ALBERT

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).

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.

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.

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 2013

Description: In this thesis we present results from inversion of data using dense arrays of collocated seismic and magnetotelluric stations located in the Cascadia subduction zone region of central Washington. In the migrated seismic section, we clearly image the top of the slab and oceanic Moho, as well as a velocity increase corresponding to the eclogitization of the hydrated upper crust. A deeper velocity increase is interpreted as the eclogitization of metastable gabbros, assisted by fluids released from the dehydration of upper mantle chlorite. A low velocity feature interpreted as a fluid/melt phase is present above this transition. The serpentinized wedge and continental Moho are also imaged. The magnetotelluric image further constrains the fluid/melt features, showing a rising conductive feature that forms a column up to a conductor indicative of a magma chamber feeding Mt. Rainier. This feature also explains the disruption of the continental Moho found in the migrated image. Exploration of the assumption of smoothness implicit in the standard MT inversion provides tools that enable us to generate a more accurate MT model. This final MT model clearly demonstrates the link between slab derived fluids/melting and the Mt. Rainier magma chamber.

Description: Funding for this work was made possible by the American Society for Engineering education through a National Defense Science and Engineering Fellowship, and by the National Science Foundation through two grants for the CAFE and CAFE MT projects.

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 May 1998

Description: Planktonic protozoan grazers have the potential to significantly affect the chemistry of particle-associated trace metals. This is due both to the importance of protists as consumers of bacterial-sized particles, and to the unique low-pH, enzyme-rich microenvironment of the grazer food vacuole. This thesis examines the role of protozoan grazers in the marine geochemistry of strongly hydrolyzed, particle-reactive trace metals, in particular Th and Fe. A series of tracer experiments was carried out in model systems in order to determine the effect of grazer-mediated transformations on the chemical speciation and partitioning of radioisotopes C9Fe, 234Th, 51Cr) associated with prey cells. Results indicate that protozoan grazers are equally able to mobilize intracellular and extracellular trace metals. In some cases, protozoan regeneration of trace metals appears to lead to the formation of metal-organic complexes. Protozoan grazing may generate colloidal material that can scavenge trace metals and, via aggregation, lead to an increase in the metal/organic carbon ratio of aggregated particles. Model system experiments were also conducted in order to determine the effect of grazers on mineral phases, specifically colloidal iron oxide (ferrihydrite). Several independent techniques were employed, including size fractionation ors9Fe-labeled colloids, competitive ligand exchange, and iron-limited diatoms as "probes" for bioavailable Fe. Experimental evidence strongly suggests that protozoan grazing can affect the surface chemistry and increase the dissolution rate of iron oxide phases through phagotrophic ingestion. In further work on protozoan-mediated dissolution of colloidal Fe oxides, a novel tracer technique was developed based on the synthesis of colloidal ferrihydrite impregnated with 133Ba as an inert tracer. This technique was shown to be a sensitive, quantitative indicator for the extent of ferrihydrite dissolution/alteration by a variety of mechanisms, including photochemical reduction and ligand-mediated dissolution. In field experiments using this technique, grazing by naturally occuring protistan assemblages was shown to significantly enhance the dissolution rate of colloidal ferrihydrite over that in non-grazing controls. Laboratory and field results indicate that, when integrated temporally over the entire euphotic zone, protozoan grazing may equal or exceed photoreduction as a pathway for the dissolution of iron oxides.

Description: This work was financially supported by a Department of Defense ONR-NDSEG Graduate Fellowship, Office ofNaval Research AASERT Award (N00014-94-1-0711), and the National Science Foundation EGB Program (OCE-9523910).

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and Woods Hole Oceanographic Institution February 1994

Description: Ambient noise in the sea has been observed for over 100 years. Previous studies conclude that the primary source of microseisms is nonlinear interaction of surface gravity waves at the sea surface. Though this source relationship is generally accepted, the actual processes by which the wave generated acoustic noise in the water column couples and propagates to and along the sea floor are not well understood. In this thesis, the sources and propagation of sea floor and sub-sea floor microseismic noise between 0.2 and 10 Hz are investigated. This thesis involves a combination of theoretical, observational and numerical analysis to probe the nature of the microseismic field in the Blake Bahama Basin. Surface waves are the primary mechanism for noise propagation in the crust and fall into two separate groups depending on the relative wavelength/water depth ratio. Asymptotic analysis of the Sommerfeld integral in the complex ray parameter plane shows results that agree with previous findings by Strick (1959) and reveal two fundamental interface wave modes for short wavelength noise propagation in the crust: the Stoneley and pseudo-Rayleigh wave. For ocean sediments, where the shear wave velocity is less than the acoustic wave velocity of water, only the Stoneley interface wave can exist. For well consolidated sediments and basalt, the shear velocity exceeds the acoustic wave velocity of water and the pseudo-Rayleigh wave can also exist. Both interface waves propagate with retrograde elliptic motion at the sea floor and attenuate with depth into the crust, however the pseudo-Rayleigh wave travels along the interface with dispersion and attenuation and "leaks" energy into the water column for a half-space ocean over elastic crust model. For finite depth ocean models, the pseudo-Rayleigh wave is no longer leaky and approaches the Rayleigh wave velocity of the crust. The analysis shows that longer wavelength noise propagates as Rayleigh and Stoneley modes of the ocean+crust waveguide. These long wavelength modes are the fundamental mechanism for long range noise propagation. During the Low Frequency Acoustic Seismic Experiment (LFASE) a four-node, 12- channel borehole array (SEABASS) was deployed in the Blake Bahama Basin off the coast of eastern Florida (DSDP Hole 534B). This experiment is unique and is the first use of a borehole array to measure microseismic noise below the sea floor. Ambient background noise from a one week period is compared between an Ocean Bottom Seismometer (OBS) and SEABASS at sub-bottom depths of 10, 40, 70 and 100 meters below the sea floor. The 0.3 H z microseism peak is found to be nearly invariant with depth and has a power level of 65 and 75 dB rel 1 (nm/ s2)2)/ H z for the vertical and horizontal components respectively. At 100 m depth, the mean microseismic noise levels above 0.7 Hz are 10 dB and 15-20 dB quieter for the vertical and horizontal components respectively. Most of this attenuation occurs in the upper 10 m above 1.0 Hz, however higher modes in the spectra show narrow bandwidth variability in the noise field that is not monotonic with depth. Dispersion calculations show normal mode Stoneley waves below 0.7 Hz and evidence of higher modes above 0.8 Hz. A strong correlation between noise levels in the borehole and local sea state conditions is observed along with clear observation of the nonlinear frequency doubling effect between ocean surface waves and microseisms. Particle motion analysis further verifies that noise propagates through the array as Rayleigh/Stoneley waves. Polarization direction indicates at least two sources; distant westerly swell during quiescent times and local surface waves due to a passing storm. Above 1.0 Hz the LFASE data shows little coherence and displays random polarization. Because of this, we believe scattered energy is a significant component of the noise field in the Blake Bahama Basin. A fully 3-D finite difference algorithm is used to model both surface and volume heterogeneities in the ocean crust. Numerical modeling of wave propagation for hard and soft bottom environments shows that heterogeneities on the order of a seismic wavelength radiate energy into the water column and convert acoustic waves in the water into small wavelength Stoneley waves observed at the borehole. Sea floor roughness is the most important elastic scattering feature of the ocean crust. Comparisons of 2D and 3D rough sea floor models show that out-of-plane effects necessitate the use of 3D methods. The out-of-plane energy that is present in the LFASE data comes from either heterogeneities in the source field (i.e. mixed gravity wave directions) or, equally likely, scattering of the source field from surface or volume heterogeneities in the sea floor.

Description: This research was supported by Office of Naval Research grants N00014-89-C-0018, N00014-89-J-1012, N00014-90-C-0098, N00014-90-J-1493 and N00014-93-1-1352.

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 1999

Description: In this thesis the analysis of natural ice events is carried out based on direct measurements of ice-borne seismo-acoustic waves generated by ice fracturing processes. A major reason for studying this phenomenon is that this acoustic emission is a significant contributor to Arctic ocean ambient noise. Also the Arctic contains rich mineral and oil resources and in order to design mining facilities able to withstand the harsh environmental conditions, we need to have a better understanding of the processes of sea ice mechanics. The data analyzed in this thesis were collected during the Sea Ice Mechanics Initiative SIMI’94 experiment which was carried out in the spring of 1994 in the Central Arctic. One of the contributions of this thesis was the determination of the polarization characteristics of elastic waves using multicomponent geophone data. Polarization methods are well known in seismology, but they have never been used for ice event data processing. In this work one of the polarization methods so called Motion Product Detector method has been successfully applied for localization of ice events and determination of polarization characteristics of elastic waves generated by fracturing events. This application demonstrates the feasibility of the polarization method for ice event data processing because it allows one to identify areas of high stress concentration and "hot spots" in ridge building process. The identification of source mechanisms is based on the radiation patterns of the events. This identification was carried out through the analysis of the seismo-acoustic emission of natural ice events in the ice sheet. Previous work on natural ice event identification was done indirectly by analyzing the acoustic energy radiated into the water through coupling from elastic energy in the ice sheet. After identification of the events, the estimation of the parameters of fault processes in Arctic ice is carried out. Stress drop, seismic moment and the type of ice fracture are determined using direct near-field measurements of seismo-acoustic signals generated by ice events. Estimated values of fracture parameters were in good agreement with previous work for marginal ice zone. During data processing the new phenomenon was discovered: "edge waves", which are waves propagating back and forth along a newly opened ice lead. These waves exhibit a quasi-periodic behavior suggesting some kind of stick-slip generation mechanism somewhere along the length of the lead. The propagation characteristics of these waves were determined using seismic wavenumber estimation techniques. In the low frequency limit the dispersion can be modeled approximately by an interaction at the lead edges of the lowest order, antisymmetric modes of the infinite plate.

Description: Support for this thesis was provided by Office of Naval Research.

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 2007

Description: Oceanic spreading centers are sites of magmatic, tectonic, and hydrothermal processes. In this thesis I present experimental and seismological constraints on the evolution of these complex regions of focused crustal accretion and extension. Experimental results from drained, triaxial deformation experiments on partially molten olivine reveal that melt extraction rates are linearly dependent on effective mean stress when the effective mean stress is low and non-linearly dependent on effective mean stress when it is high. Microearthquakes recorded above an inferred magma reservoir along the TAG segment of the Mid-Atlantic Ridge delineate for the first time the arcuate, subsurface structure of a long-lived, active detachment fault. This fault penetrates the entire oceanic crust and forms the high-permeability pathway necessary to sustain long-lived, high-temperature hydrothermal venting in this region. Long-lived detachment faulting exhumes lower crustal and mantle rocks. Residual stresses generated by thermal expansion anisotropy and mismatch in the uplifting, cooling rock trigger grain boundary microfractures if stress intensities at the tips of naturally occurring flaws exceed a critical stress intensity factor. Experimental results coupled with geomechanical models indicate that pervasive grain boundary cracking occurs in mantle peridotite when it is uplifted to within 4 km of the seafloor. Whereas faults provide the high-permeability pathways necessary to sustain high-temperature fluid circulation, grain boundary cracks form the interconnected network required for pervasive alteration of the oceanic lithosphere. This thesis provides fundamental constraints on the rheology, evolution, and alteration of the lithosphere at oceanic spreading centers.

Description: Research was funded by a MIT Presidential Fellowship and NSF grants OCE-0095936, OCE-9907224, OCE-0137329, OCE-6892222, and OCE-6897400.

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 December 1997

Description: A new tomographic technique is employed to investigate the structure and dynamics of the Pacific upper mantle. We invert band-center travel times of ScS reverberations and frequency-dependent travel times of direct S phases, upper-mantle guided waves such as SS and SSS, and the R1 and G1 surface waves for the 2D composite structure in the plane of two Pacific corridors. The frequency-dependent travel times of the turning and surface waves are measured from all three components of ground motion as phase delays relative to a radially-anisotropic, spherically-symmetric oceanic mantle model, and their 2D Fréchet kernels are constructed by a coupled-mode algorithm. The travel times of the primary ScSn and sScSn phases and their first-order reverberations from the 410 and 660 discontinuities are measured as individual phases and the 2D Fréchet kernels for these band-limited signals are calculated using the paraxial ray approximation. The model parameters include shear-speed variations throughout the mantle, perturbations to radial shear-wave anisotropy in the uppermost mantle, and the topography of the 410 and 660 discontinuities. We construct vertical tomograms through two mantle corridors: one between the Tonga subduction zone and Oahu, Hawaii, which traverses the central Pacific Ocean; and the other between the Ryukyu subduction zone and Oahu, which samples the northern Philippine Sea, the western Pacific, and the entire Hawaiian swell. Tests demonstrate that the data sets for the two corridors resolve the lateral structure in the upper mantle with a scale length of a few hundreds kilometers and greater but that the resolving power decreases rapidly in the lower mantle. The model for the Tonga-Hawaii corridor reveals several interesting features, the most significant being a regular pattern of high and low shear velocities in the upper mantle between Tonga and Hawaii. These variations, which are well resolved by the data set, have a horizontal wavelength of 1500 km, a vertical dimension of 700 km, and an amplitude of about 3%, and they show a strong positive correlation with seafloor topography and geoid-height variations along this corridor. The geoid highs correspond to a series of northwest-trending swells associated with the major hotspots of the Society, Marquesas, and Hawaiian Islands. Where these swells cross the corridor, they are underlain by high shear velocities throughout the uppermost mantle, so it is unlikely that their topography is supported by thermal buoyancy. This result is substantiated by the model from the Ryukyu-Hawaii corridor, which exhibits a prominent, fast region that extends beneath the entire Hawaiian swell. This anomaly, which resides in the uppermost 200-300 km of the mantle, is also positively correlated with the undulations of the Hawaiian-swell height. The other dominant features in the Ryukyu-Hawaii model include the high-velocity subducting slabs beneath the Ryukyu and Izu-Bonin seismic zones, which extend throughout the entire upper mantle; a very low-velocity in the uppermost 160 km of the mantle beneath the northern Philippine Sea, which is ascribed to the presence of extra water in this region; and a pronounced minimum in the amount of radial anisotropy near Hawaii, which is also seen along the Tonga-Hawaii corridor. A joint inversion of the data from the two corridors reveals the same anomaly pattern and clearly demonstrates that the swells in the Central Pacific are underlain by fast velocities. It is therefore implied that the topography of the swells in the central Pacific is supported by a chemical buoyancy mechanism which is generated by basaltic volcanism and the formation of its low-density peridotitic residuum. While the basaltic depletion mechanism can produce high shear velocities in the uppermost 200 km, it cannot explain the depth extent of the fast anomalies beneath the swells which, along Tonga-Hawaii corridor, extend well into the transition zone. It is therefore hypothesized that the central Pacific is underlain by a system of convective rolls that are confined above the 660-km discontinuity. It is likely that these rolls are predominantly oriented in the direction of plate motion (like "Richter rolls ") but the limited depth of the fast anomaly beneath the Hawaiian swell (200-300 km) suggests that their pattern is probably more complicated. Nevertheless, this convection pattern appears to be strongly correlated with the locations of the Tahitian, Marquesan, and Hawaiian hotspots, which raises interesting questions for Morgan's hypothesis that these hotspots are the surface manifestations of deep-mantle plumes.

Description: This research was supported by the National Science Foundation under grant EAR- 9628351 and by the Defense Special Weapons Agency under grant DSW A-F49620-95-1- 0051.

Description: Submitted in partial fulfillment of the requirements of the degree of Master of Science at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2004

Description: Laterally extensive, well-developed clinoforms have been mapped in Early Cretaceous deposits located in the northeastern 27,000 km2 of the Colvile Basin, North Slope of Alaska. Using public domain 2-D seismic data, well logs, core photographs, and grain size data, depositional geometries within the Nanushuk and Torok formations were interpreted in order to constrain the transport conditions associated with progradation of the shoreline and construction of the continental margin out of detritus shed from the ancestral Brooks Range. Using STRATA, a synthetic stratigraphic modeling package, constructional clinoform geometries similar to those preserved in the North Slope clinoform volume (32,400 km3) were simulated. Sediment flux, marine and nonmarine diffusivities, and basin subsidence were systematically varied until a match was found for the foreset and topset slopes, as well as progradation rates over a 6 milion year period. The ability of STRATA to match the seismically interpreted geometries allows us to constrain measures of possible water and sediment discharges consistent with the observed development of the Early Cretaceous c1inoform suite. Simulations indicate that, in order to reproduce observed geometries and trends using constant input parameters, the subsidence rate must be very small, only a fraction of the most likely rate calculated from the seismic data. Constant sediment transport parameters can successfully describe the evolution of the prograding margin only in the absence of tectonic subsidence. However, further work is needed to constrain the absolute magnitude of these values and determine a unique solution for the NPR-A clinoforms.