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p. 1 ~_ -- ~Ra~6 _ .~68 3 INTERIM REPORT # 23 - Atahmls of Sediment Samples STUDY TITLE Analysis of Perfluorobutanesulfonate (PFBS), Pcc fluorobexaaesulfonate (PFHS), and Perfluoroocianesulfonate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using. LC/MS/MS for the 3M Decatur Monitoring Program DATA REQUIREMENTS EPA TSCA Good Laboratory Practice Standards 40 CFR 792 STUDY DIRECTOR 7aisimtia Kesari P .E ., DEE Weston Solutions, Inc . 1400 Weston Way West Chester, PA 19380 . Pbone: 610-701-376 1 INTERIM REPORT COMPLETION DATE May 2, 2006 PERFORMING LABORATORY Exygen Research 3058 Research Drive State College, PA 1680 1 Phone: $14272-1039 ST UDY SPONSOR 3M Company 3M Building 0236-01-B- 1 0 St. Paul, MN 5514 4 Phone: 651-733-6374 PROJECT Protocol Number: P000113.1 Exygen Study Number: P000113 1 Total Pages: 110 p. 2 Ir3terim Report #23 - Analysis of Sediment Samples Exygen Study No. : P0001131 QUALITY ASSURANCE .STATEMEN T Exygen Resea mh's Quality Assurance Unit reviewed Exygen Study Number P0001131, entitled, "Analysis of Perfluocobutanesulfonate (PFBS), Perfluo rohexsnesulfonate (PFHS), and Per fluorooctanesul famate (PFOS) in Water, Soil, Sediment, Fish, Clams, Vegeta tion, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoring Program". AII'reviewed phasear were inspected for conduct according to Exygen Research's Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratory Practice Stand ards. All findings were reported to the Exygen Principal Investigator and Management and to the Study Director. Pbaw Date In kd Date Reported to Date Reported to Principal Exygen Date Reported to Investigm ~ Study Diroctor 2 5 . Final Raw Data Review and Interim Analytical Report Review 0 5/02l06 05/02/06 05/02/06 05/02/06 Lyd)dafffter T 'cat Lead, QuaHty , urance unit ~06 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 of the interim report and associated raw data. Exygen Research Page 3 of 110 p. 3 Interim Report #23 - Analysis of Sediment Sarr p le 4 Exygen Study No . . P000113 1 CERTMCAT~ON OF A THENTICITY This interim- report, for ExygeQ - Study Number P0001131, is a true and complete representation of the raw data . Submitted by. Exygen Resesrch 3058 Research Drive Sta te College, PA 16801 (814) 272-1039 Principal Investigator, Exygen : .,C ohn Flaherty Date Vice President Exygen Research Exygen Research Facility Management : RiC A . President Exygen R F` ~ a o Date Study Director, Solutions, Inc. O Jaisimha K . ., Weston Solutions, Inc. DE Date Sponsor Representative, 3M Company. . dl ,jW &k;J~W- IMichael Santoro Director Regulatory Affairs '5 06 Date Exygen Research Page 4 of 110 p. 4 Interim Report #23 - Analysis of Sediment Samplea Exygea Study No . : P4001131 STIUDY IDE~I~~4TION Analysis of Perfkiorobutanesulfonate (PFBS), Pafluorohexanesul#'ou8te (PFHS), and Perfluorooctanesulfonate (PFOS) in Water, Soil, Sediment, Fisb; Clams, Vegetation, Small Mammal Liver and Small Mammal Serum Using LC/MS/MS for the 3M Decatur Monitoringm Progra PROTOCOL NUMBER P0001131 - -` EXYGEN STUDY NUMBER : P000113 1 TYPE OF STUDY: Residue SAMPLE MATRIX: Sediment . - TEST SUBSTANCE : P+Grtluorobutanesalfonate (PFBS) 9 Perfluorohexanesulfonate (PFHS), and Perfluorooctanesulfonate (PFOS ) SPONSOR: 3M Company 3M Building 0236-01-B-10 St . Paul, MN 55144 STUDY DIRECTOR. Jaisimha Kesari P.E., DEE Weston Solutions, Inc. 1400 Weston Way West Chester, PA 19380 STUDY MONiTOR : Michael- A. Saartar y o3MCmpan 3M Building 0236-01-B-10 St . Paid, MN 55144 PERFORMING LABORATORY : Exygen Research 3058 Research Drive State College, PA 1680 1 ANALYTICAL PHASE Study Initiation Date : 11/05/04 TIMETABLE : Interim Analytical Statt Date: 04127/06 Interim Analytical 'Termination Daft: 04/30/06 Interim Report Completion Date : 05/02106 Exygen Research Page 5 of 110 p. 5 interim Report #23 - Analysis of Sediment Samples . Exygen Study No. : P0001131 PROJECT PEPSONNE L The Study Director for this project is Ja:sinnha Kesari at Weston Solutions, Inc. The following personnel from Exygen Research were associated with various phases of this interim portion of the study: . . .... Name Title John Fiaherty . Vice President . . Karen Rish. a _ .. S. cien~ tist : Paul Connolly Technical Lead-LC/MS Christine Edwards Techaician Mark Ammennan Sample Custodian Amy Sheehan Associate Scientist Brittany Kravets . Technician Scott C rain Technician Frances Crespi Technician Devork Ing= Techni6an Christa Gallant Technician Exygcn Research Page 6 of 110 p. 6 interim Report #23 - Analysis of Sediment Samples Exygcn Study No . : P0001131 T A 13LE OF CONTENTS Pate TITLE PAGE . . . . . . . .. . . . . . . . .. . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . .. . .. . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..1 GOOD LABORATORY PRACTICE-COMPLIANCE STATEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 QUALITY ASSURANCE STATEMENT .. . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. . . . . . . . . . .. . . . . . . . .. . . . . . . . . . . . . . . .3 CERTIFICATION OF AUTHENTICTI'Y . . . . . . . . . . .. .. . . . . . . . . . . . . .. . . . . . . . .. . . . .. . . .. . . . .. . . . . . . . . . . . . . .. . . . . . . .. .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 SUIVIMARY . . . . . .. . . . . . . . .. . .. . . . . . . . . . .. . . . .. . . . .. . . . . . . .. . .. .. . . . . . . . . . . . . .. . . . . . . . .. . . . . . . . .. . . . .. . . . . . . . ... . . . . . . .. . . . .11 2 .0 OBJECTIVE . . .. . . . . . . . .. . . . . . . . . . . . .. . . . .. . . . . . . .. . . . ... . . . . . . . . . . ... . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . .11 3 .0 INTRODUCTION. . . . . . . . . . . . . . . . . .. .. . .. .. . . . . . . . . . .. . . . .. . . .. . . . . . . . . . .. . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 4 .0 ANALYTICAL TEST SAMPLES . . . . . . . . . . . . . . . . . . . . . . .. . . . . .. . . . . . . . .. . . . . . . . .. . . .. . . . .. . . . .. . . . . . . . . . . . . .12 5 .0 REFERENCE MATERIAL . .. . . . . . . .. . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . . . . . . . . . .. . . . . . . . .. . . . . . . . . . . . . .. . .12 6 .0 DESCRIPTION OF ANALYTICAL METHOD . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . . . . . . . . . . . . .. . .1 3 6 .1 . Extraction Procedure For Sediment. ... . . . . . . .. . . . .. . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . ... . . . . . . .. . . . . . . . . . .13 6 .2 Direct Inject Extraction Procedure For Sediment .. . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. .. . . . . . . . .14 6.3 Percent So lids Procedure For Sediment . . . . . . . . . . . . . . .. . .. . . . . . . : . . . .: .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. . .14 6.4 Preparation of Standards and Fortification Solutions . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . .14 6.5 Chromatogrdphy . . . . . .. . . . .. . . . . . . .. . . . .. . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . .15 6.6 Instrument Sensitivity .. .. . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15 6.7 Description of LCfMS/MS Instrument and Operating Conditions ... . . . . . . . . . . . .. . . . . . . . . . . . 15 6 .8 Quaatitation and Example Calculations . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . .. . .. . . . ..1 6 7 .0 EXPERIMENTAL-DESIGN . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . .. . . . . . . . . . . . .. . .. . . .. . . . . . . . . . . . . . . . .. . . . . . . .. . . . . . . . .20 8 .0 RESULTS . .. . . . . . . . ... . . . . . . .. . . . .. . .. . . . .. . . .. . . . . . .. . . . . . . . . . . . . . . .. . . . .. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . .20 9 .0 CONCLUSIONS : . . .. . . . . . . . . . . . . . . . . . . . . .. . . . .. . . . . . . . . . . . .. . .. . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . .20 10.0 RETENTION OF DATA AND SAMPLES . . . . . .. . . . . . . . . . . . . . . .. . . .. .. . .. . . . . . . . . . . . . . . . . .. . . . . . . . . . . .21 Exygen Research Page 7 of 110 p. 7 Interim Report #23 - Analysis of Sediment Samples Exygen Study No. : POW 1131 LIST OF TABLES Pate Teble I. Summary of PFBS, PFHS and PFOS in Sediment Saanples . .. . . . . . . . . . . . . .. . . . . . . . . . . 23 Table U. Summary of PFOS in-Direct In'ection Sedi~nent Samples . . . . . . .. . . . . . . . . . . . . .. . . . . . . .24 Table M. Matrix Spike Recovery of PFBS, PFHS and PFOS in Sediment Samples . . .. .25 Table N. Matrix Spike Recovery of PFOS in Direct Injection Sediment Samples . . . . .. .26 Table V . Total Percent Solids in Sediment Samples . . . . . . . . . . . . .. . . . ... . .. . . . . . . . . . . .. . . . . . . .. . .. . . .27 ,_ . . Erypn Research Page 8 of 110 p. 8 Interim Report #23 - Analysis of Sediment Samples Exygsn Study No . : P0001131 LIST OF FTGUES Pasze Figure 1 . Typical Calibration G'thve for PFBS in Methanol .. . . . . . . . . . . .. . . . . . . .. . . . . . . . .. . . . .. . . . . . .29 Figure 2 . Non-Extracted Standards, of PFBS iri Methanol, O .Z.ng1mL and 0.5 nghnL. Respectively ............. ....... ...... 0 Figure 3 . PFBS in Reagent Blatilc, 0,4. ng/mL Fortified Reagent Spk A, and 4 .0 ng/mL Fortified Reagent Spk B, Respectively . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . .. . .31 Figure 4 . Chromatogram Representing a Sediment SampleAaalyzod for PFBS (Exygen II) : C0172892, Data Set : 042606F) .................................... ..............32 Figure 5 : Typical Calibration Curve for PFHS in Methanol .................... ........ ..............33 Figure 6. Non-Extracted Standards of PFHS in Methanol, 0 .2 ng/mI, and 0.5 ng/mL, Respectively ......... ............. .............. ... ........ ............ ...... .. ............ ..34 Figure 7. PFHS in Reagent Blank, 0 .4 ng/mL Fortified Reagent Spk A. and 4 .0 nglnmL Fortified Reagent Spk B, Respectively . . . .. . . . . . . . .. . . . . .. . . . . . . . .. . . . . . . . . . . . .35 Figure 8. Chromatogram Representing a Sediment Sample Analyzed for PFH S (Exygen ID : C0172892, Data Set: 042606F) .......................... ... .....................36 Figure 9. Typical Calibration Carve for PFOS in Methanol ........ ....... .... ......................37 Figure 10 . Non-Extracted Standards of PFOS in Methanol, 0 .2 ng/mL and 0.5 ng/mL, Respectively ...................... ..................................... ... ........ ...........38 Figure 11 . PFOS in Reagent Blank, 0 .4 ng/mL Fortified Reagent Spk A, and 4.0 nglmL Fortified Reagent Spk B, Respectively .. ....................... ..... ..... ......39 Figure 12 . Chromatogcam Representing a Sediment Sample Analyzed for PFOS (Exygen ID : C0172892, Data Sat:042806B) . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . .. . . . . . . . .40 Exygen Research Page 9 of 110 p. 9 Interim Report #23 - Analysis of Sediment Samples Exygen Study No .: P000113 1 LIST OF APPENDICES Pae APpendiz A . .: Study Protocol P0001131(Exygen Study No. P0001131) with Analytical Method '6001782 : "Method of Analysis for the Detarmit ation:of Partluorooctaaoic Acid (PFOA) in Sediment by Lf`lMS/IaIS", and Protocol Amendments . . . . .. . . .. . . . .. . . . . . . . . . . . .. . .. . . . . . . . . . .. . . .41 Exygen Research Page 10 of 110 P . 10 interim Report #23 - Analysis of SedimeRt Saavla Exygen Study No : i'000113 1 1 .a SUMMARY Exygen Research extracted and analyzed sediment samples for the determination of perfluorobutanesulfonate . (PFj3S), . . ~FtjuorQhexanesulfo~, , (PFHS), and perfluorooctanesulfonate (PFOS) accor~ii to Exygen Method V0001782 (Appendix A) . The limit of quantitation for PFBS and' PFHS in sediment was 0 .2 ng/g . The limit of r{uantifation for PFOS in sediment was 2 :0 ng/g. , The standard sediment method (V0001782) was originally used to extract all of the samples. Use of this method yielded poor recoveries for PFOS . Because of this, a direct injection method (Section 6 .2) was used to analyze for PFOS . Analytical resiilts for the analysis of PFBS, PFHS and PFOS found in sediment samples extracted with the original method are summarized in Table I. Analytical results for the analysis of PFOS found in sediment samples by direct injection are summarized in Table U. The average percent recoveries standard deviations for PFBS, PFHS, PFOS in sediment samples were 85 19%, 99 t 29ls, and 93 t 6%, respectively . Fortification recoveries for the analysis of PFBS, PFHS, and PFOS in sediment samples extracted with the original method are summarized in Table M . Fortification recoveries for the analysis of PFOS in sediment samples by direct injection are summarized in Table IV. The total percent solids for sediment samples are detailed in Table V . 2.0 OBJECTIVE The objective of the analytical part of this study was to detennine levels of perfluorobutanesulfonate (PFBS), perfluomhexanesulfonate (PFHS), and perfluorooctanesulfonate (PFOS) in sediment according to Protocol P0001131 (Appendix A). 3.0 INTRODUCTION This report details the results of the analysis for the determination of PFBS, PFHS, and PFOS in sediment using the analytical methods entitled, "V0001782 : Method of 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 P0001131 . The analytical start date for this interim report was April 27, 2006 and the analytical termination date for this interim report was April 30, 2006 . Exygen Research Page 11 of 110 P . 11 h terim.Repqrt #23 - Analysis of Sediment Samples Exygen Study No. : P000113 1 4.0 ANALYTICAL TEST SAMPLE 5 Three sediment samples (Exygen ID : C0172.892-C0172894) were received on wet ice on April 22, 2006 from Tim grinak at 9Veston Solu tions, Inc . The samples were logged in by Exygen personnel and placed in ref~ige.rated storage. Sample log-in and chain of custody information is located in the raw data package associated with this interim repo rt . Storage records will be kept at Exygen Research . 5.0 REFERENCE MATERIAL The analytical standards, PPS and PFHS, were supplied by 3M . PFBS was received from 3M at Exygen on May, 13, 2005 . PFHS was received from 3M at Exygen on January, 20, 2003 . PFOS was purchased from Fluka Corporation and was received at Exygen on April, 23, 2003 . The available information for the reference materials is listed below. PFBS and PFHS were stored fro zen and PFOS was stored refrigerated . ~ ExygellInverttorv No. PFBS SP0005726 LaLf Purity [%) Expiration Date 101 96.7. 12l04106 PFHS SP0002 4 Ol SE036 98 .6 - 10r18/06 } PFOS SP0002694 430180-1 101 .2 10/31107 The molecular structures of PFBS, PFHS and PFOS are given below : PFBS Chemical Name : Perfluorobutanesulfonat e Molecular Weight: 338 supplied as the potassium salt (C4F9SO3X) Transitions Monitored: 299,-+ 99 : , Structure : F F F F Oj F F F F PFHS Chemical Name: Perfluorobexanesulfonate Molecular Weight: 438 supplied as the potassium salt (C6F13SO3'K') Transitions Monitored : 399 -r 80 Exryge n Research Page 12 of 110 p . 12 Interim Report #23 - Analysis of Sediment Samples Exygen Study No. : PC00113 1 Structure : F F F F F F O3 FFF F F F PFOS Chemical Name: PerIluorooctanesulfonat e Molecular Weight: 538 supplied as the potassium salt (C$F17SO3X') Transitions Monitored : 499-- 80 Struct ure: . F. F . . . F F " F F F 3 F--~ '1-, 0 F F F F F F: F F 6.0 DESCRIPTION OF ANALYTICAL METHOD The analytical method "V0001782 : Method of Analysis for the Determination of Perflaorooctanoic Acid (PFOA) in Sediment by LC/MS/MS" was used for the analysis of PFBS and PFHS in sediment samples . A direct injection method, detailed in Section 6.2, was used for the analysis of PFOS in sediment samples. 6.1. Extraction Procedere For Sediment Before the samples were weighed for the extraction, they were mixed thoroughly by vigorously shaking the container. A 5 gram portion of sediment was weighed into a fifty milliliter centrifuge tube for the oxttac tion. After fordfication of appropriate samples, 35 mL of 1% acetic acid in water was added to the samples. The samples were vortexed and allowed to shake on a wrist action shaker for -60 minutes. The samples were centrifuged for -20 minutes at -3000 rp nn. Thet supernatant was then loaded onto a C I 8 SPE cartridge conditioned with 10 mL of 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 --20 minutes at -3000 rpm. The supernatant was then loaded . onto the s ame Crs ..SPE. -cattridge . The eluate was collected into a 500 raL Nalgene Bottle. T he column was washed with 4 mL of melhanol . The wash was collected in the same bottle as the eluate . Approximately two hundred milliliters of water was added to the bo tt les . The samples were mixed by shaking and loaded onto another C j g SPE cartridge conditioned with 10 mL of methanol Exygen Research Page 13 of 110 p . 13 In2mm Report #23 - Analysis of Sediment Samples Exygen Study No . : P0001 13 1 and 20 mL of water. The eluate was discarded. Approximately five milliliters of methanol was added to the cartridge, Five milliliters of eluate was collected into a graduated 15 mL polypropylene centrifuge tube. Each sample was analyzed by LC/MS/MS electrospray. 6.2 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 of 1% acetic acid in methanol was added to each sample. The samples were then shaken by hand, vortexed, and sonicated for thirty mirnites . The samples were then centrifuged for -10 minutes at -3000 rpm . Each sample was analyzed by LC/MS/MS electrospray . 6 .3 Percent Solids Procedure For Sediment Percent solids were determined using the procedure indicated in Exygen method V0000427 . Approximately 20 grams of sample was weighed into a pan. The weight of the sample plus the pan was racorded. The samples were then dried in an oven overnight at 104 2C. Then the samples were transferred to a dessicator and allowed to cool for - 15 minutes. Each sample was then weighed again, including the weight of the pan . The percent solid for each sample was then calculated . See Table V for percent solids results . 6.4 Preparntion .of Standards and Fordfication Solution s A mixed-'stock standard solution of" PFBS, PFHS, and PFOS was prepared at a concentration of 1000 g/mL by dissolving 100 mg of each ofthe standards (corrected for purity and salt content) in 100 mL of methanol . From this solution, the following fortification standards were prepared : Conc. of Fort Final Final Cone. Of Stock or Fort. Volume Volume Fortification Std. Solution (mf,) (ML) (ugtmL) (g/ML)' 1000 10 100 100 100 -10 .00 to 10 10 100 1 .0 1 .0 10 100 0.1 0 .1 10 100 0.01 of PFBS, PFHS, and PFOS Exygen Research Page 14 of 110 p . 14 Interim Report #23 - Analysis of Sediment Samples Exygen Study No . : P000113 1 A set of non-extracted calibration standards containing PFBS, PFHS, and PFOS was prepared in methanoi, as specified in Exygen method V0001782 . The following concentrations were prepared: Conc . of Fort Fort Final Final Canc. of or Calibration Volume Volume Calibration Std. Solution (UP ., (mL) (ng/rni,) (n8lail-)' - 100 1 .0 10 10 100 0 .5. 10 5 .0 100 0 .2 .10 . 2 .0 10 1 .0 10 1 .0 5.0 1 .0 to 0.5 2 .0 1 .0 . 10 0.2 ' of PFBS, PFHS, and PFOS The stock standard solution and all fortification and calibration stand &d solutions were stored in a refrigerator (4 t 2C) when not in use . Documentation of standard preparation is 1ocated in the raw data package associated with this interim report. 6.5 Chromatography Quan tification of PFBS, PFHS and PFOS was accomplished by LC/MS/MS elcctrospray The retention times of PFBS, PFHS and PFOS were -0.56mins, - 9.4 mins, and - 11 .4 mins, respectively. . Peaks above the LOD were. not detected in any of the reagent blank samples corresponding to the analyte reteation time . 6.6 Instrument Sensitivity The smallest standard amount injected during the chromatographic run had a concentration of 0.2 ng/mL of PFBS, PFHS and PFOS . 6 .7 Description of LC/MS/MS Instrument and Operating Conditions Instrument : API 4000 Biomolecular Mass Analyzer Interface : Turbo Ion Spray Liquid Introduction Interface Computer : DELL OptiPlex GX400 Software: Windows NT, A.nalyst 1 .4 . 1 HPLC : Hewlett Packard (HP) Series 1100 1-1P Quat Pump Exygen Research Page 15 of 110 p . 15 Interim Report #23 - Analysis of Sediment Samples Exygen Study No. : P000113 1 HP Vacuum Degasser HP Autosampler HP Column Oven HPLC Column : 'ilermo Fluopkase RP, 50 :mn x 2 1 mm Column Temp . : -30 C Injection Vol : 15 i. Mobile Phase (.4): 2 mM Ammonium Acetate in water Mobile Phase (B) : Methanol Time (min) % A 0/0 a 0.0 65 35 lA 65 35 8 .0 25 75 10 .0- 25 75 11 .Q ~ 65 35 18.0 65 35 Total run timc: -18 min Flow Rate: 0 .3 mTJmvn '> Ions monitored: Approximate An~lvte Mode Transition Retention Time Monitored (min) PFBS negative 299 --* 99 -0 .56 min. PFEIS negative 399-+80 -9 .4 min. PFOS negative 499 -a 80 -11 .4 min. 6.8 Qnantitatlos and Example Cile uLtians Fifteen microliters of sample or calibration standard were injected into the I,tr/MS/MS . The peak area was measured and the standard curve was generated (using 1/x fit weighted linear regression) by Analyst software using six concenbuflons of standards . The concentration was determined from the following equations . Equation I calculated the amount of analyte found (in nglmL, based on peak area) using the standard curve (tinear regression parameters) generated by the Analyst software program. Please note that the equations in this section are presented in a different order than the equations in the method (V0001782), but this has no effect on the final calculations. Exygen Research Page 16 of 110 p . 16 Interim Report #23 - Analysis of Sediment Sampizs = Exygen Study No. : P000I 131 Eauation 1 : Analyte found (ng/tnl,) = (Peak area - intercept) x DF Slope Where : DF = Dilution Factor, factor by which the &nal vdiume was diluted, if necessary . For samples fortified with ]mown amounts of PFBS'and~ PFHS : prior to extraction, Equation 2 was used to convert the amount of FFB8 and PFHS found in ngfmL to ng/g (ppb), Equation 2: Analyte found (ppb) _ LAnalvte found (aghnL) x &W volume (5 mL)1 sample weight (5 g) Equation 3 was used to calculate the percent recovery: Equation 3 : Recovery (%) = (analvte found (Mb) - analyte in control (rob)) x 100% amount added (ppb) Equation 4 was then used to calculate the amount of PFBS and PFHS found in ppb based on dry weight. F4mation 4 : Analyte found (ppb) dry weigbt = Anabte'fosmd (ppb) x [ 100% / total so lids(%)] An example of a calculation using 4n .actual,a~mpla follows (calculati on is for PFBS only): Sediment sample Exygn ID.- C0172$93 Spk F -(Set: 042606F), forti fied at 4 ng1mL with PFBS where: peak airea 253819 intercept = -592 slope = 42300 dilution factor ng/g PFBS added ( fort level) = 4 amt in conespond'wg aample (ngJg) = 2 .41 final volume (mL) y . - 5 sample weight (g) 151-- total solids (%) = 54 .37 Exygen Research Page 17 of 110 p . 17 ~.. .~. .~~ Interim Report #23 - Analysis of Sediment Sampl es Exygen Study No. : P000113 1 From equation 1 : Analyte found (nghnL) = j253819 1592)1 x I 42300 = 6 .01 ngttnL From equation 2: Analyte found (ppb) _ (6 .01 nalmL x 5 ml,~ 5g = 6.01 pp b From equation 3% Recovery = (6.01 pub - 2.41 4 ppb x 100% = 90'/0 From equation 4 : Analyte found. (ppb) dry weight - 6.01 ppb x(? 0(r154 .37%) = 11 .1 ppb NOTE : This value may be slightly different than that of the raw data due to rounding . A slightly different set of calculations was used for the direct injection samples analyzzd for PFOS . F.,~,}Ltlon 1 : Analyte found (ng1mL) _ (Peak area - intereent) x DF Slope Where : DF = Dilution Factor, factor by which the final volume was diluted, if necessary. For samples fortified with known amounts of PFOS prior to extraction, Equation 2 was used to convert the amou nt of PFOS found in ng/mL to ng/g (ppb). FjMalion 2 : Analyte found (Fpb) _ [An_alvte found (ng~uQ x volume each-ac teci 0 0 MU sample weight (1 g) Equation 3 was used to calculate the percent rocovery. E x y g e n Research P a g e 1 S of 110 p .18 Interim Report #23 - Analysis of Sediment Samples Exygen -SUidy No . : P0001 131 F,cauation 3 : Recovery (%) (anal_yte found n~g,) - analyte in control (nlz/Z)) x 100`/0 amount added (nS(S) Equation 4 was then used to calculate the amount of PFOS found in ppb based on dry weigt,t. Equation 4 : Analyte found (ppb) dry weight = Analyte found (ppb) x(100/Q / total solids('/o)] An example of a calculation using an actual sample follows : Sediment sample Exygen ID: C0172892 Spk D (Set: 042806B), fortified at 400 ng(mL with PFOS virbere: peakamea = 152371 intercept = 3720 slope = 22700 dilution factor = 100 ng/g PFOS added (fort level) = 4000 an* in mm ponding sevpie{ng/g) = 2360 volume extracted (mI,) 10 sample weight (g) = 1 total solids ('/o) = 66.54 From equation 1: Analyte found (ng/L) _ [152371- 37201 x 100 22700 = 654 ng/mI. From equation 2 : Analyte found (ppb) ( L4 ng(mL x 10 mL) l .g = 6540 pp b From equation 3 : % Recovery = (6540 n& - 2360 nglgl x 100% 4000 ng/$ = 105% From equation 4: Analyte found (ppb) dry weight = 6540 ppb x(100% / 66 .54%) = 9830 ppb Exygai Rcsrarch Page 19 of 110 P . 19 Interim Report #23 - Analysis of Sediment Samples . Exygen Study No. : P0001131 NOTE : This value may be slightly different than that of the raw data due to rounding . 7.0 EXPERIlVIENTAL DESIGN For sediment samples designated as lsboratory matrix spikes, PFBS, PFHS, and PFOS were added at a known concentration to the samples in the laboratory after the samples were weighed for extraction. The sediment samples were extracted in one set. The set included one reagent blank and two reagent blanks fortified at known concentrations . The set contained three sediment samples . For each sample, two laboratory matrix spikes and a duplicate were extracted . Due to poor recoveries, the three sediment samples were extracted and analyzed using a direct injection method for PFOS. This method is detailed in Sect[on 6.2 . 8.0 RESULTS Analytical results for the analysis of PFBS, PFHS and PFOS found in sediment samples extracted with the original method are summarized in Table L Analytical results for the analysis of PFOS found in sediment samples by direct injection are summarized in Table II . The average percent recoveries standard deviations for PFBS, PFHS, PFOS in sediment samples were 85 19%, 99 t 29"l0, and 93 6%, respectively. Fortification recoveries for the analysis of PFBS, PFHS, and PFOS in sediment samples extracted with the original method are summarized in Table Ill . Fortification recoveries for the analysis of PFOS in sediment samples by direct injection are summarized in Table IV . The total percent solids for sediment samples are detailed in Table V . 9.0 CONCLUSIONS The sediment samples were successfully extracted and analyzed for PFBS and PFHS according to analytical method V0001782 . The sediment samples were successfully extracted and analyzed for PFOS using an alternative method, which yielded acceptable QC data. Exygen Research Page 20 of 110 p . 20 Interim Report #23 - Analysis of Sediment SaiiV les Exygen Study-No. : P0001 1 3 1 10.0 RETENTION OF DATA AND SAMPLES When the final analytical report is complete, all ori ginal paper data generated by Exygen Research will be shipped to the study director. This does not include facility-specific raw data such as instrument or temperature logs. " Exact copies of all raw data, as well as a signed copy of the final analytical report and a ll original faci lity-speci fic raw data, will be retained in the Exygen Research archives for the period of time specified in EPA TSCA Good Laboratory Practice Standai& 40 GFR 792 . Exygen Research Page 21 of 110 p . 21 lnterim Report #2 3 - Analysis of Sediment Sampies Exygen Study No. : P(K.101 13 1 TABLES Exygen Research Page 22 of 110 p . 22 Intcrim Report #23 - Anaiysia of Sediment Sasryples Exygr,n Study No . : PQ04113 1 Table L Summary of PFBS, PFHS and PFOS in Sediment Samples PC.a4 .a.u~r..i..i....P- F. .rSS a a+*ne. PFHS CID Suiraw. PFOa 14isty% FpM d Afw W d Hripb Faud Awrd MWyb FOUOA Ma~wO CbM fA16, A yp} ACNW OO. "W AOp+aoY (Mb. ^ WY) ADVA" D SWV* ID an wow +- x w M- %) +t- C01T2062 DA4.SD-BpP01-0O000 8.14 40 64.3 30 NR NR Coll 2N2 Rep DAL-90BPP01-O -0OOG' 310 40 EA1 30 NR MR Cot72E93 DAL-40-BPPQ20-0000 4.13 30 74.3 30 NR NR C01721103 Rep O4 -S041PP0241-0000 484 30 64.7 30 MR NR C017204 C0172W4 Rip DAL -BD41PM&A .d000' 9_67 30 13 0 50 MR NR 6.73 30 123 30 NR NR 'uear+wxf~ O~~prc+ k MR Nat tiporbd due to wA iy ,aw~hq rwM L kra Sw Tabs It for n~nyrY nMwk1 . Exygen Research Page 23 of 110 p . 23 Interim Report #23 - Analysis of Sediment Samiplos ., Exygen Study No. : P000113 1 Table II. Summa ry -of PFOS in Direct Injection Sediment Samples C8 SuHonate PFOS , .. . . . . ,J . Exymn ID ! neym Found Aaftseed Mont OVb . n") Accuracy Sem ID Dry w nt C0172892 C0172892 Rep DAL-SD-BPP01 -0-0000 DAL-SDBFPO' -0-0000' 3550 30 - 3620 30 C0172893 DAL-SD-BPP02-0-0000 C0172893 Rep L1AlSD- 3PP02-0-0000 _ 41 0 0 30 3840 30 C0172894 DAL-SD-BPP03-0-0000 11900 30 C0172894 Rep DAL-SD 48PP03 -0-0000' 12000 30 "Laboratory Dupicate ExYgen Rsw=b Page 24 of 110 p . 24 Interim Report #23 - Analysis of SodimftSmnQles Exygen Study No . : P000113 I Table M. Matrix Spike Recovery of PFBS, PFHS and PFOS in Sediment Samples NTawr awnps EpibO uMr.. . w.~ anab ..o .M t w.. WWft wawrwunnatN.e Aft FWMO 1pMW t - - MRfa.~e . Hr,w.t M. A~t . in Op" ROOD wn0 Renwi, n>1rv W Nmwn! M9wr0Y Weowrtl Rmeowry .r . .e .r rr .~ MWIVMV& oaaaarrat aoaoo lavrr ftk C,aw ft*AI- 4 200 O 11,,7MR4000.48690OA/ 400 2.0P W48D41M+0140000 0 T710t71YEA0H06 0iY1 4M 200 ..47 0 9oA4e10WNtlO 212 00 OR1 aIN n - - 2070 O7. 0!.? 0100 128 MN NR NR OAIdDpP1'040000 dvanlks.4PM}+" 1DNt464PT02-00000 OnniwOfM4 4otMb 4r1 GNr9DlPP04-0-0000 1pq7101/Mq 4 MOwb3" i 4 241 O.Ot 90 . 400 211 374 93 4000 2 .41 1020 06 . .. . , 4 01 .. 746 70 - - - 40.0 0000 126 NA Mt MR OML-4040P0344000 0"73@w %* lbMW 4 430 7.71 DS OA4kI41PP004-0000 1QMiMlwLNn OMN 400 4. 30 36D 00 = 01.0 OAL404PP03.O-0000 9nnwrqaK4 uwAW 400D 4.3~0 4NO 121 01d Zp 66 - - 4 000 t11 MR NR NR M'Oi0" M 'h'rMe 00 iYUwld OwAdsn: 10 iY kdOfl0ai0ac 7;0 'Snn~N wWM~ rOwi bM6Yr MM~Nlawwj ty ~1w0 ~~R MYsa ~ m~ ~owrYvre rrMet r adailN d W btOMleMOataralerbueltet4~UYl~~MOZ~WOO~MMq . Ni~ NR IyMIYC At b Cr~IMw1w0~ nwR 41Mn19Mhd~ N brA+rMrwwM . IIe1C iW~ Ori wryYhY alwM w17M wwrR eww~wywMr~ ~lrwlra0Mi01'*ow/M ~~ In1M w rY . *mum NR 3prvdw DwYrM: an Exygen Rosearch Page 25 of 110 p . 25 interim Report #23 - Analysis of Sediment Samples Exygen Study No.: PU04113 1 TWO IV.. Matrix Sp*re Recovery, of PFOS in Direct Injection Sediment Samples ce arop.n PF06 wet w. ne Arnount M-A Found Arnount some Spibd in 8tnpls Dacriodon loan) * v4 Rowmad Recovery wetvrt % pAL400-BfP P01-0 0o0 0 lattaM apc R Moo as s0" 4000 DAL-SDBPPOt-04M fMrane ~ 1L~ OM APM +1 40000 2960 2960 6540 105 40000 94 G11L-SDBFPQ2-040000 - - le 's s t0 O, Neo vebsp" 4000 22E0 _%60 92 MLSD-8PP01-P000 0 ICe1t9Nf sp*W4 4eseo Pvs Op W 40000 2260 9f000 69 D,AL-SO-8PP030-000 0 (eWTa " pt J, rooo pps lpO y oAr.4X>-~aooo IM nw aok K.4ooa isd ipw0 4000 40000 5280 8770 87 5280 41200 90 Awrpr : 93 alandud O ~ : 6 'Snmpe ani0us mioeerM Me pAYip Nw1 alg tle anry (9a OpbM 1we1k ihwMfors, an roetwM noovary value Cannot be COMAMW NO - raaN.ctw .la above tnumRotownl a ionM1OWao.2np+ppM.tvr .IpM}. Nol sieo . 00 wmnry tieb shwas wounded u.ulb. +.oow4 , values may rsy .r6My kwm On values b 6M raw aats . Fxygm Research Page 26 of 110 p . 26 Interim Report #23 - Analysis of Sediment Samples Exygen Stuey No . : Pfi041131 Table V. Total Percent Solids in Sediment Samples mp fD DesCe~Stbri Total SoYds (%) 00172892 DALwrD-BPP01-0-0000 66 .54 00172893 DAL-6D-8PP02-40000 -54 .37 001728.94 DAL-SD-8PP03-0-0000 44 .46 . ExYgen Reswch Page 27 of 110 p . 27 Interim Report #23 - Analysis of Sediment Srmdes Exygen Study No. : P000113 1 FIGURE S Exygen Re-"cb Page 28 of 110 p . 28 Interim Report #23 y- Analysis of Sediment Samples Exygen Study No_ : P000113 1 Fignre I. Typical Calibration Curve for PFBS in Methano l ~ OQEOOi B6 rltint 1db (Pi1SjUnW / RN~Ion~+J~wNOMlnp~t .4.79~.p04x~ .0~(r0 .pppp) 4 .M6 42a6 4DQ6 22106 ae .s 9N6 32K 3.006 2tW ~ 2100 2I1W 2205 0 i 2A46 1 .806 . +.0~ .4*661 4.206 . +.0~6 eA~4 8.o.4 4A" z.o " ~ + 2 ~ 4 s e c. M ..r,r.e,nOn. L ~ r o ~o Exygen Research Page 29 of 110 p . 29 -~~ Interim Report #23 - Analysis of Sediracnt Sampks Exygen Study No : P000113 1 FiWe 2. Non-Extracted Standards of PFBS In MetiaAnol, 0.2 ng/mL and 0.5 ng/ml,, Respectively am 2 ,,. a P I, i y $ ~ d 7 a 0 10 11 12 ,3 Time . m in , 8WD1A OY6 PISS (BIaaUo*20i.OAiA anu arWa 2 rf 45 itom OA N OOf.wM l Ana : 20M eouwti NNpki 1 .40a+OOD cps RT:OA00 min 14 16 1e 17 .1 400 7200 ,~ 0~ 0 4p a 20a L z 3 4 a ' ro - - ~. s o +o - +~ - - ~< +a ~s 15 1e 117 Time . mi s Exygm Rcscmvh Page 30 of 110 p . 30 laUrim Report it23 - Analysis of Sadimebt Semples - ExygenStudy No .: .1P900113 1 Figure 3 . PFSS in Reagent Blank; 0.4 ng;rmL Fortified Reagent Spk A, and 4.0 ng/mL Fortified Reagent'Spk R9 Respectivel y ft"Mf COIUIOI Pllf 1R+Mb0M)?l1Mi1Mi~ aY~A O WI5 R6M,Eap01<iMd _ - 04,09 AlI~ .. . - . . Y ' . v . Yr. ` .. . . n ~Q 13.ay 1o9o +sp laa a 1u1 10 z .7e .49 Ma am JOY .ta 1m 4o e .ao 7 1T,o AAVXW 2 3 4 6 0 T a a 10 TleOL NO , Rupnt aphA PFDa (<1L)2ap.pYYD xo maple Y N43 from 042EOOF .wfR Area 1pWa w o MS INIsDt 1M&003 eN RT ; OA6T N 6 71 /2 13 14 141a 17 0.aa 1DO 6 100 v 1Aa 2 4 6 s T a a 10 Ti~r, niw R eaawt Spka PFRS (OC) 20aAAOA amu Ympl e 10 o(46**. 0 42lOaF .will Awa: 10a727 oowMt Height 1.11 .+004 ar RT : 0.667 ni n p 1.00 04 Oda 11 12 17 14 16 4 1T ~ EOOO DD lag D .00 h -~ . . . 2 4 6 6 T 0 10 t1 17 13 14 76 1a 17 T7u, Nn Exygen Research Page 31 of 110 p . 31 In*.erim Report #23 - Analysis of Sediment Samples Exygen Study No . : P0,00113 1 Figure 4 . Chromatogram Representing a Sediment Sample Analyzed for PFBS (Exygen ID : C0172892, Data Set: 042606F) , amM Pmas Wuroa arota ha . #atWAnW Ar.w ma *Mao js4 e am +ras . OM 2=- 2M . r,oo no o mo 1A1 In c INC ~ 1~00 ~ 1200 1= i00 000 400 40 0 0 3 p 11 12,12 / 9 14 15 10 1 7, Time . mfn Exygm Reseiob Page 32 of 110 p . 32 Interim Report #23 - Analysis of Sediment Samples Exygen Study No . : -P000113 1 Figure 5. Typical Calibration Curve far-FFRS'in Methanol 0 0416oeF s.ar.vr.ie b (vFHgZ y,rn .,r rtNw.l .n C1 he wd o hryt y- 7=0+004x* -1 .1*00n(r- CAW .. . , 7 .3.6 . 7A .0 e .s.6 ao .e a.a .e 60~0 ae.s ao.6 9A.6 Z a~6 2A .6 1.6.6 1 A .6 6.O44 1 3 4 6 0 C~ew~iabn, iphL 'I 0 10 Exygen Reseamb Page 33 of 110 p . 33 Interim Report #23 - Analysis of Sedimcat Samples, F.xygeu Study No . : P000113 1 Figure 6. Non-Extracted Standards of FFHS in Met6anol, 0 .2 ng/niI, And 0 .5 aglmL; Respectivel y , SSNl~lSli i~Flt ptNd~nQ~lO1M01a! NyN lN~6 ~FOl~ /BpiFrif M~ate Tll7l ew~dr lMj~6 TJS1+W2ip R7 Or~1fU 0 .4 0 70 0 000 Ow Zm 0,0i 0 1 2 7 4 6 0 7 0 10 11 Time, mia , sf00'1i~6 P /MS (Studab300 .000 0 sw m . upp4 2 e m earn 044EOpf .wM Ana : 9300'd ewMi MeiOnt 1 .73N4M qs RT: GAD w in 14 19 1000 tl 100 0 ~ wo 0 .4 0 . i4 16 16 17 0 1 2 s s Q B 7 - r 0- 90 it 12'-- 13 - 14 16 1e n Time . min Exyga' R8arch Page 34 of 110 p . 34 -Intierim Report #23,--: Analysis of Sedimbnt Sarnples Exygen Study No . : PQ00113 1 Figure 7. PFHS in-Reagent$Iank; 0.4 agfnrL Fortified Reagent Spk. A, and 4 .0 ng/m>r; F"urtified Reagent Spk By Respectivel y 12 .47 848A A 4_ 1-0 Am 0'0 ~13 .ti CL 4.0 0.40 12 .~1. 14.7T 1720 yM 4 .40 6a YyY 11 . 1616 ~ 40 .0 .78 3 .9p ~ : an m ~ oA 1 2 3 4 6 6 7 t 0 10 11 12 13 14 16 10 17 Time. mi n , R eayt st f6k /1- "XS (OC) 3MA!DA smr - ue6Y Y 0145 bn 04 2 OOi aiR Anx 27D7Y os+ab Height: 1 110 66OOtt ep RT : 030 mN . 1000 . , .. .. 0~ - 1000 0 1 2 3 4 6 0 7 6 0 11 VIM*. wY. , R s p eMSOY B . PiNS(Ot)3WAADA amu mmpU 10 0 461ro .oaQ6oer .re 1u" 27 9G76 Mkw1Y M4 y ht 1 .60N000 qs MT : 0 .40 win 12 13 14 16 10 17 6 tAM c 0.0O000A 0.40 Y 1 2 3 4 6 0 7 6 010 11 Time, mm 12 13 14 10 16 17 Exygen Research Page 35 of 110 p . 35 lnterim Report #23 -Analysis of Sed'ar.ent Samples- ,-. Exygen Study No. : P000113 1 Figure 8. ChromztQgram Representing a Sediment Sample Analyzed for PFHS (Exygen ID: C0172892, Data Set: 042606F) , c.m M vr;~ f*ft.aw)3 . W a..a, . . .,n,,, ow .s ft,. .awr.wss Aww ~169~ svr~b ~~ 22~+/R! y~ RI !I! rr(M 2M am xoo o ,loo ,eoo 1~0 0 IL 1200, ~c 1000 eo0 OWN- 4w . 700 IN J6. 0.4 1 2' 3 4 '- 6 Q 7 't0 /0 - 11 12 17 14 16 16 17 Time. AiN Exygm Research Page 36 of 110 p . 36 Interim Report #23 - Analysis of Sediment Samples Exygen Study rio . : POU0113 1 Figure 9. Typical Calibration Curve for PFOS In`1Vfethano l ~ 04~ Sad . o I .ree (Pion "un. .r R .yrsqa ~`~ !r n.qw .~ r 7 .v.+oD4 x+ s .rz..m7 Q O.oa16) t.4.a 2246 zoo 1.846 1446 a Pi e tA~6 i.OM ~A W 40W ~ 2494 9 a 0 7 C & eratrN*n, qhn L 6 0 10 Exygen Research Page 37 of 110 p . 37 Interim Report #23 -- Analysis of Sediment SanVies Exygen Study No . : PD00113 1 Fjgare 14> Non -Extracted Standards of PFOS in Methanol, 0 .2 ng/mL and 0 .5 ng/mL, Respectively , f3N!lffiPFOt P lydl O ALAN O + w swa/f+ld 45 AroR tM /Mlsrl ArN : f1I!lear~dr lM~ LM.NLeps RT tl.Iat~ 11q? aao 200 p. 1 2 3 ~ 5 0 7 ! Y 10 6,0Time . fb i n , 98001AI 606 Pf09 (BbnAaN)420 .041M0 a ~ saryJ e 2 .} 46 0Q/00/wff Ana: 1222b a nn& N*ivIrt 7 .72N002 W RI : 11 .4 mire 11 12 13 14 16 1E A 700 000 to f00 400 2W 11 .43 1Q~ , D 1 Z 3 4 0 0 7 ! i 10 11 12 13 i4 16 10 17 Tlma wle Exygar Research Page 38 of 110 ----- - ~ p . 38 Interim Report #23 - Analysis of Sed'unehit Samplet Bxygen Study Ntf .:, Pp0(y 1131 Figure 11 . PFOS in Reagent Blank,' 0.4 ng/mL Forti#3ed Reagent Spk A. and 4 .0 ng/mL FgrtiIIW Reagent Spk B, :Respectively , A.yMe Ci~6M Aa~ fa.Me) ALMU~ i>tMi it +~orA'! d~e A~y . i~nM7r' M~r f3rewnb M~y1~ 2Ar+Nfqp~ RT l13aL~ ' CL 20 11 .45 1D ~11 .N 0 .481 1B0 ~~ 470 3J?7 720 8 .04~ 11?2~ 1339 1437 10A4 1 2 3 4 6 0 7 9 Y 10 , TI m. min Re+"H ttk A - tr0i (OL) 4iYdq0A is . ran p l e G e1 45 from Oc000laMR ~1n~: 10E00 aNnb 11N4bk 021 MOpQ qs RT: 11 .4 min 11 12 13 14 /5 10 77 ODD - - -- 1tJ16 4w 200 10 06~ 0 1 2 = 4 6 0 7 0 10 11 Tlw *. " , W *OMtYlRYPf09(p C) 400Aq0A a in e - sample 10d45 Mn047Y00 8- O Arnc Oi701 "nab 1Mioit 6.07.a009 pr RT : 114 nN n 12 13 14 16 10 17 0000 11 .44 r 40m 3 ~ 5 2000 10 . 10 1 2 J 4 5 O 7' 8 0 10 11 12 13 14 15 10 17 Time. m in Exyge" Rcw=1i Pap 39 of 110 p . 39 Interim Report #23 - Analysis of Sediment Samples Eaygen Study No . : P000113 1 Figure 12 . Chromatogram Representing a Sediment Sample Analyzed for PFOS (Exygen ID : C0172892, Data Set :042806B) , u~rlwa-nr9ac~.e..~ws..ae ... .,..ar. "045+F.. *aM&wW ~e no 3eo 30 . azo no 2!0 zeo a.o ,, .ao aoo ISO ,eo ,4o ,20 ,oo a o eo 4020- 01 + : s a a e ' x' o ~o ~~ n Time. min Exygen Research Page 40 of 110 p . 40 Interim Report #23 Analysis of Sediment Samples Exygen Study No . : P000113 1 APPENDIX A Study Protocol P0001131 (Exygen Study No . P0001131) with Analytical Methods and- Protocol Amendments Exygen Research Page 41 of 110 p . 41 Inurim Report #23 - Analysis of Sediment Samples .'Fxygm Study No. : P0001 13 1 exno r,omooi N.me.r: ?MI i STUDY PROTOCOL Stndx Titk: An** of PofterobutanesolIbRaft (PM ), Perfi torol exa>teeaitoaaft (PFHS), and Perflhwrooctsoadfoaatt (PFQS) in Water, Soil, Sediment, Fieh . Ciams, VeSetatbn, Small Mammal Liver and Small Mammal Serum Using I .C/MS1MS for the 3M Decatur Momiftering Program Exygen Protocol Number: P0001 13 1 Ex YB n AMUM& G v Mlr8~1 A . 9mt= 3058 Resauch Drive Diiecror of Regulatory Affain SWe Coileoe. PA 16801 3M BuWdiat 0136-01-B-10 Phone: {814) 272-1039 St Prul. MN 5514 4 P11oee: (651) 733-6374 par i el 6 5 E `y gtm Racamh Page 42 of 110 p . 42 Interim Report #23 - Analysis of Sediirrefat Sarnplcs Exygea Study No:'fPfl00113 1 Erytea Ao/otet IJum6er NOOI 131 DiS7 MiTTION : 1) hvimb .xae M, SmayDa ftw. wW asoinsio.. 2) jotu M. F Maey~ MOW n voftnor, pacyaeose.e uc b 3) WmLeol A . Sanbrq Spaew Repraeatwkivr. 3M Compsuy 4) E~[7DqnRa~ea~b Qw1itT .yw~!s4o ilst 1. 4 .. 1 ' . i ~ .. '.~ . . . _" . ~ .. , ~ ~. . .. . l ' ~r I of 6~ Exygen Research Page 43 of 110 p . 43 Interim Report #23 -Analysis of Sodirneat Samples fixygee Study No . . P000113 1 Emma Peolxol Nw ba : r0001131 PROTOCOL APPROVAL Study 71qre Aralyos ofPfluoeobtAmmWMM ffBS), Pt &orohaormerutfoorae (nPiFbHB). ud (PFOB) m Wwr. son, 5eaireia 4 . C.`lase, YMOaaae Saru aQrmmal bean ad Sontt bldlmW Saum Udag LCIMsnNS the the 3M DMtie Maoitaxfng pyoy am Ex.nm Pmbaol Nomber : Pa Wl 131 .+PPxoV mizi~ MY meam w,. m sohifiam Miel+rd A smfiuw& saonor Repraeoaeire 3M ll 6104 n u flahaty; dp.t mva~dpmr Rtohwd A i . Ecy~ea *w. F~oilf;r ~ e cv- Aa;pl- Doe L Sba9ke. TeoEm ed. Qa~lily A~a~oce lJoit D Rawarrh ~ Pax J'4 61 Exygen Rseamb Page 44 of 110 p . 44 Interim Report #23 - Analysis of Sediment Satcipks ' Exygen Study No . : P000113 1 li I y8aa Prmeed Nuubrr: P0001131 r~ - TABLE OF COMILM Tnu PAGE DlSftiffilf10N___. _. . .. ._._--. ..,..,._ ....... ......... . .. .... ..._. . ._,., .___ .._...._ .. ..._., .. ..2 TABLE OPCOR~lEltf6__ . . . . .. .. .. ..... ..____ ..._. . .. .. _ TRW MATERIALS -- ...____ _~______ . .. .-__ ..___. . .---- . __------.._-_------ - .. .. .-. ._ . . . s O87BCT1VE . TH6l1N0 6 STUDY D~ . .. .. .. .. .. . ..__..7 $FONSOA ._ ._.7 PROPOSED fiXPER016KCAL START ANI)MMINATION DATE S >aEN7IIr1CA77DNANDlUb7WICATIO!(aFT~TESTSYSfB>vl .. . . . .:_ ., . .. ... .._ . . .. .. ... .. . ._ ._ ..8 SAI QI.E?AOLZJR88lPNf. R6CE OP '1' AND 11ET8N110N .. .~ . _.~_ _ _ . . . . .- . . .. ..... . .. ... .. 3AWLBIDFJf17F7GTpN ___ _ .. .~__ ~ ._ .. . _. _ . __- . _ . ...__. ... ._ 9 ANALYI'lCAL PAOlIIi 81lldGBtY .__._..__- ..,.r. .~~_~.__._._.,...__ ..___- 9 YPatIFACA7ION Gr ANALYlICAI. PiOCt1RE . __ _-- 9AFElY AND HEALTH 12 13 DATA RlCOBD>ZQQUO _ .____-.._ ..__ . .. ._._ . .. .. .__ .. .._ . .1 3 ..__ . ....._ ... . .. ..... .. . . . 14 AE7PN170NflPDATAAIiDARL7IIVRVQ ... . .. .. . .. .. ....----_---_________ .. ..14 APPElmDC 1. ANALYTICAL ~1710DB. . .. .__ ... . .. .---- .. ._ .. .. .. .. .. .. .. ..--------^------- . i s Pur I J6J Exygen Researah ~ Page 45 of 110 p . 45 Interim Report #23 -Analysis of Sediment Samples Exygen Study No . : P000113 1 EsqW Promoo! al awbw. P000 1 131 IIVTRODUG7'YON The papow of We study is to purfo imdyd s for par0uorobutasaulfonate a'FB3). (Pm) and Psdnojooetanaujfo mu (PF06) m -nqx. +091, aedimau, s ds, e1wr, vropation, =all otrmmal Uwas and mU toomwl seamt wing LGIdSJMS fo r the 3M Dacatta Mamita ciog PION The W* will be added for oOMAaaee With EPA TSCA Good IJbartory Practioe StadndS 40 QM 792 by the QoW ty Aso,sanee Unit of Exyw n RMNNCkL TEST MATBRUIS no No nu leriels am p~norobutanea~lEaoate (pF M (R'M) and (PPM ) and ae alt suppked bp 3M . _ P1~B8 . Chan" Nast : Molecufar WaigAt 33E m pplied as the poe ednm oak (GFwSO3'K' ) Lot NumE~r. 101 Pariq: 96.7'1L Tttmdt(om #6onita:e& 299 -a 99 StuattQe: FF F F SDj' F rFE18 Camiaet Jinoe: 3toleoallrVefOC 4M tflppifed as the POtWOM +MIt TVug4t7C) Lot IVtmbw: S*36 Pailr. 9RE9G 'lta sWms Maaitme d: 399-+30 Savel~ F F F F F Oj F Afte 3 of 65 Fxyga' Research Page 46 of 110 p . 46 'ltiterim Report #23 - Analysis of Sediment ~les Erygen Study No . : P000113 1 Eyra Proooea Nnmber. P0001 131 r MpO B Chamial Nana Prrfluo~ooc~oode XobouMr Weight S3 8 wippded as the potanimm LotMmber- 21t- - PoePty: 86 9X _ : 7 r~i~ ~Maedbaaed 499",- 9? SunWx` : _ _ . F F F F F F F Sp3- F it (CsF1?Sps7C) OsJZCTiVE Tim pmpao a[tbis study is to perlbetn swayde !bc parRuorobumaoNoneo (PFM (PFIM $ad e (PPM In wner. ioiL +vdirn- 1ak alemk vt pwtioa soul memmal liven aid aNIl eul Oel bumet, for the 3M Deostur biam9mft Prom ueiag The r. c~aat version of the dodoMuL ExYlpn unebMu1 med3odr. Vd001720: "Method of Azolysit !br tbq DdsimaboNon of lafhnrooaaooic Acid ("OA) in WMar by l.CIMS/!!iS" . V0001781 : 'UsIboQ oSAtrlyde Ib<tbe Deb ndusti on o( ParRuorooaanoic Acid QIFaA)inSol bTU'JbL911118" V000I R2: "Method of Aavyvis f r the DeOemiastioo of Perlluorooctmoie AdiQPOA) ia Sdimuc by LCAN3AaS ' VOODtM: Numad a[ Anelyw hr the Dab uaiaatico of Peelluotoootanoie Add MK~Wk Pib aid Cirmoe by Y~lA1S ' V00~17i4 Au tyas !Or the Dda oo6mm oFpRfluoroochnoic Acid (PPQA) in Veptudoo by LC1M3&l3" V0001795 : "Method of Andysir far the Debmumon of Pe<llooroootmoie Add "M) in Smll Mao moi I.irer by L.CJM3/lNS V0001 M: "bld6od of Atrlyvi 16r tM pl oRwAsudon of Perbwroocuooio Acid (lPOA) in 9a W l4a~r Swwnn by I.GMS/MS" Tl'$TiPI6 FACELrTY Saypo Raeoah 3058 R eaaa ca Drive State CoUeM PA 1bt01 Phone (914)M-103 9 Exygen Research Page 47 of 110 p . 47 Interim Report #23 - Analysis of Sediment,Ssatples Exygen Study No . : P000113 1 HxyW erorowl Nmrbw. PM]P0001131 STUDY PUMCIOR Jtlomba Ke a i Pl.. DER woo= Soh udwk Inc. 1460 Wamc Wq Wad ChMOer, PA 19310 Phooo:(614) 70 1-3761 Pnt :(61Q)701-7,01 ] kasi~~eh~dau .o SPONSOR RZPRES MA1TVt S~.ch W A . Sam= 3Hi cm"" uiwo~or of aeyd~oocy A~es 311s 13aildiny 023601-13-10 St . Pml, MN 55144 Pbeuo: (667) 733-6374 PRqVCIPAL INVESTLGATOR John M . Fkbwty EaY1 m Rcmud 303t Reach Aive Ste* calke-k PA 16301 PhoMrQ: (S14) 273-1~J39 johm .s~heA~~s .oo~ PROPOSED KjCpnfl1lENTAI, START AND 7ERMINATION BATES u is ympana vw !be m.truW wrcm of to Oiay >o meftua from OaMer 0 1, 2004~te 4 ess> a 31 . 300l- The *MW axpedmxanl qart and twmisAoa 4tlw wi11 b baked in the Sm! -poet pop 1005 Exygen Research Page 48of 110 p . 48 Interim Report #23 - Analysis of Sediment Saimples Exygen Study No . : Pt00l 13 1 SxYpa pmMcot MWftr. PM 113 1 IDENTIFICATION AM JUSTIFICATION OF TM TEST SYSTEM The kllowft ne on bK syatsm for this "y : WawwroOedwsper and tur5ee xaterj $ov ! Seduaopt p~ C1 m Yo~e~tpom Smdl MMM8 1 I.ivV Small Ma =1 Sums The S-Plea will be collected by Wa1DOq So4Riosr. The comzol amples will be ymehuod tod PraPuod by the Daaag Npbh P.oadnd proa =ing details hr the ooaoncl srW pks will be 1ROWed in the & al fepoet woeiued with this mdy. - The taM ryww r wee cho m to caaw Ow earilans Nmtat impact of PFBS . PPHS rod PPOS in We Deraor, A) lbl ns am SAMPLE P1LOCiJROllaNT, RECEIPT AND RETENTIO N WSW. roil. WA-Mt 1f lk clm. veo991e4 mwY mrmmal liver and = .11 it from We~on Solatlmr d~srm ~pipmoc ~ em~ ~~ ~w romtined in the 3bt wodk plan added R)~e 2 Wodt Pla for S~ mpr3ng &rvieoaaiemal 1Ned 1a" The =mbar and typM of whqAt oolbasd -will v ory depas ding availability In the Said. The WW nmbw of IMPIN moved and analyzed 16r MA ~AriY w ill be Aoamambd In the !hid tepat ayocisced with this uaAr ' - . - WNeoe. 04 and edimmt onplw will be wed a moved without thither P '00 ~*'M OXYi L rMw SM&A will be i0aeed niMIJ I raed at 2'C-8C. N+h: e1 m w~04Mi~a' and muff *AUMA9 IM amaplw will be prooewed 'or614 to me wProPdw mNydai method (me Appadlx 1}. Tme .oqv' will I. .oer.a fib= it S=1o#c. snu uwaa,d w6olo 6k,os aropbwwiU b e oateitWd in dl e Sdd At ft OM oteaikctiom aod ft umm Bud= will be wed ibr iht gudy. Small mubnul W= w ill be storod sM.e of s -to a The moiDt +od pooewfu3 of ft =mplu will be aoe= mtea in the fijW -POI and raw dua au or3a1d with the sludy . per 8 0161 Exygen Research Page 49 of 110 p . 49 Interim Report #23- Analysis of Sediment Samples Exygen Study No. : POt10113 1 FucyMo Prebd Mumber: PO170! 131 SAMPriE.$ MNNT'fPKA1ION Prior to eari,y" axb u mpLe wlpl be eudgied e Lboratory somple n}~ermce nwnber. The tefmanee aumbcc will be uokque and will distinguish cuh kbomoey wapie that in q - oeMed theouFtant the wolytiesl pzocedurc . C;hrommptphic dets will be idaaAifled by the labotatory umple reference mmbar. Spin ebnp candtiaae rod baatioat will be doom aMed throughout the smdy. ANAI.YI7CAL PpUC'MUBB SUMMARY VOOD170. `bloNwd of Aorlyaie for the DatamiaRiou of Pabuorooeunoio Acid (PFOA) as WNW by LGMSlMS" Vr7001751 : 'Malhnd of Melyen for the Ddamiqrtim of Parfluoroocteswic Acid Q'FOA) in Sad by I.t'JblSIMS' V0001782: "Medtad of Amlysis for the Daermiotttioa of Pertluoraoctmwic ~ Acid (1!FOA) ia Sndhnent by LCJINSlMS' V4W 1733 -, "Mafbod of Andyeie for tite DatamboGon of Pedlaorooctanoic Acid (PAOA) in Pith eod Cbmss by 1fiJMSMS" V0001764 : 'Metbod of AorlyiR for the DeteaNaidon of PerDnoroopmaie Acid (PFOA) in Veaautipn by LGbLSlMS ' ' VOOD178i: 'Mr16ad of Anrfytis lar the Detemrinittiop of Pwflaoroocatwic Add (PP4/1) in Small MsmnW Liva by (l1MSlMS,, Vfl001786: "Motlrod of Jlwlyris for the Determination of PaihwmocUw K Acid (PFOA) ia SmoU tt6aonrt .Se:uai by LC1Z,6SlMS" 7bs ebo m maHwdu aw auOytieal coaftow ceprble of seprating the mom of PPBS, PFH.4 and PlOS. The !leml report will include 6e womm sammed into total PPBS, total PFHS . as>i total PPOS fomd YNM 1iCATMN( F MfALY11CALMOCEDUitN A Wowtosy q,=&A uncle will be >red for do pap=am of fortified ooatlol eampt.e. The NO ab.hooe will be m. b ism solutiow es per the nethod, sad ad0ed to the matrices via a mierogipace . For wow aaqtIIYp, 8syyen will wppiy one bottle per ample eouected. The ~+ boltb wilt be SI)D mL pceetaned Sei/Spec Premier wide mouth HDPE bottbe. Tltiss boMies have beer routinely used for Auosochemiul sampl e Pqr 9 o~6S Exy8en Rcwmh Page 50 of 110 p . 50 Interim Report #23 - Analysis of Sedinccat Sunples Exygen Study No . :- P000113 1 E~ry~e. P~mca r~..b~r raoon z i coita.4oe at to tatios facility and A}w~ aho+va to '5e kw of PM . PFBSaal P["OS. 3anpbw win be added to *=aim %* a volwacaic flit iiae at 200 mL . A lfald dspHalq a l- Sdd ipits sod a hiyh riew span or aa h .amOle a M be collected. lbs low a d 1t>* field spalte bottlea will oocldn PPBB, PFM ad PPO 6 as~ u "ffo omoct.noic acid (PFOA) and 1 .2-13C pa & oroodmoia acid ('t : PFDA). - YFQA and "C PFOA are ixLoded itt tAe tplalfeaa Mod to Bpiks.tlwaaa8la. 1da M lti ON PPOA and DC PPOA wi ll not be npo fttl in tW moo. FaxyW will sy qlly one field bl.olc (cowed wow) and two field blralc apilcea tooatrol won fortified with PY7S, P'FSSamd PPOS 1tu loe, ad fiii6laYd) Porevay twwy samples ooRroftl. At ft iMft 80 'bty, each arr0a latnpla (walsding Gold duplicator ad field apfber) will be exeraeicd in ~te and will also be Wiled It a km and hijlf oceoawatioa with PlBS. PPRS 3.w PFOS and peoeaoed *"a* Ow dpesibad PtooadwU to 4alrn4iat meabod aoqraey and to ahook for Mu. For all, sodkoaqf. clama. .ad veruAdoa, Ilxyaa will supply one 500 mL peaeJeaoed ScUSpu PtMOict wide tao b HDPB battle pa smple collected or a sipaai by. All ooata6nasfbaia wed {bt armpk oollootion will be shipped to tha mnplb btatioo Samples wilt be added to each ooatainer or bs% in the fidd At the kolaag 5i 0ty. uaeb ample will be extracted in dqpliease and will aLo U faOed at a loecivn conccatntico with PFffi, PFH$ and PFOS at ,. . bath a low and 1>o level aod pmaat~ed tlnoujb the doactibod pcocalue to d leoe mse maHWd aoe o acy sod to cheek !br bis For . amalf`m "md aver. EaYSm wiD supply a SO taL polyopyleoe eenatiili r mba For =W womi l mm, P.aygea will apply a aolkcs;an kit 16r ack siqa*b ooatsaing wam atpaa0o taba (wd tap). vactweimn . rwdk ladders aid aeedla, adder pipdf om, and oolyptqpylene tures . At the tuft SetWy, auk 1Ws sad tavia rmpte wili be a+ttntad in duplicate aod will abo be I d A d at a kt7owa aooaetwtion with pFH3, PM sad PFOS at both 0 low ad >>i# Ind and pvOCacOd th~0pgh Ihs doaRtbOd ywoolWro to del eamioi Maud aeearacyMd tarJhert Ix biaa Law aed ' levcia Eos acb m oix at delfmd below: Llaeds Low "Nu tarrl ftNLaevd~ Watre 500 5000 soil 4 awl 40 a, -Wll SIMINIMINa 4 qW& 40 Pw . 16"ta 100 awl l 100 nw& V 10 100 8o" >lhmaedLivar 10 1001WI $~aafl 9~ Sannt' 1o alka, -1 100 aff/mL Arp /0 of as Exygen Research Page 51 of 110 p . 51 jnte : im Re" #2.'~ -- Analysis of Sediment Samlplcs Exygen Study No . : P000113 1 ibry~ee Tea~otd PIr~r 10001 t31 Recovaria we eoliaipped to be bat+weep 70 1b and 130% of the fortified ierrelt; brona+r+er, tb a~aet pqoirioa tae oaey ? viU be detwnifned by the mn lyos of the quality owtltol eempla deectt3e4 above. A statement of ecuewy will be imbuded in the final report. MSPREID FOR CON774L OF BD " Control 4( bin will be tld ened by taking reprNentadve ab-samples from s bomoMeowu mixture ofeach murls from imtroetod oochot aanplea and by auatysi" it lent two lawals oflbtllfemlmt s. Sr?A'!7S'f'[CAL DIE'18itl$ Sa tlrdoo will h e lhmlad to thoe opoi8ed in she wbjeot methods aod to the eababrdon of avenge amowxries, as applicabl,e GU STATEi431V'1' All aspects of ffiio stody rheII be ,terlbriaed mod reported in ow*hm= with EPA TSCA Good Llonqory Practice Stmdadt 40 CFR M . The Qeal iopoR or dale peelap (apptied to do Spa=) A A oonuvm a swenum that the r.u0y vm aam8reted in tompliwrie with cramps and appHpbk GLP atmftr& and will ou d ne my deviations in the vudy front these wndards . This win be dSmad by the Study Director and Spoasor ~ R$PC1HT A final report will be prep~+ed by the pdacipal iaverrt*W or or their desipee at she eoatdodon of do rtody. The m,aott wrilS iualvde, bw will not be 1'uniled to, of bUwmF The Ym ad Abeam of 6 s Sa-dy Dirxxor, Spextor Repmeauave . and of tLe watims fciray. A suftmMt of GLP eomqllasce (ray related dowmanwion, aich as eba 6-ofanRody:eeadr, mmt be in the aj dy mooed). ... r. ~, ya, Exygen Research Page 52 of 110 p . 52 Interim Report #23 - Analysis of Sedinatnt Saruples Exygeu Study No . : P000113 1 Facygw haaa Tndba: P=113 1 i- The fipoed sod dated staianeml by the Exy,ea Reaeaoch Qaiity Aa MWo Unit nS rdi * dMM of RWY 14 j' -r ian.d Qdea Sadiags aa* earaeet to the 8wy Dimolat add mitormamt . . A deaaiptiea of the ~sacx swytieat oonditiom aoeplorod in the study. If t1r rubjacl matbod was Aoilowad motty, it is aeoeswty to include only a c,opy of Ihe wdytiad aielbod. Any sodi6aatioat; ID @rii mtmd will be ituooaDenmed bb to tapoet. ff t6e msthod is piiolo-teduced. the projact number asd pa p nm*w man be ineludad on erbpa,e. a ' ~M~plf01lot1VD11f~ORSMOdtlIdC~iO~CoadltlWM . Al! tmmib iara aY aab aaahmed. Central aed Ioet"11ad smples niU be fdmd&d mud rie dm table r8! iacAsab Wpph =Wbw and fo>titfadon leval HAaaaladve ckaww4rmw Ow aoh aealyte in each matruc, mcfidiog dv*0wwF-== of i ti i d and a wnbo} asnpl4 mad a ctvomasWam at a Rxltsca<iw hvel. The lo=Wm of the wAty ft peaks will be clemoy ideal~ed ia a! oheoaatmo~u r ^ AA auomrtanoa that may 1we agbomd the quality or iwaSrity of Th wUl ke docnoaxed in do report. edat, Locations wNane mw data rpo4 the snrl npmt =a to be archived- 'lldd+doea or meaed~ lb Am Mad r:part ti~ be in am icrao of an an~att stp~ld by the Stidyrfleeator. Mw aaaadmeat aha@ closely idaW* that pod ottrm tapat *R is Wall aHee .a ad the ra.om for the .ieerassoa.. The .r<oieol will be aipea ad' dated by me Study nin@Ior,ea to srae.sm~ R.Raenwwe. . AII appiiabit nqabmmaoz: !a mpmif*of atady raaltt aa-pae 40 CFR 792.185. sAFE'rY AND BI ALT B - Lbanlosribaoa.d will p.olka Sooa sao midoi and health hoftL . 8wry t. ..oa.ws pnontiop rh .u'i. taken to pn..~ ia.avartau apmres of Dmso.nQ. 4 gd .16e Povfiomeaw to the rort or reference wbw~oe(sk . . Iw17 of 6S Ezyggu Research Page 53 of 110 p . 53 Interim Report #23 - Analysis of Sediment Ssarspks Exygea Study No ., P000113 1 l :YWmlt4eW Nirnbsr P0001131 AWWAMM TI8 '1'tl P'liO3'OCQL AU dVifieant dnngaa to the analytical protacol outlined here will be espiaaed in wdtie & d=rod and dated by the Study Director and Sponsor Representative. Amendments owall,r will be issued prior to inhiatiou of study pin dunSe. liowavp, when a comp is oeqttited withouRSuffieieet time for the ism of a wzilbeo amendment dim chop may be effected verbally with aippostift doc umea;1e$iott ,130001d Lid dMad, by the Study Dux- said followed with a wrium irwdo20 as soaq is ppnible. in this caee, the e>~e date of the adtlqo Pmmdmou will Defhe, 0 e of the documented chrnYe Copies of the s~ teemdmmb will be appended to all distributed study plan **ft. The original amendment will be maintained with the oriyoal +trdy ph= Any drAadons frora.d a study plan or ft= the wWyucal melbod aa provided will be dwunmmd and reyated P rocuPtly to the Sponsor Raqessenptlve. DATA RECORD KEEPING Records to be maimiaed include the follow ing (u appropriate): Sample bacons aww(s}. Sample eeoaiPt reoad~ . MoeaP history. and cMu of custody . History and preparation, of pnnda rda (alrx#c. lbrdlketioo . aallbru9on) . Dea@iplim oimy nodiseadoos to the mtwd it Instrtmroot im heoes. .eiocti-aheeb or lo{a Autylieii Aft tables All doaansaopspisie and instrumental eanditiong Samryk astrfion and aalyo s data . A oompleoe 1ioft oi oody pesa!, dgnapua and Initials Chooologiai PreaeaatioA of all study concepondenc e Amy other docoma l wx necessary for the reconstroction of the study Che+vaus*WMms- All o6tomaoojeams will contain the fa31owwitt4: Saawk dmNem don, hi eedm daK woo or other indication of the &= of fftenat, and lqjMtoa number oortapoodins to the roa . Additionally. fatilicatiom will include the atawmt of aeaiytn added and rie sample number of tYe sample that was tiixtitbed. Analytical ataada+d ehroaycopama Will additiotally include the cootmtsmion (e.6.- WmLl Pop 13 gras Exygen Researoh Page 54 of 110 p . 54 Interim Report #23 - Analysis of Sediment Samples Exygen Study Tfo. : P0001 13 1 F.xlRaa PcvbcW NioNer : ?0001131 . " - Aspn ot lM do= anution the *lbsipgahsen will beinehided ia eech M lytieal Wt It tm iheec Bdft the t+timpia to be am in the sr, cod an iartranknt candidats sheet describing the iosttro ment type and oQeradns oonditioar. . . f, . QUALITY A$SUYANCJC The QA uoit of P q#bo Raa ch .viU' iptpecc The way at iatvv, b adequate to Ulm Congo= tr;lf c3i2'; ad .n1l :eporl the ausna, of .NHU to the senay DaeoOor Bxyp9 nl.oymotm~ bit the 40 .or Repraenau .e . RETENTION OF HATA AND ARCHIVIN G AU hwd copy caw dm4 inafid'a & but not 6mrted to, the orisirml CWGM bW tmr6 woddheas, oaat gondtaroe. and raulu sha11 be inctnded with the dW p oksp nbedteed to We $A4Y Di:se,tor: These will be -dived with the or*mal mtdy Pha . =Me ft emk fiW rvport. Wd all pestiaait ~ inlocmatioa, from the . 3yon. w. . T~ talftaS &c&y Sw k" an abx6rooic raw dal a and any, iasuMmeot. IOP for 20 pitied oC tine *eaified in 40 CFR 792.l93. Ai1 mace copy Of the marei alr wibmiCed to the study director will aho be hspt at Flryytsl Rt>roegt& Buylen will obdin pmnit+t3m froen do study director betoia daemdag or tenuami "Mple L ~ - . PW 1<of6s Exygen Research Page 55 of 110 p . 55 Interim Report #23 -Analysis of Sediment S"lag Exygen Study No. : P000113 1 r - Unwftft*W Number P0001131 APPENDIX I ANALYTICAL METHODS V0001780: "AGthod of Aadypt far the Detamtenioa of PerRnorooctarroic Acid (pPOA) in Wmoer by LGAISIMS " V0001761 : "M41hod of AaM~I>w hx the DAamiaWm of PuAuomommwic Acid (PFOA) iq Soil by LCAdSIMg- VD00t7i3: "'Meflfod olAadyai for the DMe mipa9on of PerAuomoctwoic Acid {p'8OA1 in SW ment by LGIfSIl4S" V0001783: "Whod of AWyak !or the Dd=d=dw of PaiBoorooctaaoic Acid (PFOA) in Fish md ClM by LCJMSlMS " V00u1784: "Metbod of Andy* for ft Dekamiaslim of Per9uarooctaaoic Acid MCA) in Vesmioo by LClM31M3 " V09017 0: "Mfemmd of Aa dywis *r the Debmwimt oa of Perfiwrooctsooic Mid (PPOw) in S=i1 Mammai Liver by LCJMS!lYfS" V00017i& '7dedbod of Amlyair for the Delwmim4ion of Perfluwoodaooic Acid (PFOA) in SoW1 Mammal Sam by LC/A"g" p4w is aJaf Ez}'gen Research Page 56 of 110 p . 56 Interim Report #23- Analysis of Sediment Samples Exygen Study No. : P000113 1 i' _ Etypo Ptowol NMbec MW I 131 Arw .rrtcA . bCsrxoo M w IP.,w vaM 17" llrW iM~i r.lw 1~wr~YWw HlrrOrMxMMe ~uY R~'DA1 ~ ww . , biCAS~ Am"" Taw /pir. Lq~w~~et RUN" Ddw a~r L1M~ rA It~ot APPWA"I* ' ~l .,. t~ rok~/ar hM CrrM . :. Dom _ trura~ .~r,u+a~.~.+~ r..u.~ ~ - ~. t alas Exygen Research Page 57 of 110 p . 57 Interim-Report #23 - Analysis of Sedimeac S=ples Exygca Study No . : P000113 1 BYypr Probed NmMr. POOOt 131 r ro..a ..w Ir .r rr .rvor~s MW.rncAe.larlloo "~~i~d Aa~QfQA)iNYrYy 1d7160 4 IA low M& now is w M =0AlM kr IM YoMin W d W>rsseemeie aii by trl Ir hmmi a 1J1 CYdro/rb awpb/ is a on" aIr 7~wYrd.k Dreeep.CJlAram Is ww i~ >a" 11 1ti~yt MM ev lirrry'rics u !'.aWldqpa~daYl~dOMnlM~twfeirleakdPAMW<Y Mwr. 3.~ dM.lq+~.l 7. 1 uw.trrsKMNM1~MUir~mc+i~w 1.2 IdaarwUpum {rrai~alrwrrrAlw. X3 daow +nd w61wrIM a1wAl M w s.ed o NwlitMS a man t^rr~w sA -4 now adWfrdtMwrsMft wmqWarear .nra. 13 Aq W00tf wiWft " alwM a am lllrl0 Y -)006 q r br -s Wida W d SWwrdwr irfa .owlfoa z6 t,n* wlraiw Nawj.w .a be mpm er in ea aempft on ri. W. o ho w {.~ Y~/rL W!lrlt 4.1 WNW-IQLC/WM .a Mond-=Cratf 4.2 A ~Auo. - wc.i. lOr/rt aw 1.o Taa .af .ieAwr-7yr .AYAe SA 11d1idI11tlIvom d 11 A ir I~ I M so i 411ww aowo aM+k at 7oM4 0 t o 2 01110mb OpillM ~i a wdrY wYd ii~ apYY d 6~dK s~0 rl. awww~r awmanasllpwmirr q CA Wm ) 32 AinRaMwltrtsiYfr2wltfulynmiari#Waea. Li An11iu11rldaw2YNafaw/~MOJm01 i 0. 4 AnL O MMIa/ah~FMi~aWM~r an 37 baLYipriYwWd~M~a 6,i: Dl~~iit { IO~L 1~OJOO~tt~. f .7 111 ~O1. iaW a~awwa~ WOOL i l 2aLir IrtLC vIN li ~V 1>~~1~wN1 f.A A~rr{3~100D~NYlo-IODYt~,rlr~I~eYM~ . s.lt wrwf~hkvrswOq~CUflrsa+~ nR2i+ ~p~syes Exygen Research Page 580f 110 p . 58 Interim Report #23 - Analysis of Sediment SanVles Bxygen Study No . : P000113 1 Fxypn riam aai Numb . P000 1131 __ .~L ,~. .. - ` .~ ~r~r~r.rw veoei - ALrNYl1CAe.iRTtwo b CCI ~!eti 1t2 til MMONilYYl AP ar1r wrh4qi.y x .t. o~bvwv7+w . Y. r~ooo yo . y how al Ahu~~MdCblslM/YwMfX~l~MidW,2 .twsaassp Qae ns.~aorn! a : 'lOMErw wC is : 16"A. .UU : 2 arc Ati.eue- Ae1nrf2 w0 . 64 lUW 1MW 01 : IYr i aS ai~la/s tM.1~w ZMLO itl rie X! ~idil 4/ ~s u a] 1s 3s 03 /A 2f 7s 53 , '. W u u o3 y"M VOMK 1Sr1. 6= Mai+rM 1ob Ml =5*161.4 a7 QWslMkAs-~si~Yiiai~li~tu~e. ai T . -as ai.ra /.. ' 7biw~~If~aiM~Yia~/iUdr7MdrqrOiw~b epldrr39LC ft" w 7A ' MYW lrra 7- 1 lY~1Mw~11i~11wNW1 wob, weqsft4l3 - 7QN ffv:. rift awn. i Wg rr = irrlM r a /We W 1 way M tl-kp e a nis r '_ . a~lida~qriKflbqra W t WrWr ajaYdbs 1.1 N~Yi Iir~ - ~1 .1 -2btt~I~ar~Yw~rup~rMl7~OiYi{Q13~ ~d a~i~rt~~b 1~00aL d .Mr. AYnwwarM sy M7e p w[ . :4 . . - - - J paj,rl/a/IS Exygen Research Pagc 59 of 110 p . 59 Interim Report #23 - Analysis of Sediment Saapjes. Ezygen Study No . : P000113 1 etyp. vmmaa l iaowe aooot 131 APALTMAL ~araao ~r~w u~r~~ wa~Tr Lo~es~s to .PROrrtsw.Y . . . . ft .2 lawa*aartrYWad-tooW~Lof!lWb~+wtlvttonY daub" wAwwd laannoi Y Yr yak" ad Men as too ni w Y ~KYa uSi 11~!' ~Oo~ All A 10 MirLAilihmWa nYios at!}OA Y D by *won lu sL 4(w XO t WmL4a1.R b a rd wls 9I1W ip a..r .r l ll albaLt w iYfl a . !k I .], AilydWoolrfwQT/OAip*rMryDayi " in . . a6efOrtOtOhi .aalWrrafrlala .dl00 .d1A~lw+ . . at77~L1MMO. lt .1 AaI~ ~(,Mrba~Ma9lMWafROA .Mqm1 bylvispy to aS.d~aLO~LaaYIll~Ia .WlreYa~.atlaw~ .aYW . 113 A DA pjO d Mldaeen asLYr afflOA : ra}rd by Miao y to atf. dM Al MIMl. aMaliM O a iMl " Yaes of 1w MN r/rl 106 1 334.Lif!lwatr. VA rbae0cral~iearlawwhMkaawrwao+N : .~p.err q~i r~[danaoWiatka~la~sr.dolarss ea r.Lp " qdi.a . fs lydritaNrYafairn a ,a chat man" p" To 1 t q oWi an wt Y MW ww. m d aa . aa at.rla a- pwua.! 0Agqk% 00 aYaaiaa Noadu WMLatr.a vaa !~S 7b Iii i a qirl aayU: d*JW l $MCWAV ar mry br p wwiasawbl Tod Ca1rWas IaMMO~ VAa~d GtiawaMfa+ .f CYirL dlwdirYaa Mtlar ftd6i a w1 6lldfa, friad D ?s xddip -l ie w o ioo xoa .+qsa a to 40 aw xcr .rory-+ - w in 49 sao 1co~~by~s rr o LM xa.r~r lMmaa aa:r~Y~ .traeaW Wr anWtt'r pW w i. ia ~d .t *=Mob" C.01040 aMa.Ora .f*aatdrd Ari{faamr+ba{01q 7oC a~r~ ia~Waa raira r,v .w . Per 19 of QS Exygen Research Page 60 of 110 p . 60 Intaim Report #23 = Analysis of Sediaiey[ Satnptes tzygen Study No . : P00113 1 .~ - sg ys. r=0=4 Ambw, r0o0I 131 ~...~ ._ e....r.rnv.nra .W4YRAL. 178o. Moolied M at two Ommoulmodom N - ~ Awi O ic+rwa 1rN"rr b f.l] A es miWt .YY n (nqrtit MEW UNUMAMM wYh wee , trda~o.r~e .r d . . !.].A ir aal alrri irfo~ wrdrr r tS.al. podpi00ylris aou r1't:ri~G+ ~twwwYa 14f AMir~~el~rai~wrrfo~tdrrrrdo ah'repq uw r ~wtM` IOA . 1r~Zrt[ tol f * Ortl dSinging wiarM ~f ~Oeie) mor whole, rt ow now, r WW mod aWd Wool: MW yhr; ir0 ho wqwu 4WD* iNW r Iwr,a nu fw woi so" m w j, ~wwill nmwr YfAr11L . - - " IQ2 1 bYVimimqoemfmt~ e Igo,O d11ngog01bioglobb ,PNiIwpiLfars ad qOua wii be * e0af " ItA _i~waYwe6a0 . t1.] 1MrwrO 40 ALiw'bw a OrYrHrrYfYMa O d .iA~aw . lef0eL/r"wVJnogn ~~tMdd4'seMLt~Ye~til~.e mkwdl~ l ts com"M on C. Ms e1d 40 R i6 U b t'js N o et. mamma Ibm w 3 mLafZPLC (-Zdpotw), volmom sa.i rr ~ sd nan 7tA OY INS -S rt. OM MlrOl Cbir ! r[ . of among w/rwe noting (W te.s .y 0 tsa It! Aeite~lr+r'ss+oem ylCArIW. MO - cad.rlfvrtW tsA y d i s womm, w fI ..+rebd n.* ei beW m.now was the LbIWA/ "mum A e1wWw owed" Mum pwmi ori how- W Iti !~ i~lF1~OAorO oo WiMrlrtMar mum, oreeion rwis set Y WYf e e~lUi rt. 11! A~ ~1t ~1 d rtmoYd r10rrSe aYinb NOW IMP ioMiO o Iha Y~eiy a! a i e/ d a nompb rL iarwd ravii ..r ne ie~~ (wees or" 110 MoppYm . As edod.% egow mg of . ~a~i rl~rle b ay be IyMW r i MpriK of * on by NO l/ eMOMba e l* + ' 1//11/ OMry 3.4 0 vou pka . i yww{ 6, toomr/ M d SO" rrrY1. to inr ww. MINNO W etlirfelYterltlNY # mod LOS YrwYe M 0 mmpo "w 1nnow wnr or 9rrMrMa lJrr Mmii OF"" a. ir~~ f i e~0'rb 6~wrr~~ ~rt{ t/~ +rrrrMa~t~k+e ~sa* rw v of du E-x-vgcn Research Page 61 of 110 p . 61 Interim Report #23 - Analysis of Sediment Samplef ExySen Study No . : P000113 1 Saygva Aomcd Ni :haber 0001131 as .~~r w~rua~R rwn~ .a iiGlllAo imwaary ~lar 4Amnfn a a0n0 w .ear or f .K mo i vus 73 (or am-.limm) PLS == `dl rt w ar Ammedrt w p ovti Any wWs am w+r.a.r. d ,w ow. +wr a srra as. .t .i ~y..a // A Zp hwoplarQdYd. U.1 Qw~al~~rM/a}rYat.Mrolari a afNa~6~apw+ 1(411 rr 1b ~I] w NaM wnaa~a .i is M r ROA rma +li m: A~M~r ira~ ~a0 p/+a.r i .laa afa~s `eaiM . 13.2 66OW 1M& Iwn Ad =00% !/OA a Yr.>r prr fa IY IAQ. Ir a ask wiWM IMA a bob SUM 60 JO ar4 dm . w 6iok swF& awM r QYWad r+a .ra r aar w - wrna 111 1qaw~ of ~~ ;i~ n0 aawa ais aa M OaMr 76 1 IOK af rarr>vw. w4 . r . ..rd+'!a rr a.ra.8 . w.p .al. OEM a. =Yn M of r! n dO.M be 1MIwtM. Amy mom mpOa a.a1M 14 lUlr w.11 M wYis.i bdw auyr e 4reiar if waiwmlm iu ral 13.u edMllr do" ~i r M . mom* now by ARMS do M~e E tYR . q to wdvid Ago Alm; erwlrfw K Na w1bWA . am. sw .wv, s. w arar .t .o.Nd otlM.re. >nMerb * .aaw b. wcML1Y .t .d mod 2M at *r tlM aYar of faM OminOt iyn1 t 174 71r mmwWu eMddm a1 A t awwllm warm lwantl art b. 14M Pe 36914 Y iaY me =Aft 60 am" ear tluNL tk. "WNPiAR; RAW owl be who . y.0 i,..i .m arsrR WA ft M~aNiMUb1.~a~dw~l~rwMM rOl~ 1Sf Y~fr dm alla .m moffi/ wim MA IltpiW mm .01 fth mom IE+ n lN~rlW~~rlyWls K mMim tY.rdrift radtYY IiiL Mtla nM .yif~ter~tiar~arw .~tr+~ l~e C1inYrfw MI IMa i. ii.i~ a~l~ r aYdra Oa ae~t HNQA L~ri Cw yR. aa~ ~k w1 ilf ba ~r~aMr~ .rw (lrr ra~wYaw w~s~ rrwri b~a 10n I,p s~r . No/aaa: )f011 i~d0~i' ~G~L a 0 ~ a~' rr.~. y .w ~ . ew .own rr rwr. u e..arri wa.w~ Pqw l1 fjQ3 Exygen Research Page 62 of 110 p . 62 hnterim Report #23 - Analysis of Sodira~ Samples Exygen Study No . : POOQ 113 1 Fiypa hoto~+o~lhnEOr. P0001131 /a . lA~a.r~ . . . . r~qrl~ Wrn~o LOIWl6 m y ty Z bAlM sit bxw ~r at1JOA pow r .srxenx u~e .. ,, ~rfvr= rllWrr}rwxtamwy. 1~w~ef M1~ [~wliLMrlrY4~'~ +~IwdkarMWU~ x~oD h~~w7 PAWS of" Exygen Research Page 63 of 110 p . 63 hiterim Report #23 -Analysis of Sediment SuQlss Exygen Study No . : P000113 1 BzyM Pmioed Number P000)13! ANALY'IIG11. WRTHOD itMNlLnb~c w00o17~f IiAYHdA+y~Y4 W 7Wn~i~~llW~rwMdr .vNRlOAIf~ M~ Y7 MY,,k07rYif~~V ~ w1Al .s pW GOw. TA 1ii01 Alw~>tY >rL, ..~ wiu.bJ lrt~~ D+ 7reltlM 1.d~41CyR ~~r YweM aV~fYi~y Vtr >~ii~~+. Qi+nY~alr7~ Awrw~ A" Ga ~ ~' .. . . 7oW !!% e 7 PAP li oji7 Exygen Research Page 64 of 110 p . 64 interim Report #23 - Analysis of Sediment SamVks Eaygen Study -No." P000113 1 EM e,rroa~elWw " PooollJ 1 . tp ~_ ; ` . . . .. ' Adevro+u . sa~ lo- u '[W MMiis oM algMlrArr bold= of~.maw~a~.k a by MOH ft- t Alid O, ~b , =" 1Mma UM yrew'r prrtor(LAlml(i)u at i0 yr) It Alwb+~~~~f~~ Z4 Cb..* do qoqYr h~ 1rOn Mdiis @q chn-a ref rror ki r P-16- sA l~NASwi~.wl` : 3.t .A~ rM ts setlOawr to ana+ .. .. ss ._ 1.~ ~ adww" *Add r. .bow le *Fiona to ~mn 3A As +o.~~~ 6=ww IS s.or ..ra .r~ s yA wo- u s .r+ .~ wrrr ' .t wr-rrw~ ~ ~~ amoo. ~~ ~Atftft -ACl.>9~ QmY 44 MOewpe A.t-sPA>i&k 3.~ 1.Yunid A11qNP.nd 3. l A h* fTli aY- =sAL a*Nle of PMni up te 2 rl~r ~r/ wlr a wYb nrr Y Orr aWbM *r 4FWM ]-TOO rl, a~w/ rst1~ l~s ~1~+~+~ a~ S] A dwWtlltlYwsrl n Mri~~ft-d iu-*W!3 A~tl~lriir~Ml~Ldwd~ibpMM1 j. 3.4 SO .I.i~w~yPtYPi7~~ Id1 I A f .! 1fdAWi1+~11~i~- P SA Di+rM~ai~awM~(ldmost. 10,2004 5.1 IIf.t. inw .rw.+" wYt ~s ~aLawr~s.C+lrra o ~Aaat~aoe pc .rtataorU.wr dtw" stiv s.u w~9wAtvrd .p0cusr2 r '00 J.13 JPS ~ mooMbI 1. 5.17 UlrNirlwk r- Aaje l4sf6J ~~gen Research Page 65 of 110 p . 65 In:terim Report #23 - Analysis of Sediment Samples Exygen Study No . : 8000113 1 Ban= Piowwl Nrsic POOD113 7 ' - ANN* +rr~wr. v.ootwi .. ~R~G~LI~l7100 . Yi~ ~ Ilr m ' Aei/ Y SOiI by . 115{/~lit . . 7.N 11hdw+mdo~il~ f.ll C~M~L~*~A~L~rlr~i~.rllOORn u u~R+1Mi~+r + . u h.qlYrc7r~.sll~wirw~tWa~.~~A.t1 .~,aw .a~rr oNt~70J a I w~ 10'C u W1wr .W : 7dMAmww.aAsrrhw.r . . . s,0 1/ddkb9Yr A) : S . OmdI")sys Rb .- . . , li . .7r L1ROW !1A U& 1L/r1 U a 35 03 !1! f0 33 03 tS 73 03 7Q0 2S 75 03 33 ib 35 03 . i.8 1dwduY.Y/R IfpLIM~Ml~wrlQl>Y!~ MSOpI.). i.7 Qrii~G trLA~a-.erOdflrA~pYMreaOU~a u >R,aMO% -ntirr& TY~nreatlio~ln~/tla~aAiMaOwqM~Md'ewAao "idrlrlllCUrs . sp yfiMt 6"ks. 7A MMsXWSWVW NytlwMRl/ak w WilsiKN3-.7Nrsim Pl01~ . ~ 7% irwqrl~F eo~ hMi1~ . .l~4i~ti 1~1A dA~ .od Mp 0*sOrW in Mkr to U r.MnreerlsIrw. Iu lw.Pbr . l.41 :Irt ~J~ .wOM b w~r q y~~w~d b~ ddiM ai St t .r .sWm so= r lme eL dw. frlN 1 PqjeJ3d63 Exygen Research Page 66 of 1 10 p . 66 Interim Report #23 - Analysis of Sediment Samples &ygen Study 1tia. . Pt100113 1 aL]~If Tlopp6l ddllb6r P~01131 A~ 6~M1~. ._ . . .,+i . . . 1MM6Hd~ ~t711 .0~0~~6 MCA) issw by .. . !A ' 6rbdtnri~ .' . . !t lMYri~ wwl. _ . l.l .l 6popoom b dwk Own of-NO MARL by fwlj~IY O Mr r/ }dy1 rd 81M e~ 06~a1 . whit 1 ' irY~~li ~ 13aL I.diM~k 'l. 13 ~A t1 iy1aL ~nlLrMiw ie W~s 6f>'!OA N iwlr~d y ~i~p{ ~ u N } e( r 10p AM~L ")AM 1s 9 Mil wMwr of too wiR rmro- , , 1s n 13fsLl ofllnwb . . l.1D AIAM~i./wtlrfr~NMia~~fTPOAis POP- VT~'+t ^o1J ' ~I.dffi . 70~L~Y1hnq a 6aYrelrf m af100nihwalrM t 1i7 rL LRtfatr. CIA A.01l~1.lAWliwwbifw~t!!OA'sP~r4'Miyin{ 10 . A1.dM61A 1~L ~o1dw 1oa 6a11 v~r ot 100 +~ isterN m a ITf iiaRb+l %l-1 A dQ1 l61m1. feffeYU riniasdlPOA is Wepred by ~6 to ML of M. a! WA1. wwr to a aar vww of loa .,a id its t2! aS LNt,wla l.li 11n IOltf/lmmliodR oOYfYer im a M OWN Y I nOiAMOf K . .. . lwa~rtlas~W d6msNs =X11Sep"ONIM u arr.~ars.rus.wr. .lt7.4 "Ltt~ ai~YN MrWM w tM 90p in HM.C war. h commotion, r6 &eY w Teoto l iwr* an Or-tom I o~r.c 9ttt liwi/ s a y}iul rmoplu d616wN wwomm"lor r/ b rl~w6 ~ ~wid d e Fb - ~ IriWQrwl ~~ a~ao ram .T q~ ~ .rmt> o.~af.~r m~>.1 of 6 ~ O M O ~7 n ur o t6o xcaryrt fM D0~ A 210 7IQMON1111 y 4 ' - ~ >It 7M AQwmib74 46 t~ ~hf.6 71~ r~arl ~rtM~ 4t4maIYW m atl~d Y qd r Ix to in" .rirYMar~r6r'wrnr+isetbw~rdi~ArmneK~6~ MC - wosM6 wirrrs srL r.M . .n pap 26oJ6J Exygcn Research Page 67 of 110 p . 67 Iater;m Report #23 - Analysis of Sediment Sensplea Exygen Study No .: P0001 13 1 Eu~paPro~eaNnmba tooo(l3 1 )& 1~~ iyl~l/M YI00~11 ~ MLu.vruas w ..~.i.'~Aw PTKM4 a by ~c~un~s _ . .r ..+.+ . ...w~ 1C21 A Nlo ~~ II~r10~ fww*a YiW9 M& 1 LMMM .no b -- l.7.s !N ~ .d.r .+a./ . ~Yp.w la f!-wL p~it}opNrN o~t r~'C N A'C,>. tw. w.t~ . +ss erN>tY+Mr..h d .....r.4.. o[ ...irb N.r tw pePad o MUM mo sr~trvr lnl ]Nk Lr~Y d s!~ =Wmd (ryrtiy 30 R YN~ NYIt ft** N!rq >nNaMr now 0 BWW W* W" p 7 ML of NA.sn ad tw w~r 419M Y IMtW l r tfe ft rN.Ar km 0+ eNrM 4piel r veay IW L*i~oti ~r W1 W lirNST fto MN 4w M&N Will to OMAN ~ pN krlls pswif. 11.~ >I~ISleMYea IJ r~ ! 9 of N oplo Mw JO Nt plyV epl l~r aNHf(irr M. Qfoeuty rddr Ai b N6r r a's wq. 12 AtYOaird.W .11r/irrM a wdrwtlMiiN6r -U-olw Zyf~all~~N .11~10ob . . 17.1 ft" A s wl~ ; N M si. MS "ME in on ID Nt . poropopyl.e Iii LSe~ Lr~70Ni.1Nt~]p0pqa t4 ftn" e r C. 3M MoIy" U i fM[) yPNaft W ol. aKlMa ~~irYld ~f~1LwNS(-dy~w} D~aOtM~elro anYY iL7 lY*800 MrPM ft OI ofterlw Ca JK tsnidl RsW duN. 11.2 ftN vJik -s UL 100l aN1ML C!/p ! NL st Aas ipN tadral tfN[.1 % 1 1Mee~Y/lrbNpfdrola~~!d.I . ll .f . AaNkftNol1N .ing - ~N1LCNMIW. 12o - o...mWA r , . 111 1~M Yr~ss d.~l Mi4 ~1~ d frdMC NrMti ro Wr LM" QA~ A OIANIt, Moltld Ollt /waft w/ "m 4 ~W zwp4 123 91Nri~K~lGa~Y1~N11tft6r~sseN~NUNfwiw~b tI3 A1 Oft rl of NIMW w10lia rei " ~N/ 1. aWOM = i b1 ooft +N/ It 41 M Of a a" Ml a L7p1/ lamfta MW dt irNWwllwM wmy f-l0a As i .rrnvrJ dl Pop 27 of 63 E,xygen Research Page 69 of 110 p . 68 Interim Report #23 - Analysis of Sediment Snitypics F,xyM Study No . ; P000113 1 .~ - - - 15 P MEAN P=1131 . ~4. .a+ . ' AKAL ~. `~ ~.rr .rrr vo~w:W se .t4tey ~ . 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Okra ~Y~ 1U ~Y f0 t! . at aiYad to do t.Obs 1l! ia do beoow of do 50 mL emaMip U6a C76 vs w/ ib s * wo r8m dmYw kr -JO dwlia IlJ ~y~ MYMKd000y~lr-30~iw+~ 11.i Dw~i~~dtIWolrtilRM~fO~. CMMM~MSt .Up lti! 4911MO a1LL 1 O0. d sillimL Camm d@ Nuw a0 W A ID w - . N~bO~Mdi~~)I l 11. 10 A.aeo . .lw .IC~Irs .ri Ap l) a 6 6ierrVaiO -L .ra,p ' ~iwd31r70~1.t~LC~W(`2i~Nr1. pfrMMM~~Mr II. n AY Ift MrN r-300 t[. t w r r/ lr/ r ft swoM eoo~i~awi >PiarYf 1117' Ws Wh -3 ml, 100l1 s I raL t10M 3 ai. of iar iro yudrd I3it'1)pwsrr~rdi~ttiw(l+1~eW' f aL l tL13 +Mi>s~l~ .i{~wrplit~~ALt w~~r+ Pn/e 34 ofb3 Exygen Research Page 75 of 110 p . 75 Interim Report #23 - Analysis of Sadanm: Saaroles Eaygen Study No . : P000113 1 Fs"w Ptaocd Dlamber. P000133) ,~ .r.~ . r ..r. .O"vru+a .w. 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Ye+)a )ao Or sr. am be ion to mom WAMM w Awia . ad be sr~r afa a)IMrt old 1r0Ya roW~ M twYYa7i how' Aop is oI6S Exygen Research Page 76 of 110 p . 76 Interim Report #23 .- Analysis of Sediment Sanmples Exygea Study No . :- PC?00113 1 fi,rypn haoool ranea : P0001131 +os~r . _ ~rr.aw.wwim AULVWAL 131 Rrwi ifisi has618 arwr at am" air w as m . sra . . . _ . . :~~wwaa~lWl .a 8awb.G. .au .esfi.ra .a~n , :~sa~i~l~sr.bsart .n.rir d . r 141 Ur IIY ~M1~{~~MiM r doiA~N imam" dRWr how W YMw[i~rr r~t a1 ~M r~/~0 r+aw PYr A~Mr r~N )POI OW pyM [d MAM eewran a Of ~ . Yl~~bql~Yrrl~~w~.flew~w~lr. N~. 1Y~ u4b ~~YM wrr bwrt. swum of ROA FM a anctiora, ws 1w~s~l~U~ /- , [^WaM~Aad6rwrW ~aY ~dbf+hW lor~o.laaoYall~Vd~ .100 ' 1}S Ur'i. bOw1. *. qMiora r 0 we y M er d VlqA 1 Me i. 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Raw" t.W r..~ ~ AW s7o I 6s Fxygen Research Page 78 of 110 p . 78 Interim Report #23 - Analysis of Sedirjienf'Sai~les Exygen-SEi`tdy No.:- P000113 1 9cypa Propea Nmber PM) 131 ^ ~". _ ' kw rncAL Mseaus hr do 1 ; CY~h LCMlA~ )u ' aM 11i sn" Y M4 qbyN in Am i n1r a wl ~rsw~o. ot~w0uaeecsa~ am b b ~r~ ~ M " Y AoYr Y a Mfid r qsa ~rL D+wr a8NMU1 ia ad aj~ -. . . r: LO saw 11 AHpi~wMl~hro4lnrfw~. ts ~~~iw WOt Dron .o,,~ r,d cMwiut Iev p~pw Yfr~ LO S"k- 3.I AeyM70 j K~aqMlt~~naWa .32 : lwis~M 1~~wrt bibm nwaiia tYY as D ~ aqb ia a . .. . ~M1~iM'f+it;l~M1O_NI W a v M~'f i~a tYrwapiwiaa~n 10 on WNW .r4~aYa eImQ ~ ~ 'r~r w+ ` b tea~ m .e ~mt r me imt3 qb ae "r f.rO.. .a be Me asd r i. .rqft prm re. ,r- . w~ . 42 4 ri.- .c . .1 O Pw .s Anrrrir-Ut,c ..e, 43 Cob" pm+oo w " &.rr Pa" lu Y.rw- RPI.cs. r u i7Y~ I 1wao. .w-~.~+w. ~ 6 l~W (Y.NO>e.i4- pa~+ ea+. 61 3MMM LC_M -1 1Rw YMa .d 14wA-tou Pr. as iArrw .rr-i. .@=v.r. 4.36 OW~ddmahm - RaM w pub "ri lblrr-MyRpuir u: AmusrAtM Y-A.GL ta vM OYOi u) FuftwwWMMk Ael+-li n M+i+ tA Mirow"M ei" pw 7.1 A No / wft~ 4r cbomniir A~b of wAin 0 n wb~ ~M ~ a~adiY wl~ ~M~ eNYY d~ae .i~y SIDu pt a~i lo ~ Ytl~ 1r ~w~~ G+CJ~OMiI 74 A~wMMaaMtawiYir~tiM~haaMpWltryY 5.3 Am )OdbiacawpYYdn~JYrYlOm1 rr71t Pni' ituJa3 Exygcn Research Pagc 79 of 110 p . 79 Interim Report#23 .- Analysis of Sediment Samp.les Eaygen Study No . : P000113 1 E+ryesrnomee~ai.e6r poool131 ~ew~frrr r.~M M .4. 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Ji~~J of63 Exygcn Rrscarch Page 84 of 110 p . 84 Interim Report #23-- Analysis of Sediment Samples Exygen Sdidy No . : PQ00113 1 ftwn reaeoM t+e&er P0001131 r-~ - ~ . iq~tewi. _ MwMlhaa1rY010tA1 M~1XYlCLL ' Afit(tTQIa im lMMd Q isitil[ c%9WA . , 143 [Q swoU MOW DI 6lgICM= U !t PPO 0. piw b a1s0A0~ iY ~I ~~ ~Mi D Oi~s~ ~i 7st~ IRPV11 l~J(7y ~ . . . . ~M~IsfillUl~d~d ~ ii~llSeiii~fe~ei14Wt1~ ~100 Exygcn Research Ir oJE3 Page 85 of 110 p . 85 Interim Report #23 - Analysis of Sediment Samples . Exygen Study No. : P000113 1 Eny$w PROOOOeI Number PODDI 131 AxACrisc,u. MenM wAd r .b.c MUM WM~ ~f AfQI~ ~~>~rYsIM~ ~f M~ AW plOw/ M Y~II~1~Ld1M~ ArMlal 1Yft4 t'tlW. mCM~lrrr 70dil~1YM )~iw I YC&IYW IA liDl AP/ww/pF l C ! -- -1. >tic~b % r.+WW c.r. ia>m. &nr.rr... a .1 o~ vk.~.rrk o~war.~. er~ .>e~, AWl)mlpc ) P4p eJ of ed Exygtn Research Page 86 of 110 p . 86 Interim Report #23 - Analysis of Sediin ,-n : Samples Exygew, study No. : PC-001 13 1 r - Hry Pmt" lr=bw. eooo l 13 t a~..~..n. 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Report #23 - .Anaiysis of Sedinxr.t Samples EaYBcn Study No . : P000113 1 ~ - _ E3nea llauoo] Number. POOOI ] 71 AwN,YHCU. ~ar . O p ;ue.rT.s . s;ph Aw U , buwfia Mid (rraa a v.rwm 7. 4 ..n..ldWL 6.S 12ssL /~i~d~i, L7 AiM~MI~bl~w SWAP Ma Si Dl~eiUal~~ W 100~L.1~6200r1J S.! qS~rL>1/'~011w~~io1~ itf : cZ ~r10Qr.w1X Ln n(~rrw~ SIS:/1&MUIO*V [!r(1001MC/Latlal0prl,l~tiqe~~DMYp~ 1.13 t7~trrp~l~pr~iraar)AST77). sr e.ur L1~Y~ .~iMdlk.YSlO .i rryp.rl~n . .r..e2ooo~ u a .. MrP4042/,w. E` ni"lllsllr/Inve If(iq%tow Li=1lr1ck 2.3 o x 90ra.!' 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Immmaft or N sm aqw.t t~ .rrr .i.rta r.+.rIrNOw"t .,q su unow, 1a air sum. amor . +4. r~M1~`SMalYtf~wl~~f~a~La. t3 .A um alu maind sowl ht wm*A Ma Lir Mr" ~vr~a ar _. . . _ . ., .pMM1atMMIDlIrI'Boommm ies isl ft qYtlKyrtra . . . _ _ . vow emod" +erY! ommoris dot IYYLl m: 1 .7 (a a i.Uap W . - 80100qww do" at mw! ,amid Amr womp+ n r . wMd IrAli w~rw~ 11p1i1r !~Y r meid ~e{ irnlr .i ~ . . . q.0 Aw~rtLlY~ ' 1~.1 ~irrwr~lurd~~~elr~7Nrulr~wwc . _`a. c._- . .. .~. H1~ !k p3 ~~e~t a~i b Y PIOA ais~. Wdw I r .~yriw~ry~4Mrr~MbuKi~6ooYoatiia hp # af' PW SOof6S Bkygen Research Page 91 of 110 P . 91 Interim Report #23 - Analysis of Sediment Samples . F.zxgen Study No. : P000113 1 pyrp pwrOt,p1 Nnnler FOD01131 p~~~~ IMa MrYw AICALf7lGd.1S7YDD htcwar>t~ w0a1'rM Add MKW is V"WAMB ' - ' 1 u 1 M 6 waft sc - news lDOA b bNb Vr Ore an WQ. It s 4~tw~p}pA~bai V a W 0= R3A~.1oaawrtNWM wyY a~MNrWMMa+rIw~R~aLawat~or l . . , p .1 >tww~iw af a>*I *~ ~ a,ria as Y~ bKww~ 70~UOh of MY bw~ ~ra Ya ea~d~Aa ~i MeiYM seap @ YM Iirh% in . . 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Sar.ples Exygen Study No . : Pooo i 13 1 Fxyp ,, r aocol Nuzt6v : P0001131 T .--~~-~-1-.A-NA-L;~ Iac+ Au. -w:,r~ on-~-,~ .--- ' ~ww~ www~wewowww.Rnwsv+~+wl~awi ' ~Ir tJIf1Y l.C1101115 IA tw A 1hYa~hW Y oM~ri Jrr w Y~iw Mdq wYrw of ~wl~s,c b 1M ~~r Lipfi awruvrb a~d w a U rr WIao ~OwJdsl~irMwOLA'0'lil Y ih~0 vtl 9vw a .21AI~paMfwlhqPi 3i Gxm 1t Oo p mplr lAli tiin reiq mw ehmNd to MGM o<ay . . 10 tsl~IeY~c7rrt xl Atlwlla 1 StWO Mob be Was" ],~ .`711ry1~i YMMLMMwIM M" eMetlaL !Yw tM fww~ ~wP~ Y~ iiri r~or ~iM~iw ~ii iky k !Ir i wnolw in oemi~n ar1dbrMw imrN1db,WbAoi}lM00w41dp.swaw0=4hYt rAwOMrw h r- wrrrisl W*w.ra.' mdpi. AbrMly. k1Yw I. r fwMafNt 606M of mm* (-Im &W %C% irr pme mmwf is mummy nMdn nmpwa" a we Maw tryY wwYr pwr" a w7 be O ." p Y ow wavlYt OR far ur s+1 K 00. .. 4A 1Y pmsd urd pa L t ww-w1Cpr 4u lirrrl->eDC pi .7 APOOd tb -JlLC ON . u Attrrma Ae~ - w .Ci. zr~at ooN as *rrLe~.w.isAeY-~arAleiw so I.w.+ .rti~:r.s M A War w b ..m low +.ww emb wr r or r.*:s w : .rur. .~yrr,t . wra., .>,.. Y~.. .. .~.w .ry .d.,~ ~ : - ~ir~lrrlYw>tlr+owlrRCAO~Mq 33 A biwMr/M w~r Om in /ed bNow" WA qMwiMN a& Si .*mmbb ~. ..~.'~ is Nl,r"Nhb u ny.+ s+w~ww oo~.laaa~wu S.1 tss.L l.ps mww. .o+wm. Si 3rL dm 1!l.CrYlMk . .. .. . . _. . . ~ t d' Pqe 33 Or65 Exygen Research Page 94 of 110 p . 94 Interim Report #23 -?nalysis of Sediment 5eaiples Exygen Study No . : PCU0113 1 EiyI u YeeOOtol Nb~r. POOOi 131 >bOSlJ I~. ' 1rW lM~r~01~~3 Moon erhidswWW" Add 1r ~111rrbLrJJtilq i i.f DY~wiww~ MO .- A/WIyrRMI000ML r11C10o A 1.~+rft i"wNMqw. Lit Wr~sw>tiYrsrl1y1C1:7!leaeeA/ a bq . ~l++~aa.ibMt s .n n .w~ .14 P111.4 r1. e". 1sas C~rMbNO/~feeY~lsW.~o1 , oydrairrl~ppry~n. it llqrr n Of+Jr~.~7w ..dfsA s l a. a st ~. Sy 13 ai . src . . l:.1, R1rw (Q ' 1 OM ANMai1 M Arrk a Prw : 1r`1 . e . . ~ ==O-1 ~ !a1 b.S R~w* ` ltw, ~ a ~ Z . l~f i s is 43 i w 25 13 43 35 3 0.f 105 3f tS .. it L*xY=Yahim ISMi.(wMrwrMbrarft rlDr[ .~ ll arlr1l~F 1wtNr-~nwI~rd~iwYG~faov w . . L l >fat"e-77 OMiMa - ._ tlrY~rw1/~lawfrM~raPiMM~VM~rfri~. .rr . 7A Y~ASlr ~ . ' , J.1 ~d~9N~beliptau~awilafoi~lD~lpdab ~Nra~~~~)NiWw Y 6f 10 , _ _ ._ _ _ lr3af+ 10~ hw J4 c/ o ExYBen Rcscamb Page 95 of t 10 p . 95 Interim Report #23 - Analysis of Sediment Samples Exygen Study No . : 000113 1 i.. r ttsyNe horaol Number Pooo l 331 ~o~.~ - , qrr>r. .r v~e~ ~a A~fALYlICAL QIQA)uiri t 11t.st tl~ry I.CJ66~s w et~rti~Yilrt U ~rrrMr. 1.7.1 2 aN rmmia mom 4 err Y/qro by 6 fie# 0.1 SI S f . ..wr~ .o.trr loa .6uvw . vD /Wd1~rYir 0.1 *rrrarr~rrM.t.>row RL1 )tyrrarkrtrl~i-10Yyrrl.i/lOAlywr/rylorr d~iAl tirY (~~~OW a Irqr) Ow/ ft r r toa mL .nM a~lirilit~ 1ri~i.l~f! 4etM a 12 K1DqlildtrWwsd 6sellloAM 0 d y lerD q l rt . d~ 10~ r/ML rMll~ r~ dl ~ot~ d too wr rerd . . ~~3?SrLLalOMala l.tJ *02 .I.& rYIW M/POltiiylYyriyio{ 1o aLatY1Dp&ArL riiw r a iW wlwd]00 . 0 mom" is 1=S wLLM IMh i.1 4 ~M~taqlN~Iwtolr~atoMeto~NS~wilOererr Aw~tl~ 1'C rd a~ at" ir 4 raie iMpd of 6 MOON ' f~rrri*p~re ~ 9.7 lir~~Giiwtirtewi, r l3.1 LOC<oAB atM~oa ~~II w}n4~d b s11ro1 ~4 tlMd~n d6~ ~.t NArL 1riYiw wM~ba 1,13 7 110 61100Lll is lk bwtM amok W4foW aemrrrirr ~iMari L i1rD4%~w WIWWO Dbris QNrMsi MM _ . 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Analysis of Sediment Samp2es Exygen Study No .: P0001131 S=ypn Pmta,rol Number P0007 1 3 1 iJiA1.Y7TGAL Irl7H00 li1111Ir. VOOSNi6 Me ar A ..q+ ftri. uow.wrnr. d #r Sm+.me r. AM crrow~ 10 e..r "M . .a... 17 u. O aM ~rA~+~~t~+~br ~sxua~sIaMM~.arrani .. 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AA a,allw_r27a'rw. 7f~iw+r~Urar YmMdr s Aid~ rd mry M6hWrq r WWI* ~16irrILl.Lq~s iA I WA lprr 7.1 16 1R ~AfMqtiwlMFlwdi.aaw~riy 41 l-r]Nrh(m 1lO~. jb OM VINO- w iwlyd r a pW MCI MW be eYrWi ia ard . to "own i1 1m11 qil m i le~rdrdoakl r F1 1WYlY m t'rY rmmir MOM i+AIw is ptyrW fy dlN 1154 A of ~~~Ye~+rr ls IMC al d~wr ' 'a~IrYaYtrwaMM~w~ . - w X.n " M~eA1a/6f Exygen Research Page 102 of 110 p . 102 Interim Report #23 - Analysis of SedidledtSwplek"' Exygrn-Stud~ No : : PJ00113 1 &qyo Hebcol Ntmbsr: POW 1 3 1 . . .. . pa1~1~_ ' _ .- IYY/)MMvYN117M AIMLVTWAL 09"M ' IY~MfwRrrLC/1(fMf In SMU . . fA SwsbA?nfwias " !.1 > :aiifr~AlriSadrSlris fL l.l h~wsMtrYlirtd-IiO~LK>l9AOywilyKlDwj daDylwt atrdd Ia~od Rr fwitY) w~i ARM n 1DD n L ,a . . frr~1ks/9SiL1LlLMM4 "A 1A phd. 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MtCwf!C.Ar~rala 92A AT~a~aior~lewwa4Wara[atrrrA~mqMynp .Mr aMlai lOA LItLl1fi' . . . . - .. . !wj iaY W,da+.7 m 404 41W pf~rb 70 w law mu iwhii w km .. . rtt 1Irrd ataal at ow som e rwoi lriMe a 1wo.n wrarra7lwpr aW IOW r awib rwwRiwl nwr.rf hr *w rdt 112, 1M 0m Irr br MY old L10~Iref iq 1Wra aa0 ii rri6 ia aps+6d :9r~4 arwrrN+kr dY~w. rarad` - - - - - - - - - ---- - . . . __ Pop a F163 Exygcn Rcsearch Pagc 103 of 110 p . 103 Intcrim Repore #23 - Analysis of Sediment .Sanples Exygen Study No. : P000113 1 Dlrytjen PmmtO1 N " ec P0001131 10~ . .. lwrlY~a M~1~ MYr YOR7~Aa AI~fA(. 11as/ fwastq LGUflil 6 AaM Q i. Ea 1t.0 3mb two" tt .t . Yata e al90 wt , i~pY~aMriMipa~/w(finiy mm"=-WO= wi4 I!w 1s alutiwl r dwos of a r%o 3U iqb>i<+brl a1~of70~ tyWl I.1.J YoFs,lr~la~ra ILA DNI& S nI. of ` waf pb i% a 4*@ aAY pom 'or a 13 nl. . dwNMMwIMrnAa 113. ML7 ~4dafrYiia W LLWlr-OOwiwaam ardryoti M afir. ltA Cyd4p Itnuiwat 4mq w bs- 4 aYna .1 t.~ OOla/ Oa /o~ Ir a!0 aI, r1oWh a~ Git OY am ] s s at .+s tt .{ Come r0 co OR stW% . tt & 6 .L) tir 1 embs 10 .c .Me.m UwM1tI2nLwlMrCwe!-2isP tNo. 1>rstYtesum waY tva l.r.r MW*1. . .a. 1lf..ecA BS 1Wtli . oin.el .k. a :Lq Ws +3N .1 w (. aladirLL l'AMMS 2 st of 6rr Yr a+a/rW IA w4r.ihrA7J~s wMHY1r ~M UW wlttr~ 2 oW. . . 'U, Aw4waMm rYtw1ae~Rt I.qfAl[ 4mm arP*l P At 11O IY arr asis alftd M i4 aAr ard 4Y8si wa ple re ltr IYJMM qMa A O1REW Y MawN IIOt TM W Oft * atl mm"dumv- 12.2 lYriAY A!*0% Iw4aiR Igo lsw tna c auan umome iaa ttnY . . asalbirMdisasa+~l,,Wat - IL Arrhatd~MwOws~Atls~ultiaiuYOMatMlrjris~rr s taa!fessoviarc t46a*arlM Wepwud eqwws q.arY1u ' a FApM N r atMSWp% r onto am of safYmwiw Aa+wi ft ary be i4" /= Ir kqirYft at a r bear/ by aslYSlha siais ir.~.t.wqsto ..~i.Ar .worrr .M..ewer .odily he tttw as aaN..ua a.rb : be m. eiw .+ rt i{jus + n.a Ei. ;r.r rrr.+ wn.. hr o modwiM. L .w word wrw as )~MIIL lrfa afiJ~ Yt It~r af~a~aisa r~ IN w o flaf afprt a*r new asOhm<w arn d mqnrat4a some Na d.I ns 13 (w qw.alww) eMnr rsMa .124 i Mytr rpm IrW no on" 40ftd "WORM An anew so owY odd awafr *mm b & 1L aiYd m i 1rd,,at hw1dl #01 p q1. gw a 65 Exygen Research Page 104 of 110 p . 104 Interim Report #23 - Analysis of Sediment Sampled Exygoa Sttidy No . :"P0W113 1 ts)Fa Pr.ftw 1tm*w. 10001 t31 .~. _ wrw...+awoa rrssa.o~o ., ~rrrr f~ by uvhe+w MW MKW :sm . ,^ fa0 eWa.ti.ii ..w. .rwww.Kr~..r.,. .oM ~.a> abba . .- 13.t' .p[+N Ty '=y~, .t . Y~ . w. al 3w ae. f .., ~rb~ , - 1 0 %=bd .q~~ b r MOA sii wbM tlM . : . . " ~~~~ 1*b~ V IAa(M , ~~. SS3- ~l -Ot aN CbYil mA Y b* vn R W tw LOQ. 1( a ' 1r' NOW l10A i ism* f Y1/ 0m 10 ybl, q m a a. bYnt 70.13M. d ` ' Wi'If~w +r & d . rrwl ~3. Y~ arMr b aqMb W m b .. .. . . . .rr . ~ v 10 we be /..bei av ...k *i. otoe. +o. y v . ~30K ~W/ w'waY " by a w~l~ w awlr ~t nwewioo r s Ow.rC . , 1]A 0, 4viMWM MM" r,M b be aw,i,foY arr by aft ,Y N W 1ZW Mw7Wqt w r NoM>e,1YaMdNrolsbY. arYsauYfftrW91IN00 aAalliYMrrelpaOraM no&at "M170Nafflrl MWOsdpMrifyq. L .. . 133 9r ..rnYln w 0m w 0ir (q !, aipbw abw O aArM -wt br OO Ll ft If wirl ww. Y waid, nrs ee . r . Ww/dlli1 MP /bt M Oka b Nobt WO- a pwsiaR ~ dr 1316 11m~,Y" ~r1tYlrsIlWw.l= t sYo,f/a~Y1~wmeosmooMn1wuawwpf " .w O~i4 aaw 6r+ -. .3~1~~U~{s~rpWdns tln,d.wirM~aNw~tialiaiiwid4~ . nMlri~l,~i~+Vrartbwri~a. a ue Crww " al i1~A.Ywr~Kwlwawlw~war~ebre14MkreAa~AJbd 1 *,i.. 7 min/ Is "mad Ow" fwwr wrwWa pwaw,wl rMW YF Y MW LPa rwib. pag- . . NGlw i bqfi{.iw9%*JMM--111MMa Oldorot dM. MwwdMrw70 ~ . lU _ 1 arMb ~1 ~~ laa ~r, af 110A 1~or b evan{0.. W _. . jrrlr,rbb~l6~L~ - a~YblrNa .mral(yhi~i , iQD a~iarlih.a.l~ wra .r+ ~ ~bt i/sJ6 ~ Exygen Research Page l 05of 110 p . 105 Interim Rpport #23 - Analysis of Sedimmt $auopks Lxygez Study No . : Ffl0U113 1 r~ - BotylmtooW Nm*w : p0001137 _. , . :lr~tL~asb ~.CAISnlf ~ Ia . fL~ JwlrMdig oWwM w orwnbro~dllOAtaeia+rmLw . 1* ` "aPOY1lMi 60) . ~I~wt~r W .~ . . . . . . , .- ~.~ , .. .. . ~ , . - ' ,. . . ~ , . . Pot 63 0161 Exygon Research Pap 106 of 110 p . 106 Interim Report #23 - Analysis of Sediment. SamVIes Exygai Study No . :,P000113 , E It ESEAfiC N 3 M Aesurch DOW State Cold{e. PA 1iap1 PAont: a 1+272-10Q9 Ax 81+231-ISM PROYaCOL /tAiEli1D~,~ MtMSfiiint Mwilr,_t_ pi)~L'pM,DM~:-- , QIlIY~06 ExypM19L*MIRNbN' : PO0011 st G7t1! Sh* NN11fbK tb~1d1 MM OF AAM"n MLIM1) Ar dO al Proadur~ ~mmr)I V0001780:8s o/on 9.1 2) Vidkttlon d/4~y~ca1 P~oqdus Nons AMEKSM 1) Add b SAlan & 1 : 3.7on 9.1 .0. Adnmb w oiplo d rhrdsrds mey betwQ b iPorOoWtlc~~do0c5Gmolui rooroNna4N1y10a0wYoabrsdpwIbpd--c~Kd. 4war an n IoNSwy. Abnyes WvNk of 2) Low and Mph ip1ft 4NN d ti arwilyls s for each rtwWc mW be dbnd depsrdnp on ~npN dM aNY" tor aom~ P lfa~ wdbr b Wwr wlyb oonanrafforx wpc%d Mf IM wnpbs. ~~" RATON&E 1) f~1Mr oonosnkabns of sfard~+ ft need to be p rpr~d In cider to spiMe to = m * Id mom ~ s~pM awlabf fcr smd ntrrNtbl Iwr and sutn wrs tn~M~r tlian ro~obd. 8piiip M 11~ O~dNemM>,d IsrMa In tlM proba :~l puls b rp~ad conanlrron JowM IM the d ftrlon inR, A b% ft ai*4 l~rMs h fh~ sound "IN wnr~ a~ a~d b p~wly rao~~d b p~OMrn~d ~klnp la~ww If~d !~ fri~ P robcoL Wlwf tlr Mwb b!sf aMrplq p bW*m owd ft ap" IwMs. an sestrab rummy VAN a~not be nloiiftd ta tlr QC wiw* Flpiwr rpldi* Nals h b baqhs wa MM ft wrlyk ooncaMrIft r opmb d In to wWr ~mpM~. l0h.0e1 IMALCMism1p0t0~ndprp-sinorrlse0r.n1rpr~wl >ntVnI ndt sn~i nm mMl fl w and h 1000 nphnL ior @ ~~ d spidnp tot b r~tet sanlpiq wi rwu~ v ui moi~ QC noo~ry ti~b . 7 Lk ~91oe e1w RaMw ! ;LS eL,ar~ r ~` . l~RM1 aw~0o,7~sa~ _. . . .. . . ACWNIi,,iAnIEfaw ,._.,.. _ _~. Eaygen Research Page 107 of 110 p . 107 Interim Report #23 Analysis of Sedimest Samples Exygen Study No . : P000113 1 ~ 301~ ~ Drive Phair /1~2721039 Sha Callqe, FA 16l01 FeC e14 231-15l0 RESEARCN - PROTOOOL AAIEiJDAENT M e1ufOnddUirrwDok1N0:umbsr. ~ 2- Pa - . w t ExyW 8Wdy Number P000i131 _ GeMSM*Nwnbar. ott Nom ~) Fhport p~pa 11 d i~i --. . .2} rMt w.leelMa, p6 w E6! PFOS va *11a ma~ed 1~ ~ qa 1) blli~d if Cu~AW ~Of~ MMtl1~ I~p01~ M~ 1itu~' ~) ~os a.~~eo~,,~a,Nowd ,,~er sr.ce. d~-~ eo. !) Dua i~ yr ao~oerl+~ * a Otto deb so* irMrie P4rb A bs i.wwd b alowihm d~'it b nniw dim in a 4n~r+~w MwW o4yl.r 4w , ) 41M API Iooo ~cd~IS1~B RySMn1R dM~et ~~~+ eo aFOa r.11~On wMl ~roarr .WM* >l,.r to 400 a w tra i1 ZIN dN1t wf Or ~hb b noMs and wA* w r1s dsbm n qnkidy. ~~ d0~ Can br 41YICUd xih Of~MYr iNa~My, f~rMoir, plrln0 DMW Da . s k~ or.~.~..~ ~.~.. ` ~---- :-~p -os or. ~~r ~ or erApn CM RW#'*w Q ~,.R~, ~,~,:~~ .: _ ... AoMNWMIW FQW Exygen Research Page 108 of 110 p . 108 Interim Report #23 - Analysis of SodimenfSaraples Farygan Stucty No. : F0001 13 1 RESEARC H 3058 ResaaRtt Orive Phone: 814-272-1039 State CO(tegc, ?A 16D01 Fax : 814-231-1380 DEVIATION FORM POO 1 2 X Pro(act SAadc DWAaLbn _ 'Fecift-011v4aft_ . _ DsQa d0tcurcena: 0126/08 Exlipsn PnOOct 5 : P7e0fP1131 Oa VialfOn 5 Clint Fhnject # : NA . Asisrsnr.a / : 0"78 Raadamn Oritei_r_ gnWon Tra : llhclxJs VS for msfhOQs and, ) (MAP . x GLP X Prob001' Osier VA: NA None Nolabook ealsranca: MA _ Malboa . . SOP sas7olb Darybtfon: . . .. Login* : L'{10081 W Carqaina 8 : MK 01 0 : NA * n ) exim sunxrarr o( Daviatlen Ths three 44*nont sqmp as in L8 (GOt 8A2 - C017Zb0'i ,wans usk~y fm sBa~dc4snuesnstc~fett1i1s3. dtlwV0s0lu~d?yt Mip.onPsootrlFMreqcauiAarsletssdw"oiu*aaibOlefi~osndiN!oafrnPaf9OvaBw,~cFtrOacAkwnafdo-rCfPtF"OA . oompouods. as Edbws: Dlr+sst Mpotlon Matfwd : 8afors ~hs Am 'Pro weighed tor ft extr acdon. they were ftxed ftrougay by v0MAGly daft to ooaldner. A ansqnm portion at sadbnaM was waiqhad into a t5 mll~ar ea~ MAqa tuba !br ths autradfon Tan mINAlxs bf 1% aatlc .aM in marmnd was added laeedh semple. TTr sarqMs wara ftn adwftby. han6, vatexad. and saNealsd for Ihirty mnutes . The samples fwere then anstrYgsa for -10 mUx-2as^at -3000 rpm . Eaft sampe was analyza0 by LGMSIIMS alacaoapay. Using this )method acoaphbM dab was oDlahadio~PFOS, but 1M racovsrlea for PFOA and "C PPDA weca .qW poor. Arrolpec , .. adnrrshe eiqrefoa , was: am used for PFOA and 8C PFOA, as IoMOws: Atanaqw WE M~- The samples diet were preytnC In 1'X idUc acid for the direct Injection method waq usad /or ads sntrdla PlwInMlNlars ot aach sampla waa allqucMQ inb a 50niL PaYVq*ww amcRupa tube and the volume was utca n a 40 raL with water. The samplse were am oantrRupad fa.-1QnM1MAas at -~000 ~pa The supamatan! wsa tAaa loadad or,to a C,, SPE cartrldps OondUmnO wah 10 mL o( maMwql and b mt af waMr. The aiuata was dseaidad. Appwximsby rtvs rn1U110M of MbMrid was added b the eanridpe. FtvS mMwlers of NuaDa was ooitaAed kmo a yra 610 esd 15 aL polypropylene aantrft0s babs. Each sample was anelysaC by LGM3IMS W*dM"- Cauw: ^ Prsparatlon - Anoysls InstrssnsrN ~ Client RaMSt X Other IQ1~ More usable data was obtakied. UBRARY lo- VOGGt5404 ADMINISTRATIVE FORM Idxygen Research Page 1 t1y 01 11 U p . 109 Iatorim Report #23 - Analysis of Sediment Samples Exygen Study No . : P000113 1 CNEM EHSA 236 15 651 733 1958 05/01 '06 13 :46 N0,106 03/03 "-MI 9J:Mn fm4m fA N Rlai + T~lN .OIt/W! h2 11 ~ .. . .` . . '~ ' . . . '.~~5*t E*IL . .- . ` . . ., ~, :. :,r. . ~'p'~Mk. N ~" .;~ ,. ,Ira 4~Mlst;w~l~hn ,~,,t~!l~rli~e f we Ow~n~d ;c'~,,_. ~wii A~eis : ..~~ir~~,d~i,,.. owltAldr . , y: ; :~;r~:~ `'~ . r --~~a,~ , ~~~1' ..~r;:i::.qr : . " ' -> '~ . :~ , . , . ;~ . . . '; ;: : t. ; ~, <' ~a , ,~;~.;;',~~ : ; ;' :. ; : . ~ /400 . ~ V P: ~ . . - ;; : ; , ;++;:;ti~~~~r ;: ; , , . , '~ , M . . . bY .. M~ ~ , ~ t' . . ' . . . 1?` :' . f.'' 'h. .+``' ,I ' + - . . . : I . . 'Z, ~ 41 '~ ,y ' ' . - , , - . . - .. ,~ . , ~~ <~~, :~ ~' . . . . ,''M .:, ;F~H, . .v r . , ;~, , - .1 . , ~ ' . .. . *,1 .,~ ' .. . , . , ' :w, ~` :< . ; ` . : :' ,,, , . ; .. . . : J : ;~ :i. v .~' r. . . . .. , - t, ' ' . ~ , , . ~'~~r~,~ , ,,, ' . ' . . ' ~ , ~ ' ' r'~ ~ r . -, A /! . ~-y .' .y :}/ . .~! ~ ' :P' ' '',. ., .. .. .. . . . ~ - ~.:)~~ '~ '/ ~ '3: . . . . .` .. _ ,~ - .'1. ; Y ; ~a , : , . Li~IR 1~1~ODfia~ ' ' ' ' .. . .~', . . ~~~ : . . . Exygca Rcuarch Page 110 of 110 p . 110 Interim Report #23 - Analysis of Sediment Samples Exygen Study No . : P000113 1 tKEM EHSA 236 1B 651 733 1958 05/01 '06 13 :46 NO-106 03/03 h~s .. IHt-l011 9l :Ilor FrM'~lf/~ , fOIRIa{ -~ ., . , . ; ." : ; . : ' . . . . . . o ' , ~ ~~. . ~ . . EV SkM WWA PA 4W PW 1i1~ ' s AlIfK \ , . . . , , . . '~~: : . ~ ~!, .' . ~~' ", . ~ ! ~: . . \ , .. > . ! ~s;:1 wr.elr: ..~_;_ - ' .o:i~i~.+~ 4 ' ~'Y' ~ : .. :~:.:.~:.~.. : .' ~ ..._. .o~..~;, . .., . : r , }'= . . '''i . . . . .. ; ;.'' .~; ' ; : ~; ~r.' ;~ ; ! : .~',`, : `~ ; :, t . ;~ :~ . . . , . ,. t dr~ tA. tal _ tiAAbr ~1p1 ' , ~ . .; . , . > .. . . ~ . ' . ' +., i~ .t~ Y \ . . ' , ~\\~h . . ' ' , , ' . ~ ~ ' ' " ~, !y.'N~ , t~ .,'I,~ ! :','~ , ,,, 1 , _ ' ~! + 'ri." : .`~ 7 . i. . . ' . 'C .'~ `i ,t \', , . , ' . 1~ ~ 1'~ ~ t ~ ~I ~ \ , . . ' f . w ' . ' . - .-' ' . .'''~t ~~~~~~~ y t - , .- .~ , , _ \ + \ / . . : . .- . . ; t, . . . = - . .M!' ~y\ .i( . .' . , ~ ~! ' ,, . . ' f! . . !V Y . . v .~ ! [ . - . . '. 4 , r , ,+"~,~.rY~,~ . , ~~' , . C ~ ' ' ., . : . . . . , - ; . , ,'~ .' ' . M .y`~ ~ '', M ' .. ' . . ~ ; \ ., ;; '~ . ' ~ %~~~~'+~ ' 't . , ' - , .. , . ' C ~,M ~ ' . ,. . ' . .. .. ' . .~ ~A `~',.Y ~4r' ;~: .i` ., . . . . . .! . wt . . 'w ` . . F,xygui Rcscsrch Page 114 of 110