Search

This study aimed to assess the molecular properties of dissolved organic matter (DOM) and dissolved black carbon (DBC) using analytical pyrolysis (Py-GC-MS). The sample set was comprised of ultrafiltered DOM (UDOM) from North American headwater streams associated with Long Term Ecological Research network sites. Pyrolysis products for each UDOM sample were categorized as being sourced from non-pyrogenic sources and DBC. Major non-pyrogenic components of the headwater stream UDOM were comprised of phenolic compounds derived from lignin and chitin markers from microbial biomass, and their relative contributions indicated differences in organic matter dynamics of these ecosystems. The DBC pyrolyzates included benzene, PAHs and benzonitriles, which accounted for 12.5 ± 4.5% of total quantified peak area (TPQA), and decreased in the order Alaskan boreal forest (19%), Alaskan tundra (17%), Appalachian deciduous forest (11%), Colorado alpine tundra (9%), Puerto Rican mountainous tropical rainforest (9%) and Kansas tallgrass prairie (7%). Pyrolysis products were compared to DBC content as determined by the benzenepolycarboxylic acid (BPCA) method. Although Py-GC-MS has quantitative limitations, this technique can detect weakly condensed and other DBC structures which fall outside of the BPCA analytical window.

Fluorescent dissolved organic matter (DOM), a fraction of chromophoric DOM, has been known to be produced in the deep ocean and has been considered to be bio-refractory. However, the factors controlling fluorescence properties of DOM in the deep ocean are still not well understood. In this study, we determined the fluorescence properties of DOM in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). One protein-like, two humic-like components, and one uncertain component, that might be derived from a fluorometer artifact, were identified by EEM-PARAFAC. Fluorescence intensity levels of the protein-like component were highest in the surface waters, decreased with depth, but did not change systematically in the bathypelagic layer (1000 m - bottom). Fluorescence characteristics of the two humic-like components were similar to those traditionally defined as marine and terrestrial humic-like fluorophores, respectively. The fluorescence intensity levels of the two humic-like components were lowest in the surface waters, increased with depth in the mesopelagic layer (200 - 1000 m), and then slightly decreased with depth in the bathypelagic layer. The ratio of the two humic-like components remained in a relatively narrow range in the bathypelagic layer compared to that in the surface layer, suggesting a similar composition of humic-like fluorophores in this layer. In addition, the fluorescence intensities of the two humic-like components were linearly correlated to apparent oxygen utilization (AOU) in the bathypelagic layer, suggesting that both humic-like components are produced in situ as organic matter is oxidized biologically. These findings imply that optical characteristics of humic-like fluorophores once formed might not be altered further biologically or geochemically in the deep ocean. On the other hand, relationships of fluorescence intensities with A

Fluorescent dissolved organic matter (DOM), a fraction of chromophoric DOM, has been known to be produced in the deep ocean and has been considered to be bio-refractory. However, the factors controlling fluorescence properties of DOM in the deep ocean are still not well understood. In this study, we determined the fluorescence properties of DOM in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). One protein-like, two humic-like components, and one uncertain component, that might be derived from a fluorometer artifact, were identified by EEM-PARAFAC. Fluorescence intensity levels of the protein-like component were highest in the surface waters, decreased with depth, but did not change systematically in the bathypelagic layer (1000 m - bottom). Fluorescence characteristics of the two humic-like components were similar to those traditionally defined as marine and terrestrial humic-like fluorophores, respectively. The fluorescence intensity levels of the two humic-like components were lowest in the surface waters, increased with depth in the mesopelagic layer (200 - 1000 m), and then slightly decreased with depth in the bathypelagic layer. The ratio of the two humic-like components remained in a relatively narrow range in the bathypelagic layer compared to that in the surface layer, suggesting a similar composition of humic-like fluorophores in this layer. In addition, the fluorescence intensities of the two humic-like components were linearly correlated to apparent oxygen utilization (AOU) in the bathypelagic layer, suggesting that both humic-like components are produced in situ as organic matter is oxidized biologically. These findings imply that optical characteristics of humic-like fluorophores once formed might not be altered further biologically or geochemically in the deep ocean. On the other hand, relationships of fluorescence intensities with A