ALBERT

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Science at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2019.

Description: Ocean surface transport is at the core of many environmental disasters, including the spread of marine plastic pollution, the Deepwater Horizon oil spill and the Fukushima nuclear contamination. Understanding and predicting flow transport, however, remains a scientific challenge, because it operates on multiple length- and time-scales that are set by the underlying dynamics. Building on the recent emergence of Lagrangian methods, this thesis investigates the present-day abilities to describe and understand the organization of flow transport at the ocean surface, including the abilities to detect the underlying key structures, the regions of stirring and regions of coherence within the flow. Over the past four years, the field of dynamical system theory has adapted several algorithms from unsupervised machine learning for the detection of Lagrangian Coherent Structures (LCS). The robustness and applicability of these tools is yet to be proven, especially for geophysical flows. An updated, parameter-free spectral clustering approach is developed and a noise-based cluster coherence metric is proposed to evaluate the resulting clusters. The method is tested against benchmarks flows of dynamical system theory: the quasi-periodic Bickley jet, the Duffng oscillator and a modified, asymmetric Duffing oscillator. The applicability of this newly developed spectral clustering method, along with several common LCS approaches, such as the Finite-Time Lyapunov Exponent, is tested in several field studies. The focus is on the ability to predict these LCS in submesoscale ocean surface flows, given all the uncertainties of the modeled and observed velocity fields, as well as the sparsity of Lagrangian data. This includes the design and execution of field experiments targeting LCS from predictive models and their subsequent Lagrangian analysis. These experiments took place in Scott Reef, an atoll system in Western Australia, and off the coast of Martha's Vineyard, Massachusetts, two case studies with tidally-driven channel flows. The FTLE and spectral clustering analyses were particularly helpful in describing key transient flow features and how they were impacted by tidal forcing and vertical velocities. This could not have been identified from the Eulerian perspective, showing the utility of the Lagrangian approach in understanding the organization of transport.

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 June, 1982

Description: Oceanic fluctuations are dependent on geographical location. Near intense currents, the eddy field is highly energetic and has broad meridional extent. It is likely that the energy arises from instabilities of the intense current. However, the meridional extent of the linearly most unstable modes of such intense jets is much narrower than the observed region of energetic fluctuations. It is proposed here that weaker instabilities, in the linear sense, which are very weakly trapped to the current, may be the dominant waves in the far field. As a preliminary problem, the (barotropic) instability of parallel shear flow on the beta plane is discussed. An infinite zonal flow with a continuous cross-stream velocity gradient is approximated with segments of uniform flow, joined together by segments of uniform potential vorticity. This simplification allows an exact dispersion relation to be found. There are two classes of linearly unstable solutions. One type is trapped to the source of energy and has large growth rates. The second type are weaker instabilities of the shear flow which excite Rossby waves in the far field: the influence of these weaker instabilities extends far beyond that of the most unstable waves. The central focus of the thesis i: the linear stability of thin, twolayer, zonal jets on the beta plane, with both horizontal and vertical shear. The method used for the parallel shear flow is extended to the two-layer flow. Each layer of the jet has uniform velocity in the center, bordered by shear zones with zero potential vorticity gradient. The velocity in each layer outside the jet is constant in latitude. Separate linearly unstable modes arise from horizontal and vertical shear. The energy source for the vertical shear modes is nearly all potential while the source for the horizontal shear modes is both kinetic and potential. The most unstable waves are tightly trapped to the jet, within two or three deformation radii for small but nonzero beta. Rossby waves and baroclinically unstable waves (in the presence of vertical shear) exist outside the jet because of a nonzero potential vorticity gradient there. Weakly growing jet instabilities can force these waves when their phase speeds and wavelengths match. In particular, westward jets and any jets with vertical shear exterior to the jet can radiate in this sense. The radiating modes influence a large region, their decay scales inversely proportional to the growth rate. Two types of radiating instability are found: (1) a subset of the main unstable modes near marginal stability and (2) modes which appear to be destabilized neutral modes. Westward jets have more vigorously unstable radiating modes. Applications of the model are made to the eddy field south of the Gulf Stream, using data from the POLYMODE settings along 55°W and farther into the gyre at MODE. The energy decay scale and the variation of vertical structure with latitude in different frequency bands can be roughly explained by the model. The lower frequency disturbances decay more slowly and become more surface intensified in the far field. These disturbances are identified with the weak, radiating instabilities of the model. The higher frequency disturbances are more trapped and retain their vertical structure as they decay, and are identified with the trapped, strongly unstable modes of the jet.

Description: This work was supported by a grant from the National Science Foundation, Office of Atmospheric Science.

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: This thesis investigates the evolution of the oceanic lithosphere in a broad sense from formation to subduction, in a focused case at the ridge, and in a focused case proximal to subduction. In general, alteration of the oceanic lithosphere begins at the ridge through focused and diffuse hydrothermal flow, continues off axis through low temperature circulation, and may occur approaching subduction zones as bending related faulting provides fluid pathways. In Chapter 2 I use a dataset of thousands of microearthquakes recorded at the Rainbow massif on the Mid-Atlantic Ridge to characterize the processes which are responsible for the long-term, high-temperature, hydrothermal discharge found hosted in this oceanic core complex. I find that the detachment fault responsible for the uplift of the massif is inactive and that the axial valleys show no evidence for faulting or active magma intrusion. I conclude that the continuous, low-magnitude seismicity located in diffuse pattern in a region with seismic velocities indicating ultramafic host rock suggests that serpentinization may play a role in microearthquake generation but the seismic network was not capable of providing robust focal mechanism solutions to constrain the source characteristics. In Chapter 3 I find that the Juan de Fuca plate, which represents the young/hot end-member of oceanic plates, is lightly hydrated at upper crustal levels except in regions affected by propagator wakes where hydration of lower crust and upper mantle is evident. I conclude that at the subduction zone the plate is nearly dry at upper mantle levels with the majority of water contained in the crust. Finally, in Chapter 4 I examine samples of cretaceous age serpentinite sampled just before subduction at the Puerto Rico Trench. I show that these upper mantle rocks were completely serpentinized under static conditions at the Mid-Atlantic Ridge. Further, they subsequently underwent 100 Ma of seafloor weathering wherein the alteration products of serpentinization themselves continue to be altered. I conclude that complete hydration of the upper mantle is not the end point in the evolution of oceanic lithosphere as it spreads from the axis to subduction.

Description: Funding was provided by the National Science Foundation through grants OCE-1029305 and OCE-0961680, the Deep Ocean Exploration Institute - Ocean Ridge Initiative, and by the WHOI Academic Programs office

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: La détermination de la chloruration des eaux de mer est effectuée depuis de nombreuses années par la méthode volémetrisque de Moher.

Description: Published

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: The daily heating of the ocean by the sun can create a stably stratified near-surface layer when the winds are slight and solar insolation is strong. This type of shallow stable layer is called a Diurnal Warm Layer (DWL). This thesis examines the physics and dynamics of DWLs from observations of the subtropical North Atlantic Ocean associated with the Salinity Processes in the Upper ocean Regional Study (SPURS-I). Momentum transferred from the atmosphere to the ocean through wind stress becomes trapped within the DWL, generating shear across the layer. During SPURS-I, strong diurnal shear across the DWL was coincident with enhanced turbulent kinetic energy (TKE) dissipation (𝜖, 𝜖 〉 10−5 W/kg) observed from glider microstructure profiles of the near-surface. However, a scale analysis demonstrated that surface forcing, including diurnal shear, could not be the sole mechanism for the enhanced TKE dissipation. High-frequency internal waves (𝜔 ≫ 𝑓) were observed in the upper ocean during the daytime within the DWL. Internal waves are able to transfer energy from the deep ocean into the DWL through the unstratified remnant mixed layer, which is the intervening layer between the DWL and seasonal thermocline. As the strength of the stratification of the DWL increases, so does the shear caused by the tunneling internal waves. The analysis demonstrates that internal waves can generate strong enough shear to cause a shear-induced instability, and are a plausible source of the observed enhanced TKE dissipation. Vertically-varying horizontal transport across the upper ocean occurs because a diurnal current exists within the DWL, but not in the unstratified remnant mixed layer below. Therefore, when a DWL is present, the water within DWL is horizontally transported a different distance than the water below. Coupled with nocturnal convection that mixes the DWL with the unstratified layer at night, this cycle is a mechanism for submesoscale (1-10 km) lateral diffusion across the upper ocean. Estimates of a horizontal diffusion coefficient are similar in magnitude to current estimates of submesoscale diffusion based on observations, and are likely an important source of horizontal diffusion in the upper ocean.

Description: Supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program and the National Science Foundation under Grant No. OCE-1129646. The collection and analysis of data from the SPURS-I central mooring were supported under National Aeronautics and Space Administration (NASA) Grant No. NNX11AE84G and NNX14AH38G.

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 2016

Description: Since the Last Glacial Maximum (LGM, ~ 20,000 years ago) air temperatures warmed, sea level rose roughly 130 meters, and atmospheric concentrations of carbon dioxide increased. This thesis combines global models and paleoceanographic observations to constrain the ocean’s role in storing and transporting heat, salt, and other tracers during this time, with implications for understanding how the modern ocean works and how it might change in the future. • By combining a kinematic ocean model with “upstream” and “downstream” deglacial oxygen isotope time series from benthic and planktonic foraminifera, I show that the data are in agreement with the modern circulation, quantify their power to infer circulation changes, and propose new data locations. • An ocean general circulation model (the MITgcm) constrained to fit LGM sea surface temperature proxy observations reveals colder ocean temperatures, greater sea ice extent, and changes in ocean mixed layer depth, and suggests that some features in the data are not robust. • A sensitivity analysis in the MITgcm demonstrates that changes in winds or in ocean turbulent transport can explain the hypothesis that the boundary between deep Atlantic waters originating from Northern and Southern Hemispheres was shallower at the LGM than it is today.

Description: Support for this work came from an MIT Presidential Fellowship, an NSF Graduate Research Fellowship, and grants NASA NNX12AJ93G – Gravity data for ocean circulation and climate studies, NSF OCE-0961713 – Collaborative Research: The Physics and Statistics of Global Sea Level Change, NSF OCE-1060735 – Collaborative Research: Beyond the Instrumental Record - the Ocean Circulation at the last Glacial maximum and the deglacial sequence, and NASA NNX08AR33G – Application of Satellite Altimetry Gravity Winds and in Situ Data to Problems of the Ocean Circulation.