Effects of pockmark activity on iron cycling and mineral composition in continental shelf sediments (southern Baltic Sea)

Pockmarks are formed as a result of gas (methane) or/and groundwater outflow from the sea bottom. Methane, the second most important (after CO₂) greenhouse gas, has a significant impact on biogeochemical processes in the bottom sediments by affecting the cycling of some elements, e.g. C, Fe, and S. Active pockmarks may also lead to changes in water column conditions by causing nutrients release from sediments. In the present study, we have focused on the impact of biogeochemical processes in pockmarks (methanogenesis, anaerobic methane oxidation, and groundwater seepage) on the transformation of iron (Fe) and the mineral composition of the sediment. In pore water, concentrations of hydrogen sulfide, phosphate, ammonia, sulfate, chloride, dissolved inorganic carbon, iron, and methane were analyzed. In the sediment, Fe speciation was performed using sequential extraction. The mineral composition was determined using powder X-Ray diffraction and scanning electron microscopy. The results from two pockmarks (with active gas seepage and groundwater infiltration) and two reference stations in the southern Baltic Sea show that geochemical conditions in pockmark sediments are significantly different from those in the typical muddy sea bottom. Pore water in pockmarks is characterized by lower sulfate and higher dissolved carbon concentrations as compared to areas of the seafloor where such structures are absent. This is due to the outflow of groundwater, which was confirmed by lower chloride concentration. In addition, sulfate is used to oxidize methane diffusing from deeper layers. Sediments in pockmarks are enriched in Fe(II) carbonates and depleted in Fe(III) (oxy)hydroxides, resulting from the anaerobic oxidation of methane with Fe(III) (Fe-AOM). Ferrous iron produced in large quantities during Fe-AOM is precipitated with carbonates.