Iron oxides are important structural and biogeochemical components of soils that can be strongly altered by redox-driven processes. This study examined the influence of temporal oxygen variations on Fe speciation in soils from the Luquillo Critical Zone Observatory (Puerto Rico). We incubated soils under cycles of oxic-anoxic conditions (τ:τ = 1:6) at three frequencies with and without phosphate addition. Fe(II) production, P availability, and Fe mineral composition were monitored using batch analytical and spectroscopic techniques. The rate of soil Fe(II) production increased from ∼3 to >45 mmol Fe(II) kg d over the experiment with a concomitant increase of an Fe(II) concentration plateau within each anoxic period. The apparent maximum in Fe(II) produced is similar in all treatments, but was hastened by P-amendment. Numerical modeling suggests the Fe(II) dynamics can be explained by the formation of a rapidly reducible Fe(III) phases derived from the progressive dissolution and re-oxidation of native Fe(III) oxides accompanied by minor increases in Fe reducer populations. The shift in Fe(III) reactivity is evident from Fe-reducibility assays using Shewanella sp., however was undetectable by chemical extractions, Mössbauer or X-ray Absorption spectroscopies. More broadly, our findings suggest Fe reduction rates are strongly coupled to redox dynamics of the recent past, and that frequent shifts in redox conditions can prime a soil for rapid Fe-reduction.

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The facultative anaerobe Shewanella oneidensis MR-1 respires a variety of anaerobic electron acceptors, including insoluble Fe(III) oxides. S. oneidensis employs a number of novel strategies for respiration of insoluble Fe(III) oxides, including localization of respiratory proteins to the cell outer membrane (OM). The molecular mechanism by which S. oneidensis adheres to and respires Fe(III) oxides, however, remains poorly understood. In the present study, whole cell fractionation and MALDI-TOF-MS/MS techniques were combined to identify a serine protease (SO3800) associated with the S. oneidensis OM. SO3800 contained predicted structural motifs similar to cell surface-associated serine proteases that function as bacterial adhesins in other gram-negative bacteria. The gene encoding SO3800 was deleted from the S. oneidensis genome, and the resulting mutant strain (DeltaSO3800) was tested for its ability to adhere to and respire Fe(III) oxides. DeltaSO3800 was severely impaired in its ability to adhere to Fe(III) oxides, yet retained wild-type Fe(III) respiratory capability. Laser Doppler velocimetry and cryoetch high-resolution SEM experiments indicated that DeltaSO3800 displayed a lower cell surface charge and higher amount of surface-associated exopolysaccharides. Results of this study indicate that S. oneidensis may respire insoluble Fe(III) oxides at a distance, negating the requirement for attachment prior to electron transfer.