Kinetic Model for Fe(II) Oxidation in Seawater in the Absence and Presence of Natural Organic Matter

Abstract

A detailed kinetic model has been developed to describe the oxidation of Fe(II) in seawater in both the absence and the presence of natural organic material. Experimental data were collected using a luminol chemiluminescence-based method to measure Fe(II), assuming that both the inorganic and the organically complexed species were detected. In the absence of organic matter, the data were modeled based on the Haber-Weiss mechanism with the inclusion of a back-reaction of Fe(III) with superoxide and precipitation of Fe(OH)3. Both reactions were found to be significant using sensitivity analysis. When organic matter is present, the model was extended by organic complexation of Fe(II) and Fe(III) with the creation of a parallel oxidation pathway for Fe(II). Fe(II) oxidation at natural (nanomolar) concentrations was accurately predicted for a range of organic concentrations. The model also accounted for scavenging of superoxide by sub-nanomolar levels of dissolved copper and by organic matter when present. The presence of a relatively strong Fe(III) binding ligand was observed to significantly increase the rate of Fe(II) oxidation, while ultimately retaining most of the iron in the system in dissolved (organically complexed) form. The complexation reactions and reaction of inorganic and organically bound Fe(II) with oxygen were found to be critical reactions in the system, while Fe(III) hydrolysis became unimportant even at low organic concentrations. The superoxide radical was also observed to have a major role in the cycling of iron due to its ability to act as both an oxidant and a reductant. The model indicates that the rate constant for the reaction of Fe(II) with O2 has generally been underestimated in previous work and that the secondary oxidation of Fe(II) by H2O2 and subsequently OH* plays a relatively minor role in these systems.