Tooeleite Transformation and Coupled As(III) Mobilization Are Induced by Fe(II) under Anoxic, Circumneutral Conditions

Abstract

Tooeleite [FeIII6(AsIIIO3)4SO4(OH)4.4H2O] is an important As(III) host phase in diverse mining-impacted environments. Tooeleite has also received attention as a target phase for immobilizing As(III) in environmental and engineered settings. However, little is known regarding tooeleite's environmental stability, with no previous research examining the possible role of Fe(II) in inducing tooeleite transformation (as occurs for Fe(III) oxide minerals). We investigated shifts in solid-phase Fe and As speciation and associated As mobilization into the aqueous phase during exposure of tooeleite to aqueous Fe(II) under anoxic conditions at pH 4 to 8. Our results demonstrate that environmentally relevant concentrations of aqueous Fe(II) (i.e., 1 to 10 mM) induce significant mobilization of As(III) from tooeleite under near-neutral pH conditions, with greater As(III) mobilization occurring at higher pH. Extended X-ray absorption fine structure spectroscopy at both the As and Fe K-edge reveals that the observed As(III) mobilization was coupled with partial Fe(II)-induced transformation of tooeleite to As(III)-bearing ferrihydrite at pH 6 to 8. These results provide new insights into the environmental stability of tooeleite and demonstrate a novel pathway for As(III) mobilization in tooeleite-bearing systems.