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 February 2021.

Description: This thesis explores the volatile content of the mantle, subducted oceanic crust, and arc magmas as well as the structure of slow spreading ocean crust and the heterogeneity of Earth’s upper mantle. In Chapter 2, I directly explore the halogen (F and Cl) content of mantle minerals in situ, then use these measurements to assess the halogen content of the upper mantle. In Chapter 3, I investigate the volatile content of Raspas eclogites (SW Ecuador), a proxy for deeply subducted oceanic crust, to evaluate volatile transfer from crustal generation at divergent plate boundaries (e.g., mid-ocean ridges) to recycling of ocean crust at subduction zones. In Chapter 4, I use the H2O content of nominally anhydrous minerals in plutonic arc cumulates to elucidate the H2O content of the melts from which the rocks crystallized. In this way, I assert that primitive arc magmas may contain 4–10 wt.% H2O and through fractional crystallization up to ~20 wt.% H2O, making them far more hydrous than traditional methods (i.e., olivine-hosted melt inclusions) surmise. In Chapter 5, I show that mantle peridotite exposed along the 16ºN region of the Mid-Atlantic Ridge originated in an arc setting and has been remixed into subridge mantle, indicating that the sub-ridge mantle is more heterogeneous and depleted than inferences made from mid-ocean ridge basalts suggest. Chapter 6 surveys the life cycle of oceanic core complexes through zircon geochronology and posits an updated framework for understanding the termination of oceanic core complexes, and more broadly oceanic detachment faults. Together, this contribution highlights the chemical heterogeneity of the mantle, and quantifies the full extent of volatiles hosted by mantle and crustal reservoirs.

Description: The Stanley Watson Fellowship (WHOI) provided financial support during my first year of graduate school. The Academic Programs Office Ocean Venture Fund (WHOI) provided seed funding which initiated Chapters 3 and 4, and ultimately led to two funded NSF proposals. These resources are vital to JP students, and I am incredibly grateful for them. Primary support was provided by the National Science Foundation grants to Veronique Le Roux (EAR P&G #1524311, #1839128, #1855302) and Henry Dick (MG&G #1637130, #1657983).

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 2021.

Description: Oceanic fronts at the mesoscale and submesoscale are associated with enhanced vertical motion, which strengthens their role in global biogeochemical cycling as hotspots of primary production and subduction of carbon from the surface to the interior. Using process study models, theory, and field observations of biogeochemical tracers, this thesis improves understanding of submesoscale vertical tracer fluxes and their influence on carbon cycling. Unlike buoyancy, vertical transport of biogeochemical tracers can occur both due to the movement of isopycnals and due to motion along sloping isopycnals. We decompose the vertical velocity below the mixed layer into two components in a Lagrangian frame: vertical velocity along sloping isopycnal surfaces and the adiabatic vertical velocity of isopycnal surfaces and demonstrate that vertical motion along isopycnal surfaces is particularly important at submesoscales (1-10 km). The vertical flux of nutrient, and consequently the new production of phytoplankton depends not just on the vertical velocity but on the relative time scales of vertical transport and nutrient uptake. Vertical nutrient flux is maximum when the biological timescale of phytoplankton growth matches the vertical velocity frequency. Export of organic matter from the surface and the interior requires water parcels to cross the mixed layer base. Using Lagrangian analysis, we study the dynamics of this process and demonstrate that geostrophic and ageostrophic frontogenesis drive subduction along density surfaces across the mixed layer base. Along-front variability is an important factor in subduction. Both the physical and biological modeling studies described above are used to interpret observations from three research cruises in the Western Mediterranean. We sample intrusions of high chlorophyll and particulate organic carbon below the euphotic zone that are advected downward by 100 meters on timescales of days to weeks. We characterize the community composition in these subsurface intrusions at a lateral resolution of 1–10 km. We observe systematic changes in community composition due to the changing light environment and differential decay of the phytoplankton communities in low-light environments, along with mixing. We conclude that advective fluxes could make a contribution to carbon export in subtropical gyres that is equal to the sinking flux.

Description: The work in this dissertation was funded by a NDSEG fellowship, Martin Fellowship, Grassle fellowship, Montrym grant, WHOI Academic Programs Office, and Office of Naval Research CALYPSO DRI grant N00014-16-1-3130.

Description: Submitted in partial fulfillment of the requirements for the degree of Master of Science in Mechanical Engineering at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 2021.

Description: Operations in the Arctic Ocean are increasingly important due to the changing environment and the resulting global implications. These changes range from the availability of new global trade routes, accessibility of newly available resources in the area, and national security interests of the United States in the region. It’s necessary to build a greater understanding of the undersea environment and how it’s changing since these environmental changes have a direct impact on adjusting future operations in the region and looming global changes as less Arctic ice is present. The recent presence of the Beaufort Lens is changing the acoustic propagation paths throughout the Arctic region. Here a network of buoys were employed to communicate with an Autonomous Undersea Vehicle (AUV) while it operated under the ice throughout the Beaufort Lens with the goal of achieving near GPS quality navigation. The acoustic communications paths were compared using a vertical array throughout the Beaufort Lens. This beam forming was compared to the prediction from BELLHOP. As well, since acoustic communications are affected by multi-path, attenuation and interference from other sources it was interesting to note that bottom bounce was sometimes a reliable acoustic path.

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 2021.

Description: Chromium (Cr) isotopes have shown great potential as a paleo-redox proxy to trace the redox conditions of ancient oceans and atmosphere. However, its cycling in modern environments is poorly constrained. In my thesis, I attempt to fill in the gap of our understanding of chromium cycling in the modern ocean, with a focus on the redox processes in global oxygen deficient zones (ODZs). Firstly, we developed a method to analyze Cr isotopes of different Cr redox species. Tests on processing conditions demonstrated its robustness in obtaining accurate Cr isotope data. It is applicable to both frozen and fresh samples. This method allows us to investigate the redox cycling of Cr that is hard to unravel by existing total Cr methods. Secondly, in the Eastern Tropical North Pacific (ETNP), Eastern Tropical South Pacific (ETSP) and Arabian Sea ODZs, their total dissolved Cr profiles show preferential reduction of isotopically light Cr(VI) to Cr(III), which is scavenged and exported to deeper oceans. Applying our new method to ETNP and ETSP ODZ seawater samples, we observed Cr(VI) reduction in both ODZs with a similar fractionation factor. This indicates similar mechanisms may be controlling Cr(VI) reduction in the two ODZs. Cr(III) maximum coincides with Fe(II) and secondary nitrite maximums in the upper core of both ODZs. Shipboard incubations with spiked Fe(II) showed fast Cr(VI) reduction occurring in the ETNP ODZ. But neither Fe(II) nor microbes were reducing Cr(VI) directly. Thirdly, we calculated the isotope effects of Cr scavenging in the ETNP and ETSP ODZs. Thetwo ODZs show a similar isotope partitioning during Cr scavenging. And spatial variability is observed in the ETNP ODZ. Our calculated scavenged Cr isotope ratio is lighter than that of the total dissolved Cr from the same depth. It is also comparable to that of reducing or anoxic sediments, which implies that Cr isotopes can be used as an archive for local redox conditions.

Description: This research was supported by an anonymous MIT Fellowship, Praceis Presidential Fellowship, Frederick A. Middleton Fellowship, the US National Science Foundation (NSF Award No. OCE-1459287, OCE-1736996, OCE-1924050 and DEB-1542240) and the Center for Microbial Oceanography: Research and Education (C-MORE, NSF-OIA Award No. EF-0424599).

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 2022.

Description: Detection, classification, localization, and tracking (DCLT) of unmanned underwater vehicles (UUVs) in the presence of shipping traffic is a critical task for passive acoustic harbor security systems. In general, vessels can be tracked by their unique acoustic signature due to machinery vibration and cavitation noise. However, cavitation noise of UUVs is considerably quieter than ships and boats, making detection significantly more challenging. In this thesis, I demonstrated that it is possible to passively track a UUV from its highfrequency motor noise using a stationary array in shallow-water experiments with passing boats. First, causes of high frequency tones were determined through direct measurements of two UUVs at a range of speeds. From this analysis, common and dominant features of noise were established: strong tones at the motor’s pulse-width modulated frequency and its harmonics. From the unique acoustic signature of the motor, I derived a high-precision, remote sensing method for estimating propeller rotation rate. In shallow-water UUV field experiments, I demonstrated that detecting a UUV from motor noise, in comparison to broadband noise from the vehicle, reduces false alarms from 45% to 8.4% for 90% true detections. Beamforming on the motor noise, in comparison to broadband noise, improved the bearing accuracy by a factor of 3.2×. Because the signal is also high-frequency, the Doppler effect on motor noise is observable and I demonstrate that range rate can be measured. Furthermore, measuring motor noise was a superior method to the “detection of envelope modulation on noise” algorithm for estimating the propeller rotation rate. Extrapolating multiple measurements from the motor signature is significant because Bearing-Doppler-RPM measurements outperform traditional bearing-Doppler target motion analysis. In the unscented Kalman filter implementation, the tracking solution accuracy for bearing, bearing rate, range, and range rate improved by a factor 2.2×, 15.8×, 3.1×, and 6.2× respectively. These findings are significant for improving UUV localization and tracking, and for informing the next-generation of quiet UUV propulsion systems.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Oceanography at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2022.

Description: Radioactive isotopes act as nuclear clocks that are utilized to trace and measure rates of chemical, biological, physical, and geological oceanographic processes. This thesis seeks to utilize both artificial (e.g., released from anthropogenic sources) and natural radioisotopes as tracers within the Pacific Ocean basin. Artificial radioisotopes released as a result of the 2011 Fukushima Daiichi nuclear power plants accident have the potential to negatively impact human and environmental health. This study evaluates 137Cs, 90Sr, and 129I concentrations in seawater off the coast of Japan, reconciles the sources of contaminated waters, and assesses the application of 137Cs/90Sr, 129I/137Cs, and 129I/90Sr as oceanic tracers. The analysis of activity ratios suggests a variety of sources, including ongoing sporadic and independent releases of radiocontaminants. Though decreasing, concentrations remain elevated compared to preaccident levels. Future planned releases of stored water from the reactor site may affect the surrounding environment; and thus, continued efforts to understand the distribution and fate of these radionuclides are warranted. Naturally-occurring radioisotopes (e.g., the 238U-234Th series used in this thesis) can give insight into surface export and remineralization of particulate organic carbon (POC) and trace metals (TMs). POC and TMs play a vital role in regulating the biological carbon pump (BCP), which in turn helps to moderate atmospheric CO2 levels by transporting carbon to the deep ocean, where it can be sequestered on timescales of centuries to millennia. Through this thesis we utilize the 238U:234Th disequilibrium method throughout the GEOTRACES GP15 Pacific Meridional Transect in order o provide basin-scale estimates of POC export and remineralization. There is only limited, recent use of this method to constrain TM fluxes, and as such this study also seeks to further develop this method for use in understanding TM cycling through comparative flux studies in the North Pacific.

Description: Funding sources for this thesis include the Gordon and Betty Moore Foundation, the Deerbrook Charitable Trust, NSF OCE award no. 1356630 and no. 1735445, and the NSF GRFP.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Biological Oceanography at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution May 2020.

Description: Highly productive marine microbial communities in the coastal Southern Ocean sustain the broader Antarctic ecosystem and play a key role in Earth’s climate via the biological pump. Regional phytoplankton growth is primarily limited by iron and co-limited by cobalamin (vitamin B12), a trace cobalt-containing organometallic compound only synthesized by some bacteria and archaea. These micronutrients impact primary production and the microbial ecology of the two keystone phytoplankton types: diatoms and Phaeocystis antarctica. This thesis investigates microbe-driven cobalamin cycling in Antarctic seas across multiple spatiotemporal scales. I conducted laboratory culture experiments with complementary proteomics and transcriptomics to investigate the B12-ecophysiology of P. antarctica strain CCMP 1871 morphotypes under iron-B12 co-limitation. We observed colony formation under higher iron treatments, and a facultative use of B12-dependent (MetH) and B12-independent (MetE) methionine synthase isoforms in response to vitamin availability, demonstrating that this strain is not B12-auxotrophic. Through comparative ’omics, we identified a putative MetE protein in P. antarctica abundant under low B12, which is also found in other marine microbes. Across Antarctic seas, community-scale cobalt and B12 uptake rates were measured by 57Co radiotracer incubation experiments and integrated with hydrographic and phytoplankton pigment data. I observed significant correlations between uptake fluxes and environmental variables, providing evidence for predominantly diatom-driven uptake of these micronutrients in warmer, fresher surface waters with notable regional differences. To date, this work is the most comprehensive attempt to elucidate the processes governing the co-cycling of cobalt and B12 in any marine system. At the ecosystem-scale, I developed and tested a hypothesis of micronutrient-driven community dynamics through a trait-based model with cross-feeding interactions. The model demonstrates how the observed seasonal succession of springtime P. antarctica from solitary to colonial cells, bacterioplankton, and summertime diatoms may be explained by the microbial cycling of iron, dissolved organic carbon, and B12. Overall, this dissertation provides new information about the micronutrient-driven ecology of Antarctic marine microbes and adds to our understanding of the interconnections between organismal life cycle, trace metals, and trace organics in marine environments.

Description: My training as a scientist during my time in the MIT–WHOI Joint Program (2014-2020) and the work presented in this dissertation were financially supported by the Academic Programs Office (APO) at the Woods Hole Oceanographic Institution (WHOI) and various funding agencies. My first semester was supported by the WHOI Von Damm Fellowship (2014). Subsequent years and endeavors were supported by awards from the Gordon and Betty Moore Foundation to Professor Michael Follows (Award 3778, M.J.F.) and Simons Collaboration on Computational Biogeochemical Modeling of Marine Ecosystems (Award 549931, M.J.F.); National Science Foundation (NSF) grant to Dr. Stephanie Dutkiewicz (Grant number 1434007, S.D.), and NSF Office of Polar Program (OPP) grant to Dr. Makoto Saito (M.S.) for the CICLOPS research expedition (OPP-1643684, OPP-1643845, and OPP-1644073).

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Biological Oceanography at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 2020.

Description: Little is known about how Atlantic hurricane activity changes on long timescales. This thesis uses proxy development and proxy-model integration to constrain the spatiotemporal variability in hurricane activity in the Bahama Archipelago over the past millennium. I present annually-resolved archives of storm activity derived from sediment cores from blue holes on three islands in the Bahama Archipelago: South Andros, Long Island, and Middle Caicos. Dramatic differences between these records suggest localized controls on the hurricane patterns observed by each island. Thus, compiling these records together more accurately captures regional variations in hurricane strikes. Integrating our new Bahama Archipelago compilation with compiled paleohurricane records from the U.S. coastline indicates shifting patterns of hurricane activity over the past millennium between the Gulf Coast and the Bahama Archipelago/New England. Finally, I address whether variability in hurricane strikes observed in Bahamian paleohurricane records is related to climate or random variability using hurricane model output. The signal observed in any individual record of paleohurricane activity from the Bahama Archipelago is driven more by random variability in hurricane tracks than by climate. This thesis lays the groundwork for creating high-resolution paleohurricane records from blue holes and using hurricane models to inform our interpretations of these records.

Description: This work was funded by the National Science Foundation Graduate Research Fellowship (to E.J.W.), National Science Foundation grant OCE-1356708 (to J.P.D. and P.J.vH.) and the Dalio Explore Foundation.

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 2020.

Description: Speleothems, or sedimentary rocks formed in caves, act as valuable archives of past climate change due to their suitability for U-series dating and high-resolution proxy analysis. These records can provide insights into water availability and controls on hydrology prior to the instrumental record. In this thesis, I present three records from newly-analyzed Mexican stalagmites using stable isotope (oxygen and carbon) and trace element to calcium (Mg/Ca and Sr/Ca) ratios as proxies for changing hydroclimate. Chapter 2 presents a precisely dated, mid-Holocene record of high rainfall and limited precipitation variability in the Yucatan Peninsula, Mexico. Chapters 3 and 4 present novel climate records from northeastern Mexico, an understudied region of North America. Both records come from cave sites within the Mexican arid zone, which is simultaneously experiencing increased water scarcity and a rapidly growing population. In Chapter 3, I examine a speleothem from the first millennium of the Common Era, which showed that there is a precipitation dipole between northern and southern Mexico. Chapter 4 highlights, for the first time at decadal resolution, the northeast Mexican response to the 8.2 ka event and the Younger Dryas. These chapters show that the San Luis Potosí region is vulnerable to droughts under multiple climate mean states, and is subject to drying as Atlantic Meridional Overturning Circulation weakens due to anthropogenic climate change. The climate records detailed in this thesis improve our understanding of controls on Mexican hydroclimate and can serve as benchmarks for climate models.

Description: This work was funded by US National Science Foundation (NSF) grants AGS-1702848 (M. Medina-Elizalde), AGS–1502877 (S. Burns), AGS-1804512 and AGS-1806090 (K. Johnson and D. McGee). I was also supported by the NSF Graduate Research Fellowship and the MIT School of Science Dean’s Fellowship. Fieldwork and analysis were funded by the WHOI Ocean Ventures Fund, the MIT EAPS Student Research Fund, and the MIT International Science and Technology Initiatives (MISTI) Mexico program. Initial work for this project was also supported by UC MEXUS-CONACYT Collaborative Grant from the University of California Institute for Mexico and the United States (UC MEXUS CN-16-120). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author and do not necessarily reflect the views of the National Science Foundation.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Oceanography at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution May 2022.

Description: Marine diatoms are abundant photoautotrophic algae that contribute significantly to photosynthetic carbon fixation and export throughout the oceans. Zinc is an important micronutrient in algal metabolism, with scarce dissolved concentrations in the upper euphotic zone reflecting high biological demand. In this thesis, I investigated the response of marine diatoms to Zn scarcity to characterize metabolic mechanisms used to combat Zn stress. I began by assaying the ability to metabolically substitute cobalt (Co) in place of Zn in four diatom species and found that enhanced abilities to use Co are likely an adaptation to high surface dCo:dZn ratios in the native environment. I next demonstrated that Zn/Co metabolic substitution in diatoms is not universal using culture studies of Chaetoceros neogracile RS19, which has an absolute Zn requirement. Using global proteomic analysis, I then identified and characterized diatom ZCRP-A and ZCRP-B, a putative Zn-chaperone and membrane-tethered Zn acquisition protein, respectively, as two proteins involved in the low-Zn response. I demonstrated that these proteins are widespread in marine phytoplankton and can be deployed as protein biomarkers of Zn stress in the field. I furthermore documented both the detection of ZCRPs in the Southern Ocean and the existence of Zn/Fe co-limitation within the natural phytoplankton population in Terra Nova Bay, demonstrating that Zn co-limitation can indeed occur in the field, even in high macronutrient waters. Lastly, I explored the relative demand of Zn and cadmium (Cd) within the Southern Ocean community using stable 67Zn and 110Cd tracers, documenting a high demand for both metals during the austral 2017-2018 summer season and investigating the cycling of these elements within this important region. Overall, this dissertation provides new information regarding Zn acquisition and homeostasis mechanisms within marine algae and demonstrates that Zn co-limitation in the field is not only possible, but detectable via protein biomarkers.

Description: I am very fortunate to have been financially supported over the course of my PhD by awards granted to the Saito Lab, specifically by National Institutes of Health (NIH) grant R01GM135709, Gordon and Betty Moore Foundation grant 3782, and National Science Foundation (NSF) grants OCE-1657766, OCE-1658030, OCE-1736599, OCE-1850719, and OCE-1924554.