A Mechanistic Study of Goethite-Based Fenton-Like Reactions for Imidacloprid Degradation

Biotic transformation of imidacloprid (IMD) has been widely investigated in the environments. However, little was known about IMD degradation via abiotic pathways, such as reactive oxygen species (ROS)-based oxidation processes. Here we systematically investigated the mechanism of hydroxyl radical (^•OH) production and the associated IMD degradation in the goethite (α-FeOOH)-based Fenton-like systems. Results showed that IMD can be efficiently degraded in the α-FeOOH/H₂O₂ systems, with degradation rate exceeded 80% within 48 h. Based on the examination of electron paramagnetic resonance (EPR) and chemical probes, ^•OH was identified as the key ROS that responsible for IMD degradation. IMD can be decomposed via hydroxylation or removal of -N-NO₂ to produce hydroxylated IMD, cyclic urea and 6-chloronicotinic acid, with the associated toxicities also evaluated. In addition, the increasing H₂O₂ concentration and decreasing solution pH both significantly increased IMD degradation. This study provides theoretical understanding for the implications of soil mineral-based Fenton-like reactions in the abiotic transformation of pesticide pollutants.