Redox reaction between solid-phase humins and Fe(III) compounds: Toward a further understanding of the redox properties of humin and its possible environmental effects

Redox reactions between humic substances and Fe(III) compounds play a critical role in the biogeochemical cycle of pollutants. Most humic substances in soils and sediments are in a solid form (i.e. humin (HM)). In order to assess the contribution of electron shuttling via HM within the electron transfer network in natural environments and to predict environmental fate of pollutants associated with iron oxides, it is necessary to understand the electron transfer processes from HM to the environmentally relevant Fe(III) minerals, and to examine the redox reversibility of HM. The results of this study demonstrated that non-reduced HMs could only donate electrons to dissolved ferric citrate and poorly crystalline ferrihydrite, but reduced HMs could also reduce hematite and magnetite that had high crystallinity. The degree of reduction depended on the difference in redox potential and the crystallinity of the Fe(III) compounds. The electron-accepting capacities of different HMs correlated well with their organic carbon content, and quinones and Fe-bound organic component were important electron-accepting groups in HMs. Furthermore, the redox reversibility experiments demonstrated that HMs could maintain stable electron transfer capacities over three reduction-oxidation cycles, indicating that the HM could be an environ-mentally sustainable electron shuttle. Our results suggest that (1) HM may play an unrecognized and important role in biogeochemical cycles of pollutants in Fe(III) mineral-rich environments; (2) electron shuttling through HM to ferric citrate and ferrihydrite can occur even in the presence of O-2; and (3) HM would be a promising material for environmental remediation.