Removal of thallium by MnOx coated limestone sand filter through regeneration of KMnO₄: Combination of physiochemical and biochemical actions

Treatment of industrial thallium(Tl)-containing wastewater is crucial for mitigating environmental risks and health threats associated with this toxic metal. The incorporation of Mn oxides (MnOx) into the filtration system is a promising solution for efficient Tl(I) removal. However, further research is needed to elucidate the underlying mechanism behind MnOx-enhanced filtration and the rules of its stable operation. In this study, limestone, a cost-effective material, was selected as the filter media. Raw water with Mn(II), Tl(I), and other pollutants was prepared after a thorough investigation of actual industrial wastewater conditions. KMnO₄ was added to induce the formation of MnO₂ on limestone surfaces, while long-term operation led to enrichment of manganese oxidizing microorganisms (MnOM). Results revealed a dual mechanism. Firstly, most Mn(II) were oxidized by KMnO₄ to form MnO₂ attaching to limestone sands, and both Tl(I) and residual Mn(II) were adsorbed onto the newly formed MnO₂. Subsequently, enzymes secreted by MnOM facilitated oxidation of remaining Mn(II), resulting in the generation of biogenic manganese oxides (BioMnOx) with numerous vacancies during long-term operation. The generated BioMnOx not only adsorbed Mn(II) and Tl(I) but also promoted their oxidation process. This approach offers an effective and sustainable method for removing both Mn(II) and Tl(I) from industrial wastewater, thereby addressing the challenges posed by thallium-contaminated effluents.