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A High Resolution Study of the Spatial and Temporal Variability of Natural and Anthropogenic Compounds in Offshore Lake Superior Sediments

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A High Resolution Study of the Spatial and Temporal Variability of Natural and Anthropogenic Compounds in Offshore Lake Superior Sediments A HIGH RESOLUTION STUDY OF THE SPATIAL AND TEMPORAL VARIABILITY OF NATURAL AND ANTHROPOGENIC COMPOUNDS IN OFFSHORE LAKE SUPERIOR SEDIMENTS. A THESIS SUBMITTED TO THE FACULTY OF THE GRADUATE SCHOOL OF THE UNIVERSITY OF MINNESOTA BY JON D. VANALSTINE IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE MAY 2006 Acknowledgements I would like to acknowledge the Geological Society of America, Sea Grant, UMD Department of Geological Sciences, and the Large Lakes Observatory for support and funding of this project. Mike King and the crew of the Blue Heron for a great cruise, Tom Johnson and Steve Colman for their insight and help as my advisors, Paul Wilkinson, Dan Engstrom, and Erin Mortenson for prompt 210Pb Analyses, Kris Rolfhus for MeHg analysis, Joe Werne and Jay Austin for help on issues with my thesis, Nigel Wattrus for many figures and creating visual effects in my presentation, Sarah Grosshuesch and Yvonne Chan for assistance in the lab, and Isla Casteneda, Lindsay Powers, Andy Breckenridge, and Jim Russell for advice and help throughout my two years at LLO. ii Abstract Nine multi-cores were recovered during the summer of 2005 from an eight square kilometer area that is typical of the deep depositional environments found in the central and western parts of Lake Superior. Core sites were located in the troughs, centers, edges, and ambient regions around ring structures, which are believed to be the surface expression a polygonal fault system generated from the dewatering of underlying glaciolacustrine sediments (Cartwright et al. 2004 ). One sub-core at each site was extruded at 0.5 cm intervals to 10 or 12 cm depth, and analyzed for 210Pb, biogenic silica (BSi), total organic carbon (TOC), total organic nitrogen (TON), and methyl mercury (MeHg). The accumulation of bulk sediment, BSi, TOC, and MeHg cumulative inventories display large temporal and spatial variation among core sites throughout the study area. The total inventories of all three parameters vary by nearly a factor of two among the core sites. A comparison of BSi and TOC inventories to bulk sediment inventory reveals a direct relationship between the total compound accumulation at a particular core site and its bulk sedimentation rate. MeHg analyses show that spatial and temporal variability in MeHg appears to be due primarily to proximity to ring structures rather than variable bulk sediment accumulation. Our 8 km 2 study area exhibits a larger range of MeHg values than shown in previous lake-wide studies of MeHg. Lake Superior is subject to a similar mass balance problem found in the oceans; a previous study determined that up to 80% of the river input of dissolved silica to the lake is not accounted for by either outflow of dissolved iii silica or by deposition of biogenic silica. However, new estimates based on the mass accumulation of BSi in this study suggests that there is only little imbalance, if any, and that silicate mineral authigenesis is not required to explain the fate of dissolved silica flowing into the lake. Single core analysis is not valid in regions of complex lake-floor terrain found throughout the central and western basins of Lake Superior. To accurately asses the accumulation of natural and anthropogenic compounds future investigations need to recover cores in the regions around complex lake-floor terrain that have exhibited 'normal' sedimentation, or attain duplicate cores to establish the degree of sediment and compound variability. iv Table of Contents Section Pages Acknowledgments . i Abstract .................................................... iii-iv Table of Contents ............................................ v-vi List of Figures ............................................... vii-viii List of Tables ................................................ viii 1.0 Introduction .............................................. 1-2 2.0 Background . 3-16 2.1 An Introduction to Lake Superior ......................... 3 2.1.1 Geology ..................................... 3-4 2.1.2 Stratigraphy .................................. 4-5 2.1.3 Modern Sediment Sources and Depositional Environments . 5-7 2.1.3 Physical Processes Affecting Sediment Accumulation .. 7-12 2.1.4 Contaminant Impacts, Inputs, and Cycling in Lake Superior ........................ 13-16 3.0 Methods ................................................. 17-27 3.1 Field Methods . 17-23 3.1.1 Sediment Coring . 17-18 3.1.2 Sampling Locations and Dates . 19-20 3.1.3 Core Processing on Board the RN Blue Heron ....... 21-23 3.2 Lab Methods ........................................ 24-27 3.2.1 Water Content and Porosity ...................... 24 3.2.2 Analysis for Biogenic Silica ...................... 24 3.2.3 Analysis for Total Organic Carbon, Total Organic Nitrogen, and C/N Ratios ........................ 25 3.2.4 Stratigraphic Analysis ........................... 25 3.2.5 Smear Slides ................................. 26 3.2.6 Analysis (HgT and MeHg) .................... 26 3.2.7 21 Pb Analysis ................................ 26-27 4.0 Results ................................................. 28-90 4.1 Core Descriptions .................................... 28-31 4.2 Magnetic Susceptibility ................................ 32-41 4.3 Water Content ...................................... 42 4.4 Geochronology ...................................... 43-66 v 4.4.1 210Pb Background ............................ 43-46 4.4.2 210Pb Age Models ............................ 46-53 4.4.3 Sediment Focusing and 210Pb Flux to Sediments .... 54-56 4.4.4 Dry Mass Calculations and Inventories of 210Pb ..... 57-60 4.4.5 Bulk Sediment MARs and Cumulative inventories ... 61-66 4.5 Biogenic Silica (BSi) ................................. 67-70 4.5.1 Biogenic Silica Concentration . 67 4.5.2 Smear Slides ................................ 68 4.6 TOC, TON, and C/N Ratios ............................ 71-81 4.6.1 Total Organic Carbon . 71 4.6.2 Total Organic Nitrogen . 72 4.6.3 C/N Ratios .................................. 77 4.7 Biogenic Silica and TOC MARs ........................ 82-85 4.8 Methyl Mercury (MeHg) ............................... 86-88 4.9 Compound Diagenesis ............................... 89-90 5.0 Discussion ............................................. 91-122 5.1 Compound Distributions and Links to Recent Sediment Accumulation .............................. 89-119 5.1.1 Inventories of BSi and TOC. 89-106 5.1.2 A Revised Silica Budget for Lake Superior .........107-110 5.1.3 C/BSi Ratios ................................ 110-112 5.1.4 Methyl Mercury .............................. 112-119 5.2 Compound Variability Relative to Previous Studies ......... 120-121 5.3 Implications for Future Sediment Coring ............ .... 121 -122 6.0 Conclusions ............................................123-124 7.0 References ............................................ 125-128 8.0 Appendices ............ ............................... 129-144 APPENDIX A: Core locations and depths ................... 129 APPENDIX B: 210Pb data ................................130-132 APPENDIX C: Water content data .............. ......... 133-135 APPENDIX D: C, N, C/N, BSi, and MeHg data ............... 136-139 APPENDIX F: LRC data ................................ 140-144 vi List of Figures ............................................... vii-viii Figure 1. Satellite image of sediment resuspension in western Lake Superior. 8 Figure 2. The nine depositional basins of Lake Superior . 8 Figure 3. Color bathymetric map of ring structures on the lake floor ........ 11 Figure 4. Distribution of ring structures in western Lake Superior .......... 11 Figure 5. A high resolution seismic reflection profile from the study area .... 12 Figure 6. Contaminant cycling in Lake Superior .................. .... 14 Figure 7. RN Blue Heron ........................................ 18 Figure 8. Ocean Instruments multi-corer ............................. 18 Figure 9. A high resolution seismic reflection profile .................... 19 Figure 10. Core locations and color bathymetric map of study area . 20 Figure 11. Core extruder with threaded rod ............................ 23 Figure 12. Core extruders with pins and threaded rod .................... 23 Figure 13. Image and plot of MS for core 2 ............................ 33 Figure 14. Image and plot of MS for core 3 . ........................... 34 Figure 15. Image and plot of MS for core 4 ............................ 35 Figure 16. Image and plot of MS for core 5 ............................ 36 Figure 17. Image and plot of MS for core 6 ............ ............... 37 Figure 18. Image and plot of MS for core 7 .... ....................... 38 Figure 19. Image and plot of MS for core 8 .............. ............. 39 Figure 20. Image and plot of MS for core 9 ............................ 40 Figure 21. Image and plot of MS for core 10 ........................... 41 Figure 22. Water content of recovered cores .......................... 42 Figure 23. 238U decay series .............................. ........ 44 Figure 24. Geochemical cycle of 210Pb ........................ ...... 44 Figure 25. Unsupported 210Pb activities ............................... 51 Figure 26. CRS age/depth relations . 53 Figure 27. Flux of unsupported 210Pb to sediments ...................... 56 Figure 28. Focus factors .......................................... 56 Figure 29. Trend line used to calculate 210Pb inventories . 60 Figure 30. Total 210Pb inventories for recovered cores .... .............. 60
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