First "unsaturated soils" view towards quantitative adsorption and immobilization mechanisms of Cd by biochar in soils during aging.

Instead of traditional batch and column experiments with large water-soil ratios, this study investigated the behaviors and mechanisms of Cd adsorption and immobilization by biochar in unsaturated soils, in which the soil moisture conditions were closer to those in the actual field. The transport, transformation, and immobilization of cadmium (Cd) by pristine and KMnO-modified biochars in unsaturated soils were investigated during a 48-week mild aging process. Biochar acidified with HCl solution was employed to quantify the contributions of mineral and non-mineral components in biochar to Cd adsorption and immobilization in unsaturated soils with a three-layer mesh method. The behaviors and mechanisms of Cd adsorption by biochar in unsaturated soils significantly differed from those in aqueous solutions. The equilibrium times of Cd adsorption by biochar in unsaturated soils (weeks) were much longer than those in aqueous solutions (hours). The percentages of the Cd adsorbed by pristine and modified biochar remained relatively constant relative to the total Cd in unsaturated soils, which accounted for 39.50-49.39 % and 57.35-68.94 %, respectively. The contribution of mineral components to Cd adsorption dominated in both unsaturated soils (45.00-94.09 %) and aqueous solutions (70.73-95.51 %). The process of Cd immobilization in unsaturated soils was that biochar firstly adsorbed the exchangeable Cd from the soil, and then converted it to relatively stable Cd. After aging for 48 weeks, the contributions of non-mineral components to Cd immobilization dominated in unsaturated soil with a low concentration (1.23 mg·kg), and the contributions of mineral components to Cd immobilization dominated in unsaturated soil with medium-high concentrations (4.08-51.26 mg·kg).