Differential photodegradation processes of adsorbed polychlorinated biphenyls on biochar colloids with various pyrolysis temperatures

Despite the crucial role of photodegradation in the environmental transformation of organic pollutants, the photodegradation process of organic pollutants irreversibly absorbed on biochar colloids (BCCs) remains poorly understood. This study investigated the photodegradation processes and mechanisms of 2,4,4′-trichlorobiphenyl (PCB28) adsorbed on BCCs released from bulk biochars derived from bamboo chips at pyrolysis temperatures of 300, 500, and 700 °C. Results show that BCCs-adsorbed PCB28 could be degraded under simulated solar illumination (95–105 mW·cm⁻²) but at decreased photodegradation rates compared to the dissolved PCB28. The inhibition effect of BCCs on the PCB28 photodegradation increased with increasing pyrolysis temperature. After adsorptive binding to BCCs, the half-life of PCB28 (0.1 mg/L) was prolonged from 2.65 h for the dissolved PCB28 alone in deionized water to 7.48, 40.67, and 81.82 h in the presence of BCC300, BCC500, and BCC700 (5.0 mg/L), respectively. Mechanistically, the photodegradation of adsorbed pollutants was regulated by the photogenerated free radicals and surface functional groups of the low-temperature BCCs, as well as the defects and direct electron transfer capabilities of the high-temperature BCCs; PCB28 adsorbed on the low-temperature BCCs accepted electrons from persistent free radicals under light illumination, which led to PCB28 dechlorination, followed by ring-opening oxidation through hydroxyl radical attack, ultimately resulting in progressive mineralization; singlet oxygen caused preferential ring opening of adsorbed PCB28 on the high-temperature BCCs, preceding dechlorination. The photodegradation of BCCs-adsorbed PCB28 remained significant though more or less being inhibited under the effects of water pH, ionic strength, dissolved organic matters (humic acid and fulvic acid), and in natural water samples. These findings contribute to a better understanding of the structural properties of BCCs that impact phototransformation processes of adsorbed pollutants and facilitate an accurate assessment of the environmental risk associated with biochar application. © 2024 Elsevier Ltd.