Mechanisms for thallium(I) adsorption by zinc sulfide minerals under aerobic and anaerobic conditions

The highly toxic heavy metal thallium is widely distributed in sulfide ores and released into the environment by sulfide mining. However, the interface between the sulfide minerals and Tl(I) is unclear. In this study, the capacity for adsorption of thallium(I) by a common sulfide mineral (zinc sulfide) was investigated in aerobic and anaerobic environments, which revealed three mechanisms for adsorption on the ZnS surface (surface complexation, electrostatic action and oxidation promotion). Batch experiments indicated that the Tl(I) adsorption capacity of ZnS in an aerobic environment was approximately 9.3% higher than that in an anaerobic environment and was positively correlated with the pH. The adsorption kinetic data showed good fits with the pseudosecond-order model and the Freundlich isotherm model. The Tl(I) adsorption mechanism varied in different oxidative and pH environments. XPS, FTIR, and EDS results implied that complexation with surface hydroxyl groups was involved in the adsorption process. pH experiments and zeta analyses suggested that electrostatic attraction was also involved. Surface complexation and electrostatic attraction were the dominant mechanisms at pH values above 6. Furthermore, oxidative dissolution of ZnS and hydrolysis of Zn2+ enhanced the complexation with hydroxyl groups on the mineral surface and facilitated Tl adsorption. In this study, this interface mechanism provided new insights into thallium migration in sulfurized mineral environments in aerobic and anaerobic transition regions.