Variations in the chemical and stable isotope composition of carbon and sulfur species during organic-rich sediment alteration: An experimental and theoretical study of hydrothermal activity at guaymas basin, gulf of california

Abstract

Organic-rich diatomaceous ooze was reacted with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity at 325–400°C, 400–500 bars, and fluid/sediment mass ratios of 1.56–2.35 to constrain factors regulating the abundance and stable isotope composition of C and S species during hydrothermal alteration of sediment from Guaymas Basin, Gulf of California. Alteration of inorganic and organic sedimentary components resulted in extensive exchange reactions, the release of abundant H 2S, CO 2, CH 4, and C organic, to solution, and recrystallization of the sediment to an assemblage containing albitic plagioclase, quartz, pyrrhotite, and calcite. The δ 34S cdt values of dissolved H 2S varied from −10.9 to +4.3‰ during seawater-sediment interaction at 325 and 400°C and from −16.5 to −9.0‰ during Na-Ca-K-Cl fluid-sediment interaction at 325 and 375°C. In the absence of seawater SO 4, H 2S is derived from both the transformation of pyrite to pyrrhotite and S released during the degradation of organic matter. In the presence of seawater SO 4, reduction of SO 4 contributes directly to H 2S production. Sedimentary organic matter acts as the reducing agent during pyrite and SO 4 reduction. Requisite acidity for the reduction of SO 4 is provided by Mg fixation during early-stage sediment alteration and by albite and calcite formation in Mg-free solutions. Organically derived CH 4 was characterized by δ 13C pdb values ranging between −20.8 and −23.1‰, whereas δ 13C pdb values for dissolved C organic ranged between −14.8 and −17.7%. Mass balance calculations indicate that δ 13 C values for organically derived CO 2 were ≥ − 14.8%. Residual solid sedimentary organic C showed small (≤ 0.7‰) depletions in 13C relative to the starting sediment. The experimental results are consistent with the isotopic and chemical composition of natural hydrothermal fluids and minerals at Guaymas Basin and permit us to better constrain sources and sinks for C and S species in subseafloor hydrothermal systems at sediment-covered spreading centers. Our data show that the sulfur isotope composition of hydrothermal Sulfide minerals in Guaymas Basin can be explained by derivation of S from diagenetic sulfide and seawater sulfate. Basaltic S may also contribute to hydrothermal sulfide precipitates but is not required to explain their isotopic composition. Estimates of seawater/ sediment mass ratios based on sulfur isotopic composition of sulfide minerals and the abundance of dissolved NH 3 in vent fluids range from 3–29 during hydrothermal circulation. Sources of C in Guaymas Basin hydrothermal fluids include thermal degradation of organic matter, bacteriogenic methane production, and dissolution of diagenetic carbonate.