Biogeochemistry of surface sediments in mud volcanoes of the Gulf of Cádiz

The shallowest sediment of three mud volcanoes (MVs) located in the middle slope of the Gulf of Cadiz, Anastasya, Pipoca and St. Petersburg, have been seasonally studied during June and December 2016. These structures are locally important contributors of many biogeochemical active substances to the water column, with a special attention in the emission of methane (CH4). Along this study, the role of organic matter diagenesis and its contribution to the diffusive fluxes estimated in the sediment–water interface from the three MVs have been investigated mainly. For this, the first combined analyses of sediment properties (granulometry, porosity, density, organic carbon) and pore water chemistry (major elements, dissolved inorganic carbon (DIC), nutrients, CH4 and nitrous oxide) have been carried out. Anastasya and St. Petersburg MVs presented similar behaviours, with a slight concentration variation for the chemical variables in the top layers of the sedimentary record followed by a more intense vertical variation in deeper layers. Anastasya MV showed some typical processes of these structures, such as the clay dehydration, the dissolution of halite and the precipitation of authigenic carbonates, which was also observed in St. Petersburg MV. Organic matter diagenesis clearly altered the biogeochemical profiles, except for Pipoca MV. Moreover, mud breccia with a mousse-like texture has been identified in the deepest levels of Anastasya and St. Petersburg MVs. Here, anaerobic oxidation of methane is linked to the decrease of $${\mathrm{SO}}_{4}^{2-}$$ and the increases of CH4 and DIC with the core depth. Changes across the sediment–water interface presented low diffusive fluxes in the three MVs due to the presence of other processes as the irrigation by benthic macrofauna, the action of bottom currents and/or the upward fluid migration. From the obtained results, we can conclude that Anastasya MV presents a certain venting activity at present.