Document Type

Dissertation

Degree

Doctor of Philosophy (PhD)

Major/Program

Chemistry

First Advisor's Name

Rudolf Jaffé

First Advisor's Committee Title

Committee Chair

Second Advisor's Name

Yong Cai

Second Advisor's Committee Title

Committee Member

Third Advisor's Name

Piero Gardinali

Third Advisor's Committee Title

Committee Member

Fourth Advisor's Name

Anthony DeCaprio

Fourth Advisor's Committee Title

Committee Member

Fifth Advisor's Name

John Kominoski

Fifth Advisor's Committee Title

Committee Member

Keywords

Dissolved Black Carbon, Dissolved Organic Matter, Rivers, Biogeochemistry, Land Use

Date of Defense

5-11-2018

Abstract

Black carbon (BC) is an organic residue formed primarily from biomass burning (e.g., wildfires) and fossil fuel combustion. Until recently, it was understood that BC was highly recalcitrant and stabilized in soils over millennial scales. However, a fraction of the material can be solubilized and transported in fluvial systems as dissolved BC (DBC), which represents on average 10% of the global export of dissolved organic carbon (DOC) from rivers to coastal systems. The composition of DBC controls its reactivity, and it has been linked with a variety of in-stream processes that induce both carbon sequestration and evasion of CO₂ from aquatic systems, which suggest DBC may have a significant contribution within the global carbon cycle. The primary objectives for the thesis were to elucidate environmental factors that control the fate and transport of DBC in fluvial systems. Ultra-high resolution mass spectrometry was used to characterize DBC on a molecular scale whereas benzenepolycarboxylic acids were used to quantify and characterize BC in both dissolved and particulate phases (PBC). Sinks for polycondensed DBC were linked to a series of in-stream biogeochemical processes (e.g., photodegradation, metal interactions); whereas photooxidation of particulate charcoal led to production of DBC, suggesting photodissolution as a previously unrecognized source of DBC to fluvial systems. Coupling of DBC with PBC, however, was hydrologically constrained with sources varying over temporal scales and land use regimes. For DBC in particular, an enrichment of heteroatomic functionality was observed as a function of anthropogenic land use. Furthermore, land use coupled with stream order (a proxy for in-stream processing as defined by the River Continuum Concept) could explain significant spatial variability in organic matter (e.g., DOC) composition within an anthropogenically impacted system. With an increase in wildfire frequency projected with on-going climate change trends, parallel projections for increases in BC production are also expected. Furthermore, conversion of natural landscapes for urban and agricultural practices is also expected to continue in the coming decades. Thus, it is imperative to reach a comprehensive understanding of processes regulating the transport of DBC in fluvial systems with efforts to constrain future BC budgets and climate change models.

Identifier

FIDC006880

Available for download on Friday, January 18, 2019

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