Photolysis of the novel meta-diamide insecticide broflanilide in solutions: Kinetics, degradation pathway, DFT calculation and ecotoxicity assessment

Abstract

Broflanilide, as a novel meta-diamide insecticide, presents high bioactivity against agricultural pests. However, there was limited report regarding the photolysis fate of broflanilide. In this study, the photodegradation kinetics and influence factors of broflanilide, including different solvents, pH, iron, S2O82− and SO32− were investigated under UV condition, and the reaction mechanism and transformation pathway were explored. The reaction rates (k) showed solvent-specificity in ultrapure water (0.015 min−1), ethyl acetate (0.051 min−1), methanol (0.084 min−1) and acetonitrile (0.193 min−1), correspondingly. The photolysis of broflanilide was slowest in the acid condition (pH = 4.0) compared with that in the neutral (pH = 7.0) and alkaline (pH = 9.0) conditions. The iron (Fe2+ and Fe3+) presented significant inhibition on the photodegradation due to the light shielding effect. Additionally, the UV/peroxydisulfate (S2O82−) and UV/sulfite (SO32−) technologies could effectively accelerate the photodegradation of broflanilide, which has the potential for rapid treatment of pesticides in the aqueous environment. Six transformation products (TPs) were detected in water, peroxydisulfate and sulfite solutions, and the possible transformation pathways, including dehalogenation, cyclization, N-dealkylation, oxidation, reduction and hydrolysis, were proposed. Importantly, the reaction mechanism was explained through the analysis of molecular electrostatic potential and molecular orbitals. The predicted toxicity of the TPs indicated that several highly toxic TPs need to pay more attention in future risk assessments. This study provides a new perspective for evaluating the ecological fate and risks of pesticides.