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Fe and Nutrients in Coastal Antarctic Streams: Implications for Marine Primary

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Fe and Nutrients in Coastal Antarctic Streams: Implications for Marine Primary Fe and Nutrients in Coastal Antarctic Streams: Implications for Marine Primary Production in the Ross Sea THESIS Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in the Graduate School of the Ohio State University By Sydney A. Olund, B.S. Graduate Program in Earth Sciences The Ohio State University 2017 Thesis Committee: Dr. W. Berry Lyons, Advisor Dr. Yu-Ping Chin Dr. Michael Durand Copyright by Sydney Olund 2017 ABSTRACT The Southern Ocean (SO) has been an area of much biogeochemical interest due to the role of Fe limitation for primary production. Primary production is associated with increased carbon sequestration, making it important to characterize and quantify the fluXes of Fe and other nutrients to the ocean. Water samples were collected in the McMurdo Dry Valleys, Antarctica (MDV) from four subaerial streams flowing into the Ross Sea. They were analyzed for macronutrients (N, P, Si) and Fe to determine the potential impact of terrestrial water input on the biogeochemistry of coastal oceanic waters. Our stream data yield an average filterable composition of N3P1 Si100Fe0.8, which is substantially different from the planktonic composition as demonstrated by empirical measurements, and suggests that these streams are a potential source of Fe and P, relative to N and Si, to coastal phytoplankton communities. The behavior and potential colloidal/nanoparticulate speciation of the Fe in these streams was investigated through analysis of three physiochemical forms of Fe - environmentally active Fe (acid-soluble/no filtration), filterable Fe (filtered through 0.4 µm), and dissolved Fe (filtered through 0.2 µm). It has been suggested that the dissolved ii fraction is mainly nanoparticulate and represents a more bioavailable form of Fe, as compared with colloids and particles. Overall, the combined average annual fluX from two MDV streams is approXimately 240 moles fFe yr-1, which is consistent with previously predicted values. The dissolved fraction of Fe (<0.2 µm) was between 18% and 27% percent of the fFe, meaning the fFe pool is mostly colloidal. While the Fe fluX from these streams is several orders of magnitude less than aeolian and iceberg sources, terrestrial streams are eXpected to become a more significant source of Fe to the Ross Sea. As the Antarctic climate warms, ice-free regions similar to the MDV should increase in eXtent and glacier melt. This study questions how, and in what quantities, Fe is solubilized and transported from the landscape into the SO to better inform predictions of Fe fluXes following continued warming iii ACKNOWLEDGEMENTS First and foremost, I would like to thank Dr. Berry Lyons for providing the opportunity to eXperience the wonders of Antarctic fieldwork, the encouragement to “do good things”, and the guidance I needed to succeed in my graduate career. I will be forever grateful for the eXperiences you provided me during these past two years. I’d like to give a huge thanks to Elsa Saelens for assisting with fieldwork and being my Antarctic confidant throughout our adventures on the ice and in the lab. Thank you to the 2015- 16 LTER field crew for introducing me to “the dude” and providing fieldwork assistance, conversation, laughs, and advice. A special thanks to Adam Wlostowski, for letting me tag along on an impromptu helicopter tour of the Dry Valleys and for being a model of scientific enthusiasm that encouraged me to keep questioning and learning throughout the past year and a half. Thank you to Chris Jaros and Christa Torrens for answering my many flow-related questions, and specifically for the use of Chris’s flow model outputs. Thank you to the Trace Element Research Lab, especially Anthony Lutton, for help and support with my Fe analyses. Thanks to Kathy Welch for teaching me everything from how to use a pipette to how to communicate science effectively. Your assistance with lab work, field work, presentations of data, and life have been invaluable to me. Thanks to Sue Welch for your help with nutrient analyses, SEM analyses, and feedback on iv presentations. Thanks to Chris Gardner for your straightforward and eXtremely helpful review on multiple posters and talks. Thank you to Melisa Diaz for being a great friend, office mate and science coach. Thank you to my committee for providing feedback on this research. Thank you to NSF ANT 1115245 for funding support, to ASC for logistical support, and to PHI for helicopter support. Lastly, thank you to my family for your love and support. You mean the world to me. v VITA April 25, 1992……………………………………………. Born – Evanston, Illinois May 2014…………………………………………………… B.S. Geology and Earth Systems, Environment, and Society, University of Illinois at Urbana-Champaign August 2015 to present……………………………… Graduate Research and Teaching Associate, School of Earth Sciences, The Ohio State University Fields of Study Major Field: Earth Sciences vi TABLE OF CONTENTS ABSTRACT……………..….……………..………………....…………………….…………………………………………ii ACKNOWLEDGEMENTS.……….………………………………….….…………………………………………….....iv VITA……………………………………..………………………….………………….………………………………………...vi LIST OF TABLES………………………..….………………………….…..….……………….…………………..……….iX LIST OF FIGURES…….………………………..….………..….…………………..…………………….…………..…...Xi 1 INTRODUCTION..………………………..………………..….………………………………………………….………1 1.1 Rationale for work..….…….……..….………………………..….……………………………….…..1 2 STUDY AREA.. ……………………….………..….………………………..……………..………………………..……6 2.1 Site Description….…………………………………………………………...….………………………..6 3 METHODS……....……….………………..….………………….…..….………………………….………..…………11 3.1 Cleaning. ………………………..….………..…..……………….…………..….….………….……….11 3.2 Sampling….……………………….……………..……………………………...….……………………..11 3.3 Processing…...………………..….………………………..….…………….…………….……………..12 3.4 Analysis………………..…….………………………..….………………….……………………….......12 4 RESULTS…..….…………….……………..….………………………..….………………………………….………….15 vii 4.1 Fe and nutrients along stream transects and partial diels…………..….….……….15 4.2 Hysteretic behavior in Commonwealth….………………………..………………..……..…18 4.3 Nutrient Stoichiometry……………….….…..………..….…………………….………...…..…..20 4.4 Physiochemical forms of Fe. ………………………..….…….……………………………….….21 4.5 Fe flux. ………………………..….…………….……………………..…....….……………….………...22 5 DISCUSSION….…..….………………………..….…………………….……………..….………………………..….23 5.1 Fe and nutrient ratios in terrestrial stream and the Southern Ocean…....…….23 5.2 Comparison to previously studied fluXes……….………………………..………………….25 5.3 Potential impacts of climate change on streamflow in the MDVs.…...............26 5.4 Fate of Fe in the Southern Ocean…..………….………………………………………………..27 6 CONCLUSIONS……………………………………………………………………………………………………………29 6.1 Summary of research……………………….…………....…….………………………………….…29 6.2 Future work……………………………………………………………….………….…………………...29 7 REFERENCES CITED…………………….……………………………………………………….…………………….31 APPENDIX A: TABLES AND FIGURES…………………………..………………………….………………………39 APPENDIX B: MAJOR CATIONS AND MAJOR ANIONS.……….………………………….…….………..73 APPENDIX C: TITRATION ALKALINITY AND pH……………..………………………………………………..80 viii LIST OF TABLES Table 1. Precision and accuracy of major ion and nutrient data….…………………………………40 Table 2. Precision and accuracy for three Fe analyses using inductively coupled plasma………………………………………………………………………………………………………………………….41 Table 3. Previously calculated Fe fluXes from various sources to the Southern Ocean…………………………………………..…………………………………………………………….…………...…..42 Table 4. Stream characteristics of coastal MDV streams………………..............………………….43 Table 5. Annual discharge for the Commonwealth, Wales, Garwood, and Miers Streams……………………………………………………………………………………………………….……………....44 Table 6. Average Fe concentrations in four coastal MDV streams……………..…..……………..46 Table 7. Average Fe fluX from Commonwealth and Wales…..…………..….………………………..47 Table 8. Ratios of average molar concentrations of filterable (< 0.4 µm) nutrients N, P, Si, and Fe for 3 streams………………………..……..….………………………..….………………………..…………48 Table 9. Major cation concentrations for all samples collected……………………………………..74 Table 10. Major anion concentrations for all samples collected……………………………………77 ix Table 11. Titration alkalinity for several samples collected along Commonwealth, Wales, Garwood and Miers between November 2015 - January 2016……………………………………..81 x LIST OF FIGURES Figure 1. Coastal streams in the McMurdo Dry Valleys, Antarctica………………………….……48 Figure 2. Sampling locations at Commonwealth Stream, Taylor Valley, Antarctica…..…...49 Figure 3. Sampling locations at Wales Stream, Taylor Valley, Antarctica………………..………50 Figure 4. Sampling locations at Garwood Stream, Garwood Valley, Antarctica………………51 Figure 5. Sampling locations at Miers Stream, Miers Valley, Antarctica. ……………………....52 Figure 6. Fe concentrations along Commonwealth Stream…….………..….……………………….53 Figure 7. Fe concentrations along Wales Stream.……………..….………………………..…………….54 Figure 8. Fe concentrations along Miers Stream.. ………………………..………………..….…………55 Figure 9. Fe concentrations along Garwood Stream. ………………………..….………………………56 Figure 10. Hysteretic behavior of Fe in Commonwealth Stream….…………..….………………..57 Figure 11. Soluble reactive phosphorus (SRP) concentrations along Commonwealth…...58 Figure 12. N as NO3- concentrations along Commonwealth…………......…………….………….59 Figure 13. Si concentrations along Commonwealth….…………..….………………………..………..60 Figure 14. Soluble reactive phosphorus (SRP) concentrations along Wales……….……..….61 Figure 15. N as NO3- concentrations along Wales….………………………..….……………..………..62 Figure 16. Si concentrations along Wales……..…………………………………..….………..…………….63
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