Matrix protected organic matter in a river dominated margin: A possible mechanism to sequester terrestrial organic matter?

The provenance of organic matter in surface sediments from the northern Gulf of Mexico was investigated by analyzing the compositions of lipid biomarkers (n-alkanes, fatty acids, sterols) liberated after a series of chemical treatments designed to remove different organo-mineral matrix associations (i.e. freely extractable, base-hydrolyzable, unhydrolyzable). Bulk analyses of the organic matter (carbon content, carbon:nitrogen ratios, stable and radiocarbon isotopic analyses) were also performed on the intact sediments and their non-hydrolyzable, demineralized residue. We found recognizable lipids from distinct sources, including terrestrial vascular plants, bacteria and marine algae and zooplankton, within each of the isolated fractions. Based on the lipid signatures and bulk compositions, the organic matter within the unhydrolyzable fractions appeared to be the most diagenetically altered, was the oldest in age, and had the highest abundance of terrigenous lipids. In contrast, the base-hydrolyzable fraction was the most diagentically unaltered, had the youngest ages and was most enriched in N and marine lipids. Our results indicate that fresh, autochthonous organic matter is the most important contributor to base-hydrolyzable lipids, whereas highly altered allochthonous sources appear to be predominant source of unhydrolyzable lipids in the surface sediments from the Atchafalaya River shelf. Overall, the lipid biomarker signatures of intact sediments were biased towards the autochthonous source because many of the organic compounds indicative of degraded, terrigenous sources were protected from extraction and saponification by organo-mineral matrices. It is only after these protective matrices were removed by treatment with HCl and HF that these compounds became evident.