RESUMO
Organic pollutant degradation by biochar could be promoted by Fe because of the Fenton-like reaction. However, studies have also confirmed that reactive oxygen species (ROS) play only a limited role in organic pollutant degradation by biochar. Herein, we quantitatively identified 2,4-dichlorophenol (2,4-DCP) adsorption and degradation in Fe-biochar systems and obtained degradation (k1) and adsorption rate constants (k2) by two-compartment first-order kinetics modeling. The k1 was approximately 7-10 times lower than the corresponding k2 and the positive correlation between k1 and k2 illustrated that adsorption and degradation were kinetically associated. ROS quenching only slightly inhibited 2,4-DCP degradation. Chemicals with similar structures to ROS quenchers (without quenching ability) also inhibited 2,4-DCP degradation, probably because of the competition of the active degradation sites on biochars. Electrochemical analysis and pH-impact experiments further elucidated that 2,4-DCP underwent oxidation-dominated degradation in the adsorbed phase via direct electron transfer. Fe(III) obviously increased 2,4-DCP adsorption through cation bridging and enhanced electron density by Fe-O conjugations on the biochar surface, which facilitated subsequent degradation. This study emphasized the importance of degradation on the biochar solid phase and that a breakthrough of the mass transfer bottleneck of adsorption will greatly promote degradation.