Biogeochemical Studies of the South Pacific Ocean Using Thorium and Protactinium Isotopes

Biogeochemical Studies of the South Pacific Ocean Using Thorium and Protactinium Isotopes Frank J. Pavia The ocean is both a repository and reactor for chemicals at the Earth’s surface. As chemicals enter the ocean they are taken up by organisms, transported by currents, reacted with particle surfaces, and eventually buried at the seafloor. This dynamic set of chemical processes and exchanges are encapsulated by the term biogeochemistry. Marine biogeochemistry can be broadly deconstructed into two parts: ocean interfaces and internal cycling. Ocean interfaces are where chemical constituents enter and leave the ocean, including the air-sea boundary, mid-ocean ridges, continental margins, and rivers. Internal cycling is how chemical constituents are reacted, transported, taken up by organisms, and redistributedwithin the ocean. For a complete understanding ofmarine biogeochemical cycles, the input, output, and internal cycling rates of major and trace elements must be quantified. However, this rate information is difficult to infer from the observational snapshots of chemical concentrations typically collected on oceanographic expeditions. The long-lived radioisotopes of thorium (Th) and protactinium (Pa) provide an opportunity to quantify these elusive biogeochemical rates. The radiogenic isotopes 230Th and 231Pa are produced at a uniform rate throughout the water column by uranium decay. A third isotope, 232Th, is primordial and brought to the ocean by the dissolution of lithogenic matter. While uranium is highly soluble, Th and Pa are highly insoluble, and are rapidly removed from solution by adsorption onto settling particle matter. Due to their insolubility and known input rates, 230Th and 231Pa have well-constrained 1-d mass budgets between radiogenic production and scavenging removal. This thesis explores new ways Th and Pa isotopes can be used to understand and quantify rates of biogeochemical processes in the South Pacific Ocean, and to assess how measurements of sedimentary Th and Pa isotopes can be used to study these processes in the geologic past. In chapter 1, I characterize the effects of submarine hydrothermal activity on the distributions of 230Th and 231Pa, finding strong removal due to adsorption by Fe and Mn oxide particles. In chapter 2, I utilize the radioactive disequilibria of two additional radiogenic thorium isotopes with much shorter half-lives, 234Th and 228Th, to constrain the kinetics of Th scavenging by hydrothermal particles. Chapter 3 switches gears towards quantifying the internal cycling of particulate organic carbon in the subtropical South Pacific. Using a new method based on measurements of particulate 230Th, I generated high-resolution water column profiles of particulate organic carbon flux to constrain carbon regeneration lengthscales in both oligotrophic and oxygenminimum zone settings. In chapter 4, I demonstrate the importance of isopycnal mixing in transporting 230Th, 231Pa, and 232Thinto the Pacific Southern Ocean, showing the first high-resolution dissolved Th and Pa data from the region. Chapter 5 provides estimates of dust input spanning the South Pacific using twomethods based on paired 230Th-232Th, evaluates the flux of dust-borne iron, and discusses the impacts on measured and modeled nitrogen fixation rates in the South Pacific gyre. Finally, in chapter 6 I present enigmatic profiles of Th and Pa isotopes from the semi-enclosed Peru and Bauer Basins, with anomalous Th and Pa removal extending 1-2km above the seafloor. I hypothesize that these depletions are related to the extent of watermass contact the seafloor, allowing for scavenging removal of Th and Pa by resuspended sediments.