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  • Climatic changes  (4)
  • Chemistry  (3)
  • Inorganic Chemistry
  • Massachusetts Institute of Technology and Woods Hole Oceanographic Institution  (7)
  • 2015-2019  (7)
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  • 1
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Physical Oceanography at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2019.
    Description: Global patterns of ocean salinity arise from the exchange of freshwater between the sea surface and the atmosphere. For a quasi-steady state system, these surface fluxes are balanced by compensating transports of salt in the ocean interior. In a warming climate, the atmosphere holds additional water vapor which acts to intensify the global water cycle. Amplified freshwater fluxes are then absorbed at the surface and propagate along ocean circulation pathways. Here, we use coupled model results from the CMIP5 experiment to identify coherent responses in the atmospheric water cycle and in ocean salinity patterns. Some aspects of the response are consistent across models, while other regions show large inter-model spread. In particular, the salinity response in the North Atlantic subpolar gyre, where the mean salinity plays a role in maintaining high surface density for deep-water formation, has low confidence in CMIP5 models. To understand how differences in ocean circulation may affect this response, we use two techniques to diagnose the role of salt transports in the present-day climate. The first is a salt budget within the surface mixed layer, which identifies major transport processes. The second is a Lagrangian particle tracking tool, used to understand the regional connectivity of water masses. From this analysis, we find that anomalous freshwater signals become well mixed within the ocean gyres, but can be isolated on larger scales. The subpolar Atlantic salinity response generally shows freshening at the surface, but is sensitive to the transport of anomalously salty water from the subtropics, a largely eddy-driven process. As CMIP5 models use a range of eddy parameterizations, this is likely a source of uncertainty in the salinity response. Finally, we investigate the effect of salinity changes on the deep overturning cells and other circulations, and find a complex influence that also depends on the details of advective pathways. In a warming scenario, water cycle amplification actually works to strengthen the Atlantic meridional overturning circulation due to the influence of enhanced subtropical evaporation.
    Description: Funding for this thesis was provided by NASA grant NNX12AF59GS03, a NASA Earth and Space Science Fellowship award 80NSSC17K0372, and the WHOI Academic Programs Office.
    Keywords: Salinity ; Climatic changes ; Ocean ; Dissertations, Academic ; North Atlantic Ocean
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 2
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 2018
    Description: Many chemical constituents are removed from the ocean by attachment to settling particles, a process referred to as “scavenging.” Radioisotopes of thorium, a highly particle-reactive element, have been used extensively to study scavenging in the ocean. However, this process is complicated by the highly variable chemical composition and concentration of particles in oceanic waters. This thesis focuses on understanding the cycling of thorium as affected by particle concentration and particle composition in the North Atlantic. This objective is addressed using (i) the distributions 228,230,234Th, their radioactive parents, particle composition, and bulk particle concentration, as measured or estimated along the GEOTRACES North Atlantic Transect (GA03) and (ii) a model for the reversible exchange of thorium with particles. Model parameters are either estimated by inversion (chapter 2-4), or prescribed in order to simulate 230Th in a circulation model (chapter 5). The major findings of this thesis follow. In chapters 2 and 3, I find that the rate parameters of the reversible exchange model show systematic variations along GA03. In particular, 𝑘1, the apparent first-order rate "constant" of Th adsorption onto particles, generally presents maxima in the mesopelagic zone and minima below. A positive correlation between 𝑘1 and bulk particle concentration is found, consistent with the notion that the specific rate at which a metal in solution attaches to particles increases with the number of surface sites available for adsorption. In chapter 4, I show that Mn (oxyhydr)oxides and biogenic particles most strongly influence 𝑘1 west of the Mauritanian upwelling, but that biogenic particles dominate 𝑘1 in this region. In chapter 5, I find that dissolved 230Th data are best represented by a model that assumes enhanced values of 𝑘1 near the seafloor. Collectively, my findings suggest that spatial variations in Th radioisotope activities observed in the North Atlantic reflect at least partly variations in the rate at which Th is removed from the water column.
    Description: This work was supported by the US National Science Foundation. Two US NSF grants have supported the research in this thesis (OCE-1232578 and OCE-155644).
    Keywords: Thorium ; Chemistry
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 3
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2018.
    Description: The biological carbon pump (BCP) helps to moderate atmospheric carbon dioxide levels by bringing carbon to the deep ocean, where it can be sequestered on timescales of centuries to millennia. Climate change is predicted to decrease the efficiency of the global BCP, however, the magnitude and timescale of this shift is largely uncertain and will likely impact some areas of the global ocean more significantly than others. Therefore, it is imperative that we (1) accurately quantify surface export and remineralization of particulate organic carbon (POC) via the BCP over large regions of the global ocean, (2) examine the factors controlling these POC fluxes and their variability, which includes the cycling of biologically-relevant trace metals, and (3) establish if and how the BCP is changing over time. This thesis focuses on addressing various aspects of these objectives using the 234Th-238U method across basin-scale GEOTRACES transects. First, the export and remineralization of POC were examined across large gradients in productivity, upwelling, community structure, and dissolved oxygen in the southeastern tropical Pacific Ocean. Although low oxygen zones are traditionally thought to have decreased POC flux attenuation relative to other regions of the global ocean and the low oxygen Pacific locations followed this pattern, regions that were functionally anoxic had enhanced attenuation in the upper 400 m. Second, trace metal export and remineralization were quantified across the Pacific transect. Because many trace metals are necessary for the metabolic functions of marine organisms and can co-limit marine productivity, the controls on the cycling of trace metals in the upper ocean were examined. Lastly, POC export was determined across two transects in the Western Arctic Ocean, where light and nutrient availability drive the biological pump. Upper ocean export estimates in the central basin did not reflect a substantial change in the biological pump compared to studies from the last three decades, however, an extensive maximum in 234Th relative to 238U deeper in the water column indicated that rapid vertical transport had occurred, which could suggest a more efficient biological pump in the Arctic Ocean.
    Description: I was funded under the NASA Earth and Space Science Fellowship Program grant (NNX13AP31H) for three years. I was also funded for work on the U.S. Pacific and Arctic GEOTRACES campaigns under two National Science Foundation grants (OCE-1232669 and OCE- 1458305). The MIT Henry G. Houghton Fund provided support for the purchase of computers and textbooks and the MIT Scurlock Fund allowed for my travel to Bermuda for cruise training. WHOI Academic Programs supplemented the aforementioned funding and also provided additional support for travel to conferences.
    Keywords: Carbon ; Climatic changes ; Ocean ; Thomas G. Thompson (Ship) Cruise TN303
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 4
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2017
    Description: This thesis documents the origin, distribution, and fate of methane and several of its isotopic forms on Earth. Using observational, experimental, and theoretical approaches, I illustrate how the relative abundances of 12CH4, 13CH4, 12CH3D, and 13CH3D record the formation, transport, and breakdown of methane in selected settings. Chapter 2 reports precise determinations of 13CH3D, a “clumped” isotopologue of methane, in samples collected from various settings representing many of the major sources and reservoirs of methane on Earth. The results show that the information encoded by the abundance of 13CH3D enables differentiation of methane generated by microbial, thermogenic, and abiogenic processes. A strong correlation between clumped- and hydrogen-isotope signatures in microbial methane is identified and quantitatively linked to the availability of H2 and the reversibility of microbially-mediated methanogenesis in the environment. Determination of 13CH3D in combination with hydrogen-isotope ratios of methane and water provides a sensitive indicator of the extent of C–H bond equilibration, enables fingerprinting of methane-generating mechanisms, and in some cases, supplies direct constraints for locating the waters from which migrated gases were sourced. Chapter 3 applies this concept to constrain the origin of methane in hydrothermal fluids from sediment-poor vent fields hosted in mafic and ultramafic rocks on slow- and ultraslow-spreading mid-ocean ridges. The data support a hypogene model whereby methane forms abiotically within plutonic rocks of the oceanic crust at temperatures above ca. 300 C during respeciation of magmatic volatiles, and is subsequently extracted during active, convective hydrothermal circulation. Chapter 4 presents the results of culture experiments in which methane is oxidized in the presence of O2 by the bacterium Methylococcus capsulatus strain Bath. The results show that the clumped isotopologue abundances of partially-oxidized methane can be predicted from knowledge of 13C/12C and D/H isotope fractionation factors alone.
    Description: The research activities documented in this thesis were made possible by grants to my advisor from the U.S. National Science Foundation (NSF award EAR-1250394), the National Aeronautics and Space Administration (NASA) Astrobiology Institute (NAI, University of Colorado, Boulder, CAN 7 under Cooperative Agreement NNA15BB02A), the Department of Energy (DOE, Small Business Innovation Research program, contract DE-SC0004575), the Alfred P. Sloan Foundation via the Deep Carbon Observatory, and a Shell Graduate Fellowship through the MIT Energy Initiative. I completed the bulk of the work in this thesis while being supported by a National Defense Science and Engineering Graduate (NDSEG) Fellowship awarded through the Office of Naval Research of the U.S. Department of Defense. The StanleyW.Watson Fellowship Fund provided support during my first summer term at WHOI.The Charles M. Vest Presidential Fellowship at MIT supported me in the first year of my Ph.D. studies. I received additional support that year through NSF award EAR-1159318 (to S. Ono and T. Bosak) and theWalter & Adel Hohenstein Graduate Fellowship of Phi Kappa Phi. The MIT Earth Resources Laboratory and PAOC Houghton Fund funded my attendance at several conferences.
    Keywords: Methane ; Chemistry ; Isotopes ; Oxidation
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 5
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2017
    Description: Salt marshes are physically, chemically, and biologically dynamic environments found globally at temperate latitudes. Tidal creeks and marshtop ponds may expand at the expense of productive grass-covered marsh platform. It is therefore important to understand the present magnitude and drivers of production and respiration in these submerged environments in order to evaluate the future role of salt marshes as a carbon sink. This thesis describes new methods to apply the triple oxygen isotope tracer of photosynthetic production in a salt marsh. Additionally, noble gases are applied to constrain air-water exchange processes which affect metabolism tracers. These stable, natural abundance tracers complement traditional techniques for measuring metabolism. In particular, they highlight the potential importance of daytime oxygen sinks besides aerobic respiration, such as rising bubbles. In tidal creeks, increasing nutrients may increase both production and respiration, without any apparent change in the net metabolism. In ponds, daytime production and respiration are also tightly coupled, but there is high background respiration regardless of changes in daytime production. Both tidal creeks and ponds have higher respiration rates and lower production rates than the marsh platform, suggesting that expansion of these submerged environments could limit the ability of salt marshes to sequester carbon.
    Description: Financial support for my doctoral research was provided by the United States Department of Defense through the National Defense Science and Engineering Graduate Fellowship Program, the National Science Foundation under grant OCE-1233678, and the Woods Hole Oceanographic Institution (WHOI) under grants from the WHOI Coastal Ocean Institute, Ocean and Climate Change Institute, and Ocean Life Institute. WHOI Academic Programs Office also provided funding support for research, through the Ocean Ventures Fund, and for my stipend, as graduate research assistantships including an assistantship from the United States Geological Survey administered by WHOI.
    Keywords: Marshes ; Chemistry ; Metabolism ; Knorr (Ship : 1970-) Cruise KN210-04
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 6
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2017
    Description: Significant changes occurred during the last deglaciation (roughly 10-20 thousand years (ka) before present) throughout the climate system. The ocean is a large reservoir of carbon and heat, however, its role during the deglaciation is still not well understood. In this thesis, I rely on radiocarbon measurements on fossil biogenic carbonates sampled from the seafloor to constrain deglacial ocean ventilation rates, using new data, an extensive data compilation, and inverse modeling. First, based on a sediment core that is absolutely dated from wooden remains, I argue that the deglacial 14C reservoir age of the upper East Equatorial Pacific was not very different from today. Combined with stable carbon isotope data, the results suggest that the deglacial atmospheric CO2 rise was probably due to CO2 released directly from the ocean (e.g., in the Southern Ocean) to the atmosphere rather than first mixed through the upper ocean. Then using a high-deposition-rate sediment core located close to deep water formation regions in the western North Atlantic, I show that compared to today, the mid-depth water production in the North Atlantic was probably stronger during the Younger Dryas cold episode, and weaker during other intervals of the late deglaciation. However, the change was not as large as suggested by previous studies. Finally, I compile published and unpublished deep ocean 14C data, and find that the 14C activity of the deep ocean mirrors that of the atmosphere during the past 25 ka. A box model of modern ocean circulation is fit to the compiled data using an inverse method. I find that the residuals of the fit can generally be explained by the data uncertainties, implying that the compiled data jointly do not provide strong evidence for basin-scale ventilation changes. Overall, this thesis suggests that, although deep ocean ventilation may have varied at some locations during the last deglaciation, the occurrence of basin-scale ventilation changes are much more difficult to be put on a firm footing. An imbalance between cosmogenic production and radioactive decay appears as the most natural explanation for the deglacial 14C activity decline observed in both the atmosphere and the deep ocean.
    Description: This research was supported by NSF-OCE grants 0822854 to Lloyd Keigwin, 1031224 to Lloyd Keigwin, 1204045 to Lloyd Keigwin, 1301907 to Olivier Marchal, Geoffrey Gebbie and Lloyd Keigwin, and 1405160 to Lloyd Keigwin, WHOI Academic Programs Endowed Funds, the Ocean Ventures Fund from WHOI, and a graduate student internship from NOSAMS.
    Keywords: Climatology ; Climatic changes ; Glaciers ; Carbon dioxide
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 7
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2016
    Description: Characterizing global and regional climate variability and climate-carbon cycle interactions in the past provides critical context for evaluating present and future climate trends. In this thesis, I use stable isotope and radiocarbon analysis of vascular plant biomarkers in lacustrine and marine sediment cores to explore late Quaternary climate variability and connections between past climate change and terrestrial carbon cycling in tropical South America. I investigate temporal and spatial trends in South American Summer Monsoon precipitation by reconstructing hydrologic variability over the past 50,000 years at two sites: the Lake Titicaca drainage basin in the Central Andes and the Pantanal wetlands in the interior lowlands. Diverging hydrologic trends at these two sites during the last glacial period suggest altered monsoon circulation patterns under glacial conditions, while changes in summer insolation appear to be an important control of precipitation at both sites during the Holocene. I next assess the relationship between climate change and the age structure of terrestrial biospheric carbon exported from two tropical catchments over the past 20,000 years. Radiocarbon dating of leaf waxes in Cariaco Basin and Lake Titicaca sediment records indicates that waxes preserved in sediments are likely composed of a fresh component transported to sediments within decades of production by vegetation and an old component derived from aged soil organic matter with an average age on the order of millennia at time of deposition. Results from both sites show that past hydrologic variability had a significant impact on the mobilization and export of different pools of terrestrial biospheric carbon. In particular, results from Cariaco Basin suggest that wetter conditions in the past resulted in increased export of fresh biospheric carbon to the ocean, representing a potentially important climate feedback mechanism on geologic timescales.
    Description: The work described in this thesis was supported by an MIT Presidential Fellowship, a WHOI Ocean and Climate Change Institute Fellowship, an EPA STAR Fellowship (Grant F13B20322), and the Joint Program Academic Program Office. Other funding was provided by grants from the WHOI Ocean Ventures Fund and Coastal Ocean Institute and NSF grants OCE-1400805 (VG) and DEB-0447281 (KAH).
    Keywords: Paleoclimatology ; Climatic changes
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
    Format: application/pdf
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