BIOGEOCHEMISTRY OF IRON OXIDATION IN A CIRCUMNEUTRAL FRESHWATER HABITAT

Iron(II) oxidation in natural waters at circumneutral pH, often regarded as an abiotic process, may be biologically-mediated when it occurs in iron-rich redox gradients. West Berry Creek, a small circumneutral tributary flowing 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 biofilms intimately associated with the iron (hydr)oxide precipitates, which accordingly may be of microbial origin. Water sampling revealed strong correlations between the concentrations of aqueous inorganic species, suggesting a rock-weathering source for most of these solutes. Liquid chromatography-mass spectrometry detected significant concentrations of organic exudates, including low molecular mass organic acids and siderophores, indicating active biogeochemical cycling of iron is occurring in the creek. X-ray diffraction and elemental analysis showed the iron precipitates to be amorphous minerals, such as ferrihydrite. Microbial biofilm communities are associated with the iron (hydr)oxide deposits. Clone libraries developed from 16s rDNA sequences revealed the presence of microorganisms related to the neutrophilic iron-oxidizing bacteria Gallionella and Siderooxidans. Sequences from these libraries also indicated the presence of significant populations of organisms related to bacteria in the genera 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.