Biochar inhibited hydrogen radical-induced Cd bioavailability in a paddy soil

Herein, hydrogen (H·) radical was observed as a new pathway to produce hydroxyl (OH·) radicals that promoted cadmium sulfide (CdS) dissolution and thus Cd solubility in paddy soils. In soil incubation experiments, the bioavailable Cd concentrations in flooded paddy soils were increased by 8.44 % as the soil was aerated for 3d. For the first time, the H· radical was observed in aerated soil sludge. The association of CdS dissolution with free radicals was thereafter confirmed in an electrolysis experiment. Both H· and OH· radicals in electrolyzed water were confirmed by the electron paramagnetic resonance analysis. In the system with CdS, water electrolysis increased soluble Cd²⁺ concentration by 60.92 times, which was compromised by 43.2 % when the radical scavenger was introduced. This confirmed the free radicals can lead to oxidative dissolution of CdS. The H· radical was generated in systems with fulvic acid or catechol irradiated by ultraviolet lights, indicating soil organic carbon could be an important precursor for H· and OH· radicals. Biochar application decreased soil DTPA-Cd by 22-56 % invoking mechanisms besides adsorption. First, biochar quenched radicals and reduced CdS dissolution by 23.6 % in electrolyzed water in which -C-OH of biochar was oxidized to CO. Second, biochar boosted Fe/S-reducing bacteria and thus compromised CdS dissolution, as affirmed by a reversal correlation between soil available Fe²⁺ and DTPA-Cd concentrations. A similar phenomenon occurred in Shewanella oneidensis MR-1-inoculated soils. This study provided new insights into the bioavailability of Cd and offered feasible measures to remediate Cd-contaminated paddy soils with biochars.