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 June 2016

Description: The Southern Ocean is one of the most energetic regions of the world ocean due to intense winds and storm forcing, strong currents in the form of the Antarctic Circumpolar Current (ACC) interacting with steep topography, and enhanced mesoscale activity. Consequently, the Southern Ocean is believed to be a hotspot for enhanced oceanic mixing. Due to the remote location and harsh conditions, few direct measurements of turbulence have been collected in the Southern Ocean. Previous studies have used indirect methods based on finestructure observations to suggest that strong mixing is ubiquitous below the mixed layer. Results from a US/UK field program, however, showed that enhanced internal wave finestructure and turbulence levels are not widespread, but limited to frontal zones where strong bottom currents collide with steep, large amplitude topography. This thesis studies the processes that support turbulence and mixing in the surface boundary layer and at intermediate depths in the Drake Passage region. Direct measurements of turbulence show that previous estimates of mixing rates in the upper 1km are biased high by up to two orders of magnitude. These biases are discussed in the context of the internal wave environment and enhanced thermohaline finestructure. The dissipation rate of thermal variance is enhanced in the upper 1000m, with the highest values found in northern Drake Passage where water mass variability is the most pronounced. Double diffusive processes and turbulence both contribute to buoyancy flux, elevating the effective mixing efficiency above the canonical value of 0.2 in the upper 1km. Despite the prevalence of energetic wind events, turbulence driven by downward propagating near-inertial wave shear is weak below the mixed layer. The results of this study inform large-scale modeling efforts through parameterizations of mixing processes in the highly undersampled Southern Ocean.

Description: My time in the Joint Program was funded by the National Science Foundation through OCE-1232962.

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 1998

Description: This thesis is written in two parts. The first part deals with the problem oflateral dispersion due to mesoscale eddies in the open ocean, and the interaction between the mesoscale strain and horizontal diffusion on spatial scales less than 10 km. The second and major part examines lateral dispersion over the continental shelf on scales of 100 m to 10 km and over time scales of 1- 5 days. PART I: Lateral Dispersion and the North Atlantic Tracer Release Experiment Mixing and stirring of Lagrangian particles and a passive tracer were studied by comparison of float and tracer observations from the North Atlantic Tracer Release Experiment. Statistics computed from the NATRE floats were found to be similar to those estimated by Ledwell et al. (1998) from the tracer dispersion. Mean velocities computed from the floats were (u, v) = ( -1.2±0.3, -0.9±0.2) em s-1 for the (zonal, meridional) components, and large-scale effective eddy diffusivities were (KP. 11 , K:e 22 ) = (1.5±0. 7, 0. 7±0.4) x 103 m2 s-1 . The NATRE observations were used to evaluate theoretical models of tracer and particle dispersal. The tracer dispersion observed by Ledwell et al. (1998) was consistent with an exponential growth phase for about the first 6 months and a linear growth at larger times. A numerical model of mesoscale turbulence that was calibrated with float statistics also showed an exponential growth phase of tracer and a reduced growth for longer times. Numerical results further show that Garrett's (1983) theory, relating the effective small-scale diffusivity to the rms strain rate and tracer streak width, requires a scale factor of 2 when the observed growth rate of streak length is used as a measure of the strain rate. This scale factor will be different for different measures of the strain rate, and may also be affected by temporal and spatial variations in the mesoscale strain field. PART II: Lateral Dispersion over the New England Continental Shelf Lateral dispersion over the continental shelf was examined using dye studies of the Coastal Mixing and Optics (CMO) program. Four experiments performed at intermediate depths and lasting 3 to 5 days were examined. In some cases, the dye patches remained fairly homogeneous both vertically and horizontally throughout an experiment. In other cases, significant patchiness was observed on scales ranging from 2- 10 m vertically and a few hundred meters to a few kilometers horizontally. The observations also showed that the dye distributions were significantly influenced by shearing and straining on scales of 5- 10 m in the vertical and 1- 10 km in the horizontal. Superimposed on these larger-scale distortions were simultaneous increases in the horizontal second moments of the dye patches, with corresponding horizontal diffusivities based on a Fickian diffusion model of 0.3 to 4.9 m2 s-1 . Analysis of the dye data in concert with shear estimates from shipboard ADCP observations showed that the existing paradigms of shear dispersion and dispersion by interleaving water-masses can not account for the observed diffusive spreading of the dye patches. This result suggests that some other mechanisms provided an additional diffusivity of order 0.15 to 4.0 m2 s-1 . An alternative mechanism, dispersion by vortical motions caused by the relaxation of diapycnal mixing events, was proposed which could explain the observed dispersion in some cases. Order-of-magnitude estimates of the effective lateral dispersion due to vortical motions showed that this mechanism could account for effective horizontal diffusivities of order 0.01 to 1.1 m2 s-1 . The upper range of these estimates were within the range required by the observations for two of the four experiments examined.

Description: The work in Part I relating to the North Atlantic Tracer Release Experiment was supported by the National Science Foundation under grant OCE90-05738. The work in Part II relating to the Coastal Mixing and Optics program was funded by the Office of Naval Research under grant N00014-95-1-0633 (tracer experiments) and grant N00014-95-1-1063 (AASERT fellowship).

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

Description: Submesoscale ocean dynamics and instabilities, with characteristic scales 0.1–10 km, can play a critical role in setting the ocean’s surface boundary layer thickness and associated density stratification. Submesoscale instabilities contribute to lateral stirring and tracer dispersal. These dynamics are investigated in the Bay of Bengal, motivated by the upper ocean’s potentially coupled interactions with Monsoon winds and convection. The region’s excess precipitation and runoff generates strong salinity gradients that typically set density fronts and stratification in the upper 50 m. Since we cannot synoptically measure currents containing fast-evolving and oscillating components across the submesoscale range, we instead analyze passive tracer distributions (spice ⌘ density-compensated temperature (T) and salinity (S) anomalies), identifying signatures of flows and testing dynamical theories. The analysis is based on over 9000 vertical profiles of T and S measured along ⇠4800 km of ship tracks in the Bay of Bengal during ASIRI and MISO-BOB expeditions in 2013, 2015, and 2018. Observations in the surface mixed layer reveal ⇠1 km scale-selective correlation of surface T and S, with compensation reducing cross-front density gradients by ⇠50%. Using a process study ocean model, we show this is caused by submesoscale instabilities slumping fronts, plus surface cooling over the resultant enhanced salinity stratification, potentially thwarting the forward cascade of energy. In the stratified interior, we present a spectral analysis of horizontal spice variance statistics from wavenumber k ⇠0.01 cpkm to ⇠1 cpkm. At scales 〈10 km, stratified layers that are closer to the surface exhibit redder passive tracer spectra (power spectra k−3, gradient spectra k−1) than predicted by quasi-geostrophic or frontogenetic theories. Complimentary observations reveal spice patterns with multiple, parallel, ⇠10 m thin layers, crossing isopycnals with O(10−4) slopes, coherent over at least 30–80 km, with coincident layers of stratification anomalies. Comparison with shear measurements, and a numerical process study, suggest that both submesoscale sheared eddies, and thin near-inertial waves, form such layers. Fast formation timescales and large aspect ratios suggest they enhance horizontal mixing by shear dispersion, reducing variance at ⇠1–10 km scales.

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.