Kinetic models for hydroxyl radical production and contaminant removal during soil/sediment oxygenation

Abstract

Hydroxyl radical (•OH) oxidation has been identified as a significant pathway for element cycling and contaminant removal in redox fluctuating environments. Fe(II) has been found to be the main electron contributor for •OH production. Despite the recognition of the mechanisms of •OH production from the oxidation of Fe(II) in soils/sediments by O2, the kinetic model about Fe(II) oxidation, •OH production and contaminant removal is not yet clear. To address this knowledge gap, we conducted a series of experiments to explore the variation of different Fe(II) species, •OH and trichloroethylene (TCE, a representative contaminant) during sediment oxygenation, followed by the development of a kinetic model. In this model, Fe(II) species in sediments was divided into three categories based on the sequential chemical extraction method: ion exchangeable Fe(II), surface-adsorbed Fe(II) and mineral structural Fe(II),. Results showed that the kinetic model accurately fitted the concentration time trajectories of different Fe(II) species, •OH and TCE in this study as well as in previous studies. Model analysis indicated that the relative contribution of surface-adsorbed Fe(II) and reactive mineral structural Fe(II) in •OH production was 16.4%–33.9% and 66.1%–83.6%, respectively. However, ion-exchangeable Fe(II) not only fails to contribute to •OH production but also reduces the •OH yield relative to H2O2 decomposition. Poorly reactive mineral structural Fe(II) can serve as an electron pool to regenerate these reactive Fe(II) and facilitate •OH production. Regarding TCE degradation, Fe(II) species plays a dual role in contributing to •OH production while competing with TCE for •OH consumption, with the quenching efficiency being related to their content and reactivity toward •OH. This kinetic model offers a practical approach to describing and predicting •OH production and associated environmental impacts at the oxic-anoxic interface.