Mechanism of birnessite-promoted oxidative dissolution of antimony trioxide

Abstract

Environmental contextThe release of antimony and its compounds to the environment can present a toxic hazard for humans. We evaluated the use of birnessite to dissolve antimony trioxide and found that birnessite accelerated the dissolution process, and ~50% of the oxidised antimony was absorbed. The results can help evaluate the bioavailability of antimony in the environment. AbstractThe most important naturally occurring forms of antimony (Sb) are the ore mineral stibnite (Sb2S3) and its principal weathering product antimony trioxide (Sb2O3). Moreover, most Sb is released into the environment as Sb2O3 from manufacturing, formulations, processing, and the use and disposal of Sb products. In this study, birnessite (δ-MnO2) was employed to promote Sb2O3 dissolution. The Sb2O3 dissolution rate accelerated from ~2% to >99% after 9 days of reaction, and more than 98% of the dissolved SbIII was oxidised into SbV in the presence of birnessite. The birnessite-promoted oxidative dissolution mechanism of Sb2O3 was studied through experiments on the effects of the reaction time and pH. The release rate of Sb in the aqueous phase at the initial stage (335.4 μmol L−1 day−1, pH 6.5) was much higher than that at the late stage (13.28 μmol L−1 day−1, pH 6.5), and when the pH increased from 4.7 to 8.0, the Sb release rate decreased from 351.2 μmol L−1 day−1 to 257.7 μmol L−1 day−1. The dissolution promotion effects of birnessite on Sb2O3 were the most evident under acidic and neutral conditions (the percentages of dissolved Sb2O3 under acidic and neutral conditions were 98.3% and 100.0% after 9 days of reaction). Not all of the produced SbV was released in the reaction solution because ~50% of it was adsorbed by birnessite, and the amount of Sb adsorbed increased with increasing pH. Therefore, alkaline conditions are shown to reduce the release of SbV by inhibiting Sb2O3 dissolution (86.7%) and enhancing SbV adsorption. These results could help clarify the geochemical cycle and fate of Sb in the environment.