Redox-induced mobilization of Ag, Sb, Sn, and Tl in the dissolved, colloidal and solid phase of a biochar-treated and un-treated mining soil

The aim of this work was to study the redox-induced mobilization of Ag, Sb, Sn, and Tl in the dissolved, colloidal, and sediment phase of a mining soil treated and untreated with biochar as affected by the redox potential (E_H) -dependent changes of soil pH, dissolved organic carbon, Fe, Mn and S. The experiment was conducted stepwise at two E_H cycles (+200 mV → -30 mV → +333 mV → 0 mV) using biogeochemical microcosm. Silver was abundant in the colloidal fraction in both cycles, indicating that Ag might be associated with colloids under different redox conditions. Antimony, Sn and Tl were abundant in the colloidal fraction in the first cycle and in the dissolved fraction in the second cycle, which indicates that they are retained by colloids under oxic acidic conditions and released under reducing alkaline conditions. Release of dissolved Sb, Sn, and Tl was governed positively by pH, Fe, S, and dissolved aromatic compounds. Biochar mitigated Ag release, but promoted Sb, Sn, and Tl mobilization, which might be due to the wider range of E_H (-12 to +333) and pH (4.9-8.1) in the biochar treated soil than the un-treated soil (E_H = -30 to +218; pH = 5.9-8.6). Also, the biochar surface functional groups may act as electron donors for the Sb, Sn, and Tl reduction reactions, and thus biochar may play an important role in reducing Tl³⁺ to Tl⁺, Sb⁵⁺ to Sb³⁺, and Sn⁴⁺ to Sn²⁺, which increase their solubility under reducing conditions as compared to oxic conditions. Thallium and Sb exhibit higher potential mobility in the solid phase than Sn and Ag. Biochar increased the potential mobility of Sb, Sn, and Tl under oxic acidic conditions. The results improve our understanding of the redox-driven mobilization of these contaminants in soils.