o f Regulatory Affairs 3M Building 0236-01-B -10 St. Paul, MN 55144 Phone:(651)733-6374 Pag* I o f5 Exygen Research Page 42 of 110 p. 43 Interim Report #23 - Analysis of Sediment Samples Exygen Study No,: P0000760 JExyyeitProtocol Number P000076C DISTRIBLTION: 1) Jaiiimhx K snri, Stady Director, Western Solutions 2) John M. Waherty, Principi) lnvestigalor, Exygen Xeaoirch 3) M ichui A. Samolo, Sponsor Repreienwtivo, 3M Company 4) Exygen Research Quality Anunmee Unii Exygen Research Pegr l 465 Page 43 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exypo ProtocolNmb P000076Q PROTOCOL APPROVAL Study Title: Analysis or Perfluorooctanoic Acid (PFOA) in Water, Soil, Sediment, Fish. Clami, Vegetation, Small Mammal Livers and Small Mammal Serum Using LC/MS/M5 for the 3M Decatur Monitoring Program Exygen Protocol Number: P0000760 APPROVALS Jaiam&i Kesari, Study Director Weston Solutions Michael A. Saniro, Sponsor Representative 3M Company ' Exygen Research P a ft J o f65 Page 44 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exyjen Protocol Nuntfeer. POOW7&0 TABLE OF CONTENTS distributio n _______________________ _____ _________ ____,, . ________________ .,,2 PROTOCOL APPROVAL--------------------- ----------------------------------------------------------------- 3 TABLE OP CONTENTS ___________ . ______________________ - ........... ......................... 4 INTRODUCTION------------------------------------------------------- --- --------------------- -------- ----- TEST MATERIAL____________________________________ _______ ______ ______ ___ _ J SURROGATE FIELD SPIKE COMPOUND___________ __ _______ ________*.________ _____ 5 OBJECTIVE___________________ ___ _____________ ____________ _______ __________ 6 TESTING FACILITY_____________ ___ _________ ____ ...................................................... .. 6 STUDY DIRECTOR.......................................................... ........ .................... ...... .............. ............6 SPONSOR REPRESENTATIVE............................................................. .......................................... 7 PRINCIPAL INVESTIGATOR ...................... .................... .................................. ........... ......,,... 7 PROPOSED EXPERIMENTAL STARTANDTERMINATION DATES.................. ..............................7 IDENTIFICATION AND JUSTIFICATIONOP THETEST SYSTEM............... .......................... ........7 SAMPLE PROCUREMENT, RECEIPTAND RETENTION ........ ................................. .....................g SAMPLE IDENTIFICATION................. ................ ...................................... ............ ..................... 8 ana ly tica l procedure sum m ary__________ ___ _____ ______________ _____ ___ 9 VERIFICATION OP ANALYTICAL PROCEDURE................... ........................ ................................9 METHOD FOR CONTROLOF BIAS............................................................................................... 11 STATISTICAL METHODS......................... ........................ ............................................ .......... II OLP STATEMENT.......................... ........................... .............. ............................... ........ .......... 11 SAFETY AMD HEALTH....................................... ........... ........ .................................................... 12 AMENDMENTS TO PROTOCOL....... ........................... ....... .......... ............... ............................... 13 DATA RECORD KEEPINO.................. ........................... ............. ................. .......................... 13 QUALITY ASSURANCE_____________________ _______________________ _______ ____ 14 RETENTION OF DATA ANDARCHIVING _______________________________ ____________14 APPENDIX l. ANALYTICAL METHOD__ _____________ ____ ____________ _____ ______ IS Pig* 4 0/65 Exygen Research Page 45 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exygas Protocol Numb-. P0000760 INTRODUCTION The purpose of thil study is to perform analysis for perfluoroocunoic acid (PFOA) in water, toil, sediment. flab. clams, vegetation, until mammal livers and email mammal serum using LC/MS/MS for the 3M Decatur Monitoring Program. The study will be audited for compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792 by die Quality Assurance Unit of Exygen Retouch. TEST MATERIAL The teat material it perfluorooctanoic acid (PFOA) and w at purchased from Sigma-AUtrich. PFOA Chemical Name: Perfluorooctanoic acid Molecular Weight: 414 Lot Number 23116HB Purity: 97.64% TranaiUona Monitored: 413 -+ 369 (for quantification) and 413 -*219 (for confirmation) Structute: SURROGATE FIELD SFERE COMPOUND The starsgate field aptking compound ia UC labeled perfluorooctanoic acid (llC PFOA) and wa* purchased by 3M from Perkin-Elmer Life and Analytical Scieooea. "C PFO A Chemical Name: 1.2-13C petfluorooctaaaoic acid Molecular Weight: 416 Lot Number. 3507-19S Purity. 97% Transition Monitored: 415 -v 370 Pag* 3 o f 63 Exygen Research Page46ofll0 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exyjeu Protocol Number; 1*0000760 o b je c t iv e The fiuipote of (hit study it to perforin analyst for perfluorooctanoic acid (PPOA) in water, toil, aedintem, fith, dama, vegetation, muli mamma] liven and sudi mammal tenui for the 3M Decatur Monitoring Program using the current vottoni of(tie following Exygen analytical methods V0001780: "Method of Analyst for the Detominilioo of Perfluorooctanoic Add (PPOA) is Water by LC/MS/MS'* V0001781; "Method of Analyeit for tie Detenninaiioti of Perfluorooctanoic Acid (PPOA) in Soil by LC/MS/MS" V0001782: "Method of Analyst far fot Determination of Perfluorooctanoic Add (PPOA) in Sediment by LC/MS/MS** V0001783: "Method of Analyst for the Determination o f Perfluorooctanoic Acid (PPOA) in Pith and Clams by LC/MS/MS** VQ001784: "Method of Analyst for foe Determination o f Perfluorooctanoic Acid (PPOA) is Vegetation by LC/MS/MS" VG001785: "Method of Analyst for foe Determination of Perfluorooctanoic Acid (PPOA) in Small Mammal liv er by LC/MS/MS** V0001786: "Method o f Analyeit for the Determination of Perfluorooctanoic Add (PPOA) in Small Mammal Scrum by LC/MS/MS" TESTING FACILITY Exygen Research 3058 Rotearci) Drive State College, PA 16801 Phone: (814)272-1039 STUDY DIRECTOR Jaitimha Cestri P.B., DHE Wetton Sohitiona, Inc. 1400 Weaton Way Weal Cheater, PA 19380 Phone: (610)701-3761 Pa*; (610) 701-7401 jAe$ari@weatemohition5.c<xn Pag* 6 o f65 Exygen Research Page 47 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No. . P0000760 Eyjso Protocol Nwnbtr. W000760 SPONSOR REPRESENTATIVE Michael A. Sentore 3M Company Director ofRegulatory Affaire 3M Building 0236-01-B-10 St. Paul, MH 55144 Phone: (651)715-6374 PRINCIPAL INVESTIGATOR John M. Flaherty Exygen Reaearch 3054 Research Drive Sure College. PA 16801 Phone: (814)272-1039 john.flaherty@exygen.com PROPOSED EXPERIMENTAL STAKT AND TERMINATION DATES U ir promoted that (he analytical portion of (hit atudy be conducted from October 01, 2004 to December 11, 200$. The actual experimental start and termination dates will be included in the final report. roENTTFICATION AND JUSTIFICATION OF THE TEST SYSTEM The following are the teat system! for thia study: Water (groundwater and surface water) Soil Sediment Fiah Ciana Vegstaticn Small Mammal Liver Small Mammal Seram The samples will be collected by Weston Solutions. The control sample will be purchased and prepared by the toting facility. Purchase and processing Pm pivfts Exygen Research Page 48 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: PO0OO76O Esygtn Protocol Number- P0000760 details far toe control sample* will be included in the final report associated with this study. The test systems won chosen to access the environmental impact o f PFOA in the Decatur, Alabama area. SAMPLE PROCUREMENT, RECEIPT AND RETENTION W at; aoil. aedimoA fish, clam, vegetation, small mammal liver and small mammal actum samples will be received at Exygen directly from Weston Solution*. The details o fsample procurement for this study ar* outlined in the 3M wodt plan entitled `This 2 Wot* Plan for Sampling Environmental Media." The numbs and types o f samples collected will vary depending availability in the field. The total number o f samples received and analyzed for each matrix will be documented in the final report associated with this study. Water, soil, and sediment samples will be used aa received without further processing at Exygen. These samples will be stored refrigerated at 2C-8,>C. Fish, dam , vegetation and small mammal liver samples will be processed according to the appropriate analytical method (see Appendix 1). These samples will be stored frozen at S -1D*C. Small mammal whole blood samples will be centrifuged in the field at the time o f collection and the serum fraction will be used for the study. Small mammal scrum will be stored frozen at S-10*C The receipt and processing o f foe samples will be documented in the final report and raw data associated with the study. SAMPLE IDENTIFICATION Prior to analysis, each sample will be assigned a laboratory sample reference number. The reference number will be unique and will distinguish each laboratory sample that is processed throughout foe analytical procedure. Chromatographic data will be identified by foe laboratory sample reference Sample storage ccoditiona and locations will be documented throughout the study. Page & c f 65 Exygen Research Page 49 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Eaygea FrancaiNumber POOOOTHO ANALYTICAL PROCEDURE SUMMARY Reference: V000I78Q: "Method of Analysia for the Determination of Perfluorooctanoic Add (PFOA) in Water by LC/M&MS" V0001781: "Method of Analytic for die Detennination ofPerfluoroocianoic Add (PFOA) in Soil by LC/MS/MS" V0001782: "Method of Analytit for the Determination o f Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" V0001783: "Method of Analysis for the Determination of Perfluorooctanoic Add (PFOA) in Fish and Clam by I.C/MS/MS" V00017M: "Method of Analytit for the Detennination o f Perfluorooctanoic Acid (PFOA) in Vegetation by LC/MS/MS" VC00178S: "Method of Analytit for the Detennination of Perfluorooctanoic Acid (PFOA) in Smtll Mammal Liver by LC/MS/MS" V0001786: "Method of Aaalyait far the Determination of Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LC/MS/MS" The above methods use analytical condition capable of separating the isomers of PFOA. The final report will include the isomers summed into total PFOA found. VERIFICATION OF ANALYTICAL PROCEDURE A laboratory control sample will be used for the preparation of fortified control samples. The teat tubttaoce will be made into solutions as per the method, and added to the matrices via a micropipette. For water sampling, Exygen will supply one bottle per sample collected. The bottle will be 500 mL precleaned Sci/Spec Premier wide mouth HDPE bottle*. The bottles have been routinely used far PFOA ample collection at the totting facility and have been thown to be free o f PFOA. All oontainera used for water sample collection will be shipped to the sample location containing 100 eg of ,JC PFOA (equivalent to 500 ng/L in the final sample). Suimle* wiS bo added to each contain la volumetric fill liiw at 200 mL A field duplicate, a tow field spike and a high Celd spike of each sanqsie will be collected. The low and high field spikes will contain PFOA u well as perfluorobatanesulfbntte (PFBS). perfluorohexanetulfooate (PPHS), and pcrfiuorooctaneaulfonate (PFOS), These compounds are included in the solutions used to spike the simples. The results for PFBS, PFHS and FFOS will not be reported is this study. Exygen will supply one field blank (control water) and two field blank pikes (controt water fortified with PFOA at a low Pagt 9 o j 65 Exygen Research Page 50 Of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exypo Protocol Niunbei: P0000760 and high level) for every twenty samples collected. At the testing facility, each water temple (excluding field duplicates and field spile) will be extracted in duplicate and will also be fortified at a low and high concentration with PPQA and proceasod through the described procedure to determine method accuracy and to check for b is. For oil, sediment, clams, and vegetation, Exygen will supply one 500 mL proctamed Sci/Spec Premia wide moutb HOPE bottle per simple collected or a zip-seal bag. All coatainerWbags used for sample collection will be shipped to the sample location. Sample* will be added to each container or bag in the field.' At the testing facility, each sample will be extracted in duplicate and wilt also be fortified at a known concentrabou with PFOA at both a low sod high level and processed through the deecribed procedure to determine method accuracy and to check for bias. u C-PPOA will also be added to each sample in the laboratory prior to extraction at foe level specified below. For email mammal liver, Exygen will apply a $0 mL polypropylene centriftige tube. For small mammal scrum, Exygen will supply a collection kit for each ample cmdasning serum separator tub (ted lop), vacuiamers. needle holders and needles, transfer pipettes, and polypropylene tub At the testing facility, each Eves and serum sample will be extracted in duplcate and will also be fortified at a known concentration with PFOA at both a low sod high level and processed through foe described procedure to determine method accuracy and to check for bisa. u C-PFOA will also be added to each simple is the laboratory prior to extraction at foe level specified below. low and high spfldng levels for each matrix are defined below: M atrix Low PFOA High PFOA ,JC-PFOA Spiking Level SDiktat Level Spiklut Level Water S00bs/L 5000 nj/L 500 ngfiL Soil 40ng/g 40ng/g Sediment 4ng/g 40ng/g 40 njFg Fish lOngfg ...... lOOngfg lOOng/g Cisma Vegetation lOngfg lOngfg .... lW .M fc ..... I00ng/g lOOng/g 100ng/g Small Mammal Liver lOnglg lOOng/g lOOnf'g Small Mammal.Semin lOngfg lQOng/mL 100ng/mL Reeovaries we anttcipatad to tie between 70k end 130% of the fortified levels; however, the exact precision and accuracy will be determined by the analysis of foe quality control aaraptos described above. A statement of accuracy will be included in the final repost. Print to sample analysis, a laboratory control spike itudy will be conducted in wrier to justify the use of 13C PFOA results to establish precision and accuracy of PFOA samptat. The foliowing ismplei are to be prepared Pa$* /o f S Exygen Research Page 51 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 E xygta Protocol N um ber POO076O control wtftfMtflk Two control water samples fortified el 250 ng/L with 1}CPFOA Two control waterample# fortified at 250 ngfL with UC PFOA and at 250 ng/L with PFOA. Two control water ample fortified wl 5000 s^ L with " C PFOA and I 5000 ng/L with PFOA. The hove ample are to be extracted and analyzed according to method V0001780 entitled "Method o f Analyiia for tbs Determination of Pcrfluorooctsnoic Add (PFOA) in Water by LC/MS/MS* METHOD TOR CONTROL OF BIAS Control of bias wit] be addressed by taking representative sub-samples from a homogeneoua mixture of each matrix from untreated control ample, and by analyzing at leaal two levels of fortifications. STATISTICAL METHODS Statistics will be limited to those specified in the subject methods and to the calculation of average recoveries, as applicable. GLP STATEMENT All aspects of this study shall be performed and reported in compliance with EPA TSCA Good Laboratory Practice Standards 40 CFR 792. The final report or data package (supplied to die Sponsor) d u ll contain a statement that the study was conducted in compliance with current and applicable GLP standards and will outline any deviations in the study from those standards. This sutemort will be signed by the Study Director and Sponsor Representative. RETORT A final report will be prepared by the principal investigator or their designee at the conclusion of the study. The report will include, bur wtu not be limited to, the following; Paf* II ofts Exygen Research Page 52 o f 110 p. 53 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: POOOO760 I x r tta Protocol Number: W 000760 The name and address of the Study Dinxto, Sponsor Representative, and ofthe letting faciJtty. A statement of GLP compliance (any related documentation, inch as chaln-of-custody record, meat be in die study records). .. The signed and dated etatement by the Exygen Research Quality Assurance Unit regarding dates of study inspections and dates findings were reported to the Study Directorand Management. A description of die exact analytical conditions employed in the study, (f the subject method was foBowad exactly, it is necessary to include only a copy of the analytical method. Any modifications to this method wilt be incorporated into the report. If the method is photo-redaced, the project number end page number mustbe included on each page. Description o f`die instrumentation used and operating conditions. AD results from all sets analyzed. Control and fortified samples will be identified and the data table will include sample number and fortification level. Representative chromatograms for each analyte in each matrix, including chromatograms ofa standard and a control sample, and a chromatogram at a fortification leveL The location of the analyte peaks will be clearly identified in all chromatograms. All circumstances that may have affected the quality or integrity o f the data will be documented ia the report. Locations where raw data and the final report are to bo arehivod. Additions or corrections to the final report shall be in the form of an amendment signed by the Study Director. The amendment shall clearly identifythst part of the report that is being altered and the reasons for the alterations. Tbe amendment will be signed and dated by the Study Director and tbe Sponsor Representative. SAFETY AND HEALTH e Laboratory personnel will practice good sanitation and health habits. Every resaonable precaution shall be taken to prevent inadvertent exposure of penmans] and the environment to the test or reference subttance(s). Page 12 o f61 Exygen Research Page 53 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exygen Protocol Number P00007SO r * AMENDMENTS TO PROTOCOL AO significant changes to die analytical protocol outlined here will be expressed in writing, signed and (Uted by the Study Director aid Sponsor Reprisenative. Amendmeeti usually will be iaauod prior to initiation o f study plan change. However, what a change it required without sufficient time for the iaauo of a written amendmau, Out clung may be effected verbally with lupporting documentation signed and dated by the Study Director and followed with a written amendment a toon aa possible In this esse, the effective date of the written amendment will be the date o f the documented change. Cepiee o f foe riffled amendments will he appended to all distributed tudy plan copies. The original amendment will be maintained with the original study plan. Any deviathma from foe study plan or from the analytical method as provided will be documented and reported promptly to the Sponsor Representative. DATARECORD KEEPING Records to be maintained include the following (as appropriate): Sample tracking aheet(s) Sample receipt records, storage history, and chains o f custody History and preparation o fstandards (stock, fortification, calibration) Description o f any modifications to the method Instrument run sheets, bench-sheets or logs Analytical data tables All chromatographic and instrumental conditions Sample extraction and analysis dates A ccmplete listing ofstudy personnel, rignatures and initials Chronological presentation of all study correspondence Any other documentation necessary for the reconstruction of the study Chromatograms- An chromatograms will contain the following: Sample identification, injection date, arrow or other indication o f the area of interest, sad injection number corresponding to the run. Additionally, fortifications will include foe mount o f analyte added and foe sample number offoe sample that w it fortified Analytical standard chromatograms will additionally concentration (e.g., jig/toL). the Puf* U o f65 Exygen Research Page 54 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exyg Protocol Number F00007C0 . As part of the documentation the following sheets will be included in each uulyticsl set; run sheet fating tbe sample* to b cru n in th eset.u K l* n instnimenl conditions sheet describing the instrument type and operating conditions. All applicable requirements tor reporting of study results as per 40 CFR QUALITY ASSURANCE The QA Unit of Bxygen Research will inspect the study at intervals adequate to usure compliance with GLP's, tnd wifi report the findings of audits to the Study Director. Exygea Management, n d tbe Sponsor Representative. RETENTION OF DATA AND ARCHIV ING All hud copy raw data, including, but not limited to. the original chrmnatogranu. worksheets, correspondcnee, and results shall be included with the data package submitted to the StudyDirector. These will be archived with the original study p in , amendments, final report, and all pertinent information from the Sponsor. The testing facility shall keep all electronic raw data and any mstniment, equipment, n d storage logs for the period of time specified in 40 CFR 792.195. An exact copy of the materials submitted to the study director will also be kept at Exygea Research. Exygon will obtain permission tom tho study director before discarding or returning samples. Exygen Research ftrf H a J U Page 55 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exyfen PKHQcat Number. POOOC760 APPENDIX I ANALYTICAL METHODS V0OQ1780: "Method o f Analyst for the Determination of Perfluorooctanoic Acid (PFOA) in Water by LC/MS/MS" V0001781: "Method o f Analyst for the Determination of Perfluorooctanoic Acid (PFOA) in Soil by LC/MS/MS" V0001782: "Method of Analyst for foe Determination of Perfluorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" V0001783: "Method of Analyst for the Determination of Perfluorooctanoic Add (PFOA) in Fiah and Clama by LC/MS/MS" V0001784: "Method of Analyst for foe Determination of Perfluorooctanoic Add (PPOA) in Vegetalion by LC/MS/MS" V0Q017&5: "Method of Andys* fot the Determination of Perfluorooctanoic Acid (PPOA) in Small Mammal Liver by LC/MS/MS" V001786: "Method of Analytic for foe Determination of Perfluorooctanoic Acid (PFOA) in Small Mammal Serum by LQMS/MS" Exygen Research PojT 5 o f65 Page 56 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 E xygn Protoooi Number; 0000760 /*** A H A IY D C A L METHOD M M to k e VDMI7W * * * * * * * Om nill.u I i r f rT* WNwrlwulA M (fT O A f k V lttr IjllOM Ha bn B lam d MBKu w ch Oriv teO rta*FAIi0i Afpmtdly; f_ J.L fmalICCmammoUilyr ' TutaimlLMr.tCW, b )p tom it SfesM 'p?/JmT ______ __ /M m TU bm f 7 ' Ve rxndml. Opmiom, b y m -j& k- Exygen Research ToalP^m: 7 ta g t I t oft} Page 57 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No,: P0000760 Ejrygt Protocol Number. P000076G Vjff l Unmh U iM M itW ilig I -! ,-ft-:.ft.rft.TtrvnHTA---Lrfynn-cf*f!yMll,i,TIn,,,ona,,!, Ad (TFOA) in W w LOUMa l>u mw1 ,* , ei* wl^wdiei, " * * W * l t w bkjiM r b w w im iliy M | U < andem M w l| * o w * Owe* (LCMSM9 m . U Mttjr ll Alwy nhti mh liinn)'pwuim, ).o T--hnm.in--rt 3.1 AtlMM*tfcL4ftaiainc4fcrcmctfc& y.i Ha ii wy k mm 3J *m jm n i lafeamtM Mid * aJWvid *qui!csic to won mjMCtMM. X4 All i l k thnriinMyahtid bdbw bw f rampbd feewfaw 3.3 A3M 0 OTtfiWai prirfw * * i bf u -3900 pm ter -3 wdH aal ft M^vMiaatMd<mUmmvkUm . U 5aa*J* colaciioA ffocadra wiBbe j e tte d io * t anpUiii pi* far fet 4.0 AaafsntavdSteidaada AI Waiar-lffLCfnub 4J idi-- l -PLCy*d> J A M diM A iM e.A C i.iN |iD (G r^ A4 hiHwimwiiiiiiii Acid~ 8tp u AMricfc 10 3.1 A feJjh >r t w m ^ad * m Uo^ H opatM af poopia* up *> ? o h <w ed ^ v a ii^ le ie * eteeer Mpeble ef iaieesfis IX*) 13 Kl e w iri s Iw d* Mw ly e e a n w <LOMSAO). Adrmc m taa am dtf* ftrpaak ia b p u a art qunuwioa 3.3 Aatiyiied W i**ca|M #aimdh|to0Lfl000l * II 30mL dhp-- Hoplxanpylm nwHhftp mim. 5J llaLBlT--MiylUWtpyln ra--iftptaba* id Puy-- bWrwrrp p ir. (SD-MOal ttteOOaU ii U^wtUggwrow lawrtkai. 1IjuSf1i0 liaLrtaarHPtCitait*. AwpiyW*(WHIOO|iLerflO.IOO^U W aai% takVae6c(3|)iClf OTIcartridpa. tip*. A|ff t7of6) Exygen Research Page 58 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exyten Protocol Number: P0000760 Uip .1--- e I w uuutw,vWti?t<) AjwiyncALMtnw ... | HidCrAidieefcfeCw lMdm N>fleiean eile AcM(WOA)iiyiietty um tm Mi a iw -- iiiiM t l.U Owrtfcp m e>l f X L ro irp a vjm * Mb y w o tT *0 Omi ilm > iig j n 11 Amb^iwIOib-- :WiiiflmeP(IC )elM |tiK ae^ t l m i H i m , tu (MNitntsumjD) 12 te p w K *rc 11 tM 0eneW : l e U 2 i W V 4. tM e n u a P )-. HrtKmil U (lw i ) > W f : Vm0S21m A 14 14 000 23 5 HA <1 <5 25 65 FW lau Hl 35 0.1 35 0.3 15 03 M 1 35 0 1 <.f h^etiee V tte er |5nL (cobincra--<l to * > 30 nt). 4.T foiWtaM, h tk An* - atonal *tawl*4Mlibmion carve. M Rm TSm ; -2 3 mmm. / " * l^a*mv<HtitSwema4sdiii|ideedmiyiekiayduigrtti ytfadmWKTlC ryiiim. 7 0 MSMCSjM m 7.1 M W TU * * nHdhic * iacttM m fuiU a d n iy b <W pd a wfc* oftmm Om MBMS . I4> hfMntrSilMiNi 4.1 MbUkMu X.1.1 Z mM H M M M aW a water s p f p--rd Oy a ttis f ft 154 g *f emdiei i1066eU,efwwir. AUnnh 'iiwl--iw--yUn^piwd. Exygen Research Patt18oftf Page 59 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Bxyftct Protocol Kombor. P000076Q Mnhfadof ANALYTICAL MCTBOft rbiirwiiuiwicfywrfWc>rOiin<irAridfffOAiWurby LGWS/M5 0.1.1 FMvweiowkrnfabooof-IOlita^LermXAkywm^BnslOn^ of iljrin l riwilwd (towwHd f a yohty) dilute ICOm i wnh wflwwt Io 12$Li m bo. L U A IOj#riaLfadld iiW m of PTOA frpwpwwl by&ofttm lu *Lof*160#nA*l>wli*looloa6*l vekwof I wiii iaaUInLIJPPf bMtt. f.lj Am1LJ>ouftfoa1l0f>a*ifitfolLaattrkiuwtiwototfocoofoafrPiPO!A)if*pw?1p0f0dwbiy*brtnitmlmbItmn kl3S*LL0rb0tte. 0X4 A0.1 fcitilWtoi f a i n afPfO * U p ry w d by fa* Hi aiLaM* >^|ifhpLlwkwoaiPriiflhwMf IQOwOi *< in laSaLLMMOa .1J AM l pgfaL fatiferiMB Mfafai ofPPOA b pifarfa Oybriafi 10 mL Of fa (X! |i#M. MriHtiOB10 4 flMl rataKWf IOQWttti mAhmIw IV m L U M b tU t.1.4 TVnodr ad faiflntoiawk WAomtob otod A4ratkfVMOf at topmfadriy#C faM iffaofa wum pwwd oft smmas fa Jd*tfpiayriiij. 92 StandardCabntuaIm m XI LOMSMI rritofak m r iM t m y y d HPLC au* Tb* lArtti--Mdardt we ptocfftcd ttoa0fc tfa curacy prcdur. idandod ipto yloa. 0X2 Tin fcttowiff it a tjjk ti u m t# m adflHocrt rpnraudoat nay b* 0ml CaaoMniw ftwiflniM V fam af C w t r i a r f T M ta d a VoiMtt ftrtHfaftottal C U ta t e SafafatfaN fvU M a in O j 3tMdH<A*y 40 b 1 40 25 (4 M0 40 SO I 4M 40 IM Mft |M 4 0 100 m 40 J40 _____i s ____ 4M ______a ______ ___ SB ___ QdiWiio MP (aamolt) XCfaafarH X O m M fri X C m ettn t XCbwddyy-1 XOMNtoyy-* XQaflridyyJ XOmddwA w-- mtfen, d u n k * iin iio ni^ fO tn a d tn i dwtoflto ntraukwCSf&) Page l9af6S Exygen Research Page 60 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.; P0000760 BoteoPfetoeol Numktr PQCQ076C I - - j i ^ y j j r ' i T "" Hatol afAMlytototo Ptomtotvocinci&tomrtowpow niAdd(FlkU)mWi JJU A --*-*-1f--|-- TiMtin --"tti~rr atafjm totowsnmd. >W tow li WfcMWdtotoeHealiwdarfr1S-mLyotyyppyfcr ttoa >1] AAwiatouna>id6MramBettilMMa>yUptpan*M tO.O B*cb$*Uf l.) Wtdk to to a tM ftm t t i r w l ftypfciy or Im ) a u t iartudt m t*m m m p a i M M M d t h a t w i HFIC n w ) d taw m m *\ mamk anUM ac fcaeini aMmnafoM (I* cmrcf apU> n vfrify IdJ mflqato1yhh r ItB im mpkilitlouitmotiyp*dwvfmHt m Md tfO m 4Mbf ayofied 11.0 iM jli PHrirtna 114 M Mlin4pLftrM ^I*ta^aticiifipia A iM M 40LrA wMr to>SOi.ylfrrajylw eMrifhqaMb--(totifr*<w+clupt- aMMd *& U.3 CmmU t o CmI f l cmddlp 0 j 0 14 bf la u fet 10 mL atom l tt a v a ify im L a fB tlC w m fh ito a ftm l- Deaadvtookmnruadry 1 U I,M i 9 tm h m tm im irtC IW uartridj DtoardtoWa. 11.4 mm M H , I W Unfit, Caaet JMLW*eiektor<h*ii IS wlynljpwpylMa --miMhp ff* (toO stow a Sat.). U J >Mfrw im y to w*a# riartTNimy LfftdSW . 12.1 dtf1* * * MM MMUtfof sack A n ted , aaMpi Md totifled MMfi mb die IM SA tt q m A ealtom Md--d a m p t - r i t Md IbKew ad M aijMiimpl U J Slw <w *f?f0A 6m *keihm *w erm reow epew m #l -- ito toM idfcMm frltotm 3 A* mir* a* a t axfcetiad d t o M ftaatodi o w t W InriaiM * t* t o | i m d t o a d a t > rni pli m . tssao ad m t o * a m te i m i m i b u w i aaay frMMm pto . A* m ahecMtiv, m m to art of unmd writoii Mstototo way M Md to bayim af A feHr--bjr Mbadad eatoUlM -- toM h i r f n l m ttry 5*10 Nunpta flw a r n t o a tm ad m or attrau d taodada). h d t n m M t i e w l to to M * im d iwh i-- i> m ftw m iiw ii i iefiBBiaim n it U.4 \>ift Timm toatod o n iw mftMIm liu v m m aitnria t j^ m r n i t o iw eelyta by im w iiem e m m qg 1Awei|Miig ef imk #m H>al'> JPa&Xtfi} Exygen Research Page 61 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Bxyfcfi Protocol Number. POO0O76O Mm*VOMITI c).<Hbeo<A*]y*ttftrtUr MAirMmhaiOmo%c/uNrMi!kMrfoMo^Mb in^rAc^(PFQA)tWtlcVy] IGM3AII VMM t \ m m ornim i twnmtntirm mt$ M m Lym ) } { t* equivalent) wN ih lyim 12.3 SsapU fl# m m -- U a * m arni w t - l r--iiem . Any mmM wfl--tl a m im i M pH M MmM H Ibrtwr dttMM MdiMMlysvd. 1J.0 AiMfngCrUm> 13.1 Ch-Hop----lMoipbor*it*--rwoHb--bnop--i of i l l m l TU <U mm $rnm pnaap-- to a PPOA mmn. wh tf* *--r Mt k-- Wcarttaii<**). 1 U lliMftif M--fci -- t at -- MMPPOA x I-- 1 pr-- t -- 0 tOQ. if* H a* -- fFOA m b*-- pMMTtino SOpft, tf-- i i n r Mm* taiy lt w * WdHewei w * * * * eewiIm meeMd. 13.3 1-- mrta ofcommi q m m i motri* ipi-- i t te l i n i 7M3QS of dMrfc-- ah--. If tw l --fcoflJH amp'--* -- --Mil -- >fi M i O r f --phi --n il to -- od. Aoy otra --bo ommM >0- 1WH a-- bo e*-- * by -- immym fi--nwior if mmnaion n w w M rii 13.4 Aoy h IiVm'm oam hti to m i > poHa bymgibH>-- Enei Taw wnf be cH W tm 0 ml-- too of fi calibra w h ll--o ii; fi Mil am* of e-- d tibOMmi oknhi *ai emlfi be 4 'n o --rillt Miffii-- (X) fi* fB m ikw o w n t -- i d o--t bc mm> U D <** ttH S y li a M a ta * w l b AU i M tmm Sm. tm HuwpMi -- pi m -- m a * a i tun-- i npcrwtoo. m th Mafia-- o rto -- --tM e f----fcMabooUbem--lysofi. 134 ftc-- Mi M -- to m * M l-- m 4 wnp-- o-- i oat drill ore iHm 1 4K v- lm al)--* na. Iftaati--i--ftfiri*Keeo6tdh tiew ***** m anlj--al nm m t o -- -- atb* -- lyood. 1*0 Cokoh-- i H.l Um M>0oM*t n oto min ia taa -- imoofFfOA hm (io np/l. tuoi m ptOk aie) u ug tbMnfierfi con* {Uaur top-- >poreroeurtl pMOr--dby UmM lg-- aoAwvn m y . rfO A M M l) xPP *Joy* CT - to -- by Utb fi ft-- vot--o am filtawfi, If tm n m y. p--4tP Pof* 2 of 43 Exygen Research Page 62 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Eaygm Protocol Nuntoer *0000760 iiiin i vmim 1 AfOllfnCAI. MlTHOt) --------------1 MaltolirfAialyihtorfcOto.iMiriiliiiii.ffiiftiwi MtoMliW'ffPOAlicWiMtty LOMS1MS MJ fWM--tfoldttfototo"iI1*nlIwtaMMmitaoooIvMlk fmmYwfp.rior to unco. ,,c ImmmyQVi- Exygen Research of65 Page 63 o f l 10 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.; PQ000760 Exyfeq ^iotol Number. POCKXV760 ANALVTJCAL METHOD U u M M u ak V00017I1 Matfcctf Ar 1M OcmmJMtiM i f M w r w r w ite AcM (PfA> u s+u by lcao/m AublMT*tg?*;: fecyf1--wek VUl IUc--Pt Prfrc StateC*D*t>A 1*101 TteJwkal Imtr, LC-US,Bxnpa RcmkUi i6tafUwty ^ / Vice ftwidiwt, OyiirtteM, l y y Ib waret '>hh4 -Bete M Exygen Research Totti?*** 7 -Paj* </d.J Page 64 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Bxygra Protocol Nurob*r; PWXMO NwiNrveootm AAtyncALMrraoD * * * * * * hftrunwHiUtMhiHtlfVNHMrr8ftimmxxM*A'id(W<hA)8o.!h, TU* -*ft*d m W * > * H * * * * * * ofpffOMMCtMeic ^ ***D_t*fM'*Mr&CAOM8)*L ompM taWcrnMut l! Ai**;/*AmenmMMamtypteiitm. 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A te m * w4mmaay W jpm4. ****** Pag* 25 q f 65 Exygen Research Page 66 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Bxygtn Preloco) Number: F00007M 1M M (S 0A)i50Tlby 4 B U a i -100 * W . r?O A by M m, Mf>gb|itlgI1--|lj,hl<.tlogwglre<nhkr.riW--l Ohmm iC0o.woh .U mkUmoflTOA. H m H m t*e*tra*n4LUt DMRMMLhmLM n >ml mtoat oflOOw ubw iw i W J eAUlUla>OL*ML1M^0fiScMWrtMO.min.MtimwmIiiloMolrfiarhomAWl.pIOrO^Jwkvkmn.mp-lOj. A M |i|fU M lN rim alafeB tfn> 0A ta**m 4bykm iailB i UJh*L U1J)MMtM.a W m t a t Iba)m )b >( 0 iaha a u A)tmo Li >f*y ,tlfcWirjt^ierwl fLwhMmmiffFOfiAndit mf HMfmttmwl*bTy1V0o0vemi* 916 M tee allftliV LLDPftMUt. TMM*keMl)rtceee***wNKorMksrefcpKetoiN mI mnitiNfieNto(/*TfpCnpaawdM* *LMW fee >xurtnwg petiod f twwi> 2 Ik iM C tf ifaWm >4.1 Uggftl crittniaiM i 1 faHWCwxr. 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IC Mad aamiaaWOA a m a t m e a t d a i K r*/L a a a a > MaauMwk M DaMakaka d da aaln M aaat ka a m d . 13J Kwwailaa fd aaal apifcaa aad eaaaia aptikaa anac ka keectaaa 70IW o f tMirlMwandam V a e td a d o t U a otadtle d a aee*itaMa lin u . a a h a w a ra a v ta ik a a U k a ia a a k a d a i Aay auaix qaka outiida 34- dated ka aaaluM bjr * a aaljal M daaxniai if ta a m e ia a h 114 Aay ^Bhna'ia ta l a ) dtad k l d d l a B t a l altarky ta k a On Hup b m T a^n o y k <aek>4M 9aa> d a a l n l a a a ad d a n a k m m c a rt Haaaaa. d a M d aaadac afatkaM d adkM ioa a a d a d c dal cacM kt atikdad taaa a a aacaak XM a f d a mol a n b a r af actnnal tan d u * IIS Tkt eaaabdaa ead lk iaa (I) ka eaUbaabaa naaaa a a a a h k aaw kt I4M 3 | ) l kDM$) if c a tta ta a caaaltt dB aokdkt Staat Ecaata Chat k d ^ k a a a p a a a a ka akaa a^kw taana iaii apteaut, a d de taaCiitkgi d t ttjttaal a t a f -- pla d o tid k aa taciyaat . 114 latoeiea Boat kaatreea adarka a d aaaplaa awa aol d i ) aaxt daa 44a4iM aaakdealm a. lfietaaaameM *eaetakt4tlW t>*i)u> ac aapkcal a a ikai mt ca a a a karaacatyoad. Exygen Research Papi 2 o fSS Page 69 of 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PQ000760 Exygeti Protocol Nuoiter: P00007SQ I * im v n cA i. ttiro ________________ uaofta --| 14.0 M.1 U*.6*im*,^elmi.ak**llKoe<wirfrTOAfc4r,e^,l. <Kooot n rw w MmnoUn) j-- B M i-rr OP** M* tw Soolyohmon 4 M , ilooonooi) ,4 ` i T ? 1 *'*** *1* ! fT O A prior a m w , ux* U M * A U U ioaokohH 9 p m n w m , tm vm f (K)` MCMWtaQll.)] UmtfaoM M * quoii I ooovot li . c w a t of fJOA ftood w 1*0. w upiov*0l0 0WOA M odImM ny>, nmj fn i,} . --tcuoI Kl m ; 11 w'4 Mfojfo*A*y*w "o*^!a*L* * " `1"* *> t a * 0* WMiat of ffO A faool io Oft ttO K km 4 <ffl) d trw ^ h :- m>A fand (ppk) 1 1I00HIn u i mW * ) ) Exygen Research P o p 19 o f SS Page 70 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Hxyjeo Protocol Nuanber P0000760 ANALYTICAL MSTOOD U*ad)hmbm V00017S2 --ibfiamonfM*x i t < f i t i l i r i i l w i r r t H i t r u o m m m a m (Woa)H AjMfytealIMFtey. B^ewBewrdi IMMiWfftflw stMtc*ipvPAtei Pm"iCvHtn-l^L C -lLI Tiebwel Uo*t, LC-lil, Bx)e Itwiicb __ iSkaieL Om twi Exygen Research TotalH w * F o g t 30 o f SS Page 71 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Bxygra Protocol Norober PQ0Q0760 b n nliM . ..............*WAi.yncJLi<gnoc MOat __ 1 *jut (WQA) s^in trt by ttm IV m M i t o pptoyto tor tto iaototaiato nmnrtina of parfloorndM** add Vjr Hi* to tfin to n Lfd OMMkqpnpIqr wayM w Own Mm 3prtiw^rP^iin(LCWMS)ii<otoat. 2.0 to*Qr . 2.1 At o i y *w w tf c laVnwwy jnr.iirnt. 12 CtotoHtot ^ P Hiril i fcCPI totow h id ing m j dwmtol to prop lafay 2/1 3.1 3.2 3.3 24 1,5 A U m t o f f m i-- iflofcfwniidiiw. H i --g )i pn w i l l I u r t i I >c Mrti n w pt . U n p in waM M H jtM i d itouM to altowto w M w lib n it room MpMln. 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SJi rM iitp t iriUi t f nimiimttamLptlitnnlmtmkmmJOOO^B. 0 O -- i i l i l l y H <.l *-- fn-- m H 4>(XiyMi.SotlfclLM n u n io wo, 1B (NH: 4 i Ti -- ii x r c 44j HkknMHtki Wlt-- iU)):: UrMt--l Am>u t 41 O -- lNo-- ; XkKXnfe} 00 14 14 20Q 22.3 SU 6J <5 23 25 15 flow Rat SU ilRLttA) 35 Oi 35 05 TS 05 n 03 35 0.3 *4 M o V l t a l : U (J.(n>Orwmtl m u iclm S a iiL). 47 Qi-- : M M - m r a l i M i i caXMoa m v. .t l a l t a c n i i m i i TWWivi m 4Mm m ktm M pMa b 4 w r 4ctaufaii ioante. to ftiai 4 HPLC >-- . 7.0 UMS))-- T-l U a U X tm n in y X t r n U H . -- 1-- 411 - W W IW 4 m u Mm -- 4U m i fad*m i y W4 -- 4 -- W tattM M -- 10 ta-- kaUM-- e 41 MafeikfUe* 1--K a m--1a0r--00i--(!IIp.n-- 1 Oy ld4iaf lI M io r hnjyi Pot* 12 o ft} Exygen Research Page 73 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygcn Study No.: P0000760 S x y |ta Protocol Nunfccr P0000760 1 AtW.mCM.KWUTO" LOMMM ............. ~1 " til !%wl.iji.eWhFvmdby 1000mL*fwaMr. * Aliwiart^)--wnjjrbtpwywW. 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Aag#3d^ 6) Exygen Research Page 79 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exygen ?nxscol Number P0000760 wt I AffALvncALMrrooo M eaJfAel|iblen im <liiliii nfbfti i S OambtLCMMtf HM M am mi An*<WOA)in!>>*>( M InfMMWe 5.5 Tlwm *. ja m u *rii*nii 5.7 5tH ^eeM e>lm rj*w e lftimbw. 54 l5 l t4fmMiellt n* " | J Pibjiirtli iinrelMI(5b-UlOL. lOMOOuL). 5.10 IISLLOTSM-M MXUK 5.11 3b I.<Iw I*LC>UM. 9.12 D^N*Myripi>. 9.U A W fV * <100-1100kL ^ 10-10MLXwiAhyewbiet. S.U 5 r a te p te U (S * te i L a ^ 1 7 7 ) . $i.l1i6 CWnriaastMtotteeJMM*o.oftjteafJOnLiMtomwJiMte*2000rp*. 40 CWi--PppTmSym m . 41 M ifrnlCaliM r H w p te IP q u i t e * Sctetifc^. U pen t $0 fwo. iy (HR KtfGMKltXO 62 T ^ W i : 3*C 69 MOW#te a * (A). lorfAiniMMMAMMiiW Mr 6 M *W *PtefB): U i* w l 4$ OnimPwfr"* Zabhb} 60 10 6 200 aj &A 69 69 29 29 65 FlowlU* ft* fmiJmtpi 35 0.3 39 63 35 63 39 03 35 63 66 fcVMtotVvtaifcUuL(wWamwd$eiww6si$0#4.), 6? 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M SurfirtJitecrftatatoftfeM * 1-J te|M a MnekaJKte #-100 pjtaL of PTQAby wdjku.| iOm* t i m i d (m w id rputity) nd d iu (c 100rot with w b M l iI2 M U Ik d i(. 9 1 J A I.OjiftaL IrtlfledM aoMtoe fWQA ynpaMd by braying 1 m i fti lOflnidlL aetem to * final vote ot 100li imuuoX UStoLLDVCtoait. t . A M M ^ t w i l w icx MlMi i o f f f O A x jiripn d bylrtHiMtf IC mL *t4* JOpiftaL Btedm to M v o te * af wtb nW O w il& a& U& flb*. 9.1A A 001 jt1!. fcfltfcdhtoadwte affFOA X popm d by towfift* 10 nL f fl fl.) njM * --hiti-- m Aad dun* of ISO wi#> d te d fc a i t t m t U M M f e M i H MMckm i bn itcaim aotvoan 101tend io *i|nucr m Pftadnddy 4*C * d tm Mate Ar t mmtmun. prb4 of < moiekt /*cge <3o/<ji Exygen Research Page 81 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Bcyiw Prometti Number P0000760 hnwiawil 1 .................. \*M,vncjn,umwo _________________________CtaanbytCHB/WS mnOmiMm voown> AcU (PPOA) is PiA ant M SamliadCalibeati SeMaiia i l ' X W I W 11 --. noli paepaaac to mtkmel via A to . ( b a l l Mail. battutati a w w m Tba btiaai i IrjUaJ apple adabaimal o o n M a a may be CCMIMbtltM favi T M U mi Dm iw C--WBMIMI M i MJ ! " ICO #. l t U ICO 0023 1.1 1. 100 0 10 10 .01 0003 U 1 100 0.9023 IO 100 0001 ____ s _____ __ !S____ 300 0.00M re iltfacwffimmieutaih,a l a l tf>?B t*giw a *3A battali wlamaa aod aamaw abma of auaittuda maj be pupe! at too taacbSalUp 10.1 O r t baaAePaaaaplaa aeaciaii rpbeaby 10 e r I.) a m iacbiac ai b . inraalrilliiii 0A awol apAai la wrlpaBca<iiiHtaeevaryIta ibi tota. MU Papio--i la fa Salti nati lAcaaanay dapilaaiaa and a p lu | ba ti f i a d ie ba aOH|>aaaaaaaaeaNm 6 Ma paatan. 110 SaaaplaSlttacttae 1U Wtt|b I I af bea largii leas 30 I polyyittayle tm m ktt bai <lai6(r aaaM. aaidaecIWaaalMa aaal). IU AtitiWati,tiw aatiititiaaM atabc>awrtii acne abati Ita -u incita 110 H a aa b a ataa h a laa a e llr-llw IM Paco aM rao(lMaa OlaOTiahaaaal alla AaamttahacMIlawfca ILJ Taci b a 2 L 9M kibat * laiae i arib 2 1 caia, ] j bea p i. J . aaAm .aM loLC.Nlla. CbiaMa* ba aaaiaaaa ari* 20 ti. c f meihare.1. Oaa 30 aiL a l acaacanmla. Diieaati aDaaaabaa. Da a d alca ha celiami io n o & M aa atte 125 L acati Ottica b* tinaia, ari* he 30)4 U km t by bacai (Urna tictac). Dir ba taba cataoMOr beim a. AbarbpaMrbtarvMiam * ' fP f* Pag* 4 / o f 65 Exygen Research Page 82 o f 110 Interim Report #23 - Analysis ofSediment Samples Exygen Study No.: P0000760 B in PmiocolNumber POOOOTiO __ : /WMmcALMrraoo OMbyLOX&M3 1 11.7 4 5> mL rctr n myflm* a*m o--tttauaa m m m oftoc r D M ItM M aeiw M M aiukw M uM .t.M ky . . - * Calmati.mein fee l U e L r i M i l p w i M p H > M d w mi. w maaaniylla * marta ik. JO L mmn(w u bi * "" 11 b e g e h t ; H w - J O w o M e . w ) n w >1 -- * .... *t -10 w t ef n iiiailn li mm tub.. J1.M Ikakeaaawyfe ip ii f c - i O w l n i ,, u r i .n i . . 11.11 klaealielakaeia.ftaamvfer-1 1 I I . atea-M%alMt fHeee50 *H lF n ^ la.r 1 M m mpia i | . l W > n IW ulama. Cattai fee tata ja aw a> tha th a n am n* m l ll.H kim lO ed.afiaiM M ItitnN |kfeelK aaliinna.daklM ttctlaani tiaawBiyair fewiiiifrw. ll.JJ AM 4 M a f 1 -ooawl Iw a m k * aam-akawd u t ma atm en* at mene yneanammiinaary maona I U I Mika fee laalmktaa,byifelkiB3 mLef 2H laaaakia aeil in natiaael w a f ilia il (ta l aal ill aibWliaol.. l l .i r f ta m A * * a m a n H n c vialeaaincaiaB4MMeam. ll . l t Aaaly amn m mi a t kaiaiiy n yLCfetgMI. 13.1 lOlCMM aal batik laaifla mo Hk ' 1 feile Hl I abavi amfelav. Mm*a(a efWOAammwrmliaiB at lernt Hm er n o n aeaecainricn lavali aawlbalnli(ieiaam Hycalnt 1SJ ****aaamtlaiaL^i^a^mim^M WmaS'Zia'jiio .W fe fee tawaaiif of a aal U m l ty ca k lm a. nane** lnriratiwal aaiyI.|Oaaa laa(la>mawibfaaaaaIwo(iaaaIarIi3 ln k * man * n a i a ita k man te feat nw Ima a io a 13A a m W ikaaad) ky llaam mvmlM aaiw Ife aiBaifei ofaam arca *--**n ttn laa ml aaaamkaiiaB aaiai Mmatym 3J (ar hu#! ~Pttgt42 O ft Exygen Research Page S3 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exjrjca Prorocoi Nuotwr *0000760 MkM. f A nU * fcr * __________ >i-- i iiia> w m n i W<aYTICAtMTIK)D Dmtrtam: o/hrfhnraOTm AcidfffoA) mFirn m ClambylC/M&MS | IJ 5 j a * . lapona MM k> mead rarjknl rimali*. Ar a i i , , mmt m a * * m )w ikwMh. IW*! W ml U.9 AcovtanetCttKiii 13.3 O im m w m --t * y f c T umm3*9 rau ihm paravi f 413 mm 7 k 03 -- fnm nani i n ila iot PPQA amo, tuia ft *u*tt iM<MmnpraMa Iwteak OoiKk. 1U MWiKaksmmaalmaFICAakv.}.paarunIbtLOQif, t frOA a k " * p alam m o .) )ph. ihm n v Nwk anipk 1) 3 m > m i f a a l * * a m l m a i. * h a mm I I m XMJcrs of M rk w n w d im ir . i. m .lk l.m m o a k *,m m upahkU m .D h a imi f mapki minili h* kia*l IM * d k * i * I M . | , i M W ^ | , f c a T m .-w lw w tw Ite .k .M le ik tm rfoibt .c*Jflfalwmmtim*i c*^rv,*,. Ih.*kWmmbm *1 c ooiMIaMd30Kraaw a i i i i 9mt 909W W cxciaCKi cfwnCghyaiaL b*l , J Th. M l*. a u m cw I---------------------- ---------- ----- X U (*' MM). ifm Jkifaiw m k. M m utt. t a . I n k . Hg * f * hl k * i h j w k n m w paaim. ^ ^ m k * l.a .i* w im ^ -- t k . hw U b.rw lyim 13.6 a m ia mm h n m mudali m* mnpla mm a dnR mon mi XhhM kiimmaykalna. HmmdmihMlittinmodiiiMiliviilii. m imlyaml n a I w Du ml n a h. n w ly u i W l U t * MtowO(|imlai a dicala. I h m m i f FFOA Smml : numi, h a il m p a k m ) wing I * m a i u rm {haw a g n a a pawmaenl p a o n i hym.Mai Iw k t a y n p m itehFQA turni ttm ttU -g w a m . fau r^ci 1 Ua to M a n * o p a l m it m it i if TFOAIh m in (hnLu FFOAkm* (pph) *Q W'&aahywhiOillml ia a * { g )......... ifnaoary. h a 'a'i F a f 4 io /U Exygen Research Page 84 o f 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exygen ProtocW Number P00007$Q I__. .. Mdrnc.sLMSrHom .. ....... *tAwlxfa kr no wnBiriwifM rffcimwiiHofe Ae* fP FpIlW irt and _____ C b attfay U ftS fttt I O ft* m p 111 M I U w*k kaov mtwm f PFOA pir >e n tm t a, * * ** n lw tf* imrom ' -irfa-di.ogTOi(^ ; ' w5^3Z2655 Exygen Research Nr*ll Pag* 44 o f6 i Page 85 o f 110 interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Ex* Protocol N un*: KMOffMO ANAlYTTCAt MBTHOD MtowdNurt: VKO|T4 Mato* t f AMl)>h hr VBaacamradlwudbaytlOtoMMSMmIdmumk iu u (w q X) i> Aadjrtka} T a te f FmUHjt: n n w Kca^di WMimwMMv SewCaOei^FA 1W1 A##medByr TaJafcjl Ldtr,iJO M f,tana)taH B <k tz f '-------- ^ ybemJhmiim {,Opmmo9^BxypmUmmnk Exygen Research Totei PtfM: ? Pn& 45 q f 65 Page 86 o f 110 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exyfta Protocol Number POOCC7 Mtn<M-- m ow m . . . VIM .1T1CAI. M rr O D t ofAool)olo fa fa n m nwioHMic^fafaMoootoooio Ac (PP^Ajitt Vw w w o ' faLCftO M t 10 $00*0 TU afa!! f a l l o fa > ioilotloo to faintifaio ofpotflw iooofat mM Or a u o ro nroitotl UfaM O o H i n O cmplad to > atxUa Mm Op t r a . nrii rum H it (LOMWW) n(M*>m to locor t l AOry i l i m > M t t i ) m a im 14 Cwi1l* y i o<iiMIWOfc0i)lio i<>rcliwicolt>|oM<>ir 10 foifafapfamm 1.1 Atfact 30 g o f f a fa'omwOoi 14 l m >la fa u M fa fi ;m w fa Mnctlfa. lfa > f a la m i io * tn iiw iim iy O o y y n o o ilO ty w M H U im io O iM iim f a MM oral b f a m M O rfa iQlii I aOov f a utboa nodo M m Hioi SmI f a f a W i--p fa 1o A tm Mono fa ll I of 14 U f a fa n te rn o o fa n wi* bo affato (* f a Maplioo ffat f a tint faM* O.0 f a a p f a f a l b o f a * 41 Vmt-HKCral. 4342 tf a f a M o - M n C j n * CtofaOOOOO M ob)- XMoMonO. 44 UHhOBOi-MtCfrafa 43 JBM ) (00400 a f a ) - U | M p a l . 44 rfa M 0-100 iw k ) - ( o y r iy O o 4? OepoidMiUM06- **e* fa* 41 l-O rnfa-K FLC.. 4f I I w f a o O -O iy tfa i 419 41) 412 M m w Ii--A w - A C lI m n f O n d 413 NftwWHiwK fipy/>li4 50 Tnitwaif m i F f iliw w 5.) A U|fc paritaoMM* SfaM tiw > ifc)in4 twpM * ef ym ipii| tp to ? m tm t vili miaMi rnkmm y** m ggM of ^cetir^ $ . 1 ftwfcuMinrOC/IHS'Mg) 3.2 A *--w* ottw** m far pmk ingr'nii u ti qw U rto * . >1 Amurnoi M m giM* ofn ato IQ0.00001 $. P a ft 46 o f61 Exygen Research Page 87 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exygen Protocol N urcten P0000760 mMMk ir VWiTM ....... AiuimcALfcomaoo.......... ' M t W r f A w dyittortoa Diw iiiIh i Ibii ofParflaarooctaiwk AckAOTOA) VeteSiST bylCfcOMS 14 lUtwyt^nntnr 5.5 A q w tly b . l i Sflwl U ftn liliH ffw ip )> w w i ih |iato i. 5.7 ffa. SJ n iiim H i u l.... . iii(5IOOlL 1030CU 19 -- u Wtto. 116 Iw L U m tm jC rU k . S.fJ ttfI M U lto lil . S.H Aw--igton <109-1009pL md IM 69 itL).wto> h tif*. 5.33 S ie e * 0 W < S i ri* a * .e e .> e )$ 7 |7 ^ S.I4 W ill M in ih lw 3.19 C triB m a p rillt fir ii m i3 P L |o b>wylt <tttoOOiw 4.0 ClinwarctoHSyaMn Al .4fyowl Ch-- a W t*|hm KP(Kylc-- Sei--rite). 3.1awm 50 nun. 5y CX04QI3) M T u w n rtr 3TC A3 2M Am iaadMi Aotocc in W *r Mcfaib Pta (B): Mrtoinl CMMMhapitt.* XUtoJBfl M 1.9 1.9 309 223 95 95 25 25 43 ntnrIUU *1 35 9.3 35 0.3 75 13 75 13 35 13 M l|i*ri*V fcw ; l5|iL(wetoemHIsaMdiei90nL>. 17 QnMfcihnr fm k Am-aPra^naodanlcri^fM tensurvt 1t KmTIm ; -23*Uu. tbariwttwfM--i iwirtwilH--pridmdm>yto<hinl ordjMo gtiiwMAOTCiyitia. 7j9 MSAfSBvM 7.1 Mwte Pt<Aoptiy NipMarlfl04 770*. mowwrifif 413 -* \& m tz ib* # ip ) ft PagtlTafSS Exygen Research Page 88 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 E x y g n Protocol N um ber P0000760 1. . M U tractL M IllIO O -----1 * * * * * - y*a " OftMaotooMMijom puto *) m r,W in ortn 1.1 MotfiPtoM tll lall. mate * torto pnpnd byton MM( 0/ lOOOaLofwta. U S lflk n lilil " "P " 14*"*** t f n > m ^Oii^lfktlWInto elrowkpirondtybmeuiaL e#M fcytf rHlirnilaa SeaJ v o ta f 10mL witii tokuoc. AJfcranwitaMj-- r b o n ji m i MA ' . . ---- ---------- rru \ oy wajrana ivdu I m M ftr parity) ato m IM m!. bk A.aM2 KtoM lto lU o i. LO P tm to ^ f1,*U*}L*L*D*fl*br1o"to"*ttrroKlU' 7,bktowwt 1 I IttnlLPIttoHli>.U "*** * rTOA P"*! *r>TM**t 1 tkOlto U n | U t k k ( ii> o ilib m km q f IbOwitkiatWicl m t.M * " **" " * *fptoai*pntMMkr M** .U MlOkaML ktof kto1ttloLkLctOkLnto--tkoto.oa 10 S u l veiun of 100 an < R M iM q r 4 <C M i N k ii ib r im im n poiod o/6 moori ftoa * dpi* ofpwfiMrfii-M. 9J f m d t a Cttftnrioe M ita , A ' if **** tottoto ro.Koto kflto 1.0Mftol.MBMn*lMlto. M t o l vit diwen M1 xygen Research Page 89 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exygwt Protocol Number P0000760 [ analyticalwrMQO MtoM dAMitymfcrt o OmmmMimilM to n K U M it A4 (M^A) i toratCM bjrLCMfi/MS 2 1toawrnIlypicdgon^r Mattonaicramtiomtmyto C M N ujgi i M f m i Vara ---------Trai------- OM Cl-- torn M K wUto M J i. u *09 0AU *1 li M 19 w 19 OnL) w Ito to 100 Ito 100 M39 MI o ra u ro MW ___ l ____ IM ...... MOM ra t au tiifcnBflft mmtorti fe i i Shal l p w m irow m m r a j 21: * * & * -- 4*. M.4 Arami m i-- m i m i u n i i m o f i t o f e mayW pnpind i iftc tochll* t a l Bn to to og i-- lw w--m d KyykJy lm) m m inetti k tu *mm"*mr da p*mr(al*t*omml ^i mwetimyymM4temmii*ieefweriyifefderitobtioicml. to.2 Mpiir-- I r r id a m i Itooattiy ftprmw m i g to wBI bem^ified nun i ptmfcfMpDjaoc. HO SanpttBxratfc ll.t Wai|fc I i o f fie ra to te feto 90 a l, polypmpyt* cmtri&tc tuUt U2 (fetb/y t r a lto. wpfect Bi md mi mtl). A M M ^efm m Btotm lctakeanaw naiaeiioii btfer AmU reMs. H J CininAitc t o 50 mL paJypnn** tufca ttntiumKf Ample K -2000 rpm 114 * * * ' 31U M ira, m l l i LC'NHk r i Arrian * *>hi-- 2*n - f -jf nrmftmrt Oho30al.ofmamutife Bluettiai)wmKm. DowtaUa*dieng-himni **IM S * 1 al. p*N k*tf t u ly riamt n j n M v W a B W U -ie w lw B W * M M *nuk.i*tkM e'. w M trat WM), fty * . (M i m im i; M n 11.7 * k ek y * * } ie|iin rw tem ei fBeep ^ e.* w * WtM i*d sreIwn eiwdM * w.*w ,f * >*> < ** O d M W W w l a k t l ^ t l M u d w W n P i 49 o f0 Exygen Research Page 90 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 Exygca haloed Hwnr P0000760 UrthN fA-- nautical e rr a to fetta Diha iMiMirB o fyiftw im n -- k Acol fFPQA) m Vc-- lion tytO M SM S 11.1 AMXaLfaiMiMllitinpliAi)lHlBHili|itaW 11.1 ttrt -- >111 n i ir r-- *utM. n .io c u r i a to 4* IO flL d i n iMKNlsbdl im p ii d 2000 tpm 11.12 M pU JttiM feiU t pia. I M I AM M * * r I Matt tta w --at Om ?tm * * 4 Aa* iod iir^iumrtit rnttmad; imiiw -- f t f--ry nyiPrMwft * 40*0- It.U Makptt* fall citan, fey attm 3 it of IH awwtw Mi ia --1--d t C--ttrtrtna*w4fMMiMI--h, HJ5 H w M tta*w lH nC viM N tt^ew W lN ^ U Jf AiMpt --M tfcf tloflMj* tOMSflO. IXQ C feM lW M ^ 12.t lapaatttM-- ----atcfaahat----4. itwpli --1fcrtiiarf-- tylc im the C M SA api-- A nfihirtiw fodsrd Mt prmcda ml fato al! MtipaiMBpfc* 112 3----daofTPOAaaaraapoartisc tort lat tr tv m a n cumriwrtoia lenb n W A M m tm ifyk t*L I U A Mit Mt of aotacwl talttirtuo a n d a rti aouA ha iactedad at Ow fetjiMriac m i tt Mi ai a -- pia art. Ks-- 4 --aderta cauti t t mtaaapc--dbatvcano--yS-IO--pioa. M -- rta-- rtivo m afa# w af m n a id attttntioa -- tari oajr fea Mpwwd tfao hcgta--ip of a tat fcfta--4 feyM i M cafehwlMi --otarta 0--1-- 4 ovaty 5-10 aunpiu m .0 o aaouta Amtt h n m aalof t artr t P r t t t i ) . to fear caos. owcikJ Bbiti-- M r tM t m m ha tt in k tt hatfe-- cakaoIn-- opta 1X4 Uta few r omM -- h r quawfeali-- U mw Maidod corrai an pMHM<ftrttotr t iyrthyttM it er--too tobt** --Itttfioiafp--fc tt* m m nMhntiw m M c-- frati-- w o Manly-- >J (or qurrticMf cotton y--ft. 1X5 MpkvopoMoaMomwartnMnap-- ayampioihot w r til--lort--p--tafcaiMfeaftrt-- dfortsd--lccnaly--i 15. A map-- raCMario 1X1 Qv-- C--oaMtilMwapcakof *4--0*01-- * 344 mm Aon cyonut f 411 mm. Tho 413 o-- p m rt a--porta t ITOA *-- <M* toc 4n#oar hm(MI awo)spN-- mh m of A m tm t. h^ort? P a g S a /6 5 Exygen Research Page 91 o f 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 E xypo Protocol Numbv: P0000760 MadwOhniirVracvm *x'Ai.Yncq Taco -- IU __ WO* M i oaaaa Hw t e LOQ. ir> WOA>t e * rm rn do O.J*0, ten i a Midi aan.lv IM . . O te . * io M U*MhteuaBal--W0.- * . . )n m of tertam o n te a. r r . i y - . --~ifTa,, ,,, i,>i| |- . . MnMtlMotaOwMWiMUrMM. IU Aoyntlfcwilic iwofccf te te te I 4 anteara) tete by aan te Hua *" Tte mmr U cMa) toa te M i t a f t e tefeatet cano Hwwxr, t e cal HMtbtr faitean. . - - `Htea bm i te awWM MetaaateJOHi n M i w * r e O M UJ Tte rnliili H H M tn t e Hateo. am a paamM OUX m " * V a 'at e t e atea W aaaaWa te lunit, te 0 W * " apa m te ateo teja fr-...m m r - , _ . . . ateteten te ia te te M o f lir te atete) hanoter M4 toaaaaiao tea tatem atete* ate opte amia not *i* ora un 1 4%H a M anjetete. tfteaatMtwteflaatMtdahniraniiao m alyal no tec te te n te te nam>ite. M.1 yanteteateofayadc a.caloteat e aaaoataafpFOAfoted finrap'ini.. laate ao paak ana) Mina t e a t e t e corva {laaar raaraaaim paranaataaai pinm i r byt e Ha l.yoi kaftwaaapaop-am; PPOAte te (faiL- (Iate ana. ian~n nop* I4.J UrtMtet*eXMotemnpwtnioeaiviaiteawoaiomOAtetehiiivinLu >TOA te te lM fc l-lteOA ute faan .n . Un! V .nnl-1 r.i| aanpl Wal (j) t e IPOA prior aclte. i *aoaaiyp*[ m a l a l a n t e t e aaafttatetemacaaml W l ) ] afraaatete ( i raaiiai'i Page U a ft Exygen Research Page 92 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PQ0Q076Q Exygen Protocol Humber P0000760 ANALYTICAL METHOD MnlnOlnwHr V00017W - MiiiHUfMlpiifcrtteflwMMi-- Adi(ryOA$letm>i . HiiwuiliM rbyUVW M liymknwih JMtStMMKb Drive 8NCoe.?A 14161 ^ r ^ i r A C nrmlrnfll PnJCraneOy I Trefcufcal Leedac, UC-M*,f c y y Wmmtvk o /jlu iM ____ rViaPmirtani,OjtnWnM,8yf1mat* Due *A / r . 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Exygen Research /age S3 a / 63 Page 94 o f! 10 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exjf|tn Protocol Number: P0000760 1 *A*i.VTlCALUT01> ... ...................................iiliiJ iT^ <lii.itgtl.n.lt AcMffPO)5'hail ________________ . .......... 1U rrrbylC /N M C f j DfcpMUapif* 1)1 1)) W wS^MVwl 1)3 I H w ww-- l ll 3.11 - -- f l- $.14 WiiWMiMliateK. l l i h tiraint 1$aLpofrpwyytantu b * M KUrytn. JO OtMHlPWiM l)MW 4.) (P K 133054931)0) ' anniQoft.^ o UM M klwf IrtlA n .o U U i.W w M MbinwM(B): Mrt--I 15 Ornmk ft> y : FfevRjU h A & A MUt 18 13 33 ftj 1. 4J 35 9 ) 10 2$ 75 0 ) 204 39 79 19 213 85 33 U bpm V ahM r 19 QmOUtiar N it Am 11 tmTmm Wwanacb 50 kL). **M*t ulibntttoa cw n lfcaabwQ4tti>acaiiBHnMi*|ttid*laiy Wchao^M inwdir optiniM*lVtCMn. 7.0 U*US SyrtMi 7.1 MaW; BMkMpny WOA. N qtfw M tM note. 0M ttU | 4 t ) - + )69 nttr tor . I te * MOiJtioM * a la M a> p * n l iy W hup* 4 Otfatitatha MSMB qfMML Exygen Research $4 o f i J Page 95 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 E x y i Protocol N um ta: r0000760 MtotoKiO rwini L A*<q.vncAt.wrnioo Kw--iLiwbrlotena~ito<to'rfton>;fc>iSD-- l n t t o o f rri O n r n w iU i A d<(frO A litaM l) [ I I ttoWtoltoH 1U .l M M n im i U M to M b KOMCto V) Mio* ,i>* t M M t o I * 10 MWa L t f wtor. AHanMttvmmm wmf Wjn p n i. f.o Sm dMtFnjMKfe M ta M to Stadfc/ftftiioto Sotok 9.1. IDflnt U -- ty to i m ttiu i (wnwiiil ^ purity} wd A b u> |00mL with M tM B la i U5hkL UffEbSRl. * U A 14 pjML M B ttt m aotafeo ofPFOA it pnvotod by fcnn*m* I L o t to ICOM taL toW fU dv6)um ri tOOwith iuHMwif tatlZS^LDTZtoto. M .J A0.1 m W M iftflOfwa >!--r f f f O A tty ppMOd by 10 L o tto 1.0ujtaLtfuttm io 1 toolvobnt a f)00 wstit i 9.M TWatodciodfcflUkflNnmOtom* Mond *raftifervoc* MpnittmaioTy 4*C mt4 v t mbirn far > u w porio* a/S sH*uh 9a ftaodto CitfarortooUfatt--i All OU3tMtoMaij5ofWiaiLWfatroiJtioootdo--rt#rnoivt)kWm,(poridyiMtoBttvio4toi<m 9.2.2 TV to to iv f mt typte UMplr aA&Mftfti MecnCntioi m*y be pwpwlMC--ito. "SSSSnSX ` RST"" finiftiwiai V ite i D il*tie OaUAiafoAtaL) ...wu . ImU Cam nen IM l IM i.p IM 2.9 W 1.9 WO CO m JO t 10 wo 1) tP w IM *3 .___ u? __IS..... m ft! 9 J J Skm f f tn o o o w totlt kUS-m L LDfS am Zm oM k W ito at 2*C fa <*C, wf ab o o to otoL90.4 Afcwu '*Vmm *4 mmwlnaitot of wm tirii wayMpwporad u P a tt S i e f 65 Exygen Research Page 96 of 110 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 B*y*ra FtoikoI Number P00007SO " W . . I . VWHU A m LY lK A L MITMOP ' MMbaSofAaalywaAriSalba i M illia a f Fwftin n iiMiuta AcU(yOA)iaSiaall' MaMaatUaarbuLCIMMCI m s kucbttu MU Saak ta*b * f MMptM a m a r i M l l l f iS aa laaa) M M a * K kan " * aakal 4 " o m m aoaBota M M k a m ... I Summ >la)lTwi<yt ro 4 ^ r liW 7 fc n > k >nh fcftrtJ Mk litMay Mfke * 4 + k n win I fea aaaMy a w n iM p m ** * jao aat IIS Swafrf*tttsM loo 1U W ii^lfsrM fM lM sslSiaLfalyFnpykM tM M IIisiM UM ftnKVH aaaM,Kp<aalMaa* <>*<} Nmariat ikm aia Maria ru r nay b< M a n i * s d k | m aia pis Mm rallaM kr >m. Sj ^ " "t*[l*||T|s|*1>r*.ll**f*--uoad. 1M Tnaaftt I mL U * urnfto balm a Skpeaabla s a * ina a ! mL -W------------ *-----11J AM>n l afarim ikilaaMMika h e-2 a u a Ioa a w nantiloa itili 11J r -- .A jataak aa -XSOrya far-3 aliagli 11.7 -Dacaal a mmmmm ..*..a...a...W.....a..t..t..S..iifaaaHa aanariAifa Mba aas <44 7} aaLafaate. I U *a n a ja i (I fc S b fai I a i laadBoal ftaaa<b|rlnLarmCwalar{-}^Aac). 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Mm Stori iiMraMivcw w *mtmimrnmU uHbtmb*Mmwmni bdwM wry J-lft of m m m atiy * ft f t * - * * i M ttto to d by f t- !1* * * *** *!10 `V**jf t OOWMfarawcood mi auotM f) In ' ' ba lbs fini od Ism irysctjcs m tt.4 Um lo m Madori LbmtMAdani stavaI an r fT r iiii wrr| Inr n|hiin | nfput: MCI NOT Page S o f 65 Exygen Research Page 97 o f 110 interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 fexyi**ProtocolM unter P0000760 ANALYTICALMETHOD Huhod c f W ) M f r 0 4 S o ondM ea afywfVMnortbcr tr AMd(PfOA) in Steal M * w t U w ly 10M8A9 wmm wlhnrir lundvd oaeontotiMi M ag M ml yiw J 3 { pi}) i l l f,--It m fm m * w U m* m tm i Mntort rmpamm. Any m m i m OMm m m m m mm* ftntot OUumo M nmoyied. ibM 13,0 AnmtwmOn*** 13.1 CliTWM>fTmm m atoir *yU oftdoM O v vm at 369 Own a px* f 433 mm. Tto <13 mm pmm iiwiMfnidi I ft W M uto. tin dMftMiM 0 m ** tvpuMMift* ten ofaotoa dtato. 134 Mei*4 tied W W * e l * i PTOA4 lm 4i jn Mottfaw ilw UH>. 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W.J Uitoftfi*fc#OtoMjMeafaiitoitoamKorn0Afctti4{)iiiifnL ModOAym k na)BangtoM d cvrv*(KamtnfmmiparutMUro m M bjrtto Uaat Lynx Mftwaft ntfraM: HFOAMMftfteL)*OftfcJBldBlM&aO.D?*4iqMftotar W * <M r by whM M final v d a ww ctikMC if tweHry. AtowMftcMf 10 hfiitT t*ttS7qfS) Exygen Research Page 98 of 110 interim Report #23 - Analysis o f Sediment Samples Exygen StudyNo.: P0000760 Ejy j Protocol N um ber roOOOTSO tltm t -- > r iM M a H W II AWALynCM.MgTHOD ............. ~ 3 . .UamMUwtylOMSniS Mia (VPOA)laSm S H J Pet unpin M IH I Mk t i n t unnmn of rTOA prior 1 umnjoo, w ko M to n f poppa* nlnM > h i p m u n tM ). RnowjiPU"' . atyuaMMMlIfaU * 14.) Uw > mw RWMW ip ewwrt tt* ir w it f FFOA 6>mdin n>mL*n Exygen Research P s t* S t e f 65 Page 99 of 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 E*yteo Protocol Number: P0000760 AKALmCAL MBTHOO M utoONntar vooci'io rfAMtnh bi-ltMP ialwn Mhlficgnnmilgl frLOllKMMmtMiiMili AOBITWJ;)! 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M000160 | AWAlVTICAl.k*THOP "^ MiirdafAaaftiOyy iWeieileeafFefliieriniaeiiiAfJd(^FOA}u Small M iw IS e w b y U D M S A IS 1.0 $op* TMM h M l tlM mfkym I h r A * io hriow m4 yieithere erffirflw NMUw it t* &T f itM iin U fM Chreeeempky uplei tt t untern Me* $ * * * * * P m m m {LCMIAtt} M i IM M d mow. 10 Mb) M 12 ACaba^fMlBf^tM^tWMp^riaUpibMifiiMRynyiSnMdibMrviteANiasychiMeU fcrfcopwefciy 10 SJ.1eqattAXthaqeaeinlMe ell'f*ee--ptoferiibeiton 32 N***e*e*|t--efmMto*A*tetwvtdbha`epfcteij e mmlenper a lufcwum. 11 S eifte MSenttn y m e ie e wfll te e c cifiod in the empties plan for tbu yeejatt 40 I4n]neWree*arS-Hie7telrfcjnte 1 MaM-otc** 44434J \Aeai eoenMteel iA- HoaKttttC- yAt.Ce JLImpel Orate Muea*taatfAetf-Sy*AMri* 3.0 lettanM etanABypeal 11 AUypetimMeui by* tlwfwwfr^ti npatteI puopi*pts 2 jDiLinraeene^*n**at*te^h1erMetmtOIlahCwMbiMi Uipry(I*C*WepMMS*),of*vc*if3-2U0 12 A te v e a ttw te * wertet far jufr u p e w M aiyeftaieke 13 AretjtealteleM eprfteW retfue O.OOOOI 1JJ4 3I0Seelltedp^reewtOefTopreyflyrypartaeptyekMe ternetielttterpeievbhrme.. 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Ajfrtfd</42 Exygen Research Page 101 o f 110 p. 102 Interim Report #23 - Analysis of Sediment Samples Exygen Study No.: P0000760 ExyjCB Protocol Number (*0000760 *** 1 Uofto4W>Ajw)ji ANu.yt>CAL M im o a Manratf S m m by IjOMftWS IM M ManfeMV90#l*l* "J k Acid(PPOA)ia Small 1 5.14 W ill mhwiilrtwr 60 CbKMH#ibM(t|Ma> (1VN:CMS-I1U1M)11 matytinfttC oktm :n ftM f tXnyPco.Sinii60< 7.1 m . 20 .2p U Twftftw c JTC 1fMt2j IMOMltHMb--5l.intPaewmiWy<ifu):: 2MmadMUAMmlmoniumAMMtaW Flow KM* & 1 fatlAniwl 00 <s 35 0.5 1.0 H 35 0.3 L0 21 7J 03 200 25 T5 OJ m 5 55 CJ 1 beeelm Vriunt: IS p i ( e t w m l wO m 30 |iL). 17 quitiM il. 7>akAlM--Mttl>UiiMc>l>lx*iaaxv. 1ft Rm Tim : - aftMUNUC. nulftew d ' li-- edniiftim C ijiftB i nd ~ J i 6>MndimitBW 10 MSAft53yW.il 7.1 Mnfte giM uiyiyNftlwHm noJ.eio<lnilftll rrOA. . 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IM M aVW W AXAkmcAi-wrHOD ' MmaMiSamkflOMSiMS SinSari f wfm m . a i h d / M f a i n 8*Mmw 5 x f h m * --&kutai W *- of KOa ty *4<olnli>n if wlyiii rt w W fumimif * prrrtfl an UtiTT n IM !.>> - I - - " -- U AI. fa t. fcni&xli leMio <FTOA Fafarad Vkm* I MLfAt Iw h u .um--> SawivtOumaf toonahm m i usBLionhm I.IJ aAiLkatfflMO Ut f cHHiSklHLiamkkiihaMa<hfTilOiAmifiin(MllMkM]rkiiaami>i1a0 > 125mLLDK koala. 5.1.4 I ta m k a rita M m a o M iM iin i W a to n tfia > ra 6 i| * io r If f loaiowoly 4*C Md o lUkla h r wanTOMn farlpd o / awoaha 3 IrniiM CalikaaHm akuleai Al tCMWS lalkiaBaa aaaoMa frapiaod wk-- l nianliii fk o a i f f s l OnWlinini lnSrn .2.1 Tka m ioWn I O fiM l M if k d d m l ih ii oo i > I FM VaMnt M4h Cmmmmsa* Injurittifir*-'* MD tw U l U m 1.* ICO 1$ m 2.1 ICO 5J IJ IC MC KW 0i.ti 21 s 1J >100 MC IOC M M 9.2.4 rC f* G ip t ihsDonii. Akammolu amaamnaieaaiofumdufa *yU paafaradm 100 SaaeiSeU lf.) ( t kadi of am* mal (typaeally20 olaaa>mm toeluia al an au Iiiiina anl Md Mo oimnM manofc fcrtiel o Inawn 10.1 mian--fr--r*~~ *~r*~'--- :*rr---1------- - **-***** rn ....... l to OcUoaOlaboaaaoaydaptlceuaaod1t will MifKlOw 1|MnaakayMMfiwnafl t* ft* fifjaai. noa, o' Pat t 62 c f iS Exygen Research Page 103 o f 110 p. 104 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 Exygen Protocol Nunbbmr 1*0000740 toy* I MmW Mi.wfcwVOMPU ajuiyuciU. m rn o p Md)dfAilybllbrM3rairail1iraifT *iinrairaMii Acid (PPQA) to iaull MraMuDmabylC/MSMS u o Jm tkltneiiM 11.1 I liu m 1raif rarayli n SO I pbtyyrapylra u rariftiy ml (fco.fr m nil 111, wfl Id raid * oU). VtU * u d n * wHanra bf rawm I U AdaraHrraOraiwMfeH * m Wrauof 2M- Csttgdty 1L3 11.4 VMir iKi tlem-iMl ft . -->1 sky l i pniM r f m IJ mi dra|Mblb s n d ig lab*. II. Aral1 ra i of uraaniral mi raubfat ~20ram m ra uut.clran ra4< II.4 QSddMMrabrara-JSCTryrato-draurara. 1 L? ft rawt o f i s r a r bin i T* i l f *"*-- *-** '* l i t QsdM u toC raO T rabidyra l l | 4 m i) 4 p m | 10 I raiinl M m adkr*sl.<H rU ;m M s(-*toy*K ). Ooradls u S su r i* dry 1L4 Lradtommyli ramdkioradCiiirP unndlx. DracradtiiuK. 1 1 .1 6 N s wi* -3 *i iintrail. CKt ] L d u n in (nduMd II U.rMMnNM SMri*l Wbd(llwl *'- 3 41 11.11 Aradyra IM ill H > l9UxO*xm*yLC/d(3/US. 12.1 bust t o Mraacral of racb llrayirad, n o f h Md feud'd Iranplc into IM IOUS/US D M . A oSfantia Sradud a m t fraud* *o4 M o dl lid | lid -- ||lra IU B r i r*- r~ ' - ------r- ..-j - - . ----- -- i-- i. amtaiadxM a uMera rat 12J AOdra Ml oruUnWM raillid* sura W lacMmi m lie bcfiiMHU MCII tbradolraraylHL S r a M i raw b raunyraMd bateua 1 fell iiryl-rr A m U rawIra m din rat 4 ulibnusa *idsdi nray ix b u n 4 K 0 utlraina t l i Murad by u u m u u uuntt um M riirnirM aM aplM levM iadfc'taM cntN t'j'uMdaftk). m dtbra M , u&bntiora Mradwdb m m b lira flat ad bral iaicetmi in 124 Ura dura madrail twrara fer uctuuloa LiMU aluidird u n s ut yrarawilto to raraljMby la w ravsraarauno* I/ wiifhlitif atyuk era rsraa u&bnrtMM>ludd MMelradM bras MrabLyiu )J Ira s r a W O wdraraa lySiSI U U m flt m yUl ibmdd w su e d uindsd m um m . Any nmpla 1M1 urad totdsd nuMMMirauUb* totter dUaudraidrraulyud. liralor' Page i l o f i l Exygen Research Page 104 o f 110 p. 105 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 ProtocolTfciufecr P0000"?60 tifpmMmmkk 7IliftiiilMn nm VMH H i : ANA4VTK4LHlWO..... .. M rtM c T A S ro fc to & ilM M lto n ^ w te rim rtn iitm A*d(PyOA) in Smalt .. - - MMriSmaftrlOM&MS 1)4 A M yOM tM l ' )).l O ijaM >pa K t a l t e v i p t a t o f l t a ^ t a t a MM a (me ip v i . . T. 411-- . t a i i n u m * m y f O * naiv tail uw 113 u A iJ M a tt 1 * WO* m h n k m lm a m t a LOQ. If * UMap*ltm(BmHiImlOCtatMOlAMdMttafltWaOwBmfe*fmtMmWmM1teaIMgtXeLSMtiad. am t a It U ) M W M tof ntoot ^toft nto MMriaM toi --M to f c w --7CH)0Hof . to o M m M m . H i w i I to M h M t o t o -- M b h bato, ,ii M tf ii a f ( N * N U b iH il itw i. A * y M i* *lmjto ftlm M M to M i l to to t o n aitowim if n-wnrnnan * natal . KM Aay a i i t o M Mm * to M M iil cito to tag t o Hmj iM bmI Mtol--lorfMMiIqprita 1>4 Ito m m M m tolirtta 0 0 fer i i f t t o cwvw p H n M mm to i M n (R* to-NS). |f itM Irtoi i w l i tJ M to t mm lin , tto* taf* m m bn b * ta t* fcMfMMT apnotia*, md * toM * to ito--t Mcf--mIh M H torwMlyito 1)4 taM iM tom tatw* aato*i to Mnptw m m w* On moi ton ' i4%witop--lytirilnm. IfiMmto n*cdriftcMAalrnwh,n mtoyiimln e * * ti M WMto mmttyied. 14.0 Cafctotow 14.1 U m to fc P *M | to M to c M w ta B to m m tofP O A fom d (i* i^m L. tond mi f* k mm) mat t o < M ur* (immr m r w iw yum m ut) pM M d^teM m L paiitonm pw totITOA toto tN to ^ (Zaim tjeiHaall * DPa toter E * to arto ito t o Itoel voMme WMdtkWd, if aectomry. Aftor- 142 Per l|iM ktiaA witfaImnm waotaM of PFOA |ver io lumctoe. me to to lowiMto*1-- n mtmhm t o pnrmmmoimy. > " ) (H) omlmlymM--ngtol) --frwfcMdfatoaanUa/!.)] _____ ;_____ --M talta6 M U _________ H**' Pogt t4 * f 6$ Exygen Research Page 105 o f l 10 Interim Report #23 - Analysis o f Sediment Samples p. 106 Exygen Study No.: P0000760 Bxy$co Protocol Number P00C0760 Utaiui AWaUTOCU. METHOD M ama) i n ty LOM3/MS VMWI7M iM ti- t o Um A fe&Mria| a^MliM to m t tiu acxmt fPfOA fniod m ti|ftnL u " flA Hwniri fTMrtmt >i Hn^ --tr-~ fnml ti W f b n r f w <l) Exygen Research rap?*? P a p <V o f 6S Page 106 of 110 p. 107 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 senrE\ygRESEARCH 3058 Research Drive Phone: 814*272-1039 sute College, PA 14801 Fa: 81A-231-15*0 ERQTPQQLAMENDMENT Amendment Number: 1 Effective Dele: 01/188 Exygen Study Number..P0Q01131 Clent Study Number lofi " Hone DESCRIPTION OF AMENDED SECTION 1) Analytical Procedure SummaryV0001780:Sectton 9.1 7) Verification of Anetytlcai Procedure AMENDED TO 1) Add to Section B.1: Section 9.1.8, Alternate weight* at stancfaitf may be ueod pmpam alternate concentrations of stack eolulione as neceeaaty. Alternate level of fortification eotutions may atoo be prepared. 2} Low and high spWnQ lamie of (he analytes tor each matrix may be altered depending on sample size auaHoDle tor extnxaion and/orto cover enMyte concentrations expected In the empiee. . . . . . ^ BATKme 1) Wgher ooroentretlon# of etandarde need to be prepared In order to pike the sample bottlee at higher level. 29 The ample size avalabte for erne mammal her end aerumwee emaler than expected. Spiking at the predetermined level* in tea protocol pule the spaced concentration tower than the detection limit. Also, the analyte levels In the gnxmd water eampiee are expected to gmatiy exceed *w predetermined spiking ievela Sited In the protocol. When toe level Intoe ample* graadyemeed the spicing levels, an accurate mammy value cannot be calculated for toe Q C sample. Higher spiking level m the bottlee win cover the tnotyte concentration expected In the weter wangle. _ ,, IMPACTONm O X The LOQ is 100 ngfe for a 0.1 g ampia o smell mammal ttvarand it 1000 ngAnL for a 0.01 mL empie of nel mammalaerum. Higher levels of spiking fo rti* water samples wtf ensure tiat mom Q C recovery data can be used. ir Wtm U SfR V ID :W O O O t2JM Jfiurfo _ J ^ * L Exygen QAU Review I A S o zi i f ADMINISTRATIVEFORM Exygen Research Page 107 of 110 p. 108 Interini Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 n RESEARCH 3058 Research Drive Rhone: 814-272-1039 Stet* CoUeje, PA 16W1 Tax: 814-231-1580 Amendment Number Effective Date: Exygen Study Number PROTOCOL AMENDMENT 2 03/07/05 P0001131 Client Study Number PeoelcM Nona _*_S_R_S_I_5_i_K_J_K_i .AMENOeOSEgnPN 1) Report, page 11 of 85 2) Teel Materials, page 8 o( 65: PF08 transition monitored 499 -> 89. AMcNPH>TP 1 ) Instead ofone ftnetreport, interim reportswM be lesuad. 2) PFOS transition monitored may eleo be 499-> 80. RATIONALE 1) Due to tie excessive storesof the date tele, Interim reports w ll be issued to allow the client to receive dete In a ttmefiermen u m-- '- ei^t/nr -u 2) The API 4000 LC/MS/MS systems detect tie 49 *> 90 PPOS transition with greater ssneflvlty than the 499 -> 99 traneWon. ,, _ _ Jiiu IMPACIQN STUDY 1 ) The dent will be able to receive and review the date more quidcty,. 2) The 499 - 80 transition can be detected with greater sensMMty; therefere, giving bettor chromatography. awdyOndar Exygan Ummg 55 Spereor acn^CM (lfrqi*J) o IBAAJTYICSVW0122W- Exygen GAU Review U e o lttk s ADMINISTRATIVE FORM Exygen Research Page 108 o f 110 p. 109 Interim Report #23 - Analysis o f Sediment Samples Exygen Study No.: P0000760 n RESEARCH 3058 Research Drive Phone: 814-272-1039 State College, PA 16801 Fax: 814-231-1580 DEVIATION FORM G eneral: X Project Specific Deviation Facility Deviation Panelo<2 Date of Occurrence: 04/2WW Exygen Prqject # : P78WP1131 Deviation # : 5 Client Project# : NA Reference#: 06-076 Regulatory Driver: Deviation Type: {lochxto V# far m ethods and SOPS) GMP GLP Other None Sam ple Peecrlotion: X Protocol _____ Method V#:NA Notebook reference: NA ____ SOP Login#: L0008191 Container#: NA Lot: NA Summary of Deviation: " ----------------------- -- The three sediment samples in L8191 (C0172892 - C0172894) were originally extracted wing the sediment method V0001782. Poor recoveries were obtained for PFOS. PFOA and HC PFOA. Because of this, the study sponsor requested the use of an alternative extraction for these compounds, es follows: Direct Injection Method: Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A one-gram portion of sediment was weighed kilo a 15-mflMitercentrifuge tube for the extraction. Ten mMiters of 1% acetic acid In methanol was added to each sample. The samples were then shaken by hand, vortexed, and sonicated for thirty minute The samples were then centrifugad for -10 minutes at -3000 rpm. Each sample was analyzed by LC/MS/MS elect/osprey. '' tht* 'n* thod "" aptabte data was obtainedfor PFOS. but tha recoveries fo r PFOA wto UC PFOA were sill poor. Another alternative method ras then wed for PFOA and ,JC PFO A as follows: Alternative SP E fctethod^The samples thatwere prepared In 1% acetic add for the direct injection n^thod were used for N s extraction. Five m#itterB of each sample we elfouoted Into a SO-mL n W u o * tubeand file volume was taken to 4 mL with atar. The samples wore than cenWfoged for -10 minutes at -3000 rpm. Tha supernatant m s then loaded onto a C ,, SPE cartrxfo condkionod wlthlOm L of methanol and 5.mL of water. Tha d u e * was dncardod. Approximately five milWters of methanol was added to the cartridge. Five mimitar* of eluata was collected W o a oindrojpruy8 polyprwten* c<n,,ihjC* h*e. Each sample was analyzed by IC/M S/M S Cause: Preparation Impact: More usable data was obtained. Analysis Instrument Client Request X Other LIB R A R Y ID: V0001840-6 fcxygcn Research ADM tM tSTRATIVE FO RM Page UW ol 11U p. 110 Interim Report #23 - Analysis of Sediment Samples Exygcn Study No.: P0000760 CHEH EHSR 236 1B 651 733 1958 tt-tl-tOM it;Mm FraHifTOI SOLtlTien 05/01 '06 1 3 : MO.106 03/03 m m t.mm t m i * W tonrlifW ^iW f ftw C altop.M tW i `a s ar 1 |Yl*TX*FOHv \t" > *iipn ,. U*'i i, *t JfmtHUi - 1 OM fM Hti: NMlMn'- ' .yj S S w S n iS r^ . -- i. M .-, ? ' h . /. *, t .*> `% * . .. ) ' * b . '. i ' . ' * , ' S. A . ' V s '! . . v 1 i - , .* .i ' . ' . 7 `\ ! f a k J jA ( S I t t f c M N rD ttafar W t, ' t e fe m. ; URMKVIRVatBfMM : ^ ;VVV*i? j a 1 ^ v% v.*:-*- V.tv7%**w*'V<,*k*.,**, , .v**. " ,,> * t9 ' ' I-'--. -. .wV.%v v.:.'it:.'*" * *' * ; , .*: *%'. 't,*>.-*v},^*Si/''**'*v**'**. *:#!./.**'V '* --/ .* .. , ^ * , , ,*f , , **!* *( *> , v* " 3 ,!. '* **H Exygen Research Page 110 of 110