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Hydrogen generation from low-temperature water–rock reactions

Nature Geoscience volume 6, pages 478–484 (2013)Cite this article

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Abstract

Hydrogen is commonly produced during the high-temperature hydration of mafic and ultramafic rocks, owing to the oxidation of reduced iron present in the minerals. Hydrothermal hydrogen is known to sustain microbial communities in submarine vent and terrestrial hot-spring systems. However, the rates and mechanisms of hydrogen generation below temperatures of 150 °C are poorly constrained. As such, the existence and extent of hydrogen-fuelled ecosystems in subsurface terrestrial and oceanic aquifers has remained uncertain. Here, we report results from laboratory experiments in which we reacted ground ultramafic and mafic rocks and minerals—specifically peridotite, pyroxene, olivine and magnetite—with anoxic fluids at 55 and 100 °C, and monitored hydrogen gas production. We used synchrotron-based micro-X-ray fluorescence and X-ray absorption near-edge structure spectroscopy to identify changes in the speciation of iron in the materials. We report a strong correlation between molecular hydrogen generation and the presence of spinel phases—oxide minerals with the general formula [M2+M23+]O4 and a cubic crystal structure—in the reactants. We also identify Fe(III)-(hydr)oxide reaction products localized on the surface of the spinel phases, indicative of iron oxidation. We propose that the transfer of electrons between Fe(II) and water adsorbed to the spinel surfaces promotes molecular hydrogen generation at low temperatures. We suggest that these localized sites of hydrogen generation in ultramafic aquifers in the oceanic and terrestrial crust could support hydrogen-based microbial life.

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Figure 1: Hydrogen production from water–rock reactions at 55 and 100 °C.
Figure 2: Distribution of minerals in the fayalite experiment reacted at 100 °C.
Figure 3: Geochemical maps of San Carlos peridotite and petedunnite reacted at 100 °C.
Figure 4: Schematic representation of spinel-surface-promoted H2 generation.

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Acknowledgements

G. Lau and E. Swanner participated in collection of reference spectra. We thank the Smithsonian National Museum of Natural History for minerals used as Fe model compounds. We acknowledge F. Luiszer, J. Drexler and P. Boni, at the University of Colorado-Boulder, for IC-OES, ICP-MS and electron microprobe analyses, and sample preparation work, respectively. We thank F. Majs (U. Alaska) for conducting XRD analyses. This work was directly supported by the David and Lucille Packard Foundation (A.S.T.) and a DOE Early Career grant (A.S.T.) (DE-SC0006886). Synchrotron analyses were conducted on beamlines 2-3, 11-2, and 4-1 at the Stanford Synchrotron Radiation Lightsource (SSRL), a national user facility operated by Stanford University on behalf of the Department of Energy, Office of Basic Energy Sciences, through the Structural Molecular Biology Program, supported by DOE Office of Biological and Environmental Research and the National Institutes of Health.

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Authors and Affiliations

  1. Department of Geological Sciences, UCB 399, University of Colorado—Boulder, Boulder, Colorado 80309, USA

    L. E. Mayhew, E. T. Ellison & A. S. Templeton

  2. Laboratory for Atmospheric and Space Physics, UCB 392, University of Colorado—Boulder, Boulder, Colorado 80309, USA

    T. M. McCollom

  3. Department of Chemistry and Biochemistry, PO Box 756160, University of Alaska—Fairbanks, Fairbanks, Alaska 99775, USA

    T. P. Trainor

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Contributions

L.E.M. and A.S.T. conceived of and designed the experiments. L.E.M. and E.T.E. assembled the experiments, conducted gas chromatography analyses, and sampled for aqueous, synchrotron and XRD analyses. L.E.M. and A.S.T. conducted synchrotron-based X-ray spectroscopy and microprobe mapping data collection. L.E.M. processed and analysed all data. L.E.M completed the data interpretation and wrote the manuscript with input and critical discussion from A.S.T., E.T.E., T.P.T. and T.M.M.

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Correspondence to L. E. Mayhew.

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Mayhew, L., Ellison, E., McCollom, T. et al. Hydrogen generation from low-temperature water–rock reactions. Nature Geosci 6, 478–484 (2013). https://doi.org/10.1038/ngeo1825

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