Structural Characterization and Reactivity of Pyrogenic Water-Soluble Organic Matter Derived from Biomass Combustion

Combustion processes, whether from natural or anthropogenic origin, are major sources of particulate matter (PM), black carbon (BC), and volatile organic carbon to the atmosphere as well as soils and aquatic environments. The ubiquitous presence of biomass combustion by-products in atmospheric particles and soils could potentially lead to a large transfer of pyrogenic water-soluble organic matter (Pyr-WSOM) to the surface of watersheds and aquatic systems. In spite of this, there is a dearth of studies that have characterized the sources, and particularly the fate, of Pyr-WSOM to aquatic systems. In the present study, Pyr-WSOM was extracted from plant-derived chars (feedstocks: honey mesquite, cordgrass, and loblolly pine) produced at a range of temperatures (150-850C), and were then characterized using elemental analyses and ATR-FTIR. Low temperature (250C) Pyr-WSOM, extracted from honey mesquite and cordgrass biochars, were then incubated with aliquots of filtered water from the Trinity River (TX) for one month under dark conditions. Consistent with prior studies on combustion molecular markers such as anhydrosugars and methoxylated phenols, the total amount of dissolved organic carbon (DOC) released from biochars peaks around 200-250C and then decreases with increasing temperature of combustion. Elemental and structural analyses of biochar-derived WSOM reflect the selective solubility of certain functional groups. For example, despite the predominance of aromatic units and soot structures in biochars formed at high temperatures, such functionalities are not as predominant in their respective Pyr-WSOM. In addition, the high proportion of O-containing functionalities suggests that Pyr-WSOM may be more biodegradable than the particulate residues of biomass combustion. Indeed, low temperature Pyr-WSOM decomposed rapidly with half-lives ranging ~30 days for total DOC to 4-5 days for specific molecular markers of biomass combustion. These rapid turnover rates are in contrast to reported half-lives of hundreds of years for low temperature biochars. Considering the fast turnover rate of Pyr-WSOM, the vast majority of dissolved BC is not expected to "survive" in aquatic environments beyond the transit time of water along the land-to-sea continuum (weeks). The substantial contribution of char BC to the oceanic dissolved OM pool thus seems hampered by a combination of the very minimal Pyr-WSOM yields from high temperature biochars and the high reactivity for Pyr-WSOM from low-temperature biochars.