Shallow microbial recycling of deep-sourced carbon in Gulf of Cadiz mud volcanoes

Based upon the molecular and isotopic composition of hydrocarbons it has been proposed that the source of CH4 in Gulf of Cadiz mud volcanoes (MV) is a mixture of deep sourced thermogenic CH4 and shallow biogenic CH4. We directly investigated this possibility by comparing porewater CH4 concentrations and their δ13C values with the potential for Archaeal methanogenesis in Gulf of Cadiz mud volcano (MV) sediments (Captain Arutyunov, Bonjardim, Ginsburg and Porto) using 14C-rate measurements. The CH4 has a deep sourced thermogenic origin (δ13C ∼ -49) but becomes 13C-depleted in and beneath the zone of anaerobic oxidation of methane (AOM) where the rates of hydrogenotrophic methanogenesis increase. Thus we infer that a portion of AOM-produced CO2 is being recycled to CH4 by methanogens yielding further 13C-depleted CH4, which might be misinterpreted as indicative of a fully shallow biogenic origin for this gas. Production of H2 is related to compositional changes in sedimentary organic matter, or to upward flux of substrate-enriched fluids. In contrast to other MVs in the Gulf of Cadiz, Ginsburg MV fluids are enriched in SO42- and contain very high concentrations of acetate (2478 μM below 150 cmbsf); however, the high levels of acetate did not stimulate methanogenesis but instead were oxidized to CO2 coupled to sulphate reduction. Both anaerobic oxidation of thermogenic CH4 linked to shallow methanogenesis and fluid geochemistry control the recycling of deep-sourced carbon at Gulf of Cadiz MVs, impacting near-surface δ13C-CH4 values