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Fate of Nitrogen During Submarine Groundwater Discharge Into Long Island North Shore Embayments a Dissertation Presented by Cait

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Fate of Nitrogen During Submarine Groundwater Discharge Into Long Island North Shore Embayments a Dissertation Presented by Cait Fate of Nitrogen during Submarine Groundwater Discharge into Long Island North Shore Embayments A Dissertation Presented by Caitlin Young to The Graduate School in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Geosciences Stony Brook University December 2013 Copyright by Caitlin Young 2013 Stony Brook University The Graduate School Caitlin Young We, the dissertation committee for the above candidate for the Doctor of Philosophy degree, hereby recommend acceptance of this dissertation. Gilbert Hanson Distinguished Professor, Geosciences Michael Sperazza Professor, Geosciences Henry Bokuniewicz Professor, School of Marine and Atmospheric Sciences Robert Aller Professor, School of Marine and Atmospheric Sciences Kevin D. Kroeger Senior Research Scientist US Geological Survey Woods Hole Coastal & Marine Science Center This dissertation is accepted by the Graduate School Charles Taber Dean of the Graduate School ii Abstract of the Dissertation Fate of Nitrogen during Submarine Groundwater Discharge into Long Island North Shore Embayments by Caitlin Young Doctor of Philosophy in Geosciences Stony Brook University 2013 Long Island Sound experiences periods of hypoxia attributed to eutrophication, but the magnitude of nitrogen contributed to surface water via submarine groundwater discharge (SGD) entering Long Island’s north shore embayments is not well characterized. The coastal aquifer, where fresh groundwater mixes with saline coastal water is termed the subterranean estuary (STE). Advective flow combined with sharp salinity and dissolved oxygen gradients make the STE a zone of intense geochemical cycling. However, the fate of nitrogen during transit through Long island embayment STEs is not well understood, particularly how sediment heterogeneity influences nitrogen attenuation in discharge zones. Nitrate attenuation mechanisms, principally denitrification, were investigated in three Long Island north shore embayments; Stony Brook Harbor, Setauket Harbor and Port Jefferson Harbor. In Stony Brook Harbor an investigation of freshwater nitrate dynamics over two spring-neap tidal cycles found oscillations in depth stratified nitrate concentrations. Calculation of fresh fraction discharge revealed that water table over-height is responsible for these oscillations, which result from shore perpendicular movement of the coarse sediment freshwater discharge point. High resolution sampling of STE porewater from Stony Brook Harbor and Setauket Harbor revealed discharge of freshwater continues for tens of meters offshore, which results in two zones of nitrogen removal. When SGD discharges into surface water near low tide through coarse-grain sand iii or marsh sediments, denitrification rates are 15 - 50% lower than when SGD passes through into a fine grain sediment layer offshore. In Port Jefferson Harbor, results from a combined shallow porewater nitrate concentration and geochemical tracer (222Rn) study indicate SGD accounts for similar nitrogen flux to surface water as direct inputs from a local sewage treatment plant. Overall, embayment scale sediment heterogeneity is positively correlated with availability of dissolved organic carbon, which in turn controls the extent of microbially mediated denitrification found in each of the studied embayments. iv Dedication Page To my father, who taught me the value of hard work, dedication and that a person does not need education to be truly intelligent. It was a long journey, and you supported me every step of the way. Even today I hear your voice on the phone, calling me from miles away. Remember the days we traveled together, looking for the ‘audubunzoo’ and eating alligator on Bourbon Street. You taught me to reach for the stars ‘I’ll tell you a story about Jack a Nory and now my story’s begun I’ll tell you another about jack and his brother and now my story’s done’ v Frontispiece Conceptual model of fate of SGD driven nitrate into Long Island north shore embayments. vi Contents LIST OF FIGURES ..................................................................................................................................... xi LIST OF TABLES ...................................................................................................................................... xiv Acknowledgments ....................................................................................................................................... xv Eutrophication of coastal zones resulting from anthropogenic nitrogen ............................................... 1 Submarine Groundwater Discharge (SGD): Physical drivers and measurement techniques ................ 2 Nutrient transport through the Subterranean Estuary (STE) during SGD ............................................ 3 Purpose and outline of the thesis ........................................................................................................... 6 References ................................................................................................................................................. 8 Tables and Figures .................................................................................................................................. 14 CHAPTER II: NUTRIENT DYNAMICS IN A SUBTERRANEAN ESTUARY OVER TWO SPRING- NEAP TIDAL CYCLES ............................................................................................................................. 16 Abstract ................................................................................................................................................... 16 Introduction ............................................................................................................................................. 16 Materials and Methods ............................................................................................................................ 17 Site Description ................................................................................................................................... 17 Sample Collection and Analysis ......................................................................................................... 18 Tide Data ............................................................................................................................................. 18 Silica Dissolution Experiment ............................................................................................................ 19 SGD Flux calculations ........................................................................................................................ 19 Results ..................................................................................................................................................... 20 Salinity ................................................................................................................................................ 21 Dissolved oxygen ................................................................................................................................ 21 Dissolved inorganic phosphate ........................................................................................................... 22 Dissolved inorganic nitrate ................................................................................................................. 22 Water table overheight ........................................................................................................................ 23 Comparison with other spring-neap studies ........................................................................................ 24 Conclusion .............................................................................................................................................. 26 References ............................................................................................................................................... 27 Tables and Figures .................................................................................................................................. 30 Supplemental data ................................................................................................................................... 40 vii CHAPTER III: DENITRIFICATION AND NITRATE BIOGEOCHEMISTRY IN A SUBTERRANEAN ESTUARY OF STONY BROOK HARBOR ............................................................................................. 43 Abstract ................................................................................................................................................... 43 Introduction ............................................................................................................................................ 43 Methods .................................................................................................................................................. 45 Site Description ................................................................................................................................... 45 Sediment Sampling and analysis ......................................................................................................... 46 Porewater sampling and analysis ....................................................................................................... 46 Calculation of N2 denitrification and excess air incorporation .................................................................... 47
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