Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO₄²⁻-CH₄ transition where H₂S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H₂S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe²⁺ diffusing up from below. The H₂S-Fe²⁺ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO₄²⁻ and 10 yr for H₂S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO₄²⁻-CH₄ and H₂S-Fe²⁺ cause the trapping of isotopically heavy iron sulfide with δ³⁴S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO₄²⁻ diffusing downward into the SO₄²⁻-CH₄ transition has an isotopic composition of +19‰, close to the +23‰ of H₂S diffusing upward. These isotopic compositions are, however, very different from the porewater SO₄²⁻ (+43‰) and H₂S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H₂S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.