Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2013. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Iron is a redox active trace metal micronutrient essential for primary production and nitrogen acquisition in the open ocean. Dissolved iron (dFe) has extremely low concentrations in marine waters that can drive phytoplankton to Fe limitation, effectively linking the Fe and carbon cycles. Understanding the marine biogeochemical cycling and composition of dFe was the focus of this thesis, with an emphasis on the role of the size partitioning of dFe (<0.2 jm) into soluble (sFe<0.02 jm) and colloidal (0.02ptm<cFe<0.2 m) size fractions. This was accomplished through the measurement of the dFe distribution and size partitioning along basin-scale transects experiencing a range of biogeochemical influences. dFe provenance was investigated in the tropical North Atlantic and South Pacific Oceans. In the North Atlantic, elevated dFe (>I nmol/kg) concentrations coincident with the oxygen minimum zone were determined to be caused by remineralization of a high Fe:C organic material (vertical flux), instead of a laterally advected low oxygen-high dFe plume from the African margin. In the South Pacific Ocean, dFe maxima near 2000m were determined by comparison with dissolved manganese and 3He to be caused by hydrothermal venting. The location of these stations hundreds to thousands of kilometers from the nearest vents confirms the "leaky vent" hypothesis that enough dFe escapes precipitation at the vent site to contribute significantly to abyssal dFe inventories. The size partitioning of dFe was also investigated in order to trace the role of dFe composition on its cycling. First, the two most commonly utilized methods of sFe filtration were compared: cross flow filtration (CFF) and Anopore filtration. Both were found to be robust sFe collection methods, and sFe filtrate through CFF (10 kDa) was found to be only 74±21% of the sFe through Anopore (0.02pjm) filters at 28 locations, a function of both pore size differences and the natural variability in distribution of 1 OkDa- 0.02 [m colloids. In the North Atlantic, a colloidal-dominated partitioning was observed in the surface ocean underlying the North African dust plume, in and downstream of the TAG hydrothermal system, and along the western Atlantic margin. However, cFe was depleted or absent at the deep chlorophyll maximum. A summary model of dFe size partitioning in the North Atlantic open ocean is presented in conclusion, hypothesizing that a constant dFe exchange between soluble and colloidal pools modulates the constant partitioning of nearly 50% dFe into the colloidal phase throughout the subsurface North Atlantic Ocean, while sFe and cFe cycle independently in the upper ocean. / by Jessica Nicole Fitzsimmons. / Ph.D.

Thesis (S.M.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2013. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Nitrogen and trace metal biogeochemical effects on phytoplankton productivity were compared through whole water bottle incubations and proteomic evaluation of in situ harvested particulate matter from two distinct oceanographic regions: the Equatorial Pacific Upwelling and the South Pacific Gyre. Phytoplankton growth in both regions was stimulated by nitrogen additions with equivalent response from nitrate and urea. In the gyre, trace metal additions did not yield a chlorophyll response, however nickel treatments showed evidence of nickel-limited nitrogen fixation. In contrast, cell growth at the upwelling site was primarily iron-limited and iron plus urea or nitrate additions further enhanced the chlorophyll response, indicative of secondary nitrogen limitation. Nitrogen stress proteins and urea transporters from cyanobacteria in these field sites showed similar trends, with both increasing in waters containing lower dissolved inorganic nitrogen. Together with bottle incubations, the abundant urea transporters and nitrogen stress proteins indicate the importance of urea in these field sites. Representative cyanobacteria cultures (Synechococcus strain WH8020, and Prochlorococcus strain MED4) were evaluated to constrain urea uptake rates and explore the potential for compound specific uptake rates. Together, results from this study indicate that urea may represent an under-recognized component of the marine microbial nitrogen cycle. / by Tyler Jay Goepfert. / S.M.

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2007. / Includes bibliographical references (p. 215-225). / The five noble gases (helium, neon, argon, krypton, and xenon) are biologically and chemically inert, making them ideal oceanographic tracers. Additionally, the noble gases have a wide range of solubilities and molecular diffusivities, and thus respond differently to physical forcing. Tritium, an isotope of hydrogen, is useful in tandem with its daughter helium-3 as a tracer for water mass ages. In this thesis, a fourteen month time-series of the five noble gases, helium-3 and tritium was measured at the Bermuda Atlantic Time-series Study (BATS) site. The time-series of five noble gases was used to develop a parameterization of air-sea gas exchange for oligotrophic waters and wind speeds between 0 and 13 m s-1 that explicitly includes bubble processes and that constrains diffusive gas exchange to ± 6% and complete and partial air injection processes to ± 15%. Additionally, the parameterization is based on weeks to seasonal time scales, matching the time scales of many relevant biogeochemical cycles. The time-series of helium isotopes, tritium, argon, and oxygen was used to constrain upper ocean biological production. Specifically, the helium flux gauge technique was used to estimate new production, apparent oxygen utilization rates were used to quantify export production, and euphotic zone seasonal cycles of oxygen and argon were used to determine net community production. The concurrent use of these three methods allows examination of the relationship between the types of production and begins to address a number of apparent inconsistencies in the elemental budgets of carbon, oxygen, and nitrogen. / by Rachel H.R. Stanley. / Ph.D.

Thesis: Ph. D., Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2014. / This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. / Cataloged from student-submitted PDF version of thesis. / Includes bibliographical references. / The great geologic and climatic diversity of the Fraser River basin in southwestern Canada render it an excellent location for understanding biogeochemical cycling of sediments and terrigenous organic carbon in a relatively pristine, large, temperate watershed. Sediments delivered by all tributaries have the potential to reach the ocean due to a lack of main stem lakes or impoundments, a unique feature for a river of its size. This study documents the concentrations of a suite of dissolved and particulate organic and inorganic constituents, which elucidate spatial and temporal variations in chemical weathering (including carbonate weathering in certain areas) as well as organic carbon mobilization, export, and biogeochemical transformation. Radiogenic strontium isotopes are employed as a tracer of sediment provenance based on the wide variation in bedrock age and lithology in the Fraser basin. The influence of sediments derived from the headwaters is detectable at the river mouth, however more downstream sediment sources predominate, particularly during high discharge conditions. Bulk radiocarbon analyses are used to quantify terrestrial storage timescales of organic carbon and distinguish between petrogenic and biospheric organic carbon, which is critical to assessing the role of rivers in long-term atmospheric CO2 consumption. The estimated terrestrial residence time of biospheric organic carbon in the Fraser basin is 650 years, which is relatively short compared to other larger rivers (Amazon, Ganges-Brahmaputra) in which this assessment has been performed, and is likely related to the limited floodplain storage capacity and non-steady-state post-glacial erosion state of the Fraser River. A large portion of the dissolved inorganic carbon load of the Fraser River (>80%) is estimated to derive from remineralization of dissolved organic carbon, particularly during the annual spring freshet when organic carbon concentrations increase rapidly. This thesis establishes a baseline for carbon cycling in a largely unperturbed modern mid-latitude river system and establishes a framework for future process studies on the mechanisms of organic carbon turnover and organic matter-mineral associations in river systems. / by Britta Marie Voss. / Ph. D.