Ferrous iron oxidation under acidic conditions – The effect of ferric oxide surfaces

In this study, the kinetics of Fe(II) oxidation in the presence of the iron oxyhydroxides ferrihydrite, Si-ferrihydrite, schwertmannite, lepidocrocite and goethite are investigated over the pH range 4–5.5. Despite limited sorption of Fe(II), the rate of Fe(II) oxidation is up to 70-fold faster than in the absence of any Fe oxyhydroxide phase over pH 4.5–5.5. Enhanced Fe(II) oxidation was minor or negligible at pH 4 with undetectable amounts of Fe(II) adsorbed to the iron oxyhydroxides at this pH. Heterogeneous rate constants derived from kinetic modeling were normalized to the concentration of adsorbed Fe(II) and deviated by no more than 13.8% at pH 4.5, 5 and 5.5, indicating that oxidation is proportional to the concentration of adsorbed Fe(II). Average rate constants were found to be: 2.12 ± 0.20, 1.30 ± 0.09, 1.69 ± 0.22, 1.20 ± 0.08 and 0.68 ± 0.09 M−1 s−1 for ferrihydrite, goethite, lepidocrocite, schwertmannite and Si-ferrihydrite, respectively. The role of reactive oxygen species, such as hydrogen peroxide, the hydroxyl radical and superoxide, towards the overall oxidation of Fe(II) was examined but found to have only a minor impact on Fe(II) oxidation when compared to the effect of heterogeneous oxidation.