A Mechanistic Approach Toward Enhanced Remediation Potential of Thiacloprid by Zero-Valent Iron/Biochar Supplemented with Organic Acids

The excessive levels of neonicotinoid insecticides, particularly thiacloprid (THI), in the environment have become a significant threat to ecosystems. This study investigates the catalytic degradation of THI using pinewood biochar (PBC), zero-valent iron (ZVI), and ZVI/PBC composite, with a particular focus on the reaction activity modulation mediated by organic acids (humic acid: HA and oxalic acid: OA). Reductive dechlorination dominated THI degradation as observed by Cl^- release kinetics. Compared to HA (39.73%), the OA (73.44%) addition markedly increased the THI removal efficiency by ZVI/PBC, which alone has a lower removal efficacy, i.e., 37.29%. The increase in the THI removal rate was attributed to its enhanced electron transfer capacity. As confirmed by electrochemical characterization, the addition of organic acids promotes electron transfer between THI and catalysts (ZVI, PBC, or ZVI/PBC), thereby improving the removal efficiency of THI. XRD/XPS analyses elucidated that OA preferentially converted passivating Fe₂O₃/Fe₃O₄ on ZVI/PBC to reactive FeOOH and formed electron-conductive Fe-COO bonds, thereby suppressing oxide layer formation. PBC amplified these effects through ZVI dispersion and electron shuttling, reducing aggregation-induced activity loss. These findings provide a mechanistic framework for optimizing ligand-engineered iron composites, offering practical strategies to enhance pesticide remediation efficiency in organic acid-rich environmental systems.