Role of bottom water chemistry in the formation of fibrous magnesium calcite at methane seeps in the Black Sea

Abstract

Climate change poses a significant challenge for life on Earth. Different climate modes have been shown to come along with changes of the magnesium/calcium (Mg/Ca) ratio of seawater, and such changes are believed to control the primary mineral phase of marine authigenic carbonates. However, factors controlling marine carbonate phases other than seawater Mg/Ca ratios exist. Fibrous cements forming at methane seeps in the Black Sea provide new insight into the factors governing elemental and mineral phase compositions of fibrous carbonates. In this study, the distribution of aragonite and fibrous Mg calcite cements from three seep sites in the Black Sea is described as a function of water depth. The Mg/Ca ratio of seawater, as well as the ratio in shallow pore water, is close to four at the examined sites. Fibrous Mg calcite postdated aragonite cement in seep carbonates from shallow water depth of 120 to 190 m, whereas Mg calcite is the only cement at a greater depth of ca 2000 m. The primary formation of fibrous Mg calcite is confirmed by its zonation under cathodoluminescence, crystal morphologies agreeing with competitive growth, uniformly distributed MgCO₃ contents and precipitation in equilibrium with local conditions calculated from δ¹⁸O values. The MgCO₃ contents (4.5 to 12.2 mol%) are negatively correlated with δ¹³C values, indicating that the incorporation of Mg into the calcite crystal structure was favoured by high concentrations of sulphide generated by sulphate-driven anaerobic oxidation of methane. Unlike open oceanic basins, stratification in the Black Sea leads to euxinic conditions in the deeper water column, favouring fibrous Mg calcite formation. This observation is consistent with sulphide catalysis as a critical agent for the formation of low-Mg calcite to very high-Mg calcite at high Mg/Ca ratios and is possibly relevant to carbonate cements forming during times of oceanic euxinia.