Photochemical transformation of hexachlorobenzene (HCB) in solid-water system: Kinetics, mechanism and toxicity evaluation

As one of the first batch of persistent organic pollutants (POPs) included in Stockholm Convention, hexachlorobenzene (HCB) has attracted great attention because of its wide occurrence and great environmental risks. Considering the easy adsorption of HCB on solids and the complexity of natural particles, we systematically investigated the photodegradation of HCB on the surface of silica gel (SG) in aqueous solution in this work to reveal its fate in natural waters. Under mercury lamp irradiation, more than 90% of HCB loaded on SG could be removed after 240 min. Moreover, the effects of solution pH and water constituents were examined, and results showed that the presence of NO 2 − , NO 3 − , Fe 3+ and humic acid (HA) significantly inhibited the reaction due to the scavenging of ROS and/or competitive absorption of light. According to radical quenching experiments and electron paramagnetic resonance (EPR) spectra, hydroxyl radicals and singlet oxygen generated on the surface of SG could participate in the transformation of HCB, but •OH played a dominant role. Based on products identified by high performance liquid chromatography-mass spectrometry (HPLC-MS) and gas chromatography-mass spectrometry (GC-MS), two main pathways were proposed for the removal of HCB, including dechlorination and hydroxylation which represent direct and indirect photodegradation, respectively, and the occurrence of these two reactions was further supported by density functional theory (DFT) calculations. From the quantitative analysis of penta-chlorobenzene, it was estimated that dechlorination and hydroxylation contributed to approximately 44.4% and 55.6% of initial HCB degradation, respectively. Furthermore, toxicity predictions by the ecological structure–activity relationship model (ECOSAR) suggested that the toxicity of HCB was decreased in the photodegradation process. This study would provide important information for understanding the photochemical transformation mechanism of HCB at the solid/water interface. • Photodegradation of HCB adsorbed onto silica gel in water was investigated. • The generation of ROS (.•OH and 1 O 2 ) on the surface of silica gel was verified. • Direct and indirect photolysis both played a role in HCB degradation. • Dechlorination and hydroxylation account for 44.4% and 55.6% of initial HCB removal.