Aggregation, retention and transport of γ-MnO2 nanoparticles in water-saturated porous media: Impact on the immobility of thallium

Abstract

Nano-scale Mn oxides can act as effective stabilizers for Tl in soil and sediments. Nevertheless, the comprehensive analysis of the capacity of MnO2 to immobilize Tl in such porous media has not been systematically explored. Therefore, this study investigates the impact of γ-MnO2, a model functional nanomaterial for remediation, on the mobility of Tl in a water-saturated quartz sand-packed column. The mechanisms involved are further elucidated based on the adsorption and aggregation kinetics of γ-MnO2. The results indicate that higher ionic strength (IS) and the presence of ion Ca(II) promote the aggregation of γ-MnO2, resulting from the reduced electrostatic repulsion between particles. Conversely, an increase in pH inhibits aggregation due to enhanced interaction energy. γ-MnO2 significantly influences Tl retention and mobility, with a substantial fraction of γ-MnO2-bound Tl transported through the column. This might be attributed to the high affinity of γ-MnO2 for Tl through ion exchange reactions and precipitation at the surface of γ-MnO2. The mobility of Tl in the sand column is influenced by the γ-MnO2 colloids, exhibiting either inhibition or promotion depending on the pH, IS, and cation type of the solution. In solutions with higher IS and Ca(II), the mobility of Tl decreases as γ-MnO2 colloids tend to aggregate, strain, and block, facilitating colloidal Tl retention in porous media. Although higher pH reduces the mobility of individual Tl, it promotes the mobility of γ-MnO2 colloids, facilitating a substantial fraction of colloidal-form Tl. Consequently, the optimal conditions for stabilizing Tl by γ-MnO2 involve either high IS and low pH or the presence of competitive cations (e.g., Ca(II)). These findings provide new insights into Tl immobilization using MnO2- and Mn oxide-based functional materials, offering potential applications in the remediation of Tl contamination in soil and groundwater.