Organic matter cycling across the sulfate-methane transition zone of the Santa Barbara Basin, California Borderland

• Published in: Geochimica et cosmochimica acta 2016-03, Vol.176, p.259-278
• Main Authors: Komada, Tomoko, Burdige, David J., Li, Huan-Lei, Magen, Cédric, Chanton, Jeffrey P., Cada, Abraham K.
• Format: Article
• Language: English
• ISSN: 0016-7037; 1872-9533
• DOI: 10.1016/j.gca.2015.12.022

Consumption of sulfate (SO42−) in the sulfate-methane transition zone (SMTZ) has often been considered to be due solely to anaerobic oxidation of methane (AOM). However, recent studies show SO42− fluxes into the SMTZ that exceed methane (CH4) fluxes, thereby challenging this conceptual model. Co-occurrence of organoclastic SO42− reduction (oSR) with AOM in the SMTZ has been hypothesized to be the cause for this flux imbalance, but conclusive evidence is lacking. To address this knowledge gap, we investigated organic matter cycling in the SMTZ of the organic-rich sediments of the Santa Barbara Basin, California Borderland, and examined the occurrence of oSR within this zone using bulk solute profiles and Δ14C and δ13C values of selected carbon pools. We also tested the hypothesis that the SMTZ acts as an oxidation front not just for CH4, but also for dissolved organic carbon (DOC) that is produced below the SMTZ and migrates upward. Mass balance calculations for the SMTZ based on reaction stoichiometry and Δ14C and δ13C values of associated carbon fluxes indicate that ∼35–45% of total SO42− reduction in the SMTZ occurs via oSR, with the remainder attributable to AOM. The δ13C value of net DOC production is distinct from that of the fraction of bulk POC undergoing degradation, suggesting that pore-water DOC represents a compositionally unique slice of the metabolizable POC pool. DOC diffusing upward at 450cm is virtually free of 14C and contain low levels of short-chain organic acids. Radiocarbon mass balance shows that >30% of this pre-aged, and presumably refractory, DOC is removed from the pore waters within or immediately below the SMTZ. Although the SMTZ does not appear to be a major net DOC oxidation front, these results show that DOC dynamics provide unique insights into organic matter processing in these subsurface sediments.