Thioglycolate-based task-specific ionic liquids: Metal extraction abilities vs acute algal toxicity

Abstract

We studied the extraction behavior of two thioglycolate-based ionic liquids (ILs), for heavy metals from aqueous solutions; substances of interest were methyltrioctylammonium S-hexyl thioglycolate [N₁₈₈₈][C₆SAc] and methyltrioctylphosphonium S-hexyl thioglycolate [P₁₈₈₈][C₆SAc]. Theses ILs previously have shown very good extraction abilities towards cadmium and copper, therefore we investigated time-dependent metal removal experiments with aqueous solutions of cobalt(II), nickel(II) and zinc(II). The highest distribution ratio (R_IL/Water) was determined for zinc (R_IL/Water=2000). Recovery studies for zinc after extraction were performed with different stripping agents showing a successful recycling. Additionally, the two ILs were immobilized on active charcoal, displaying great potential for solid-liquid extraction. Regarding the extraction mechanism, quantum-mechanical calculations were included, which indicate that the metal extraction depends on the stability of the metal-water cluster. Ligands (water as well as ILs) are planar coordinated in nickel complexes but showed a tetrahedral configuration for zinc. As a first estimate of the ecotoxicity of the ILs, in vivo tests toward three freshwater green algae species Tetradesmus obliquus, Desmodesmus armatus and Raphidocelis subcapitata were carried out. The EC₅₀ values (effective concentration after 72 h) confirm high toxicity of all tested ILs to all species, displaying only small differences between the species and EC₅₀ies.