Low-temperature hydration, oxidation and hydrogen production from Oman peridotite

Peridotite in the shallow subsurface undergoes hydration and oxidation (serpentinization) during reactions with percolating fluids, generating hydrogen gas and releasing magnesium, iron, and calcium into solution. In the presence of fluids enriched in dissolved carbon dioxide, extensive precipitation of carbonate minerals occurs. This reaction has large-scale implications for mitigating climate change by providing a stable, geological carbon repository. The Samail Ophiolite in Oman contains large quantities of ultramafic rocks that are currently undergoing serpentinization at low temperatures (30°C) and forming carbonate minerals. The production of hydrogen gas provides an electron donor for subsurface chemolithoautotrophic life which can contribute to carbon cycling in the subsurface as microorganisms utilize carbon dioxide as an inorganic carbon source. Serpentinization reactions require the oxidation of Fe (II) to Fe (III) to reduce water to H2, but the mechanisms of hydrogen generation in low-temperature systems is poorly characterized. To address this question, we conducted low temperature (100°C) water-rock reactions with Oman peridotite, measured H2 and characterized the speciation of Fe-bearing minerals before and after water-rock interaction using micro-X-ray Absorption Near Edge Structure (μXANES) spectra obtained from Stanford Synchrotron Radiation Lightsource. The experimental water-rock reactions produce H2 at a pH of 9, which corresponds with observations of ultrabasic springs in the Samail ophiolite and the presence of H2 in these spring waters. Significant hydrogen production occurs for two and a half months of reaction, peaking at 400 nmol/gram of reacted peridotite and then steadily decreases with time. These maximum values of hydrogen production from Oman peridotite are greater than observed by our laboratory and others during aqueous alteration of San Carlos peridotite and isolated pyroxenes and olivines (e.g. Mayhew et al. 2013 [1]). The products of low-temperature serpentinization, as determined by least squares fits of model spectra to sample μXANES spectra, include serpentine minerals, altered olivines and Fe(III) minerals. X-ray fluorescence (μXRF) maps of the distribution of Fe-bearing phases reveal extensive alteration of pyroxenes to a mixture of Fe(II) and Fe(III)-bearing phases during the 100°C water-rock interactions, while olivine grains are only incipiently altered along fracture networks, suggesting an important role for pyroxenes in low temperature H2-generating reactions. The serpentinization reactions in the Oman peridotite are producing significant levels of hydrogen at a low temperature within the habitability limit for life, suggesting Oman provides a subsurface niche for hydrogen-utilizing microorganisms. The microbiology of the Oman subsurface is important to consider when investigating carbonation reactions aimed for carbon capture and sequestration because microbial life can affect carbon availability, and the injection of CO2 into the aquifer may significantly alter the ecosystem. [1] Mayhew et al. 2013. Nature Geoscience