Organic Phosphorus Dynamics and Contributions to Eutrophication in a Shallow, Freshwater Bay

Indiana University-Purdue University Indianapolis (IUPUI)Phosphorus (P) is essential for aquatic life; cycling between both inorganic and organic forms to maintain an ecological balance. Its addition into P-scarce freshwaters, either through terrestrial (external) or sedimentary (internal) loading, may disrupt this balance causing blooms of phytoplankton to flourish, often resulting in harmful environmental and anthropogenic consequences. Accordingly, reduction of external P loading has been commonly implemented with a recent focus on sediment-bound legacy P that is mobilized into the water column during dynamic redox conditions. Mobile P species have been identified as both inorganic and organic, with the former representing the most bioavailable fraction, and the latter serving as a source for labile P in freshwaters when in high demand, particularly during blooms. Missisquoi Bay in Lake Champlain, VT experiences harmful cyanobacterial blooms driven by internal P loading and has been the target of numerous geochemical and hydrological studies. This thesis describes a high-resolution investigation of both the organic P and organic matter compositions of the bay with respect to mobility, reactivity, and bioavailability using Fourier Transform-Ion Cyclotron Mass Spectrometry (FT-ICR MS). Sediment from Missisquoi Bay was extracted with a diverse set of reagents, resulting in fractionation of both organic matter and organic P, and illustrating the distribution of various labile and recalcitrant compounds. Many of these molecules are associated with porewater or easily extractable mineral surfaces providing a link to the benthic organic matter and phosphorus fractions available to microorganisms. Additionally, the organic chemistry of the bay was investigated seasonally from May 2017 to January 2018 revealing biological processing from the spring runoff season through the post-bloom summer season. The transition from late summer to under ice conditions in winter was less severe with a higher commonality between both organic matter and organic P compounds, suggesting reduced biological and abiotic degradation. Moreover, short-term anoxic incubations of sediment cores from each season revealed the presence of diverse organic signatures from sorption processes, and a significant contribution of benthic microbial activity to the benthic organic geochemistry