Systemic assessment of the chiral insecticide pyriproxyfen in a citrus nectar source system: Stereoselective degradation, biological effect and exposure risk

BACKGROUND: Balancing the safety and efficiency of chiral pesticides can help protect pollinators. We evaluated the stereoselective behavior, bioactivity, toxicity and exposure risk of the chiral insecticide pyriproxyfen in a citrus nectar system. RESULTS: Density functional theory (DFT) and ultra-performance liquid chromatography tandem mass spectroscopy (UPLC-MS/MS) were applied for absolute configuration appraisal and chiral analysis validation, respectively. The recoveries ranged from 72.3% to 100.5% with an relative standard deviation (RSD) ranging from 1.2% to 9.7%. In a field trial, we determined insecticide half-lives in citrus leaves and flowers, which were 7.0 and 8.6 days for R-(+)-pyriproxyfen, and 11.7 and 14.7 days for S-(-)-pyriproxyfen, respectively. We found that the bioactivity of R-(+)-pyriproxyfen was 3.39 and 2.37 times higher than S-(-)-pyriproxyfen against Unaspis yanonensis and Diaphorina citri nymphs, respectively. S-(-)-pyriproxyfen had 3.8 times higher acute toxicity than R-(+)-pyriproxyfen on Apis mellifera L., and its exposure risk was moderate based on the hazard quotient. CONCLUSION: The phenomenon of stereoselective degradation and biological effect demonstrated that the high-risk stereoisomer of S-(-)-pyriproxyfen degraded more slowly than R-(+)-pyriproxyfen, but R-(+)-pyriproxyfen with better efficiency for target. Therefore, an increased duration of R-(+)-pyriproxyfen activity on citrus was beneficial for efficacy. Our results could guide the scientific application and evaluation of chiral pesticides on nectar plants.