Organic phosphorus in marine sediments : chemical structure, diagenetic alteration, and mechanisms of preservation

Abstract

Phosphorus, an essential nutrient, is removed from the oceans only through burial with marine sediments. Organic phosphorus (Porg) constitutes an important fraction (ca. 25%) of total-P in marine sediments. However, given the inherent lability of primary Porg biochemicals, it is a puzzle that any Porg is preserved in marine sediments. The goal of this thesis was to address this apparent paradox by linking bulk and molecular-level Porg information. A newly-developed sequential extraction method, which isolates sedimentary Porg reservoirs based on solubility, was used in concert with 31P nuclear magnetic resonance spectroscopy (31P-NMR) to quantify Porg functional group concentrations. The coupled extraction/31P-NMR method was applied to three sediment cores from the Santa Barbara Basin, and the first-ever high-resolution depth profiles of molecular-level Porg distribution during diagenesis were generated. These depth profiles were used to consider regulation of Porg distribution by biomass abundance, chemical structure, and physical protection mechanisms. Biomass cannot account for more than a few percent of sedimentary Porg. No evidence for direct structural control on remineralization of Porg was found. Instead, sorptive protection appears to be an important mechanism for Porg preservation, and structure may act as a secondary control due to preferential sorption of specific Porg compound classes.