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Manganese-Driven Carbon Oxidation at Oxic–Anoxic Interfaces

  • Morris E. Jones
    Morris E. Jones
    School of Earth & Sustainability and Stockbridge School of Agriculture, University of Massachusetts, Amherst, Massachusetts 01003, United States
  • Peter S. Nico
    Peter S. Nico
    Earth and Environmental Sciences Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  • Samantha Ying
    Samantha Ying
    Department of Environmental Sciences, University of California Riverside, Riverside, California 92521, United States
  • Tom Regier
    Tom Regier
    Canadian Synchrotron Lightsource, Saskatoon, Canada
    More by Tom Regier
  • Jürgen Thieme
    Jürgen Thieme
    NSLS-II, Brookhaven National Laboratory, Brookhaven, New York 11973, United States
  • , and 
  • Marco Keiluweit*
    Marco Keiluweit
    School of Earth & Sustainability and Stockbridge School of Agriculture, University of Massachusetts, Amherst, Massachusetts 01003, United States
    *Address: School of Earth & Sustainability, Stockbridge School of Agriculture, University of Massachusetts, Amherst, 162 Holdsworth Way, Amherst, MA 01003. E-mail: [email protected]
Cite this: Environ. Sci. Technol. 2018, 52, 21, 12349–12357
Publication Date (Web):September 27, 2018
Copyright © 2018 American Chemical Society

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    The formation of reactive manganese (Mn) species is emerging as a key regulator of carbon oxidation rates, and thus CO2 emissions, in soils and sediments. Many subsurface environments are characterized by steep oxygen gradients, forming oxic–anoxic interfaces that enable rapid redox cycling of Mn. Here, we examined the impact of Mn(II)aq oxidation along oxic–anoxic interfaces on carbon oxidation in soils using laboratory-based diffusion reactors. A combination of cyclic voltammetry, X-ray absorption spectroscopy, and X-ray microprobe imaging revealed a tight coupling between Mn(II)aq oxidation and carbon oxidation at the oxic–anoxic interface. Specifically, zones of Mn(II)aq oxidation across the oxic–anoxic transition also exhibited the greatest lignin oxidation potential, carbon solubilization, and oxidation. Microprobe imaging further revealed that the generation of Mn(III)-dominated precipitates coincided with carbon oxidation. Combined, our findings demonstrate that biotic Mn(II)aq oxidation, specifically the formation of Mn(III) species, contributes to carbon oxidation along oxic–anoxic interfaces in soils and sediments. Our results suggest that we should regard carbon oxidation not merely as a function of molecular composition, which insufficiently predicts rates, but in relation to microenvironments favoring the formation of critically important oxidants such as Mn(III).

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