Electron Transfer, Atom Exchange, and Transformation of Iron Minerals in Soils: The Influence of Soil Organic Matter.

Despite substantial experimental evidence of electron transfer, atom exchange, and mineralogical transformation during the reaction of Fe(II) with synthetic Fe(III) minerals, these processes are rarely investigated in natural soils. Here, we used an enriched Fe isotope approach and Mössbauer spectroscopy to evaluate how soil organic matter (OM) influences Fe(II)/Fe(III) electron transfer and atom exchange in surface soils collected from Luquillo and Calhoun Experimental Forests and how this reaction might affect Fe mineral composition. Following the reaction of Fe-enriched Fe(II) with soils for 33 days, Mössbauer spectra demonstrated marked electron transfer between sorbed Fe(II) and the underlying Fe(III) oxides in soils. Comparing the untreated and OM-removed soils indicates that soil OM largely attenuated Fe(II)/Fe(III) electron transfer in goethite, whereas electron transfer to ferrihydrite was unaffected. Soil OM also reduced the extent of Fe atom exchange. Following reaction with Fe(II) for 33 days, no measurable mineralogical changes were found for the Calhoun soils enriched with high-crystallinity goethite, while Fe(II) did drive an increase in Fe oxide crystallinity in OM-removed LCZO soils having low-crystallinity ferrihydrite and goethite. However, the presence of soil OM largely inhibited Fe(II)-catalyzed increases in Fe mineral crystallinity in the LCZO soil. Fe atom exchange appears to be commonplace in soils exposed to anoxic conditions, but its resulting Fe(II)-induced recrystallization and mineral transformation depend strongly on soil OM content and the existing soil Fe phases.