Document GmddeZn3r78w6QbaQmY4Y8Le4

ORIGINAL DOES NOT CONTAIN CBI 3M Environmental, Health and Safety Operations 3M Center, Building 0224-05-W-03 St. Paul, MN 55144-1000 Certified Mail f\ C u i' D Ur \ pryrr~1 1 C* f; i 2013 FED 12 Pii 12=58 February 6, 2013 Document Processing Center EPA East - Room 6428 Attn: Section 8(e) Office o f Pollution Prevention and Toxics, U.S. EPA 1200 Pennsylvania Avenue NW Washington, DC 20460-0001 NO CBI Re: TSCA 8(e) Substantial Risk Notice: Sulfonate-based and Carboxylic-based Fluorochemicals, Docket 8EHQ-0598-373 - Results from 2011 Analyses o f Fish and Surface Water from the Mississippi River Dear Sir or Madam: 3M is submitting this notice to supplement previous submissions on sulfonyl and carboxylic-based fluorochemicals (FCs), and more specifically our June 20, 2006, November 9, 2009 and February 11, 2010 submittals concerning fish studies conducted by the Minnesota Pollution Control Agency (MPCA) and our own study that was the subject o f correspondence dated December 23, 2011. The aforementioned December 23, 2011 submittal documented an extensive study of Pool 2 o f the Mississippi River that was commissioned by 3M to evaluate the summer 2011 levels o f FCs in fish tissue and surface water. At that time, the analytical work for perfluorooctane sulfonate (PFOS) for the study had been completed and was documented in a report entitled Mississippi River Pool 2 PFOS Assessment - Fish Tissues and Surface Water - Summer 2011. This report, along with three supporting analytical reports, was submitted to the subject docket in December 2011. Subsequently, final analytical results have been generated for the twelve additional FC analytes that were also part o f the 2011 Mississippi River Pool 2 study. These include perfluorobutane sulfonate, perfluorohexane sulfonate, perfluorooctane sulfonamide, perfluorobutyric acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid and perfluorododecanoic acid. Results for these constituents, along with the previously submitted perfluorooctane sulfonate data, for both fish tissue and surface water, have recently been compiled in a comprehensive report entitled Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 (enclosed). CONTAINS NO CBI 1 i I Page 2 of 2 While 3M does not believe that any o f these data taken alone or cumulatively meet the "substantial risk" reporting threshold, we nevertheless recognize the ongoing work by U.S. EPA to assess fluorochemical exposure pathways. Therefore, we are placing these results in the 8(e) docket as a supplement to previous submissions. If you have any questions, please contact Deanna Luebker at 651-737-1374 or diluebker@.mmm .com . Sincerely, Jean B. Sweeney Vice President Environmental, Health and Safety Operations Enclosure ^ m Cardno E N TR IX Shaping the Future Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water-Summer 2011 November 2012 Project No. 70784004 Prepared For 3M Company Mississippi River Pool 2 PFC Assessment - Fish Tissues and W ater-Sum m er 2011 November 2012 Project No. 70784004 Prepared for 3M 3M Company St.Paul, MN Prepared by Cardno ENTRIX 4295 Okemos Rd, Suite 101, Okemos, Ml 48864 Tel 517 381 1434 Fax 517 381 1435 www.cardnoentrix.com Mississippi. River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table of Contents Executive Summary.......................................................................................................................................ix Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Introduction, Objectives, and Scope of 2011 Fish and Water Collection Efforts................... 1-1 1.1 Introduction and Objectives.................................................................................I-1 1.2 General Site Description..................................................................................... 1-1 1.3 Target Analytes................................................................................................... 1-2 1.4 Target Fish Species............................................................................................. 1-3 1.5 Tables and Figures.............................................................................................. 1-3 Sample Collection Summary............................................................................................... 2-1 2.1 Fish Collection and Shipment............................................................................ 2-1 2.2 Water Collection.................................................................................................2-1 2.3 Pool 2 Sampling Rounds.....................................................................................2-2 2.4 Fish and Water Collection Rounds..................................................................... 2-3 2.4.1 Round 1: May 31 - June 9, 2011........................................................... 2-3 2.4.2 Round 2: August 1 - August 11, 2011.................................................. 2-3 2.4.3 Round 3: September 11 - September 15,2011..................................... 2-4 2.5 Fish Lengths and Weights...................................................................................2-4 2.6 Field QA/QC Measures.......................................................................................2-4 2.7 Tables and Figures..............................................................................................2-5 Sample Handling and Processing........................................................................................ 3-1 3.1 Sample Tracking................................................................................................. 3-1 3.1.1 Sample ID key........................................................................................3-1 3.2 Fish Filleting and Homogenization.................................................................... 3-2 3.2.1 Blind Duplicate and Interlaboratory Comparison Samples................... 3-2 3.3 Sample Processing QA/QC Measures................................................................ 3-3 3.4 Post-Study Fish Tissue Evaluation..................................................................... 3-4 PFC Analysis by 3Mand AXYS............................................................................................4-1 4.1 Sample Preparation and Analysis: 3M Environmental Laboratory.....................4-1 4.1.1 Fish Tissue Samples.............................................................................. 4-1 4.1.2 Surface Water Samples......................................................................... 4-2 4.2 Sample Preparation and Analysis: AXYS Analytical Services.......................... 4-3 4.2.1 Fish Tissue Samples.............................................................................. 4-3 4.2.2 Surface Water Samples......................................................................... 4-4 4.3 Samples Analyzed...............................................................................................4-4 4.4 Tables and Figures..............................................................................................4-5 QA/QC Results.................................................................................................................... 5-1 5.1 3M Laboratory QA/QC Samples.........................................................................5-1 5.1.1 Fish Tissue QA Results..........................................................................5-1 5.1.2 Surface Water QA Results.....................................................................5-2 5.2 Field QA/QC Samples.........................................................................................5-4 5.3 Fish Processing QA/QC Samples........................................................................5-4 PFOS Results...................................................................................................................... 6-1 6.1 Intralaboratory Blind Duplicate Samples............................................................6-1 NOVEMBER 2012 Cardno ENTRIX Table of Contents i Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Sommer 2011 Chapter 7 Chapter 8 Chapter 9 Chapter 10 6.2 Interlaboratory Comparison Samples................................................................. 6-1 6.2.1 Fish Tissue..............................................................................................6-1 6.2.2 Surface Water.........................................................................................6-1 6.3 Study Fish Tissue Samples................................................................................. 6-1 6.4 Study Surface Water Samples............................................................................ 6-3 6.5 Post-Study Fish Tissue Evaluation..................................................................... 6-3 6.6 Tables and Figures..............................................................................................6-4 Perfluorosulfonate R e su lts.............................................................................................................................7-1 7.1 Intralaboratory Blind Duplicate Samples............................................................ 7-1 7.2 Interlaboratory Comparison Samples................................................................. 7-1 7.2.1 Fish Tissue..............................................................................................7-1 7.2.2 Surface Water.........................................................................................7-2 7.3 Study Fish Tissue Samples..................................................................................7-2 7.4 Study Surface Water Samples............................................................................ 7-4 7.5 Tables and Figures..............................................................................................7-5 Perfluorocarboxylate R e su lts........................................................................................................................8-1 8.1 Intralaboratory Blind Duplicate Samples............................................................8-1 8.2 Interlaboratory Comparison Samples................................................................. 8-1 8.2.1 Fish Tissue..............................................................................................8-1 8.2.2 Surface Water.........................................................................................8-2 8.3 Study Fish Tissue Samples..................................................................................8-2 8.4 Study Surface Water Samples.............................................................................8-5 8.5 Tables and Figures..............................................................................................8-6 C o n c lu s io n s .........................................................................................................................................................9-1 R e fe re n c e s......................................................................................................................................................... 10-1 Appendices Appendix A Fish Sample Collection, Tables & Figures Appendix B Water Sample Collection, Tables & Figures ii Table of Contents Cardno ENTRIX NOVEMBER 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Tables Table ES-1. Mean Concentrations of Target Analytes in Fish Tissue (ng/g ww) and Surface Water (ng/L) Samples (ND= 1/2LOQ)............................................................................... x Table 1-1. Targeted PFCs in Tissues of Fish and Water Samples Collected from the Mississippi River, MN......................................................................................................................... 1-3 Table 2-1. Fish and Water Sample Collection Summary During Round 1 (June 2011)........................... 2-5 Table 2-2. Fish and Water Sample Collection Summary During Round 2 (August 2011)....................... 2-6 Table 2-3. Fish Sample Collection Summary During Round 3 (September 2011).................................. 2-6 Table 2-4. Descriptive Statistics for Sample Size, Age, Length, Mass and Condition Factor of Target Fish Species collected from Pool 2 ..................................................................... 2-7 Table 2-5. Descriptive Statistics for Sample Size, Age, Length, Mass and Condition Factor (CF) of Target Fish Species Collected from Pool 2 by Reach................................................ 2-8 Table 4-1. Target Analytes and Surrogate Standards for 3M Environmental Laboratory......................... 4-5 Table 4-2. Target Analytes and Surrogate Standards for AXYS Analytical Laboratory.......................... 4-7 Table 4-3. Summary of Samples Shipped to Analytical Laboratories..................................................... 4-8 Table 4-4. Species and Number of Fish Analyzed by 3M from Pool 2 of the Mississippi River, 2011..................................................................................................................................4-8 Table 6-1. Intralaboratory Blind Duplicate Comparison of PFOS (ng/g, ww) in Fish Collected from Pool 2 and Analyzed by 3M ....................................................................................6-4 Table 6-2. Interlaboratory Comparison of PFOS (ng/g, ww) in Fish Collected from Pool 2 and Analyzed by 3M and AXYS.......................................................................................... 6-6 Table 6-3. Interlaboratory Comparison of PFOS (ng/L) in Surface Water Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS.............................................. 6-8 Table 6-4. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Pool 2 (2011) and Analyzed by 3M.............................................................................................6-9 Table 6-5. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 1 of Pool 2 (2011) and Analyzed by 3M .................................................................................6-9 Table 6-6. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 2 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-10 Table 6-7. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 3 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-10 Table 6-8. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 4 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-11 Table 6-9. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 5 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-11 Table 6-10. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 6 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-12 Table 6-11. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 7 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-12 Table 6-12. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 8 of Pool 2 (2011) and Analyzed by 3M ............................................................................. 6-13 Table 6-13. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 9 of Pool 2 (2011) and Analyzed by 3 M ............................................................................. 6-13 Table 6-14. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 10 of Pool 2 (2011) and Analyzed by 3M ......................................................................... 6-14 Table 6-15. Correlations of PFOS with Species-Specific Fish Characteristics (ND=0)........................ 6-14 Table 6-16. Summary of Average PFOS Concentrations (ng/L) in Water Collected from Pool 2 in Round 2 (August) and Analyzed by 3M .................................................................. 6-15 Table 6-17. Post-Study Fish Tissue Samples analyzed for PFOS by the 3M Lab and AXYS............... 6-16 NOVEMBER 2012 Cardno ENTRIX Table of Contents I Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-18. Summary of PFOS (ng/g, wet weight) in Post-Study Fish Tissue Samples Analyzed by the 3M Lab and AXYS............................................................................................. 6-17 Table 6-19. Average PFOS (ng/g, wet weight) in Post-Study Fish Tissue Samples Analyzed by 3M and AXYS................................................................................................................6-18 Table 6-20. Relative Percent Difference (RPD) of Average PFOS Concentrations (ng/g, wet weight) in Post-Study Fish Tissue Samples Analyzed by 3M and AXYS................... 6-18 Table 7-1. Intralaboratory Blind Duplicate Comparison of Perfluorosulfonate Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011)............ 7-5 Table 7-2. Interlaboratory Comparison of Perfluorosulfonate Concentrations (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M and AXYS (2011)........................... 7-7 Table 7-3. Interlaboratory Comparison of Perfluorosulfonate Concentrations (ng/L) in Surface Water Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS (2011)...................................................................................................................7-9 Table 7-4. Descriptive Statistics for PFBS (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................7-10 Table 7-5. Mean and 95% Confidence Intervals for PFBS Concentrations (ng/g, wet weight) in All Fish Collected in Pool 2 by Reach (2011).............................................................. 7-10 Table 7-6. Descriptive Statistics for PFHS (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................7-11 Table 7-7. Mean and 95% Confidence Intervals for PFHS Concentrations (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011).................................................................... 7-11 Table 7-8. Descriptive Statistics for PFOSA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................7-12 Table 7-9. Mean and 95% Confidence Intervals for PFOSA Concentration (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011)..................................................................... 7-12 Table 7-10. Correlations of Perfluorosulfonate Concentrations with Species Specific Fish Characteristics (ND=0)...................................................................................................7-13 Table 7-11. 3M Analysis of Round 2 (August) Surface Water Samples for Perfluorosulfonates (ND=RL)........................................................................................................................7-14 Table 7-12. 3M Analysis of Round 1 (June) Surface Water Samples for Perfluorosulfonates (ND=RL)........................................................................................................................7-15 Table 8-1. Intralaboratory Blind Duplicate Comparison of Perfluorocarboxylates (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011)............................. 8-6 Table 8-2. Interlaboratory Comparison of Perfluorocarboxylates (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M and AXYS (2011).................................... 8-8 Table 8-3. Interlaboratory Comparison of Perfluorocarboxylates (ng/L) in Surface Water Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS (2011).............................................................................................................................8-10 Table 8-4. Descriptive Statistics for PFBA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................8-11 Table 8-5. Mean and 95% Confidence Intervals for PFBA Concentration (ng/g, ww) in Fish Collected in Pool 2 by Reach (2011)............................................................................. 8-12 Table 8-6. Descriptive Statistics for PFPeA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................8-12 Table 8-7. Mean and 95% Confidence Intervals for PFPeA Concentration (ng/g, ww) in Fish Collected in Pool 2 by Reach (2011)............................................................................ 8-13 Table 8-8. Descriptive Statistics for PFHxA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................8-13 Table 8-9. Mean and 95% Confidence Intervals for PFHxA Concentration (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011)..................................................................... 8-14 iv Table of Contents Cardno ENTRIX NOVEMBER 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-10. Descriptive Statistics for PFHpA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011)......................................................................................... 8-14 Table 8-11. Mean and 95% Confidence Intervals for PFHpA Concentration (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011).................................................................... 8-15 Table 8-12. Descriptive Statistics for PFOA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011)................................................................................................8-15 Table 8-13. Mean and 95% Confidence Intervals for PFOA Concentrations (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011).................................................................... 8-16 Table 8-14. Descriptive Statistics for PFNA (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011)................................................................................................8-16 Table 8-15. Mean and 95% Confidence Intervals for PFNA Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 by Reach (2011)............................................................... 8-17 Table 8-16. Descriptive Statistics for PFDA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011).................................................................................................8-17 Table 8-17. Mean and 95% Confidence Intervals for PFDA Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 by Reach (2011)............................................................... 8-18 Table 8-18. Descriptive Statistics for PFUnA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011)...........................................................................................8-18 Table 8-19. Mean and 95% Confidence Intervals for PFUnA Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 by Reach (2011)........................................................... 8-19 Table 8-20. Descriptive Statistics for PFDoA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011)...........................................................................................8-19 Table 8-21. Mean and 95% Confidence Intervals for PFDoA Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 by Reach (2011)............................................................... 8-20 Table 8-22 Correlations of Perfluorocarboxylates Fillet Concentrations with Species Specific Fish Characteristics (ND=0)...................................................................................................8-21 Table 8-23. 3M Analysis of Round 2 Water Samples for Perfluorocarboxylates (ND=RL)..................8-23 Table 8-24. 3M Analysis of Round 1 (June) Water Samples for Perfluorocarboxylates (ND=RL)...... 8-25 Figures Figure 1-1. Overview of Sampling Area and Approximate Reach Boundaries of 2011 Fish and Water Collection............................................................................................................1-4 Figure 2-1. Fish Collection Locations for Pool 2 of the Mississippi River, 2011.................................... 2-9 Figure 2-2. Water Sampling Locations for Pool 2 of the Mississippi River, 2011................................ 2-10 Figure 2-3. Mississippi River Pool 2 Water Levels 2008-2011............................................................. 2-11 Figure 2-4. Mississippi River Pool 2 Water Levels During 2011 Fish and Water Collection............... 2-12 Figure 6-1. PFOS in Fish Tissues from Pool 2 (2011)........................................................................... 6-19 Figure 6-2. PFOS in Fillet Tissues of Bluegill Collected from Pool 2 (2011)...................................6-20 Figure 6-3. PFOS in Fillet Tissues of Freshwater Drum Collected from Pool 2 (2011)....................6-21 Figure 6-4. PFOS in Fillet Tissues of Smallmouth Bass Collected from Pool 2 (2011)....................6-22 Figure 6-5. PFOS in Fillet Tissues of White Bass Collected from Pool 2 (2011)..............................6-23 Figure 6-6. PFOS Concentrations (ng/L) in Surface Water Samples Collected from Pool 2 in 2011 (Round 2) and Analyzed by 3M ....................................................................................6-24 Figure 6-7. Blind Duplicate Fish Tissue Comparison of PFOS Results (3M Lab Only), 2011............ 6-25 Figure 6-8. Interlaboratory Fish Tissue Comparison of PFOS Results, 2011........................................ 6-26 Figure 6-9. Interlaboratory Surface Water Comparison of PFOS Results, 2011................................... 6-27 NOVEMBER 2012 Cardno ENTRIX Table of Contents v Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 vi Table of Contents Cardno ENTRIX NOVEMBER 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 ASTM ccv CoC DI ECF GPS HPLC/MS/MS IQR LC-MS/MS LCS LIMS LLOQ LMS LOQ MDH MDNR MPCA MRM MSU OPR PFC PFAS PFCA PFOS List of Acronyms ASTM International; formerly known as American Society for Testing and Materials Continuing Calibration Verification Chain of Custody Deionized (water) Electrochemical fluorination Global Positioning System High Performance Liquid Chromatography/Tandem Mass Spectrometry Interquartile Range Liquid Chromatography/Mass Spectrometry or Triple Quadrapole Mass Spectrometry Laboratory Control Spike Laboratory Information Management System Lower Limit of Quantitation Laboratory Matrix Spike Limit of Quantitation Minnesota Department of Health Minnesota Department of Natural Resources Minnesota Pollution Control Agency Multiple Reaction Monitoring Michigan State University Ongoing Precision and Recovery Perfluorochemical Periluoroalkyl Sulfonate Perfluorocarboxylic Acid Perfluorooctane sulfonate NOVEMBER 2012 Cardno ENTRIX Table of Contents vii QAPP QA/QC RPD RSD SOP SPE TMDL USEPA USFWS WTL WW Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Quality Assurance Project Plan Quality Assurance/Quality Control Relative Percent Difference Relative Standard Deviation Standard Operating Procedure Solid Phase Extraction Total Maximum Daily Loading United States Environmental Protection Agency United States Fish and Wildlife Service Wildlife Toxicology Laboratory, Michigan State University wet weight viii Table of Contents Cardno ENTRIX NOVEMBER 2012 Executive Summary The presence o f perfluorochemicals (PFCs) in the ambient environment is of interest to numerous stakeholders. In Minnesota, there is a growing dataset o f measured levels o f PFCs in surface waters and fish tissue. The Mississippi River, and more specifically Pool 2 of the river, is one water body that has experienced such an increase in monitoring data in recent years. In May 2011, Cardno ENTRIX was contracted by 3M to collect fish and water samples from Pool 2 o f the Mississippi River. Cardno ENTRIX and Cardno JFNew personnel made three trips to Pool 2 throughout the summer. The study objective called for the collection of ten samples of each of four fish species (freshwater drum, bluegill, smallmouth bass and white bass) from ten reaches within Pool 2 for a total fish collection target of up to 400 fish. This goal was essentially met with the collection of 396 fish. A contemporaneous collection of 30 water samples, 3 from each of the 10 reaches, was also completed. Blinded fish tissue and water samples were analyzed for 4 perfluoroalkyl sulfonates (PFAS) including perfluorooctane sulfonate (PFOS) and nine other perfluoroalkyl carboxylates (PFCAs) at the 3M Environmental Laboratory (3M lab, ISO17025 Accredited) and at the AXYS Analytical Services laboratory (AXYS, ISO 17025 Accredited). The 3M lab in St. Paul, MN received all fish fillet and water samples while AXYS served as a third-party confirmation laboratory and received splits of 68% of the water samples and ~10% of the fish fillet tissue samples generated. In November 2011, a report titled "Mississippi River Pool 2 PFOS Assessment - Fish Tissues and Water - Summer 2011" was prepared by Cardno ENTRIX. At that time, the analytical results for PFOS had been finalized. Subsequently, final analytical results for additional analytes have been completed. This report has been written to present all o f the results, including those previously reported for PFOS, in one comprehensive document. While the focus of this study was on PFOS, this report presents analytical results for PFOS and twelve other PFCs that have been measured in 30 surface water samples and in 396 fish tissue samples. Arithmetic mean results, by species and for the water samples collected, are summarized in Table ES-1. For fish tissue, PFOS was clearly the dominant analyte in terms of measured concentrations with arithmetic means ranging from 36 to 64 ng/g across the four species. The means for all species for all of the other twelve analytes were less than 4 ng/g and the means were less than 0.5 ng/g for seven of the twelve (PFBS, PFHS, PFBA, PFPeA, PFHxA, PFOA and PFNA). For the surface water samples, arithmetic means were from highest to lowest: PFBA (32 ng/L) > PFBS (12 ng/L) ~ PFOA (10 ng/L) > PFOS (6.1 ng/L) with the means for all other analytes being at or below 5 ng/L. To elaborate on the PFOS results, the concentration of PFOS in the surface water samples ranged from less than the limit of quantitation (LOQ) up to 136 ng/L with 21 of the samples being less than the LOQ. PFOS concentrations based on the arithmetic and geometric means for Pool 2 were 6.14 and 1.67 ng/L, respectively. The median PFOS water concentration was equivalent to the LOQ. The concentrations of PFOS in the 2011 Mississippi River fish samples ranged from 3.17 to 757 ng/g. Arithmetic mean, geometric mean, and median PFOS concentrations for all fish samples from Pool 2 were 46, 31 and 34 ng/g, wet weight (ww), respectively. The arithmetic means for bluegill, freshwater drum, smallmouth bass, and white base were 36, 46, 39, and 64 ng/g ww, respectively. November 2012 Cardno ENTRIX Executive Summary ix Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table ES-1. Mean Concentrations of Target Analytes in Fish Tissue (ng/g ww) and Surface W ater (ng/L) Samples (ND= 1/2LOQ) PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA Bluegill 0.06 0.42 36 0.08 0.27 0.17 * 0.19 0.04 0.09 0.10 1.4 0.83 0.59 Freshwater drum 0.09 0.09 46 0.33 0.38 0.18 0.24 0.03 0.12 0.28 1.7 1.1 1.1 Smallmouth bass White bass 0.06 0.04 0.06 , 0.12 39 64 0.97 0.21 0.21 ; o.i6 1.3 0.26 0.15 0.20 0.04 0.08 0.05 1.7 0.03 0.08 0.51 3.6 1.2 1.8 1.2 1.5 Water 12 3.0 6.1 1.0 32 5.1 2.2 1.0 10 , 1.0 1.0 1.0 1.0 With the exception o f PFBS, the agreement between laboratories for reported fish and water sample concentrations was good with the average relative percent differences (RPD) for PFASs and PFCAs generally being 25% or less. Interpretation of PFBS result was confounded by the fact that two of the 30 samples had concentrations greater than the LOQ as reported by both laboratories. For PFOS, the RPD for fish tissue concentrations was generally less than 25%. The interlaboratory comparison of water PFC concentrations was limited due to the large number of non-detects reported by both laboratories. Based on water samples that had reported concentrations from both laboratories, the RPD ranged from 1.6 to 135% with an overall arithmetic average and median of 36% and 33%, respectively. For PFOS, the RPD ranged from 17 to 56% with an average of 35%. An additional post-study validation exercise, focused on PFOS, was also completed at both the 3M Environmental and AXYS laboratories. This effort included the analysis of blinded duplicate standard reference fish tissues (SRM) from the National Institute of Standards and Technology (NIST) and splits of previously analyzed archived Pool 2 fish tissue samples. Results from this exercise showed good agreement between PFOS concentration measured in this study to that reported in the previous analyses conducted by both laboratories. In addition, PFOS concentration reported by both laboratories for the SRM samples fell within the acceptable range reported by NIST. This report summarizes the field sampling activities, the analytical procedures followed throughout the study, and the analytical results associated with the Mississippi River fish and water samples. x Executive Summary Cardno ENTRIX November 2012 Chapter 1 Introduction, Objectives, and Scope of 2011 Fish and Water Collection Efforts 1.1 Introduction and Objectives The purpose of this study is to provide current and comprehensive site-specific measures of perfluorooctane sulfonate (PFOS) and 12 other perfluorochemicals (PFCs) in fish fillet tissues and surface water samples from Pool 2 of the Mississippi River. Previous studies have reported varying concentrations of PFOS in a variety o f fish species and surface water from various locations within Pool 2 (Weston 2006; MPCA 2010); the current collections are meant to improve the knowledge base concerning PFOS and other PFCs in these media. The data from this study is intended to be used to evaluate current levels of PFCs in fish fillet tissue and water surface samples from Pool 2. In addition, these data support the formulation of a baseline that can be used to identify and characterize the impact of potential sources throughout the pool as well as evaluate the potential effects of mitigation efforts to reduce PFCs within Pool 2. Furthermore, it was envisioned that data gathered in this study might be helpful in preparing a Total Maximum Daily Loading (TMDL) for PFOS in Pool 2 should the impairment status remain unchanged. Sample collection and analysis activities were carried out under guidelines introduced in the project work plan titled "Work Plan for the Collection o f Fish and Surface Water from Pool 2 of the Upper Mississippi River, Minnesota" (Cardno ENTRIX, 2011) and the Quality Assurance/Quality Control (QA/QC) conditions specified in the associated Quality Assurance Project Plan (QAPP). These documents are available upon request. 1.2 General Site Description The upper and lower extent of Mississippi River Pool 2 is defined by two dams and locks (see Figure 1-1). The upper extent of this pool is bounded by Lock & Dam #1 (River Mile 847.9) located between Minneapolis and Saint Paul just north of the confluence of the Mississippi and Minnesota Rivers. The lower extent of Pool 2 is defined by Lock & Dam #2 located upstream of Hastings, MN (River Mile 815.2). To date, several studies have evaluated the presence of multiple PFCs in several fish species within Pool 2. Early work was focused on very limited areas within the pool and generally involved small numbers of fish collected. More recently, a study conducted by Minnesota Pollution Control Agency (MPCA) in 2009 (MPCA, 2010) focused on 5 fish species collected from four unequally divided reaches within the pool. For the current study, a total of 10 sampling reaches of approximately three miles in length were identified between the Ford Dam (Dam/Lock #1) and the Hastings Dam (Dam/Lock #2). The exact size and coordinates of each reach was adapted to take into account factors such as input from Minnesota Department of Natural Resources (MDNR) personnel, conversations with local anglers, amount of suitable habitat for each targeted species, proximity to public access sites and other recognizable landmarks (e.g. public parks and fishing areas, boat launches), etc. The approximate November 2012 Cardno ENTRIX Introduction, Objectives, and Scope 1-1 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 location of reach boundaries is provided in Figure 1-1 and general descriptions of geographic landmarks that correspond with reach boundaries is provided below. Field crews used these approximate locations as guides and final reach boundaries were selected based upon landmarks and points of reference that could be easily identified in the field. The field crew also incorporated 100 200 m "buffer zones" between reaches. Reach 1: Ford Dam (River Mile 847.9) downriver to the Pike Island Daymark (River Mile 844.7R) Reach 2: Pike Island Daymark downriver to the ADM Dock Lights (River Mile 841.7L) Reach 3: ADM Dock Lights marker downriver to the Farm Bureau Dock Lights (River Mile 838.6R) Reach 4: Farm Bureau Dock lights to the tip o f Pigs Eye Island #1 (River Mile 835.3L) Reach 5: Pigs Eye Island #1 marker downriver to the South St. Paul Access boat launch (River Mile 832.4R) Reach 6: South St. Paul Access boat launch downriver to the Merimac Island Light and Daymark (River Mile 829.2R) Reach 7: Merimac Island Daymark downriver to the Robinson Rocks Light and Daymark (River Mile 825.9R) Reach 8: Robinsons Rocks Daymark downriver to the Grey Cloud Landing & Daymark (River Mile 822.4L) Reach 9: Grey Cloud Daymark downriver to the Freeborn Island Light and Daymark (River Mile 818.9L) Reach 10: Freeborn Island Daymark down river to the Hastings Dam (River Mile 815.2) This stretch of river is historically heavily industrialized and populated. Sources of discharge to this water body include municipal storm water, publicly owned treatment works, refineries, airports and industrial facilities. 1.3 Target Analytes Based on numerous PFC assessments that have been conducted in Minnesota, a broad suite of analytes were targeted in this study (see Table 1-1). The selection of these constituents took into account previous fish tissue monitoring activities, thereby enabling the possibility o f comparisons over time. Limits of quantitation for all target analytes were 5 ng/L for water and 0.25 ng/g for fish fillet tissue. This report contains the results for all target analytes. 1-2 Introduction, Objectives, and Scope Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and W ater-Summer 2011 1.4 Target Fish Species The target species in this study were smallmouth bass (M ic r o p te r u s d o lo m ie u ), white bass (M o ro n e c h r y s o p s ), freshwater drum (A p lo d in o tu s g r u n n ie n s), and bluegill (L e p o m is s p p ). These species were chosen for a variety of reasons: They represent several species that may be harvested by licensed anglers for consumption; They are species that have been previously assessed relative to PFC levels and represent those most inclined to have higher levels; and/or They constitute a representative scientific assessment of the water body. A basic study objective was to collect 10 samples of each species in each of the 10 reaches defined in this study, i.e., total fish collection of 400 specimens. 1.5 Tables and Figures Table 1-1. Targeted PFCs in Tissues of Fish and W ater Samples Collected from the Mississippi River, WIN Compound Acronym CAS# Molecular Formula Perfluorosulfonates P erfluorobutane sulfonate PFBS 29420-49-3 C F 3(C F 2 )3 S 0 3H Perfluorohexane sulfonate PFHS 432-50-7 C F 3(CF2)5S 0 3H P erfluorooctane sulfonate PFOS 1763-23-1 C F 3(C F 2 )7 S 0 3H P erfluorooctane sulfonam ide PFOSA 4151-50-2 C F 3(C F 2)7 S 0 2N H 2 P e rflu o ro carb o xylates , ' * ` :i * ' ... . P erfluorobutyric acid PFBA 375-22-4 C F 3(C F 2)2C 02H P erfluoropentanoic acid PFPeA 2706-90-3 C F 3(C F 2)3C 0 2H P erfluorohexanoic acid PFHxA 307-24-4 C F 3(C F 2)4C 02H P erfluoroheptanoic acid PFHpA 375-85-9 C F 3(CF2)sC 0 2 H P erfluorooctanoic acid PFOA 335-67-1 C F 3(C F 2)6 C 0 2H P erfluorononanoic acid PFNA 375-95-1 C F 3(C F 2)7C 02H P erfluorodecanoic acid PFDA 335-76-2 C F 3(CF2)8C 0 2H P erfluoroundecanoic acid PFUnA 2058-94-8 C F 3(C F 2)9C 02H P erfluorododecanoic acid PFDoA 307-55-1 C F 3(C F 2)ioC 0 2H November 2012 Cardno ENTRIX Introduction, Objectives, and Scope 1-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Figure 1-1. Overview of Sampling Area and Approximate Reach Boundaries of 2011 Fish and W ater Collection jiduction, Objectives, and Scope Cardno ENTRIX November 2012 r Chapter 2 Sample Collection Summary 2.1 Fish Collection and Shipment Electrofishing was the primary sampling method utilized in this effort. Field personnel operated a Smith-Root boat-mounted electrofishing unit with one person navigating and two persons stunning and capturing fish. Non-target species (e.g., channel catfish) were returned to the river. In order to collect fish where electrofishing was not effective, hook and line sampling was also conducted during the last two days of the sampling effort. The sample collection was conducted under a Scientific Collector's Permit granted to Cardno ENTRIX by the MDNR. All practices were conducted in such a way to ensure public and worker safety. Upon arriving at a given reach, the field crew assessed the area for habitat suitable for the targeted fish species. Once a starting point had been identified, the crew collected GPS coordinates and began an electrofishing "run." Electrofishing runs varied in length depending on the availability of suitable fish habitat, boat traffic, etc. GPS coordinates were collected at the end of each run as well, providing start and end coordinates (See Appendix A, Table A -l). The number of runs conducted in each reach varied but in general, ranged between 10-20 total. Field crew worked both sides of the river in each reach. Figure 2-1 provides an overview of fish collection locations for Pool 2 and the maps in Appendix A show start and end points for electrofishing runs from which fish were collected in a given reach. Upon collection, fish were placed in clean coolers containing bagged wet ice until the end of a electrofishing run. After this each fish was tagged with a unique ID number and stored in a clean cooler containing bagged wet ice. When the day's collection activities were finished, fish were placed in an individual bag and the bagged fish were then transferred to clean coolers containing double-bagged wet ice. Chain of custody (CoC) forms were filled out for each cooler and placed inside a Ziploc bag. Coolers were taped shut with the CoC form inside and one or more custody seals were affixed to each cooler. In most cases, coolers were shipped (FedEx or UPS Priority Overnight) at the end of each collection day. Occasionally, fish needed to be held overnight and shipped out the next morning. Shipments were sent to the Wildlife Toxicology Laboratory (WTL) at Michigan State University (MSU). Upon receipt, WTL personnel cross-referenced fish in each cooler against the accompanying CoC form(s). Once the information was verified as correct, the CoC was signed, dated, and stored in a three-ring binder. 2.2 Water Collection Water samples were collected from 3 locations within each sampling reach (Figure 2-2). However, due to high water levels (Figures 2-3 and 2-4), sampling was conducted in two sampling rounds (see Sections 2.3 and 2.4 for a summary of sampling periods). Water samples were taken from the water column approximately 12 to 24 inches below the surface and from the main river channel and/or locations from which fish were collected. All samples were collected as grab samples using a 1.5 L wide-mouthed Nalgene polyethylene bottle. Water was then poured from the 1.5 L bottle into November 2012 Cardno ENTRIX Sample Collection Summary 2-1 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 smaller (generally 250 ml) bottles supplied by the analytical laboratories. All water samples (44 total) were sent to the 3M Environmental Laboratory (3M lab) for analysis. Splits o f -68% of the water samples were sent to AXYS for confirmatory analysis. Sample bottles for each set were provided by the respective analytical laboratory. Bottles provided by the 3M lab were weighed and then spiked with internal standard, surrogate, or target analyte for QC purposes prior to providing the bottles to Cardno ENTRIX field personnel. Water samples sent to the AXYS lab were spiked with surrogate standards at the laboratory. Water samples were transported to the laboratory on wet ice and refrigerated until analyzed for PFCs. In Round 1, GPS coordinates as well as field measurements of water temperature, dissolved oxygen, pH and conductivity were recorded at each sampling location. In Round 2, GPS coordinates, water temperature, and dissolved oxygen measurements were also recorded, but due to equipment failure pH and conductivity measurements were not taken. 2.3 Pool 2 Sampling Rounds The original study design called for all fish and water sampling activities to be completed in a two to three week period commencing May 3 1st. However, due to precipitation events preceding the start of field efforts, water levels in Pool 2 were highly variable and elevated (see Figures 2-3 and 2-4). As a result of these unusually high water levels, electrofishing was hampered by at least the following factors: Defined structure (e.g., rip rap, downed timber, etc) where fish would normally hold was under significant amounts of water and therefore not available; High river current decreased the general effectiveness of electrofishing and specifically the amount of time the crew had to net stunned fish; Water clarity was extremely low (< 3ft) making fish capture more difficult; and Increased safety concerns related to high current and invisible underwater obstacles. Accordingly, after a concerted two week effort, a decision was made to postpone fish and water collection and resume a few weeks later after water levels had dropped. With the suspension of fish collection efforts due to high water levels, it was decided that the full longitudinal water sample collection needed to be repeated with the next round of sampling. Accordingly, it is the full set of water samples collected on August 11, 2011, (Round 2) that is considered primary for this study. At the close of the scheduled August sampling period, the number of fish collected was ait approximately 90% of the study objective. In an effort to meet the study objective o f 10 fish per species per reach, a third sampling period was arranged for early September. In summary, three sampling trips, or rounds, were required to complete the fish collection. Round 1 took place from May 31-June 9; Round 2 from August 1-10, and Round 3 from September 11-15. Details concerning each of these sampling periods are provided in Section 2.4. 2-2 Sample Collection Summary Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 2.4 Fish and Water Collection Rounds 2.4.1 Round 1: May 31 - June 9.2011 A total of 148 fish and 14 water samples were collected during Round 1 (Table 2-1). During discussions leading up to the field effort, MDNR fisheries biologists informed Cardno ENTRIX and Cardno JFNew personnel that large (> 5 in) bluegills were relatively scarce in Pool 2 and that target numbers of bluegill may be hard to collect in all reaches. Therefore, the work plan called for the collection of any L e p o m is species including sunfish as they share many similar traits (e.g., preferred prey and habitat) with bluegills and would likely be a suitable surrogate species in the event that target numbers of bluegill could not be collected from a given reach or reaches. One sunfish was collected from Reach 2 during Round 1. Since this fish was the only L e p o m is individual collected from Reach 2, the decision was made to process and analyze the fish because at that time, it was not clear whether or not the field crew would be able to collect 10 bluegill of sufficient size from Reach 2. Ultimately, 10 bluegill were collected and analyzed from this reach. As a result, the data from the sunfish is not presented in this report but PFC results can be found in Appendix A, Table A -l. During Round 1, a total of 15 drum were collected from Reach 10. The extra 5 drum (beyond the study objective of 10) were collected in error when the field crew inadvertently did not check the drum tally sheet upon ending an electrofishing run. The error was caught by the MSU lab during sample check-in and the decision was made to process the drum in sequential order, send the first 10 drum for PFC analysis, and archive the extra 5. During Round 1, water sample collection was conducted in Reaches 1, 2, 3, 8, and 10 as those reaches are where the majority o f fish were collected. A total of 14 water locations were sampled at this time. Splits of each water sample were provided to the 3M and AXYS labs as part of the data validation process. Results from these water samples were used only for the interlab comparison (As previously discussed the Round 2 samples are considered the primary data from this study). 2.4.2 Round 2: August 1- August 11.2011 A total of 206 fish and 30 water samples were collected during Round 2 (Table 2-2). Pool 2 water levels and current were decreased from Round 1 conditions. One green sunfish was collected from each of Reaches 4 and 5 during Round 2. These fish were processed and analyzed. The rationale for keeping the green sunfish was that the majority of bluegill that had been collected through Rounds 1 and 2 were small (4-5 in) and it was not apparent if the bluegill would yield sufficient tissue mass for PFC analysis. In addition, there was still doubt that the target sample size of 10 bluegill per reach could be obtained. Ultimately, 10 bluegill were collected and analyzed from all reaches. As a result, the data from the green sunfish are not presented in this report but PFC results can be found in Appendix A, Table A -l. Water samples were collected on August 11, 2011, from all reaches (3 samples per reach) and delivered to the 3M lab. AXYS received a subset of the water samples from reaches that had not been sampled in Round 1 (3 samples from Reaches 4, 5, 6, 7, and 9 each, plus 1 sample from Reach 10) for a total of 16 samples. When combined with the 14 water samples collected in Round 1, a grand November 2012 Cardno ENTRIX Sample Collection Summary 2-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 total of 30 water samples, 3 from each of the 10 reaches were shipped to AXYS. Results from the samples sent to AXYS were used for the interlab comparison. 2.4.3 Round 3: September 11 - September 15.2011 A total of 51 fish were collected during Round 3 (Table 2-3). Pool 2 water levels and current had decreased compared to Rounds 1 and 2 and the visibility had improved. In order to reach study objectives, the field crew mainly focused on freshwater drum and white bass during this effort. An extra bluegill was collected from Reach 9, bringing the bluegill collection total to 11 from Reach 9. The extra bluegill was collected because the 10th bluegill kept was a small fish and the field crew was not certain whether sufficient tissue mass could be obtained for analysis. It was later determined during processing at the MSU lab that the 10th bluegill was large enough for analysis so the extra Reach 9 bluegill was archived and not sent for analysis. No water samples were collected in Round 3 since a full representative set was obtained in August. 2.5 Fish Lengths and Weights Fish length (cm) and weight (g) was recorded prior to filleting. Fish age (yr) was determined from otoliths. Condition factors (K) were determined as K= Weight* 100/ Length3. Average values for target fish species analyzed for PFCs are provided on a whole pool basis in Table 2-4 and on a reachspecific basis in Table 2-5. 2.6 Field QA/QC Measures Collection equipment used during investigation activities that could come into contact witfi potentially chemically affected materials were thoroughly cleaned with Liqui-Nox (a laboratorygrade detergent) and rinsed with deionized (DI) or distilled water. Four field equipment blank samples (Field IDs: FEB060111W1, FEB060211F1, FEB06(D611W1, and FEB081111 W l) were collected during this effort. These samples were generated by pouring laboratory reagent water supplied by the 3M lab in/over equipment that could come into contact with samples during the field effort such as the 1.5 L polyethylene water sample collection bottle and a cooler used to hold fish. This water was then poured directly into a sample container(s) and sent to the 3M lab for analysis. A set of field blank samples was provided by the 3M lab during Rounds 1 and 2. Each set of field blank samples consisted of a field blank (Milli Q water), and a 25 ng/L trip blank spike, which were prepared at the 3M lab and sent with the sample bottles for each sampling round. In addition, consumable samples utilized in the field effort such as acetonitrile gloves, polyethylene bags, etc. were analyzed at the 3M lab prior to study commencement to confirm the presiance/absence of PFCs. Field efforts were documented on bound, waterproof field logbooks with waterproof ink. Deviations from protocol described in the work plan and/or QAPP were documented and, if necessary, corrective action documents were generated. 2-4 Sample Collection Summary Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 2.7 Tables and Figures Table 2-1. Fish and W ater Sample Collection Summary During Round 1 (June 2011) ____________________ Sampling Reach Species 1 2 3 4 5 6 7 8 9 10 Total " Bluegill 10 6 6' -- - - 1 1 4 4 32 Freshwater drum 5 1 5 -- - - 1 9 10 15 46 Smallmouth bass 9 -- 2 -- ,S i P ' 1 4 1 5 10 31 Sunfish - 1 - -- - - -- - - - 1 White bass 2 3 2 - - - 7 6 8 10 38 Water _3 3 3 - - -- __ 3 2 14 - Not sampled during this round November 2012 Cardno ENTRIX Sample Collection Summary 2-5 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 2-2. Fish and Water Sample Collection Summary During Round 2 (August 2011) Sampling Reach Species Blueglll 123 4 56 7 3 4 10 8 10 9 * Freshwater drum 5 5 2 6 9 10 1 % re ensiriffeh -- 1 1- -- Smallmouth bass 1 10 8 6 10 10 6 fvhlte bass .= - 7 8 8 3 8 3 Water 333 333 3 1AXYS received a subset of the round 2 water samples - Not sampled during this round 8 9 1 9 4 3 Table 2-3. Fish Sam ple Collection Summary During Round 3 (September 2011) Sampling Reach Species .. * Bluegill 123 4567 8 ', 1 L - I * - " / > . 2 -- - Freshwater drum Smallmouth bass..... 4 3 4 1 -- 8 - i ? f Y" `" i f 4 ..... * " 4 ip -- i* - - White bass 4- - 272- - Not sampled during this round 9 10 Total 5 2 60 - 39 -2 4 - 64 - 41 3 3 30 1 9 10 Total . 9 4. -- 20 1 -- 5 2 - - 17 2 - hple Collection Summary Cardno El* Noveri Table 2-4. Descriptive Statistics for Sample Size, Age, Length, Mass and Condition Factor of Target Fish Species Collected from Pool 2 Characteristic Bluegill Number (N) Age (year) Length (cm) Mass (g) 100 3.3 (2.0) 15(2.4) 77(42) Condition Factor (K) 2.304 (0.597) Arithmetic mean and standard deviation in parentheses Freshwater drum 100 9.9 (5.8) 36(5.0) 657 (424) 1.354(0.685) Species Smallmouth bass 100 3.3 (1.4) 32(5.8) 497 (287) 1.406(0.164) White bass 96 4.5 (2.6) 34(5.5) 540 (223) 1.313(0.352) Sample Collection Summary 2-7 Mississippi River Pool 2 PFC Assessment Fish Tissues and Water Summer 2011 Table 2-5. Descriptive Statistics for Sample Size, Age, Length, Mass and Condition Factor (CF) of Target Fish Species Collected from Pool 2 by Reach Species Number (N) 2 10 10 Avg Age (yr) 5.4 4.5 Bluegill ' Avg Length (cm) * a 14.8 Avg Mass (g) * ' 72.6 15.4 79.8 Avg CF 2.241 2.027 Number (N) 10 10 Age (yr) 9.2 6.9 Freshwater drum Avg Length (cm) 36.1 32.8 Avg Mass (g) 589 455 Avg CF 1.222 1.236 Number (N) /V -K T J 10 V Avg Age (yr) 4.1 2.9 Smallmouth bass Avg Length (cm) ? 35.2 31.4 Avg Mass (g) 655 AvgCF 1-346 t " f Number (N) 6 10 Avg Age (yr) 4.8 4.8 White bass Avg Length (cm) Avg Mass (g) 33.2 37.2 544 608 Avg CF 1.284 1.172 34 10 10 4.9 3.0 15.2 13.5 82.4 60.0 2.382 2.301 10 10 7.0 10.0 32.0 37.7 386 1210 1.145 2.265 10 - 10 3.1 3.5 29.2 34.5 412 692 1.450 1.574 , 10 10 5.5 4.3 36.5 34.5 666 592 1.361 1.411 Sampling 5 10 2.8 13.8 69.4 2.422 : 10 11.7 37.8 775 1.346 / ftf 2.7 30.6 376 10 4.4 35.1 500 1.372 6 10 3.9 15.0 79.4 2.001 10 10.3 33.4 543 1.401 2.9 30.3 436 1.466 10 5.3 37.4 698 1.330 7 89 10 10 10 2.0 2.5 2.0 13.0 14.4 15.8 53.8 75.6 99.1 2.555 2.377 2.276 10 10 10 13.6 8.7 13.0 40.1 32.4 37.9 871 416 691 1.305 1.170 1.220 - 10 10 3.3 2.6 3.8 32.9 28.9 32.2 515 J 342 533 1.361 . 1.328 % 1.338 10 10 10 3.6 2.6 5.0 33.4 29.3 34.6 501 335 565 1.226 1.235 1.513 10 10 2.2 15.7 102 2.457 10 8.2 36.4 637 1.231 10 3.6 32.6 514 1.378 10 4.4 29.2 rtn* 1.202 2 - Iple Collection Summary Cardno Eh Novem 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Figure 2-1. Fish Collection Locations for Pool 2 of the Mississippi River, 2011 November 2012 Cardno ENTRIX Sample Collection Summary 2-9 Figure 2-2. Water Sampling Locations for Pool 2 of the Mississippi River, 2011 2^ imple Collection Summary Cardno Ef Novenr. _(_____' ____________________________________________________________<Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summ( er 011 Mississippi River at South St. Paul (CP2) From 01/01/2008 To 10/04/2011 Gage Zero = 683.35 Ft. MSL 1912 Figure 2-3. Mississippi River Pool 2 Water Levels 2008-2011 November 2012 Cardno ENTRIX Sample Collection Summary 2-11 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Mississippi River at South St. Paul (C P 2) From 01/01/2011 To 12/31/2011 Round 1 Ro jnd2 Round 3 1 Pool Level in Feet k 1 "$ 1 Feb 2011 1 Apr 2011 Gage Zero = 6$3.35 F t MSL 1912 1 Jun2011 Figure 2-4. Mississippi River Pool 2 W ater Levels During 2011 Fish and W ater Collection 1 Aug 2011 1 Od20* 2- jmple Collection Summary Cardno Ef Novenv J12 Chapter 3 Sample Handling and Processing 3.1 Sample Tracking Sample labeling, preservation and tracking procedures were conducted as outlined in project-specific Standard Operating Procedure (SOP) documents and as detailed in the project QAPP. The following field observations and measurements were recorded: Species and number of fish collected; Field ID associated with each fish; General location of fish collection (See Section 2.1 and Appendix A for more information); Date and approximate time of collection (beginning/ending time of electrofishing run); and Initials of field crew 3.1.1 Sample ID key Unique IDs were assigned to individual fish tissue samples to ensure accuracy in sample tracking. The section below describes the sequence of ID assignment and a description of each ID. All IDs listed below are in the project database. 3.1.1.1 FieldID Upon collection in the field a tag displaying a number (started with 001) was affixed to each fish (through the mouth or jaw). This number is the field ID associated with that individual fish. Example Field ID: 008 (the eighth fish collected) 3.1.1.2 Tissue ID Tissue IDs were assigned to individual fillet samples during the filleting process. Each tissue ID consists of the three-digit field ID number and a two-letter abbreviation "FN", indicating the tissue type (fillet, skin-on). All fish samples were scaled and skin-on fillets. Example Lab ID: 008FN (the eighth fish collected, fillet skin-on) Field ID 008 Tissue ID 008FN 3.1.1.3 Lab ID Lab IDs are tissue IDs with a single number appended that ensures tracking of samples sent to the two analytical labs. November 2012 Cardno ENTRIX Sampling Handling and Processing 3-1 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Example Lab ID: 008FN2 (the eighth fish collected, fillet skin-on, tissue split #2) Field ID 008 Tissue ID 008FN Lab ID 008FN2 3.2 Fish Filleting and Homogenization The processing of fish tissue samples was consistent with methods previously established by Cardno ENTRIX. Fillets were removed from fish based on United States Environmental Protection Agency (USEPA) guidelines (USEPA, 2000). The fillet type for all fish species was scaled and skin-on (major bones removed), which is consistent for data used by the Minnesota Department of Health (MDH) to establish fish consumption advisories for these species. Given the species and size of fish that were collected in the study, a single fillet was collected from each fish for homogenization. For smaller fish such as bluegill, however, fillets from both sides o f the fish were sometimes collected to achieve necessary tissue mass for analysis of PFCs. Prior to filleting, fish were sorted by species, size, and reach in accordance with sample handling procedures. Before filleting, each fish was photographed and the length and mass of each fish was recorded in carbon-copy laboratory notebooks. Otoliths were removed from each fish and stored for aging. All fish samples were filleted on the day they were received. Fillets from individual fish were deposited into clean and labeled polyethylene bags that were labeled with fish ID number, date collected, species, and reach collected. The fillet samples were stored frozen in accordance with the QAPP until they were homogenized. Homogenization was performed using a freeze-fracture technique in accordance with the appropriate Cardno ENTRIX SOP. Briefly, fish fillets were transferred from polyethylene storage bags into a Robot Coupe industrial food processor and enough liquid nitrogen was added to ensure sample solidity. The tissue was then homogenized until a smooth, sawdust-like texture was achieved. The homogenate was distributed to several analytical-grade sample containers and stored frozen in accordance with the QAPP until shipment to the analytical laboratory or laboratories. Blind duplicate samples were designated during the filleting process (see section 3.2.1 for more details). All remaining fillet tissue was deposited into clean polyethylene bags and stored prior to shipping to 3M for archiving. The carcass and any other materials from each fish were disposed of using the appropriate methods for handling biological materials as outlined by Michigan State University regulations. 3.2.1 Blind Duplicate and Interlaboratorv Comparison Samples In accordance with the QAPP, approximately 10% (41 total) of all fish tissue samples were split and sent in duplicate to the 3M lab. These splits were prepared as "blind" samples so that laboratory personnel were not able to tell that both tissue splits were from the same fish. In all cases, when a blind duplicate sample was created from a given fish, an additional tissue split was generated for AXYS as part of the interlaboratory comparison. Blind duplicate samples were designated during the filleting process by selecting every tenth sample on the chain of custody and assigning a Field ID number that was withheld from circulation prior to commencing field efforts and randomly selected during fish filleting. If the 10th sample mass was less than 60 grams, the following sample (11th) was selected until a fish with sufficient tissue mass was encountered. 3-2 Sample Handling and Processing Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 As an example, a blind duplicate sample was created based on the fish with Field ID 010 and the following steps were taken: 1) Verify that selected fish is large enough to generate multiple tissue splits; 2) Create primary 3M and AXYS tissue splits (Lab IDs 010FN1 and 010FN2); and 3) Create duplicate sample for 3M and assign "blind" ID; in this case the Lab ID for the 3M blind duplicate sample was 012FN1. The following table illustrates the relationships between the various tissue splits and IDs. Field ID 010 010 010 Tissue ID 010FN 010FN 010FN Lab ID 010FN1 010FN2 012FN1 Notes Primary 3M sample AXYS split 3M blind duplicate 3.3 Sample Processing QA/QC Measures The sample processing area and equipment at the WTL was decontaminated using general laboratory techniques including washing of sample processing equipment in Liqui-Nox detergent followed by copious rinsing with tap water and then generous rinsing with ASTM type II reagent water. Equipment then received an acetone rinse followed by a methanol rinse. Solvents were allowed to evaporate from the equipment surfaces prior to use. Prior to the initiation of sample filleting, a daily laboratory processing (start) blank was collected. This blank was generated by rinsing a selection of processing hardware (knives, cutting board, bench paper, etc.) with 100 mL of ASTM type II reagent water and collecting the rinsate in a polypropylene sample bottle. After all sample filleting was completed for the day, a second rinse (end) blank was generated using the same protocol. Rinse blanks were frozen in accordance with the QAPP for later analysis, if necessary. Prior to homogenization, a daily homogenization (start) blank was generated using the technique noted above for the Robot Coupe bowl, blade, lid, and lab spatula. Fillet tissue samples were homogenized using a freeze-fracture technique employing liquid nitrogen. The homogenate was split into two fractions if the mass was greater than 20 g, and into four fractions if a primary aliquot, sample split, blind duplicate, and archive were requisite. Homogenization end rinse blanks were collected at the conclusion of daily sample processing and all blanks were archived (frozen) in accordance with the QAPP. In total, upwards of 50 processing or homogenization rinse blanks were generated during the study. Since it was not necessary to analyze every blank, the archived blanks were only analyzed if PFCs were detected in QC samples at unacceptable concentrations. The 3M lab provided the WTL with three control fish tissue samples with known concentrations of PFOS to evaluate for contamination before, during, and after the sample processing (homogenization, splitting) was completed at the WTL. These tissue samples underwent the same homogenization and splitting process as did all the other fish tissue samples. One control fish tissue sample (bass fillet, "pre-study process control") was subjected to the homogenization process prior to the processing of any experimental samples. Analytical results for the pre-study sample were determined to be acceptable and indicated no laboratory contamination issues, therefore processing was initiated. The November 2012 Cardno ENTRIX Sample Handling and Processing 3-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 second control fish tissue sample (bluegill fillet, "mid-study process control") was processed in between samples 164FN and 165FN. The third control fish tissue sample (bluegill fillet, "post-study process control") was processed at the conclusion of the project. The IDs reported in 3M analytical reports for these control fish tissue samples were Ell-0356-01-001, Ell-0356-01-316, and El 1 0356-01-443, respectively. See Section 5.2 for more discussion of results associated with control fish tissue samples. 3.4 Post-Study Fish Tissue Evaluation In addition to the QA/QC procedures outlined in the original QAPP, additional fish tissue samples were sent to 3M and AXYS for a post-study PFOS analysis in November 2011. The goal of this study was to further evaluate potential interlaboratory differences as well as to assess the accuracy and precision of the individual laboratories. The additional samples were comprised of tissues from three sources: National Institute of Standards and Technology standard reference material (NIST SRM) for lake trout tissue from Lake Superior (SRM 1946) and Lake Michigan(SRM 1947) for which PFOS values have been generated and were provided to Cardno ENTRIX (personal communication with Dr. Michele Schantz o f NIST); splits of control fish tissue provided by 3M (see last paragraph of Section 3.3 for more detail) which were analyzed previously as part o f the primary PFC study; and tissues from fish collected from Pool 2 which were also analyzed previously as part of the primary PFC study. The post-study samples were analyzed for PFOS following the same methods employed for the analysis of the fish collected in the summer and fall of 2011. Cardno ENTRIX started with 8 samples: 2 NIST SRM tissue samples, 3 control fish tissue samples provided by 3M, and 3 Mississippi River fish tissue samples that were collected and analyzed as part of the primary study. Four duplicate tissue splits were created from each of these samples and all splits were assigned four digit IDs that were blind to the analytical labs. Two duplicates were provided to both the 3M and AXYS labs for a total of 16 samples per lab (Table 6-16). Tissue samples were split at WTL facilities and shipped for overnight delivery in coolers containing ice. The sample processing area and equipment was decontaminated using the same techniques described previously. 3-4 Sample Handling and Processing Cardno ENTRIX November 2012 Chapter 4 PFC Analysis by 3M and AXYS 4.1 Sample Preparation and Analysis: 3M Environmental Laboratory 4.1.1 Fish Tissue Samples Once received at the 3M lab, all samples were checked into the electronic laboratory information management system (LIMS) where each sample was assigned a unique 3M LIMS sample ID and then stored frozen until they could be prepared for analysis. Analysis of fish tissues followed the validated 3M lab method ETS-8-045.1 "Determination of Perfluorinated Alkyl Acids (PFAAs) via Protein Precipitation of Fish Tissues (Fillet or Whole Body) and Analysis by High Performance Liquid Chromatography with Tandem Mass Spectrometry" (Malinsky e t a l., 2011). Briefly, samples were prepared for analysis by re-homogenizing with dry ice and allowed to sit overnight, or longer, in a refrigerator to allow the dry ice to dissipate. Then, duplicate 0.5 grams aliquots of each sample were transferred to centrifuge tubes, with accurate weight of each aliquot determined. Each analytical batch typically consisted for 20 samples extracted in duplicate with the following QC elements: (1) for every 10th fish sample, two additional aliquots were prepared as laboratory matrix spike (LMS) preparations with a low-level LMS fortified with predominately linear isomer reference material at a nominal 2.0 ng/g each and second high-level LMS fortified at 40 ng/g each; (2) a set of calibration standards that was fortified with internal standards (IS), surrogate recovery standards (SRS), and predominately linear forms of each reference materials, with the exception of PFOSA which was a technical grade material; (3) a set of normal "linear isomer" laboratory control spikes (LCS) consisting of control bluegill homogenate fortified with linear reference materials and technical PFOSA; (4) a set of ECF-LCS samples consisting of control bluegill homogenate fortified with technical PFOS (30.3% branched isomers), technical PFOA (22.2% branched isomers), and technical PFHS (15.6% branched isomers); (5) method blanks consisting of bluegill homogenate with and without ISs and SRSs, and (6) solvent blanks prepared with and without ISs and SRSs. Each sample aliquot received a fixed quantity of stable isotope labeled internal standard and surrogate for use in quantitation and for evaluation of analyte recovery, respectively. The LCS samples were used to determine the accuracy (average recovery) and precision (RSD) for the PFC analytes. PFC recovery was determined directly via LMS in 10% of the samples. In some samples prepared as LMSs, the endogenous PFC levels were greater than the low-level LCS concentration and were insufficient for proper analyte recovery determination. Those samples were re-prepared with a higher level LMS and the original samples results were not used. In the remaining samples, PFC recovery was based on the measurement result of the appropriate surrogate. Each batch of samples had two freshly prepared sets of LCSs, each consisting of 3 levels of nominal 1.00 ng/g, 10.0 ng/g, and 100 ng/g concentrations of each target analyte. The first set of LCS samples were fortified with "normal" linear isomer reference materials (PFOA, PFHS, PFOS, and PFOSA) similar to that used to construct the calibration standards. The second set of LCS samples were fortified with mixed linear and branched PFC isomers (PFOA, PFHS, and PFOS) to verify the quantitative accuracy of PFC compositions that are typically found in environmental samples. Extraction of each sample was performed by an acetonitrile protein precipitation method followed by centrifugation and transfer to autosampler for analysis by high performance liquid November 2012 Cardno ENTRIX PFC Analysis by 3M and AXYS 4-1 1Bi- Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 chromatography/tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the multiple mass transitions (Table 4-1) used to analyze PFCs are outlined in Malinsky e t a l. (2011) as well as in the 3M Laboratory analytical reports. The relative percent difference (RPD) of duplicate analytical sample results was tiled as a measure of sample-specific analytical precision. The determined recoveries of fortified target analytes from LMS samples were used as a measure of sample-specific analytical accuracy while the recovery of SRSs in each analytical sample was used as a secondary measure of target analyte recovery from each sample. 4.1.2 Surface Water Samples Analysis of water samples followed the 3M lab Method ETS-8-154.4 "Determination of Perfluorinated Acids, Alcohols, Amides and Sulfonates in Water by Solid Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry" (Wolf e t a l., 2011). Briefly, all samples, calibration standards, and associated quality control samples were extracted by passing 50imL water samples through a pre-conditioned solid phase extraction (SPE) cartridge followed by the elution of PFCs with 2.5 mL methanol. Surface waters samples were extracted using a Waters tC18 $PE cartridge (0.5 g, 3 cc) for PFNA, PFDA, PFUnA, PFDoA, PFBS, PFHS, PFOS, PFOSA, 13C4-PFOS and 13C2-PFUnA. An Oasis HLB SPE cartridge (0.5 g, 3 cc) was used to extract PFBA, PFPeA, PFHxA, PFOA, and 13C4-PFOA. This procedure concentrates the samples by a factor of twenty-five. All samples and quality control samples were analyzed for 13 target analytes using high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Pertinent instrument parameters, the liquid chromatography gradient program, and the specific mass transitions analyzed (Table 4-1) are described in their respective 3M analytical reports. Three types of blanks were prepared and analyzed with samples including method blanks, solvent blanks, and field/trip blanks. Each blank result was reviewed and used to evaluate method performance to determine the LOQ for etch analyte. Calibration standards were prepared by spiking known amounts of PFC analytes into Millii Q water and internal standards were added from a separate spiking solution at the same levels as those used in water samples, 0.1 ng/ml. A total o f 12 spiked standards were prepared. The data for each analyte was fitted to a quadratic, weighted calibration curve that was not forced through zero. If necessary, low and/or high curve points were disabled to help meet linearity or accuracy criteria of 100 25% (100 30% for the lowest curve point). The limit of quantitation (LOQ) was defined as the lowest non-zero calibration standard in the calibration curve that met linearity and accuracy requirements. Laboratory control spikes (LCSs) were prepared by spiking analytes into Milli Q water to produce three concentrations: low, mid and high. In Round 1, all PFCs and SRSs were spiked at nominal concentrations of 5, 50, and 500 ng/L with the exception of PFBA, which was spiked at 10, 50, and 200 ng/L. In Round 2, PFNA, PFDA, PFUnA, PFDoA, 13C2-PFUnA, PFBS, PFHS, PFOS (linear), and PFOSA were spiked at a nominal concentration of 5, 50, and 500 ng/L. For PFBA, PFPeA, PFHxA, PFHpA, PFOA (linear), and 13C4-PFOA nominal spike concentrations were 5, 50, and 250 ng/L. For PFOS and PFOA that contained both linear and branched isomers, samples were spiked at 5 and 500 ng/L. The spiked water samples were extracted and analyzed in the same manner as the water samples. Field matrix spikes (FMS) were collected at each sampling point to verify that the analytical method was applicable to the collected matrix. FMS recoveries within the method acceptance criteria of 100% 30% confirm that unknown components in the sample matrix do not significantly interfere 4-2 PFC Analysis by 3M and AXYS Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 with the extraction and analysis o f the analytes of interest. Samples were collected in 250 ml Nalgene bottles spiked with 25 ppt (nominal) field matrix spike that were marked with a "fill to line" line at 200 ml. In Round 1, five of the 12 samples were overfilled by more than 10% while in Round 2, 15 of 30 samples were overfilled. In each of these instances, the true value of the FMS was adjusted based on the volume determined from the pre- and post-fill bottle weights. 4.2 Sample Preparation and Analysis: AXYS Analytical Services 4.2.1 Fish Tissue Samples Samples were received by AXYS and stored frozen in accordance with the QAPP prior to extraction and analysis. Samples were analyzed in multiple batches; each batch included a procedural blank, a lab-generated reference Ongoing Precision and Recovery (OPR) sample, and a duplicate sample. OPR samples were prepared using a fish tissue that was free of PFCs. Sample extraction, instrumental analysis, and analyte quantification procedures were in accordance with AXYS method MLA-043 "Analytical Procedure for the analysis ofPerfluorinated Organic Compounds in Tissues Samples by LC-MS/MS". The surrogate and recovery standards were sourced from Wellington Laboratories while the authentic standard used in OPR samples was sourced from Sigma Aldrich. Samples were prepared in batches that consisted of a set of calibration standards, laboratory control samples, blanks, and tissue samples. Briefly, the samples were accurately weighed (approximately 2 g), spiked with surrogate standards (Table 4-2) and extracted in basic methanol by shaking. Extracts were then cleaned up by SPE extraction using disposable cartridges containing a weak anion exchange sorbent. The resulting extracts were instrumentally analyzed using HPLC coupled to a triple quadrapole mass spectrometer (LC-MS/MS) that was run in the multiple reaction monitoring (MRM) mode. Pertinent instrument parameters, liquid chromatography gradient program and mass transitions (Table 4-2) used to analyze PFOS are described in the AXYS analytical report. Analyte concentrations were determined by isotope dilution/intemal standard quantification, comparing the area response of the quantification ion to that of the 13C-labeled standards and correcting for response factors. Linear quantification equations with 1/X2weighting fit were determined from a multi-point calibration series using matrix matched calibration solutions prepared alongside the samples. For the calculated concentrations, a maximum of 1 point per calibration solution with a maximum of three points for all the calibration solutions had to fall within 60 to 140% of actual concentrations provided that all remaining points including those for PFOA, PFOS and PFDA fell within 70-130% of actual concentration. A mid-level calibration solution was analyzed at least after every 20th sample with concentrations having to be within 30% of the actual concentrations. The reporting limit was defined as the concentration equivalent to the lowest calibration solution run with a particular batch of samples, or the sample specific detection limit, whichever was greater. The range of acceptable matrix spike recoveries for PFBA, PFPeA, PFBS, PFHS, and PFOSA was 40 to 150%. The acceptable recovery range for 13C2 -PFBA was 20 to 150% while for 13C2-PFHxA, 13C2-PFOA, 13C5-PFNA, 13C2-PFDA, 13C2-PFDoA, 180 2-PFHS, 13C4-PFOS and 13Cg-PFOA it was 40 to 150%. The reported concentrations of PFCs in fish tissues were not blank corrected and the data were evaluated with consideration of the procedural blanks. All linearity, calibration/verification, OPR, duplicate, and labeled recovery samples met the method specifications with the exception of two samples. In one sample the percent recovery of PFUnA in an OPR was slightly above the method upper limit specification and as a result, the concentration reported for this sample may have been over reported. In a second sample, the percent recovery of the surrogate 13C-PFBA (154%) was November 2012 Cardno EN TRIX P FC Analysis by 3M and AXYS 4-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - S u m m e r 2011 slightly above the upper limit, but given that the analyte was not detected, it had no effect on the reported value. 4.2.2 Surface Water Samples Samples were received by AXYS and stored at 4C prior to extraction and analysis. Samples were analyzed in multiple batches; each batch included a procedural blank, lab-generated reference Ongoing Precision and Recovery (OPR) sample, and a duplicate sample. OPR samples were started with the samples and carried through in the same analytical batch. The blanks were prepared using Canadian Springs TM water. Sample extraction, instrumental analysis and analyte quantification procedures were in accordance with the AXYS method MLA-060 "Analytical Procedure for the Analysis of Perfluorinateid Organic Compounds in Aqueous Samples by LC-MS/MS". Briefly, the unfiltered samples were accurately weighed and adjusted to pH 6.5. They were then spiked with surrogate BC-labeled surrogate standards (Table 4-2) and extracted using SPE with a weak anion exchange cartridge. Elutttes were spiked with a 13C2 -PFOUEA recovery standard and then analyzed using liquid chromatogtfaphy/mass spectrometry (LC-MS/MS). Pertinent instrument parameters, liquid chromatography gradient program, and mass transitions used to analyze PFCs (Table 4-2) are described in the AXYS analytical report. Analyte concentrations were determined by isotope dilution/intemal standard quantification, comparing the area response of the quantification ion to that o f the 13C-labeled standards and corrected for response factors. Quadratic quantification of the 1/X2 weighting fit was determined from multi-point calibration series using matrix matched calibration solutions prepared alongside the aqueous samples. Acceptance criteria for the calculated concentrations based on the initial calibration curve was 75-125% of actual concentration (lowest calibration point may be 70-130%) with a coefficient of determination (R2) of 0.990 or greater. The reporting limit was defined as either the concentration equivalent to the CS0 calibration standard, the lowest calibration solution run with a particular batch of samples, or the sample specific detection limit, whichever was greater. The acceptable OPR recovery range was 80% to 120% for perfluoroalkyl carboxylate analyte# while for perfluoroalkyl sulfonates it was 70-130%. With the exception of 13C-PFBA, the surrogate standard acceptable recovery range was 40-150% while for 13C-PFBA it was 20-150%. In Round 1, all linearity, CAL/VER, OPR, duplicate, and labeled compound standards met recovery specifications. In Round 2, all standards also met recovery specification with the exception o f two samples where ,3C2-PFDoA did not meet the criteria and were flagged accordingly. However, given that the isotope dilution method o f quantification produces data that are recovery corrected, the slight variance from the method acceptance criteria was deemed to not have significantly affected the quantification of analytes. 4.3 Samples Analyzed The number fish tissue samples, surface water samples and additional QA/QC samples analyzed by 3M and AXYS for this study are reported in Table 4-3. Table 4-4 reports the number collected and fish species analyzed on a reach-specific basis. 4 4 PFC Analysis by 3M and AXYS Cardno ENTRIX November 2012 Mississippi River Pool 2 PFOS Assessment - Fish Tissues and Water - Summer 2011 4.4 Tables and Figures Table 4-1. Target Analytes and Surrogate Standards for 3M Environmental Laboratory Compound Target A nalytes PFBA (C4 Acid) PFPeA (C5 Acid) PFHxA (C6 Acid) PFHpA (C7 Acid) PFOA (C8 Acid) PFNA (C9 Acid) PFDA (C10 Acid) PFUnA (C11 Acid) PFDoA(C12Acid) PFBS (C4 Sulfonate) PFHS (C6 Sulfonate) PFOS (C8 Sulfonate) FOSA (C8 Sulfonamide) Internal S tandards (IS) [13C4]-PFBA [13C5]-PFPeA [13C2]-PFHxA [13C2]-PFHxA [13Cs]-PFHpA [13Cs]-PFOA [13Cs]-PFNA [13Cg]-PFNA Analyte Description Target Target Target Target Target Target Target Target Target Target Target Target Target IS for PFBA IS for PFPeA IS for PFHxA IS for PFPeA, PFHxA and PFHpA IS for PFHpA IS for PFOA and [13C4]-PFOA IS for PFNA IS for PFNA Water MRM Transition(s) 213>169 263>219 313>119 313>269 363>319 363>119 413>369 413>219 413>169 463>419 463>219 463>169 513>469 513>219 513>269 563>519 563>269 563>219 613>569 613>319 613>269 299>80 299>99 399>99 399>80 499>99 499>80 499>130 498>78 217>172 268>223 315>270 368>273 421>376 472>427 Fish MRM Transition(s) 213>169 263>219 263>119 313>269 313>119 363>319 363>169 413>369 413>219 413>169 463>419 463>219 463>169 513>469 513>269 513>219 563>519 563>269 563>219 613>569 613>319 613>169 299>80 299>99 399>80 399>99 499>80 499>99 499.130 498>78 217>172 315>270 421>376 468>423 November 2012 Cardno ENTRIX PFC Analysis by 3M and AXYS 4-5 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 4-1. Target Analytes and Surrogate Standards for 3M Environmental Laboratory Water Compound Analyte Description MRM Transition(s) [,3C2]-PFDA IS for PFDA 515>470 [13C6]-PFDA IS for PFDA 519>474 PCrJ-PFUnA IS for PFUnA and [13C2]-PFUnA 570>525 [,3C2]-PFDoA IS for PFDoA 615>570 [,80 2]-PFBS IS for PFBS 303>84 [13C3]-PFHS IS for PFHS 402>80 [13Cs]-PFOS IS for PFOS and [13C4]-PFOS 507>80 [13Cs]-PFOSA ISforFOSA 506>78 S urrogate R ecovery S tandards (SRS) , ^ [13C4]-PFOA Surrogate (C4-C9 Carboxylates) 417>372 [13C4]-PFOS Surrogate (PFBS, PFHS, PFOS and PFOSA) 503>80 [13C2]-PFUnA Surrogate (C10-C12 Carboxylates) 565>520 Multiple MS/MS ion transitions are summed when more than one transition is listed for the analyte. - F ill MRM TraMition(s) 515M70 565>$20 615>$70 303*84 402*80 507>80 506>78 ` lilt 417M372 503>80 565W520 4-6 PFC Analysis by 3M and AXYS Cardno ENTRIX November 2012 Mississippi River Pool 2 PFOS Assessment - Fish Tissues and Water - Summer 2011 Table 4-2. Target Analytes and Surrogate Standards for AXYS Analytical Laboratory Compound Target A nalyte Perfluorobutanoate (PFBA) Perfluoropentanoate (PFPeA) Perfluorohexanoate (PFHxA) Perfluoroheptanoate (PFHpA) Perfluorooctanoate (PFOA) Perfluorononanoate (PFNA) Perfluorodecanoate (PFDA) Perfluoroundecanoate (PFUnA) Perfluorododecanoate (PFDoA) Perfluorobutane sulfonate (PFBS) Perfluorohexane sulfonate (PFHS) Perfluorooctane sulfonate (PFOS) Perfluorooctane sulfonamide (PFOSA) . S urrogate Standard ' 13C4-Perfluorobutanolc acid (13C4-PFBA) 13C2-Perfluorohexanoic acid (13C2-PFHxA) 13C2-Perfluorooctanoic acid (13C2-PFOA) 13C5-Perfluorononanoic acid (13Cs-PFNA) 13C2-Perfluorodecanoic acid (13C2-PFDA) 13C2-Perfluorododecanoic acid (13C2-PFDoA) 1802-Perfluorohexanesulfonate (1802-PFHS) MRM Transition(s ) Quantified Against 'is ;* JK \;y \ * " * * i> ` - fl , Is. 213>169 13C4-PFBA 263>219 13C2-PFHxA 313>269 13C2-PFHxA 363>319 413>369 413>169 13C2-PFHxA 13c 2-p f o a 463>419 13C5-PFNA 513>469 13c 2-p fd a 563>519 13c 2-p f d a 613>569 13C2-PFDoA 299>80 299>99 18o 2-p f h s 399>80 399> 99 399>119 18o 2-p f h s 499>80 449>99 13c 4-p f o s - , '4 1 ; * .t ; ' . 498>78 13C4-PFOS < - "* ` 9 i ' 1 * if iif* 1,9 , 9 3 ,? * .......- .............,* J> 217>172 13C4-PFOA 315>270 13c4-p f o a 415>370 13C4-PFOA 468>423 13C4-PFOA 515>470 13C4-PFOA 615>570 13C4-PFOA 403>84 403>103 13C4-PFOA 13C4-Perfluorooctanesulfonate (13C4-PFOS) 503>80 503>99 13C4-PFOA C lean-up S tandard , 13C8-Perfluorooctanoic acid (13C8-PFOA) R ecovery S tandard ' ,3C2-2H-Perfluoro-2-decenoic acid (13C2-PFOUEA) 13C4-Perfluorooctanoic acid (13C4-PFOA) # * v* 421>376 ) . * , / S! ^ fc 459>394 417>372 T '- 13c 4-p f o a If . - - November 2012 Cardno ENTRIX P FC Analysis by 3M and AXYS 4-7 Table 4-3. Summary of Samples Shipped to Analytical Laboratories Interlaboratory Blind Duplicate Lab Fish Tissue Samples Fish Tissue Samples Water Samples 3M 39912 44 AXYS 413 1Field and MSU laboratory equipment rlnsate blanks and control fish tissue processing blanks 2Includes 396 target species plus two non-target green sunfish and one sunfish 3Duplicates of 41 samples sent to 3M 30 Other QA/QC Samples1 Target Analytes PFBS PFHS, PFOS, PFOSA, PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA Same as above Table 4-4. Species and Number of Fish Analyzed by 3M from Pool 2 of the Mississippi River, 2011 Sampling Reach Blueglll 1234 5 6 ' -T O . 10 * * 10 ` ' 10 10 10 Freshwater drum 10 10 10 10 10 10 Green sunfish -- - -- 1 / - Yf Smallmouth bass 10 10 10 10 10 10 Sunfish f* 1 - - - iiSIt White bass 6 10 10 10 10 10 1The first 10 blueglll collected from Reach 9 were analyzed; tissues from an 11"' were archived 2The first 10 drum collected from Reach 10 were analyzed; tissues from an extra five (11-15) were archived - Not sampled during this round 7 10 10 10 10 8 : '.io / 9 *, - 1 p C % 10 10 _ 10 10 "" 10 10 10 10 102 -- 10 10 Total 100 100 2 100 1 96 4- ); Analysis by 3M and AXYS Cardno Ef Noveri Chapter 5 QA/QC Results 5.1 3M Laboratory QA/QC Samples 5.1.1 Fish Tissue QA Results Calibration curves were not forced through zero and when calculated standard concentrations from the calibration curve were compared to known concentrations, the accuracy of each curve point was within 100 25% with a coefficient of determination that was greater than 0.990. The lower limit of quantitation (LLOQ) was the lowest non-zero calibration standard in the curve that met linearity and accuracy requirements (100 30%) and for which the area counts were at least two times that of the average response determined from the method blanks. In this study, the LLOQ for C7-C12 PFCAs, PFBS, PFHS, PFOSA, and the surrogate reference standards was in nearly all instances the nominal concentration of 0.25 ng/g (0.025 ng/ml acetonitrile), or less. However, in no more than eight analytical batches, the LLOQs for PFBA, PFPeA and PFHxA were raised to 0.35 ng/g, 0.5 ng/g, or 1.0 ng/g fish tissue. For PFOS, the required 0.250 ng/g LLOQ was met for all analyses. Continuing calibration verifications (CCV) were performed during the course of each analytical batch by injection of mid-level calibration standards to help verify instrumental response and that the initial calibration curve was still in control. The average recoveries for all CCVs (n > 190) from all analytical batches were within 100% 15% and had RSDs less than 15%. The CCV for PFOSA in all analytical batches met the method criteria of 100% 25%. All other analytes met the same criterion with only a few exceptions. The number of exceptions for each analyte was never greater than 15% of the total number of CCVs and the exceedences typically were not greater than 30% of the acceptable range. The average LMS recovery for all target analytes ranged from 91.7% to 113% with RSDs less than 20%. Additionally, the average LMS recoveries for the three stable isotope labeled surrogate recovery standards (SRS) showed good precision and accuracy with average recoveries of 107%, 107%, and 112%, and RSDs < 20%, for 13C4-PFOS, 13C4-PFOA and 13C2-PFUnA, respectively. The SRS recovery results from LMSs were similar to the overall accuracy and precision achieved for the SRSs added to fish tissues prior to extraction (sample and sample duplicate, n = 880), with average recoveries and RSDs of 103% 10% for 13C4-PFOS, 107% 13% for 13C4-PFOA, and 106% 11% for 13C4-PFUnA. The results determined from LMSs and SRSs indicated excellent overall data accuracy and precision for the study sample fish results. The recoveries of fortified PFOS from the 45 LMS samples prepared from samples analyzed throughout the study were within the acceptance criterion of 100 30% recovery and ranged from 77.1% to 120%, with an average recovery and standard deviation of 102% 11%. Additionally, the surrogate recoveries from all samples were within 100 30%, indicating good analytical accuracy for PFOS in all samples. The average recovery for all 13C4-PFOS surrogate recovery standards in the study samples and duplicates was 99.9% with an RSD of 10.3%. The analytical method uncertainty was determined from the analysis of LCS sets prepared with each extraction batch by spiking PFOS in control fish tissue homogenates at nominal concentrations of 1.0, 10.0 and 100 ng/g. The method November 2012 Cardno ENTRIX QA/QC Results 5-1 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water-Summer 2011 uncertainty was determined to be 17% for linear PFOS (linear isomer) and 19% for PFOS (mixed linear + branched isomers), determined at the 95% confidence interval (i.e. 2 standard deviations). The LCS average accuracy and precision results for the target analytes in fish tissues were as follows: 113% 21% for PFBA, 106% 24% for PFPeA, 102% 13% for PFHxA, 93.6% 10% for PFHpA, 96.1% 15% for PFOA, 99.2% 11% for PFNA, 102% 11% for PFDA, 96.7% 9.7% for PFUnA, 98.9% 9.8% for PFDoA, 98.8% 13% for PFBS, 97.0% 9.8% for PFHS, PFOS 96.4% 8.9%, and 95.8% 6.9% for PFOSA. Overall, the inter-batch average recovery for linear LCS recoveries were within the 100 30% with RSDs of less than 20% with the exception of PFBA and PFPeA. The average SRS recovery and RSD for linear LCSs were as follows: 109% 12% for 13C4-PFOA, 105% 8.6% for 13C2- PFUnA and 105% 8.5% for 13C4-PFOS. The LCS results indicated excellent method performance for all target analytes. The ECF-LCSs average and RSD recovery results for technical PFHS, technical PFOS, and technical PFOA fortified into bluegill control fillet homogenate were 100% 8.6%, 116% 8.1%, and 87.8% 13%, respectively. The SRS average recoveries and RSDs for ECF-LCSs were 109% 8.6% for 13C4-PFOA and 104% 8.7% for 13C4-PFOS. Overall, the ECF-LCS results showed that mixed and linear branched isomer reference materials for PFOA, PFHS and PFOS were quantified with excellent accuracy and precision using linear isomer calibration. The analytical method uncertainties (95% confidence interval) were determined as two-times the standard deviation of recovery results for all linear LCS samples and were as follows: 48% for PFBA, 50% for PFPeA, 26% for PFHxA, 20% for PFHpA, 28% for PFOA, 22% for PFNA, 22% for PFDA, 19% for PFUnA, 19% for PFDoA, 26% for PFBS, 19% for PFHS, 18% for PFOS, and 13% for PFOSA. Measurement uncertainties for the SRSs were as follows: 25% for 13C4-PFOA, 18% for 13C2-PFUnA, and 18% for 13C4-PFOS. 5.1.2 Surface Water QA Results For both Round 1 and 2 water collections, correlation coefficients (r) for calibration curves for all PFC analytes and surrogate recovery standards were 0.995 or greater and met the acceptance criteria. During the course of the analytical sequence, several continuing calibration verification (CCV) samples were analyzed to confirm that the instrument response and the initial calibration curve were still acceptable. The method acceptance criteria of 100% 25% was met for almost all reported data with exception of four instances, one each for PFBA, PFPeA, PFHxA, and PFHpA. The limit of quantitation (LOQ) for Round 1 water samples was 2.0 ng/L for PFHpA, PFOA, PFNA, PFBS, PFHS, and PFOS while the LOQ for PFBA was 5.0 ng/L. For PFPeA, PFUnA, PFDoA, and PFOSA, the LOQ was 4.0 ng/L. The LOQ for PFHxA and PFDA was 2.5 ng/L. However, for sample 505SF1, the LOQ for PFHxA and PFOSA was 2.0 ng/L while for PFBA it was 2.5 ng/L. In Round 2, the LOQ for nearly all PFCs was 2.0 ng/L. Exceptions were observed for PFBA, PFPeA, 13C4-PFOA, and 13C4-PFOS where the LOQs were 10.0, 5.0, 2.99, and 2.87 ng/L, respectively. For Round 1 water samples, the low set of LCS samples for PFBA did not met the acceptance criteria with an RSD of 41% while the mid and high sets met method acceptance criteria of 100 20% with RSDs < 20%. For PFPeA and linear PFOA and PFOS, the high curve points were disabled to meet accuracy and linearity criteria. Acceptance criteria were met for all analytes with the exception of the low level set of LCS samples for PFUnA which had an average recovery o f 76.6%, with an RSD of 21%. For Round 2 water samples, all three sets of LCS samples for PFNA, PFDA, PFUnA, PFDoA, 5-2 QA/QC Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 PFBS, PFHS, PFOS (linear), PFOSA, 13C4-PFOS, 13C2-PFUnA, PFOA, and 13C4-PFOA met the acceptance criteria of 100% 20%, with an RSD of <20%. For PFBA and PFPeA, the low set of LCS samples were below the LOQ and recovery could not be determined. For PFHxA, all replicates for the high set of LCS samples exceeded the calibration range and were disabled to meet method linearity criteria. When considering all LCS sets, all PFC analytes met the acceptance criteria of an RSD <20%. Given that reference materials used for quantitation of PFOS and PFOA are predominately linear isomers while surface water samples collected from Pool 2 contain both linear and branched isomers, laboratory control samples (LCS) containing both linear and branched isomers were prepared to evaluate the potential for analytical bias. LCS samples were prepared at the same time as the calibration curve and SPE extraction of the samples. For Round 1 water samples, the average recovery for the low set of LCS samples for PFOA was 66.1% 7.9%(RSD) and did not meet the method criteria . In contrast the mid set for PFOA and both sets of LCS samples for PFOS met the method acceptance criteria. For Round 2 water samples, both sets of LCS samples met the method acceptance criteria. For PFOS, the low set of LCS samples met method acceptance criteria while 2 out of the 3 replicates in the high set inadvertently did not receive internal standard spikes, therefore recovery could not be calculated. However, the peak count areas for those 2 samples were very similar to the third replicate that was quantified to have a recovery of 109%. Analytical uncertainty was determined using historical QC data that is control charted and used to evaluate method accuracy and precision. The method uncertainty is calculated as the standard deviation for a set of accuracy results (%) obtained for QC samples. The expanded uncertainty is calculated by multiplying the standard deviation by a factor o f 2. This corresponds to a confidence level of 95%. For Round 1 water samples, the analytical uncertainties were 28% for PFBA, 34% for PFPeA, 27% for PFHxA, 24% for PFHpA, 25% for PFOA, 17% for PFNA, 18% for PFDA, 24% for PFUnA, 20% for PFDoA, 22% for PFBS, 17% for PFHS, 32% for PFOS, and 16% for PFOSA. For Round 2 water samples, the analytical uncertainties were 35% for PFBA, 35% for PFPeA, 31% for PFHxA, 27% for PFHpA, 27% for PFOA, 16% for PFNA, 17% for PFDA, 22% for PFDoA, 22% for PFBS, 17% for PFHS, 23% for PFOS, and 16% for PFOSA. In Round 1, a total of 6 out of 12 samples met the acceptance criteria for all PFCs in the field matrix spikes. In the 6 samples that did not meet the acceptance criteria, no single exceedence was greater than 40%. The recovery for PFHxA was 31% in one sample while in 4 other samples the recovery for PFPeA ranged from 134% up to 139%. In each instance, the analytical uncertainty was adjusted for these exceedences. The sixth exception, due to the level of analyte detected in the sample, the 25 ppt FMS was not an appropriate spike level for PFBA, PFOA, and PFOS. However, the 13C4-PFOA and 13C4-PFOS surrogates met the method acceptance criteria and as a result, no additional matrix spikes were prepared. In this sample the recovery was 132% and the analytical uncertainty was adjusted accordingly. In Round 2, a total of 14 out of 30 water samples met the acceptance criteria for all PFCs in the field matrix spikes. In 12 samples, recoveries for PFBA exceeded the criteria and ranged from 135% up to 165%. For PFPeA, 8 samples had recoveries that exceeded their criteria and ranged from 132% up to 163%. In all but two of these instances, the analytical uncertainty was adjusted for the exceedence. For the other two instances, the recovery was within the analytical uncertainty of 35% and no further adjustment was made. For one sample, the 25 ppt FMS was not an appropriate spike level for PFBA, PFPeA, PFOA, PFBS, PFHS, and PFOS due to the low level of analyte detected. However, November 2012 Cardno ENTRIX QA/QC Results 5-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 the 13C4-PFOA and 13C4-PFOS surrogates met the method acceptance criteria and no additional matrix spikes were prepared. 5.2 Field QA/QC Samples Four field equipment blanks were analyzed as part of this study. With the exception of PFOS, all target analytes were reported as less than their LOQ in all 4 blank samples. In 3 of the 4 blanks, PFOS was less than the LOQ (2 ng/L), while PFOS was detected in the 4th blank with a reported result of 6.38 ng/L. This sample was a rinsate blank from a cooler used to temporarily store fish during collection. These coolers were routinely washed and rinsed during the collection and it is highly unlikely that cross contamination would occur through contact with coolers. 5.3 Fish Processing QA/QC Samples In the pre-study process control, concentrations of target analytes in bass tissue that had been homogenized at WTL remained relatively unchanged when compared to non-WTL homogenized tissue. Exceptions to this were observed for PFBA, PFPeA, and PFHxA where concentrations increased by 3.7 ng/g, 0.73 ng/g, and 1.93 ng/g, respectively and for PFHpA and PFOA where concentrations decreased by 0.06 ng/g, and 0.07 ng/g, respectively. The relative percent difference (RPD) for PFBA, PFPeA, PFHxA, PFHpA, and PFOA were 26%, 64%, 22%, and 25%, respectively. In the mid-study process control, only PFOSA did not meet the acceptance criteria with a concentration difference of 0.041 ng/g and a RPD of 85%. In the post-study process control, concentrations in the WTL-homogenized samples were increased from non-homogenized values for PFHxA (0.81 ng/g), PFNA (0.23 ng/g), PFOA (0.11 ng/g), and PFUnA (0.042 ng/g) with RPD values of 154%, 121%, 59%, and 32%, respectively. All other analytes in the three process controls samples, including PFOS, met the acceptance criteria (RPD < 20%) for WTL versus non-WTL homogenized tissue samples. The changes in analyte concentrations observed in the pre-, mid- and post-study process control samples did not appear to be due to gross contamination from the homogenization process at the WTL-MSU laboratory. This is based on the fact that the variability within these sets of process samples were within the acceptance criteria for most target PFCs, including PFOS. Furthermore, the largest variations on a ng/g basis were predominately with the C4C6 PFCA analytes, all of which were infrequently measured at levels above the LOQs in fish collected from Pool 2 of the Mississippi River. As a result, the changes in PFC concentrations observed between the WTL and non-WTL homogenized samples did not appear to have significantly affected the data reported for fish collected in this study. A rinse blank (ID HSR060911F1) containing approximately 100 mL o f water was generated by WTL personnel prior to the processing of the pre-study control fish tissue sample mentioned above. With the exception for PFOA, PFNA, and PFOS, all analyte concentration reported in this sample were less than their LOQ. For PFOA, PFNA, and PFOS, concentrations reported in this blank were 2.66, 2.30, and 20.8 ng/L, respectively. However, in the fish tissue pre-study control sample (El 1-0356 01-001) that was processed after this blank was generated, PFOA, PFNA and PFOS concentrations were reported as 0.209, <0.250, and 0.576 ng/g, respectively, which indicates there was no apparent cross-contamination from equipment to sample. In addition to the analysis of fish tissues, consumable supplies (baggies, bench paper, rinse water, etc.) used at MSU for fish processing were sent prior to the commencement of the study to the 3M lab for analysis to ensure that contact contamination would not occur by using those supplies during fish processing. The results from the extraction with methanol: water (1:1) and analysis by 5-4 QA/QC Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 LC/MS/MS of those consumable supplies are documented in the 3M final analytical reports and showed all PFCs were less than their respective LOQ, and therefore sufficiently demonstrated that the consumable supplies used at MSU for fish processing did not have significant extractable PFOS at levels that would pose a contact contamination concern. November 2012 Cardno ENTRIX QA/QC Results 5-5 Chapter 6 PFOS Results 6.1 Intralaboratory Blind Duplicate Samples PFOS was detected in all 41 of the intralaboratory blind duplicate samples analyzed by the 3M lab. PFOS concentrations ranged from 7.07-305 ng/g ww in the primary fish samples (Figure 6-7). In the blind duplicate samples, PFOS ranged from 7.79-257 ng/g ww. A comparison of the primary and blind duplicate samples showed that PFOS concentrations differed by less than 20% in 38 of the 41 tissue samples. The average relative percent difference (RPD) between the primary and blind duplicate samples was approximately 9% (Table 6-1). 6.2 Interlaboratory Comparison Samples 6.2.1 Fish Tissue PFOS was detected in all 41 of the interlaboratory fish tissue samples in both laboratories. PFOS concentrations for all fish ranged from 9.33 to 356 ng/g ww from AXYS and 7.07 to 305 ng/g ww from the 3M lab (Figure 6-8; Table 6.2). A comparison of PFOS concentrations measured in individual fish samples indicated good agreement between laboratories. PFOS concentrations reported by AXYS were greater than those from the 3M lab for 38 of the 41 samples with RPDs that ranged from 1.27 to 53.6% with an average value of 16%. When evaluated on a percent difference basis, values ranged from 1.2 to 73% with an average of 19%. While there was a systematic difference in the reported PFOS concentrations between both laboratories, this is not unexpected given the differences in analytical methodologies used at each laboratory (Lindstrom e t a l. 2009). For instance, the use of linear isomer PFOS calibration with a 499 to 80 MS/MS transition for data acquisition as was used by AXYS, not the 3M lab, can bias high the quantification of mixed branched/linear PFOS in environmental samples by 8% (Riddell e t a l. 2009). Given what is known about the variability in the quantification of PFOS in biological tissues, results from this interlaboratory comparison reinforce the validity of the results of this study. 6.2.2 Surface Water The interlaboratory comparison of PFOS concentrations in the 30 surface water samples shows good agreement with concentrations reported by 3M being approximately 1.24-fold greater than those reported by AXYS (Figure 6-9). For AXYS, 25 out of 30 the samples had PFOS concentrations less than the reporting limit while for the 3M lab, 23 of the 30 samples had PFOS concentrations below the reporting limit (Table 6-3). For samples where PFOS was detected, concentrations ranged from 3.45 to 84.9 ng/L for AXYS and 2.15 to 136 ng/L for the 3M lab. While the RPD for all 30 water samples ranged between < 1 to 107%, it is important to note that for the five samples where PFOS was detected by both laboratories, the relative percent difference (RPD) ranged from 17% to 56% with an average of 33%. 6.3 Study Fish Tissue Samples All bluegill, freshwater drum, smallmouth bass, and white bass tissue samples were successfully analyzed for PFOS with concentrations being reported as greater than the limit of quantitation. The November 2012 Cardno ENTRIX PFOS Results 6-1 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - $|ummer 2011 concentrations of PFOS in the 2011 Mississippi River fish samples ranged from 3.17 to 757 ng/g ww. The arithmetic mean, geometric mean, and median PFOS concentrations for all fish from Pool 2 were 46.3, 31.1 and 34.1 ng/g ww, respectively. In total, the number of samples with PFOS concentrations greater than 40 ng/g ww was 165 while there were 11samples with PFOS concentrations greater than 200 ng/g ww. No sample had a PFOS concentration greater than 800 ng/g ww. PFOS concentrations as reported by 3M for each fish are provided in Appendix A, Table A -l. Summary statistics for species PFOS concentrations for the entirety of Pool 2 are provided in Table 6-4. In Figure 6-1, box plots provide additional summary statistics on a species specific basis for the entirety o f Pool 2. By species, the arithmetic mean and its 95% confidence limits are: bluegill - 36 (24-47) ng/g ww; freshwater drum - 46 (32-61) ng/g ww; smallmouth bass - 39 (25-54) ng/g ww; and white bass - 64 (56-72) ng/g ww. The rank order of PFOS concentrations based on arithmetic means from least to greatest was bluegill, smallmouth bass, freshwater drum and white baas with average PFOS concentrations ranging from 36 to 64 ng/g ww. The rank order of PFOS concentrations from least to greatest based on median values was bluegill, followed by freshwater drum, smallmouth bass and then white bass with median PFOS concentrations ranging from 18 to 58 ng/g ww. An examination of the interquartile ranges in Figure 6-1 as a measure of the variation of PFOS concentrations on a species specific basis shows the greatest degree of variation was associated with bluegill and least for white bass. In general, the concentration of PFOS in the target fish species did not vary greatly between reaches (Tables 6-5 through 6-14). Based on median values, Reach 6 was highest for bluegill, Reach 5 for freshwater drum, and Reach 10 for smallmouth bass and white bass. For bluegill, PFOS concentrations levels generally increased from Reach 1 (where the lowest levels were observed) through Reach 6, decreased in Reach 7 and then steadily increased through Reach 10 (Figure 6-2). For freshwater drum, median values for the reaches only varied between 12 ng/g (Reach 9) to 38.2 ng/g (Reach 5) with no clear patterns evident from upstream to downstream (Figure 6-3). Bn similar fashion, the median values for smallmouth bass between reaches were relatively uniform with the exception of Reach 10 which had the highest value of 55 ng/g (Figure 6-4). The white bass results showed the least variability and had fairly consistent median values across all reaches with a minimum of 47 ng/g in Reach 3 and a maximum of 71 ng/g in Reach 10 (Figure 6-5). Correlation analysis was conducted to evaluate the potential association between fish characteristics (mass, length and age) and fillet PFOS concentrations (Table 6-15). Statistically significant, positive correlations between mass and PFOS concentrations were observed for bluegill (p==0.026) and white bass (p= 0.024) while a statistically significant, negative association was observed in freshwater drum (p=0.024). However, all these associations were weak with only up to 5% of the total variation being accounted for in both bluegill and white bass while only 9% of the variation was acaounted for in freshwater drum. There were no statistically significant (p< 0.05) species-specific association between mass and PFOS concentration with less than 2% of the total variation being accounted for by these associations. For length and PFOS concentrations, the only statistically significant correlation was observed for freshwater drum (p =0.006); however, this association was negative and only accounted for approximately 7% of the total variation. There was statistically significant positive association between PFOS concentrations and age for white bass (p=0.010), however this association only accounted for approximately 6.8% of the total variation. Overall, there were no strong associations between mass, length, or age with PFOS concentrations in any fish species collected during the study. 6-2 PFOS Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 6.4 Study Surface Water Samples O f the 30 water samples collected in Round 2 (August) from Pool 2,21 samples (70%) had PFOS concentrations that were less than the LOQ of 2.0 ng/L (Table 6-15; Figure 6-6; Appendix B, Table B -l). The majority of the non-detect samples were collected from Reaches 1 through 4 where all results were less than the LOQ. Of the 9 samples that had measurable PFOS concentrations, the greatest PFOS concentration was measured in Reach 10 at Station 517 (136 ng/L) while the second greatest PFOS concentration was measured in Reach 5 at Station 530 (7.1 ng/L). Both of these locations likely are impacted by point source mixing zones, i.e., they may not be representative of the composite river concentration for that cross section or transect of river. This hypothesis appears to be supported by downstream concentrations that decrease (in the case of Reach 10, rather dramatically). Finally, as presented in Table 6-15, with the exception of Reach 10, the average PFOS concentrations in water samples from all reaches are well below 7.0 ng /L, which is the site-specific Water Quality Criterion for PFOS established by the MPCA (http:/www.pca.state.mn.us/cleanup/pfc/index.html). As previously noted, given the nature o f the Station 517 result (i.e., likely taken within a point source mixing zone), it is most likely not representative PFOS concentrations in Reach 10 and as such, PFOS concentrations that reflect the actual exposure to fish may be less than the PFOS water quality criterion. Fourteen water samples were also collected in Round 1 (June) when it was believed that a single sampling period would be needed for the study. These 14 samples were split, sent to both laboratories, analyzed and became part of the interlaboratory validation element of the study. Because the June sampling locations were replicated by the complete sample set collected in August, the results from the June to August collections were compared at these 14 locations. As summarized in Table 6-3, there are no observable differences in PFOS concentrations observed for these specific locations. 6.5 Post-Study Fish Tissue Evaluation Based on average PFOS concentrations, the relative percent difference between the reported NIST SRM 1945 concentration and those measured by 3M and AXYS labs was less than 10% indicating excellent accuracy by both laboratories (Table 6-20). However, for the NIST SRM 1946 sample AXYS reported PFOS concentrations as less than the LOQ (detection limits reported for the duplicate tissue splits were 4.81 and 5.1 ng PFOS/g, ww) and as a result the accuracy could not be assessed for this sample (Tables 6-17 and 6-18). Intralaboratory precision was also excellent with RPDs of less than 6 and 10% for all blind duplicate pairs analyzed at 3M and AXYS labs, respectively (Table 6-19). In addition, the average PFOS values reported by 3M and AXYS labs were very consistent, with RPDs ranging from 7-16% providing further support for the overall quality of the analytical data reported by these labs. November 2012 Cardno ENTRIX PFOS Results 6-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - SJummer 2011 6.6 Tables and Figures andTable 6-1. Intralaboratory Blind Duplicate Comparison of PFOS (ng/g, ww) in Fish Collected from Pool 2 Analyzed by 3M Primary Samples Blind Duplicates Reach Species Lab ID PFOS Lab ID PFOS Relative Percent Difference 10 Freshwater drum 010FN1 ... 29.1 .5 012FN1 27.4 6. 12 10 , Bluegill 022FN1 305.0 019FN1 257.0 1/ .1 8 White bass '' 033FN1 42.1 :`:i 042FN1 37.8 -s.; 1C 8 White bass 045FN1 59.5 043FN1 51.4 14.6 3 Smallmouth bass 054FN1 30.0 060FN1 27.7 7.97 2 White bass 065FN1 34.9 068FN1 32.8 6.2 , Freshwater drum 078FN1 35.2 073FN1 33.1 6. It 1 Smallmouth bass 092FN1 13.5 077FN1 13.3 ' : 1. it Smallmdth bass " 102FN1 44.2 089FN1 41.6 6. )( 7 White bass 113FN1 45.3 090FN1 44.9 0.B9 9 Bluegill 126FN1 21.6 105FN1 23.3 7.57 9 Freshwater drum 137FN1 11.9 121FN1 11.6 2.55 9 White bass 149FN1 71.4 - 122FN1 68.9 3. 5( 10 - Smallmpuih b a ss; 159FN1 76.7 , s 139FN1 . 82.5 7. 2! 6 Freshwater dru m .... 170FN1 28.6 147FN1 27.7 - ; ....... | 2 5 Smallmouth bass 180FN1 13.7 169FN1 11.1 21 5 Freshwater drum 192FN1 41.9 173FN1 44.1 5.12 5 Smallmouth bass 203FN1 41.9 182FN1 52.7 22.$ 6 White bass . .^ .. 214FN1 73.4 184FN1 89.8 2( ). 4 Smallmouth bass ` 4 , White bass - ..... -. , 224FN1 232FN1 23.5 54.7 196FN1 210FN1 27.9 59.0 .... r !;>. 5I . . . . - 4 Smallmouth bass 246FN1 18.6 225FN1 19.0 2.13 4 Freshwater drum 258FN1 7.1 228FN1 7.8 9:69 1 Freshwater drum 2 Smallmouth bass ` ' 269FN1 280FN1 40.3 233FN1 46.1 - 244FN1 39.5 50.0 2.01 I' 1 | 7 Smallmouth bass 7 Smallmouth bass 291FN1 302FN1 42.3 36.8 245FN1 255FN1 35.8 ' ' 32.7 - 1' 1 i,j| 8 Freshwater drum 315FN1 27.0 265FN1 31.6 15.7 6 Freshwater drum 323FN1 14.6 275FN1 13.7 6.36 6 Freshwater drum 334FN1 31.3 284FN1 30.4 2.92 3 White bass 4 346FN1 34.8 I 314FN1 40.5 1 ' -, - 6 4 PFO S Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-1. Intralaboratory Blind Duplicate Comparison of PFOS (ng/g, ww) in Fish Collected from Pool 2 and Analyzed by 3M Primary Samples Blind Duplicates Reach ,, 3 2 8 9 5 1 9 4 3 1 Species Smallmouth bass White bass Smallmouth bass Smallmouth bass White bass White bass White bass Smallmouth bass Freshwater drum White bass j , Lab ID 360FN1 370FN1 383FN1 390FN1 400FN1 411FN1 425FN1 436FN1 447FN1 450FN1 PFOS 32.6 66.3 40.1 9.5 56.7 62.2 66.4 39.1 10.1 68.0 Lab ID 324FN1 327FN1 339FN1 347FN1 348FN1 357FN1 371FN1 375FN1 376FN1 406FN1 PFOS 33.0 52.1 35.8 8.3 57.6 67.3 67.7 41.3 9.5 68.4 Relative Percent Difference 1.22 24 11.3 14 1.57 7.88 1.94 5.47 6.02 0.59 November 2012 Cardno ENTRIX PFOS Results 6-5 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - trimmer 2011 Table 6-2. Interlaboratory Comparison of PFOS (ng/g, ww) in Fish Collected from Pool 2 and Analyzed by 3M and AXYS Reach Species Field ID PFOS 3M Split AXYS split Relative Percent Difference 9 Bluegill 10 Bluegil! 1 Freshwater drum 126 22 78 21.6 305 " 35.2 ' ' 37.4 356 42.15 .6 .4 3 1 Freshwater drum 269 40.3 44.4 9l68 3 Freshwater drum 4 Freshwater drum 5 Freshwater drum ,ji 6 Freshwater drum 6 Freshwater drum 447 258 192 170 J 323 10.1 7.07 41.9 28.6 14.6 11.8 9.33 45.3 29.3 17.5 .. 15.5 2T.6 f f2 6 8 9 10 .. A 1 2 3 Freshwater drum Freshwater drum Freshwater drum Freshwater drum Smallmouth bass Smallmouth bass Smallmouth bass Smallmouth bass 334 315 137 ' T * iff) 92 102 280 54 | 31.3 27 11.9 29.1 13.5 44.2 46.1 30 , 31.7 31.3 12.6 34 15.6 51.3 52.5 34.3 1.27 14.8 5.71 .5 .4 .9 13 13.4 3 Smallmouth bass Smallmouth bass . 4 Smallmouth bass 4 Smallmouth bass 5 Smallmouth bass 5 Smallmouth bass 7 Smallmouth bass 360 224 246 .... 436 180 203 291 32.6 23.5 18.6 1 ..,.ii!i 13.7 41.9 42.3 f 33.8 31.1 21.6 43 13.2 61.9 44.6 3i61 .8 .9 .5 3l72 38.5 5.29 `"7 8 9 10 1 1 2 2 3 Smallmouth bass Smallmouth bass Smallmouth bass Smallmouth bass White bass White bass White bass White bass White bass 302 V." ' 1 8 3 390 159 411 450 65 370 346 36.8 , / C 40,1 9.5 76.7 62.2 68 34.9 66.3 34.8 1 35.6 t ... f 1 .51.5 .......................- V ', 1.0-9 '' 112 83.3 80.6 .. 40 ' ,, 75.5 45.7 . ' 1 " I 31 j f .9 I.7 3I7.4 29 17 (.6 3 hM 6-6 PFOS Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-2. Interlaboratory Comparison of PFOS (ng/g, ww) in Fish Collected from Pool 2 and Analyzed by 3M and AXYS Reach Species 4 White bass 5 White bass 6 White bass 7 White bass 8 White bass 8 Whitebass 9 White bass 9 White bass Field ID 232 400 214 113 33 45 149 425 PFOS 3M Split 64.7 56.7 73.4 45.3 42.1 59.5 71.4 66.4 AXYS split 79.4 66.9 89.1 59.5 44.6 75.3 88.6 65.2 Relative Percent Difference 20.4 16.5 19.3 27.1 5.77 23.4 21.5 1.82 November 2012 Cardno ENTRIX PFO S Results 6-7 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - fjummer 2011 Table 6-3. Interlaboratory Comparison of PFOS (ng/L) in Surface Water Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS AXYS Lab 3M Lab Reach Field ID PFOS Qualifier1 Qualifier1 Relative Percent DMfrrence 1 512 <1.98 U 1 513 <2.50 U 1 514 <2.00 ,:< ''U 2 509 <1.99 u <2.00 <2.00 < 2.00 <2.00 U U U U NA NA NA NA 2 510 <2.00 u <2.00 U NA 2 511 <2.03 u <2.00 U NA 3 506 <1,99 v . V, " , , <2.00 3 T 507 `i <1.95 4 .u ' <2.00 U u 3 508 <1.98 u .. <2.00 . u NA ! NA I NA | 4 533 <3.17 u <2.00 u NA 4 534 <6.62 u <2.00 NA 4 535 <3.53 u <2.00 u NA 5 530 9 .1 7 5 531 <3.67 u 7 .1 0 <2.00 / u " * 4/25.4 I -, NA | 5 532 <4.28 6 527 3 .4 5 6 528 <3.74 , <2.00 2.60 u <2.00 u u NA 2 8 .1 NA 6 529 <3.53 u <2.00 u NA 7 524 4 .9 4 2.77 5 6 .3 7 if 7 W 525 526 <4.94 <4.94 u u <2.00 <2.00 u u NA NA . 8 503 <1.97 u <2.00 u NA 8 504 <2.48 8 505 <2.30 u u <2.00 <2.00 u u NA NA 9 :9 518 / < 4 4 3 ' 519 < 3,65 u u 2 .1 5 <#o u "* NA NA 9 520 <3.46 U 1 i* 2.77 NA 10 501 8 4 . 9 136 4 6 .3 10 502 <2.69 u <2.00 u NA 10 515 4.96 4 .2 0 1 6 .6 1U = undetected B o l d i t a l i c i z e d values indicate detected PFOS results 6-8 PFO S Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-4. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Pool 2 (2011) and Analyzed by 3M ALL SAMPLES Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] Bluegill 100 36 57 392 4 18 20 Freshwater drum 100 r 46 75 607 3 30 28 Species Smallmouth bass 100 39 75 757 5 30 29 White bass 96 64 41 394 13 58 58 Table 6-5. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 1 of Pool 2 (2011) and Analyzed by 3M REACH1 Statistic " N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] *C ,^ -. Bluegill 10 e ,0 i 7 2 11 4 6 7 Freshwater drum 10 53 59 213 13 33 37 Species Smallmouth bass 10 23 15 56 8 17 20 White bass *6 53 22 76 13 56 46 f November 2012 Cardno ENTRIX PFO S Results 6-9 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-6. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 2 of Pool 2 (2011) and Analyzed by 3M REACH 2 Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] Bluegill 10 12 6 27 7 11 ___________ sPecies Freshwater drum i 1Q Smallmouth bass 10 40 30 33 15 97 52 65 30 29 29 25 ^ White bass 10 61 16 89 35 63 59 Table 6-7. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 3 of Pool 2 (2011) and Analyzed by 3M REACH 3 Statistic N of Cases ^ Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] ..Geometric Mean PFOS] *% Bluegill 4 <'< * .. ' f r ' " 34 20 72 9 29 29 Freshwater drum 10 36 15 55 9 37 31 Species Smallmouth bass ." V , 29 9 45 16 31 28 J \ White bass '% J o '; . " 47 18 70 20 47 44 t 6- 'OS Results Cardno EK Noveni H" (. Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Table 6-8. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 4 o f Pool 2 (2011) and Analyzed by 3M REACH 4 Species Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean PFOS] Bluegill 10 33 20 66 10 26 27 Freshwater drum 10 24 23 76 3 14 16 Smallmouth bass 10 34 9 44 19 38 33 i White bass 10 64 20 91 36 61 61 Table 6-9. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 5 of Pool 2 (2011) and Analyzed by 3M REACH 5 Species Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] % % Bluegill io 32 16 56 7 34 27 Freshwater drum ; 10 70 91 316 10 38 44 Smallmouth bass 10 30 10 46 14 31 28 White bass 10 66 30 152 51 58 63 November 2012 Cardno ENTRIX PFO S Results 6-11 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-10. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 6 of Pool 2 (2011) and Analyzed by 3M REACH 6 Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] Bluegill 10 95 121 392 10 52 52 Freshwater drum 10 26 14 57 10 27 23 Species Smallmouth bass r 10 31 11 51 19 29 29 ; White bass 10 % 63 18 105 47 58 61 Table 6-11. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 7 of Pool 2 (2011) and Analyzed by 3M rccH u n i Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Me.nIPfQSL..... Bluegill Freshwater drum Smallmouth bass White bass 10 % 10 10 1 ** f / 11 26 32 61 5 29 11 29 21 105 48 139 49 7 36 X, X i l "* 17 '7 -------------- 40--------------- -----------------IS---------------------- ..................... 29 * 52 --------------------- 57------------------ 6- ,'OS Results Cardno Eh Novem *2 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-12. Descriptive Statistics fo r PFOS (ng/g, wet weight) in Fish Collected from Reach 8 of Pool 2 (2011) and Analyzed by 3M REACH 8 Species Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] Bluegill 10 16 6 28 10 14 15 Freshwater drum 10 39 17 79 15 34 ** 36 Smallmouth bass 10 31 13 60 16 27 28 White bass 10 52 11 71 34 50 51 Table 6-13. Descriptive Statistics fo r PFOS (ng/g, wet weight) in Fish Collected from Reach 9 of Pool 2 (2011) and Analyzed by 3M REACH 9 Species Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] Bluegill 6 10 39 31 99 11 22 30 Freshwater drum 10 37 64 215 5 12 18 Smallmouth bass 10 - ,1 19 * 10 35 7 17 16 White bass 10 66 26 112 33 67 62 November 2012 Cardno EN TRIX PFO S Results 6-13 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 6-14. Descriptive Statistics for PFOS (ng/g, wet weight) in Fish Collected from Reach 10 of Pool 2 (2011) and Analyzed by 3M REACH 10 Statistic N of Cases Arithmetic Mean [PFOS] Standard Deviation Maximum [PFOS] Minimum [PFOS] Median [PFOS] Geometric Mean [PFOS] Bluegill 10 79 103 305 5 26 36 Freshwater drum : 10 114 186 607 12 26 48 Species Smallmouth bass 10 135 222 757 35 55 76 White bass ,,.= f i'v< 10 103 105 394 41 71 80 Table 6-15. Correlations of PFOS with Species-Specific Fish Characteristics (ND=0) Bluegill Freshwater drum Mass vs [PFOS] ,, jSpearmant ; p-value ^ *' ' ; 0.2224 0.0261 v 100 ' '*' -0.3020 0,0023 100 Length vs [PFOS] Spearman r p-value n Spearman r 0.1936 0.0536 100 -0.1244 -0.27213 0.0062 100 -0.0124 Aqe vs [PFOS1 p-value 0.2198 0.9028 ~ r . ... 7 ===- - - - - ..... Smallmouth bass 0.1255 0.2136 ! 100 0.0651 0.5196 100 0.0583 0.5646 .... .......-taa . White bass / 0.2309 r \ 0.0234 96 0.1984 0.0527 96 0.2614 0.0101 .... _as._............. 6- OS Results Cardno El* Noveri. 12 ( l Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 0 1 1 Table 6-16. Sum m ary of Average PFOS Concentrations (ng/L) in W ater Collected from Pool 2 in Round 2 (August) and Analyzed by 3M Reach 1 .1 2 2 2 3 3 3 4 4 4 5 5 5 6 6 6 *7 ,7 X ,r % 8 8 8 Field ID 542SF 543SF 544SF 539SF 540SF 541SF 536SF 537SF ' 538SF * 533SF 534SF 535SF 530SF 531SF ^ 532SF 527SF 528SF 529SF 524SF 525SF 526SF 521 SF 522SF 523SF # Lab ID Detection limit 542SF1 2 543SF1 2 544SF1 2 539SF1 2 540SF1 2 541SF1 2 536SF1 . 2 537SF1 2 538SF1 , 2 533SF1 2 534SF1 2 535SF1 2 530SF1 2 531SF1 . , % 2 532SF1 2 527SF1 2 528SF1 2 529SF1 2 524SF1 2 525SF1 2 526SF1 2 521SF1 2 522SF1 2 523SF1 2 " .x ;i\ ,,, ' Units Results1 ng/L <2.0 ng/L j j ; ' <2.0 ng/L V - <2.0 f ng/L <2.0 ng/L <2.0 ng/L <2.0 ng/L <2.0 ng/L <2.0 ng/L ' ` < <2.0 ng/L <2.0 ng/L <2.0 ng/L <2.0 ng/L 7.1 ng/L ; - - - <2,0 ng/L , * ^ <2.0 ng/L 2.6 ng/L <2.0 ng/L <2.0 ng/L 2.77 ng/L <2.0 ng/L <2.0 ng/L 2 ng/L 3.51 ng/L <2.0 Average by Reach2 1.00 ' 1.00 1.00 r 1.00 3.03 1.53 1.59 2.17 November 2012 Cardno EN TRIX PFO S Results 6-15 Table 6-16. Summary of Average PFOS Concentrations (ng/L) In Water Collected from Pool 2 in Round 2 (August) and Analyzed by 3M Reach ,? 9 9 9 10 10 10 Field ID 518SF 519SF 520SF 515SF 516SF 517SF Lab ID 518SF1 519SF1 520SF1 515SF1 516SF1 517SF1 Detection limit 2 2 2 2 2 2 1<2.0 ng/L = undetected sample 2Average values were calculated using % the detection limit for non-detect samples Units ng/L ng/L ng/L ng/L ng/L ng/L '*! Results1 2.15 <2.0 2.77 4.2 <2.0 136 Average by Reach2 1.97 47.07 ___________________ Table 6-17. Post-Study Fish Tissue Samples analyzed for PFOS by th e 3M Lab and AXYS Sample Class 3M Fish Tissue Control 3M Fish Tissue Control 3M Fish Tissue Control NIST-SRM Lake Michigan Fish Tissue NIST-SRM Lake Superior Fish Tissue Pool 2 Fish Pool 2 Fish * Pool 2 Fish Tissue ID Split 1 Lab ID (3M) E11-0356-01-316 " 1000 E11-0356-01-001 1020 E11-0356-01-443 SRM1947 1028 1012 SRM1946 1008 436FN3 1004 214FN3 1016 323FN3 1024 Split 2 Lab ID (AXYS) Split 3 Lab ID (3M) 1001 1021 -% ' -r 1022 1029 1030 1013 1014 1009 1005 1010 1006 1017 1018 1025 1026 Split 4 Lab ID (AXYS) 1003 1023 1031 1015 1011 1007 1019 1027 6- /OS Results Cardno Eh Novern Mississippi River Pool 2 PFC Assessm ent - Fish Tissues and Water - Summer 01 1 Table 6-18. Summary of PFOS (ng/g, w et weight) in Post-Study Fish Tissue Samples Analyzed by the 3M Lab and AXYS ` Duplicate (1013-D) reported by AXYS - 6.68 ng/g PFOS 1NIST-SRM 1947 value 5.90 0.39 2NIST-SRM 1946 value 2.19 + 0.08 Bold font = PFOS not detected; detection limit provided PFOS Results 6-17 Table 6-19. Average PFOS (ng/g, wet weight) in Post-Study Fish Tissue Samples Analyzed by 3M and AXYS PFOS Sample Class S lrts h fO s s u e C o rilrp I 3M Fish Tissue Control 3M Fish Tissue Control NIST-SRM Lake Michigan Fish Tissue1 NIST-SRM Lake Superior Fish Tissue2 Pool 2 Fish Pool 2 Fish Pool 2 Fish 5* ', <\ 3M 0.74 0.60 0.71 6.30 2.24 40.95 86v73 : S ' 14.42 AXYS ND ND ND 5.85 ND 466 93.0 16.9 Relative Percent Difference -" 7.39 " 12.8 6.92 15.8 1NIST-SRM 1947 value 5.90 0.39 2NIST-SRM 1946 value 2.19 0.08 Bold font = PFOS not detected so average not calculated, DLs for non-detect samples ~ 5 ng/g, wet weight Table 6-20. Relative Percent Difference (RPD) of Average PFOS Concentrations (ng/g, wet weight) in Post-Study Fish Tissue Samples Analyzed by 3M and AXYS PFOS1 Sample Class NIST-SRM Lake Michigan Fish Tissue NIST-SRM Lake Superior Fish Tissue Tissue ID SRM1947 SRM1946 3M AXYS 6.30 5.85 2.24 ND NIST Value 5.90 2.19 3M-NIST RPD 6.54 2.15 AXYS-NIST RPD 0.85 -- 'Samples analyzed In duplicate, average result of duplicates Is presented Bold font = PFOS not detected so average not calculated OS Results Cardno Eh Noverri. 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 1000 100 O (0 <ocu ou 10 to Ou_ o. Bluegill (n=100) Freshwater drum Smallmouth bass (n=100) (n=100) White bass (n=96) Figure 6-1. PFOS in Fish Tissues from Pool 2 (2011) November 2012 Cardno EN TRIX PFO S Results 6-19 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Bluegill PFOS concentration (ng/g, wet weight) 123456789 n=10 per reach Reach Figure 6-2. PFOS in Fillet Tissues of Bluegill Collected from Pool 2 (2011) 6-, OS Results Cardno E f 10 Noverr. E Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer1011 x x 123456789 n=10 per reach Reach Figure 6-3. PFOS in Fillet Tissues of Freshwater Drum Collected from Pool 2 (2011) 10 November 2012 Cardno EN TRIX PFO S Results 6-21 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Smallmouth bass PFOS concentration (ng/g, wet weight) Jli 123 456789 10 n=10 per reach Reach 1 Figure 6-4. PFOS in Fillet Tissues of Smallmouth Bass Collected from Pool 2 (2011) 6- !OS Results Cardno Ef Noven*. ^7 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 White bass C<uu cou i/> Ou . Q. 1234 (n=6) 567 n=10 per reach except for Reach 1 Reach Figure 6-5. PFOS in Fillet Tissues o f White Bass Collected from Pool 2 (2011) 89 10 November 2012 Cardno ENTRIX PFOS Results 6-23 OS Results Cardno Ef Noveri Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Type Primary Duplicate Figure 6-7. Blind Duplicate Fish Tissue Comparison of PFOS Results (3M Lab Only), 2011 November 2012 Cardno EN TRIX PFOS Results 6-25 1000.00- PFOS (ng/g ww) 100.00- 10.00- 1.00- .06-*----------------------- -------- " 1" PFOS n = 41 Figure 6-8. Interlaboratory Fish Tissue Comparison of PFOS Results, 2011 6- )OS Results Cardno Et Lab 3M AXYS Noven Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Lab 3M AXYS PFOS (ng/L) Figure 6-9. Interlaboratory Surface W ater Comparison of PFOS Results, 2011 Chapter 7 Perfluorosulfonate Results 7.1 Intralaboratory Blind Duplicate Samples Results from the analysis of fish tissue in both the primary and blind duplicate sample sets indicated good agreement for all perfluoroalkyl sulfonates (Table 7-1). PFBS was detected in 3 of 41 samples in both the primary and blind duplicate sample sets with concentrations ranging from 0.27 to 0.55 ng/g and 0.059 to 1.26 ng/g in the primary and blind duplicate sample sets, respectively. O f the 3 samples in both datasets, only 2 samples had matched IDs with an average fold difference of 1.7 and an average RPD of 92%. Taking into consideration the small sample size and low concentrations, a definitive evaluation of the data quality is not possible but appear to be of acceptable. PFHS was detected in 14 of 41 samples in the primary sample set and 12 of 41 samples in the blind duplicate sample set. The concentration range in the primary dataset was 0.04 to 1.7 ng/g while it was 0.05 to 0.22 ng/g in the blind duplicate set. With one exception, there was less than a two-fold difference in measured concentrations with an average RPD of 19%. The exception was observed in one fish sample (Field ID 370) that had a 32-fold difference and a RPD of 188% in measured concentrations. This relatively large difference was due the primary sample having a measured concentration of 1.7 ng/g while in the blind duplicate it was 0.05 ng/g, a value that approaches the LOQ. Based on the results from the other 8 matched samples, this sample was considered to be an outlier and not indicative of the quality o f the data for this analyte. PFOSA was detected in all 41 samples in both the primary and blind duplicate sample sets with concentrations ranging from 0.09 to 8.54 ng/g and 0.09 to 9.37 ng/g, respectively. Fold differences between sample sets ranged from 0.18 to 1.3 with an average RPD of 7.7%. Overall, perfluoroalkyl sulfonate concentrations reported by 3M for both the primary and blind duplicate sample sets were in close agreement demonstrating the accuracy and precision of the data reported by the 3M lab. 7.2 Interlaboratory Comparison Samples 7.2.1 Fish Tissue The interlaboratory comparison of PFBS, PFHS and PFOSA was limited in scope due to the large number of non-detects (Table 7-2). While the 3M laboratory reported PFBS concentrations in three of the 41 interlaboratory fish samples, all the samples analyzed by AXYS were reported as less than the LOQ. Likewise for PFHS, the 3M lab reported 14 of the 41 samples with measured concentrations while all of the samples analyzed by AXYS had concentrations less than the LOQ. As a result, an interlaboratory comparison was not conducted for these two analytes. PFOSA was detected in all 41 fish tissue samples by the 3M lab while AXYS measured concentrations in 4 fish samples. Based on the results for the 4 matched samples, PFOSA concentrations ranged from 1.74 to 8.54 ng/g and 2.54 to 13.0 ng/g as reported by the 3M lab and AXYS, respectively. PFOSA concentrations measured by AXYS were approximately 23% greater than those reported by the 3M lab with RPDs ranging from 21 to 42% with an average of 31%. Overall, while the average RPD was greater than 20%, there was good agreement between the analytical results given by both laboratories when compared to results typically observed in other interlaboratory studies. November 2012 Cardno ENTRIX Perfluorosulfonate Results 7-1 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 7.2.2 Surface Water The interlaboratory comparison for PFBS, PFHS, and PFOSA in the 30 water samples were limited by the predominance of non-detects associated with the data reported by both laboratories (Table 7 3). For PFBS, both laboratories reported measured concentrations in three matched surface water samples that ranged from 2.4 to 26 ng/L and 2.3 to 29 ng/L for the 3M Lab and AXYS, respectively. In general concentrations reported by 3M were 24% less than that reported by AXYS with an average RPD of 47%. PFHS was measured in only one matched surface water sample with a concentration of 12.5 and 6.3 ng/L reported by the 3M Lab and AXYS, respectively. The relative percent difference was 67%. PFOSA concentrations in all surface water samples analyzed by both laboratories had reported values that were less than the LOQ. As such comparison was not done for this analyte. 7.3 Study Fish Tissue Samples Concentrations of PFBS in all fish samples collected from Pool 2 were dominated by non-detects (93%) and of the samples with measurable concentration, only a single sample was greater than 1.0 ng/g ww (Table 7-4). With non-detects set to half the LOQ, concentrations of PFBS in all fish ranged from 0.03 to 1.70 ng/g ww with an overall arithmetic mean, geometric mean and median of 0.6, 0.49, and 0.4 ng/g ww, respectively. Species-specific arithmetic means (95% confidence limit) were: bluegill 0.05 (0.04-0.07) ng/g ww, freshwater drum 0.09 (0.06-0.13) ng/g ww, smallmouth bass 0.06 (0.05-0.07) ng/g ww, and white bass 0.06 (0.05-0.07) ng/g ww (Table 7-5). Species-specific median PFBS concentrations were: bluegill 0.03 ng/g ww, freshwater drum 0.05 ng/g ww, smallmouth bass 0.05 ng/g ww and white bass 0.03 ng/g ww. Due to the large number of non-detects, the low measured PFBS concentrations, and variability observed in those measured values, no speciesspecific trend in PFBS concentrations was identified for fish collected in Pool 2. Likewise, when average PFBS concentrations for all fish by reach were compared, no discernible trend in PFBS concentration was observed in Pool 2. All PFBS concentrations as reported by 3M for each fish are provided in Appendix A, Table A -l. PFHS concentrations in fish tissues were also dominated by the presence of non-detects, however the frequency of non-detects was species specific (Table 7-6). For instance, the number of samples with measured PFHS concentrations for bluegill, freshwater drum, smallmouth bass and white bass were 38, 31,7 and 53, respectively. PFHS was detected in at least one sample from each reach for bluegill, freshwater drum, and white bass while for smallmouth bass, concentrations are only reported for Reaches 9 and 10. Concentrations of PFHS in all fish ranged from 0.01 to 22.9 ng/g ww with arithmetic mean, geometric mean and median of 0.17, 0.048 and 0.03 ng/g ww, respectively. Only one sample had a concentration greater than 10 ng/g ww. Species-specific arithmetic averages (95% confidence limits) for Pool 2 were: bluegill 0.42 (0.0-0.90) ng/g ww, freshwater drum 0.9 (0.04-0.14) ng/g ww, smallmouth bass 0.04 (0.03-0.05) ng/g ww, and white bass 0.12 (0.07-0.17) ng/g ww (Table 7-7). Species-specific median PFHS concentrations for bluegill, freshwater drum, smallmouth bass and white bass were 0.05, 0.03, 0.03, and 0.06 ng/g ww, respectively. The species-specific rank order, from least to greatest PFHS concentrations based on either arithmetic mean or median, was smallmouth bass, freshwater drum, white bass, and bluegill. With the exception of smallmouth bass, a comparison of species-specific average PFHS concentration by reach showed that reaches with the greatest concentrations tend to cluster into three groups, regardless of species (Table 7-6). The first cluster included Reaches 2 and 3, the second cluster consisted of Reach 6 and the third cluster included Reach 10. While the higher PFHS concentrations in Reach 6 and 10 are most likely are due to the presence of upriver PFC, the relatively great concentration observed for bluegill and white bass 7-2 Perfluorosulfonate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 in Reaches 2 and 3 were unexpected and cannot be accounted for at this time. All PFHS concentrations as reported by 3M for each fish are provided in Appendix A, Table A -l. Measured PFSOA concentrations were reported for 100% of the freshwater drum, smallmouth bass, and white bass samples while only 93% of the bluegill samples had measured concentrations (Table 7-8). PFOSA concentrations in all Pool 2 fish ranged from 0.1 to 31.5 ng/g ww with arithmetic mean, geometric mean and median of 0.67, 0.28 and 0.28 ng/g ww, respectively. O f the 396 samples that were analyzed, 60 samples had PFOSA concentrations greater 1 ng/g ww, 5 samples with concentrations greater than 5 ng/g ww and 2 samples with concentrations greater than 10 ng/g ww. Species-specific arithmetic mean (95% confidence limits) PFOSA concentrations were: bluegill 0.08 (0.07-0.10) ng/g ww, freshwater drum 0.33 (0.23-0.43) ng/g ww, smallmouth bass 0.97 (0.32-1.62) ng/g ww and white bass 1.31 (1.05-1.57) ng/g ww (Table 7-9). Species-specific median PFOSA concentrations were 0.07, 0.18, 0.40, and 0.92 ng/g ww for bluegill, freshwater drum, smallmouth bass and white bass respectively. The species rank order of PFOSA concentrations from least to greatest based on either mean or median values was bluegill, freshwater drum, smallmouth bass and white bass. In general, there was less than a 5-fold difference in mean PFOSA concentrations across all 10 reaches for all species (Table 7-8). However, the trend in PFOSA concentrations across all 10 reaches was not monotonic, rather it appeared to be biphasic with PFOSA concentrations being greatest in Reach 9-10 followed by Reaches 3 and 5 with concentrations between these two reach sets being less. All PFOSA concentrations as reported by 3M for each fish are provided in Appendix A, Table A -l. Correlation analysis was conducted to evaluate the potential association between fish mass, length and age with fillet PFAS concentrations (Table 7-10). For PFBS, negative but statistically significant (p < 0.05) correlations were observed between bluegill tissue concentrations and mass, length), and age; however, these associations were weak and accounted for less than 5% of the total variation. With the exception of age in freshwater drum, correlations coefficients between PFBS tissue concentrations and mass, length and age in freshwater drum, smallmouth bass and white bass were not statistically significant (p > 0.10). There was a statistically significant (p =0.01) but weak negative association (1^= 0.0677) between PFBS concentration and age in freshwater drum. No statistically significant (p > 0.30) associations between PFHS tissue concentrations and mass, length, and age were observed for freshwater drum, smallmouth bass and white bass with typically coefficients of determination (r2) generally being less than 0.0256. For bluegill, there was positive and statistically significant correlation with age and PFHS (p< 0.05) with approximately 15% of the total variation accounted by this association. PFOSA fillet concentrations in bluegill were not significantly correlated (p > 0.20) to mass, length and age, these metrics were significantly correlated (p < 0.005) to PFOSA fillet concentrations in freshwater drum, smallmouth bass and white bass. For freshwater drum and smallmouth bass, there was a positive correlation between PFOSA concentrations and mass, length and age while for white bass there was a negative correlation between tissue concentrations and these metrics. Coefficients of determination (r2) for freshwater drum, smallmouth bass, and white bass ranged from 0.0759 for age in bluegill up to 0.1804 for length in bluegill with an overall average r2 of 0.1145. Overall the association between fish mass, length and age with PFAS tissue concentrations were weak with all associations accounting less than 30% of the total variation. November 2012 Cardno ENTRIX Perfluorosulfonate Results 7-3 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 7.4 Study Surface Water Samples In Round 2 (August), PFBS was measured in 3 of the 30 samples with all other samples having reported values less than the LOQ (Table 7-11). For PFHS, only one sample had a concentration greater than the LOQ while for PFOSA no water sample had a concentration greater than the LOQ. For surface water samples that had measurable concentrations, the greatest concentrations of PFBS (336 ng/L) and PFHS (61 ng/L) were observed at Station 517. In Round 1 (June), the only detectable concentration of PFBS and PFHS were observed in surface water collected from Station 501 the same locations as Station 517 sampled in Round 2. In Round 1, water concentrations of PFBS and PFHS at Station 501 were 26 and 13 ng/L, respectively (Table 7 12). At Station 517, the Round 1 PFBS concentration was approximately 13-fold greater than Round 2 while for PFHS it was approximately 1.8-fold less. The basis for these differences is unknown but most likely due to multiple factors including changes in river water levels as well as changes in discharge concentrations from sources to the river. 7-4 Perfluorosulfonate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 7.5 Tables and Figures Table 7-1. Intralaboratory Blind Duplicate Comparison of Perfluorosulfonate Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011) Relative Percent Difference (RPD, %) Reach Species Field ID Primary Lab ID Duplicate Lab ID PFBS PFHS PFOSA 10 ' Bluegill ' 9 * Bluegill 022 022FN 126 126FN 019FN1 ' 1 105FN1 15.5 9.98 . . . 11-7 8.68 \ 10 Freshwater drum . 010 1 Freshwater drum 078 010FN 078FN f 012FN1 073FN1 1' * 8.01 0.59 0.89 9 Freshwater drum 137 137FN 121FN1 5.08 6 Freshwater drum 170 170FN 147FN1 2.16 5 Freshwater drum 192 192FN 173FN1 1.61 4 Freshwater drum 258 258FN 228FN1 21.0 1 Freshwater drum 269 269FN 233FN1 9.34 8 Freshwater drum 315 315FN 265FN1 1.92 6 Freshwater drum 323 323FN 275FN1 10.7 6 Freshwater drum 334 334FN 284FN1 4.30 3 Freshwater drum 447 447FN 376FN1 102 24.9 3 Smallmouth bass 054 * 054FN 060FN1 * 0.46 1 Smallmouth bass 092 092FN 077FN1 8.27 1 Smallmouth bass 102 102FN 089FN1 5.47 10 Smallmouth bass 159 159FN 139FN1 9.31 5 Smallmouth bass 180 180FN 169FN1 81.9 2.01 5 Smallmouth bass 4 Smallmouth bass 203 224 203FN 224FN ii 182FN1 : 196FN1 i, 15.4 17.5 ; 4 ' Smallmouth bass 2 Smallmouth bass 246 280 246FN 280FN 225FN1 244FN1 v . H ,. 3.31 , 4.18 7 Smallmouth bass 291 291FN 245FN1 28.0 7 Smallmouth bass 302 302FN 255FN1 18.7 3 Smallmouth bass 360 360FN , 324FN1 -i ,:k ;; 3.03 8 Smallmouth bass 383 383FN J 339FN1 , 6.34 :i 9 > Smallmouth bass 390 390FN 347FN1 2.32 4 Smallmouth bass 436 436FN 375FN1 4.68 8 White bass 033 033FN 042FN1 5.66 8 White bass 045 045FN 043FN1 45.9 4.16 2 White bass ; 065 065FN 068FN1 2.48 7.89 7 White bass 113 113FN 090FN1 10.2 2.66 9 White bass " f 149 > 149FN 122FN1 43.3 0.04 November 2012 CardnoENTRIX Perfluorosulfonate Results 7-5 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 7-1. Intralaboratory Blind Duplicate Comparison of Perfluorosulfonate Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011) Relative Percent Difference (RPD, %) Reach Species Field ID Primary Lab ID Duplicate Lab ID PFBS PFHS PFOSA 6 White bass 214 214FN 184FN1 16.7 4 White bass 232 232FN 210FN1 3.83 3 White bass 346 346FN 314FN1 15.6 2 , White bass 370 370FN 327FN1 188 9.25 5 White bass a 400 400FN .. 348FN1 2.47 1 White bass 411 ' 411FN 357FN1 5.63 9 White bass 425 425FN 371FN1 8.05 1 White bass 450 450FN 406FN1 18.0 2.40 All reported RPD values were for samples that had paired results greater than the LOQ 7-6 Perfluorosulfonate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 7-2. Interlaboratory Comparison of Perfluorosulfonate Concentrations (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M and AXYS (2011) Relative Percent Difference (RPD, %) Reach Species Field ID 3M Lab ID AXYS Lab ID PFBS PFHS PFOSA 10 Blueglll 022 022FN 019FN1 9 Bluegill 10 Freshwater drum 1 Freshwater drum 126 126FN 105FN1 010 010FN ...012FN1 078 078FN 073FN1 9 Freshwater drum 137 137FN 121FN1 6 Freshwater drum 170 170FN 147FN1 5 Freshwater drum 4 Freshwater drum 192 192FN ` 173FN1 258 258FN 228FN1 1 Freshwater drum 269 269FN 233FN1 8 Freshwater drum 315 315FN 265FN1 6 Freshwater drum 323 323FN 275FN1 6 Freshwater drum 334 334FN 284FN1 3 Freshwater drum 447 447FN 376FN1 3 Smallmouth bass 1 Smallmouth bass 1 Smallmouth bass 054 ... 054FN ' 092 092FN 102 102FN 060FN1 077FN1 089FN1 10 Smallmouth bass 159 159FN 139FN1 42 5 Smallmouth bass 180 180FN 169FN1 5 Smallmouth bass 203 203FN 182FN1 4 Smallmouth bass 224 224FN 196FN1 4 Smallmouth bass 246 246FN 225FN1 2 Smallmouth bass 280 280FN 244FN1 7 Smallmouth bass 291 291FN 245FN1 7 Smallmouth bass 302 302FN 255FN1 3 Smallmouth bass 360 360FN 324FN1 ; 8 Smallmouth bass 383 383FN 339FN1 9 Smallmouth bass 390 390FN 347FN1 4 Smallmouth bass 436 436FN 375FN1 8 White bass 033 033FN 042FN1 8 White bass 045 045FN 043FN1 21.4 2 White bass > * 065 065FN 068FN1 7 White bass , 113 113FN 9FN1 9 White bass j 149 149FN 122FN1 6 White bass 214 214FN 184FN1 4 White bass 232 232FN 210FN1 3 White bass 346 346FN 314FN1 November 2012 Cardno ENTRIX Perfluorosulfonate Results 7-7 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 7-2. Interlaboratory Comparison of Perfluorosulfonate Concentrations (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M and AXYS (2011) Relative Percent Difference (RPD, %) Reach Species Field ID 3M Lab ID AXYS Lab ID PFBS PFHS PFOSA 2 "W h ite bass ' , 5 White bass 370 370FN 400 1' 400RN * 327FN1 348FN1 23.4 1 White bass 411 411FN 357FN1 9 White bass 1 White bass 425 425FN 450 450FN 371FN1 406FN1 37.1 All reported RPD values were for samples that had paired results greater than the LOQ 7-8 Perfluorosulfonate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 7-3. Interlaboratory Comparison of Perfluorosulfonate Concentrations (ng/L) in Surface W ater Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS (2011) Relative Percent Difference (RPD, %) Reach Field ID 3M Lab ID AXYS Lab ID PFBS PFHS PFOSA 1:' 1 512 513 512SF1 513SF1 512SF2 513SF2 * .............................................................................. ........... ..... 1 , 1 514 514SF1 ( 514SF2 ,, 2 509 509SF1 509SF2 2 510 510SF1 510SF2 2 511 511SF1 511SF2 3 .3 3 4 . 506...... 506SF1 507 ; 507SF1 ` 508 508SF1 533 533SF1 506SF2 508SF2 533SF2 **,.. _ .. . .` n,<. ^ 1 .., .. '' , vt s I1 , ... ' ..... ...... ... . .... * ....... . A:..- .ii..... \ . .. ....... . . . ...... .. ...... * 4 534 534SF1 534SF2 4 535 535SF1 535SF2 5 530 530SF1 530SF2 47.4 . 5 531 531SF1 531SF2 5 532 532SF1 532SF2 6 527 527SF1 527SF2 6 528 528SF1 528SF2 6 529 529SF1 529SF2 7 524 524SF1 524SF2 ... , - **' SI-' i!'.. . .I:''' - ; ' - .. ' , 7 525 525SF1 525SF2 , 7 526 526SF1 526SF2 * 8 503 503SF1 503SF2 * ................................................... . 8 504 504SF1 504SF2 8 505 505SF1 505SF2 9 518 518SF1 518SF2 9 519 519SF1 519SF2 9 520 520SF1 520SF2 10 501 501SF1 501SF2 31.1 66.7 10 502 502SF1 502SF2 10 515 515SF1 515SF2 61.4 All reported RPD values were for samples that had paired results greater than the LOQ November 2012 Cardno ENTRIX Perfluorosulfonate Results 7-9 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water --Summer 2011 Table 7-4. Descriptive Statistics for PFBS (ng/g, w et weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Statistic Bluegill Arithmetic Mean [PFBS] 0.06 Number of Detects 7 Number of Non-detects 91 Number of Samples Not Reported 2 Maximum [PFBS] 0.46 Minimum [PFBS] 0.03 Median [PFBS] 7 :* 0.04 Geometric Mean [PFBS] 0.04 Standard Deviation 0.06 1/2 RL was used as a proxy value for all non-detects Freshwater drum 0.09 8 89 3 1.70 0.03 0.05 f 0.06 0-18 Species Smallmouth bass 0.06 1 93 6 0.13 0.03 0.05 0.05 0.04 White bass 0.06 2 89 5 0.19 0.03 0.03 0.05 J 0.05 Table 7-5. Mean and 95% Confidence Intervals for PFBS Concentrations (ng/g, wet weight) in All Fish Collected in Pool 2 by Reach (2011) Reach Species Bluegill Statistic . le a n ... . 95% Cl , 1 0 ;0 i% # P'iSfr 1 2 0.051 34 0.031 * r . I b :7 - ' ;F002^17] 5 67 70.042 | J. 72 7 . 0.112 r f T .K 7 - ' % i * . # ", 1! " 1'',4 - .. -i - * 8 0.04' " 9 i ' 0.072 " Freshwater drum Mean 95% Cl 0.042 - 0.112 - 0.12 [0.03,0.21] 0.051 0.03' 0.05' - 0.05' - 0.242 0.11' ~ SmallrfibUthBass Mean * 7 IM S *." 1 ,f '* 95% Cl ' - 0.071 * 0.031 ' ` - 0.06' 0.03' 0.11' ; 0.092 ' * ! r. -- ^ - , 0.07' f " 0.06' i' White bass Mean 95% Cl 0.072 - 0.101 - 0.031 0.031 - 0.03' - 0.09' - 0.07' 0.08' " 0.08' " 1All samples < LOQ; only mean DL reported 2 Sample size ^ 2; only mean reported 10 0.051 ^ ,, - ... I 0.13' " 0.05' =74 7 t 0.10' 7- jrfluorosulfonate Results Cardno Et* Novem Mississippi River Pool 2 PFCS Assessment - Fish Tissues and Water - Summer 2011 Table 7-6. Descriptive Statistics for PFHS (ng/g, w et weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Species Statistic Arithmetic Mean [PFHS] Number of Detects Number of Non-detects Number of Samples Not Reported Maximum [PFHS] Minimum [PFHS] Median [PFHS] Geometric Mean [PFHS] Standard Deviation Bluegill 0.42 38 62 0 22.89 0.01 0.05 0.07 2.43 Freshwater drum 0.09 31 69 0 2.45 0.03 0.03 0.04 0.26 Smallmouth bass 0.04 7 93 0 0.26 0.01 0.03 0.03 i* 0.04 White bass 0.12 53 43 0 1.70 0.01 0.06 0.06 0.24 1/2 RL was used as a proxy value for all non-detects V Table 7-7. Mean and 95% Confidence Intervals for PFHS Concentrations (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011) Species Statistic 1 2 O COO Bluegill Mean : 95% Cl 0.1 [0.05,0.14] ;i: [0.05,0.15] Freshwater drum Mean 95% Cl 0.13 [0.02,0.24] 0.05 [0.02,0.08] Smallmouth bass White bass Mean 95% Cl Mean 95% Cl 0.021 0.071 *1*1 lift 0.05 0.34 [0.01,0.08] [-0.07, 0.74] 1All samples < LOQ; only mean DL reported Reach 3 4 56 2.49 [-2.64, 7.62] 0.132 ,4 ,4 J: 0.08 [0.02,0.14] 1.06 [-0.89,3.01] 0.04 0.10 0.06 0.062 [0.03,0.04] [-0.05,0.24] [0.02,0.10] - 0.021 I 0.041 0.041 0.031 4.4''" - , | : > j 0.03 0.092 0.05 0.16 [0.02,0.05] - [0.03,0.07] [0.07, 0.26] 7 8 9 10 0.092 : 0.042 4 0.042 0.052 0.042 - 0.062 , -,4 i:f 0.042 - 066 0.081 0.12 - - [-0.21, 0.87] 0.031 0.032 0.06 'V 14 f 4 [0.01,0.11] 0.06 0.06 0.21 [0.04, 0.20] [0.03,0.10] [0.03, 0.10] [-0.07, 0.50] 2Sample size s 2; only mean reported November 2012 Cardno ENTRIX PerfluorosuIfonate Results 7-11 Mississippi River Pool 2 PFC Assessment --Fish Tissues and Water --Summer 2011 Table 7-8. Descriptive Statistics for PFOSA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Statistic Arithmetic Mean [PFOSA] Number of Detects , Number of Non-detects Number of Samples Not Reported Maximum [PFOSA] Minimum [PFOSA] Median [PFOSA] Geometric Mean [PFOSA] Standard Deviation Bluegill 0.08 93 7 0 0.49 0.01 0.07 0.07 0.07 Species Freshwater drum Smallmouth bass 0.33 0.97 100 100 00 00 2.97 31.45 0.05 0.12 0.18 0.40 0 21 0.45 0.48 3.28 White bass 1.31 96 0 0 10.40 0.34 0.92 1.05 1.26 1/2 RL was used as a proxy value for all non-detects Table 7-9. Mean and 95% Confidence Intervals for PFOSA Concentration (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011) Reach Species Statistic Bluegill " Mein: o 95% Cl Freshwater drum Mean 95% Cl ia llrfi b th bass ` Mean" 95% Cl White bass Mean 95% Cl 12 0.05 0.07 [0.04,0.06] [0.04,0.09] 0.20 0.30 [0.07,0.34] [-0.14,0.75] 0.35 , 0.25 [0.25,0,45] [0.21,0.30] 0.96 1.04 [0.28,1.65] [0.71,1.37] 3 4 56 7 8 0.13 0.06 ,* 0.09 " ' 0.06 - 0.05 0.06 [0.05,0.22] [0.04,0.08] [0.06,0.13] ' p o i 0.0 8]4 [0,03,0.06] 3 . 0 1 0 . 0 7 } 0.19 0.18 0.29 0.14 0.24 0.15 [0.12,0.26] [0.11,0.26] [0.16,0.42] [0.09,0.19] [0.19,0.291 [0.12, 0.17] 0.37 0.59 . 0.46 . 0.40 > 0.38 0.25 [0.27,0.47] ; [0.50,0.67] [0.39,0.54] [0.34,0.45] [0.23,0.54] [0.18,0.33] 0.66 1.42 1.70 0.79 1.52 1.26 [0.50,0.82] [0.43,2.41] [1.13,2.28] [0.65,0.92] [0.80,2.24] [0.53,1.98] 1All samples < LOQ; only mean DL reported 2 Sample size ^ 2; only mean reported 9 10 - 0.09 0.18 [0.07,0.11] "! [0.10,0.27] 0.44 1.17 [0.27,0.60] [0.44,1.90] 0.57 6.05 [0.34,0.79] [-0.60,12.70] 1.07 2.53 [0.72,1.43] [0.43,4.63] 7- Jrfluorosulfonate Results Cardno Eli Noveni 1\2 Mississippi River Pool 2 PFCS Assessment - Fish Tissues and Water - Summer 2011 Table 7-10. Correlations of Perfluorosulfonate Concentrations with Species Specific Fish Characteristics (ND=0) Correlation Statistic Spearman r Mass vs [PFC] - p-value n Spearman r Length vs [PFC] p-value n Spearman r Age vs [PFC] p-value . in * PFBS Bluegill PFHS -0.1984 -0.1159 0.0502 , 0.2510 98 , r 100 -0.2001 -0.0620 0.0483 0.5403 98 100 -0.2137 0.3906 0.0356 <0.0001 97 99 Freshwater drum Smallmouth bass PFOSA PFBS PFHS PFOSA PFBS PFHS PFOSA 0.0708 -0.1697 0.0136 0.3984 0.0917 0.0386 0.3286 0.4838 ' 0.0966 0.8933 <0.0001 0.3792 0.7027 <0.0008 100 0.0441 97 100 -01721 0.0781 100 0.42427 94 0.1282 100 0.0418 100 0.3257 0.6628 0.0918 0.4399 < 0.0001 0.2183 0.6800 0.0009 100 97 100 100 94 100 100 -0.1278 " -0.2601 : 0.0447 0.2755 0.0997 0.0508 0.3171 0.2076 - 0.0101 0.6586 0.0055 ' 0.3391 0.6159 0.0013 99 97 100 100 * 94 1 100 100 White bass PFBS PFHS PFOSA -0.1593 : 0.0561 0.1338 0.5890 90 95 -0.1611 0.1034 0.1272 0.3162 91 96 -0.1662 ; 0.0612 -0.3110 0.0022 95 -0.3193 0.0015 96 -0.3462 0.1154 0.5337 0.0006 91 96 96 November 2012 Cardno EN TRIX Perfluorosulfonate Results 7-13 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 7 -1 1.3M Analysis of Round 2 (August) Surface W ater Samples for Perfluorosulfonates (ND=RL) Field ID Tissue ID Lab ID Reach Start Northing Start Westing PFBS PFHS PFOS 515 516 517 518 519 520 , 521 522 523 524 525 526 %, 527 528 529 530 531 532 533 534 535 536 537 538 539 540 . 541 542 543 544 515SF 516SF 517SF 518SF 519SF 520SF 521SF 522SF 523SF 524SF 525SF 526SF . 527SF 528SF 529SF 530SF 531 SF 532SF 533SF 534SF 535SF 536SF 537SF 538SF 539SF 540SF 541SF 542SF 543SF 544SF 515SF1 ' 516SF1 517SF1 10 10 10 N44 46.018' N44 45.382' N44 46.926' 518SF1 9 N44 46.207' 519SF1 9 N44 45.987' 520SF1 521SF1 # 9 g i; v N44 46.333' N44 46.444' . 522SF1 : .... 8 .... ' 523SF1 8r N44 47.081' N44 47.463' 524SF1 7 N44 48.609' 525SF1 7 N44 49.305' 526SF1 527SF1 7 6 N44 50.012' N44 50.602' 528SF1 ^ 529SF1 6....... * N44 51.126' 6 N44 52.673' 530SF1 5 N44 53.478' 531SF1 5 N44 53.772' 532SF1 5 N44 54.371' 533SF1 ,j|7 534SF1 4 > N44 55.507' N44 56.082' ' 535SF1..' <.., 4 .... N44 56.830' 536SF1 3 N44 56.586' 537SF1 3 N44 56.006' 538SF1 539SF1 540SF1 I 541SF11/ 542SF1 543SF1 544SF1 3 2 2 2 1 1 1 N44 55.616' N44 54.672' N44 53.865' N44 53.827' N44 53.637' N44 53.995' N44 54.140' W92 52.305' 2.37 W92 52.521' <2.0 W92 53.313' W92 56.501' 336 <2.0 W92 57.531' <2.0 W92 58.151' <2.0 W93" 00.988' <2.0 W93 01.130' ., < 2.0 W93" 01.516' <2.0 W93 00.424' <2.0 W93 00.573' W93 00.740' W93 00.576' <2.0 <2.0 <2.0 W93 00.620' " ' <2.0 W93 00.927' W93 01.101' W93 01.866' <2.0 4 .1 7 <2.0 W93 02.547' <2.0 W93 03.004' W93" 03.129' <2.0 <2.0 W93 04.115' <2.0 W93 05.248' <2.0 W93 06.160' W93 06.650' <2.0 <2.0 W93 07.920' <2.0 W93 09.056' <2.0 W93 09.236' <2.0 W93 10.279' <2.0 W93 11.442' <2.0 W93 11.461' <2.0 <2.0 <2.0 6 0 .5 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 4 .2 <2.0 136 2 .1 5 <2.0 2 .7 7 2 3.51 <2.0 2 .7 7 <2.0 <2.0 2.6 <2.0 <2.0 7.1 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 RL was used as a proxy value for all non-detects B o ld , ita lic iz e d te x t= D etects PFOSA <2.0 < 2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 7-14 Perfluorosulfonate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 7 -1 2.3M Analysis of Round 1 (June) Surface Water Samples for Perfluorosulfonates (ND=RL) Field ID 501 502 503 504 505 Tissue ID 501SF 502SF 503SF 504SF 505SF Lab ID 501SF1 502SF1 503SF1 504SF1 505SF1 Reach 10 10 8 8 8 Start Northing N44 46.926' N44 45.382' N44 47.471' N44` 47.086' N44 46.447' 506 506SF 506SF1 3 N44 56.048' 507 507SF 507SF1 3 N44 56.589' 508 508SF 508SF1 3 N44 55.611' 509 509SF 509SF1 2 N44 53.823' 510 510SF 510SF1 2 N44 53.865' 511 511 SF 511SF1 2 N44 54.699' 512 512SF 512SF1 1 N44 54.149' 513 513SF 513SF1 , 1 1444 54.001' 514 514SF 514SF1 1 : N44 53.636' RL was used as a proxy value for all non-detects Start Westing W92 53.313' W92 52.521' W93 01.521* W93 01.118' W93 00.999' W93 06.085' W93 05.240' W93 06.663' W93 09.231' W93 09.064' W93 07.907' W93 11.459' W93 11.443' W93 10.274' PFBS 26 <2.0 <2.0 <2.0 <2.5 <2.0 <2.0 <2.0 < 2.0 <2.0 <2.0 <2.0 <2.0 <2.0 PFHS 12.5 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 PFOS 136 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 B o ld , ita lic iz e d te x t = D etects PFOSA <4.0 <4.0 <4.0 <4.0 <2.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 <4.0 November 2012 Cardno ENTRIX Perfluorosulfonate Results 7-15 Chapter 8 Perfluorocarboxylate Results 8.1 Intralaboratory Blind Duplicate Samples The comparison of analytical results for perfluorocarboxylic acids in fish tissue indicated good agreement between the primary and blind duplicate sample sets (Table 8-1). However, due to the large number of non-detects observed in both datasets, the evaluation of C4 to C8 PFCAs was limited. For instance, while PFPeA was detected in 4 samples in both the primary and blind duplicate samples sets, no matched samples were available for conducting the analysis. Likewise, no matched samples were available for PFHxA. For PFBA, 2 matched samples had measured concentrations that ranged from 0.12 to 1.3 ng/g and 0.21 to 2.4 ng/g with an average RPD o f 20% in the primary and duplicate sample sets, respectively. For PFHpA, only 1 matched sample reported measured concentrations a RPD of 0.98%. Finally, only 1 matched sample had measured concentrations with a fold difference of 1.03 and a RPD of 2.9%. Regardless of the limited sample size, the measured concentrations of these PFCAs demonstrated that there was good agreement between the two sample sets with RPD value generally < 20%. The frequency o f samples with measured concentrations was greater for PFCAs with carbon chains greater than 8. For PFNA, 21 matched samples reported measured concentrations that ranged from 0.03 to 0.8 ng/g ww in the primary dataset and 0.05 to 0.15 ng/g ww in the duplicate dataset. The average fold difference and RPD was 1.02 and 11%, respectively. All 41 samples in both the primary and duplicate datasets had PFDA concentrations greater than the LOQ. PFDA concentrations in the primary dataset ranged from 0.48 to 11 ng/g ww and from 0.59 to 9.3 ng/g in the duplicate dataset. Likewise, all 41 samples in both the primary and duplicate sample had measured PFUnA concentrations that ranged from 0.47 to 6.3 ng/g and 0.44 to 5.24 ng/g, respectively. For PFDoA, all 41 samples in both the primary and duplicate sample sets had concentrations greater than the LOQ that ranged from 0.25 to 4.75 ng/g and 0.25 to 4.41 ng/g, respectively. The average fold difference between both sample sets for PFDA, PFUnA and PFDoA were 1.03, 1.02 and 1.02, respectively. The average RPD values for PFDA, PFUnA and PFDoA were 13%, 10% and 9.9%, respectively that indicated good agreement between the both datasets. 8.2 Interlaboratory Comparison Samples 8.2.1 Fish Tissue Due to the large number of non-detects reported by one or both laboratories, the interlaboratory comparison of PFCAs in the fish tissue could not be conducted (Table 8-2). This resulted in no matched samples where both laboratories reported concentrations of PFBA, PFPeA, PFHxA, PFHpA, PFOA, and PFNA that were above the LOQ of each analyte. As such, a comparison of analytical results for these analytes was not conducted. PFDA was detected in all 41 fish samples by the 3M lab but was only detected in 14 samples by AXYS. Based on the 14 matched samples, PFDA concentrations ranged from 2.1 to 11 ng/g ww and 2.3 and 11 ng/g ww for the 3M and AXYS laboratories, respectively. PFDA concentrations reported 8-1 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 by the 3M Lab were slightly greater with an average RPD of 11%. PFDoA was also detected in all 41 fish samples by the 3M lab but was only detected in 3 samples by the AXYS. Based on the matched samples, measured PFDoA concentrations in fish ranged from 2.7 to 4.8 ng/g and 3.1 to 4.5 ng/g for the 3M Lab and AXYS, respectively. The average fold-difference between laboratories was 0.98 with an average RPD of 6.91%. For PFUnA, 3M reported measured concentrations for all 41 interlaboratory fish samples while AXYS reported measured concentrations for 4 samples. Based on the 4 matched samples, PFUnA concentrations ranged from 2.0 to 6.3 ng/g ww and 2.4 to 5.4 ng/g for the 3M Lab and AXYS, respectively. Average PFUnA concentrations were 3.6 ng/g and 3.9 ng/g ww for 3M and AXYS, respectively with an average fold-difference of 0.88 and a RPD of 22%. Overall, these data indicate that there was good agreement between the laboratories with and overall average fold-difference for all PFCS of 0.90 with an average RPD of 16%. 8.2.2 Surface Water For surface water concentrations, an interlaboratory comparison of PFPeA, PFNA, PFDA, PFUnA and PFDoA was not conducted due to the great frequency of non-detects that resulted in no matched samples with measurable concentration (Table 8-3). For PFHxA only 1 matched sample had a measurable concentrations with the 3M Lab reporting a value of 16 ng/L and AYXS reporting a value of 6.9 ng/L. This resulted in a percent difference of 230% with a RPD of 79%. Likewise, only 2 matched samples had measurable PFHpA water concentrations with an average fold-difference of 0.42 and an average RPD of 89%. For PFBA, 12 matched samples had measurable concentrations that ranged from 11 to 74 ng/L and 9.1 to 92 ng/L for 3M and AXYS, respectively. Average PFBA concentrations were 21 and 22 ng/1 for 3M and AXYS, respectively with an average fold-difference of 1.1 and a RPD of 12%. For PFOA, 3M reported concentrations for 10 samples while AXYS reported concentrations for 22 samples for a total of 10 matched samples. PFOA water concentrations ranged from 1.3 to 77 ng/L and 2.5 to 137 ng/L for 3M and AXYS respectively. The average interlaboratory fold-difference between measured PFBA concentrations was 0.66 with an average RPD of 39%. Overall, there was good agreement between the target analyte concentrations reported by both laboratories. Percent differences for target analytes detected in surface waters by both laboratories ranged from 20% to 140% with an overall average of 80%. Relative percent differences ranged from 1.6% to 135% with an overall average of 33%. The greatest divergence in reported PFCA concentrations was observed for one sample where the concentration o f PFHpA reported by 3M was approximately five-fold greater than that reported by AXYS. Without this sample, the average fold difference between the two laboratories was approximately 1.0. 8.3 Study Fish Tissue Samples Of the 9 perfluorocarboxylates that were analyzed in fish, the concentrations reported for PFBA, PFPeA, PFHxA, PFHpA and PFOA were dominated by values less than the LOQ (Table 8-4, 8-6, 8 8. 8-10, and 8-12). PFBA was detected in 37 of 396 fish samples with species-specific detection rate that was less than or equal to 16% (Table 8-4). PFBA was detected in 9 bluegill, 16 freshwater drum, 4 smallmouth bass and 8 white bass with concentrations that ranged from 0.05 to 5.59 ng g ww. The grand arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 0.28 (0.24-0.32) ng/g ww and 0.13 ng/g ww, respectively (Table 8-5). O f the 37 samples with detected values, only 12 samples had PFBA concentrations greater than 1 ng/g ww and none were greater than 5 ng/g ww. PFPeA was detected in 38 of 396 fish samples with species-specific detection rate that was less than or equal to 12% (Table 8-6). PFPeA was detected in 7 bluegill, 6 freshwater drum, 22 smallmouth November 2012 Cardno ENTRIX Perfluorocarboxylate Results 8-2 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 bass, and 9 white bass with concentrations that ranged from 0.03 to 1.37 ng/g ww. The grand arithmetic mean and median for all fish were 0.18 (0.16-0.19) ng/g ww and 0.13 ng/g ww, respectively (Table 8-7). O f the 38 samples with detected PFPeA concentrations, only 1 sample was greater than 1 ng/g ww. PFHxA was detected in 46 of 396 fish samples with species-specific detection rate that was less than or equal to 15% (Table 8-8). PFHxA was detected in 12 bluegill, 15 freshwater drum, 10 smallmouth bass, and 9 white bass with concentrations ranging from 0.03 to 1.19 ng/g ww. The grand arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 0.20 (0.18-0.22) ng/g ww and 0.13 ng/g ww, respectively (Table 8-9). O f the 46 samples with detected concentrations, none had concentrations greater than 5 ng/g ww and only 2 had concentrations greater than 1 ng/g ww. PFHpA was detected in 33 of 396 fish samples with species-specific detection rate that was less than or equal to 14% (Table 8-10). PFHxA was detected in 10 bluegill, 14 freshwater drum, 3 smallmouth bass, and 6 white bass with concentrations ranging from 0.01 to 0.15 ng/g ww. The grand arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 0.04 (0.03-0.04) ng/g ww and 0.03 ng/g ww, respectively (Table 8-11). O f the 33 samples with detected concentrations, none had concentrations greater than 1 ng/g ww. PFOA was detected in 46 of 396 fish samples with species-specific detection rate that was less than or equal to 25% (Table 8-12). PFOA was detected in 11 bluegill, 25 freshwater drum, 1 smallmouth bass, and 9 white bass with concentrations ranging from 0.03 to 1.86 ng/g ww. The grand arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 0.09 (0.08-0.10) ng/g ww and 0.05 ng/g ww, respectively (8-13). O f the 46 samples with detected concentrations, 3 had concentrations greater than 1 ng/g ww. While concentrations of C4 to C8 PFCAs in fish collected from Pool 2 were dominated by nondetects, longer chain PFCA were detected at a much greater frequency with 55% of the fish samples reporting detected concentrations for PFNA and 100% of the sample reporting PFDA, PFUnA and PFDoA. PFNA was detected in 41 bluegill, 86 freshwater drum, 7 smallmouth bass and 84 white bass with concentrations that ranged from 0.01 to 1.13 ng g ww (Table 8-14). The grand arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 0.23 (0.21-0.26) ng/g ww and 0.13 ng/g ww, respectively (Table 8-15). Of the 218 samples with detected values, only 3 samples had PFNA concentrations greater than 1 ng/g ww and none were greater than 2 ng/g ww. Species-specific arithmetic mean (95% confidence limits) PFNA concentrations were: bluegill 0.10 (0.08-0.12) ng/g ww, freshwater drum 0.28 (0.25-0.32) ng/g ww, smallmouth bass 0.05 (0.05-0.06) ng/g ww, and white bass 0.51 (0.46-0.56). Median PFNA concentrations were 0.08, 0.26, 0.03, and 0.51 ng/g ww for bluegill, freshwater drum, smallmouth bass, and white bass respectively. The rank order from least to greatest concentration was smallmouth bass, bluegill, freshwater drum, and white bass with an overall difference of 10-fold between the least and greatest species-specific values. However, much of this difference was derived from the large number of non-detects observed for smallmouth bass, when this species was removed, the difference was only 5.6-fold. Comparison of fish tissue PFNA concentrations over the 10 sampling reaches in Pool 2 indicated that while the greatest concentrations typically were observed in Reach 10, no gradient or trend was observed across all the reaches for any o f the fish species (Table 8-15). PFDA was detected in 100% of the fish sampled in Pool 2 with concentrations ranging from 0.32 to 10.9 ng g ww (Table 8-16). The overall arithmetic mean (95% confidence limit) and median for all 8-3 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 fish analyzed in this study were 2.11 (1.97-2.25) ng/g ww and 1.79 ng/g ww, respectively. O f the 396 samples with detected values, 310 samples had PFDA concentrations greater than 1 ng/g ww, 17 samples greater than 5.0 ng/g ww and 1 sample greater than 10.0 ng/g ww. Species-specific arithmetic mean (95% confidence limits) PFNA concentrations were: bluegill 1.41 (1.11-1.71) ng/g ww, freshwater drum 1.74 (1.57-1.91) ng/g ww, smallmouth bass 1.74 (1.60-1.87) ng/g ww, and white bass 3.61 (3.4-3.9) (Table 8-17). Median PFDA concentrations were 0.90,1.52,1.63, and 3.44 ng/g ww for bluegill, freshwater drum, smallmouth bass, and white bass respectively. The rank order from least to greatest concentration was bluegill, freshwater drum, smallmouth bass, and white bass with an overall three-fold difference between the least and greatest species-specific values. Comparison offish PFDA concentrations across all 10 sampling reaches indicated that while the greatest concentrations typically were observed in Reach 10, a concentration gradient was not apparent for any of the 4 fish species in the rest of Pool 2 (Table 8-17). PFUnA was detected in 100% of the fish sampled in Pool 2 with concentrations ranging from 0.19 to 6.32 ng g ww (Table 8-18). The overall arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 1.22 (1.15-1.30) ng/g ww and 1.11 ng/g ww, respectively. O f the 396 samples with detected values, 221 samples had PFUnA concentrations greater than 1 ng/g ww, 10 samples greater than 3.0 ng/g ww and 3 samples greater than 5.0 ng/g ww. Species-specific arithmetic mean (95% confidence limits) PFUnA concentrations were: bluegill 0.83 (0.66-1.01) ng/g ww, freshwater drum 1.07 (0.96-1.18) ng/g ww, smallmouth bass 1.22 (1.13-1.32) ng/g ww, and white bass 1.79 (1.65-1.93) (Table 8-19). Median PFUnA concentrations were 0.61, 0.89, 1.20, and 1.69 ng/g ww for bluegill, freshwater drum, smallmouth bass, and white bass respectively. The rank order from least to greatest concentration was bluegill, freshwater drum, smallmouth bass, and white bass with an overall 2.8-fold difference between the least and greatest species-specific values. Comparison of fish tissue PFUnA concentrations across all 10 sampling reaches indicated that while the greatest concentrations typically were observed in Reach 10, equivalent concentrations of PFUnA were observed in Reaches 5 through 7 and as a result, a concentration gradient was not apparent for any o f the 4 fish species in Pool 2 (Table 8-19). PFDoA was detected in 100% of the fish sampled in Pool 2 with concentrations ranging from 0.13 to 4.75 ng g ww (Table 8-20). The overall arithmetic mean (95% confidence limit) and median for all fish analyzed in this study were 1.08 (1.01-1.14) ng/g ww and 1.00 ng/g ww, respectively. O f the 396 samples with detected values, 199 samples had PFDoA concentrations greater than 1 ng/g ww, 36 samples greater than 2.0 ng/g ww and no samples greater than 5.0 ng/g ww. Species-specific arithmetic mean (95% confidence limits) PFDoA concentrations were: bluegill 0.59 (0.48-0.70) ng/g ww, freshwater drum 1.05 (0.92-1.18) ng/g ww, smallmouth bass 1.16 (1.07-1.25) ng/g ww, and white bass 1.51 (1.39-1.64) (Table 8-21). Median PFDoA concentrations were 0.46, 0.85, 1.16, and 1.40 ng/g ww for bluegill, freshwater drum, smallmouth bass, and white bass respectively. The rank order from least to greatest concentration was bluegill, freshwater drum, smallmouth bass, and white bass with an overall three-fold difference between the least and greatest species-specific values. Comparison of fish tissue PFDoA concentrations across all 10 sampling reaches indicated that while the greatest concentrations typically were observed in Reach 10 followed by Reach 5, a concentration gradient was not observed for any of the 4 fish species in Pool 2 (Table 8-21). Correlation analysis of PFBA, PFPeA, PFHxA, PFHpA, and PFOA tissue concentrations with fish mass, length and age resulted in few statistically significant correlations and of those correlations that were statistically significant, the correlations accounted for only a small amount of the total variation (Table 8-22). For PFCA's with carbon chains of 8 or less, the only statistically significant correlations observed in bluegill were for PFHxA and mass (p= 0.02) and length (p= 0.034) as well November 2012 Cardno ENTRIX Perfluorocarboxylate Results 8-4 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 as for age and PFBA (p= 0.02) and PFHpA (p= 0.002). In freshwater drum, the only significant correlation was observed between mass and PFHpA (p=0.037) where as all correlations for smallmouth bass and white bass were not statistically significant (p< 0.05). In contrast, with exception of bluegill and age (p= 0.46), all correlations of PFDoA were statistically significant for all fish species. Furthermore, the all correlations between PFUnA and fish characteristics were statistically significant (p< 0.05) while for PFDA the only correlations that were not statistically significant were for mass and length in bluegill and mass in freshwater drum. Unlike the other long chain PFCAs, PFNA demonstrated the greatest interspecies differences in that while all correlations in freshwater drum and smallmouth bass were not statistically significant (p> 0.18), all correlations with fish characteristics for bluegill and white bass were statistically significant (p< 0.05). Overall, fish mass, length and age were poor predictors of PFCA tissue concentrations. 8.4 Study Surface Water Samples Concentrations of PFDA, PFUnA and PFDA in surface water samples collected in Round 2 (August) were all reported as less than their LOQ (Table 8-23). Furthermore, only 1 sample had detectable concentrations of PFHpA and PFNA while PFPeA and PFHxA had detectable concentrations in 3 and 4 samples, respectively. In contrast, PFBA was measured in 16 of the 30 surface water samples while PFOA was measured in 20 of 30 samples. In all instances, the location with the greatest frequency of PFC detection, as well as measured PFC concentration, was observed in the water sample collected in Reach 10 at Station 530. The location with the second greatest number of PFC detections, as well as PFC concentrations, was in water collected from Reach 5 at Station 517. In general, the surface water samples collected throughout the entirety o f Pool 2 had PFCA concentrations that were predominately non-detects with the exception of those sample collected immediately downriver of known point sources to the river. The exceptions to this general finding PFBA and PFOA that were measured in surface water samples throughout Pool 2 but that had their greatest concentrations downriver of two known point sources. While Round 1 (June) surface water samples were collected from only 14 locations and as a result can be used to evaluate the distribution of PFCs throughout the entirety of Pool 2, the results from these samples can be used to explore temporal changes in PFC concentrations at these locations (Table 8-24). The total number of detects for PFBA, PFPeA, PFHxA, PFHpA, PFNA and PFOA in these samples were 3, 3, 2, 1, 1, and 13, respectively. In general, concentrations reported in Round 1 were less than those reported in Round 2 for the same locations. For instance, the average foldconcentration difference between Rounds 2 and 1 were 3.0,2.3,1.7,1.7,1.1, and 1.3 for PFBA, PFPeA, PFHxA, PFHpA, PFNA, and PFOA, respectively. The greatest differences observed between the two sampling Rounds were observed for samples collected at Station 517/501, downstream of the 3M facility. At this location the fold difference between Rounds 2 and 1 for PFBA, PFPeA, PFHxA, and PFOA were 7.0-, 4.7-, 2.5 and 1.6, respectively. For all other locations and analyte combinations, the fold-differences ranged from 0.7 to 2.0. 8-5 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 8.5 Tables and Figures Table 8-1. Intralaboratory Blind Duplicate Comparison of Perfluorocarboxylates (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011) Relative Percent Difference (RPD, %) Reach Species Field ID Primary Lab ID Duplicate Lad ID PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA 10 'Bluegill 022 022PN ^ "^ 'i-O ftF N I- p 33.29 2.89 IlS F 16.3 18.7 . 18.5 9 Bluegill . 126 ~ 126FN **" 105FN1 i 8.36 f 4 B ,i" 30.5 10 Freshwater drum * 0 1 0 ; 1 Freshwater drum 078 010FN ,1' 078FN 012FN1 073FN1 6.95 15.1 2.79 18.7 1.15 0.98 17.4 0.2 2.38 9 Freshwater drum 137 137FN 121FN1 0.2 13.6 9.8 7.94 6 Freshwater drum 170 170FN 147FN1 6.73 10.0 9.58 5 fre sh w a te r drum 192 192FN ' T 173FN1 6.5 3.99 # 7.40 4 ,, Freshwater drum 258 258FN / 'ii F N I U p 7.52 p O 0.34 . 1f iit - Freshwater drum 4 8 Freshwater drum 269 .^ 315 269FN ' 315FN 233FN1 265FN1 ;m 30.4 25.2 31.3 13.7 14.5 13.4 19.3 6 Freshwater drum 323 323FN 275FN1 10.1 4.52 6.5 20.4 6 Freshwater drum 334 334FN 284FN1 >,447i3 Freshwater Stum v _ 447FN _ , 376FN1 * 11.1 0.26 19.7 , 19.1 1.8 13.2 3.0 ; 6.84 3 Smallmouth bass Smallmouth bass < 054 092 054FN 092FN 060FN1 077FN1 19.2 '" 16.4 #6>17.42 0.72 1 Smallmouth bass 102 102FN 089FN1 3.92 6.0 0.83 10 Smallmouth bass 159 159FN 139FN1 7.01 3.0 1.53 5 Smallmouth bass 180 180FN 169FN1 28.5 28.2 11.6 5 , Smallmouth bass is 203 ' 'lO S F lC * / " P ^ 182FM1 " " , 28.9 32.4 15.1 4 Smallmouth bass 224 224FN 196FN1 , 18.2 13.8 5.9 7.91 4 Smallmouth bass 246 246FN 225FN1 1.79 2.3 2.61 2 Smallmouth bass 280 280FN 244FN1 8.44 8.4 4.34 7 Smallmouth bass 291 291FN 245FN1 20.3 14.8 13.3 7 Smallmouth bass 302 302FN 255FN1 12.4 7.3 2.54 Nt > 2 0 1 2 Cardno EK Perfluorocarboxylate R e i Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-1. Intralaboratory Blind Duplicate Comparison of Perfluorocarboxylates (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011) Relative Percent Difference (RPD, %) Reach Species Field ID Primary Lab ID Duplicate Lad ID PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA 3 Smallmouth bass 360 360FN 324FN1 8 V" Smallmouth bass 383 383FN 339FN1 9 Smallmouth bass 390 390FN 347FN1 4 Smallmouth bass 436 436FN 375FN1 8 White bass 033 033FN 042FN1 8 White bass 045 045FN 043FN1 2 White bass 065 065FN / ^ 068FN1 * ' f % White bass " 113 113FN 090FN1 9 fe .White bass , 149 149FN 122FN1 6 White bass 214 214FN 184FN1 4 White bass 232 232FN 210FN1 3 White bass 346 346FN 314FN1 2 White bais White bass V " 370 *;;v 370FN 400 400FN i ' 327FN1 348FN1 1 White bass \ 411 411 FN 357FN1 9 White bass 425 425FN 371FN1 1 White bass 450 450FN 406FN1 2.0* 4.1 9.0 8.8 20.3 23.3 13.1 0.2 0.8 18.9 2.41 7.70 15.3 16.0 26.8 21.0 9.38 6.82 6.91 12.3 7.06 14.2 33.5 10.1 16.5 14.6 3.17 3.1 15.6 11.8 7.58 5.4 5.56 15.9 18.3 5.6 17.3 8.9 17.9 7.8 0.73 8.7 " 8.78 9.3 12.2 16.8 4.33 3.1 7.94 15.8 17.6 ,s24.4 4 15.1 7.18 * 6.3 8.73 14.3 6.97 4.8 7.52 All reported RPD values were for samples that had paired results greater than the LOQ 8-7 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-2. Interlaboratory Comparison of Perfluorocarboxylates (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M and AXYS (2011) Relative Percent Difference (RPD, %) Reach Species 10 'J "" Bluegill Bluegill 10 " 'Freshwater drum 1 Freshwater drum 9 Freshwater drum 6 Freshwater drum 5 , Freshwater drum 4 ' Freshwater drum 1 Freshwater drum 8 Freshwater drum 6 Freshwater drum 6 Freshwater drum 3 _ Freshwater drum ~ r` ,, 3 v Smallmouth bass I ,4 , 3^mallrnouitfbass _ 1 Smallmouth bass 10 Smallmouth bass 5 Smallmouth bass 5 Smallmoutlf tsass 4 Smallmouth bass 4 Smallmouth bass 2 Smallmouth bass 7 Smallmouth bass 7 Smallmouth bass 3: Smallmouth bass Field ID 3M Lab ID AXYS Lab ID 022 022FN 019FN1 126 126FN 105FN1 ' O f t F ' * " 010FN - f ' 012FN1 078 078FN 073FN1 137 137FN 121FN1 170 170FN 147FN1 192 V 192FN t 173FN1 258 " 258FN 228FN1 " 269 5 269FN 233FN1 315 315FN 265FN1 323 323FN 275FN1 334 334FN 284FN1 447 447FN s 376FN1 054 054FN ^ 060FN1 092 ^ ; 102 092FN 102FN 1 077FN1 089FN1 159 159FN 139FN1 180 180FN 169FN1 203 203FN 182FN1 224 . 224FN ` ` lle F N l, 246 246FN 225FN1 280 280FN 244FN1 291 291FN 245FN1 302 302FN 255FN1 360 360FN ? 0Z4riN 1 PFBA PFPeA PFHxA PFHpA ; PFOA PFNA 200.00 PFDA 3.0 PFUnA 15.1 PFDoA 1.6 *, 13.38 9.0 22.98 ' 1 3 ;**' 3 *= # N( ^ ^ 2 0 1 2 ----------------------------------------------------------------------------------- C M * Perfluorocarboxylate R e i >8 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer z011 Table 8-2. Interlaboratory Comparison of Perfluorocarboxylates (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M and AXYS (2011) Reach Species 8 Smallmouth bass 9 Smallmouth bass 4 Smallmouth bass 8 White bass 8 White bass 2 White bass 7 White bass 9 White bass 6 White bass 4 White bass 3 W h ite bass Field ID 383 390 436 033 045 065 113 149 214 232 346 3M Lab ID 383FN 390FN 436FN 033FN 045FN 065FN 113FN 149FN 214FN 232FN 346FN AXYS Lab ID 339FN1 347FN1 375FN1 042FN1 043FN1 068FN1 090FN1 122FN1 184FN1 210FN1 314FN1 PFBA 2 W h ite bass 370 370FN 327FN1 5 W h ite bass 400 400FN 348FN1 1 W h ite bass 411 411FN 357FN1 9 W h ite bass 425 425FN 371FN1 1 W h ite bass 450 450FN 406FN1 All reported RPD values were for samples that had paired results greater than the LOQ PFPeA Relative Percent Difference (RPD, %) PFHxA PFHpA PFOA PFNA PFDA 0.3 3.1 11.90 23.8 5.93 16.4 6.7 0.7 12.2 24.3 16.99 PFUnA 22.8 16.7 34.3 PFDoA 5.73 8-9 Perfluorocarboxylate Results Cardno EN TRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-3. Interlaboratory Comparison of Perfluorocarboxylates (ng/L) in Surface W ater Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS (2011) Relative Percent Difference (RPD, %) Reach Field ID 3M Lab ID AXYS Lab ID PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA r -. %V ..ta 1 1 1' 2 2 2 3 4 4 4 5 5 5 6 6 6 IT 't - 7 1 7 '<. 8 8 8 ......... 512 > 512SF1 r A 5f2SF2T't v A W 513SF1 513SF2 ; , A I A "A AAAA A A A /A , A A -: i 514 509 ' 514SF1 509SF1 514SF2 * 509SF2 510 510SF1 510SF2 511 511SF1 511SF2 506 ' S0SSF1 507 07SF1 508 533 533SF1 506SF2 507SF2 508SF2 533SF2 , "L p ,r V I ' A ' v s A'.- "'P pL *- A a ^ a a \ . ir a . a 1.25 -- p : .a -rfr ' P ' , i* =. /P p. '- . -P -- f > 534 534SF1 534SF2 535 535SF1 530 - 530SF1 _ 535SF2 530SF2 i s: 17.52 -A 24.57 24.58 531 531SF1 i* A 531SF2 532 532SF1 527 527SF1 532SF2 527SF2 3.51 37.69 528 528SF1 528SF2 6.57 529 529SF1 524 524SF1 529SF2 524SF2 6.94 32.87 525 525SF1 525SF2 526 526SF1 526SF2 503 503SF1 504 504SF1 505 505SF1 503SF2 504SF2 505SF2 32.98 69.42 66.32 t r 2012 Cardno Eh Perfluorocarboxylate Rest Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-3. Interlaboratory Comparison of Periluorocarboxylates (ng/L) in Surface W ater Collected from Pool 2 During Rounds 1 and 2 and Analyzed by 3M and AXYS (2011) Reach Field ID 3M Lab ID AXYS Lab ID PFBA PFPeA 9 " 518 : 518SF1 518SF2 2.76 9 519 519SF1 519SF2 5.41 9 520 520SF1 520SF2 5.92 10 501 501SF1 10 502 502SF1 501SF2 502SF2 21.72 33.81 86.23 10 515 515SF1 515SF2 1.60 All reported RPD values were for samples that had paired results greater than the LOQ Relative Percent Difference (RPD, %) PFHxA PFHpA PFOA PFNA PFDA i 28.30 25.00 60.21 67.02 34.71 55.60 42.62 PFUnA PFDoA Table 8-4. Descriptive Statistics for PFBA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Species Statistic Bluegill Arithmetic Mean [PFBA] 0.27 -Number of Detects 9 Number of Non-detects 90 Number of Samples Not Reported 1 Maximum [PFBA] Minimum [PFBA] Median [PFBA] Geometric Mean [PFBA] Standard Deviation 3.12 0.05 0.13 0.16 TM 0.42 1/2 RL was used as a proxy value for all non-detects Freshwater drum 1 0.38 16 84 0 4.59 0.05 0.18 0.22 0.63 Smallmouth bass 0.21 4 96 0 0.54 0.05 0.18 0.17 0.15 White bass 0.26 8 88 0 2.41 0.05 0.13 0.17 5 0.32 8-11 Perfluorocarboxylate Results Cardno EN TRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-5. Mean and 95% Confidence Intervals for PFBA Concentration (ng/g, ww) in Fish Collected In Pool 2 by Reach (2011) Species Statistic Bluegill Mean 95% Cl Freshwater drum Mean 95% Cl 5 Mean Smallmouth bass ' 95% Cl White bass Mean 95% Cl 1 0.241 - 0.231 _ 0.361 0.091 - 2 0.381 - 0.171 _ 0.162 - 0.512 " 3 45 0.351 0.112 0.432 - ;r ~ - 0.291 0.312 0.131 - -- 0.241 - 0.361 ~ 0.241 0.131 * . " 0.202 0.152 Reach 6 7 0.222 0.12 - [0.08, 0.16] 0.562 0.572 -- 0.222 " 0.242 0.081 * " 0.161 89 10 0.442 0.071 0.332 -- - 0.481 0.15 0.93 - [0.09, 0.22] [0.34, 1.53] 0.251 0.172 0.292 , ' * 4 ..I .J 0.502 0.091 0.252 1All samples < LOQ; only mean DL reported 2 Sample size < 2; only mean reported Table 8-6. Descriptive Statistics for PFPeA (ng/g, w et weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Statistic Arithmetic Mean [PFPeA] Number of Detects Number of Non-detects Number of Samples Not Reported Maximum [PFPeA] Minimum [PFPeA] Median [PFPeA] Geometric Mean [PFPeA] .'Standard Deviation Species Bluegill Freshwater drum Smallmouth bass White bass 0.17 1 0.18 .. j, , 0 2 1 ' , * , , f" ir ^ ; & 1 5 | '' 76 22 3 X % 9X ' 1 94 0 78 0 93 0 0.50 0.50 1.37 0.50 0.01 0.01 0.13 0.13 0.03 0.13 0.01 0.13 0.11 0.12 0.15 0.09 0.17 0.16 0.20 ;, - 0.16 1/2 RL was used as a proxy value for all non-detects n( )r2012 Cardno El PerfluorocarboxyIate Resi! E Mississippi River Pool 2 PFC Assessm ent - Fish Tissues and Water - Summer z0^^ Table 8-7. Mean and 95% Confidence Intervals for PFPeA Concentration (ng/g, ww) in Fish Collected In Pool 2 by Reach (2011) Reach Species Statistic 1 2 3 4 5 67 8 9 Bluegill Freshwater drum Mean 95% Cl Mean 95% Cl 0.191 0.371 0.351 0.09 0.122 ; - A " [0.05,0.14] \ g W 't 0.192 0.141 0.291 0.111 0.121 --- - - 0.071 0.132 - T ifi# " 0.082 0.081 -- 0.121 0.052 1r : 0.461 0.04 - [0.02, 0.06] Smallmouth bass Mean : 0.412 0.141 0.222 0.18 0.181 0.162 0.172 0.32 95% Cl 1 Ii* f f - 'si'**19" ' [0.10,0.25] * Tv m % . .K * if ** . [0.18,0.47] 0.17 [0.03,0,31] White bass Mean 95% Cl 0.051 - 0.222 - 0.201 - 0.082 - 0.071 - 0.111 - 0.112 - 0.341 - 0.041 - 1All samples < LOQ; only mean DL reported 10 0.261 0.251 - 0.231 - 0.211 - 2 Sample size s 2; only mean reported Table 8-8. Descriptive Statistics for PFHxA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Species Statistic Bluegill Arithmetic Mean [PFHxA] 0.19 i t Number of Detects 12 Number of Non-detects 87 Number of Samples Not Reported 1 Maximum [PFHxA] 1.07 Minimum [PFHxA] 0.03 Median [PFHxA] 0.13 Geometric Mean [PFHxA] ............. 0.1 3..... Standard Deviation 0,19 1/2 RL was used as a proxy value for all non-detects Freshwater drum 0.24 15 85 0 0.79 0.03 0.14 0.18 0.17 Smallmouth bass 0.16 10 90 0 0.50 0.03 0.13 0.12 0.14 White bass 0.20 9 87 0 1.19 0.03 0.13 0.15 0.18 8-13 Perfluorocarboxylate Results Cardno EN TRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-9. Mean and 95% Confidence Intervals for PFHxA Concentration (ng/g, wet weight) In Fish Collected in Pool 2 by Reach (2011) Species Statistic 1 ` Bluegill Mean 0.241 ... . 95% Cl 5 - Freshwater drum Mean 95% Cl 0.222 - Smallmouth bass Mean 0.351 95% Cl r White bass Mean 95% Cl 0.131 - Reach 23 456 789 10 0.381 0.332 0.15 0.141 V ' 0.07? - v 0.09 - o . l # ; , 0.12' ` X 0.281 - - [0.08,0.22] - - [0.05,0.12] - - - 0.171 0.342 0.222 0.131 0.10 0.141 0.472 0.37 0.251 -- - - [0.05,0.15] - - [0.18,0.56] - 0.111 : 0.18 - [0.05,0.31] \ 0.241 0.231 0.172 H 0.132 0.131 1' 1 0.151 0.112 - 0.141 0.082 0.122 0.092 - 0.332 0.112 - 0.17 , 0.281 , *'; , 0.37 -- --- - - [0.09,0.24] [0.15,0.59] 1All samples < LOQ; only mean DL reported 2 Sample size < 2; only mean reported Table 8-10. Descriptive Statistics for PFHpA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Statistic Arithmetic M eahIPFBpf Number of Detects * * < Number of Non-detects # \ Number of Samples Not Reported Maximum [PFHpA] Minimum [PFHpA] Median [PFHpA] Geometric Mean [PFHpA] Standard Deviation # Bluegill m ,* 10 ~ r x 90 . 0 0.13 0.01 0.03 0.03 0.03 Species Freshwater drum Smallmouth bass o.o3 * s , " :0.04'>l, 14 3 86 97 00 0.15 0.13 0.01 0.01 0.03 0.03 0.03 0.03 0.03 0.04 White bass o.o3 " ; 6 90 0 0.13 0.01 0.03 0.03 0.03 ' 1/2 RL was used as a proxy value for all non-detects ------- Nt yfer2012 Cardno Ef Perfluorocarboxylate Rest M Mississippi River Pool 2 PFC Assessment --Fish Tissues and Water - Summer z011 Table 8-11. Mean and 95% Confidence Intervals for PFHpA Concentration (ng/g, wet weight) in Fish Collected in Pool 2 by Reach (2011) Species Statistic 1 Bluegiil Mean 95% Cl 0.04 [0.02,0.05] Freshwater drum Mean 95% Cl 0.05 [0.02,0.09] Mean Smallmouth bass : 95% Cl White bass Mean 95% Cl : 0.022 11 ] 0.032 - 1All samples < LOQ; only mean DL reported Reach 2 3 45 6 0.04 0.032 [0.03,0.05] I f j | l * % ' 0.042 0.04 0.031 .ill > 0.041 0.042 0.061 * i | 11 0.031 0.052 , 0.051 [0.02,0.06] 0.03' 0.051 0.041 0.111 ill 0.041 0.031 i # ;4! 0.031 0.031 0.082 - - -- - 7 8 9 10 0.091 1 0.031 -j, 11K l 0.021 0.021 -- 0.021 0.011 - 0.021 - 0.032 - 0.081 - 0.031 0.032 . 0.012 - k 1 s'ill' 0.041 0.042 0.021 0.012 -- -- 2 Sample size < 2; only mean reported Table 8-12. Descriptive Statistics fo r PFOA (ng/g, w et weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Species Statistic Bluegiil Arithmetic Mean [PFOA] 0.09 Number of Detects 11 i Number of Non-detects 89 Number of Samples Not Reported 0 Maximum [PFOA] 1.10 Minimum [PFOA] 0.03 Median PFOA] 0.05 1 Geometric Mean [PFOA] 0.06 Standard Deviation 0.11 1/2 RL was used as a proxy value for all non-detects Freshwater drum 0.12 25 75 0 1.86 0.03 0.05 m 0.08 0.24 Smallmouth bass 0.08 1 99 0 0.18 0.03 0.05 0.07 0.04 White bass 0.08 9 ` 87 0 0.40 0.03 0.05 0.07 0.05 8-15 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-13. Mean and 95% Confidence Intervals for PFOA Concentrations (ng/g, w et weight) in Fish Collected in Pool 2 by Reach (2011) Reach Species Statistic 1 2 3 4 5 Bluegili .A M ea rk 95% Cl 0.062 0.071 > 0.197 " ' - 0.051 - Q.082 .T Freshwater drum Mean 95% Cl 0.091 - 0.112 - 0.09 [0.07,0.12] 0.05 [0.03,0.08] 0.13 [0.05, 0.22] Mean Smallmouthbass ' ..,,A, * 95% Cl ' 0.061 0.131 ` 0.061 0.041 *r ... A * -- 'a 'X. ' i f * - 0.062 White bass Mean 95% Cl 0.072 - 0.091 - 0.061 " 0.042 - 0.092 6 7 8 9 10 0.042 r'O .TPt" 0.041 '' 0.101 0.12 * I a ?- i 0.06 ' - : 0.092 0.072 0.071 [0.02,0.09] - - - [0.05,0.19] 0.45 [-0.03,0.93] *0051 0.102 0.111 0.081 - A S'* 0.101 0.082 0.111 1i , 0-051 ' 0.071 0.082 : "" 1All samples < LOQ; only mean DL reported 2 Sample size < 2; only mean reported Table 8-14. Descriptive Statistics for PFNA (ng/g, wet weight) in Fish Collected from Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Statistic Arithmetic Mean [PFNA] Number of Detects ^ Number of Non-detects Number of Samples Not Reported Maximum [PFNA] Minimum [PFNA] Median [PFNA] Geometric Mean [PFNA] Standard Deviation f ^ Bluegili 0.10 > 41 59 0 0.56 0.03 0.08 0.08 0.08 Species Freshwater drum Smallmouth bass 0.28 0.05 ~ 8 6 \ ;i> > 7 14 93 00 0.95 0.13 0.03 0.01 0.26 0.03 0.24 0.04 0.17 0.04 White bass > * 0.51 84 12 - " * 0 1.13 0.05 0.51 0.42 0.26 1/2 RL was used as a proxy value for all non-detects N------ N(. >2012 Cardno Eh Perfluorocarboxylate R e st )e Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Table 8-15. Mean and 95% Confidence Intervals for PFNA Concentrations (ng/g, w et weight) in Fish Collected from Pool 2 by Reach (2011) Species Statistic 1 2 3 4 Bluegill Freshwater drum Mean 95% Cl Mean 95% Cl 0.162 0.12 0.092 0,08 ^ ^ h'1 # [0.05,0.19] # J ill s 1 [0.04,0.11] 0.27 0.37 0.33 0.25 [0.14, 0.40] [0.20, 0.55] [0.21,0.46] [0.17,0.32] . ..Mean Smallmouth bass " 95% Cl White bass Mean 95% Cl . 0.121 0.031 # 0.052 ::>;V a si - ,A ? '"t i l l 0.47 0.63 0.50 [0.21,0.73] [0.39,0.87] [0.32,0.69] 0.032 0.68 [0.56,0.79] 1All samples < LOQ; only mean DL reported Reach 5 6 7 8 9 10 0.08 0.07 0.061 0.06 0.12 0.16 [0.03,0.13] 0.30 [0.22,0.39] [0.04,0.09] 'Vt.. 0.25 0.30 [0.15,0.36] [0.19, 0.41] [0.03,0.08] 0.21 [0.11,0.31 [0.08,0.17], [0.05,0.28] 0.29 0.26 [0.15,0.43] [0.09,0.44] 0.03 0.031 [0.02,0.04] P i 0.45 0.71 [0.37,0.52] [0.53,0.89] 0.081 A s, `111 0.44 [0.32,0.55] 0.041 0.071 0.081 F j, " f tsrfl 4 1 1 Hi 0.42 0.47 0.33 [0.20,0.64] [0.26,0.68] [0.15,0.52] 2 Sample size s 2; only mean reported Table 8-16. Descriptive Statistics for PFDA (ng/g, w et weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Species Statistic Bluegill 5Arithmetic Mean [PFDA] 1.41 Number of Detects 100 Number of Non-detects 0 Number of Samples Not Reported 0 Maximum [PFDA] 10.92 Minimum [PFDA] 0.32 Median [PFDA] 0.90 Geometric Mean [PFDA] * 1.04 Standard Deviation r L53 1/2 RL was used as a proxy value for all non-detects Freshwater drum 1.74 100 0 0 4.78 0.47 1.52 1.54 0.87 Smallmouth bass 1.74 100 0 0 3.84 0.53 1.63 1.60 0.69 i White bass 3.61 96 0 0 7.47 0.92 3.44 3.42 1.19 8-17 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-17. Mean and 95% Confidence Intervals for PFDA Concentrations (ng/g, wet weight) in Fish Collected from Pool 2 by Reach (2011) Reach Species Statistic 1 Mean J Bltiegllf ,, " 95% Cl 1.51 [0.66,2.35] Freshwater drum Mean 95% Cl 1.57 [0.87,2.28] iSmaiirfibuth bass* Mean , 1.48 95% Cl [0.97,1.98] White bass Mean 95% Cl 3.65 [1.94, 5.37] 2 345 1.81 I ' * 41" ! 0.99 " "'117 > [0.57,3.05] y ` [1 3 1 ,2 .6 1 * ; [0,71,1.27] 'p /3 ,1 ,5 6 ] 1.57 1.50 1.14 2.30 [0.76,2.39] [0.97,2.04] [0.80,1.48] [1.69,2.90] 2.20 1.81 2.13 1" 1.75 [1.51,2.89] 1 [1.34,2.28] [1.74,2.51] [1.43,2.06] 4.12 3.24 3.35 3.68 [3.31,4.92] [2.24,4.24] [2.73,3.96] [2.80,4.57] 67 89 0.86 [0.66,1.07] 0.51 f " 0.78 #, 1.46 [0.39,0.64] [0.56,1.01] < [0.82,2.10] 1.34 2.13 1.66 2.06 [0.88,1.79] [1.56,2.69] [1.22,2.11] [1.54,2.58] 1.73 1.74 1.47 1.20 [1.30,2.16] [1.35,2.13] [0.95,2.00] [0.88,1.52] 3.91 3.57 3.11 3.89 [3.24,4.59] [2.48,4.66] [2.70,3.53] [3.15,4.64] 1All samples < LOQ; only mean DL reported 2 Sample size 5 2; only mean reported 10 3.04 i [0,39,5.70] 2.13 [1.37,2.89] 1.85 [1.30,2.40] 3.60 [2.48,4.72] Table 8-18. Descriptive Statistics for PFUnA (ng/g, w et weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Statistic Arithmetic Mean [PFriA] *t ` NtlrribeifofpteGts i fiumbelW fcri-detects- ,? Number of Samples Not Reported Maximum [PFUnA] Minimum [PFUnA] Median [PFUnA] Geometric Mean [PFUnA] Standard Deviation Species Bluegill Freshwater drum Smallmouth bass " l . / 0.83 - r i 100 - 4.07 . r ; ; , 100 1.22 100 0 -. 0 0_ 00 0 6.32 2.65 3.87 0.19 0.27 0.27 0.61 0.89 1.20 0.65 0.94 1.15 0.86 0.54 0.48 White bass J." ,,1 7 9 l 96 ' ; or 0 5.46 0.58 1.69 1.69 0.67 1/2 RL was used as a proxy value for all non-detects Tif " \ 2 0 1 2 Cardno El* Perfluorocarboxylate Rest Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-19. Mean and 95% Confidence Intervals for PFUnA Concentrations (ng/g, w et weight) in Fish Collected from Pool 2 by Reach (2011) Species Statistic 1 Bluegill Mean 0.65 95% Cl [0.43,0.88] Freshwater drum Mean 95% Cl 0.95 [0.60,1.29] Mean Smallmouth bass 4 95% Cl 1.08 [0.76,1.40] White bass Mean 95% Cl 2.01 [0.94,3.07] 1All samples < LOQ; only mean DL reported 2 0.99 [0.45,1.53] 1.01 [0.53,1.48] 1.27 [1.00,1.54] 1.94 [1.55,2.34] 3 1.13 [0.77,1.50] 0.76 [0.60,0.92] 1.11 [0.92,1.30] 1.51 [1.14,1.88] 4 0.59 [0,48,0.69] 0.76 [0.55,0.97] 1.56 [1.05,2.08] 1.65 [1.36,1.94] Reach 56 0.59 0.68 [0,46,0.72] [0.44,0.93] 1.44 0.92 [1.06,1.83 [0.46,1.38] 1.29 1.29 [1.16,1.42] [1.06,1.52] 1.81 2.01 [1.31,2.30] [1.63,2.39] 7 0.36 [0.29,0.43] 1.50 [1.14,1.85] 1.08 [0.84,1.32] 1.87 [0.95,2.80] 8 0.51 [0.40,0.62] 0.81 [0.59,1.03] 1.01 [0.80,1.22] 1.60 [1.39,1.81] 9 0.89 [0.50,1.27] 1.21 [0.90,1.52] 0.97 [0.75,1.19] 1.85 [1.39,2.32] 2 Sample size < 2; only mean reported 10 1.94 : [0.38,3.50] 1.32 [0.87,1.76] 1.57 0.95,2.19] 1.75 [1.42,2.07] Table 8-20. Descriptive Statistics for PFDoA (ng/g, wet weight) in Fish Collected From Pool 2 and Analyzed by 3M (2011) ALL SAMPLES Species Statistic Bluegill Freshwater drum Smallmouth bass White bass Arithmetic Mean [PFDoA] Number of Detects Number of Non-detects 0.59 J 100 |0 1.05 100 0 1.16 100 0 1.51 96 0 Number of Samples Not Reported Maximum [PFDoA] Minimum [PFDoA] Median [PFDoA] Geometric Mean [PFDoA] Standard Deviation 00 3.91 3.13 0.13 0.25 0.46 0.85 0.47 0.88 0.56 0.65 0 3.36 0.24 1.09 1.08 0.46 0 4.75 0.29 1.40 1.41 0.60 1/2 RL was used as a proxy value for all non-detects 8-19 Perfluorocarboxylate Results Cardno EN TRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-21. Mean and 95% Confidence Intervals for PFDoA Concentrations (ng/g, w et weight) in Fish Collected from Pool 2 by Reach (2011) Reach Species Statistic Blueglll J ' Mean > 95% Cl Freshwater drum Mean 95% Cl Mean -- Smallmouth bass ; 95% Cl White bass Mean 95% Cl 1 0.35 [0.25,0.46]' 0.82 [0.43,1.21] 1.08 [0.80,1.36] 2.01 [0.44,3.59] 23 4 56 7 8 , , ' s 0.82 0.53 ' ; * 0.44 :t 1 0.52 0.32 0.48 [0.26,0.68] j[0>51, f p f > [0.36,0.69] [0.36,0.69] , [0.24,0.39] |0!36O,)]' 0.95 0.74 0.89 1.57 0.98 1.59 0.62 [0.29,1.62] [0.44,1.04] [0.57,1.21] [0.95,2.18] [0.57,1.39] [1.13,2.06] [0.46,0.79] 1.17 1.00 1.26 1.32 1.11 0.97 , . 1.08 [0.92,1.43] [0.78,1.23] [1.03,1.50] [1.08,1.55] [0.93,1.29] [0.74,1.19] [0.65,1.51] 1.62 1.28 1.46 1.34 1.84 1.38 1.51 [1.29,1.94] [0.92,1.64] [1.10,1.81] [0.95,1.74] [1.48,2.20] [0.97,1.80] [1.22,1.80] 9 10 0.62 i( r 1-38 ' [0.33,0.91] *p 4 3 ; 2;34J 1.07 1.29 [0.77,1.38] [0.89,1.70] 0.91 [0.69,1.12] [1.15,2.27] 1.51 1.39 [1.22,1.80] [1.10,1.68] 1All samples < LOQ; only mean DL reported 2 Sample size < 2; only mean reported Nt }r 2 0 1 2 Cardno Et1 Perfluorocarboxylate Rest, V Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8-22 Correlations of Perfluorocarboxylates Fillet Concentrations with Species Specific Fish Characteristics (ND=0) Correlation Mass vs [PFC] Length vs [PFC] Age vs [PFC] Statistic PFBA Spearman r -0.0167 p-value 0.8701 n 99 , Spearman r -0.0614 p-value 0.5460 n 99 Spearman r -0.2531 p-value 0.0119 n - 98 PFPeA PFHxA 0.1338 -0.2342 0.1869 0.0196 99 99 0.1603 -0.2129 0.1131 0.0344 99 99 0.0004 * -0.1122 0.9970 0.2713 98 98 PFHpA -0.0867 0.3908 100 -0.1382 0.1703 100 0.3642 0.0002 99 Bluegill PFOA 0-1137 0.2601 100 0.0637 0.5290 100 -0.0902 0.3749 99 PFNA PFDA -0.2001 0.0728 0.0460 0.4716 100 100 -0.2135 0.1253 0.0329 0.2142 100 100 -0.3409 0.2260 0.0006 ' 0.0245 99 99 PFUnA 0.2745 0.0057 ; 100 0.3142 0.0015 100 0.2396 0.0169 99 PFDoA 0.3368 0.0006 100 0.2923 0.0032 100 -0.0750 0.4604 99 Correlation Mass vs [PFC] Length vs [PFC] Age vs [PFC] Statistic Spearman r p-value n Spearman r p-value n Spearman r p-value n PFBA 0.0114 0.9107 - 100 0.0660 0.5142 100 0.2303 0.0212 100 PFPeA PFHxA f "0.0(13 - .j 0.0017 0.9822 0.9866 100 . 1 0 0 0.0348 -0.0302 0.7309 0.7654 100 100 0.0899 -0.1413 0.3740 *; 0.1609 100 100 Freshwater drum PFHpA PFOA PFNA PFDA PFUnA -0.2085 0.0228 -0.1141 . 0.1678 0.4569 0.0374 0.8219 0.2584 0.0952 .. <0.0001 100 100 1 100 " v - 100 100 -0.1787 0.0124 -0.1259 0.2139 0.4707 0.0752 0.9028 0.2120 0.0326 < 0.0001 100 100 100 100 100 -0.1185 -0.1308 -0.1331 0.4338 0.3999 0.2404 0.1947 0,1868 <0.0001 < 0.0001 100 100 100 100 100 PFDoA 0.5744 <0.0001 100 0.5332 < 0.0001 100 0.3284 0.0009 100 8-21 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Correlation Mass vs [PFC] Length vs [PFC] Age vs [PFC] Statistic PFBA `'Spearman r 0.0821 p-value 0.4166 * n ^ '100 V Spearman r 0.0764 p-value 0.4500 n 100 Spearman r ; 0.1016 p-value 0.3146 n 100 PFPeA -0.0759 0.4530 100 -0.0897 0.3747 100 -00898 0.3745 100 Smallmouth bass PFHxA PFHpA PFOA PFNA PFDA a 0.1092 0.1949 0.0348 1 0.0384 j 0.3422 0.2797 0.0519 0.7309 0.7043 0.0005 100 100 100 100 100 0.1093 0.2054 0.0174 0.0054 0.2721 0.2791 0.0404 0.8634 0.9578 0.0062 100 100 100 100 100 0.1081 0.2151 *..j f * , -0.0385 0.2470 0.2845 0.0316 0.7040 0.0132 100 '! 100 100 100 , 100 199% of samples were ND Correlation Mass vs [PFC] Length vs [PFC] . Age vs [PFC] Statistic PFBA PFPeA Spearman r ,, 0.1147 ` ' <*0.0ft5 p-value 1 0.2685 , r 0.7769 n ' 96 ' 96 _ Spearman r 0.1034 0.0461 p-value 0.3163 0.6559 n 96 96 Spearman r 0.0908 -0.0175 p-value n 'V " " 0.3789 96 0.8655 - i4. ggte . PFHxA -0.1705 0.0986 96 -0.1800 0.0793 96 -0.1546 0.1327 96 PFHpA -0.0850 0.4124 96 -0.0892 0.3876 96 -0.1247 0.2261 96 White bass PFOA -0.0992 0.3389 96 -0.0777 0.4516 96 -0.0714 0.4897 96 PFNA PFDA 0.5422 0.4764 <0.0001 < 0.0001 96 96 0.4937 0.4828 < 0.0001 < 0.0001 96 96 4 1 1 2 5 " , 0.4426 0.0019 <0.0001 96 96 PFUnA 0.3373 0.0006 100 0.2791 0.0049 100 0.2428 0.0150 100 PFUnA 0.4266 <0.0001 96 0.4065 < 0.0001 96 0.3901 <0.0001 96 PFDoA 0.3191 0.0012 100 0.2752 0.0056 100 0.2718 0.0062 100 PFDoA 0.3935 <0.0001 96 0.3960 < 0.0001 96 0.3345 0.0009 96 t r 2012 Cardno EH Perfluorocarboxylate Rest F Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Table 8 -2 3 .3M Analysis of Round 2 W ater Samples for Perfluorocarboxylates (ND=RL) Field ID Tissue ID Lab ID Reach PFBA PFPeA PFHxA PFHpA PFOA 515 % 515SF ' 515SF1 * 18.6 6 .0 5 2.96 <2.0 6 .1 2 516 516SF 516SF1 10 19.5 <5.0 <2.0 <2.0 3.96 517 517SF ' 517SF1 10 648 74.6 3 1 .7 8.4 219 518 518SF 518SF1 9 1 4 .7 <5.0 <2.0 <2.0 3 .5 9 519 519SF 519SF1 9 11.4 <5.0 <2.0 <2.0 2.52 520 520SF 520SF1 9 16.4 <5.0 <2.0 <2.0 3.55 521 521SF 521SF1 8 17.2 6.02 <2.0 <2.0 3.46 522 522SF 522SF1 8 20 <5.0 2 .1 5 <2.0 3 .9 5 523 523SF 523SF1 8 <10.0 * <5v0y <2.0 <2.0 <2,0 524 524SF 524SF1 7 16.7 <5.0 <2.0 <2.0 4.57 525 525SF 525SF1 7 <10.0 <5.0 <2.0 <2.0 2.75 526 526SF 526SF1 7 <10.0 <5.0 <2.0 <2.0 <2.0 527 527SF 527SF1 6 16.8 <5.0 _ <2.0 <2.0 4.73 528 528SF 528SF1 ; 6 10.3 <5.0 <2.0 <2.0 2.26 529 . 529SF * 529SF1 6 <10.0 ' <5.0 <2.0 <2.0 <2.0 530 530SF 530SF1 5 39.1 <5.0 3 .2 9 <2.0 23.3 531 531 SF 531SF1 5 <10.0 <5.0 <2.0 <2.0 2 .9 7 532 532SF 532SF1 5 <10.0 <5.0 <2.0 <2.0 <2.0 533 533SF 533SF1 * 4 12.1 / <5.0 s <2,0 <2.0 L <2.0 534 534SF , 534SF1 , 4 <10.0 " <5.0 <2.0 <2.0 2.32 535 535SF , 535SF1 4 <10.0 <5.0 <2.0 <2.0 2.51 536 536SF 536SF1 3 <10.0 <5.0 <2.0 <2.0 <2.0 537 537SF 537SF1 3 <10.0 <5.0 <2.0 <2.0 <2.0 538 538SF 538SF1 3 12.8 <5.0 <2.0 <2.0 2.77 539 539SF 539SF1 2 <10.0 <5.0 <2.0 <2.0 3 .1 6 540 540SF 540SF1 2 <10.0 <5.0 <2.0 <2.0 <2.0 PFNA <2.0 <2,0 2 .0 2 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 PFDA PFUnA PFDoA <2.0 <2.0 1 < 2 .0 ; <2.0 <2.0 <2.0 ; <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 < 2.0 <2.0 <2.0 <2.0 <2.0 , <2.0 : <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 i <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 , <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 < 2.0 r <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 ' < 2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 . <2.0 <2.0 8-23 Perfluorocarboxylate Results Cardno EN TRIX November 2012 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 541 541SF 541SF1 2 <10.0 <5.0 <2.0 <2.0 2 .3 4 <2.0 ' <2.0 : <2.0 <2.0 542 542SF 542SF1 1 <10.0 <5.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 543 543SF 543SF1 1 11 <5.0 <2.0 <2.0 2 .5 3 <2.0 <2.0 <2.0 <2.0 544 544SF 544SF1 1 12.2 <5.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 B o ld , ita lic iz e d te x t= D e te c ts Ni M 2012 Cardno Eti Perfluorocarboxylate R est Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table 8 -2 4 .3M Analysis of Round 1 (June) Water Samples for Perfluorocarboxylates (ND=RL) Field ID Tissue ID Lab ID 501 501SF 501SF1 502 502SF 502SF1 503 503SF 503SF1 504 504SF 504SF1 505 505SF 505SF1 506 506SF 506SF1 507 507SF 507SF1 508 .501 ' 508SF 508SF1 509SF : 509SF1 510 510SF 510SF1 511 511 SF 511SF1 512 512SF 512SF1 513 513SF 513SF1 514 514SF 514SF1 B o ld , Ita lic iz e d te x t = Detects Reach 10 10 8 8 8 3 3 3 2 2 2 1 1 1 PFBA PFPeA PFHxA 9 2 .4 16 12.9 9 .2 4 4 .4 3 <2.5 5 <4.0 <2.5 9 .1 4 <4.0 <2.5 <5.0 <4.0 <2.0 <5.0 <4.0 <2.5 <5.0 <4.0 <2.5 <5.0 <4.0 <2.5 <5.0 <5.0 ' <0'<4.0 <2.5 <2.5 <5.0 <4.0 <2.5 <5.0 5 .1 5 <2.5 <5.0 <4.0 <2.5 <5.0 <4.0 <2.5 PFHpA 5 < 2 .0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 PFOA 137 2.39 <2,0 4 .5 6 2.53 2.81 2 .2 5 2 .2 4 2 .0 6 2 .1 5 <2.0 <2.0 <2.0 2 .2 3 PFNA <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 PFDA PFUnA PFDoA <2.5 <4.0 ' <4,0 <2.5 <4.0 <4.0 <2.5 <4.0 fc <4.0 : <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 1 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 <4.0 <4.0 <2.5 ' <4.0 ' - <4.0 8-25 Perfluorocarboxylate Results Cardno ENTRIX November 2012 Chapter 9 Conclusions The analysis of all fish and water samples for perfluorinated compounds was conducted by the ISO17025 Accredited 3M Environmental Laboratory. For quality assurance, 30 water samples representing all 3 sampling locations within each reach and 41 fish representing 10% of the total number of fish analyzed by the 3M Laboratory were also analyzed by ISO17025 Accredited AXYS Analytical Ltd. With one exception, the data agreement for fish tissue samples was good between the laboratories with the average relative percent differences (RPD) for PFAS and PFCAs generally being 25% or less. PFBS was the exception with an average RPD of approximately 90%; however, the significance of this difference is difficult to evaluate given that it was based on only 2 samples. A comparison of the PFOS analytical results for fish indicated a very good match (RPD range 1.3-54%, mean of 17%) between the two laboratories. The interlaboratory comparison based on water PFC concentrations was limited due to the large number of non-detects reported by both laboratories. Using data from matched samples with measured concentration in both laboratories, the RPD ranged from 1.6 to 135% with an overall arithmetic average and median of 36% and 33%, respectively. For PFOS, the RPD ranged from 17 to 56% with an average of 35%. PFOS water concentrations were detected only in Reaches 5, 6, 7, 8, 9, and 10 with all other samples having concentrations less than the LOQ. The greatest concentration was measured in Reach 10 at Station 517 with the second greatest concentration being measured in Reach 5 at Station 530. PFOS concentrations decreased with distance downriver from these two locations indicating the potential presence of point sources of PFOS to the river. With the exception of Stations 517 and 530, all water concentrations were less than the site-specific water quality value of 7.0 ng PFOS/L established by the MPCA. With the exception of PFBA and PFOA, the other PFAS and PFCA compounds were detected in patterns similar to that observed for PFOS with concentrations being greatest near Reaches 5 and 10. Measurable surface water PFBA and PFOA concentration showed a more ubiquitous distribution in that, while concentrations were greatest in Reach 10, they were also measured throughout the entirety of Pool 2 indicating that additional sources of these compounds to the river may exist. Detectable concentrations of PFOS were measured in all fish collected from Pool 2. PFOS concentrations in all fish samples from Pool ranged from 3.17 to 757 ng/g ww. Arithmetic mean, geometric mean, and median fish PFOS concentrations were 46.3, 31.1 and 34.1 ng/g ww, respectively. The arithmetic means for bluegill, freshwater drum, smallmouth bass and white bass were 36, 46, 39, and 64 ng/g ww, respectively. While some statistically significant correlations were observed between PFOS concentrations and fish length, weight and age, for the targeted species, the correlations were weak and typically accounted for less than 20% of the variation for any specific correlation. Based on arithmetic average, the greatest concentrations were observed in white bass followed in decreasing order by freshwater drum, smallmouth bass, and bluegill. Concentrations of PFBS, PFHS, PFOSA as well as that of the other nine PFCAs were measured in all fish species but the species-specific average concentrations were less than 5 ng/g ww on a pool wide basis. Overall, the most dominant PFC measured in fish collected from Pool 2 of the Upper Mississippi River was PFOS. November 2012 Cardno ENTRIX Conclusions 9-1 Chapter 10 References Cardno ENTRIX, 2011. Work Plan for the Collection of Fish and Surface Water from Pool 2 of the Upper Mississippi River, Minnesota. Submitted to the 3M Company May 26, 2011. Lindstrom G., Karrman A., and van Bavel B. (2009). Accuracy and precision in the determination of perfluorinated chemicals in human blood verified by interlaboratory comparisons. J. Chromatogr. A 1216: 394-400. MPCA 2010. Mississippi River Pool 2 Intensive Study o f Perfluorochemicals in Fish and Water: 2009. Minnesota Pollution Control Agency, MN. 37p. Malinsky MD., Jacoby CB., and Reagen WK. (2011). Determination o f perfluorinated compounds in fish fillet homogenates: Method validation and application to fillet homogenates from the Mississippi River. Analytica Chimica Acta 683: 248-257. Riddell N, Arsenault G., Chittim B., Martin JW., McAlees A., and McCrindle R. (2009). Branched perfluorooctane sulfonate isomer quantification and characterization in blood serum samples by HPLC/ESI-MS/(/MS). Environ. Sci. Technol. 43: 7902 7908. Stiras, J.K. 2008. Major River Report, Initial River Survey, Upper Mississippi River, Pool 2, 2008. Minnesota Department o f Natural Resources. Division of Fish and Wildlife. MN. 36p. USEPA. 2000. Guidance for Assessing Chemical Contaminant Data for Use in Fish Advisories Volume 1: Fish Sampling and Analysis Third Edition. United States Environmental Protection Agency, Office o f Water (4305). EPA 823-B-00-007. November 2000. Washington, D.C. Weston 2006. Fluorochemical (FC) Data Assessment Report for the 3M Cottage Grove, MN Facility. April 2006. Wolf, S. T., W.K. Reagen. "Method for the Determination o f Perfluorinated Compounds (PFCs) in Water by Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)" Anal Methods; 2011, 3,1485. November 2012 Cardno ENTRIX References 10-1 Appendix A Fish Sample Collection Tables & Figures Appendix A Fish Sample Collection A.1 PFBS PFHS PFOS PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA VSOdd 001 H B M j 002 ^ | | 002FN1 003 003FN 004 004FN 004FN1 005 005FN 005FN1 006 006FN 006FN1 007 | H H | 007FN1 008 009 009FN 010 010FN 010FN1 011 011FN 011FN1 013 013FN 013FN1 014 T i ' \ 014FN1 015 i B g g 015FN1 016 016FN 91Cr V 017 0T7FN 017FN1 018 018FN 018FN1 020FN 020FN1 021 H M p i n FdrtJm 37.5 10 M l i m N44* 47.108' N44* 46.926' * ." r - j | l p 24 10 l j j .' N44 46.926' Fdrum i l i s i j i 35 i j i f c l l l 1 . t i l l N44M7.1G8' M4 /* '- y Fdrum 376.48 32 5 10 1 N4447.108' N4446.926' Fdrum 798.32 39.5 10 10 1 N44 47.108' N4446.926' W bass 426.38 34 3 10 1 N4447.108' N4446.926' 1247.38 45 1 1 P I P 10 N44* 46.426' N44 45.382' V fi m a m l l l l l l l 10 2 N44* 46.426' Fdrum 376.48 32 r n m 10 p | S l ' M ' t ' i y M r .: w; Fdrum 326.59 30 5 10 2 N44 46.426' N4445.382' Fdrum 326.59 31 8 10 2 N44"46.426' N44' 45.382' Wbass 235.87 27 2 10 2 N44e46.426' N44* 45.382' W 1 1 1 10 N44* 45.426' N44M5.382' illU K lB lllill l a N44* 46.426' w - A - . j a Wbass Wbass 226,80 24,5 B i l l l l l i M l l l l i i N44M6.42S' fly 26 2 10 2 N4446.426' N4445.382' Bluegill 99.79 16 2 10 2 N44646.426' N4445.382' Bluegill 13608 17 5 3 . N44 46 426' N44 45 382' Bluegill i H P I I 19.5 I M l l l s P i l l V - i W92"56.010' .r-2- V3 W92` 55.01(7 W92* 53.313* vw W92 55.010' W9253.313' W92* 55.010' W9253.313' W92 55.010' v s r 34 b W92" 53313' .'.c?' ">, W92` 54.778* l l l i l f i l M m W92* 54.7781 W92* 52 521' W9254.778' W92 54 778' W92 52.521' W92 52.521' W9254 778' W92 52.521' AV ' 4 W92* 64.778 W92 52.521' W92* 54.778' ,r W9254 778' W92a52.521' W92 54.778' W92 52.521' W92* 54 778' W92" 52521` W92 54,778' 0.40 83.5 V 0.21 2J5.0 <0.25 2.4S 87.1 <0.25 0.11 607.0 <0.25 <0.05 23.2 <0.25 0.11 77.8 <0.05 17.7 <T7- I M I S g B 11.9 0.05 20 7 V <0 05 29.1 <0.25 <0.05 21.5 <0.25 <0.05 40.5 <0.25 005 I V <0.25 013 98.7 <0.1 012 48.8 <01 1.33 394.0 <0.1 <0,05 214.0 <0.1 <0 05 S2.0 <0.1 <0.05 p l H B 1.79 049 l l l l i l t l l l <0.025 6.29 0.12 2.00 2 97 1.14 1.86 0 28 1.93 1.57 l i f a i S t l <0.5 <0,025 0.20 0.17 2 45 2.56 0.86 <05 <0.5 1.57 0.95 4.78 1.19 <0.5 <0.5 <0.5 <0.025 0.22 0.23 1.91 0.93 <0.05 <0.5 <0,5 <0 026 022 0.34 2.70 0.45 1.80 052 <0.5 I j p i W I j m m <0.025 <0.025 0.15 H i l l l p ! <0.1 0.12 2 78 1.70 0 27 2.86 i i l l l i 0.15 0.11 0.17 1.24 0.17 0.94 <0.5 <05 <0.025 <0.1 0.16 1.48 0.20 0.51 <05 <0.5 <0025 <0.1 0.26 1.06 1.00 <05 <0.5 <0.5 0.03 <0.1 <0.1 2.21 3.67 B l H I l l ' n W M jg M <0.025 - <0.1 020 3.13 1.66 0.38 <0.5 <: jih <0.1 0.48 - 3.05 2.83 <1.0 p M <1.0 <0.025 I J i i l i i l 0.33 286 10.40 <10 <1.0 1.19 0.13 0.84 7.47 0.16 <10 <1.0 <1.0 <0.025 <01 <0 25 7.96 0.19 <10 <1.0 <1.0 <0.025 0.36 <0.25 2.10 0.18 <1.0 <1.0 <0.025 Q12 <0.25 0.73 1.63 144 0.84 0.92 2.19 2 01 1.07 1.29 1.86 2.05 1.31 1.11 219 1.71 132 1.60 0 76 0 80 0.88 0.80 0.44 0.32 1.27 1.15 1.70 1.24 1.84 142 1.69 1.01 2.56 2.28 5.28 3.18 1.57 1.30 w sM im 0.77 0.76 [ Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1.3M Analysis of Fish Tissue Samples for PFCs (ND = RL) Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; W hite bass = W bass; Green sunfish = G sunfish PFOA PFNA PFDA PFUnA PFDoA PFHxA PFHpA PFPeA PFBA PFOSA PFOS PFHS PFBS End Westing Start Westing End Northing Start Northing Field ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach c IS liilli BluegJI 023 023FN 023FN1 :* f.V liBBf c j ||8 llllil 111 N44* 46.426' 217.72 Ipi10 *M--'.= V" N44845.382' *.44 4- x / 024 024FN 024FN1 Smbass 335.66 28 3 10 2 N44846.426' N44845.382' 025 025FN 025FN1 Smbass 285.76 27.5 3 10 2 N44 46.426' N44845.382' 0?fi 02BFN 026FN1 Smbass 789,25 39 5 10 2 N44* 46.426' H I llllil in i WifeII*027 027FN1 F drum 666.78 Na4 47.743* frifj028 G28FN1 F drum 657.71 37 13 8 V-1' : 029 wmm lB BIIIIeUjMB a ililll IInII IMI Bill iW 47.743* N44845.382' N44847.47V N44s4/* V N44847.47V 030 030FN 030FN1 Fdrum 399.16 32.5 10 8 1 N44* 47 743' N44 47.471' 031 031FN 031FN1 Smbass 249.48 27 2 8 1 N4447.743' N44847 471' 032 032FN 032FN1 Blueaill 36.29 14 4 8 1 N44 47.743' N44 47 471' 033 ?TK 033FN1 034 034FN Wbass rl 2jf. " l2.:;:": Wbass Id U iMiUMljpM "'Til8 N44 47.74 ib i8 N44847.743' V * `8 ` N44847.47V -of"1.!035 035FN Vl-j v- ? . `W 3 N44* 47.743' N44947.47V 036 036FN 036FN1 Wbass 199.58 26 8 2 N44847.649' N44 47 086' 037 037FN 037FN1 Wbass 235.87 27 2 8 2 N44"47.649' N44847086' 038 038FN 038FN1 Fdrum 039 n i ISWili Fdrum 498.95 36 8 8 3 N44847.171' 426.38 ililll 10 llllil pi W 47.171' N44846.447' ry." -*-'J-:1 040 040FN 040FN1 041 : : n 041FN1 Fdrum 308.44 Fdrum llBMii 8 8 111 N44847.17V lllllll llllil lilla M4447.171' N44*46.447* 044 044FN 044FN1 F drum 439.98 32 13 8 3 N44847 171' N44646.447' 045 045FN 045FN1 Wbass 185.97 25.5 2 8 3 N44847171' N44846.447' 046 047 Ml 049 046FN 047rM 04AFN Q49FN 01grNi 'Ll M -.A- ';i 049FN1 mm F drum Fdrum F drum 26 2 7 4 gill33 T ' 3 llllil 1III M i B | !illii 8 lilJ ji|t MU'* 48.258' 1444"46280' r w ! - - - .'- ' "i S r 58.(3 N44": - : o `..J vi N44* 55.5091 N*4` **8 W92* 54.778' A 2" -V. Ve W92" 54.778' W92 54.778' W92854 778' W93 01.399' W93901.399' W93 01.399' W93 01.399' W93801.399' W93" 013991 A'*"*!"" W83 01.399' W93 01,340' W93801.340' W93"01.438' .V:.r * Mr-3' t,i 4'jff A--.-' W93 01 438' W93801 438' WP3* 00,454' ' W93* 6.77T W93B08.777` ?{W9--367 --IIIv \V 0 26 305.0 v" / *7V <0.1 44.4 W92952.52V <0.1 <0.05 44.4 W92 52.52V <01 <0.05 41.7 W92852.521' <0.1 <0.05 35.0 W93801.52V W93801.52r ,\v sr /' <0.1 IJprii <0.1 0.13 0.12 <0.05 14.9 48.7 39.3 W93801.521' <0.1 <0.05 34.9 W93801.52V <0.1 <0.05 16.0 W93801 52V <0.1 0.18 9.7 W93801.52V W93801.521' <0.1 ta-- <0.05 0.06 42.1 48.4 W93 01.52V <o.r <0.05 34.0 W93801 118' <0.25 0.14 53.5 W93* 01 118' <0.25 <0.1 50.1 W93800.999' <0.25 <01 33.5 W93800.999' <0.25 <0.1 79.0 17 <0.1 33.3 av W93800 999' <0,25 < 0 25 <0,1 <0.1 44 9 33.9 W93800.999' <0.25 0.17 59.5 W93800.833' <025 <01 66A K V K X S- < il in siliW93 06.085' M -- a 36.5 W93806.085' <0!05 0.03 37J8 I l l l l i l049 f.03 !i i i <0.025 0.15 0.56 10.92 6.32 m m0.69 <1.0 ---- <025 -- n 1.67 072 <10 <10 <1.0 <0.025 <0.1 <0.25 1.55 1.20 1.10 <1.0 <1.0 <1.0 <0.025 <01 <0.25 1.83 1.40 0.91 <1.0 <1.0 <1.0 <0.025 <01 <0.25 1.44 0.89 0.11 lllllll MB-- <1.0 lipHBIBIS 0 85 0.53 015 <1.0 --Hi<: 0.23 1.79 0.67 013 <1.0 iil^M<1.0 <0.1 <. s 158 0.91 0.22 <1.0 <1.0 <1.0 <0.025 <0,1 <0,25 1.93 0.95 0.49 <1.0 <1.0 <0,1 <0.025 <01 <0,25 1.29 1.23 0.09 <10 <1.0 1.07 <0.025 <01 <0.25 1.57 0.72 lllllll0.96 w ; <1.0 <0.025 <025 00 1.52 0.89 H I ilpBp yijpjl 0.12 Bpill 0.51 jta d ii 1.78 0.59 <1.0 <1.0 <1.0 1**11 <025 2 63 1.28 0.98 <1.0 <1.0 <1.0 <0.05 <01 0.24 3.12 1.43 1.19 <10 <1.0 <1.0 <0.05 <0.1 0.31 3.01 1.72 0.12 <1,0 015 l l l i i <1.0 <10 <0.05 <0.1 <1.0 t a l Bllpljl i j i i l 0.18 0.51 1.25 0.67 3 02 1.46 013 <1.0 <1.0 021 IlliML'l n < '.C <0.05 L 1 <01 llii<1.0 M IS H B 0.29 104 0.59 1 65 0.50 0.15 <1.0 <10 <1.0 <0.05 <01 0.20 2.16 1.15 3.90 <1.0 <1.0 <1.0 <0.05 <01 <0.1 2.07 1.16 122 <10 < 1J3 <1D <005 <01 0 39 63 2J4 o u < 1.'0 ' 013 ~ i u 180 098 019 <1,0 M B -- llllil<1,0 -- I 0.11 109 0.58 012 <i:- illip 0.06 0 70 191 0.80 3.91 1.75 1.36 1.34 0.65 0.46 0.47 0.48 0.78 1.09 0.28 1.52 '1.51 1.29 1.59 1.32 0.45 0.76 058 0 50 1.16 0.91 1M 0.65 0.42 048 A- Card TRIX Novenr, 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and W ater-Sum mer 2011 Table A-1.3M Analysis of Fish Tissue Samples for P FC s (ND = RL) ______________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish Field ID Tissue ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA 5 3 Oc3' CmLOLO.. CO Xu. CL CoLQOL. 050 050FN 050FN1 F drum 226.80 29 8 3 1 N44855.509' N44 56.048' W93806.777' W93 06.085' <0.05 0.03 43.7 0.14 <1.0 <1.0 <1.0 0.09 <0.25 0.38 2.59 1.07 0.70 051 051FN 051FN1 F drum 426.38 35 16 3 1 N44* 55.509' N44856.048' W93806.777' W93806.085' <0.05 0.04 37.1 0.18 <10 <1.0 <1.0 0.06 <0.25 <0.25 2.72 0.84 0.45 052 052FN C52FN1 W bass 526 17 35.5 7 3 1 N44 55.509' N44 56 048' W93 06 085' <0 05 0 05 29.1 1.17 <10 <10 <0 25 * r 2.46 1.12 0.80 053 A ".S'! f a t t i 40 l I l M M M S B I I I N44855.509* N44856,04? Abe* ` ' i a -v j-.i <0.05 <0.025 57.5 0.63 <1.0 <1.0 <0.05 1 | 0.50 8.03 2.08 2.11 054 Q54FN 054FN1 Smbass - ilfflli! 055 . N i b B I M Ill 056 056FN 056FN1 Bluegill 86.18 15 S J j f l p i i i l iJ U 'f* l?'!1 VJJ 'y 583* W93* 06.01? W93 05,240' <0.05 <0025 30.0 0 43 <1.0 IjjilllB p l \ `.A" I M m f c i l j A">- <0.05 71.9 O.ff 9; m: W93 06019' W93805.240* 0.85 29.2 0.15 <1.0 <1.0 <0.05 <0.25 <0.25 <1.0 <1.0 IfM f m m . : <10 0.05 <0 25 <0 25 2 92 1.43 1.60 2.44 1.04 0.51 3.25 1.64 1.32 057 057FN 057FN1 Bluegill 7711 14 4 3 2 N44856.139' N44 56.589' W93806.019' W93805.240' <0.05 0.18 17.2 0.10 <10 <1.0 <1.0 <0.05 <0.25 <0.25 2.16 1.33 0.83 058FN *. Bluegill 7711 15.5 5 3 .. N44 56 139' N44856.589' W9306 019' W93 05 240' 016 26.6 0.12 <005 <0 25 <025 1.91 1.35 0 91 059 059FN Bluegill 86.18 i l B i m m i t e r i l i f j j j N44856.139* N44856.589' f." A V O 1' / * ' <0.05 <0.025 20.6 006 <10 <1.0 -./H IM 061FN1 I B I B i l i i | | H 15 J j l l q j | | s | N44856.528* `1^ " r Av ' 0*0 /. m* j r /y <0.05 0 69 28.7 0.20 <10 <1.0 I B H i . -!2-: <0.25 2 29 1.35 0.85 3.09 2.05 175 062 082FN 062FN1 Smbass 367.41 j j | j | l | ?t % . f l i 3 3 N44856.528* N44855.611* *. 8 6c3* W93806.683' <0.05 <0.025 34.3 0.81 <1.0 <1.0 <1.0 063 063FN 063FN1 Sunfish 86.18 16 4 2 1 N44853.659' N44853.823' W93 09.916' W93 09 231' 0.40 0.35 34.1 0.22 <1.0 <1.0 <10 <0.25 'tv * .... 203 1.17 0 94 1.15 0.72 1.05 064 064FN 064FN1 W bass 467.20 35 5 2 2 N44853.664' N44853.865' W93809.874' W93 09.064' <0.05 <0.025 66.7 2.10 <1.0 <1.0 <10 <005 <0.25 <0.25 3.85 1.72 1.31 065 065FN 065FN1 A` 26.5 . * . N44 53664' W93809 874' <0.05 0.05 34 9 1.48 <10 <1.0 <01 2.09 1.10 1.10 066 066FN . Bluegill B IM H N44853,684* .. V-1* ,-w* A !* '-` ?v4 W93809.064* <0.05 <: 26.9 0.13 < ` c <1.0 H R j K 608 2.87 124 067 067FN IV 069 s p M B l l p p S H 070 070FN 070FN1 Bluegill Bluegill 13.5 E e s ^ ii l l iM H ilB IlM i p l l i l N44' `uJ N44853.664' 49.90 13 5 2- iw-- A!-*** "3874 N44853.885* :.!* a , y : > y j W93* 09.084* W93-09064' W93 09.064' <0.05 ' . 'Ci <0 05 012 0.21 8.1 008 <1.0 <0.05 <0.25 0.32 3 31 1.72 047 7,2 l i p i B <1,0 IBBBKI1BIFi" l | | j j j | j <0.1 | B i B 1.17 0.74 0.32 11.0 0.07 <10 <10 0.06 <0.25 1.47 0.82 0.36 071 071FN 071FN1 Bluegill 36.29 13 5 2 2 N44853.664' N44853.865' W93809.874' W93809.064* <0,05 0.12 9.5 0.10 <1.0 <1.0 <1,0 0.06 <0.1 0.25 2.02 1.02 0.40 072 072FN 072FN1 Bluegill ' 52 N44953664' N44853 865' W93809 874' A---------- * 0 06 7.0 004 <10 ~ :r 171 0.74 0 24 074 W N 074FNI j p i a p v l 42.5 K f l I l l l l l N44853.871* ' N44854.699' A*9V A V O 7 I B K 1 <0.025 41.5 0 69 <1.0 B l l i l l B ip 076 OWI C '^ 078 078FN '75 ' M :7CFN1 078FN1 F drum F drum 517.10 716.68 33 B l l l l l l ( I B w M 35 m 6 s 8 f l U 36 8 1 1 N44853.871' N44854.611* N44 54611' 5 4 -%? N44854.14? N44 54149' W93808.945* W93812.04? A _ . * 1 A V 37 W938 11.459' W93 11 459' 'CC5 -it: <0 05 003 0.50 0.05 37,1 0.10 <1.0 <1.0 81.3 0.41 B i p o l i <1.0 35.2 0.12 <1.0 <1.0 <10 <1.0 <0.05 i K f i B I 0.84 0M <0.1 0A2 013 <0.1 0.30 0.10 <0.1 <0.25 3.97 2.19 2.39 1.95 0.93 0.40 1.78 1.51 1.51 1.33 0.78 0.25 079 079FN 079FN1 Smbass 1165.73 44.5 7 1 1 N44854.61V N44" 54 149' W938 12.049' W938 11 45? <0.05 <0.025 16.9 0.33 <10 <10 <1.0 005 <0.1 <0.25 1.28 1.07 1.31 November 2012 Cardno EN TRIX A-3 Table A-1.3M Analysis of Fish Tissue Samples for P FC s (ND = RL) -r...... .kknuiirfinni!' craehuiator Hrum = F drum: Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish W* *? W93 11.459' <0.05 <0025 27.3 0.67 <1.0 < 1.0 081 081FN 082 082FN 083 n 084 084FN 085 085FN 086 086FN 087 j B l l I f e 088 088FN 091 091FN 092 092FN 093 093FN 094 * 095 . T 1 096 096FN 097 s S nB 099 099FN 100 100FN M ite 102 101FN 102FN 103 103FN 106 106FN 107 107FN 108 108FN Olrhi 082FN1 083FN1 084FN1 085FN1 086FN1 Smbass Bluegill Bruegill 108862 l i f t p tii 4A*v* 33 1 M M I r l i IB llJ I llliiiii 199,58 26 3 11 7711 15 6 11 17 11 ` 6 11 m em087FN1 G88FN1 Bluegill M B i l i i v I l l t l L J 49.90 p a 092FN1 093FN1 Bluegill Smbass Fdrum F drum 77.11 607,81 349,27 A- 15 35 34 35 4 8 6 12 12 12 095FN1 Fdrum 417.30 r a IR iip 096FN1 * n i b 4 H | | | m m m I l i i M Bluegill 58.97 098FN1 Bluegill 8618 15,5 6 12 099FN1 Bluegill 68.04 14 5 12 100FN1 Bluegill " 145 5 12 10irM 102FN1 A tx * Smbiass 317.51 498.95 30 I f f l t i i 1 4 1Q3FN1 104FNI 106FN1 107FN1 108FN1 Smbass Smbass A o. r - ': . 675.85 648.64 185.97 36 39 2- 4C 72 72 N44 54.61V N44 54.6- N44" 54.61V N44 54,611' N44s 54 611' N44" 54.61V N4454.61V M44" 54.611' N44a54.606' N44 54.606' N44" 54 606' N44 54.606' \4 J- 1-'' : N44* 54.606' N44 54.606' N44 54.606' N44 54 606' '. 4 ' *0/1 N4453,972- `. " W 1 r 1 " r-* m m 1 N44" 50.286' N44` 50.286' N4454.14? iBlSH W93* 12049' N-i-J` 01 M' N44B54149` N44 54,149' W93* 12.049' W93 12.049' N44 54 149' V~J' \A M'V M44*54k149* N44* 54.149' N44" 54,001' N44* 54.001' W93 12.049' W93` 12049W93 12,049f W93 12.036' W93 12.038' N44854 001' N4454,001' N4454.001' N4454.001' N44c54.001' N44 54.001' W93* 12036' \\j`' 1?0" Wi-*' Tv W93 12.036' W93 12.036' 53636 W93* 11.44V -V-r *I * ,v-y - 44i 12.036' N44 49 790' W93 00.813' N44" 49.79C W93* 00.813' N44a49.79(7 vV'** 0n8` 3 W93 11.459 <0.05 <0.025 555 0 38 <1.0 < 1.0 <0.05 M i ^ S p u I B l B B l I 0.40 <1.0 f t i H I W93 11.459' <0.025 144 0.45 <1.0 137 W93M1.459' <0.05 <0.025 14.4 0.28 <1.0 <1 ,u W9311 459' W93 11 459' <0.05 <005 0.10 0.03 55 0.04 <10 <1.0 6.4 0.05 <10 <1.0 W93 11.459 W93" 11.459' W93 11.459' <0.05 <".5 <0.05 0.03 0.17 006 36 0.03 <1.0 <1.0 9.2 0.05 <0.25 <0.1 9.4 0.05 <0.25 <01 W93 11.443' <0.05 <0,025 13.5 0.30 <U.25 <U.l W93 11.443- <0.05 0.03 25.5 0.06 <0.25 <01 m m 443' <0.05 0 29 50.0 0.22 <025 0.19 W93-1U43' 0.05 0.04 17.7 0.06 H i B ! <0.1 W9311.443' <0.05 004 6.0 0.05 <0.25 <0.1 W93" 11.443' W93 11443' <0.05 <0.05 0.10 0.11 6.2 0.05 <0.25 ( j | | S P 4.7 0.05 <U.4D <0.1 W93 11 443' <0.05 0.22 11.0 0.08 <0,25 <0.1 WQ3 11 443' <0.05 005 5.7 0.04 <0.25 < 0.1 W".3f 102-4' <0.05 007 477 1.83 < 0.1 illllilS til .V`3 JC7-' <0.05 44.2 0 29 M i t m <0,1 /..v C /.'i I j i M K l <0.025 55 015 < 0.1 ru m < tt cftOfi MM fltft <tt2> <6.1 W93 00.580' <0 05 < 0.025 29.0 0.6f <0.25 < 0.1 W93 00.580' W93"00.580- 0.05 <0.05 <0 025 0415 32.7 70.4 0.88 405 <01 <0/ <0.25 0.03 0.14 <0.25 <0.1 < 0.1 <0.25 0.03 <01 <0.25 0.12 <0.1 0.29 0.04 <0.1 *: /> 0M 0.11 <0.25 0.08 <0.1 VU-ZO 0.06 <0,1 <0.25 0.04 <0.1 <0.25 <0.025 <0.1 *-:vz liiiiiiil <025 0.03 w m <0,25 <0.1 <^Q2& <0.25 <0.025 <0.1 <0.25 <0.025 <01 <0.25 <0.025 <0.1 0.28 2 25 0.78 103 0.68 0.47 <0.25 0 91 0.75 1.04 <0 25 126 0.51 0.39 0.56 1.53 0.89 0.79 <0.25 0 79 0.40 0.36 <0.25 0.80 0.52 021 ; <0.25 134 0M 0.27 0.77 0.34 0.20 0.31 4.45 1.37 0.52 <0.25 0.68 0.41 0.18 025 287 1.46 123 feM N ( 2 24 180 178 <az' 0.82 048 9M 4.13 240 2M <0.25 1.87 0.91 0.77 <0.25 2.34 130 1.03 0 37 2 74 134 132 Noverr, 12 Cara Vr i x A- ( Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Table A -1 .3 M Analysis o f Fish Tissue Sam ples for PFCs (ND = RL) __________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA I Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Lab ID Tissue ID Field ID PFOA PFNA PFDA PFUnA PFDoA c3c < Q. X U. Q. j 109 109FN * 8 110 110FN Bluegill m m U B I M I p p l | 6 pB i Wbass 226.80 i i ^ W 81IB 111 111FN 111FN1 Wbass 739.36 38.5 4 7 4 N44 49 719* 112 112FN 112FN1 W bass 467.20 33 3 7 4 N44 49.719' 113 113FN 113FN1 W bass 1016.05 42.5 7 7 4 N44849,719' 114 114FN 114FN1 m Ai m i i I M M j j j j i i l N44* 49.719* 115 115FN1 B j p l M j l l M j B B j N44849.719' 116 I B M 116FN1 Smbass 476.27 32 i l l l l l l l l l l l l f i l l N44849.719' 117 117FN 117FN1 F drum 36741 32 7 7 4 N44 49 719* 119 119FN 119FN1 Smbass 1106.77 44 8 9 1 N44846.322' 120 120FN 120FN1 W bass 258.55 18 2 9 1 N44846.322' 123 123FN1 Smbass 648.64 B I B M i mm 24 124FN m m m Fdrum g M 44 lljllM lijjK J:v 125 125FN 125FN1 126 126FN 126FN1 Bluegill m m IIIIIB IH H B Im 158.76 20 4 9 B I 2 N44846.162' 127 127FN 127FN1 W bass 616.89 37 4 9 3 N44845.972' 128 128FN 128FN1 Smbass 129 129FN 130 H P bh b w 131 131FN F drum 807.39 39 4 9 3 N44845.972' llBj[426.38 M M M l | l j B ! I 1IIBMI1 N44845.972' W l43 M l S B lill! *> > 698.53 lilMlIM B S M j j p l j l * --- ; 132 132FN 132FN1 Fdrum 889.04 41 13 9 3 N44845.972' 133 133FN 133FN1 F drum 399 16 32 6 9 3 N44845972' 134 134FN 134FN1 llPIlMHl 135FN1 136 136FN 136FN1 137 WN Wbass 55792 37.5 6 9 3 N44845.972' M ill M B jjjB|j j j I .4-'" ? I j p l l l i li68.04 l i i l l l l l l I j p B l l M i l l N44846.725' 40 m m jbj N44849.790' N44849.900' N44849.047' N44849.047' N44849.047' r.4* tr r.iv N44849.047' N44846.000' N44846 000' N44846.244' N44846.244' N44846.210' N44846.210' `. `i: 4 - / ` ' MA' W 7' N44846.210' N44846.210' N44846.210' N44846.982* i; W93 00.813' A ' : <0.05 0.06 7.1 W93800.595* - W93 00.5321 0.11 49.8 W93800.664' W93800.475' <0.05 0.12 139.0 W93800.664' W93 00.475' <0.05 0.05 59.0 W93800.664' W93800.475' <0.05 0.06 45.3 W93800.664' <0.05 0 09 43.3 W93800.664' /.o.-/ v <0.05 a i B W l i 7.3 AjV '";*. W93800.475' <0.05 25.7 W93800.664' W93800.475' <0.05 <0.05 31.0 W92858.180' W92857.239' <0.05 <0.05 20.3 W92858.180' W92857.239' <0.05 0.13 68.4 ,\9, ** A*-.- 'V C m / m <0,05 8.0 As.** W928 56.370' 6.7 W92857.877' W92 56.370' <0.05 011 39.8 W92857.877' W92 56.370' <0.05 0.05 21.6 W92 56.343' W92855.880' <0.05 0.13 45.0 W92856.343' W92855.880' <0.05 <0.05 34.2 W92856.343' A'V <0.05 H b M I 18.9 A -.-v v y W92 55.880' 9.7 <0.25 22.9 W92 56.343' W92 55.880' <0.25 <0.05 4.8 W92856.343' W92855.880' <0.25 <0.05 10.2 W92856.343' AV-y-O** W92856.028' W92855.880' A '>?322' W928 56.022' <0.25 < 0.05 74.4 <0.25 99.1 <0.25 1IBB 214 W92fl 56.022' <0.05 11.9 0.08 I l f ! B M w b <0.25 <0.025 <0.1 <0.25 1.89 <0.25 <005 <0.025 <0.25 0.40 1.75 <0.25 <0.05 <0.1 <0.025 <0.25 0.65 1.89 <0.25 <0.05 <0.1 <0.025 <0.25 < 0.25 1.12 <0,25 <0.05 <01 <0.025 <0.25 0.35 0.95 <0.25 <0.1 <0.25 0.60 0 34 <0.25 012 B U M <0.25 <0.25 0.36 l i l l l l 0.44 <0.1 <0.025 <0.25 <0.25 0.13 <0.25 <0.05 <01 <0.025 <0.25 0.30 0.62 < 0..25 0.15 <0.1 <0.025 <0.25 <0.25 1.93 <0.25 <0.05 <0.1 <0.025 <0.25 0.27 0 70 0.54 0.17 0.18 B B M I I l l l l l l W <0.25 0 72 <0.25 <0.05 r a r i & l M i 0.33 0.19 <0.25 <0.05 <0.1 I B m I I <0.25 0.75 0.12 <0.25 0.05 <0.1 <0.025 <0,25 < 0.25 1.44 <0.25 <0.05 <0,1 < 0.025 <0.25 0.44 1.02 <0.25 0.12 <0.1 <0.025 <0.25 <0.25 1.03 <0.25 <0.05 <0.1 <0.025 m K k <0.25 0 38 0 29 <0.025 0.53 <0.1 0.265 0.32 0.21 0.03 053 <0.1 0.58 0.18 0.05 0.47 <0.025 <0.1 <0.25 0.26 <0.1 0.09 0.65 <0.025 <0.1 <0.25 < <0.58 <0.1 0.025 <0.25 0.025 <0.1 <0.25 H i0.13 <0.1 <0.025 <0.025 <0.25 010 <0.1 <0.025 <0.25 <0.025 <0.1 <0.25 Biisiili0 57 <0,1 <0.025 <0.025 <0.1 0.44 0 76 0.45 0.26 258 1.22 1.12 7.46 5.46 2.82 3.59 1.77 1.43 3.19 1.33 0.99 3.06 1.27 1.11 0.53 0.27 C24 1J32 0.93 C ! 1.52 0.70 0.45 1.89 0.86 0.75 4.67 2.19 1.95 0.96 0.80 0.76 345 1.84 1.72 2 32 1.04 0 82 1.12 0.60 0.31 2.89 1.34 1.21 2.12 1.63 1.29 101 1.13 102 1.25 0.88 0 79 1M 0.58 0.51 2.89 1.53 1.50 1.31 0.94 1.00 4.53 1.82 1.38 292 1.75 115 0 77 0.57 0 29 2.05 1.42 1.15 November 2012 Cardno EN TRIX A-5 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1 .3 M Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; W hite bass = W bass; Green sunfish = G sunfish e oe < 0u. Field ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFNA PFDA PFUnA PFDoA 138 138FN 138FN1 W bass 979.76 43 11 9 5 N44847 011' N44a47115' 140 140FN 140FN1 Fdrum 739.36 36.5 8 9 5 N44a47 011' N44* 47115' 141 141FN Fdrum 657.71 37 9 5 N44 47011' N44 47115' 142 142FN1 ^ i m h r 358.34 iiil 144 I I 145 145FN H m s IiJ i i-v Wbass 145FN1 ij. 267.62 __: 33 17 28 /7 ( I 95 10 3 10 i l l 9 * ; N44847.1151 N44* 48.4301 :.;i :.y,* N44a46.299' 146 146FN 146FN1 Wbass 598.74 36 3 9 8 N44a46.060' N44846.234' 148 148FN 148FN1 149 149FN1 150FN | | | | iib b I 1 m | Wbass 458.13 35 Wbass 40 1065.94 4V. I TM i i 35 Wbass 566.99 37 4 9 9 N44a45.970' N44a46,163' ||f i l l9 N44847.038' 10 ill m a47.103' N44fl47.1081 \V-Z H 1| | H ip P B MN44 47.103' 4 :.?J \ N44a47 025' 158 158FN 158FN1 Smbass 639.57 35 10 5 N44a46.526' N44a46.230' 159 159FN 160 160RN 161 161FN 162FN 163 163FN 159FN1 161FN1 163FN1 Smbass Smbass Smbass- 'Wbass Smbass 458,13 31 3 10 5 467.20 H 1 t n E 10 - I f 276.69 2 10 5 || |i H IlgiliB IIlliB IIP 1256,45 46 7 9 12 N44a46.526' -.44 N44a46.526' N44" 45.900' N44a46.341' N44846.230' 4; N44" 46_230` N44845.914' N44a46.299' 164 164FN 164FN1 Bluegtil 36.29 13 9 12 N44a46.341' N44" 46.299' 165 165FN .166 -IBSEN 165FN1 Wbass 576.06 . ,-- 1 666.78 35.5 46 5 .....6 .. N44 51.331' ri-:4' 5' N44a52.020' . W92" 55.997' W92a55.997' W92a55997' W92* 55.997' .`. r - ' . - v . :-- v * W92856.769' W92*55897* W928 55.049 W92a 52.724' W92852.724' A ,792- . 2 .74' W92- 53.408' W92 58.173' W92` 58.173' W93 00.625' W92855.353' <0.25 012 W92855.353' <0.25 <0.05 W92855.353' <0.25 <005 W92* 55.353' <0.25 Q.13 W92 54.8931 f t p 0 23 W92 54.8931 0.07 <0 25 <0.05 W92856.381' <0.25 <005 <0.25 <005 W92" 55-335' 009 W92a54.306' ^ J J j 0.07 W92 54.306' < 0.1 0 2S I*.-.: < 0.1 0 03 W92 52.438' <01 0.03 W92852.438' < 0.1 004 W92* 52.438 < 0.1 0 03 W92* 52.4361 <0.1 0.04 W92 53.419* <01 <0.025 W928 58.093' <01 <0.025 W92858.093' 0.13 0.05 W93 00.780' NR liM f 0.13 0 39 112.0 127 215.0 32.5 125.0 55.9 33.0 37.9 49.8 71.4 167.0 757.0 48.5 61.2 76.7 48.0 74 2 70.0 15.1 18.3 47.4 55.8 1.25 <01 <0 025 0.33 <0.025 <0.1 0.96 0.81 <0.1 <0.025 0.36 <0.025 <01 0.32 0.42 0.28 0.08 0.79 <0.025 <01 <0.25 0.12 0.18 <0.025 <0.25 <0.025 <0.1 0.27 2 23 <0.1 0.45 <0.025 <0.1 0.41 H H I1.10 p t f U l < 0.025 0 31 <0.025 i 0.54 1.78 <01 <0025 0.33 <0 025 <01 <0 25 0.79 <0.1 <0.025 <0.25 <0.025 <0,1 0.28 0.61 <0.1 <0.025 0.29 <0.025 <0.1 0.37 m m0M <0.25 <0 25 <0.025 <0.1 0.73 m m2 93 <0.1 <u 2: < 0.1 B p - J B ^ B I I J B31.45 <0.25 l i l j p i i h0.03 | | | | i 0.89 <0.25 < 0.1 <0 25 <0025 * <01 4.06 0.30 < 0.1 <0.25 <0.025 <01 < 0.1 8.54 <0.25 < 0.1 <0.25 <0.025 < 0.1 < 0.1 3 79 <0.25 <0.25 <0.025 <0.1 < 0.1 631 <0.25 0.61 M i l < 0.1 < 0.1 <0.25 ' *?: < 0,025 <0.1 <0.1 < 0.1 0.42 <0.1 013 <0.25 <01 <0.25 <0.025 < 0.1 0.11 0.94 <0.25 <0.25 <0.25 <0.1 < 0.1 0.42 0.84 <0.25 0.17 098 4.51 1.73 255 1A8 5.14 2 67 1.95 2.99 3.90 4.26 2 87 3.56 3.18 1.33 139 1.16 1.46 3.60 1.15 0.54 2.96 4M 1.90 1.86 1.64 1.46 1.53 1.33 0.68 046 2.52 1.68 H ill 1.40 1.04 0.92 0.99 1.41 0.99 1.68 1.35 2.02 147 1.67 .1.19 3,87 336 1.80 1.79 1.33 1.78 1.66 2.73 0.87 1.07 1.12 1M 1.58 1.19 1.10 1.03 0.26 021 1.48 1.52 2.18 2 66 168 168FN 170 170FN 168FN1 170FN1 Wbass Fdrum `j "4 449.06 33 I6 H44* >\33a N44a51.331' 'M' 6.V.20 N44 52020' W93800625' - W93 00.7801 W93 00 780' 00 TO 61.3 0.84 <0.25 < <C5 <01 c <0.1 0.52 3 71 1.83 168 0.21 28.6 0.17 <025 <0.25 <025 <0.1 <01 <0.05 1.33 0.88 0.96 171 171FN 171FN1 Fdrum 807.39 39 17 5 N44a53.736' N44a53.279' W93801 757' W93 01129' NR 0.15 35.5 0.33 <0.25 <0.25 <0.25 <01 < 0.1 0.31 2.65 2.26 3.10 2A- Card It r ix Noverr. Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1.3M Analysis of Fish Tissue Samples for PFCs (ND = RL) ------------------------------Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass: White bass = W bass; Green sunfish = G sunfish PFDA PFUnA PFDoA PFNA PFOA PFHxA PFHpA PFPeA PFHS PFOS PFOSA PFBA PFBS End Westing Start Westing Start Northing End Northing Field ID Tissue 10 Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach c3c ! 172 172FN 172FN1 174 174FN 175 -175FN 75-,V 176 176FN 177FN1 178 178FN 178FN1 179 179FN 179FN1 180 1*:- -, 181 M M 183 Hssjjil 181FN1 183FN1 185 185FN 185FN1 186 186FN 186FN1 187 187FN 187FN1 188 -188FN 188FN1 189 189FN1 190 190FN1 191FN 191FN1 192 192FN 192FN1 193 193FN 193FN1 194 '195 lashM lhNI- J |||||g 197FN 197FN1 198 198FN1 199 199FN 199FN1 200 20FN 200FN1 r ,i 201FN 201FN1 F drum 1505.93 Afir. Smbass | j p ^ \ 49 24 5 1 N44853.736' KM |d l||| Mi BB NM '" 'i N';-J '> '=: N44853.279' W93801.757' N44853.2791 A ri : ft},' N44853.2791 W93801.129' A 13- :i -?j A* r NR <0.1 <0.1 umUoo uw741 O, Smbass 258.55 27 Smbass 508.02 32 Smbass I p l i l Binili Bluegill 18.14 . 10.5 F drum 1197.48 4o Smbass 349.27 29 Bluegill 7711 15 * F drum 399.16 "IIIMl l l i l i f c 0 0i N44 53.736' N44" 53.736' 5 1 N44853.736' 5 1 N44853.736' SlBH i p M l I % | l l l j 5 ||i[j ''UBI l y i pH N44* 53.736' N44" 53.736' i5 0 2 N44" 53.430' 25 N44853.430' 2 5 2 N44853.430' | bM| a s N44* 53.430' j j J B M | ( | | J "4-j *-; N44 53.279' N44853.279' N44853.279' N44853.279' N44* 53,279' N44` 53.2791 N44853.279' N44853.066' N44853.066' N44853.066' \4-`':A X C N44853.066' A-'-- '.v W93" 01 757' W93801,757' W93 01 757' W93* 01.75r W93801.757' W93801.069' W9301.069' W93 01.069' W93801.069' V*' : ? A v. J' l l * 7 W93801 129' NR <0.1 <01 W93801 129' NR <0.1 W93801 129' NR <01 .T -rc jjIllJj p i A i.l8.'1 ? NR W93801.129' iiMlljjl < 0.1 018 W93800,922' W93800.922' <0.05 <0.05 018 <0.05 W93800 922' <0.05 <0.05 W93800.922' ooe 006 <0,05 1 Mioir, F drum Smbass Wbass Wbass * F drum Fdrum Bluegill Bluegill eiuegnF 399.16 32 5 jliij N44` 53.066' W93801,069' A V '3 922- 0 02 449 06 33 5 52 498.95 32 3 52 pialli T lllf i N44- 53.430' N44853.430' N44853.430' N44854.153' N44853.066' N44853.066' N44853.066' N44853.732' W93801.069' W93801.069' W93801.069' V W93800 922' W93800922' W93800 922' A'b -02 639.57 58.97 70 R7 ." K P ig li w p |3 MI S i g K M i l B i N44854.153' oy ? 5 4 N44" 54.153' 13.5 2 "c NA raai, 5 4 N44854.153' c * N44 54 153' SI5 N44* 54.153 %4-f"53 732 m r o z m . W93"01.76? I11M11I A.-i A--J- 7 ^ N44853.732' W93802 478' W93801 769' N44853.732' W93802.478' W93801 769' N44853.732' N44' ' jJ V,v ??4,'!! W93801 769' W93801.769' <0,05 <0.05 <0.05 <0.05 <0.05 <0,05 <0.05 <0.05 <0.05 <0.05 <0.05 0.06 <0,05 <0,05 <0 05 0.0$ 006 <0.05 <0.05 0.09 0.27 185 50.7 36.7 32 2 28.6 35.3 301 13.7 36.3 33.7 27.5 19.2 7 56.1 64.3 316.0 113.0 41.9 461 4.3 38.6 10.3 22.2 34.9 45.4 0.25 "'? c <0 25 ... <01 0.20 3.76 176 048 037 l l i l B <0.25 <0.25 <0.1 <0.1 0.48 B B B HUM<0.25 i I J i l l l i <0.1 I "!!(t ^ l l l f ijiU <0.05 307 1.37 1.88 0.38 <0.25 <0.25 <0.25 < 0.1 < 0.1 <0.05 1.91 0.47 <0.25 0.68 noe 0.40 P B <0.25 <0.25 < 0.1 <0.1 0.08 ' n 2c <0 25 <0' <0 05 <0.25 H R mm M l HMm 2.00 1.53 1.25 016 <0.25 <0.1 0.08 122 0.12 <025 <0.25 <0.1 0.08 143 0.45 <0.25 <0.25 <0.25 <0.05 043 059 2.67 0.52 <0.25 <0.25 <0.25 <0.05 <01 0.04 1.16 0 03 <01 0.04 0.47 010 <0.25 ` 25 <0.25 ^ : * <0.1 1A8 019 * ** 5 <0.25 <0.25 <0.05 <0.1 0.36 1.32 014 <0.25 <0.25 <0.25 <0.05 <J* 0.21 259 0.73 <0.25 <0.25 < 0.25 <0.05 0.20 0.39 3.36 0.24 <0.25 <0.25 <0.25 <0.05 0.2 0.21 1.79 0.42 <0.25 ' n ?c <?Ar 0.18 0.03 2.39 H r '096 '" 25 J jJ B l 0 57 4 32 0 68 049 7 25 < 0:25 . i f < 0.1 0.54 015 1bSs31 M M M B l i i l 0.29 4.20 1.72 0.17 <0.25 <0.25 <0.25 < 0 05 0.11 0.28 1.22 0.06 <0.25 <0.25 <0.25 <0.05 0.12 0.09 0.99 0.17 <0.25 <0.25 <0 25 0.07 < 0.1 0.06 1.15 009 <0.25 <0.25 <0.05 0.15 0 27 2.32 2.19 2 92 1.41 1.06 1.05 0.99 1.02 0.93 1.26 1.37 1.38 1.32 1.49 2.05 1.24 149 0.52 030 0.58 0.30 1.98 1.39 1.24 1.05 0.35 0.28 0.95 1.09 0.61 0.39 1.23 0.88 1.25 1.06 1.28 1.47 1.61 1.21 2.54 171 2.19 145 1.20 138 0.95 1.17 0.61 0.51 0.54 038 0.69 0 37 November 2012 Cardno EN TRIX A-7 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1. 3M Analysis of Fish Tissue Samples for PFCs (ND = RL) Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; W hite bass = W bass; Green sunfish - G sunfish Reid ID Tissue ID Lab ID Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFNA PFUnA PFDoA 0 E 1o. 0c3 1--ns <uoQ.. <Qu0.. 202FN m s Gsunfish <:? 203FW m s S m Smbass 204 204FN 204FN1 Smbass 205 205FN 205FN1 Bluegill 206 206FN 206FN1 Wbass ?"v f i l i l i s li l l i l 607.81 44 4 7711 15.5 9 707.60 37 4 5 l l l i i N44854.153* 5 jfs B 54 5 4 '" N44854.153' 5 5 N44853.048' 6 3 N44852.916' N44* 53.73? EW853.737 N44853.732' N44852.931' N44852171' K w i i /*' / ' } 208FH1 I H G n i i i 467.20 209 199,58 211 211FN 211FN1 Smbass 557 92 212 212FN 212FN1 Smbass 199.58 213 213FN 213FN1 Smbass 217 72 214 214FN 839.15 - 215 f s U l 215FN1 625,96 216 216FN 216FN1 Smbass 217 217FN 217FN1 Smbass 326,59 11 i s ? i l l 32 UHI 34 3 24 2 24 2 .75 6 y l^ lfrn 3- 4 29 3 6 N44 52.916' 6 I I I B N44 52.916' Illlm m 63 N44852.916' N44 52.916' 6 3 N44 52.916' 6 3 N44852,916' j j p g||B ? y jp ' bB S I I N44 52.01V 6 5 N44* 51,916* 6 5 N44851 916' iw H .irr N44#52.17V N -i-'W .W N44852.171' N44852.17V N44852.17V N44* 51.810' N44851.810* N44* 51.655' N44851.655' 218 218FN 218FN1 Wbass 716.68 38 5 6 5 N44851.916' N44851 655' 219 219FN 219FN1 Fdrum 625.96 36 7 6 5 N44851.916' N44851 655' 111f c u I M l I M I IH B m 155 6 a i l I B B B h 52"'. l I B f e 221FN .222 BIi m M 22TJ- bm m W K K t . ^Fdrum ^ Ijljlft/ H m 6m 3 ills607.81.... 37 ig it i l l f ill 223 223FN 223FN1 Smbass 521.63 41 5 41 V.V h .' .,( M p H N44 56.797' N44* 56.885' 224 224FN 224FN1 Smbass 317,51 34 4 4 1 N44856.797' N44856.885' ____ 27 2 4- i g t ttt1 227FN 227FN1 Wbass 199.58 31 4 N44* 56,797* N44* 56,885* 229 22S"N 229FN1 322.05 37 I t 1 B W I N44856.797 VM" tr-BdO- 230 230FN 230FN1 Wbass 36 I l l l l l l l l l ' N44` 56,8W W93" 02.478' * .* 0.08 <0.05 W93" 02.4781 i H M I M M <0.05 <0.05 W93802.478' W93801 769' <0.05 <0.05 W93801.079' W93801 014' <025 0.06 W93800.857' W93800.606' <0.25 <0.05 W93800.857' W93800.606' 8.80 .V'* "-57 <0.25 <0.05 A-* W93 00.857' IM M g B i W93800.606' <0.25 <005 W93800.857* W93800.606' <0.25 <0.05 W93800.857' W93800.606' <0.25 <0.05 W93* 00.853' '.V-Y O f 0.06 WS3800.853' W93 00.647' <0.25 0.08 W93* 00.528* W93*00.461* <0.25 <0.05 W938 00.528' W93800.46V <0.25 <0.05 W93 00.528* W93800.46V <0.25 0.07 W93 00.528' W93 00.46V <0.25 <0.05 A'**' '* -.-* <0.25 <0.05 w w : :2J1 .\9'8-.'4c r- f-v A'\. M B 0.05 W93804.519' W93804.305' <0.25 <0.05 W93804.519' W93804.305' <0.25 <0 05 W flT 'tM .SW ..... .............- W93804,305 <0.05 <ft25 <0.25 W93804.519' W938 04.5191 A V U ^ 'i tr.*' * *5* <0.05 <0.05 < 25 <0.25 72 6 41.0 18.7 48.8 48.6 44.6 26.6 20.$ 28.6 29.6 33.2 73.4 49.4 50.9 20.5 48.9 11.0 17.8 19.1 37.2 44.2 235 m 91.0 52.7 35.8 0.16 <0.25 7 77 <0,25 < . '.5 <0.1 0.09 0.75 0 33 i l a i l B E p i l l i c;:. <0.05 <0.1 M i l j i j t e 2.40 0.59 <0.25 <0.25 <0.25 <0.05 <0.1 <0.025 f.63 0.03 <0.35 <0.25 <0.25 <0.25 <01 <0.05 1.21 088 1.11 <0.25 <0.25 <0.25 <0.1 0.68 3.38 0.04 l l j l S i . ?5 <0.25 <0.25 p l ^ p t 0.f4 1.07 0.35 0.44 <0.25 <0.25 M H B <0.1 B i g 1.93 0.33 <0.35 <0.1 g i M B p 1.10 0.39 <0.35 <0.25 <0.25 <0.25 <0.1 <0.05 1.47 0.40 <0.35 0.42 <0.25 <0.25 <0.1 <0,05 1.18 0.29 <0.35 0.28 <0.25 <0.25 <0.1 <0.05 1.52 0 54 -- p illi > <0.25 <0.1 B M i l S 4.44 0.61 <0,35 <0.25 <0.25 <0?6 045 2 99 0 4 0 <0.35 <025 *vi* <0.1 <0.05 2.56 0.39 <0.35 <0.25 <0.25 <0.25 <01 <0.05 1.41 0.66 <0.35 <0.25 <0.25 <0.25 <0.1 0.55 3.10 0.07 <0.35 <0.25 <0.25 <0.25 <0.1 0.15 0.83 007 <0.35 I B M M M 0.37 <0.35 <0.25 <0.25 <0,1 . <0.1 0.091 0.05 0.80 156 0.13 <0.35 < ' ?: H M I m am 2 02 0.40 <0.35 <0.25 <0.25 <0.25 <0.1 <0.05 3.21 0.51 <0.35 <0.25 <0.25 <0.25 <0.1 0.06 2.00 6 $ < 8 i <81 M l <01 <006 2 * 7 1 3 6 <0.1 <0.1 <0.1 <0.05 <0.1 0 74 502 1.08 0.76 0.15 <0.05 <0.1 0.49 3.79 0 34 <0.1 <0.1 <0.1 <005 | * | H 1 041 2 54 0.60 0 67 1.22 1.25 1.39 7.50 0.56 0.13 1.62 1.27 0.65 0,57 1.34 7.28 1.08 0.85 1.23 1.29 0.98 0.90 1.22 0.95 2.23 2.14 1.44 '1,18 1.52 1.30 1.18 1.01 1.49 1.57 0.68 0.88 0.55 0A2 1.24 7.76 1 4 4 105 1.81 1.79 1.21 1.47 tM tM 2.24 2.33 7.80 1.34 7.79 0.79 A Cara F r Ix Novera F7 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1 .3 M Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; White bass - W bass; Green sunfish = G sunfish Field ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHpA PFOA PFNA PFDA PFUnA PFDoA cc3n 3X ol 231 231FN 231FN1 Wbass 335.66 37.5 5 4 N44 56.797' 232 232FN 232FN1 Wbass 362.87 38.5 8 4 N4456.797' 234 234FN 234FN1 Bluegill 36.29 16.5 8 4 N4456.797' 235 235FN f a g l i l i ir.oj 36.29 v> 4 p l r i s N44* 56.7971 236 236FN 23SFN1 Bluejll 18.14 237FN B P B M BB 13.61 S ill. V 238FN Bluegill 13.61 12 i C f l l 1 " B VA' :-w IBB!10.5 C i p n i i i i N44" 56.797* 10.5 1 4 N44a56 797' 239 239FN 239FN1 Gsunfish 9.07 10 3 4 N44856.797' 240 240FN 240FN1 Bluegill 63.50 18 4 4 N44 56.848' 241 241FN ; v - T Bluegill MBIll S i i l i i88m lll( N44"56.848' 1 B 1 II BlBn 13 MSI N44* 56.848' ? :i 243FN 246 246FN 246FN1 fel'3li':1 Smbass 222.26 10.5 ijj(j MB W N44 56.848' - 3 * _ N44 56848' 247 247FN 247FN1 Bluegill 22.68 13 2 4 2 N4456.848' 248 248FN 248FN1 Wbass 367.41 38 5 4 2 N44a56 848' 249 249FN \ j lj l33 F g g jlip I I M N44a56.848' K B I M B l l Smbass 251 251FN i S H W l PBMfc m mj l p M j | m | M B lilil r.A/'-iy p | filili l | ] l l 252 252FN 252FN1 Fdrum 508.02 44 *3 253 253FN 253FN1 Wbass 172.37 30 2 4 3 N44a56.670' 254 254FN 254FN1 Fdrum 1238.31 38 6 4 ` -. 256 . 256FN x n ,\ ppHHt ICPB! 7.5 t-S B ilp l SBilll M-5' 102 257 25:r T 1 17237 323 17 ilBBIIIlllll N44a55.805- 278 258FN 258FN1 Fdrum' 1143.05 34 6 4 j j r444` K.805 259 259FN 259FN1 W bass 299 37 35.5 5 3 N44* 56 795' 260 260FN 260FN1 Wbass 367.41 38 7 3 4 N44a56.795' N44* 56.885' N44 56.885' N44a56.885' N44 56,885' N44 56.885' r.4' 5 h W N441' 56.885' N44a56.885' N44 56.553' N44' 56.553' N44a56,553' N44a56 553' N44 56.553' N44a56 553' N44* 58.553' NW 56.V7 N44" 56.522' N44a56 522' N44a56.522' N44a56 035` N44-56.035' m * 55.458' N44* 55.458* N44a56.834' N44" 56.834' W93 04.519' W93a04.519' W93 04.519' W93*04.51r A g yciv\\;?V W93 04.519' W93a04.519' W93" 04.049' W93* 04.049/. W93a04.049' W93a04 049' W93 03.592' W93a03.592' W93a03148' W93* 02890' viDrojasc W93* 04.887' W93a04.305' <0.05 < 0.25 59.2 1.06 <01 0.11 <01 <0.05 <0.1 0.92 W93a04.305' <005 <0.25 64.7 0.76 0.12 <01 <01 <0.05 <01 0.80 W93a04.305' <0.05 <0.25 52.5 0.05 <0.1 <01 <01 <0.05 <0.1 W93 04.305* <0.05 <0.25 ` 23.2 006 <0.1 <01 018 <0.05 <0.1 0.09 W93a04.305- ;<0.05 -rb 12.6 0.03 <0.1 <0.1 0.27 <0.05 <0.1 W93 04.305' 046 <0.25 9.5 0.11 <0.1 022 0 28 <0,05 <0.1 0.11 W93a04 305' <0 05 <025 15.0 0.08 0.24 <01 <0,05 0.14 W93 04.305' <0.05 < 0.25 23.5 0.11 <01 0.11 <0.1 <0.05 <0,1 <0.05 W93a03.620' <0,05 <0.25 27.9 004 <0.1 0.14 <0.05 <0.1 <0.05 W93" 03.620' 0 06 W93 03.620' 0.06 C;.. J1 <0.05 W93a03620' <005 <025 22,1 0.08 <0.1 016 <0.25 47.4 0 04 Bllffl <0.25 `m54.0Hl 0.06 lBiiiilSlInn <0.1 <0.05 16.6 0.60 <10 0.41 0.22 <0.1 0.11 II|I(k <0.1 <0.1 dpljl m a m <05 0.05 0.06 0.11 W93a03.620' <0.05 0.18 66.1 0.05 <1.0 <0,25 <0.5 <0.05 <0.05 0.15 W93a03.620' <0.05 0.14 90.5 5.28 <1.0 <0.25 <0.5 <0.05 <0.05 0.85 vV".!e <0.05 <0.05' 884 f t ? * <0.05 38.1 A ""C ` , \ l i p B B j 41.8 108 <1.0 <0.5 llBiBl <0.05 0.68 MBBI0 68 <1.0 B i l l <35 <0.05 <0.05 i l i0 76 I B I I B B i l I f c o J l B i l p l <0.05 0.06 <0.05 3.2 0.17 <1.0 <0.25 9.06 0.15 W93 03.290' <0.05 <0.05 63.3 1.03 <10 <0.25 < 0.5 <0.05 <0.05 0.57 W93 03.132' <005 v/y / r?` <:ct W93o02S09- <0.05 <0 05 <0.05 <0.05 39.5 0.10 16.4 0.08 76.2 014 <1.0 <0,25 <1.0 <0.25 <1.0 <0.25 <0.5 <0.05 <0.05 <0.5 ' tisB I J | | | | <05 <0.05 <c;- 0.33 0.42 0.30 a*r a y w <0.05 <0.05 7.1 0.10 <1.0 <025 <0.5 <0.05 <0.05 0.19 W93a04.785' <0.05 68.7 0.73 <1.0 <0.5 <0.05 <0 05 0 71 W93 04.785' <0.05 <0.05 64.4 0.79 <1.0 <0.25 <0.5 <0.05 <0.05 0.45 3.25 1.46 1.21 4.00 1.77 1.39 107 0.57 0.25 1.16 9.70 047 0.42 0.35 0.52 0.50 0.33 0.32 0.75 0.68 0.83 0.71 0.62 0.61 0.84 0.61 0.48 0.86 0.56 0.24 1.28 0.72 0 92 1.67 0.72 0 73 1.50 1.26 1.73 1.35 0.62 0.49 4.00 2.11 1.68 370 2.02 155 231 1.43 108 2 53 1.50 1.36 090 0.74 1.26 3.15 1.67 1.44 0.94 0.65 0.36 092 0.41 0.32 183 0.66 0 78 0.59 0.47 0 61 3.89 1.96 1.55 4.03 2.07 1.84 November 2012 Cardno ENTRIX A-9 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1 .3 M Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; W hite bass = W bass; Green sunfish = G sunfish <0O>) Ocs' <zLQi.- <auQo.. Field ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFDA PFUnA 261 261FN 261FN1 V f' 283FN | | K d K ite 264FN 264FN1 266 266FN 266FN1 267 267FN 267FN1 268 268FN 268FN1 s il N A j-M 270FN1 271 272 272FN 272FN1 273 273FN 273FN1 274 274FN 274FN1 276 276FN 276FN1 m mm 277FN1 i 278FN ./rv 279 279FN 279FN1 280 280FN 280FN1 281 281FN 281FN1 282 i i l f i i i j 282FN1 /V3 283FN 263FN1 m ^WFM 3B6B44 287 287FN 287FN1 288 288FN 288FN1 289 289FN 289FN1 W bass 208.65 31.5 2 3 4 N44" 56.795' N44* 56.834' W93804.887' W93804.785' <0.05 <0.05 20.4 0.34 <10 <0.25 <05 < 0.05 <0.05 0.24 Smbass 158.76 mml i l i m 40 f t | B | H N44* 56.795r `. `.a 56i>"' ` .i-1-1i'5 W93* 04.887.*.'**' O1- 7~3 W93804.785* W93 06.517* <0.05 0 06 44.7 0 53 <1.0 ; p l j | B I P S <0.05 <0.05 50.0 0 73 ( H i l l M H E <0.5 <0,05 <0.05 0.75 r~i ! 40 j .jg itf! Ci-SC7' ;c ' ti-'-'i1 WS3*06.773 W93* 06.517' 702 0.55 <0,35 <0.25 <0.25 I p l l | t v;S: <0.25 097 1.34 0.75 0.60 2 29 1.51 1.19 2 78 1.42 1.09 446 2.0S 172 F drum 185.97 34 7 1 5 N44854 735' N44854,567' W93811 972' W93 11.988' <0.1 <0.1 24.2 0.07 <0.35 <0.25 <0,25 <0.05 <0.25 0.36 0.98 0.64 0.58 Smbass 240.40 32 3 1 5 N44 54.735' N44854.567' W93811.972' W93811.988' <01 <0.1 20.3 0.27 <0.35 <0.25 <0.25 <0.05 <0.25 <0.05 2.23 1.45 1.24 F drum 439 98 43 17 1 6 N44*54 71T N44854.345' W93812.106' W93811 730' <0.1 <01 12.8 023 <0.35 <025 <0.25 <0.05 <0,25 0.10 1.28 1.29 1.98 F drum . 331.12 38.5 J l j l I l B 1 -`m t m W U ' *. N44" 53.634' W93M1.382* /"i- - ' W <0.1 0.17 40.3 0.10 <0.35 M I M I <0.25 <2 2' siigli258.55 I 1 f N44 53.815' .*.* A1'1" ' ** W93" 10.577' <0.1 h H | 0.10 B B <0.25 *Z 'r 199.58 35 1 8 \W " 5? N44* 53.657' p p S l M f W93" 10.577' <0.1 <0.1 2iao 0.64 <0.35 .w/-; <0.25 <0.05 <0.25 0.59 0.13 0 29 132 0.79 0 75 123 0.72 0.63 4.29 1J2 0 94 Smbass 199.58 33 2 2 4 N44 53.661' N44" 53.833' W93809.812' W93809.348' <0.1 <0.1 4.9 0.16 <0.35 <0.25 <0.25 < 0.05 <0.25 <0.05 0.53 0.61 0.63 Smbass 244.94 33 3 2 4 N44853.661' N44853.833' W93 09.812' W93 09.348' <01 <0.1 19.5 0.25 <0.35 <0.25 <0.25 <0.05 <0.25 <0.05 1.64 1.66 149 F drum 86.18 F drum r * ; F drum 1 26.5 5 3.: 10 35 J i M M l j 27 2 / 5 N44653.878' N44854.205' W93808.835' W93808.361' <0.1 <0.1 N44* 53.8781 N44" 54.205' W93* 08.83? W93 08.36V J l l l <0.1 44.9 0.08 <0.35 <0.25 <0.25 <0.05 <025 0.26 P i l i94.1 0.30 <0.35 <0.25 <0.05 <0.25 0.89 5 N44853.878' A'1"' i ^ 6' W93- 08.361* <0.1 B l i l i 005 i h p H H F <0.25 m m <0.25 0.25 V-1 -4 37 W93808.26Q' W93* 07.886* <0.1 I l i 024 j j p j j C *32' <0X55 1.76 0.69 0.50 3 87 2.11 313 0 63 0.63 0.50 2 72 1.28 1.10 Smbass 9072 24 2 2 6 N44 54.265' N44854.879' W93808.260' W93807 886' <0.1 <01 47.5 0.33 <0.35 <0.25 <0.25 < 0..05 <0.25 <0.05 2.92 119 1.06 Smbass 131.54 26 2 2 6 N44854.265' N44854.879' W93808.260' W93807.886' <0.1 <01 46.1 0.29 <0.35 <0.25 <0.25 <0.05 <0.25 <0.05 3.84 1.88 1.67 Smbass 385.55 38 335.66 . 355 $*W 226.80' ' 32.5 . Smtot 36 205 3 3 f. A 27 / M SB !M I 7 7 27 N44* 55.094' N44 55.337' N44* 55.094" N44*55.337' i*4J55.094' ' N44* 65.337* \<-J* 5' Ari' mui* ^ n w N44 55,337' IBTSSSr W93807.872' A\yC7G"2 a :-*' fA? wov t/Tfify W93807.496' <0.1 <0.1 27.1 0.26 <0.35 W93807.496' 'A :?*' <01 <01 VIM INI 6 21 <0.35 i i M fe i||jp p i |:g|f|g W 14.9 035 AM* V 4b0 < 0.25 52.1 0 25 <0.25 <0.25 <025 <025 PS ili&iii <Zik <0.25 il^ W <01 W93*<ff.4W <ft25 <5 ft? ft Ml <035 <0.1 <0,05 <0.25 <0.05 1.80 1.22 1.14 <0.05 <0.25 <0.05 289 1.46 115 ;iliWE i iiiili! -Mzmii&iksgSI <005 <025 | H M 111 0.97 1.06 < 9 .* <0.25 <99 <0.1 2.42 1.42 169 0*2 t *72 Bluegill 49.90 16 2 2 7 N44855.094' N44" 55.337' W93807.872' W93807 496' <0.25 <0.25 16.4 0.09 NR NR NR <0.05 <0.05 008 0.58 0.60 053 F drum Al-r-i mm358.34 39.5 276.69 I I P ! 17 7 5 7 y iiB t N44 49.797' i44* 9.7 N44 49.284' W93 00.683' W93800.585' V.4' 41234 IB M IifiJIl AM* V! 85' <0.25 <0.25 0.21 043 105.0 0.23 4.59 <0.1 <0,25 <0.05 0.11 0.54 ."'MMbl54.2 088 <0,25 0.10 <0,25 <0.05 0.57 3.05 1.95 2.21 3.49 1.53 122 A. Cart F r Ix Noverr 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Table A -1 .3 M Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish Field ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA e K < llW lI Wbass 35 llilll m M8SMI N44" 49.284' W93" 00.683* <0.25 1 48.0 2S1 291FN Smbass = 8 8 1 ! p l I l j M i M b i h N4449.797' N44* 49.284' W93 00.683' W93"00.585- <0.25 i p B I B 42.3 292 292FN 292FN1 Smbass 208.65 32.5 3 7 5 N44 49.797' N44849.284' W93 00.683' W93800.585' <0.25 <0.25 39.9 293 293FN 293FN1 Sm bass 249.48 35 4 7 N44 49,797' N44849.284' W93800.683* W93 00.585' <0.25 <0.25 27.3 294 294FN 294FN1 295 M H B IliB ill 296 296FN 296FN1 Smbass Smbass Bluegill 90.72 25 2 7 M illI M B t l u rn | B ppa13.61 - g a p II 5 N44849.797' BBB N44 49.797* BBS N44 49.797* N44849.284' N44* 49.284' W9300.683' W93800.683' W93800.683* W93 00.585' <0.25 <0.25 585' <0.25 = j j j p | ' <0.25 47.5 34.6 12.5 297 297FN 297FN1 Blues 18.H H P H v..J N44B49.284' A'-* : . i r p f l P P 0 26 I p i l l l 5.2 298 298FN 298FN1 Bluegill 13.61 10 1 7 5 N44 49.797' N44 49.284' W93800.683' W93800.585' <0.25 <0.25 3.6 299 299FN 299FN1 Bluegill 22,68 14 1 7 5 N44849.797' N44 49.284' W93 00.683' W93800.585' <0.25 <0.25 11.2 300 300FN 301FN g ill -Oo I f i P 300FN1 303FN1 Bluegill Bluegill 36.29 14.5 2 7 5 N44849.797' B IH l ||l||lj I B 226.80 M I M I IJBIIll f i l l 111 i l ill131.54 28.5 \<w -v- ;r N4449.270* N44849.284' N44 49.284' N44* 49.133' W93800.683' W93 00.683' ,Y-S . \- V W93B00.587' W93800.585' W 3 W .m <0,25 <0.25 m HllfcM B 11.2 12.3 W93B00.429' <0.25 I B I SSlS!v r -v r 429' <0,25 36.8 357 304 304FN 304FN1 Wbass 285.76 36.5 4 8 4 N44847.832' N44847144' W93 01.351' W93801.443' <0.05 <0.05 49.9 305 305FN 305FN1 Wbass 181.44 31 2 8 4 N44" 47.832* N44 47144' 306 306FN X6FN1 Smbass 267 62 35 4 8 4 N44 47.832' N4447.144' Hflf jjBMB Bjtt IIIHI307 i'-.'-N 1*1 4! lllilll 1 N44* 47.832' N4447.144' sip!( M M SIMMi i l j MIBB Ils308 Smbass lllilll U44M7.83Z N44847.144* 309 |8 H| 309FN1 P illi M jjjl 26.5 ( i l l l|||l| ppm 310 310FN 310FN1 Bluegill 36.29 15 2 8 4 N44847.832' N44 47.144' W93801.351' W93 01 351' ,y:j W93" 01.351* W93801.443' W93801.443' W93BD1.4431 r 'u <0,05 <0.05 <0.05 <0.05 <0.05 I^H jl I m 65.1 19.1 59.6 41.4 W9301.443 <0.05 <0.05 30.5 W93801.443' <0.05 <0.05 21.5 311 311FN 311FN1 Bluegill 27.22 14 2 8 4 N44847.832' N44 47 144' W93801.351' W93801.443' <0.05 <0.05 22.5 312 312FN 312FN1 Bluegill 27.22 13 2 8 4 N44847.832* 313 P i p P II MMBpBli "! CC MBlllillll l i Pill N44c46.389' M i l315 .-'5 T BiwmBpmFdmm MiiBI p g l l a p i 11111B 111B 1 M l m [fg mSmbass 331.12 N44* 52.871' N44847144' N44846.256* `.4` 256' `.44* U W W93801.351' W93 01.443' <0,05 t e y y cy. W93B00.475' <0.05 W93*01.000' W93800.475' <ao5 W93" 00.992* b B b B m IB <0.05 < 0.05 m dp lllilll 16.4 24.0 27.0 32.1 Mil0.88 <0.25 f l l <0.25 lllil ll 0.34 2.66 llilliii041 <0.1 0.12 <0.25 p u h 2 09 0.26 <0.1 <0,35 <01 <0.25 <0.25 <0.1 2.22 0.20 <0.1 <0.35 0.11 <0,25 <0.25 <0.1 1.34 0.25 <0,1 <0.35 <0.1 <0.25 <0.25 <01 2.08 0.31 <0.1 M i B <0.1 M B <0.25 M M I I 1.84 0.05 M i l d i j <0.1 ' 25 f c f c H l <0.1 0.75 0.06 M M <0.35 0.11 <0.25 <0.25 <0.1 0 38 0.04 <0.1 <0,35 <0.1 <0.25 0.31 <0.1 0.32 0.04 0.21 <0.35 <0,1 <0.25 <0.25 <0.1 0.64 0.03 <0.1 <0.35 <0.1 <0.25 <0.25 <0.1 0.32 m0 06 021 i l i l l llB j li <0.1 0.49 0 23 l l j j | j <0.35 0.54 MBjlm <0.1 <0.25 l i f c i B I B B I p p076 Blggpllp 0.57 1.77 2 26 0.71 1.40 <01 <0.05 0.05 0.19 0.73 3.55 2.02 <0.5 <01 0.07 <0.05 <0.1 0.59 3.50 0.29 <0.5 0.17 0.18 <0.05 <0.1 <0.05 1.01 fPP|0 27 <0.5 0 2 6 <0.05 <0.1 B llllll 2.17 lip !016 0.16 IBMIH005 <0.05 <0.1 3.23 iiIBHi A f l0 29 <0.5 0 21 <0.05 <0.05 1.13 0.07 263 <0.1 <0.05 <0.05 <0.1 0.09 0.92 0.06 <0.5 <0.1 0.09 <0.05 <0.1 <0.05 0.90 0.04 <0.5 H p0 23 <01 <0.05 <0.05 IH J i<0.1 <0.05 <0.1 - <0.1 <0.05 PP 0.44 1.10 0 1 1 <0.5 <0.1 0 17 <0.05 <0.1 0.37 1 3 7 IliMlii0.46 ` <0.5 <0.1 <0.05 <0.05 1.63 1.69 1.18 1,39 1.38 1.45 1.27 1.08 1.13 1.24 1.06 1.13 1.01 0.50 0.36 0.24 0.16 0.24 0.19 0.40 0.35 0.29 0.33 0.38 0.41 1.10 0.9 3 1.02 0.80 1.83 2.42 1.71 1.31 0.88 0.79 1.34 1.52 1.54 2 62 0.64 0.69 0.53 0.64 0.69 0.76 0.30 0.34 0.67 0.55 0.67 0.60 1.01 0.80 November 2012 Cardno ENTRIX A-11 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Field ID Tissue ID Table A -1.3M Analysis of Fish Tissue Samples for PFCs (ND = RL) Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish PFPeA PFHxA PFBA oc .o s JS o - < CO o u. Q. PFHpA s li ti. < CL3 Li- PFNA PFDA PFDoA Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS i 317 317FN 317FN1 Smbass 254.01 33 3 6 7 N44852.87T N44c52.507- W93 00.992' 318 318FN 318FN1 F drum 594.21 36 17 6 7 N44852.871' N44852.507* W93800.992' 319 319FN 319FN1 F drum j?l 11JJIlillBM I Fdrum 176.90 32,5 26 6 9 N44 51.463' N44851.038' W93800.437* 34.5 B illlllljjilillBlI mt^ A'.-'- 321 321FN ' I M I 322FN .V " iilB B illl 322FN1 i | p l i 1H jjBfiiBll i l f 1;ij|S t a 45.36 8 6- S I * ` 1;.`, u , * 4 u 3 NW'V4U `. `.4' 51 V.4' 5' V ' Jivv.**: 323 323FN 323FN. Fdrum 258.55 -, 8 6 10 N44* 51 137' N44 50.990' W93800.623' 325 325FN 325FN1 Bluegill 18.14 12.5 2 6 h N44 50.990' N44 50.572- W93800.659' 326 326FN 326FN1 Bluegill 328 ijpiBj 329 329FN .vfs*v Bluegill 13.61 11.5 B fc 31.75 8 6 11 N44 50.990' IfIMjjjiI I B j M44850.990' filli4 6 N44* 50.99? N44 50.572* W93800.659' > l"t K p M W93800.65? 330 330FN 330FN1 331 331FN 331FN1 F drum y r- L: : 21.5 :*. 8 3 I B I N4450.990' 11 N44 50 590' N44850.572* N44 50.572* W93* 00.659' W93800.659' 332 332FN 332FN1 F drum 131.54 28 8 6 12 N44 50.689' N44 50.435' W93800.689' 333 333FN 333FN1 F drum N44 50 689' 334 3V/-M F dmm 226.80 34 2 6 12 N44 50.686- ftSj'OSrt 335 335FN 335FN1 336 336FN 336FN1 Bluegill Bluegill 4b 3C ) ( ! || B lB i N44` 50.68? W53-V63S' warnMljjfcl jiMlIll N44* 49 40? i M p I P l W93800.634* 337 337FN Bluegill 27 22 . 2 7 N44 49 400- N44849 118* ,\ 338 338FN 338FN1 Bluegill 22 68 13.5 2 7 7 N4449 400' N44849.118* W93 00.634' 340 340FN 340FN1 Bluegill 27 22 13.5 2 8 6 N44 47 945' N44847,811* W93801 507' s N44*47.81V flK'l'Ki7 W93800.983' W93800 983* W93 00 490' W93 00.490* W93 00.490' W93 00.490* W93800 659* W93800.530* -- W93 00.530' W93"00.530' W93 00.530* ,\ W93800.756' <0.05 <005 .05 <0.05 <0.05 <0.1 0.14 <0.1 < 0 .1 < 0 .1 < 0 .1 <0.* <0.1 <0.05 < 0..05 <0.05 015 <0.05 0.37 0.30 042 <0.05 0 28 <0.05 W93" 00.756' < 0 .1 <0.05 W93800.756* ffM Kii 0 30 W93* 00.490* I 8 B <0.05 W93 00,490* <01 W93800.490' <01 <0.05 W93e01.482' <01 <0.05 <Q.t 47.0 0.59 <0.5 <01 0.11 <0.05 <01 <0,05 2.99 19.8 0.29 <0.5 <01 0.06 0.05 <0.1 0.28 2.97 9.6 0.13 1.37 0.20 0.12 < 0.05 <0.1 0.06 0.52 56.9 0.15 <0.5 <0.1 * ^ * | 1 <0.05 0.f9 0 31 1.48 91.9 0.08 0.6f <0.1 0.13 <0.05 <0.1 006 0.99 35.7 0 0 3 <0.5 <0.1 <0.05 <0.05 <0.1 <0.05 0 75 14.6 0.18 <0.25 <0.1 <0.1 <0.05 0.37 133 224.0 0.08 <0.25 <0.1 <0.1 <0.1 <0,05 <0.1 0.87 62.4 0.06 <0.25 <0.1 <0.1 <0.1 <0.05 <0.1 0.50 58.6 0.10 <0.25 <0.1 <0.1 17.2 0 M <"..75 '<0.1 j B P ilil < 0 .1 <0.05 0.11 3920 0.08 ifcjiilW < 0,1 < 0.1 <0.05 <0.1 145 068 069 25.2 0.13 <0.25 0 .2 7 <0.1 <0.05 0 .16 1 2 0 29.1 0.08 <0,25 <0.1 <0.1 <0.1 0 .06 0 .42 1.10 3 21 0.10 2.90 <0.1 <0.1 <01 <005 0 2 9 133 31,2 0.09 - 0 2b <0,1 < 0.1 0.05 0 .4 7 1.27 10.3 0.05 < 0 .2 5 <0,1 <0.1 < 0.1 3.08 l ! * S i 0.44 20.6 0 07 <0.25 < 0 .1 0.18 <0.1 .iliiiB l <0.1 0.64 14.1 0.05 ... 0.15 <0.1 .... <0.1 0.46 10.7 0.05 <0.25 0.10 <0.1 <0.1 <0.05 <01 0.35 11.2 UjO 0.07 005 <0.25 <0.1 <:j <01 <0.1 <0.05 <0.1 <0.05 0.60 0 77 2.10 2.65 0.28 0.92 0.77 0.65 0.98 0.62 0.33 1,43 0.48 1.05 0.85 0.63 0.58 0.71 0.31 0.48 0.29 0.33 0.54 0.41 1.58 2.45 0.25 0 92 0 79 0.21 1.10 0.56 0.30 0.65 \ 60 4 0 93 0.90 0.72 0 .5 7 104 0 33 0.51 0.27 0.32 0.47 045 343 343FN I S l i l l M Bluegill " 344FN :* V Bluegi!' 345 345FN 345FN1 Bluegill 18,14 Mttjll ^ B ISM! 3 \:.J a ' *4* A"3 * * * ' A y -C` fit n p <0.05 13.2 0.05 <0.25 <0.25 <0.1 <005 <0.1 007 0.58 0 34 0.33 : \ 17 3 8 6 N44847 945' :.v W93801.482- <0.05 <0.05 27.6 0 05 <0.25 <0 25 <0.1 <0.05 <01 <0.05 0.74 0.70 0.69 77.11 19 4 8 6 N44* 47 945' N44847.811' W93*01 507' W93801.482* <0.05 < 0.05 11.7 0.05 <0.25 <0.25 <01 <0.05 <01 0.06 0.56 0.38 0.33 A- Cara fR IX NoveiT. 12 /, (, : Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - SummelrzO11 Table A -1. 3M Analysis of Fish Tissue Samples for PFCs (ND = RL) Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; W hite bass = W bass; Green sunfish = G sunfish Field ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Reach Start Northing Start Westing End Westing h 0> te3c s o> 1zo -o O< S. uo-. < LU D. co LL. Q. 346 346FN 346FN1 W bass 276.69 36 5 3 7 N44 55.451' 349 349FN .i : l l l I i l l B H i - I g M 1 1 p j j f N44 55.451' 350 i f i P l l W bass 351 351FN i i l l l p H h p i M i l i P l i 1 1 1 N44-55.451' i i | w !B p 1 1 N44" 55.451' 352 352FN 352FN1 Sm bass 11793 26 5 2 3 7 N44055.451' 353 353FN 353FN1 Bluegill 40.82 16 5 3 7 N44 55.451' 354 354FN 354FN1 Blue# 31 75 15 6 3 7 N44055.451' 355' i.rrN F drum 712 " IB S 8 .A.V 5c .-5i 356 356FN 356FN1 19051 i f c ;! l l p J | 8 N44* 55355' 358 358FN iB mi^ 359 359FN 358FN1 359FN1 Smbass Smbass 607.81 ; S i ^ H I I P S '.j a p s 99.79 25 23 8 8 N44* 55.955' N44" 55.955' 360 360FN 360FN1 361 361FN V Smbass Smbass 208.65 32 ,ir 3 3 8 N44" 55.955' *> * N44 55955' JlfeJlB f c S H j 9a72 i m t m 8 N44'55.955' 363 363FN1 Bluegill 15 S : | B i l i l N44* 55.95? 3- N Bluegill 36.29 p Ip i 8 N44* 55.955* 365 365FN 365FN1 Wbass 317.51 38 4 2 8 N4455.109' 366 366FN 366FN1 367 367FN 367FN1 V i liR H w 369 s i i M i l l Bluegill Bluegill 63.50 54.43 18.5 17.5 42 c2 Wbass 1 ,Vtj: ; ^MU illii* 11 8 fi 9 9 N44B55.109' M/i/i w moM44 53.870' N44* 53.870' H I370 I f i B l l l l l .Vi a Jl JS* m m IliB lj D r.4-'1.1- 1 372 372FN 372FN1 W bass 45.36 38 4 2 9 N44 53.870' 373 373FN 373FN1 W bass 281.23 36.5 5 2 9 N44 53.870' 374 374FN 374FN1 Wbass 38102 377 377FN 3/.-M i n i 0 i 49 5 2 9 m m36.5 nBIH!p | H ! N4* ^ ,A.r N4456.031' W9306.842' N*-1- ;,= \ . r N44" 56.031' N44* 56.031' l i N44 56.031' W93806.842' N44 56.031' W93 06.842' N4456.031' W93 06.842' `/ *'*' N44* 56.5281 N44- 56.528' N4456.528' N44* 56.528' V,V QfcT"4 A-?' V. ?"i ',V:3*y,3;4 W93* 06.374' W93 06.374' N4456.528' W93* 06.374' WO** C5 "A N44` 56.5281 N44 56.528' W93` 06.374' W93* 06.374' N44 55.335' N44* 55.335' W9307.830* W93 07.830* M4455.335' W9307.830' * N44"54.948* N44"54.948' N4454,948' N44* 54.948' N44* 54.948' M4A54 94fi' A'-3 '''AA w yod.M & W93" 08.846' W93" 08.846' W93808.846' HU"54.948* ArT ** `-J. W93* 06.169' W93-06.169' W93 06.169* < 0.05 <0.05 B i S a 0.05 I P <0.05 W93 06.169' <0.05 <0.05 W93e06.169' <0.05 <0.05 W93 06.169* <0.05 < 0.05 W93 06.169' <0.05 <0.05 W9305.689' <0.05 : 006 W93"05689' i ! i p s! <0.05 W93'05.689* i ^ p l l <0.05 W93" 05.689' <0.05 <0.05 W93" 05.689' <0.05 <0.05 W93 05.689' <0.05 <0.05 <0.05 W93" o s .m Listai <0.05 *V* W9307.495' <0.25 0.07 W93* 07.495' <0.25 <0.05 W93 07.495' <0.25 0.23 W93907.857* W93 07.85? l U i i W93' 07.857 M m i W93* 07.857' <0.25 0 29 1.02 1.70 0.06 W9307.857' <0.25 0.05 W93" 07.857' <0.25 0.08 W93" 07.857 <025 0.17 34.8 44.8 33.9 29 2 16.5 29.4 8.7 48.8 46 7 36.9 20.1 32.6 32.0 16.1 44.1 60.0 59.2 8.5 12.4 83 7 60.1 66.3 48.8 70.2 75.7 17.5 0.52 0 69 046 0.25 0.18 0.04 0.04 0 35 0.3$ 0.40 0.22 0.40 0.41 0.27 <0.25 <0,25 <0.25 <0.25 <0.25 <0.25 <0.25 <0,25 -e ;: <0.25 <025 <0.25 <0.25 <0.25 007 0.44 0.77 0.05 0.05 062 133 0.80 0.89 0.86 0.88 0.00 <0,25 <0.25 < 0.25 <035 0.40 0.35 0.35 2.41 <0.35 <0.35 <0.35 <0.25 <0.1 <0.05 <0.1 0.40 2.06 101 0 .8 7 <0.25 <0.05 <0.1 0 64 3 25 1.59 1 2 9 <0.25 p n i <0.05 <0.1 0 26 2.05 1.02 0.9 5 0.32 <0.1 <0.05 i s <0.05 l i i P i 0,90 0.85 <0.25 <0.1 <0.05 <0.1 < 0.05 1.09 0.81 0 .6 7 <0.25 <0.1 <0.05 <01 0.06 1.05 0.64 0.43 <0.25 <0.1 <0.05 <01 <0.05 0.65 0.53 0.47 ^J , `. 0.15 0.42 129 0.77 1.34 <0.05 <0.1 P I I 133 0.95 1.64 0.11 <0.05 <0.1 flIPPll 2 38 1.20 0.95 <0.25 0.11 <0.05 <0.1 <0.05 1.09 0.91 0.79 <0.25 <01 <0.05 <01 006 1.89 1.31 1.29 <0.25 0.16 <005 <01 <0.05 1 .9 7 1.18 1.27 <0.25 < 0.1 <0.05 <0.1 [ m m 082 0.71 0 7 0 <025 <0.25 0.14 <0.20 <0.05 <0.05 ^ p H I < u. 1 7.11 1.93 0.93 0 8 2 0 74 0.46 0M 3.40 1.44 1.11 <0.25 <0.25 <01 <0.25 <0 05 0.53 0.41 0.26 <01 <0.25 <0.05 <01 <0.05 0.49 0.53 0.49 <0.1 <0.25 <0.05 1.13 6 36 3.0 7 204 0.12 AiBIl <0.05 J i i i l i <0.1 liiS iilf <0.1 0 60 0.75 398 1.74 1.19 4 67 2.01 169 <0.25 <0.25 <0.1 <0.25 0.51 3 .6 2 7.65 1.51 < 0.25 <0.25 <0.1 <0.25 0.59 4.11 2.01 1.75 <0.25 <0.25 <0.1 <0.25 0.72 512 2.48 2.07 ?c <0.25 <0.25 0.13 0 59 0.57 088 November 2012 Cardno ENTRIX A-13 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A -1 .3 M Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum - F drum; Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish c3a <zu. CL <aLaoL. Reid ID Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFDA PFUnA 378 37BFN 378FN1 \r< r> 37.5 ; | i p W N.:.1- SV.J- W93808846` * ">* .-ai,' <0.25 0.06 SOS 017 - ~ :-5 <0.25 f i j i B <0.1 0.57 746 1.18 379 379FN 37SFN1 Smbass ig J |J i 6 N44847.66? R N 4 i l l l f e W93" 01,546' ,V".J y 486* . c;< <0.05 m i 015 <0.35 0 29 <0.25 <0.1 <0-25 <0.05 738 0.95 380 380FN 380FN1 Wbass 140.61 29 8 7 N44" 47.665' N44847.305' W93801.546* W93801.486' <0.25 0.05 47.7 0.65 <0.35 <0.25 <0.25 <0.1 <0.25 0.50 2.83 7.39 381 381FN 381FN1 Smbass 90.72 24.5 8 8 N44 46.243' N44846.286' W93800.491' W93800.022' <0.25 <0.05 28.7 0.14 <0.35 0.39 <0.25 <0.1 <0.25 <005 1.04 0.79 382 382FN 382FN1 Smbass 108.86 26,5 8 8 N44 46.243' N44 46.286' W93800.491' W93800.022' <0.25 <0.05 21.2 027 <0.35 0.72 <0.25 <0.1 <0.25 <0.05 0.72 0.70 | I | | 383FN 33TV Smbass 185.87 fip l i n N44* 46^43 W93*0049V W93800.022' PHls0.05 40.1 0 25 <0.35 049 <025 <0.1 <0.25 166 1.17 384FN 384FN1 312.98 36.5 I b i i 8 ifp .-a y w / . V. . 8 1 a *" . s O Y 0.07 71,3 0.71 *" *5 <j #: '0 * <0.25 1.04 4 24 2.14 385 385FN 385FN1 IB lillSmbass B l i S w l l l l f L . , I ; | 13 N44 46.051' *.:-' W92856.800' W92" 56.373' * ;? 0.06 jlj|jll7.3 <0.35 0 77 <0.25 <0.1 <0.05 0 95 0.98 386 386FN 386FN1 Smbass 72.57 23.5 9 13 N44 46.051' N44 46.230' W92 56.800' W92 56.373' <0.25 <0.05 11.0 0.20 <0.35 <0,25 <0.25 <0.1 <0.25 <0.05 0.72 0.54 387 387FN 387FN1 Smbass 81 65 24 9 13 N44 46.051' N44846.230' W92856.800' W92 56.373' <0.25 <0.05 26.8 0.12 <0.35 <0,25 <0.25 <01 <0.25 <005 1.17 0.72 388 388FN 389 389FN 1111 39QFN p i 391FN 388FN1 389FN1 390FN1 391FN1 Bluegill Blue# Bluegill ' 99 79 36.29 154,22 63.50 19.5 3 9 14 |H | 14 BBtll lllllis m m IjjBl M i j i l bb 15 N44845.925' `vr; N44 45.9251 N44* 46.8851 N44845.970' **T: N44845,970' ..... W92856.390' W92* 56.390* WS2 56.390' W928 56.333' <0.1 <0.1 19.1 W92 56.33 <0.1 <0.1 tlllH Jppl Ip iBW92 56.091' <0.1 70.5 9.5 50.9 0.07 <0.1 0,17 <0,25 <0.05 <0.25 B IB BHB003 <0.05 <0.05 'Q 2F 0.67 <0,1 p p0.10 H | <0.25 patii0.08 <0,1 <0.25 <0.05 <0.1 0.66 0.72 0,73 0.44 <0.1 0.69 1.13 0.10 ftiMiii 1.03 392 392FN 392FN1 Bluegill 45.36 16 9 15 N44846.885' N44846.885' W92856.091' W92856.091' <01 <01 76.5 0.07 <0,1 <0.05 <0.25 <0.05 <0.25 0.11 2.63 1.72 393 393FN 393FN1 Bluegill 40.82 15.5 2 9 15 N44846.885' N44846.885' W92856,091' W92 56.091' <01 <0.1 60.9 0 0 8 <0.1 <0.05 <0.25 <005 <0.25 0.15 2 3 7 1.31 394 394FN 394FN1 Bluegill 31 75 14.5 2 10 8 N44846.162' N44846.162' W92852.645' . BMIm395 395FN Bluegill M itili l i a P10 v.-j -.-u *v. W92* 53.470* 396 396FN 396FN1 Bluegill KsS* M B S llll |P | N44" 54.134' N4453.535* W93802.431' 397 397FN MS M W P ?,'?? SIMMI HB M l Bill N44854.134' l i 4y 398 398FN 398FN1 Wbass 308.44 36 5 N44854.134' N44853.535' W93802.431' W92852.645' <0.1 <0.1 W92 53405* <0.1 <0.1 1M1MW93" 01.343' <0.05 MlSir r v : / w <05 <0.05 W93801 343' <0.05 <0.05 777.0 0.23 <0.1 77.6 0 20 <0,1 30.2 BBta! 312 6.7 0 06 < 0.05 <0.25 <0.05 <0.25 0.32 Pf a o J i B b p <0.05 <0.25 0.12 H P iP P H I0.79 <0.35 0.07 <0.1 <0,35 <0.05 0.07 59.7 0.79 <0.25 <01 <035 <0.05 <0 25 0.53 5.73 "2 107 036 3.93 2.79 0.68 0.77 0 34 1.70 399 399FN 399FN1 Wbass 290.30 36 6 5 6 N44854.134' N44 53.535' W93802.431' W93801.343' <0.05 0.08 59.7 1.18 <0.25 <01 <0.35 <0.05 <0,25 0.57 4.14 1.65 nn nncf'j 9TTRCT 32 3 56 waa*raw a a r a i s s r W93* ftl.343* <025 <0.-05 8J zzt 'M 5 <2.1 <235 <2 <2 2# 1# l i l i l 401FN Wbass lilil? i i l j j | | 1 1 R b | H N44* 54.134' v . i - r " ;r j p H j p P <0.05 <0.05 54.5 2 85 i l <0.35 g p l l i j <0.25 0.30 2 63 7.05 111 402FN 42FN1 Wbaee 3C8A4 p i j| 5 H ip ! .4-t' s4 134* \* J- : - s: r. W93" 02.431* I J i l l l <0.05 57.6 162 <-2: <0.1 <0.35 <0.05 <0.25 0.39 279 1.52 1131403 403FN 4C3FN1 f drum 4S8.95 A3 17 5 N44* 54.134* 5r-.' WS3* 02.431* <C.C5 - <005 37.8 0 2 5 <0.25 ` <0.1 <0 > <0.05 <325 0.19 7.92 1.49 0.60 087 1.36 0.83 0.73 1.10 1.88 1.16 0.36 0.64 0.66 0.36 1.30 0.64 1.33 7.00 2.52 0.50 0 77 030 1.44 1.37 M* 0.63 7.09 7 92 A- Card fR IX Novem 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Table A-1.3M Analysis of Fish Tissue Samples for P FC s (ND = RL) ______________________ Taxa abbreviations: Freshwater drum - F drum; Smallmouth bass = Sm bass; White bass - W bass; Green sunfish = G sunfish o o Ll. c K VmUQi.. VoLQii.- Tissue ID Lab ID Taxa (common) Sample mass (whole body, g) Sample length (whole body, cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFHS PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA 404 404FN 404FN1 405 405FN 405FN1 407 407FN 407FN1 408 408FN 408FN1 o 409FN A W . ' 410 410FN H 411 411FN 411FN1 412 412FN 412FN1 413 413FN 413FN1 414FN 415 416 416FN 417 417FN 417FN1 419 419FN 419FN1 420 420FN . "V *2* 421FN 423FN 423FN1 425 ' 425FN 426 426FN 426FN1 427 427FN 427FN1 428 428FN 428FN1 429 429FN 429FN1 430 430FN 431 431FN 431FN1 432 432FN 432FN1 433 433FN 433FN1 W bass 435.45 40 7 6 13 N44 52.007' N44852.007' Wbass 276.69 35.5 5 6 13 N44852.007' N44852.007' F drum 344.73 38.5 7 7 8 N44849.280' N44849158' Fdrum ' c' - p i e r =' *42^111: 15 S t e l i J J I P 11; N44* 48.93$' 349.27 T f i l i l i l f | d h44".'9=3-- 362.87 40 24 m j j i l j l .`.in * - N4448259` W 4P 259* N44" 48.259' Wbass 340.19 37 6 1 9 N44 54 708' ,J..J 54 640' Fdrum 122.47 28 3 2 10 N44853.874' N44855.312' Fdrum 258.55 36 10 2 10 N44853.874' N44855.312' f ' f i l i H | B i l l P J N44 55.088' N44" 55.343* B M i l 35.5 p p p I I 16 \U " ^ K rj 95.25 25.5 l l B w l m 16 v :i -= :C N44* 46.205* Bluegill 13.61 .: . _ 17 N44* 45.898' N44* 45.898' Bluegill 68.04 18 3 10 10 N44 45.926' N44845.898' Bluegill 31 75 13.5 2 10 .i - 22.68 `3 Bluegill I B S B I K ^ 11 10 j j P ! N44* 45.926* S B * | 10 ` i- V . I B M I l i N B I 20 N44- 43.898' N44- 45.898* N44* 46.257* Fdrum * ,-* 7 10 N44* 48956' N44848 449' Fdrum 730.28 49 10 7 10 N44848.956' N44848.449' Fdrum 349.27 36.5 15 7 10 N44848.956' N44848.449' i- arum Fdrum -4389 38 1 j l B l I l i B j 10 49 20 J P M | l | N44* 48,449* N44" 56.89(7 Fdmm 37,5 13 W 3 k g g l j j he 3S91 N44* 56,890* Smbass 4 6 N44856.889' N44856.890' Smbass 331.12 36 4 4 6 N44856.889' N44856.890' W93800.813' W93800.813' W93800.537' W93 00.240' W93* 00.240' W93811 978' W93 08.835' W Wyj* w w w V.v4 W92856.380' W92853.478' W92853.478' W92853.478' ,*,.. ____ W93800.219' W93800.219' Wi-~ 219* W93* 4.565' W93` Q456S W93804.565' W93804.565' W93800.813' W938 00.813' W93* 00.431' az y x W93800.733* W93 00.733' W93807.331* W93807.331* W93" 07.424' W92" 57.78? AV ; * .'r,2 ;__ ; W92853.427' - - 7 ' A V" .'* AH" A'V W93* 00.543' W93800.543' W93800.543' , W 'I V,.' Aj- HJ** W93804.281' .*_ .. W93804.281' <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <01 <0.1 <0,t <0.1 <0.1 <01 <0.1 <0.1 <0.1 <01 <0.1 <0.1 <0.1 <0.1 <0.1 <01 <0.1 0.34 0.06 <0.05 <005 <005 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <005 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0 05 <0.05 59.7 0.74 <0.25 <01 <0.35 0.07 0.40 0.58 3.64 2f6 1.78 105.0 0.63 <0.25 <01 <0.35 <0.05 <0.25 0.99 5.85 3.02 2.48 20.9 0.24 <0.25 <0.1 <0.35 <0.05 <0.25 0.31 2.48 1.72 2.15 m 0 27 <0.25 o f # <0.35 <0.05 029 3 35 1.68 2.13 15J) 0.22 <0.1 <0.35 005 <0.25 0.15 1.92 1.64 162 12.3 0 22 <0.1 <035 0.58 2 62 1.33 1.07 62.2 0.61 <01 <0.35 <0.05 0.50 3.54 1.94 1.67 5.9 0.06 <0.25 <01 <0.35 <0.05 <0.25 0.18 0.47 0.27 0.26 221 0.07 <0,25 <0.25 <0.25 <0.05 <0.1 0.09 0 72 0.86 0.61 12.0 104.0 0.05 l l l i B B l <0.25 0.63 **;> <0.25 Ilip M <0.25 M M l <0.1 i P I l H <0.1 i l i l M B 0.77 5 54 0.S6 0 39 338 2.15 34.5 0.31 <025 <0.25 <0.25 <0.05 <0.1 <0.05 1.13 0.73 0.7* 14.6 0.10 <0.25 <0.25 __L 0.28 1.08 0.45 0.29 21.5 0.11 <0.25 <0.25 <0.25 <0.05 0.11 0.06 o n 0.68 0.63 10.7 0.08 0.29 <0.25 <0.25 <0.05 <0.1 0.06 0.57 0.35 0.28 16.2 0.11 j p K g B H l <025 <0,05 i M M B i 1.02 0.74 0 57 4,5 0.07 l l i M i <025 Ball 0.06 0.33 0.19 018 66.4 0.58 <0.25 <0.25 jBfc< 0.58 3.72 1.89 1.76 9.1 0.35 <0.25 <0.25 <0.25 0.20 2.28 1.97 2.09 21.0 0.16 <025 <0.25 <0.25 <0.05 <0.1 0.23 0.70 0.57 0.50 19.2 0.35 <0.25 <025 <005 <0.1 0.13 1.62 1.42 1.51 15 4 0 22 <0.25 <0.25 <0.25 <0.05 i M | 0 26 1.71 1.40 U 1 12.2 0d2 B f e i l i l -C.D <0.25 <0.05 0.11 1,18 0.96 1.84 32.1 0 20 <C.25 <0.25 <0.05 l i m i l i 014 14 0.73 0.77 31.9 0.72 0.28 <0.05 <01 <0.05 1.61 1.22 0.99 41.9 0.46 <0.25 <0.25 <0.25 <0.05 <0.1 <0.05 2.24 3.52 1.26 November 2012 Cardno ENTRIX A-15 Table A -1.3M Analysis of Fish Tissue Samples for PFCs (ND = RL) Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass: White bass = W bass; Green sunfish = G sunfish 434 434FN 434FN1 Smbass 436 436FN W i i Or -\rts 437 437FN B iifc l 438 438FN *.V: Wbass 439 439FN 439FN1 Fdrum 440 440FN 440FN1 Fdrum 442 442FN 442FN1 Wbase 443 443FN .'S'V! 444 444FN 444FN1 Fdrum 445 445FN `.C-V Fdrum 446 446FN 446FN1 Fdrum 447 447FN 447FN1 Fdrum 448 448FN 448FN1 449 449FM m s f v A j- 450 450FN 450FN1 A 'l 5 452 452FN Bold, Italicized font- Detects Wbass 181 44 30 : i 6 N4455 889' 444.52 M B T :1 6 fM *> *'? iW IW p i l l i I M I V-J i- ,v 34 B i f e j i i g M N44 56.858* 208.65 33 4 4 7 N4456.858' 467.20 44 12 4 7 N44 56.858' 394 63 8 5 " N4454 013* 204.12 M i m i * N4454.013' i a l i t i S ig i 3 122.47 m m 149.69 29.5 3 12 N4453.927' N41* 3 11 N4455.488' 276.69 36 4 3 11 N4455.488' 14969 29 5 J. ` 12 N4455611' 412.77 m m Ip lll fl! j i S l I l 10 N4454.880' N44 54.880' l n n 11 V M M ': N44 56 890' *.4A` 1/ 3gff M4456.732' N44 56.732' N4456.732' N44' 53.739* N44 54.052' N4454.052' N4455.812' N44* 55.812' N44 55.643' N44 54.688 VUQ-jrn A':i` .V-565 }4'<? A:`~' 4'?W93 04.123' W9304.123' W9302.281' W93' 02.281' W93" 08.779 W9308.779' W93" 06.763 W9306.763 W^ nfi w A * W93 12.046' -.\ro i ??** 04 ?8T W9304.281' *."*.:1,, :7 V . W9303734' W93" 03.734' W93"03.734' W9301 789' W9301.789' W93" 08.597' W930&5971 W93 06.352' W9306.352' W9306 556' W93 12.088* <0.1 <0.05 <0.05 <0.05 0.09 <005 <0,05 0 23 0.35 0.21 027 0.37 0.11 <0.05 019 <0.05 24.7 39.7 <0.05 47.4 <0.05 41.9 0.05 9.5 0.58 0.08 008 5.9 152.0 51.6 <0.05 95.7 <0.05 <0.05 <0.05 <0 05 0.06 f9.9 8.6 10.1 34.4 75.7 010 <0,05 1 0.63 <0.25 0.48 0 91 \ < 0.1 1.28 I f i l l l l 0.24 <U1 0.26 0.13 2.08 < 0.1 2.88 < 0.1 207 \ < 0.1 0.07 < 0.1 0.12 < 0.1 0.13 < 0.1 0.15 <01 < 0.1 < 0.1 < 0.1 <025 <0.25 < 0.1 < 0.1 <u i <01 < 0.1 < 0.1 < 0.1 < 0.1 <u1 < 0.1 <01 < 0.1 < 0.1 < 0.1 <0.25 <0.05 < 0.1 <0.05 < 0.1 mm OM <0.25 <0.05 j 0.41 <0.25 <0,25 <0.05 <0.05 0.07 0.15 <0.05 <0.25 <0.05 ; ( ||| <0.05 0.13 0.18 <0.25 0.06 0.12 0.48 <0,25 <0.25 <025 0.06 <0.05 0.07 0.10 <0 05 0.12 0.08 0.10 <0.05 pllfa <0.25 < 0.26 0.23 0.32 0.37 0.28 0.31 0.46 0.87 Cara FrIx Novert. 72 A- Mississippi River Pool 2 PFC Assessment - Fish Tissues and W ater-Sum mer 011 Table A-2. AXYS Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; White bass = W bass; Green sunfish = G sunfish Field ID Tissue ID Lab ID Taxa (common) Fishmass (g) Fish length (cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFNA PFDA PFUnA PFDoA e< u00.. 010 010FN :i? -V 022 022FN 033 033FN 033FN2 045 045FN 045FN2 054 054FN 054FN2 065 065FN 065FN2 078 78FN 078FN2 ':7 K *. 102 ' 2'N ' 7--.V 113 113FN 113FN2 126 126FN 126FN2 137 137FN 137FN2 IB ^ M B l M i 159 159FN 170 170FN2 180 180FN 180FN2 192 192FN 192FN2 203 203FN 203FN2 ?H 214FN 214FN2 224 ; ,v - \ !/"- *1? 232 232FN 232FN2 246 246FN 246FN2 258 258FN 258FN2 269 269FN 269FN2 280 280FN H P H IV 2S'-`J 291FN2 Fdrum | H Q 30 i b | | j 10 m N44D45.382' w: - ` Blueoll 108.86 17 j f l l 10 I j j j l j l N44` 46.426' N44845.382' -ii-. 226.80 { S B I j p l i N44* 47.743' N44" 47.471' .Vi -fl Wbass 185.97 25.5 8 3 N44847171' N44 46.447' W93801.438' Smbass 249.48 27 3 3 2 N44 56.139' N44856.589' W93806.019' Wbass 217 72 26.5 2 2 N44853.664' N44 53.865' W93 09.874' Fdrum ificS 35 8 j f l ^ ^ j f j j NAl u ' 54 -m:. fi.-y -2.'48' Smbass S j j M p M i p a i j j l l l l B i l l N44` 54.606' N44` 54.001' :ry- i;-.* Smbass Wbass - I - .-5 1016.05 33 42.5 j l l f a t i S l B N44853.972' 7 4 N44849.719' `,41 N44 49.047' W93" 11.44t* W93800.664' Bluegill 158.76 20 4 9 2 N44846.162' N44 46.244' W92 57.877' Fdrum 725.75 40 11 4 N44846.725' N44846.982' W92856.028' Smbass 458.13 40 i J B I l l I I M 31 P f i 10 N44" 47.038' Nli'4.* br. N44847.108' V 4 " ic 2j0' : W92' 52.724' F drum 449.06 33 M L N44* 51.331' N44* 52.020' W93800.780* Smbass 426.38 31.5 3 5 1 N44 53.736' N44853.279' W93801 757` F drum 449.06 33 5 5 2 N44853.430' N44 53.066' W93801.069' Smbass 276.69 26 2 5 4 N44 54.153' N44853.732' W93802.478' Wbass 839.15 66 :,4` f2 .'" ' M4"M .'IO1 W93800.853' A: 5 Smbass 362.87 222.26 m m ii ll lilB J U N448 56.7971 N44" 56851 38.5 8 ( f e t " 3 ! l | N44* 56.797* . N44"56.885' : 31.5 3 4 2 N44856.848' N44856.553' .-V W93' 04.519* W93804.049' Fdrum 1143.05 34 6 4 5 N44" 55.805' N44855.458' W93802.890' F drum 33112 38.5 8 17 N44853.743' N44853.634' W93811.382' B l I 1 I B M M4" b* 7*o Smbass 181.44 I l l y l i j i l l l t m * 7r ' N44* 49.284' W93-00.683' A"o v v m m | l j 34 i r i B j B I M B i <25 <25 M im W92* $2.521' i f i g c f i < 5.0 356 ' 2 ` <2.5 i j l f c p i I I I <25 < 2.5 10.6 5.43 385 W93801.521V u < 5.0 44.6 <2.5 l l l l l <2.5 <2.5 I t e p i 3.09 I I ! W93800 999' <5.0 < 5.0 75.3 4.63 <2 5 <2.5 <2.5 <2.5 <2.5 <2.5 <2.5 < 2.5 < 2.5 W93805.240' < 5.0 < 5.0 34.3 <2.5 <25 <2.5 <2.5 < 2.5 <2.5 <25 <25 <2.5 < 2.5 W93 09.064' <5.0 < 5.0 40 <2.5 <2.5 <2.5 <25 <2.5 <2.5 <2.5 <2.5 < 2.5 < 2.5 W938 11.459' <*5.3 < 5.0 4215 <25 <2.5 ` * 5 * e. >! <75 */ s <?-t A"1* * ! 44 1 < 5.0 15.6 I f c f i l l <25 <25 <25 7 5 <2.5 2r W938 10.274' <5.0 j l l l j y 51.3 <2.5 <25 <2? < 2.5 v?5 <25 <25 "76 <5 W93800.475' <5.0 < 5.0 59.5 < 2.5 <2.5 <2.5 <2.5 <25 <2.5 <2.5 <2.5 <2.5 <25 W92856.370' < 5.0 < 5.0 37.4 <2.5 <25 <2.5 < 2.5 <2.5 <2.5 <2.5 <25 <2.5 <2.5 W92856.022' <5.0 < 5.0 12.6 < 2.5 <2.5 <2.5 <2.5 <2.5 <2.5 <2.5 <2.5 <25 <2,5 W92" 55.336' 66.6 m m <2.5 ^H p 3.78 W928 52.4381 <5.0 <50 112 13.1 '2 5 <25 <25 <25 75 ^7? <25 <76 312 W93" 00.780' I p ^ B <4.9 29.3 <2.4 <2.4 B l i i l <2.4 <2.4 W93801 129' <4.9 <4.9 13.2 <2.5 <2.5 <2.5 <2.5 < 2.5 <2.5 <2.5 <25 < 2.5 < 2.5 W93800.922' <4.4 <4.4 46.3 <2.2 <22 <22 <2.2 < 2.2 <2.2 <2.2 <2.2 < 2 2 <2.2 W93801 769' < 4.9 <4.9 61.9 <2.4 <24 <2.4 <24 < 2.4 <2.4 <2.4 262 <2.4 < 2.4 W93* 00.847* <4.7 < 4.7 m - 23 <2? 2' <2 j 73 <2,3 3M5 281 7 3 W93804.30? <5.0 31.1 <2.5 iB li I M I <25 M B W93-Q430? 5 794 <2 ? -7 2 '2 ? <2? ` 2? <22 <7 4.24 <7? <22 W93" 03.620' <4.8 <4.8 21.6 < 2.4 <2.4 <2.4 <2.4 <24 <2.4 <2.4 <2.4 <2.4 <2.4 W93802.999' < 4.6 <4.6 9.33 <2.3 <23 <2.3 <2.3 <2.3 <2.3 <2.3 <23 <2.3 <2.3 W938 10.826' < 4 7 <4.7 44.4 <2.3 <23 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 W93 07.886' H <4.7 52A 1 I I B I 1 <2.3 <2.3 <2.3 <2.3 l l l l l l 305 Jp g W93*00585' <4,6 <4.6 44.6 23 <23 2 <73 23 <2.3 2? <73 73 November 2012 Cardno EN TRIX A-17 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table A-2. AXYS Analysis of Fish Tissue Samples for PFCs (ND = RL) _________________ Taxa abbreviations: Freshwater drum = F drum; Smallmouth bass = Sm bass; W hite bass = W bass; Green sunfish = G sunfish Reid ID Tissue ID Lab ID Taxa (common) Rsh mass (g) Rsh length (cm) Age (yr) Reach Start Northing End Northing Start Westing End Westing PFHS PFOS PFOSA PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA e CUQDl. fill 3Q2FN2 315FN2 ^ p i l p j (M 99 79 85 N44"49.270* N44846.389' 323 323FN 323FN2 F drum 258.55 35 8 6 10 N44851.137' 334FN 346 346FN 370FN 383 383FN 360FN2 37FN2 383FN2 Fdrum Wbass Wbass Smbass 226.80 VI'-'208.65 303.91 ... 2 6 12 I M slPll j|pi3 IBjf 8 f l l IlIR *31 8 8 N448 50 689' N44* 55.451' N44* 55.955' N44* 53.870' N44846.243' 390 390FN 390FN2 Smbass 154.22 400 400FN r|| 425 Vr. 400FN2 Wbass 208,65 |||PR|||P M 436 447 447FN 447FN2 450 450FN 450FN2 Bold, italicized fonts Detects Smbass Fdrum Wbass 444 27669 412.77 28.5 3 9 14 N44* 45.925' 32 3 5 6 N44854,134' IMP|jil|. IBM N44-54.708' i | jUp IM N44*46^95' 39 Bil ||| 6 N44*56.8891 ,, 4 3 11 N44855.488' 41 10 1 10 N4454.880' N44 49.133' N44* 46.256' N44850.990' N44* 50435' N44" 56.031* N44* 56.528* N44854.948' N44845.286' N44* 45,970' N44853.535' ,*y N44#46.257' N44*56.890" N44855.812' 1. W93800.623' W93 00 689' W93a06.842' .V?j-C33'4' W93* 08.846' ,\__ 4. W92 56 390' W9302.431' W9258.07T W9304565* W93806.763' W93812.046' W93* 00.429' <4.8 <4.8 35.6 | J W | <2.4 ` 24 j^RH <2.4 ` / 4 llalli ^llllSp" < ,4 <2.4 W93800475' <47 <4.7 3f.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2,3 <2,3 <2.3 <2.3 W93800.659' <4.5 <45 17.5 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <23 <2.3 W93 00 756' <47 31.7 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 <23 <2.3 tjfcI<4.8 <4.8 45.7 m <24 <2.4 jHjH '2 4 2.43 1 1 1 *74 ftlP^:W93" 05.689' 335 <23 PisH J!jpii M R <2.3 <; '2 3 WS3" 07.857' <4.2 jp^ 75.5 <2.1 M l p n i <2.1 B ill 4.37 2.36 <2.1 ' 2______ <4.5 51.5 <2.2 <2.2 <2.2 <2.2 <2.2 <2.2 <2.2 W92856.333' W93801.343' W93*12,042' W92*57.914' 'WCI2ni' W93806.352' <4.9 <4.9 <4.5 <4.5 <4.7 <4.7 <4.7 <4,6 <4.6 <4.5 <4.5 <4.5 <4.5 10.9 <2.5 <2.5 <2.5 <2.5 <2.5 <2.5 <2.5 <2.5 <25 <2.5 66.9 2.84 <2.3 <2.3 <23 <2.3 <2.3 <2.3 3.18 <2.3 <2.3 P ^ l MW fellB <2.3 <23 mppi Mi 65.2 `74 iifeiH laliiil >74 291 j! 43 1?3 <2.3 <23 <2.3 **j <2.3 233 <2.3 <2.3 11.8 <22 <2.2 <2.2 <2.2 <2.2 <2.2 <22 <2.2 <2.2 <2.2 80.6 2.535 <2.3 <2.3 <2.3 <2.3 <2.3 <2.3 5.945 5.155 4.49 A- Care Vr i x Noverr, 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 A.2 Figures Figure A-1. Reach 1 Fish Collection Locations November 2012 Cardno ENTRIX 9 000 2.4W 78* 4** a I M Wfc * .9 4 48674 Mj4m*O n 93983 MNMttwIHU MWM4.IL 88* 4 894 P*4M t F t* So* 8 Hl I M n 9 , m 48264 * f4 M H aw 4 fi O 4 W 0 * m . Ml 48488 <H * 9 w 0 9 F O 8 *k 7780 * m A *m .MI 49187 t*C9M6Lmw4 )M0 8PM* CiMM 9,0449841 Drawn By XL Reviewed By Project No 1105061.00 Date- October. 2011 " Reech Boundaries Pish Cofleefion Points May/June August O September Reach 1 A-19 Reach 2 Fish Collection Locations Mississippi River Pool 2 PFC Assessment - Fish Tissues and W ater-Summer 2011 3j -I OMm mm wmu* pim* Svft s Wm IONm , mi / MPOMB**m7TO0IONi Aw>Nb**,M mWT Drawn By' JLL Reviewed By Project No 1105061.00 Date October. 2011 Reach Boundaries Fish Collection Points May/June August O S ep tem b er Reach 2 Cara Fr x Noverr. 12 Mississippi River Pool 2 PFC Assessm ent - Fish Tissues and Water - Summer 011 Figure A-3. Reach 3 Fish Collection Locations November 2012 Cardno ENTRIX CUM 9m * Mwm.ILM4G OfMMJvmOdM 1tt1 MwW a m WmIOM M4MH Drawn By XL Reviewed By - ^ y Project No 1105061.00 Date: October. 2011 -- Reach Boundaries n th Collection Points May/June August O September Reach 3 A-21 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Figure A-4. Reach 4 Fish Collection Locations A- Care iR IX Mm 7W ltM **lttlN* w<fc*nn,W574 VtfM*. m 3 9 ! II i l 4flMNJWMM CM M JtO* CIMIMMIIOH4B241 Drawn By XI Reviewed By Project No 1105061 00 Date October. 2011 -- R each Boundaries Pish Collection Points May/June August O September Reach 4 Noveri, 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 011 Figure A-5, Reach 5 Fish Collection Locations November 2012 Cardno EN TRIX 0 70S 1 , G 4? CiMUheskt TWRMXTHftftM* W sfctrtm.m 4MP4 3V M M M C t I II m*4 NMOIm . i G CM M atiOttw 11tse L < M B in* Cheta* OH45341 Drawn By XL Reviewed By Prefect No 1105061.00 Date October, 2011 " Reach Boundaries Fish Collection Points May/June August O September Reach 5 A-23 Mississippi River Pool 2 PFC Assessm ent - Fish Tissues and Water - Summer 2011 Figure A-6. Reach 6 Fish Collection Locations o 7M ft < * I U * T4 8 SI 11 liM A 0 ** CMMJKGttM lltR M M M x CiMUM. OH 2 4 1 Draw By XL Reviewed By Project No 110506100 Date: October, 2011 -- Reach Boundaries Fish CoBectlon Points May/June August O September Reach 6 12A- Caro tRIX Novem V/ V Mississippi River Pool 2 PFC Assessment - Fish Tissues and W ater-Sum m er 011 i Figure A-7. Reach 7 Fish Collection Locations November 2012 Cardno ENTRIX A-25 Figure A-8. Reach 8 Fish Collection Locations Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 0 MS Mata S4N to * * * * . M 294 9m 4MMe*M m s i* m h a >w CM** * *77*0 4*497 Drawn By XL Reviewed By Project No 1105061.00 Date October, 2011 -- Reach Boundaries Pish Coiecdon Points May/June August O September Reach 8 Caro FrIx Noverr, *I2 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Figure A-9. Reach 9 Fish Collection Locations November 2012 Cardno EN TRIX i e a 4VM *M tCt U*47 0M M .1M 93989 CMm** OMm MM Drawn By XL Reviewed Ety Project No 1105061.00 Date: October, 2011 Reach Boundaries Pish CoHaction Points May/June August O September Reach 9 A-27 Figure A-10. Reach 10 Fish Collection Locations Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 e 0 1,000 2.000 4,000 W4wtwt, IN 40974 OMn 3V n<lm C t. t#*t7 VHMA Wl 63903 0 0 0 ) MmtL0M 40 IM iw w M ft O M M *49PMM Mm* >4 Nv*a CH0M W l<H ra. Ml 4 M Aiw* i> OWm r9*+x77m M > M i t , Ml 40107 Chtelw tJ t& ftM MISSLwdMfc 0 * C b o n * . ON 49241 Dra*fi By XL Reviewed By Prefect No 1105061 00 Date October. 2011 -- Reach Boundaries Fish Collection Pointe May/June O August O September Reach 10 Card R IX Novem 2 Appendix B Water Sample Collection Tables & Figures Appendix B Water Sample Collection B.1 Tables Table B - 1 . 3M Analysis of W ater Samples for PFCs (ND = RL) Field ID Tissue ID Lab ID I Reach Start Northing Start Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHpA PFOA PFDA PFUnA PFDoA < X X LL. Q. <z u. CL 501 501SF 501SF1 10 N44 46.926' W92 53.313' 26 12.5 136 <4.0 9 2 .4 16 12.9 5 1 3 7 <2.0 <2.5 <4.0 <4.0 502 502SF 502SF1 10 N44 45.382' W92 52.521' <2.0 <2.0 <2.0 <4.0 9 .2 4 4.43 <2.5 <2.0 2 .3 9 <2.0 <2.5 <4.0 <4.0 503 503SF 503SF1 8 N440 47.471' W93 01.521' <2.0 <2.0 <2.0 <4.0 5 <4.0 <2.5 <2.0 <2.0 <2.0 <2.5 <4.0 <4.0 504 504SF 504SF1 8 N44 47.086' W93 01.118' <2.0 <2.0 <2.0 <4.0 9 .1 4 <4.0 <2.5 <2.0 4.56 <2.0 <2.5 <4.0 <4.0 505 505SF 505SF1 8 N44 46.447' W93 00.999' <2.5 <2.0 <2.0 <2.0 <5.0 <4.0 <2.0 <2.0 2 .5 3 <2.0 <2.5 <4.0 <4.0 506 506SF 506SF1 3 N44 56.048' W93 06.085' <2.0 <2.0 <2.0 <4.0 <5.0 <4.0 <2.5 <2.0 2.8 1 <2.0 <2.5 <4.0 <4.0 lill IIBIIIf i l l507 507SF 507SF1 N44 56.589' W93 05.240' <2.0 <2.0 <2.0 <4.0 <2.5 <2.0 2.2 5 <2.0 <2.5 <4.0 <4.0 508 508SF 508SF1 3 N44 55.511' W93 06.663' <2.0 <2.0 <2.0 <4.0 <5.0 <4.0 <2.5 <2.0 2 .2 4 <2.0 <2.5 <4.0 <4.0 509 5C9SF 509SF1 2 N44 53.823' W93 09.231' <2.0 <2.0 <2.0 <4.0 <5.0 <2.5 <2.0 2.0 6 <2.0 <2.5 <4.0 <4.0 510 510SF 510SF1 2 N44" 53.865' W93 09.064' <2.0 <2.0 <2.0 <4.0 <5.0 <4.0 <2.5 <2.0 2 .1 5 <2.0 <2.5 <4.0 <4.0 511 511SF 511SF1 2 N44 54.699' W93" 07.907' <2.0 <2.0 <2.0 <4.0 <5.0 <4.0 <2.5 <2.0 <2.0 <2.0 <2.5 <4.0 <4.0 512 512SF 512SF1 1 N44 54.149' W93 11.459' <2.0 <2.0 <2.0 illll513 513SF 513SF1 N44 54.001' W93" 11.443' <2.0 <2.0 <2.0 <4.0 <4.0 <5.0 <5.0 5.15 <4.0 <2.5 <2.5 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.5 <2.5 <4.0 <4.0 <4.0 <4.0 514 514SF 514SF1 I 1 N44 53.636' W930 10.274' <2.0 <2.0 <2.0 <4.0 <5.0 <4.0 <2.5 <2,0 2 .2 3 <2.0 <2.5 <4.0 <4.0 515 515SF 515SF1 10. N44" 46.018' W92 52.305' 2.3 7 <2.0 4.2 <2.0 18.6 6.05 2.96 <2.0 6 .1 2 <2.0 <2.0 <2.0 <2.0 516 516SF 516SF1 10 N44 45.382' W92 52.521' <2.0 <2.0 <2.0 <2.0 19 .5 <5.0 <2.0 <2.0 3 .9 6 <2.0 <2.0 <2.0 <2.0 517 517SF 517SF1 10 N44 46.926' W92 53.313' 3 3 6 60.5 136 <2.0 648 74.6 3 1 .7 8.4 2 1 9 2.02 <2.0 <2.0 <2.0 518 518SF 518SF1 9 N44 46.207' W92 56.501' <2.0 <2.0 2.1 5 519 519SF 519SF1 9 N44 45.987' W92 57.531' <2.0 <2.0 <2.0 <2.0 <2.0 14 .7 <5.0 <2.0 <2.0 3 .5 9 <2.0 <2.0 <2.0 <2.0 B i l l11.4 <5.0 <2.0 2.5 2 <2.0 <2.0 <2.0 <2.0 520 520SF 520SF1 9 N44 46.333' W92 58.151' <2.0 <2.0 2.7 7 <2.0 16.4 <5.0 <2.0 <2.0 3 .5 5 <2.0 <2.0 <2.0 <2.0 November 2012 Cardno EN TRIX B-1 521 521SF 521SF1 8 N44 46.444' 522 522SF 522SF1 8 N44 47.081' 523 523SF 523SF1 8 N44 47.463* 524 524SF 524SF1 7 N44 48.609' PS525 525SF 525SF1 N44 49.305' fl526 525SF 526SF1 N44 50.012' 527 527SF 527SF1 6 N44" 50.602' 528 528SF 528SF1 6 N44 51.126' 529 529SF 529SF1 6 N44 52.673' 530 530SF 530SF1 5 N44 53.478' 531 531 SF 531SF1 u p N44 53.772' 532 532SF 532SF1 5 N44 54.371' 533 533SF 533SF1 4 N44 55.507' 534 534SF 534SF1 4 N44 56.082' 535 535SF 535SF1 4 N44 56.830' 536 536SF 536SF1 3 N44 56.586' i l l537 537SF 537SF1 N'44' 56.006' i l l538 538SF 538SF1 N44 55.616' 539 539SF 539SF1 2 N44 54.672 540 540SF 540SF1 2 N44 53.865' 541 541 SF 541SF1 2 N44 53.827' 542 542SF 542SF1 1 N44 53.637' lllf543 543SF 543SF1 N44 53.995' 544 544SF 544SF1 N44 54.140' B old, Ita lic iz e d te x t = D etects W93 00.988' W93 01.130' W93 01.516' W93 00.424' W93 00.573' W93 00.740' W93 00.576' W93 00.620' W93 00.927' W93 01.101' W93 01.856' W93 02.547' W93 03.004' W93 03.129' W93 04.115' W93 05.248' W93 06.160' W93 06.650' W93 07.920' W93 09.056' W93 09.236' W93 10.279' W93 11.442' W93 11.461' <2.0 <2.0 2 <2.0 <2.0 3.51 <2.0 <2.0 <2.0 <2.0 <2.0 2.77 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 2.6 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 4 .1 7 <2.0 7.1 <2.0 <2.0 < 2 0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 < 2 0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 ------------------------------- <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 17.2 20 <10.0 1 6 .7 <10.0 <10.0 16.8 10.3 <10.0 3 9 .1 <10.0 <10.0 12.1 <10.0 <10.0 <10.0 <10.0 12.8 <10.0 <10.0 <10.0 <10.0 11 12.2 6.02 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <5.0 <2.0 2 .1 5 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 3 .2 9 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 3.46 <2.0 3.9 5 <2.0 <2.0 <2.0 4.57 <2.0 2.75 <2.0 <2.0 <2.0 4.73 <2.0 2.26 <2.0 <2.0 <2.0 23.3 <2.0 2 9 7 <2.0 <2.0 <2.0 <2.0 <2.0 2.32 <2.0 2.51 <2.0 <2.0 <2.0 <2.0 <2.0 2.77 <2.0 3.16 <2.0 <2.0 <2.0 2.34 <2.0 <2.0 <2.0 2.53 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 if Card RIX Novem Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Table B- 2. AXYS Analysis of Water Samples for PFCs (ND = RL) Field ID Tissue ID Lab ID Reach Start Northing Start Westing PFBS PFHS PFOS PFOSA PFBA PFPeA PFHxA PFOA PFDA PFUnA PFDoA < Q. X u. Q- <z LL Q_ mi 502 503 504 505 506 507 508 509 510 511 512 513 514 515 518 519 520 524 525 526 527 528 529 530 531 532 501SF 502SF 5033" 504SF 505SF 506SF 507SF 508SF 509SF 510SF 511 SF 512SF 513SF 514SF 515SF 518SF 519SF 520SF 524SF 525SF 526SF 527SF 528SF 529SF 530SF 531 SF 532SF 501SF2 10 N44 46.926' W92 53.313' 19 6.3 502SF2 10 N44 45.382' W92 52.521' I m <2.7 503SF2 i l l l l N44 47.471' W93 01.521' 2.3 <2.0 504SF2 8 N44 47.086' W93 01.118' 2.9 <2.4 505SF2 8 N44 46.447' W93 00.999' <2.3 <2.3 506SF2 3 N44 56.048' W93 06.085' <2.0 <2.0 507SF2 I j g j N44 56.589' W93 05.240' <2.0 < 2 0 508SF2 -- N44 55.611' l l B l l l l B j l <2.0 1 509SF2 I l l l i i l N44 53.823' W93 09.231' <2.0 <2.0 510SF2 2 N44 53.865' W93 09.064' <2.0 <2.0 511SF2 2 N44 54.699' W93 07.907' 2.6 <2.0 512SF2 1 N44 54.149' W93 11.459' <2.0 <2.0 513SF2 lg | | | l N44 54.001' W53 11.443' <2.5 <2.5 514SF2 lllliB i N44 53.636' W93 10.274' <2.0 <2.0 515SF2 10 N44 46.018' W92 52.305' 4 .5 <3.4 518SF2 9 N44 46.207' W92 56.501' <4.1 <4.1 519SF2 9 N44 45.987' W92 57.531' <3.7 <3.7 520SF2 9 N44 46.333' W92 58.151' <3.5 <3.5 524SF2 M l N44 48.509' W93 00.424' 4 .7 <3.3 525SF2 l l l i l l i N44 49.305' <3.4 526SF2 1B B 1 N44 50.012' W93 00.740' <3.6 <3.6 527SF2 6 N44 50.602' W93 00.576' <3.3 <3.3 528SF2 6 N44 51.126' W93 00.620' <3.7 <3.7 529SF2 6 N44 52.673' W93 00.927' <3.5 <3.5 530SF2 1 1 1 N44 53.478' 531SF2 l l l l N44 53.772' W93 01.101' W93 01.866' 6 .8 <3.7 <3.6 <3.7 532SF2 5 N44 54.371' W93 02.547' <4.3 <4.3 85 <1.8 <2.7 M i l l <2.0 <1.0 <2.5 <1.2 <2.3 <1.2 <2.0 <1.0 <2.0 <1.0 <2.0 <1.0 <2.0 M u l l <2.0 <1.0 <2.0 <1.0 <2.0 <1.0 <2.5 <1.2 <2.0 <1.0 5.0 <1.7 <4.1 <2.1 <3.7 <1.8 <3.5 <1.7 4.94 M IM II <4.9 M M I ll <4.9 <1.8 3 .4 5 <1.6 <3.7 <1.9 <3.5 <1.8 9.2 -- <3.7 <1.8 <4.3 <2.1 74 6.4 6 .9 2.5 77 l l l i l l i <1.8, <1,8 <1.8 13 <1.4 <1.4 <1.4 <1.4 <1.4 <1.4 <1.4 <1.4 6.4 1.0 <1.0 <1.0 j i i i i i i <1.0 <1.0 <1.0 <1.0 13 <1.2 <1.2 <1.2 2 .2 <1.2 <1.2 <1.2 <1.2 6.9 <1.2 <1.2 <1.2 1.3 <1.2 <1.2 <1.2 <1.2 4 .3 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 4.4 S I M -- <1.0 <1.0 <1.0 -- <1.0 <1.0 5.5 I W B I M <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 9.1 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 M B ! <1.0 8.1 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 3.9 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 9.2 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 8.6 <1.2 <1.2 BI111111l i -- B <1.2 <1.2 <1.2 <1.2 8.0 <1.0 <1.0 <1.0 <1.0 B B IB I <1.0 <1.0 <1.0 19 <1.7 <1.7 <1.7 4 .0 <1.7 l l l i l l i <1.7 <1.7 14 <2.1 <2.1 <2.1 2 .7 <2.1 <2.1 <2.1 <2.1 11 <1.8 <1.8 <1.8 2 .0 <1.8 <1.8 <1.8 <1.8 17 <1.7 <1.7 <1.7 2 .5 <1.7 <1.7 <1.7 <1.7 18 <1.7 l-- 1 <1.7 3 .3 <1.7 <1.7 <1.7 <1.7 11 I M B llll <1.7 <1.7 <1.7 I I B M <1.7 <1.7 12 <1.8 <1.8 <1.8 <1.8 l l l l l l l l l i <1.8 <1.8 <1.8 17 <1.6 <1.6 1.9 3.2 3 <1.6 <1.6 <1.6 <1.6 11 <1.9 <1.9 <1.9 <1.9 <1.9 <1.9 <1.9 <1.9 9.9 <1.8 <1.8 <1.8 <1.8 <1.8 <1.8 <1.8 <1.8 33 <1.8 2.6 2.1 18 M i l <1.8 M B <1.8 9.0 <1.8 <1.8 <1.8 <1.8 I <1.8 <1.8 10 <2.1 <2.1 <2.1 <2.1 <2.1 <2.1 <2.1 <2.1 November 2012 Cardno ENTRIX B-3 Mississippi River Pool 2 PFC Assessm ent - Fish Tissues and Water - Summer 2011 533 533SF 533SF2 4 534 534SF 534SF2 4 535 535SF 535SF2 4 B old, ita lic iz e d te x t= D etects N44 55.507' N44 56.082' N44" 56.830' W93 03.004' W93 03.129' W93 04.115' <3.2 <6.6 <3.5 <3.2 <6.6 <3.5 <3.2 <6.6 <3.5 <1.6 <3.3 <1.8 12 <1.6 <1.6 <1.6 <1.6 <1.6 <1.6 <1.6 <1.6 10 <3.3 <3.3 <3.3 <3.3 <3.3 <3.3 <3.3 <3.3 11 <1.8 <1.8 <1.8 <1.8 <1.8 <1.8 <1.8 <1.8 Caro JFr ix " Noveri*. 2 V V; Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer Z011 B.2 Figures \ Figure B - 1. Reach 1 Water Collection Locations November 2012 Cardno ENTRIX B-5 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water --Summer 2011 Figure B-2. Reach 2 Water Collection Locations B-i Card P i x Mm TOeftM fM wftR* a WatccftM. M 46ST4 8 1 H lA w OMn 3 Utfttww Ci (Hit 7 i!s CMmoaOMm MN9MwR*4 MmwU Drawn By XL Reviewed By Project No 1105061.00 Date: October. 2011 Reach Boundaries \Afcter Coflection Points PPOS 0tgfL) fri Pool 2 SorfMi VWrtir Sw iptvt Reach 2 Novem 2 \ Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Figure B-3. Reach 3 W ater Collection Locations November 2012 Cardno EN TRIX Q 0 7M 1 , 0 2JKX> mmm*+***l 94 IS 6M PaMAn*M tat*#**M m G Drawn By JLl Reviewed By Prefect No 1105061.00 Date; October. 2011 -- Reach Boundanes V \ e r CoRecSon P oW s P FO S (n^L)inP d2 Surfaca W tfar S vrp te * Reach 3 B-7 Mississippi River Pool 2 PFC Assessment --Fish Tissues and Water - Summer 2011 Figure B-4. Reach 4 W ater Collection Locations B\ Card IR IX Novelin 12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Figure B-5. Reach 5 Water Collection Locations November 2012 Cardno ENTRIX Fm ' CumfcWw Draw By XL ReviewedBy Project No. 110506 1 00 Dal: October, 2011 -- Reach Boundaries Stater Coftecfcon Points PFOS (ngfL) in Pool 2 Surface V ttto r Samptes Reach 5 B-9 Mississippi River Pool 2 PFC Assessm ent - Fish Tissues and Water - Summer 2011 Reach 6 Water Collection Locations c)mh>i oeui TGftftMMwAftMt W*ft*rtfn.M 4MT4 VttMM.MOOH || tnlfrmfft. IN4094 4**4 M0** CMmuVMw C M M 0 49241 Drawn By JLL Reviewed By Project No 110506100 Date October, 2011 -- Reach Boundaries Vt*er CoRecfeon Points P F O S (n g ft)ln P o rf2 S ttrfsce S#wptes Reach 6 Card )rRIX FNoveri Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 Figure B-7. Reach 7 Water Collection Locations November 2012 Cardno ENTRIX B-11 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 0 0 799 1,500 3 ,0 6 0 i-igure B-8. Reach 8 Water Collection Locations .8 isi It & A l tliH M * OM)i SM PM M nm M a* M to a* *. MMM t t * 4 Kh w M m HIM MMnNJhrMM *. ** * A M A itet Offe P0twT7*O Am Aife*t, Ml 4M67 " "'" T l tH 9Lw M til ClMMJ. OBAB341 Drawn By XL Reviewed By Project No. 1105061.00 Date: October, 2011 -- Reach Boundaries VNOter e d r e d o n Points PFOS (ngflj in Pool 2 Surface Wtster Samples Reach 8 Cart F r iX Novem ,12 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 211 Figure B-9. Reach 9 Water Collection Locations November 2012 Cardno ENTRIX t-6 950 1 1 FM --3^I06 C*if* Offe* n* * m* inn Drawn By XL Reviewed By Project No. 1105061.00 Date: October. 2011 Reach Boundaries W&er e je c tio n P orts PFOS (n gfl) in Peol 2 Surface VMktarSam ptet Reach 9 Mississippi River Pool 2 PFC Assessment - Fish Tissues and Water - Summer 2011 a 3W M fcm C t Mr Ctoejf* 9Mb MS Nm m MMC Figure B-10. Reach 10 Water Collection Locations B* >/ Card F r !X Drawn B y XL Reviewed By Project No 1105061 00 Date October, 2011 Reach Boun(lanes VtterCoSect on Points PFOS (rtgfL) in Pool 2 Stiffen Wfcter Sampfet Reach 10 I Shaping the Future Toll-free 800 368 7511 www.cardnoentrix.com www.cardno.com Australia Belgium Canada Ecuador Indonesia Kenya New Zealand Papua New Guinea Peru United Arab Emirates United Kingdom United States Operations in 70 countries Deanna Luebker, PhD CT&RS 220 6E 03 fiS1 7 3 7 1 3 7 4 3M General Offices 3M Center S t Paul, M N 55144-1000 i" ,* V < f " - y ''' t 'Z - - " * '' ' ' J \ ' " > ^ \ ,a * *- '' vi S iT sr 3 ' V '1 1 !3 CERTIFIED M A IL 70101670000002250126 7G10 lb70 DODD 0225 012b