Thesis (Ph. D.)--Joint Program in Marine Geology and Geophysics (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2007. / This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. / Includes bibliographical references. / I provide constraints on mantle convection through observations of the rheology and composition of the oceanic upper mantle. Convection cannot be directly observed, yet is a fundamental part of the plate tectonic cycle. Relative motion among plates is accommodated by localized deformation at their boundaries. I demonstrate that in the ductile regime, strain localization occurs when different mineral phases are mixed together, limiting grain annealing. Upper mantle flow is by dislocation creep, resulting in seismic anisotropy due to mineral alignment. I use a shear zone in the Josephine Peridotite to quantify the relationship between mineral orientation and shear strain, providing an improved framework for the interpretation of seismic anisotropy. The upper mantle is generally assumed to be homogeneous in composition. From detailed isotopic and chemical analyses of abyssal peridotites from the Southwest Indian Ridge, I show that the mantle is heterogeneous at a range of length-scales. Abyssal peridotites recovered at ocean ridges are generally interpreted as the depleted residues of melt extraction. I find that melt-rock reaction is a significant part of the melt extraction process, modifying the composition of the lithospheric mantle. The generation of heterogeneous lithosphere provides a source for asthenospheric heterogeneity, via subduction and mantle convection. / by Jessica Mendelsohn Warren. / Ph.D.

Rare earth elements (REEs) and their isotopes (such as Nd isotopes) can be potentially used to trace a wide range of oceanic processes in both modern and ancient oceans, but their successful application as tracers requires a comprehensive understanding of REE cycling in the modern ocean. Previous studies of REEs in seawater were largely constrained by analytical difficulties in generating accurate and precise REE data from seawater, which typically contain REE concentrations at a sub-ppt to ppt level. A new, and relatively simple, analytical method for precise and accurate determination of all dissolved REE concentrations in reasonably small (∼100 ml) seawater samples is presented in this thesis. With the application of the new method, this thesis reports the first full-depth, zonal ocean section of all dissolved REE concentrations, collected during the CoFeMUG cruise along ∼12°S in the South Atlantic. The section approach of this study places the distribution of dissolved REE concentrations in a well-constrained hydrographic context, allowing the first quantitative assessment (by an inverse model) of the relative importance of hydrographic controls resulting from advection/mixing of ocean circulation, together with non-conservative controls resulting from local particle scavenging and remineralization, in controlling the distribution of dissolved REEs in this region. A noteworthy decoupling of Ce and Mn with respect to their cycling in the water column was also observed in this study. The application of Nd isotopes as a tracer to reconstruct changes in ocean circulation in the NW European chalk shelf sea during rapid climatic events, including the mid-Cenomanian Event and oceanic anoxic event 2 (OAE 2), suggests a tight coupling between ocean circulation and transient climatic cooling during the general warm Late Cretaceous. An advected volcanic signal during OAE 2 was registered in the seawater Nd-isotope record from the English Chalk, probably suggesting a period of enhanced ocean ventilation/mixing at this time.

Thesis (S.M.)--Joint Program in Marine Geology and Geophysics (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 (p. 33-37). / Mid-ocean ridge basalts (MORBs) exhibit a wide range of CO2 concentrations, reflecting saturation to supersaturation (and rarely undersaturation) relative to their emplacement depths. In this study, we explore the mechanisms of CO2 degassing and the implications this has for estimating the advance rates and durations of seafloor eruptions. We present dissolved volatile concentrations (mainly of CO 2 and H20) and vesicle size distributions (VSDs) for a unique suite of MORB glasses collected at the East Pacific Rise, ~9° 50' N. These MORB glasses were collected at -200 m intervals along an across-axis track over a single flow pathway within the recently emplaced 2005-06 eruption boundaries; systematic sample collection provides one of the first opportunities to characterize intra-flow geochemical and physical evolution during a single eruption at a fast-spreading ridge. Compared to measurements of MORB volatiles globally, dissolved H20 concentrations are relatively uniform (0.10 - 0.16 weight percent), whereas dissolved CO2 contents exhibit a range of concentrations (154 - 278 ppm) and decrease with distance from the EPR axis (i.e., eruptive vent). Ion microprobe analysis of dissolved volatiles within the MORB glasses suggest that the magma erupted supersaturated (pressure equilibrium with 920 - 1224 mbsf) and in near-equilibrium with the melt lens of the axial magma chamber (~1250 - 1500 mbsf), and degassed to near equilibrium (299 - 447 mbsf) with seafloor depths over the length of the flow. The decrease in CO 2 concentrations spans nearly the full range of dissolved CO2 contents observed at the EPR and shows that the varying degrees of volatile saturation that have been observed in other MORB sample suites may be explained by degassing during emplacement. Vesicularity (0.1 - 1.2%) increases with decreasing dissolved CO2 concentrations. We use vesicle size distributions (VSDs)-vesicle sizes and number densities-to quantify the physical evolution of the CO2 degassing process. VSDs suggest that diffusion of CO2 into preexisting vesicles, and not nucleation of new vesicles, is the dominant mechanism of increasing CO2 in the vapor phase. We also use VSDs, along with estimates of vesicle growth rates, to constrain emplacement time of the 2005-06 eruption to <~24 hours and to resolve variations in advance rate with down flow distance. / by Dorene Samantha Nakata. / S.M.

Thesis (Ph. D.)--Joint Program in Marine Geology and Geophysics (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric and Planetary Sciences, and the Woods Hole Oceanographic Institution), 2003. / Includes bibliographical references. / Prevailing wisdom holds that the vertical distribution of molybdenum (Mo) in the open ocean is conservative, despite Mo's important biological role and association with Mn oxides and anoxic sediments. Mo is used in both nitrogenase, the enzyme responsible for N2 fixation, and nitrate reductase, which catalyzes assimilatory and dissimilatory nitrate reduction. Laboratory culture work on two N2 fixing marine cyanobacteria, Trichodesmium and Crocosphaera, and a marine facultative denitrifier, Marinobacter hydrocarbanoclasticus, showed that Mo cell quotas in these organisms were positively correlated with Mo-containing enzyme activity. Mo concentrations in Crocosphaera dropped almost to blank levels when not fixing N2 suggesting daily synthesis and destruction of the entire nitrogenase enzyme and release of Mo. Trichodesmium cultures, however, retained a pool of cellular Mo even when not fixing N2. Colonies of Trichodesmium collected in the field have Mo:C tenfold higher than seen in culture, these Mo:C ratios were reflected in SPM samples from the same region. Fe:C ratios for Trichodesmium were between 12-160 pmol:mol in field and culured samples. The Fe:C ratio of Crocosphaera was established to be 15.8 =/+ 11.3 under N2 fixing conditions. Mo cellular concentrations in cultured organisms were too small to significantly influence dissolved Mo distributions, but may slightly affect Suspended Particulate Matter (SPM) distributions. Mean SPM Mo:C ratios were slightly elevated in regions of N2 fixation and denitrification.. A high precision (=/+ 0.5%) isotope dilution ICP-MS method for measuring Mo was developed to re-evaluate the marine distribution of Mo in the dissolved and particulate phase. / (cont.) Mn oxides were not found to significantly influence either the dissolved or SPM Mo distribution. Dissolved Mo profiles from the Sargasso and Arabian Sea were conservative. However, dissolved Mo profiles from the Eastern Tropical Pacific showed both depletion and enrichment of dissolved Mo possibly associated with interaction of Mo with coastal sediments. Dissolved Mo profiles in several California Borderland Basins showed 1-2 nM Mo depletions below sill depth. A more focused study of water column response to sediment fluxes using the high precision Mo analyses is necessary to determine whether these phenomena are related. / by Caroline Beth Tuit. / Ph.D.

Sedimentary basins form when water-borne sediments in shallow seas are deposited over periods of millions of years. Sediments compact under their own weight, causing the expulsion of pore water. If this expulsion is sufficiently slow, overpressuring can result, a phenomenon which is of concern in oil drilling operations. The competition between pore water expulsion and burial is complicated by a variety of factors, which include diagenesis (clay dewatering), and different modes (elastic or viscous) of rheological deformation via compaction and pressure solution, which may also include hysteresis in the constitutive behaviours. This thesis is concerned with models which can describe the evolution of porosity and pore pressure in sedimentary basins. We begin by analysing the simplest case of poroelastic compaction which in a 1-D case results in a nonlinear diffusion equation, controlled principally by a dimensionless parameter lambda, which is the ratio of the hydraulic conductivity to the sedimentation rate. We provide analytic and numerical results for both large and small lambda in Chapter 3 and Chapter 4. We then put a more realistic rheological relation with hysteresis into the model and investigate its effects during loading and unloading in Chapter 5. A discontinuous porosity profile may occur if the unloaded system is reloaded. We pursue the model further by considering diagenesis as a dehydration model in Chapter 6, then we extend it to a more realistic dissolution-precipitation reaction-transport model in Chapter 7 by including most of the known physics and chemistry derived from experimental studies. We eventually derive a viscous compaction model for pressure solution in sedimentary basins in Chapter 8, and show how the model suggests radically different behaviours in the distinct limits of slow and fast compaction. When lambda << 1, compaction is limited to a basal boundary layer. When lambda >> 1, compaction occurs throughout the basin, and the basic equilibrium solution near the surface is a near parabolic profile of porosity. But it is only valid to a finite depth where the permeability has decreased sufficiently, and a transition occurs, marking a switch from a normally pressured environment to one with high pore pressures.

Thesis: Ph. D. in Geochemistry, Joint Program in Marine Geology and Geophysics (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2016. / "February 2016." Cataloged from PDF version of thesis. / Includes bibliographical references. / Fractional crystallization of mantle-derived basaltic melts is a critical process in producing a compositionally stratified continental crust characterized by a silicic upper crust and a mafic lower crust. This thesis explores outstanding questions associated with fractional crystallization through detailed field, petrological, and geochemical studies of the Dariv Igneous Complex in Western Mongolia. The Dariv Igneous Complex records the crystallization of a high-K primitive arc melt at shallow crustal levels, preserving both biotite-bearing ultramafic and mafic cumulates, as well as liquid-like evolved plutonics, such as (quartz-)monzonites. Chapter 2 presents comprehensive field and petrographic descriptions of the complex and establishes the petrogenetic groundwork to understand the conditions under which it formed. Results of this study indicate that the observed lithologies formed through the fractional crystallization of a high-K hydrous basalt, typical of alkali-rich basalts found in subduction zone settings, at 0.2-0.5 GPa and elevated oxygen fugacities. Chapter 3 presents a quantitatively modeled liquid line of descent (LLD) for the complex based on whole rock geochemical analyses, which is able to explain the trends observed in the monzonitic plutonic series observed in continental arcs. The oxygen isotope trajectory of fractionally crystallizing melts is rigorously constrained through modeling and mineral analyses in Chapter 4. This study indicates that large (1 to 1.8%o) increases in [delta]18O as a melt evolves from basaltic to granitic in composition due to the fractionation of low [delta]18O minerals. As such, the majority of [delta]180 values of upper crustal silicic plutonics can be explained through fractional crystallization of primitive arc basalts alone without needing to invoke assimilation of high [delta]18O crustal material. Finally, Chapter 5 explores the timescales associated with fractional crystallization through high precision U-Pb geochronology of zircon from the Dariv Igneous Complex. Evolution from a basaltic melt to a silica-rich monzonitic melt in the Dariv Igneous Complex occurred in <300 ka. If rates of fractional crystallization are primarily a function of cooling, this study provides an end-member constraint for fractional crystallization of a basaltic melt at relatively cool, shallow crustal levels. Together, these studies advance our understanding of the compositional, isotopic, and temporal variations associated with the formation of the continental crust. / by Claire Elizabeth Bucholz. / Ph. D. in Geochemistry

Thesis (Ph. D.)--Joint Program in Marine Geology and Geophysics (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), September 2003. / Includes bibliographical references. / Groundwater discharge into estuaries and the coastal ocean is an important mechanism for the transport of dissolved chemical species to coastal waters. Because many dissolved species are present in groundwater in concentrations that are orders of magnitude higher than typical river concentrations, groundwater-borne nutrients and pollutants can have a substantial impact on the chemistry and biology of estuaries and the coastal ocean. However, direct fluxes of groundwater into the coastal ocean (submarine groundwater discharge, or SGD) can be difficult to quantify. Geochemical tracers of groundwater discharge can reflect the cumulative SGD flux from numerous small, widely dispersed, and perhaps ephemeral sources such as springs, seeps, and diffuse discharge. The natural radiocarbon content (A14C) of dissolved inorganic carbon (DIC) was developed as a tracer of fresh, terrestrially driven fluxes from confined aquifers. This A14C method was tested during five sampling periods from November 1999 to April 2002 in two small estuaries in southeastern North Carolina. In coastal North Carolina, fresh water artesian discharge is characterized by a low A14C signature acquired from the carbonate aquifer rock. Mixing models were used to evaluate the inputs from potential sources of DIC-A'4C to each estuary, including seawater, springs, fresh water stream inputs, and salt marsh respiration DIC additions. These calculations showed that artesian discharge dominated the total fresh water input to these estuaries during nearly all sampling periods. / (cont.) These new A14C-based SGD estimates were compared with groundwater flux estimates derived from radium isotopes and from radon-222. It is clear that these tracers reflect different components of the total SGD. The fluxes of low-A14C and of 222Rn were dominated by artesian discharge. Estuarine 226Ra showed strong artesian influence, but also reflected the salt water SGD processes that controlled the other three radium isotopes. The flux of 228Ra seemed to reflect seepage from the terrestrial surficial aquifer as well as salt water recirculation through estuarine sediments. The fluxes of 224Ra and 223Ra were dominated by salt water recirculation through salt marsh sediments. This multi-tracer approach provides a comprehensive assessment of the various components contributing to the total SGD. / by Carolyn M. Gramling. / Ph.D.