Chemical controls on the cycling and reactivity of marine dissolved organic matter

Abstract

Marine dissolved organic matter (DOM) is an actively cycling reservoir of carbon containing thousands of unique compounds. To describe the complex dynamics that govern the biological transformation and decomposition of compounds in this molecular black box, models of DOM reactivity use chemical characteristics, as well as environmental parameters, to describe trends in the turnover time of classes of DOM. In this thesis, I describe two projects that examine hypotheses regarding the turnover of two classes of DOM. In the 1st project, I test the assumption made by the size–reactivity continuum hypothesis that high molecular weight (> 1 kDa) DOM (HMWDOM) represents a diagenetic intermediate between large labile material and small recalcitrant compounds. Size-fractions of HMWDOM were collected using size-exclusion chromatography, and the changes in MW and chemical composition of the fractions were studied using diffusion-ordered spectroscopy. The size fraction carbon isotopic values were correlated with the proportion of humic substances in the fractions. Through linear modeling, the apparent radiocarbon ages of the two major components of HMWDOM were determined to be 1-3 yrs and 2-4 kyrs, respectively. Combined with the measurements of MW distribution this work demonstrates that HMWDOM is composed of two components that have contrasting decomposition pathways in the ocean. HMWDOM cannot be treated as a single DOM pool when incorporated into models of DOM diagenesis. The 2nd project in this dissertation examines the remineralization of phosphonates, compounds with a direct C-P bond, in the lower euphotic zone using a newly developed fluorescent assay, which measures the activity of carbon-phosphorus lyase. C-P lyase activity (CLA) profiles from the North Pacific Subtropical Gyre (NPSG) showed a sharp activity maximum near the deep-chlorophyll maximum (DCM). High-resolution nutrient measurements suggest that this subsurface CLA maximum is the result of a high nitrate flux at the top of the nitracline. The composition of particulate-P through the euphotic zone was also examined. While phosphonates were not detected in suspended particles, a significant amount of aminoethylphosphonate was measured in sinking material, suggesting eukaryotic material may be an important source of phosphonates to the ocean.