Photochemical interactions between pesticides and plant volatiles

Among the numerous studies devoted to the photodegradation of pesticides, very scarce are those investigating the effect of plant volatiles. Yet, pesticides can be in contact with plant volatiles after having been spread on crops or when they are transported in surface water, making interactions between the two kinds of chemicals possible. The objectives of the present study were to investigate the reactions occurring on plants. We selected thyme as a plant because it is used in green roofs and two pesticides: the fungicide chlorothalonil for its very oxidant excited state and the insecticide imidacloprid for its ability to release the radical NO₂ under irradiation. Pesticides were irradiated with simulated solar light first in a solvent ensuring a high solubility of pesticides and plant volatiles, and then directly on thyme's leaves. Analyses were conducted by headspace gas chromatography-mass spectrometry (HS-GC-MS), GC-MS and liquid chromatography-high resolution mass spectrometry (LC-HRMS). In acetonitrile, chlorothalonil photosensitized the degradation of thymol, α-pinene, 3-carene and linalool with high quantum yields ranging from 0.35 to 0.04, and was photoreduced, while thymol underwent oxidation, chlorination and dimerization. On thyme's leave, chlorothalonil was photoreduced again and products arising from oxidation and dimerization of thymol were detected. Imidacloprid photooxidized and photonitrated thymol in acetonitrile, converting it into chemicals of particular concern. Some of these chemicals were also found when imidacloprid was irradiated dispersed on thyme's leaves. These results show that photochemical reactions between pesticides and the plants secondary metabolites can take place in solution as on plants. These findings demonstrate the importance to increase our knowledge on these complex scenarios that concern all the environmental compartments.