The impact of diffusive transport of methane on pore-water and sediment geochemistry constrained by authigenic enrichments of carbon, sulfur, and trace elements: A case study from the Shenhu area of the South China Sea

Abstract

Sulfate-driven anaerobic oxidation of methane (SD-AOM) controls methane release from marine sediments to the ocean. A variety of authigenic precipitates within sediments has been widely used to identify past occurrences of SD-AOM. However, the lack of a systematic evaluation of the formation conditions of these precipitates sometimes impedes the recognition of SD-AOM in past environments characterized by diffusive transport of methane. Carbon, sulfur, and trace element geochemistry of pore-water and sediments was investigated at a site affected by upward methane diffusion in the Shenhu area of the South China Sea. Here, the sulfate-methane transition zone (SMTZ) is located ~7.6 m below the seafloor based on sulfate and methane concentrations. The slope of δ34S vs. δ18O values of sulfate is consistent with diffusive transport of methane. Concentration and isotope profiles of pore-water species point to diffusive rather than advective transport of solutes. Enhanced sulfate reduction inferred from δ34S values of sulfate agrees with the local occurrence of relatively abundant, 34S-enriched iron sulfide minerals. The time required to produce the observed authigenic iron sulfides around the SMTZ is estimated to be ~1.1 ka based on the amount of iron sulfide minerals and the present diffusive flux of sulfate. No enrichment of authigenic carbonate, barium (Ba), and molybdenum (Mo) was detected in the studied sediments. This observation is consistent with the calculation that the current fluxes of pore-water calcium, magnesium, Ba, and Mo are too low to allow for authigenic enrichments. The low fluxes are largely controlled by diffusion, which facilitates the formation of 34S-enriched iron sulfide minerals. The observed enrichment patterns – unlike those of sediments affected by advective seepage – are expected to be prevalent in modern and ancient continental-margin sediments, and may contribute to the identification of past methane-rich zones and overlying SD-AOM zones as sinks for methane in the geological record.