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 Δ14C and δ13C signatures of the isolated fractions varied dramatically, not only across different sample types, but also for a given sample. At the shale exposure, low Δ14C values ( -30?). The nonhydrolyzable fraction displayed intermediate Δ14C values (<-190?) that increased steadily downstream with decreasing δ13C 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 δ13C 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.