Light Induced Degradation of Eight Commonly Used Pesticides Adsorbed on Atmospheric Particles: Kinetics and Product Study

Pesticides are widely used all over the world whether in agricultural production or in non-agricultural settings. They may pose a potential human health effects and environmental risks due to their physico-chemical properties and their extensive use which is growing every year. Pesticides are found in the atmosphere removed from the target area by volatilization or wind erosion, and carried over long distances. These compounds are partitioned between the gaseous and particulate atmospheric phases. The increasingly used pesticides are semi-volatile compounds which are usually adsorbed on the surface of the atmospheric particles. These pesticides may undergo chemical and photo-chemical transformation. New compounds may then be formed that could be more hazardous than the primary pesticides. The atmospheric fate and lifetime of adsorbed pesticides on particles are controlled by the these (photo)chemical processes. However, there is a lack of kinetic data regarding the pesticides in the particle phase.

This current work focuses on the photolytic degradation of commonly used pesticides in particulate phase. It aims at estimating the photolytic rates and thus the lifetimes of pesticides adsorbed on silica particles as a proxy of atmospheric particles. The following eight commonly used pesticides, cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, tetraconazole, were chosen because of their physico-chemical properties. The photolysis rates of tetraconazole and permethrin were extremely slow ≤ 1.2 · 10^-6 s^-1. The photolysis rates for the other pesticides were determined in the range of: (5.9 ± 0.3) · 10^-6 < k < (1.7 ± 0.1) · 10^-4 s^-1 from slowest to the fastest: pendimethalin < cyprodinil < deltamethrin < difenoconazole < oxadiazon < fipronil. Finally, the identification of the surface products upon light irradiation was performed, using GC-(QqQ)-MS/MS and LC-(Q-IMS-ToF)-MS/MS. The potentially formed gas-phase products during these photolysis processes were followed continuously and on-line by PTR-ToF-MS. We hope that the obtained results from this study will help in the development of future environmental strategies to better understand and control phyto-sanitary product application and human exposure.