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Serpentinization of abyssal peridotites is known to produce extremely reducing conditions as a result of dihydrogen (H 2 ,aq) release upon oxidation of ferrous iron in primary phases to ferric iron in secondary minerals by H 2 O. We have compiled and evaluated thermodynamic data for Fe^Ni^Co^O^S phases and computed phase relations in fO 2 ,g^fS 2 ,g and aH 2 ,aq^aH 2 S,aq diagrams for temperatures between 150 and 4008C at 50 MPa. We use the relations and compositions of Fe^Ni^Co^O^S phases to trace changes in oxygen and sulfur fugacities during progressive serpentinization and steatitization of peridotites from the Mid-Atlantic Ridge in the 15820 0 N Fracture Zone area (Ocean Drilling Program Leg 209). Petrographic observations suggest a systematic change from awar-uite^magnetite^pentlandite and heazlewoodite^magnetite^pentlandite assemblages forming in the early stages of serpentinization to millerite^pyrite^polydymite-dominated assemblages in steatized rocks. Awaruite is observed in all brucite-bearing partly serpentinized rocks. Apparently, buffering of silica activities to low values by the presence of brucite facilitates the formation of large amounts of hydrogen, which leads to the formation of awaruite. Associated with the prominent desulfurization of pentlandite, sulfide is removed from the rock during the initial stage of serpentinization. In contrast, steatitization indicates increased silica activities and that highsulfur-fugacity sulfides, such as polydymite and pyrite^vaesite solid solution, form as the reducing capacity of the peridotite is exhausted and H 2 activities drop. Under these conditions, sulfides will not desulfurize but precipitate and the sulfur content of the rock increases. The co-evolution of fO 2 ,g^fS 2 ,g in the system follows an isopotential of H 2 S,aq, indicating that H 2 S in vent fluids is buffered. In contrast, H 2 in vent fluids is not buffered by Fe^Ni^Co^O^S phases, which merely monitor the evolution of H 2 activities in the fluids in the course of progressive rock alteration.The co-occurrence of pentlan-dite^awaruite^magnetite indicates H 2 ,aq activities in the interacting fluids near the stability limit of water. The presence of a hydrogen gas phase would add to the catalyzing capacity of awaruite and would facilitate the abiotic formation of organic compounds.

A series of laboratory experiments were conducted to examine how partitioning of Fe among solid reaction products and rates of H 2 generation vary as a function of temperature during serpentinization of olivine. Individual experiments were conducted at temperatures

The conditions of methane (CH4) formation in olivine-hosted secondary fluid inclusions and their prevalence in peridotite and gabbroic rocks from a wide range of geological settings were assessed using confocal Raman spectroscopy, optical and scanning electron microscopy, electron microprobe analysis, and thermodynamic modeling. Detailed examination of 160 samples from ultraslow- to fast-spreading midocean ridges, subduction zones, and ophiolites revealed that hydrogen (H2) and CH4 formation linked to serpentinization within olivine-hosted secondary fluid inclusions is a widespread process. Fluid inclusion contents are dominated by serpentine, brucite, and magnetite, as well as CH4(g) and H2(g) in varying proportions, consistent with serpentinization under strongly reducing, closed-system conditions. Thermodynamic constraints indicate that aqueous fluids entering the upper mantle or lower oceanic crust are trapped in olivine as secondary fluid inclusions at temperatures higher than ∼400 °C. When temperatures decrease below ∼340 °C, serpentinization of olivine lining the walls of the fluid inclusions leads to a near-quantitative consumption of trapped liquid H2O. The generation of molecular H2 through precipitation of Fe(III)-rich daughter minerals results in conditions that are conducive to the reduction of inorganic carbon and the formation of CH4. Once formed, CH4(g) and H2(g) can be stored over geological timescales until extracted by dissolution or fracturing of the olivine host. Fluid inclusions represent a widespread and significant source of abiotic CH4 and H2 in submarine and subaerial vent systems on Earth, and possibly elsewhere in the solar system.

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The hydrothermal alteration of mantle rocks (referred to as serpentinization) occurs in submarine environments extending from mid-ocean ridges to subduction zones. Serpentinization affects the physical and chemical properties of oceanic lithosphere, represents one of the major mechanisms driving mass exchange between the mantle and the Earth’s surface, and is central to current origin of life hypotheses as well as the search for microbial life on the icy moons of Jupiter and Saturn. In spite of increasing interest in the serpentinization process by researchers in diverse fields, the rates of serpentinization and the controlling factors are poorly understood. Here we use a novel in situ experimental method involving olivine micro-reactors and show that the rate of serpentinization is strongly controlled by the salinity (water activity) of the reacting fluid and demonstrate that the rate of serpentinization of olivine slows down as salinity increases and H2O activity decreases.