Manganese-Driven Carbon Oxidation at Oxic-Anoxic Interfaces

Environ Sci Technol. 2018 Nov 6;52(21):12349-12357. doi: 10.1021/acs.est.8b03791. Epub 2018 Oct 16.

Abstract

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).

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Carbon*
  • Manganese*
  • Oxidation-Reduction
  • Soil
  • X-Ray Absorption Spectroscopy

Substances

  • Soil
  • Manganese
  • Carbon