Limnetica 34

The direct contribution of microbial activity to the formation of iron-oxide minerals is difficult to prove in wetlands due to the high reactivity of solid iron phases with different compounds and the variety of redox processes that may occur at each oxic-anoxic boundary. Here, we propose an explanation for the formation of iron-oxide films in wetlands and groundwater seepage areas fed by sandy aquifers based on the interaction of hydrological, chemical and microbiological processes under circumneutral conditions. The presence of a floating iron-oxide film was found to create a boundary at the air-water interface that maintains a suboxic and slightly acidic environment below the film compared with the environments obtained in other free-film wetland areas. The water trapped below this film had an average pH of 6.1, was particularly poor in O₂, HCO₃^-, Na⁺, Ca²⁺, Mg²⁺, K⁺, and Tot-S, and has high concentrations of Tot-P, Tot-Fe, NH₄⁺ and Zn. The formation of a floating iron-oxide film was reproduced under anaerobic conditions after progressive enrichment through the incubation of natural sediment samples in the laboratory. Heterotrophic bacteria belonging to the genus Enterobacter were the dominant bacteria in the enrichments that resulted in the formation of a floating iron-oxide film. The X-ray diffraction patterns showed that the presence of two-line ferrihydrite was common to the iron-oxide films collected in both the natural environment and the laboratory cultures, whereas other iron-oxides (goethite and low-crystalline lepidocrocite) were observed only in the natural environment. This study highlights the role of ubiquitous bacteria, which are generally considered unimportant participants in iron-transformation processes in the environment, and the contribution of both biological and non-biological processes to iron oxidation in natural systems under circumneutral conditions.