Effects of extreme pH conditions on the stability of As(V)-bearing schwertmannite

Schwertmannite (Sch) is known to be an effective scavenger of arsenic (As) due to its strong binding affinity for toxic As species. However, the evolution of As-bearing schwertmannite under extreme pH conditions is poorly understood. In this study, we investigated the effects of extremely acidic and alkaline conditions on the stability of schwertmannite with structurally incorporated As(V) (CO-Sch) and schwertmannite with adsorbed As(V) (AD-Sch). The results show that both extremely acidic and alkaline conditions have significant effects on the evolution of minerals and liberation of iron and sulfate. At extremely acidic pH, the maximal release of ferric iron (Fe(III)) and sulfate from CO-Sch were greater than that from AD-Sch, whereas 6.2% and 0.3% of total As released from AD-Sch and CO-Sch, respectively. At extremely alkaline pH, aqueous Fe(III) was not observed, and Fe(III) was retained in As-bearing schwertmannite due to the chemical equilibrium between the dissolution of schwertmannite and re-precipitation of goethite; structurally incorporated As(V) promoted the liberation of sulfate. In addition, the adsorbed As on schwertmannite is more stable, which led to a minor release of As (0.8%) over a 30-d period, however, the liberated As(V) from CO-Sch accounts for up to 3.2%. Under extremely acidic and alkaline conditions, portions of AD-Sch and CO-Sch transformed from schwertmannite to goethite after 30 d, while schwertmannite was still the dominant mineral. Adsorbed As(V) inhibited the transformation of As-bearing schwertmannite to goethite more significantly than structurally incorporated As(V).