Aggregate-Scale Variation in Iron Biogeochemistry Controls Element Cycling from Nitrogen to Uranium

Abstract:

Iron exerts a major control on element cycling in soils by serving as a prominent sorbent (principally when present as an oxide phase) and as an electron acceptor (in the ferric-form) or donor (ferrous-form) in both chemical and microbially-mediated reactions. Within the aggregated structure of soils, steep chemical gradients arise from the supply of oxygen and nutrients along macropores that are rapidly consumed (relative to supply) within the micropore domains of aggregate interiors. As a consequence, iron undergoes a dynamic biogeochemical cycle whereby ferric (hydr)oxides form within aggregate exteriors while ferrous-iron generation dominates within interior regions. Further, inter-aggregate cycling of iron can transpire through the supply of electron donors and acceptors, linked with diffusive controlled response to gradients. Coupling to iron transformation are the varying retention of adsorptives such as lead and phosphorus and the redox alterations of elements from nitrogen to uranium. Nitrate, for example, diffusing into aggregate interiors encounters ferrous-iron fronts where the ensuring oxidation of Fe(II)-coupled to nitrate reduction transpires. The outcome of aggregate-scale iron transformations, described within this presentation, is fundamental controls on the cycling of redox active elements from nutrients such as carbon and nitrogen to contaminants such arsenic and uranium.