Sedimentary rocks as sources of ancient organic carbon to the ocean: An investigation through #C and DC signatures of organic compound classes

[1] Chemical and isotopic variability of particulate organic carbon (POC) was examined in samples from the Santa Clara River watershed and adjacent shelf to investigate the processing of fossil POC derived from bedrock. The Santa Clara is a small coastal river that drains mountainous terrain in southern California, United States. Organic carbon in shale, river suspended sediment, and coastal marine sediment was separated into three operationally defined organic compound classes: total extractable lipids, acid hydrolyzable material, and the nonhydrolyzable residue. In all samples, the nonhydrolyzable fraction was dominant ( 50% of POC), while lipids and acid hydrolyzable moieties were relatively minor ( 22 and 13%, respectively). The DC and dC signatures of the isolated fractions varied dramatically, not only across different sample types, but also for a given sample. At the shale exposure, low DC values (< 760%) indicated dominance of ancient C in all three organic compound classes. In downstream samples, the extractable lipids displayed the lowest DC values (< 500%), while the acid hydrolyzable fraction was predominantly modern (DC > 30%). The nonhydrolyzable fraction displayed intermediate DC values (< 190%) that increased steadily downstream with decreasing dC values ( 22.2 to 25.0%), possibly from mixing of shale and surface soil POC. Our results indicate that most of the fossil POC discharged by the Santa Clara is composed of non-acid hydrolyzable material, but its elusive molecular structure and marine-like dC signature may render its detection in the ocean difficult. In contrast, fossil lipids may be more amenable to detection if their resistant components (e.g., asphaltic material) are unique to crustal sources.