Cooperative roles of phosphate and dissolved organic matter in inhibiting ferrihydrite transformation and their distinct fates

Abstract

Phosphate and dissolved organic matter (DOM) mediate the crystalline transformation of ferrihydrite catalyzed by Fe(II) in subsurface environments such as soils and groundwater. However, the cooperative mechanisms underlying the mediation of phosphate and DOM in crystalline transformation of ferrihydrite and the feedback effects on their own distribution and speciation remain unresolved. In this study, solid characterization indicates that phosphate and DOM can collectively inhibit the crystalline transformation of ferrihydrite to lepidocrocite and thus goethite, via synergetic effects of inhibiting recrystallization and electron transfer. Phosphate can be retained on the surface or transformed to a nonextractable form within Fe oxyhydroxides; DOM is either released into the solution or preserved in an extractable form, while it is not incorporated or retained in the interior. Element distribution and DOM composition analysis on Fe oxyhydroxides reveals even distribution of phosphate on the newly formed Fe oxyhydroxides, while the distribution of DOM depends on its specific species. Electrochemical and dynamic force spectroscopic results provide molecular-scale thermodynamic evidence explaining the inhibition of electron transfer between Fe(II) and ferrihydrite by phosphate and DOM, thus influecing the crystalline transformation of ferrihydrite and the distribution of phosphate and DOM. This study provides new insights into the coupled biogeological cycle of Fe with phosphate and DOM in aquatic and terrestrial environments.