Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences, and the Woods Hole Oceanographic Institution), 2003. / Includes bibliographical references (leaves 205-214). / Pathways of exchange between the shelf and slope in the Mid-Atlantic Bight were investigated using a combination of radiochemical tracer and hydrographic measurements. The motivation was to provide evidence of transport routes for shelfwater that could be important to the balance of shelf-slope exchange, as well as to the biogeochemical fluxes across this crucial ocean boundary. The four radium isotopes, with half-lives of 4 days to 1600 years, a coastal source, and conservative properties in seawater, were used as coastal water mass tracers. The final study was comprised of data from 5 cruises, with a total of 8 cross-shelfbreak transects. Two areas were studied, a northern Mid-Atlantic Bight transect south of Nantucket Shoals, and a southern Mid-Atlantic Bight series of transects off the coast of Delaware. In addition, data were collected from the shelfbreak at Cape Hatteras crossing the western wall of the Gulf Stream to help determine sources of anomalous 224Ra enrichment which was observed on several of the shelfbreak transects. Combined with the hydrographic data, radium measurements suggested a pathway for exchange in the Mid-Atlantic Bight that was not a direct advection of shelf water toward the slope. Rather, the evidence suggested limited direct exchange of surface shelf water across the shelfbreak front. This provides observational evidence that is consistent with models (e.g., Gawarkiewicz and Chapman, 1991) which predict the shelfbreak front will impede exchange. Furthermore, 224Ra activity on the upper slope points to a rapid transport pathway for bottom water from the Cape Hatteras shelf via the Gulf Stream onto the Mid-Atlantic Bight slope. The radiochemical and hydrographic evidence suggests that recirculation around the slope sea gyre may be a more important pathway than direct cross-shelf transport. / by Linda L. Rasmussen. / 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), 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 Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 1987. / Vita. / Includes bibliographical references. / Gravity derived from Seasat altimetry has provided a means of estimating seafloor topography and its compensation, which in turn can be used to understand the evolution of oceanic lithosphere. In the first study, the correlation between the geoid, deflection of the vertical, and seafloor topography is investigated along a section of the Southwest Indian Ridge. Geoid anomalies computed from a simple thermal model fairly accurately predict the intermediate-wavelength anomalies across the fracture zones. The shorter wavelength anomalies are consistent with those calculated from topography using elastic plate compensation. The combined effect of the thermal offset and seafloor topography produces an anomaly which has a small-amplitude, short-wavelength depression directly over the fracture zone valley. Pronounced lineations in the horizontal geoid gradient do not coincide with the valley but have trends parallel to the fracture zones. In the second study, fracture zones along the Southwest Indian Ridge are identified using altimeter profiles and bathymetry. Finite poles of rotation are determined from the fracture zone locations and magnetic anomaly lineations for anomalies 6 (20 Ma), 13 (37 Ma), and 20 (45 Ma). The new poles are in general agreement with previously published poles and describe a fairly consistent direction of relative motion between Africa and Antarctica for the past 45 Myr. A present-day pole of rotation calculated from transform fault azimuths determined primarily from their geoid anomalies, agrees with published poles based on bathymetric data. In the third study, the rate of change of the geoid with age has been estimated as a function of age from geoid offsets across the Eltanin and Udintsev fracture zones and used to constrain thermal models of lithospheric cooling. Observed trends in the geoid slope versus age plots are similar on both branches of the Eltanin and the east limb of the Udintsev fracture zone. The similarity in trends argues against the effects of isolated thermal or bathymetric anomalies and appears instead to reflect a general feature of the geoid-slope versus average age relationship across fracture zones. Although the thermal plate cooling model is successful in predicting both seafloor depths and heat flow values out to ages of at least 80 m.y. B.P., it cannot explain the observed geoid slope values for these two fracture zones. It is not clear at this point whether this is due to inadequacies in the cooling model or to peculiarities in fracture zone evolution. / by Mavis Lynn Driscoll. / Ph.D.

Thesis (Ph. D. in Geology and Geophysics)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2011. / This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Hurricane activity in the Northeastern Gulf of Mexico and its relationship to regional and large-scale climate variability during the Late Holocene is explored. A 4500-year record of hurricane-induced storm surges is developed from sediment cores collected from a coastal sinkhole near Apalachee Bay, Florida. Reconstructed hurricane frequency is shown to exhibit statistically significant variability with the greatest activity occurring between 2700 and 2400 years ago and the least activity between 1900 to 1600 years ago and after 600 years ago. Proxy records of storm-relevant climate variables contain similar timescales of variability and suggest both regional and large-scale mechanisms have influenced hurricane activity on centennial to millennial timescales. In particular, low-frequency migrations of the Loop Current may exercise control over regional hurricane activity by changing the thermal structure of the upper ocean and influencing the role of storm-induced upwelling on hurricane intensification. A new method for estimating the frequency of hurricane-generated storm surges is presented and applied to Apalachee Bay, Florida. Multisite paleohurricane reconstructions from this region are developed, and the effects of geographic boundary conditions and temporal resolution on estimates of paleohurricane frequency are explored. / by Daniel Philip Lane. / Ph.D.in Geology and Geophysics

Thesis: Ph. D., Joint Program in Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2014. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Methylation of mercury (Hg) in the marine water column has been hypothesized to serve as the primary source of the bioaccumulating chemical species monomethylmercury (MMHg) to marine food webs. Despite decades of research describing mercury methylation in anoxic sediments by anaerobic bacteria, mechanistic studies of water column methylation are severely limited. These essential studies have faced analytical challenges associated with quantifying femtomolar concentrations of the methylated Hg species dimethylmercury (DMHg) and MMHg in marine systems. In addition, the complex biogeochemical cycling of Hg in natural systems require consideration of gaseous, dissolved, and particulate species of Hg in order to probe potential controls on its ultimate transfer into marine food webs. The presented work provides a comprehensive study of Hg chemical speciation and transformations in Tropical Pacific waters. We developed an analytical method for MMHg determination from seawater that has the potential to ease measurements of MMHg distributions, as well as mechanistic studies of Hg species transformations. We used this method, in addition to previously established methods, to measure dissolved and particulate Hg species distributions and fluxes along a transect of the Pacific Ocean. Over significant gradients in oxygen utilization and primary productivity, we observed a region of methylated Hg species focused in the Equatorial Pacific that appeared spatially separated from higher concentrations in North Pacific Intermediate Waters. From the first full water column depth profiles of this region, we also observed the intrusion of elevated Hg into deep waters of the Equatorial and South Pacific Ocean. In addition we observed substantial potential rates of mercury methylation in subsurface and low oxygen waters along the Pacific transect as well as the Sargasso Sea using Hg isotope tracers. We observed dynamic production and decomposition of methylated Hg in low productivity waters, despite low ambient methylated Hg concentrations. From the addition of bulk organic matter as well as individual compounds important for methylation in anaerobic bacteria, we observe no simple limitation of Hg methylation in marine waters but highly dynamic conversion of Hg between methylated and inorganic species. / by Kathleen M. Munson. / Ph. D.

Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2005. / Includes bibliographical references (p. 117-128). / The relatively simple tectonic environment of mid-ocean ridge transform fault (RTF) seismicity provides a unique opportunity for investigation of earthquake and faulting processes. We develop a scaling model that is complete in that all the seismic parameters are related to the RTF tectonic parameters. Laboratory work on the frictional stability of olivine aggregates shows that the depth extent of oceanic faulting is thermally controlled and limited by the 600⁰C isotherm. Slip on RTFs is primarily aseismic, only 15% of the tectonic offset is accommodated by earthquakes. Despite extensive fault areas, few large earthquakes occur on RTFs, and few aftershocks follow the large events. Standard models of seismicity, in which all earthquakes result from the same seismic triggering process, do not describe RTF earthquakes. Instead, large earthquakes appear to be preceded by an extended fault preparation process marked by abundant foreshocks within 1 hour and 15 km of the main- shocks. In our experiments normal force vibrations, such as seismic radiation from nearby earthquakes, can weaken and potentially destabilize steadily creeping faults. / (cont.) Integrating the rheology, geology, and seismicity of RTFs, we develop a synoptic model to better understand the spatial distribution of fault strength and stability and provide insight into slip accommodation on RTFs. / by Margaret S. Boettcher. / Ph.D.

Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2005. / Includes bibliographical references (p. 229-238). / The fate of trace metals in contaminated coastal sediments is poorly understood, yet critical for effective coastal management. The aim of this thesis is to investigate and quantify the mechanisms leading to the release of silver, lead and copper across the sediment-water interface. Two contrasting sites were investigated, a heavily contaminated site in Boston Harbor and a less impacted, offshore site in Massachusetts Bay. High-resolution porewater and solid phase samples were collected in each season to determine the diagenetic cycles and chemistry controlling the fate of these metals. The trace metals are scavenged by iron oxyhydroxides and released to the porewaters when these oxides are reduced. At the strongly reducing site in Boston Harbor, there is seasonal transfer of trace metals from oxide phases in winter, to sulfides phase in summer. At the Massachusetts Bay site, due to the lack of sulfide, the metals are focused into the surface oxide layer, giving a solid phase enrichment. There is a diffusive flux of copper to the water column throughout the year, while silver is released only in winter. Lead is strongly scavenged and is rarely released to the overlying waters. / (cont.) Analysis of reduced sulfur compounds in the porewaters has shown that there is also a significant flux of these strong ligands to the overlying waters. Polysulfide species enhance the solubility of copper within the porewaters. Sediment resuspension fluxes were quantified using an erosion chamber. Sediment resuspension leads to enhanced release of dissolved metals and is especially important in redistributing contaminants as the first particles to be eroded are enriched in trace metals. The total release of dissolved metals from the sediments by diffusion and sediment resuspension is estimated to be 60% and 10% of the riverine flux for copper and lead respectively. With continued pollution control reducing the discharge of metals from other sources, the benthic release of metals will become increasingly important terms in the metal budget of Boston Harbor. / by Linda H. Kalnejais. / Ph.D.

Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and, the Woods Hole Oceanographic Institution), 2005. / Includes bibliographical references. / The goal of this thesis is to investigate three different areas relating to the characterization of dissolved organic matter (DOM): further determination of the chemical compounds present in high molecular weight DOM (HMWDOM), the cycling of individual compounds within the HMWDOM pool, and the biological controls on DOM release. The first section of this thesis provided additional molecular level characterization of HMWDOM. While some individual components have been identified, the total yield of compounds isolated is much smaller than the amount expected by spectroscopic analysis by nuclear magnetic resonance (NMR) spectroscopy. Since the majority of the as-yet unidentified carbon was inferred to be carbohydrate, periodate over-oxidation was used to analyze this fraction. Analysis of both surface and deep water HMWDOM samples indicated that the majority of the carbon present was periodate over-oxidizable, including 70% of the aliphatic NMR signal. Comparison of the periodate demand for HMWDOM versus that for linear glucopolysaccharide standards indicated that HMWDOM had a greater degree of branching. Based on the changes in the H NMR spectra during the reaction, it was concluded that 6-deoxysugars were the primary compounds in the unidentified fraction of HMWDOM. Compound specific radiocarbon analysis can provide information about the cycling and relative ages for individual HMWDOM components. In the second section of this thesis, a new method was presented for the purification of individual underivatized amino acids hydrolyzed from HMWDOM. / (cont.) This new separation protocol utilized various chromatographic techniques, including cation exchange chromatography and high- pressure liquid chromatography (HPLC) using C18 and strong cation exchange (SCX) columns. Six amino acids were isolated from a HMWDOM sample with sufficient purity and quantity for radiocarbon analysis. These amino acids had a range of A'4C values, from 121%o to -454%o. The final section investigates biological controls on the dissolved organic nitrogen (DON) pool. Total hydrolyzable amino acids (THAA), and nucleic acids were measured for four incubations: a control incubation, a grazer added incubation, a zero virus incubation, and a 10 times virus incubation. Comparison to the control showed THAA and nucleic acid release were influenced by viruses but not grazers. / by Tracy M. Quan. / 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.

Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), February 2000. / Includes bibliographical references. / Benthic foraminiferal δ13C, Cd/Ca, and Ba/Ca are important tools for reconstructing nutrient distributions, and thus ocean circulation, on glacial-interglacial timescales. However, each tracer has its own "artifacts" that can complicate paleoceanographic interpretations. It is therefore advantageous to measure multiple nutrient proxies with the aim of separating the various complicating effects. Zn/Ca is introduced as an important aid toward this goal. Benthic (Hoeglundina elegans) Cd/Ca ratios from the Bahama Banks indicate that the North Atlantic subtropical gyre was greatly depleted in nutrients during the last glacial maximum (LGM). A high-resolution Cd/Ca record from 965 m water depth suggests that Glacial North Atlantic Intermediate Water formation was strong during the LGM, weakened during the deglaciation, and strengthened again during the Younger Dryas cold period. Comparison of Cd/Ca and δ13C data reveals apparent short-term changes in carbon isotopic air-sea signatures. Benthic foraminiferal Zn/Ca could be a sensitive paleoceanographic tracer because deep water masses have characteristic Zn concentrations that increase about ten-fold from the deep North Atlantic to the deep North Pacific. A "core top calibration" shows that Zn/Ca is controlled by bottom water dissolved Zn concentration and, like Cd/Ca and BalCa, by bottom water saturation state with respect to calcite Since Zn/Ca responds to a different range of saturation states than Cd/Ca, the two may be used together to evaluate changes in deep water carbonate ion (CO32- ) concentration. Zn/Ca and Cd/Ca ratios in the benthic foraminifer Cibicidoides wuellerstorfi exhibit large fluctuations over the past 100,000 years in a deep (3851 m) eastern equatorial Pacific sediment core. The data imply that bottom water CO32- concentrations were lowest during glacial Marine Isotope Stage 4 and highest during the last deglaciation. LGM CO32- concentrations appear to have been within a few μmol kg-1 of modern values. Deep North Atlantic Cd/Ca ratios imply much higher nutrient concentrations during the LGM. Although such data have usually been explained by a northward penetration of Southern Ocean Water (SOW), it has been suggested that they could result from increased preformed nutrient levels in the high-latitude North Atlantic or by increased aging of lower North Atlantic Deep Water (NADW). Glacial Zn/Ca data, however, require a substantially increased mixing with SOW and thus a reduction in NADW formation. Large changes in carbon isotopic air-sea exchange are invoked to reconcile benthic δ13C and trace metal data. / by Thomas Mathew Marchitto, Jr. / Ph.D.