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.

Black carbon (BC), the incomplete combustion product from biomass and fossil fuel burning, is ubiquitously found in soils, sediments, ice, water and atmosphere. Because of its polyaromatic molecular characteristic, BC is believed to contribute significantly to the global carbon budget as a slow-cycling, refractory carbon pool. However, the mass balance between global BC generation and accumulation does not match, suggesting a removal mechanism of BC to the active carbon pool, most probable in a dissolved form. The presence of BC in waters as part of the dissolved organic matter (DOM) pool was recently confirmed via ultrahigh resolution mass spectrometry, and dissolved black carbon (DBC), a degradation product of charcoal, was found in marine and coastal environments. However, information on the loadings of DBC in freshwater environments and its global riverine flux from terrestrial systems to the oceans remained unclear. The main objectives of this study were to quantify DBC in diverse aquatic ecosystems and to determine its environmental dynamics. Surface water samples were collected from aquatic environments with a spatially significant global distribution, and DBC concentrations were determined by a chemical oxidation method coupled with HPLC detection. While it was clear that biomass burning was the main sources of BC, the translocation mechanism of BC to the dissolved phase was not well understood. Data from the regional studies and the developed global model revealed a strong positive correlation between DBC and dissolved organic carbon (DOC) dynamics, indicating a co-generation and co-translocation between soil OC and BC. In addition, a DOC-assistant DBC translocation mechanism was identified. Taking advantage of the DOC-DBC correlation model, a global riverine DBC flux to oceans on the order of 26.5 Mt C yr-1 (1 Mt = 1012 g) was determined, accounting for 10.6% of the global DOC flux. The results not only indicated that DOC was an important environmental intermediate for BC transfer and storage, but also provided an estimate of a major missing link in the global BC budget. The ever increasing DBC export caused by global warming will change the marine DOM quality and may have important consequences for carbon cycling in marine ecosystem.