Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Oceanography and Applied Ocean Science and Engineering at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2020.

Description: The redox cycling of oxygen between O2, water, and intermediate redox states including hydrogen peroxide and superoxide, has profound impact on the availability and distribution of dissolved O2, the habitability of the marine biosphere, and cellular metabolic and physiological reactions that utilize O2. The sum total of processes that produce, consume, and exchange atoms with O2 in the atmosphere, oceans, and subsurface leave their isotopic fingerprints on the abundance of the three stable isotopes of O2 in the environment. In this thesis, I explore two aspects of the oxygen cycle in the past and present. First, I investigate the ability of manganese (Mn) oxide minerals to capture and retain the oxygen isotopic signature of dissolved O2 during the oxidation of aqueous Mn(II) to Mn-oxide minerals. I determine that approximately half of the oxygen atoms in Mn(III,IV) oxides are directly incorporated from dissolved oxygen, and use isotope labeling techniques to further constrain how the dissolved oxygen isotope signature may be determined from that of Mn oxides. I perform an in-depth characterization of a ferromanganese crust from the central Pacific and, using triple oxygen isotope measurements, demonstrate that Mn oxides in ferromanganese crusts from around the world retain signatures of dissolved oxygen for at least 30 million years. I next turn to a previously unconsidered aspect of the global oxygen cycle: dark, extracellular superoxide production by marine microbes. I measure extracellular superoxide production rates by some of the ocean’s most abundant organisms. I use these rates along with previous measurements to estimate that extracellular superoxide production yields a net sink of 5-19% of marine dissolved oxygen. Ultimately, the degree to which superoxide production is a sink of oxygen lies in the fate of its primary decay product, hydrogen peroxide. I determine the range of oxidative and reductive decay of hydrogen peroxide across a range of environmental conditions in a meromictic pond, thus validating several assumptions from our global estimate. Altogether, this thesis illuminates a path toward investigating the oxygen cycle on million-year timescales in Earth’s recent past and demonstrates the importance of microbial superoxide production in the biogeochemical cycling of O2.

Description: This work was funded by the following grants and organizations: NASA Earth and Space Science Fellowship (NNX15AR62H), MIT Praecis Presidential Graduate Fellowship, NASA Exobiology (NNX15AM046), NSF-OCE grant 1355720, WHOI Ocean Ventures Fund, MIT Student Assistance Fund, WHOI Academic Programs Office, and the Stanford Synchrotron Radiation Lightsource. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DEAC02-76SF00515.