Ferrous iron (Fe2+) oxidation by microbial iron mat samples, dominated by helical stalks of Gallionella ferruginea or sheaths of Leptothrix ochracea, was examined. Pseudo-first-order rate constants for the microbial mat samples ranged from 0.029 +/- 0.004 to 0.249 +/- 0.042 min(-1) and correlated well with iron content (R2 = 0.929). Rate constants for Na azide-treated (1 mM) samples estimated autocatalytic oxidation by iron oxide stalks or sheaths, with values ranging from 0.016 +/- 0.008 to 0.062 +/- 0.006 min(-1). Fe2+ oxidation attributable to cellular activities was variable with respect to sampling location and sampling time, with rate constants from 0.013 +/- 0.005 to 0.187 +/- 0.037 min(-1). Rates of oxidation of the same order of magnitude for cellular processes and autocatalysis suggested that bacteria harnessing Fe2+ as an energy source compete with their own byproducts for growth, not chemical oxidation (under conditions where aqueous oxygen concentrations are less than saturating). The use of cyclic voltammetry within this study for the simultaneous measurement of Fe2+ and oxygen allowed the collection of statistically meaningful and reproducible data, two factors that have limited aerobic, circumneutral, Fe2+ -oxidation rate studies.