http://hdl.handle.net/1721.1/7597 2017-05-25T04:14:44Z http://hdl.handle.net/1721.1/109057 Novel analytical strategies for tracing the organic carbon cycle in marine and riverine particles Rosengard, Sarah Zhou Particulate organic carbon (POC) in the ocean and mobilized by rivers on land transfers -0. 1% of global primary productivity to the deep ocean sediments. This small fraction regulates the long-term carbon cycle by removing carbon dioxide from the atmosphere for centuries to millennia. This thesis investigates mechanisms of POC transfer to the deep ocean by analyzing particles collected in transit through two globally significant carbon reservoirs: the Southern Ocean and the Amazon River Basin. These endeavors test the hypothesis that organic matter composition controls the recycling and transfer efficiency of POC to the deep ocean, and illustrate new applications for ramped pyrolysis/oxidation (RPO), a growing method of POC characterization by thermal stability. By coupling RPO to stable and radiocarbon isotope analyses of riverine POC, I quantify three thermally distinct soil organic carbon pools mobilized by the Amazon River, and evaluate the degradability and fate of these different pools during transport to the coastal Atlantic Ocean. More directly, RPO analyses of marine samples suggest that POC transfer in the water column is in fact selective. Observations of consistent biomolecular changes that accompany transport of phytoplankton-derived organic matter to depth across the Southern Ocean support the argument for preferential degradation of specific POC pools in the water column. Combining discussions of POC recycling and transfer across both marine and terrestrial systems offer new perspectives of thermal stability as a proxy for diagenetic stability and POC degradation state. The challenges of interpreting RPO data in these two environments set the stage for applying the technique to more controlled experiments that trace POC from source to long-term sink. Thesis: Ph. D., Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2017.; Cataloged from PDF version of thesis.; Includes bibliographical references. 2017-01-01T00:00:00Z http://hdl.handle.net/1721.1/109056 Dynamics of North Atlantic western boundary currents Le Bras, Isabela Astiz The Gulf Stream and Deep Western Boundary Current (DWBC) shape the distribution of heat and carbon in the North Atlantic, with consequences for global climate. This thesis employs a combination of theory, observations and models to probe the dynamics of these two western boundary currents. First, to diagnose the dynamical balance of the Gulf Stream, a depth-averaged vorticity budget framework is developed. This framework is applied to observations and a state estimate in the subtropical North Atlantic. Budget terms indicate a primary balance of vorticity between wind stress forcing and dissipation, and that the Gulf Stream has a significant inertial component. The next chapter weighs in on an ongoing debate over how the deep ocean is filled with water from high latitude sources. Measurements of the DWBC at Line W, on the continental slope southeast of New England, reveal water mass changes that are consistent with changes in the Labrador Sea, one of the sources of deep water thousands of kilometers upstream. Coherent patterns of change are also found along the path of the DWBC. These changes are consistent with an advective-diffusive model, which is used to quantify transit time distributions between the Labrador Sea and Line W. Advection and stirring are both found to play leading order roles in the propagation of water mass anomalies in the DWBC. The final study brings the two currents together in a quasi-geostrophic process model, focusing on the interaction between the Gulf Stream's northern recirculation gyre and the continental slope along which the DWBC travels. We demonstrate that the continental slope restricts the extent of the recirculation gyre and alters its forcing mechanisms. The recirculation gyre can also merge with the DWBC at depth, and its adjustment is associated with eddy fluxes that stir the DWBC with the interior. This thesis provides a quantitative description of the structure of the overturning circulation in the western North Atlantic, which is an important step towards understanding its role in the climate system. Thesis: Ph. D., Joint Program in Physical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2017.; Cataloged from PDF version of thesis.; Includes bibliographical references (pages 163-174). 2017-01-01T00:00:00Z http://hdl.handle.net/1721.1/109055 Internal hydraulic jumps with upstream shear Ogden, Kelly Anne Internal hydraulic jumps in flows with upstream shear are investigated numerically and theoretically. The role of upstream shear has not previously been thoroughly investigated, although it is important in many oceanographic flows such as exchange flows and stratified flow over topography. Several two-layer shock joining theories, characterized by their distribution of dissipation in the jump, are considered and extended to include upstream shear, entrainment, and topography. Theoretical results are also compared to 2D and some 3D numerical simulations of the full Navier-Stokes equations, which allow continuous velocity and density distributions. The solution space of idealized jumps with small upstream shear is identified using two-layer theories, which shows that upstream shear allows larger jumps to form and allows jumps for a larger range of parameters. Numerical simulations reveal several jump structures that can occur in these flows, including an undular bore, a fully turbulent jump, and a smooth front turbulent jump. At low shear, the 2D mixing efficiency is constant across simulations. As shear increases, the basic two-layer theories no longer provide solutions. Numerical simulations show that entrainment becomes significant as the shear increases, and adding entrainment and shape parameters to describe the continuous velocity profiles is required to accurately describe the simulations using two-layered theory. The entrainment depends on the upstream shear and can be predicted with a modified theory. However, use of the theory is limited due to its sensitivity to the value of the shape parameters. The 2D mixing efficiency also decreases significantly as shear increases. Finally, more realistic 2D and some 3D simulations including topography bridge the gap between the highly idealized simulations and the very realistic work of others. Simulations with topography show additional jump types, including a higher mode jump with a wedge of homogeneous, stagnant fluid similar to a structure seen in Knight Inlet. In all cases, numerical simulations are used to identify trends in the mixing and jumps structures that can occur in internal hydraulic jumps. Thesis: Ph. D., Joint Program in Physical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2017.; Cataloged from PDF version of thesis.; Includes bibliographical references (pages 233-237). 2017-01-01T00:00:00Z http://hdl.handle.net/1721.1/109054 Understanding terrestrial organic carbon export : a time-series approach Hemingway, Jordon Dennis Terrestrial organic carbon (OC) erosion, remineralization, transport through river networks, and burial in marine sediments is a major pathway of the global carbon cycle. However, our ability to constrain these processes and fluxes is largely limited by (i) analytical capability and (ii) temporal sampling resolution. To address issue (i), here I discuss methodological advancements and data analysis techniques for the Ramped PyrOx serial oxidation isotope method developed at WHOI. Ramped-temperature pyrolysis/oxidation coupled with the stable carbon (¹²C, ¹³C) and radiocarbon (¹⁴C) analysis of evolved CO₂ is a promising tool for understanding and separating complex OC mixtures. To quantitatively investigate distributions of OC source, reservoir age, and chemical structure contained within a single sample, I developed a kinetic model linking RPO-derived activation energy, ¹³C composition, and radiocarbon content. This tool provides a novel method to fundamentally address the unknown relationship between OC remineralization rates and chemical structure in various environmental settings. To address issue (ii), I additionally present results from time-series sample sets collected on two end-member systems: the Congo River (Central Africa) and the LiWu River (Taiwan). For the Congo River, bulk and plant-wax-lipid ¹³C compositions indicate that a majority of particulate OC is consistently derived from downstream, C₃-dominated rainforest ecosystems. Furthermore, bulk radiocarbon content and microbial lipid molecular distributions are strongly correlated with discharge, suggesting that pre-aged, swamp-forest-derived soils are preferentially exported when northern hemisphere discharge is highest. Combined, these results provide insight into the relationship between hydrological processes and fluvial carbon export. Lastly, I examined the processes controlling carbon source and flux in a set of soils and time-series fluvial sediments from the LiWu River catchment located in Taiwan. A comparison between bedrock and soil OC content reveals that soils can contain significantly less carbon than the underlying bedrock, suggesting that this material is remineralized to CO₂ prior to soil formation. Both the presence of bacterial lipids and a shift toward lower activation energy of ¹⁴C-free OC contained in soil saprolite layers indicate that this process is microbially mediated and that microbial respiration of rock-derived OC likely represents a larger geochemical flux than previously thought. The results presented in this thesis therefore provide novel insight into the role of rivers in the global carbon cycle as well as their response to environmental perturbations. Thesis: Ph. D., Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2017.; Cataloged from PDF version of thesis.; Includes bibliographical references (pages 169-190). 2017-01-01T00:00:00Z