Dissolution of realgar by Acidithiobacillus ferrooxidans in the presence and absence of zerovalent iron: Implications for remediation of iron-deficient realgar tailings.

Realgar (As4 S4 )-rich tailings are iron-deficient arsenical mine wastes. The mechanisms and products of the dissolution of realgar by Acidithiobacillus ferrooxidans (A. ferrooxidans) in the presence (0.2 g and 2 g) and absence of zerovalent iron (ZVI) are investigated for three stages (each of 7 d with fresh A. ferrooxidans medium addition between the stages). SEM-EDX, FTIR, XPS and selective extraction analysis are used to characterize the solid-phase during the experiments. ZVI addition causes the systems to become more acid-generating, although pH increases are observed in the first day due to ZVI dissolution. Arsenic is released to solution due to realgar oxidation (∼30 mg L-1 in the 0 g ZVI system in Stage I), but low concentrations are observed in the ZVI-added systems (<5 mg L-1 ) and in Stages II and III of the 0 g ZVI system. As(III) dominates the released As(T) at day 1 (83-89% of As(T)), but is largely oxidized to As(V) at day 7 of each stage (53-98% of As(T)). Arsenic attenuation is attributed to the formation of mixed As-Fe oxyhydroxides and oxyhydroxy sulfates that take up released arsenic and are abundant in the 2.0 g ZVI system, and to passivation of the realgar surface. Consequently, a new strategy that combines A. ferrooxidans and exogenous ZVI addition for treating in-situ iron-deficient realgar-rich tailings is proposed, although its long-term effects need to be monitored.