Thesis (Ph. D.)--University of California, San Diego, 1998. / Vita. Includes bibliographical references (p. 150-155).

Thesis (Ph. D.)--University of Bombay, 1969. / Includes bibliographical references (leaves 91-100).

Thesis (doctoral)--Chalmers Tekniska högskola, 1972. / "Akademisk avhandling för filosofie doktorsexamen i kemi ... fredagen den 2 juni 1972 ... Chalmers tekniska högskola."

Thesis (M.S.)--San Jose State University, 1997. / Includes abstract. Includes bibliographical references (leaves 112-122).

Thesis (M.S. in Physical Oceanography)--Naval Postgraduate School, June 2005. / Thesis Advisor(s): Peter C. Chu. Includes bibliographical references (p. 93-95). Also available online.

This dissertation presents results from 3-D (parallel 2-D) high resolution seismic surveys and associated studies over an area with deep sea gas hydrate occurrence. The study area is located on the accretionary prism of the northern Cascadia subduction zone offshore Vancouver Island, Canada. The major objectives of this study were the imaging of a gas/fluid vent field found in the study area and detailed mapping of the tectonic setting and geological controls on fluid/gas venting. Secondary objectives were the characterization of the gas hydrate occurrence and constraints on the seismic nature of the bottom-simulating reflector (BSR) and its spatial distribution. The main grid was 40 lines at 100 m spacing with eight perpendicular crossing lines of multichannel and single channel seismic reflection, and 3.5 kHz subbottom profiler data. In addition to the main 3-D seismic grid, two smaller single channel grids (25 m spacing) were collected over the vent field. The multichannel seismic data acquired with the Canadian Ocean Acoustic Measurement System (COAMS) streamer required correction for irregular towing depth and shot point spacing. A new array element localization (AEL) technique was developed to calculate receiver depth and offset. The individual receiver depths along the COAMS streamer varied between 10-40 m, which resulted in the occurrence of a prominent receiver ghost that could not be completely removed from the seismic data. The ghost resulted in limited vertical resolution and a coarse velocity depth function. The vent field is characterized by several blank zones that are related to near-surface deformation and faulting. These zones are 80-400 m wide and can be traced downward through the upper 100-200 m thick slope sediment section until they are lost in the accreted sediments that lack coherent layered reflectivity. The blank zones are also characterized by high amplitude rims that are concluded to result from the interference effect of diffractions. These diffractions result due to relatively sharp discontinuities in the sediment physical properties at the blank zone boundary. 2-D vertical incidence seismic modeling suggests an increase in P-wave velocity inside of the blank zone with only minor changes in density. Blanking is believed to be mainly the effect of increased hydrate formation within the fault planes. The faults are conduits for upward migrating fluids and methane gas that is converted into hydrate once it reaches the hydrate stability field. Carbonate formations at the seafloor can also contribute to blanking especially at higher frequencies. Free gas may be present in case of full hydrate saturation or strong fluid flow. Geochemical analyses of pore water and water-column samples carried out in cooperation with Scripps Institute of Oceanography indicate relatively low fluid fluxes of less than 1 mm/yr and there is no heat flow anomaly present over the vent field. Methane concentrations of 20 n-moles/L (about 8 times the ocean background concentration) were detected in water-column samples of the first 100-200 m above the main blank zone of the vent field. Venting is also believed to be strongly episodic with a recently more quiet time. However, the observed carbonate crusts indicate a long-term activity of the vents. / Graduate

This thesis investigates the variability occurring in the secondary metabolites produced by three South African marine molluscs. Chapter Two discusses the isolation and spectroscopic structure elucidation of the metabolites isolated from two Siphonaria species. The re-investigation of Siphonaria capensis yielded siphonarienfuranone (2.2) as the only common polypropionate isolated from both the 1998 and 2009 collections of S. capensis from the same areas suggesting possible seasonal or genetic variation in polypropionate production. The sterol cholest-7-en-3,5,7- triol (2.33) was also isolated form the 2009 collection of S. capensis and this is the first time this compound has been isolated from a Siphonaria species. The second species, Siphonaria oculus is closely related to S. capensis and the investigation into the former’s secondary metaboliteproduction revealed 2.2 as a major metabolite suggesting an inter-species overlap in polypropionate production. Three new polypropionate metabolites, 2.35, 2.36 and 2.37 were also isolated from S. oculus. An unsuccessful attempt was made to establish the absolute configuration of 2.37 using the modified Mosher’s method and the limited amount of 2.37 available prevented any further attempts at resolving the absolute configuration of this compound. The 1H NMR analysis of the defensive mucus collected directly from S. oculus revealed the presence of the acyclic polypropionate 2.37 as a minor metabolite. The absence of characteristic signals for the furanone containing compounds 2.2, 2.35 and 2.36, might suggest that these compounds cyclise from a hypothetical acyclic precursor (2.38) during standard work up of bulk acetone extracts of Siphonaria species. Chapter Three discusses the re-isolation and spectroscopic structure elucidation of the metabolites isolated from the nudibranch, Leminda millecra. Three known natural products, millecrone A (3.1), 8-hydroxycalamenene (3.6) and cubebenone (3.8) were re-isolated from our 2010 collection of L. millecra, as well as the new minor metabolite 8-acetoxycalamenene (3.16). The cytotoxic prenylated toluquinones and toluhydroquinones (3.9-3.15) initially isolated from the 1998 collection of L. millecra were not found in the 2010 collection supporting the hypothesis that these compounds may be of fungal origin. L. millecra clearly shows variability in the compounds sequestered by this species with millecrone A (3.1) being the only common metabolite in the three investigations of L. millecra to date. An unsuccessful attempt was made to establish the absolute configuration of 3.1, 3.6 and 3.8 through initial LAH reduction of the ketone moiety contained in 3.1 and 3.8 and esterification of the resultant diastereomeric alcohol mixtures and the phenol functionality in 3.6 with (1S)-camphanic chloride. Crystallisation of the (S)- camphanate esters of 3.6 and 3.8 for X-ray analysis were unsuccessful, while the unexpected conjugate addition of a hydride in 3.1 resulted in complex diastereomeric mixtures which could not be separated by HPLC.

The Arctic is a hotspot of global change. For example, changes caused by global warming are both amplified and are seen more rapidly in the Arctic (e.g., Serreze & Francis, 2006; Bekryaev et al., 2010; Serreze & Barry, 2011; Overland et al. 2015; Macdonald et al., 2015). Thus, the Arctic is an indicator of the state of the planet. Among the strongest changes that have been observed in the Arctic Ocean are changes in circulation regimes, hydrographic properties and freshwater content and composition. These changes have the potential of global impact through interaction with the deep-water formation regions of the North Atlantic Ocean, a major source of deep and bottom water in the global ocean. Although significant progress in understanding the signals of change in the Arctic Ocean and their causes has been made during the past decades there are still some fundamental questions unanswered. They include the stability of the circulation of the upper waters and changes in the freshwater budget and how these changes are connected to changes in the composition of the freshwater lens that covers the Arctic Ocean. In this thesis, we address these two topics using measurements of isotopes obtained during over three decades of Arctic Ocean section work.This dissertation is composed by three parts and its structure mimics the layered vertical structure of the Arctic Ocean water column. Chapter 1 is dedicated to the Atlantic waters, Chapter 2 to the halocline waters, and Chapter 3 to the freshwater sources and their distribution and variability in the surface layer. In the first two chapters, we present transient tracer (³H/³He) and hydrographic data from over 25 years of Arctic oceanographic campaign ranging from 1987 to 2013 to evaluate flow rates and circulation pathways in the Upper Halocline Water (UHW), Lower Halocline Water (LHW), and Atlantic Layer on a pan-Arctic scale. In agreement with previously established circulation schemes, tracer data show that the flow paths in the LHW and the Atlantic layer are typically topographically steered with the presence of a cyclonic boundary current along the continental shelf and separate circulation branches tracking major bathymetric features, such as the Lomonosov Ridge. Tracer data suggest that the general circulation of UHW is decoupled from the cyclonic regime observed in the deeper layer, and strongly influenced by surface stress forcing, such as the anticyclonic Beaufort Gyre. Within the limits of our method, tracer data show that the mean flow paths and spreading velocities have been more or less constant over the past three decades despite dramatic shifts in the Arctic system heat and freshwater balances from anthropogenic climate change over imposed to a high natural variability. The third and final chapter discusses the water-mass composition and the distribution of freshwater sources in Canadian Basin, the western section of the Arctic Ocean. Results are produced by performing a water-mass decomposition on the water samples collected during the 2015 Arctic GEOTRACES (GN01) oceanographic expedition. Stable isotope measurements (H₂¹⁸O/H₂¹⁶O and DHO/H₂O ratios) are used in combination with salinity and nutrients data to calculate the water-mass components for the upper 500 m Arctic Ocean (mixed layer through Atlantic Water layer). The sources of liquid freshwater into the Arctic Ocean include Pacific water, sea ice meltwater, river discharge and net precipitation. The topmost 50 meters of Canadian Basin contain the large fraction of freshwater from sea ice meltwater and meteoric water. Pacific water dominated the freshwater budget along the 2015 GN01 transects from 100 to 250 m. These depths are also characterized by a strong brine rejection signal, reflecting an enhanced annual sea ice cycle with more ice refreezing and melting each year, and an overall loss of multiyear ice. The 2015 results are compared with the overlapping 1994 and 2005 Arctic Ocean Sections (AOS94 and AOS05) and discussed in the context of regional and temporal variability of liquid freshwater and its components distribution. Our findings show significant increases in the Canadian Basin total liquid freshwater reservoir both compared to the 1994 and 2005 transects confirming a freshwater accumulation in the Canadian Basin already established by numerous observations and modeling studies (Gilles et al., 2012; Carmack et al., 2016; Proshutinsky et al. 2019; Solomon et al., 2021). The total freshwater reservoir increased by ca. 12,500 km³ from 1994 to 2015, of which ca. 5,000 km3 are within the Beaufort Gyre. Meteoric and Pacific freshwater components were the largest sources of the observed freshwater accumulation in the upper 500m of the western Arctic Ocean. An intensified Ekman transport in the Beaufort Gyre and increased availability of freshwater for accumulation are the two primary drivers for freshwater accumulation in the Canadian Basin. Within the limits of our analysis, it is not possible to quantitatively estimate the relative importance of the each forcing nor to resolve the seasonal to year‐to‐year variability. Our tracer-based analysis suggests that there is a significant variability in the freshwater components and UHL distribution while the major features of the circulation patterns and spreading velocities of the AW and the LHW have remained largely stable over the past decades. Future research should address whether in a fast changing Arctic, the dynamics of the surface layer will expand to the halocline and Atlantic layer substantially destabilizing the current Arctic Ocean water column with potentially dramatic consequences.

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), 2013. / Cataloged from PDF version of thesis. / Includes bibliographical references (p. 30-38). / Thiol substances can form stable complexes with metals (especially copper and mercury) in the surface ocean that can impact cycling and bioavailability of those elements. In this study, I present seven concentration profiles of cysteine and glutathione, two low-molecular weight thiols, from the coastal northwest Atlantic Ocean and the Bermuda Atlantic Time Series (BATS) sampling site in the Sargasso Sea, a first for these regions. These two thiols were found in the upper 200 meters of the ocean at all sites, and the total thiol concentration varied from 0.2 to 3.2 nM. The highest concentration of both thiols was found at the deep chlorophyll maximum in most samples. Thiol concentrations were higher on the continental shelf than in the open ocean. The observed distribution of cysteine and glutathione and thermodynamic stability of copper complexes suggests that Cu(I)-dithiol complexes may be the dominant surface ocean copper and thiol species. Mercury-thiol complexes were also present in thermodynamically modeled seawater, which may provide a vector for mercury uptake in the surface ocean. / by Tristan Kading. / Ph.D.

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), 2016. / Cataloged from PDF version of thesis. / Includes bibliographical references. / 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. / by Kyrstin L. Fornace. / Ph. D.