Photodegradation process and mechanism of 2,3,6-trichloronaphthalene on kaolinite surfaces under ultraviolet-A irradiation: Role of fulvic acid and density functional theory calculations.

Abstract

Polychlorinated naphthalenes (PCNs), a class of persistent organic pollutants (POPs), pose significant environmental and health risks, with trichloronaphthalene being a predominant congener in atmospheric particulate matter. This study investigates the photodegradation of 2,3,6-trichloronaphthalene (CN-26) on kaolinite surfaces under ultraviolet-A (UV-A) irradiation, focusing on the impact of fulvic acid (FA), temperature, humidity, and pH. The photodegradation mechanism of CN-26 was inferred via radical quenching experiments and density functional theory (DFT) calculations. The optimized degradation rate of CN-26 was 75.57 % at 25 °C, 70 % humidity, and pH 7 when FA was added at a concentration of 30 mg kg^-1. Based on the radical quenching experiments, •OH are the primary active species involved in the degradation of CN-26, followed by electrons. In the absence of FA, •OH contributed 82.21 %, while electronic was 17.79 %. Conversely, in the presence of FA, the contribution rates of •OH, and electronic are 68.32 % and 21.21 % respectively. DFT calculations indicated that the 6 C site of CN-26 exhibited the highest susceptibility to radical attack, with the highest FED²_HOMO+FED²_LUMO value (0.25273), corroborated by averaged local ionization energy (ALIE) analysis. In the analysis of the reaction of •OH with CN-26, the lowest transition state ΔrG value of 1.09 kcal mol^-1 was observed for compound 6 C, indicating that this site is the most susceptible to •OH attack. The degradation products of CN-26 were detected using gas chromatography-mass spectrometry (GC-MS), and the possible photodegradation pathways were proposed, which included dechlorination, hydroxylation, and aromatic ring opening. This study would provide insights into the photochemical behaviors of PCNs.