Hematite-catalysed scorodite formation as a novel arsenic immobilisation strategy under ambient conditions

Scorodite is an important mineral not only for arsenic (As) removal from industrial wastewaters but also in the mobility and final fate of As in waste rocks, contaminated soils and sediments, and mine tailings. Because of the mineral's high As-loading capacity and stability, numerous studies have been done to understand its formation. Unfortunately, most of these studies were limited to elevated temperatures (>70 °C), so the processes involved in scorodite formation under ambient conditions remain unclear. This study provides evidence of the catalytic effects of hematite on the formation of scorodite at 25 °C in a pyrite-rich natural geologic material. Scorodite peaks were detected in the XRD patterns of the leaching residues with and without hematite, but those in the former were stronger and more pronounced than the latter. These results suggest that the formation of scorodite was catalysed by hematite, a generalisation that is further supported by strong characteristic IR absorption bands of scorodite at 819 cm^-1 (As-O bending vibration), 785 and 725 cm^-1 (As-O stretching vibrations), and 2990 cm^-1 (OH-vibration) as well as the distinct XPS binding energies of Fe(III)-As (709.7 eV), As(V)-O (44.8, 44.31 and 43.7 eV), O^2- (530.5 eV) and coordinated water (531.3 eV) in scorodite. This phenomenon could be attributed to three possible mechanisms: (1) more rapid precipitation promoted by the "seeding" effect of hematite particles, (2) additional supply of Fe³⁺ from hematite dissolution under acidic conditions, and (3) enhanced oxidations of Fe²⁺ to Fe³⁺ and As(III) to As(V) on the surface of hematite.