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

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.

Thallium release from biochar-amended soil to runoff in laboratory experiments.

Biochar has been widely used for trace metal(loid) (TM) immobilisation in contaminated soils. However, studies on the physicochemical mobility of TMs related to biochar application are highly limited, hampering the evaluation of the immobilisation efficiency of biochar. Therefore, after confirming the ability of biochar to decrease soil Tl bioavailability, this study examined the release of Tl in dissolved and particulate forms in surface runoff and leachate from soil mixed with biochar at different dosages and grain sizes under artificially simulated rainfall and irrigation experiments. The rainfall experimental results showed that the dissolved Tl in the surface runoff decreased from 1.30 µg in the control group to 0.75 µg and 0.54 µg in the groups with 3% and 5% biochar application, respectively. With the same dosages (5%), the finer the biochar applied, the higher the immobilisation ability achieved in surface runoff and the lower the Tl amounts in the leachate, indicating that the grain size of biochar can impact Tl mobility in dissolved forms. Comparisons between rainfall and irrigation experiments indicated that raindrops disturb the soil-water surface and enhance Tl diffusion. The mass in particulate form accounted for more than 95% of lateral released Tl in surface runoff. However, biochar application did not decrease the enrichment ratio of Tl in the eroded sediments. Notably, the finest biochar group produced less mass of eroded Tl owing to the low flux of soil erosion, indicating that grain size would indirectly impact sediment-bound Tl lateral mobility. Colloidal particles should be highlighted as they carried a maximum TI of up to 38% in the rainfall leachate. Focusing on the effect of biochar application on Tl chemical- and physical mobility from the soil matrix to runoff, this study contributes the comprehensive understanding of the role of biochar in TM remediation.