Antimony-bearing schwertmannite transformation to goethite: A driver of antimony mobilization in acid mine drainage

Antimony(V) mobility in acid mine drainage (AMD) is often controlled by sorption and coprecipitation with schwertmannite - a poorly-ordered Fe(III) oxyhydroxysulfate mineral. However, due to its metastable nature, schwertmannite transforms over time to more thermodynamically stable Fe(III) phases, such as goethite. This study examines how transformation of Sb(V)-bearing schwertmannite to goethite impacts Sb(V) mobility, while also assessing the role that Sb(V) may play in stabilizing schwertmannite against such transformation. To address these aims, Sb(V)-free, Sb(V)-sorbed and Sb(V)-coprecipitated schwertmannite were allowed to undergo partial transformation to goethite under acid sulfate conditions. Iron K-edge EXAFS spectroscopy revealed that sorbed and coprecipitated Sb(V) partly stabilized schwertmannite against transformation. The onset of schwertmannite transformation to goethite was found to drive clear mobilization of Sb(V) into solution, regardless of the Sb(V) loading or whether Sb(V) was initially sorbed or coprecipitated with the precursor schwertmannite. This initial phase of Sb(V) mobilization was followed by subsequent solid-phase recapture of the released Sb(V), with Sb Kedge EXAFS spectroscopy revealing that this process involved Sb(V) incorporation into the newly-formed goethite. Our findings show that, although schwertmannite transformation to goethite is partially inhibited by co-existing Sb(V), the initial stage of this transformation process drives significant Sb(V) mobilization in AMD systems.