Characterization and pH-dependent environmental stability of arsenic trioxide-containing copper smelter flue dust

Increasing amounts of impurities (especially As) in Cu ores have aggravated the problem of flue dust generation in recent years. As an example from a smelter processing As-rich Cu ores, we characterized a flue dust particularly rich in As (>50 wt%) to understand its mineralogy and pH-dependent leaching behavior, with special emphasis on binding, release and solubility controls of inorganic contaminants (As, Bi, Cd, Cu, Pb, Sb, Zn). Whereas arsenolite (As₂O₃) was the major host for As and Sb, other contaminants were bound in sulfides, arsenates, alloys and slag-like particles. The EU regulatory leaching test (EN 12457-2) indicated that leached As, Cd, Sb and Zn significantly exceeded the limit values for landfills accepting hazardous waste. The pH-dependent leaching test (CEN/TS 14997) revealed that As, Sb and Pb exhibited the greatest leaching at pH 11–12, whereas Cd, Cu and Zn were leached most under acidic condition (pH 3) and Bi leaching was pH-independent. Mineralogical investigation of leached residue coupled with geochemical modeling confirmed that newly formed Ca, Pb and Ca-Pb arsenates (mimetite, Pb₅(AsO₄)₃Cl) partly control the release of As and other contaminants under circumneutral and alkaline conditions and will be of key importance for the fate of smelter-derived contamination in soils or when stabilization technology is employed.