Chemical composition of the graphitic black carbon fraction in riverine and marine sediments at sub-micron scales using carbon X-ray spectromicroscopy

The chemical composition of the graphitic black carbon (GBC) fraction of marine organic matter was explored in several marine and freshwater sedimentary environments along the west coast of North America and the Pacific Ocean. Analysis by carbon X-ray absorption near-edge structure spectroscopy and scanning transmission X-ray microscopy shows the GBC fraction of Stillaguamish River surface sediments to be dominated by more highly ordered and impure forms of graphite, together forming about 80% of the GBC, with a smaller percent of an aliphatic carbon component. Eel River Margin surface sediments had very little highly ordered graphite, and were instead dominated by amorphous carbon and to a lesser extent, impure graphite. However, the GBC of surface sediments from the Washington State Slope and the Mexico Margin was composed almost solely of amorphous carbon. Pre-anthropogenic, highly oxidized deep-sea sediments from the open Equatorial Pacific Ocean contained over half their GBC in different forms of graphite as well as highly aliphatic carbon, low aromatic/highly acidic aliphatic carbon, low aromatic/highly aliphatic carbon, and amorphous forms of carbon. Our results clearly show the impact of graphite and amorphous C phases in the BC fraction in modern riverine sediments and nearby marine shelf deposits. The pre-anthropogenic Equatorial Pacific GBC fraction is remarkable in the existence of highly ordered graphite.