Biogeochemistry of iron oxidation in a circumneutral freshwater habitat

Iron(II) oxidation in natural waters at circumneutral pH, often regarded as an abiotic process, is frequently biologically mediated at iron-rich redox gradients. West Berry Creek, a small circumneutral tributary that flows through a mixed coniferous forest in Big Basin State Park, California, contains localized iron (hydr)oxide precipitates at points along its course where anoxic groundwater meets oxygenated creek water. These mixing zones establish redox gradients that may be exploited by microbes forming microbial mats that are intimately associated with iron (hydr)oxide precipitates. Water sampling revealed strong correlations between the concentrations of aqueous inorganic species, suggesting a rock-weathering source for most of these solutes. Liquid chromatography–electrospray ionization–mass spectrometry techniques detected significant concentrations of organic exudates, including low molecular mass organic acids and siderophores, indicating that active biogeochemical cycling of iron is occurring in the creek. X-ray diffraction and elemental analysis showed the precipitates to be amorphous, or possibly poorly crystalline, iron-rich minerals. Clone libraries developed from 16S rDNA sequences extracted from microbial mat communities associated with the precipitates revealed the presence of microorganisms related to the neutrophilic iron oxidizing bacteria Gallionella and Sideroxydans. Sequences from these libraries also indicated the presence of significant populations of organisms related to bacteria in the genera Aquaspirillum, Pseudomonas, Sphingomonas, and Nitrospira. These geosymbiotic systems appear to be significant not only for the biogeochemical cycling of iron in the creek, but also for the cycling of organic species, inorganic nutrients, and trace metals.