Impact of natural organic matter coatings on the microbial reduction of iron oxides

Abstract

Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L−1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that the influence of NOM on the stability of Fe-organic associations in soils cannot easily be assessed without considering the composition of the microbial soil community.