Variations in O2 levels in soils as may occur with changes in rainfall affect the reactivity of iron in soils. As soil iron impacts the breakdown of organic matter, this affects how soils breathe.
Fe oxyhydroxides play a critical role in soils through their role as structural entities, their high sorption capacity, their role as terminal electron acceptors in the respiration of organic matter, as well as their potential to affect the reactivity of that organic matter. In soils that undergo repeated fluctuations in O2 concentrations, soil iron undergoes transformations between reduced and oxidized forms. The rate of Fe(II) oxidation can govern the nature of Fe(III) oxyhydroxides formed, and hence can affect rates of OC mineralization under suboxic conditions. But it remains unclear if this same behavior occurs in soils, where Fe(II) is mainly present as surface complexes.
We documented the impact of such redox oscillations on iron cycling through targeted experiments, in which the magnitude and frequency of redox oscillations were varied systematically on soils from the Luquillo Critical Zone Observatory, Puerto Rico. Our observations demonstrated that higher O2 concentrations led to a faster Fe(II) oxidation and resulted in less crystalline Fe(III)-oxyhydroxides than lower O2 concentrations. We further studied the dynamics of iron phases by amending soil slurries with isotopically-labeled 57Fe(II) and developed a numerical model to quantify the individual processes. Our model showed a higher rate of Fe(III) reduction and increased sorption capacity following the oxidation of Fe(II) at high O2 levels than at low O2 levels, and revealed rapid Fe atom exchange between solution and solid phase. Concurrent measurements of CO2 in our oscillation experiments further illustrated the importance O2 fluctuations on coupled Fe-C dynamics.
Meile, Christof D, Chunmei Chen, Diego Barcellos, Jared Wilmoth, Aaron Thompson (2017): Iron cycling under oscillatory redox conditions: from observations to processes (Invited). American Geophysical Union 2017 Fall Meeting, New Orleans, Louisiana, 11-15 December 2017.
This Paper/Book acknowledges NSF CZO grant support.