Anomalous δ13C in POC at the chemoautotrophy maximum in the Cariaco Basin

The Cariaco Basin is the world’s largest truly marine, permanently anoxic basin and is located on the continental shelf of Venezuela which experiences strong seasonal upwelling. The CARIACO program has been studying the hydrography, biogeochemistry and properties of sinking flux of the Cariaco Basin since 1995. One of the major puzzles of CARIACO has been the nature of the chemoautotrophic maximum which is seen at depths just below the appearance of hydrogen sulfide (~250-300 m). The identity and sources of oxidants and reductants to this active microbial community, and the identity of the chemoautotrophic organisms themselves, are still only partially known. Below about 50m (the euphotic zone), δ¹³C values of suspended particulates range from -23 to -26‰, typical of marine phytoplankton. However we have observed both enrichments (values of up to -16‰) and depletions (values of -28‰) near the redox interface. We had expected to see isotopically light POC in the chemoautotrophy maximum, since DIC δ¹³C should decrease with depth as organic carbon is remineralized. However both positive and negative isotopic excursions in POC occur at depths where dark carbon fixation is at a maximum, and at or near the transition from micro-oxic to sulfidic water. We postulate that this signal may help to define carbon fixation pathways (and dominant chemoautotrophic populations) in the oxic/sulfidic transition region.