Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2010. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Lipids have a legacy in the geologic record extending back to the Archaean. Since the phylogenetic diversity of life is reflected in the structural diversity of biomolecules, lipid biomarkers that are shown to be diagnostic of certain organisms that carry out specific biochemical processes or that are demonstrated to have unique physiological roles can be used to trace the biogeochemical influence of bacteria in modern and ancient environments. In this thesis I explore the application of two classes of bacterial membrane lipids as biomarkers for marine biogeochemical processes in marine environments: ladderanes and hopanoids. Through the detection of ladderane lipids - biomarkers for anaerobic ammonium oxidizing (anammox) bacteria - I demonstrate the presence and distribution of anammox bacteria in a subterranean estuary. Through a survey of hopanoids in marine environments and cultured marine cyanobacteria I show that hopanoids are ubiquitous in the oceans and that their presence in ancient marine sediments could provide information about biogeochemical processes in past environments. Based on novel results demonstrating that hopanoids are resistant to extraction by non-ionic detergent, I propose that they may play a role in lipid ordering and the formation of putative lipid rafts in hopanoid-producing bacteria. / by James Peter Sáenz. / Ph.D.

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric and Planetary Sciences; and the Woods Hole Oceanographic Institution), 1999. / Includes bibliographical references. / The goal of this thesis was to use high resolution analytical techniques coupled with molecular level analyses to chemically characterize high molecular weight (> 1 k Da (HMW)) dissolved organic matter (DOM) isolated from seawater in an attempt to provide new insights in to the cycling of DOM in the ocean. While a variety of sites spanning different environments (fluvial, coastal and oceanic) and ocean basins were examined, the chemical structure of the isolated HMW DOM varied little at both the polymer and monomer levels. All samples show similar ratios of carbohydrate:acetate:lipid carbon (80±4:10±2:9±4) indicating that these biochemicals are present within a family of related polymers. The carbohydrate fraction shows a characteristic distribution of seven major neutral monosaccharides: rhamnose, fucose, arabinose, xylose, mannose, glucose and galactose; and additionally contains Nacetylated amino sugars as seen by Nuclear Magnetic Resonance Spectroscopy (NMR). This family of compounds, consisting of a specifically linked polysaccharide backbone that is acylated at several positions, has been termed acylated polysaccharides (APS) by our laboratory. APS accounts for 50% of the carbon in HMW DOM isolated from the surface ocean and 20% of the carbon in HMW DOM isolated from the deep ocean. In order to identify a possible source for APS three species of phytoplankton, Thalassiossira weissflogii, Emiliania huxleyi and Phaeocystis, were cultured in seawater and their HMW DOM exudates examined by variety of analytical techniques. Both the T. weissflogii and E. huxleyi exudates contain compounds that resemble APS indicating that phytoplankton are indeed a source of APS to the marine environment. Furthermore, the degradation of the T. weissflogii exudate by a natural assemblage of microorganisms indicates that the component resembling APS is more resistant to microbial degradation compared to other polysaccharides present in the culture. Molecular level analyses show the distribution of monosaccharides to be conservative in surface and deep waters suggesting that APS is present throughout the water column. In order to determine the mechanism by which APS is delivered to the deep ocean the [delta]14C value of APS in the deep ocean was compared to the A14C value of the dissolved inorganic carbon (DIC) at the same depth. If the formation of deep water is the dominant mode of transport then both the DIC and APS will have similar [delta]14C values. However, if APS is injected into the deep ocean from particles or marine snow then the [delta]14C value of APS will be higher than the DIC at the same depth. Our results indicate that APS in the deep Pacific Ocean carries a modem [delta]14C value and is substantially enriched in 14C relative to the total HMW DOM and the DIC at that depth. Thus, particle dissolution appears to be the most important pathway for the delivery of APS to the deep ocean. / by Lihini I. Aluwihare. / 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), 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), 2015. / Cataloged from PDF version of thesis. / Includes bibliographical references. / This thesis examines the controls on organic, inorganic, and volatile species distributions in hydrothermal fluids venting at Von Damm and Piccard, two recently discovered vent fields at the ultra slow spreading Mid-Cayman Rise, Earth's deepest mid-ocean ridge. A wide variety of possible temperatures and substrates for fluid/rock reaction exist at ultraslow spreading ridges. The flux of chemicals delivered to the ocean by circulating vent fluids exerts a major control on mass transfer into and out of the oceanic crust and supports chemosynthetic ecosystems. In Chapter 2, abiotic organic synthesis is shown to occur via two distinct mechanisms in the serpentinizing Von Damm system. Longstanding questions concerning the spatial, temporal, and mechanistic nature of carbon transformations in deep-sea hot springs are addressed. In contrast with the current paradigm, CH4 is not actively forming during circulation of H2-rich vent fluids, but instead is derived from fluid inclusions in the host rocks. Chapters 3 and 4 present in-depth studies of the chemical and isotopic compositions of aqueous species in vent fluids at Von Damm and Piccard to elucidate the role of reaction temperature, pressure, substrate composition, and water/rock mass ratios during the chemical evolution of hydrothermal fluids at oceanic spreading centers. At Von Damm, sequential reaction of gabbroic and peridotite substrates at intermediate temperatures can explain generation of the observed fluids. Geochemical modeling shows that talc-quartz assemblage is expected to precipitate during fluid mixing with seawater at the seafloor. At Piccard, extremely high temperature subsurface water/rock reaction results in high temperature fluids that are richer in dissolved H2 than any previously observed fluids worldwide. At both locations, high-H2 conditions promote the abiotic reduction of [Epsilon]CO2 to formate species, which may fuel a subsurface biosphere. In Chapter 5, multiple sulfur isotopes were measured on metal sulfide deposits, So, and fluid H2S to constrain sulfur sources and the isotopic systematics of precipitation in a wide variety of seafloor hydrothermal vents. Areas studied include the eastern Manus Basin and Lau Basin back-arc spreading centers, the unsedimented basalt-hosted Southern East Pacific Rise, and the sediment-hosted Guaymas Basin mid-ocean ridge spreading centers. Limited isotope fractionation between fluid H2S and precipitating chalcopyrite implies that sulfur isotopes in a chimney lining may record past hydrothermal activity. / by Jill Marie McDermott. / 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.

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), 2015. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Fifty-six million years ago Earth experienced rapid global warming (~6°C) that was caused by the release of large amounts of carbon into the ocean-atmosphere system. This Paleocene-Eocene Thermal Maximum (PETM) is often cited as an analogue of anthropogenic climate change. Many trigger mechanisms for the carbon release at the PETM have been proposed. Common to all scenarios is rapid release of isotopically light carbon (<¹³C/¹²C values) from methane hydrates, terrestrial or marine organic matter, as indicated by a pronounced excursion to light carbon isotope values across the PETM. I test the hypothesis that the PETM warming and isotope excursion were caused by the intrusion of a magmatic sill complex into organic-rich sediments in the North Atlantic. The intrusion of magma into sedimentary rocks will cause heating and metamorphic reactions in a thermal aureole around the intrusion. If these sediments are rich in organic matter, large volumes of isotopically light carbon are rapidly released. I examine geochemical evidence from lead, osmium, and organic carbon to place constraints on the extent the carbon isotope excursion during the PETM may have been caused by contact metamorphism of organic-rich sediments. Potential terrestrial and submarine analogs are examined to determine the behavior of these elements during thermal alteration. Furthermore, geochemical evidence from sediment cores at the PETM provides additional information about what might have caused the carbon isotope excursion. I find that lead is not a suitable proxy for carbon mobilization to the overlying seawater during contact metamorphism. Osmium, however, is mobilized together with carbon. Making reasonable assumptions for the ¹⁸⁷Os/¹⁸⁸Os of the sediments from the North Atlantic Magmatic Province (NAMP), constrained by the ¹⁸⁷Re/¹⁸⁸Os of organic-rich sediments and the depositional age of the sediment, the entire marine osmium isotope anomaly at the PETM could be explained without the need to invoke enhanced continental weathering. Based on estimates of the extent of mobilization of organic carbon relative to osmium, approximately 47% to 60% of the carbon released at the PETM may have been derived from thermal alteration of organic-rich sediments in the NAMP. / by Andrea Rose Dubin. / Ph. D.

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2009. / Includes bibliographical references. / The application of elemental and isotopic metal palaeoredox tracers to the geologic past rests on an understanding of modern metal cycles. This study reevaluates the surface-cycling of Mo and Re in near-surface reservoirs. Revised river averages of Mo and Re are 1.8- and 7.9-fold larger than previous estimates. The river concentrations of 8.0 nmol Mo kg-1 and 11.2 pmol Re kg- (pre-anthropogenic), result in shorter seawater response times of 4.4 x 105 yr ([Tau]Mo) and 1.3 x 105 yr ([Tau]Re pre-anthropogenic). These metals, especially Re, are more sensitive to changing source and sink fluxes than previously thought. Evaluation of Mo and Re concentrations in high temperature fluids from the Manus Basin indicate that Re is essentially absent from the hydrothermal end member and Mo is present at concentrations considerably lower than ambient seawater. The sink fluxes represented by hydrothermal circulation are negligible in comparison to the revised river source fluxes. Anthropogenic contributions to the Re flux to seawater are seen in the high concentrations of certain impacted water samples such as those associated with mining sites. It may also be seen in a significant, variable, Re enrichment feature in the Hudson River estuary. This Re enrichment feature is not the result of estuarine mixing or the remobilization of sediment-hosted Re. On the basis of a Re - SO2- correlation we are able to quantify and correct for the anthropogenic Re, which corresponds to ~33% of the modern river average. This study documents the development of an analytical method for stable Re isotopes. / (cont.) Though complicated by analyte requirements and 187Re 1870s decay, Re isotope measurements have a reproducibility of ±0.05%o for analyte concentrations of 20 ng Re mL-1. Total Re isotopic variability to date is 0.9%o. This includes 0.3%0 across five commercially available Re products, and 0.5%0 across a black shale weathering profile. 6187Re variability across the weathering profile was systematic with the most weathered samples showing the most significant [delta]187Re depletions. The Re isotopic weathering profile is well described by both two-component mixing and Rayleigh fractionation. There are currently insufficient data to discriminate between the two models. / by Christian Alexander Miller. / Ph.D.

Thesis (S.M.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences and the Woods Hole Oceanographic Institution), 2001. / Includes bibliographical references (leaves 65-72). / A comparison of monthly biogeochemical measurements made from 1993 to 1995, combined with hydrography and satellite altimetry, was used to observe the impacts of nine eddy events on primary productivity and particle flux in the Sargasso Sea. Measurements of primary production, thorium-234 flux, nitrate+nitrite, and photosynthetic pigments made at the US JGOFS Bermuda Atlantic Time-series Study (BATS) site were used. During the three years of this study, four out of six high thorium- 234 flux events over 1000 dpm/m 2/d occurred during the passage of an eddy. Primary production nearly as high as the spring bloom maximum was observed in two modewater eddies (May 1993 and July 1995). The 1994 spring bloom at BATS was suppressed by the passage of an anticyclone. Distinct phytoplankton community shifts were observed in mode-water eddies, which had an increased percentage diatoms and dinoflagelletes, and in cyclones, which had an increased percentage cyanobacteria (excluding Prochlorococcus). The difference in the observations of mode-water eddies and cyclones may result from the age of the eddy, which was very important to the biological response. In general, eddies that were one to two months old elicited a large biological response; eddies that were three months old may show a biological response and were accompanied by high thorium flux measurements; eddies that were four months old or older did not show a biological response or high thorium flux. Our conceptual model depicting the importance of temporal changes during eddy upwelling and decay fit the observations well in all 7 upwelling eddies. Additional information is needed to determine the importance of deeper mixed layers and winter mixing to the magnitude of the eddy impacts. Also, sampling generally captured only the beginning, end, and /or edge of an eddy due to the monthly to semi-monthly frequency of the measurements made at BATS. Lagrangian studies, higher resolution time-series, and/or more spatial coverage is needed to provide additional information for improved C and N budgets in the Sargasso Sea and to complete our understanding of the temporal changes that occur in an eddy. / by Erin N. Sweeney. / S.M.

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2011. / Cataloged from PDF version of thesis. / Includes bibliographical references. / A combination of uptake field studies on natural phytoplankton assemblages and laboratory proteomic and physiological experiments on cyanobacterial isolates were conducted investigating the interactions of cadmium (Cd), zinc (Zn), and phosphorus (P) in marine Synechococcus. Enriched stable isotope field uptake studies of ¹¹⁰CD in the Costa Rica Upwelling dome, a Synechococcus feature, showed that uptake of Cd occurs in waters shallower than 40 m, correlates positively with chlorophyll a concentrations and is roughly equivalent to the calculated upwelling flux of cadmium inside the dome. In laboratory experiments, Synechococcus WH5701 cells exposed to low picomolar quantities of free Cd under Zn deficiency show similar growth rates to no added Cd treatments during exponential growth phase, but show differences in relative abundances of many proteins involved in carbon and sulfur metabolism suggesting a great metabolic impact. During stationary phase, chronic Cd exposure in this coastal isolate causes an increase in relative chlorophyll a fluorescence and faster mortality rates. The interactions of acute Cd exposure at low picomolar levels with Zn and phosphate (PO4³-) were investigated in Synechococcus WH8102, an open ocean isolate. The presence of Zn appears vital to the response of the organism to different PO4 ³- cocentrations. Comparisons with literature transcriptome analyses of PO4 ³- stress show similar increases in relative abundance of PO4 ³- stress response proteins including a PO4 ³- binding protein and a Zn-requiring alkaline phosphatase. A bacterial metallothionein, a Zn-associated protein, appears to be correlated with proteins present under low PO4 conditions. Together, these experiments suggest that the interactions of Cd and Zn can affect Synechococcus and play a role in the acquisition of PO4 ³-. / by Alysia Danielle Cox. / Ph.D.

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2007. / Includes bibliographical references. / Zinc (Zn) stable isotopes can record information about important oceanographic processes. This thesis presents data on Zn isotopes in anthropogenic materials, hydrothermal fluids and minerals, cultured marine phytoplankton, natural plankton, and seawater. By measuring Zn isotopes in a diverse array of marine samples, we hope to understand how Zn isotopes are fractionated in the oceans and how Zn isotopes may be used as tracers of marine biogeochemical processes. Common forms of anthropogenic Zn had [delta]66Zn from +0.08 %o to +0.32 %o, a range similar to Zn ores and terrigenous materials. Larger variations were discovered in hydrothermal fluids and minerals, with hydrothermal fluids ranging in 666Zn from 0.02 %o to +0.93 %o, and chimney minerals ranging from -0.09 %o to +1.17 %o. Lower-temperature vent systems had higher [delta]666Zn values, suggesting that precipitation of isotopically light Zn sulfides drives much of the Zn isotope fractionation in hydrothermal systems. In cultured diatoms, a relationship was discovered between Zn transport by either high-affinity or low-affinity uptake pathways, and the magnitude of Zn isotope fractionation. We established isotope effects of [delta]66Zn = -0.2 %o for high-affinity uptake and [delta]66Zn = -0.8 %o for low-affinity uptake. This work is the first to describe the molecular basis for biological fractionation of transition metals. Biological fractionation of Zn isotopes under natural conditions was investigated by measuring Zn isotopes in plankton collected in the Peru Upwelling Region and around the world. / (cont.) Seawater dissolved Zn isotopes also reflect the chemical and biological cycling of Zn. The [delta]66Zn of deep seawater in the North Pacific and North Atlantic is about 0.5%0, and the dissolved [delta]66Zn gets lighter in the upper water column. This is unexpected based our observations of a biological preference for uptake of light Zn isotopes, and suggests that Zn transport to deep waters may occur by Zn adsorption to sinking particles rather than as primary biological Zn. The thesis, by presenting data on several important aspects of Zn isotope cycling in the oceans, lays the groundwork for further use of Zn isotopes as a marine biogeochemical tracer. / by Seth Greeley John. / Ph.D.