Photodegradation of organophosphorus pesticides in aqueous solution and clays: mecanistic study
Photodégradation de pesticides organophosphorés en solution aqueuse et sur argiles : étude mécanistique
Résumé
The work presented inhere concerns the study of the photochemical behavior of the organophosphorus azinphos-methyl (AZM) and its model molecule, benzotriazone. For both compounds, the photodegradation efficiency increases with the excitation energy. Such effect can be attributed to a difference in the excited states reactivity or to homolytic bond dissociations of the triazone moiety. The degradation of azinphos-methyl involving direct excitation leads to the formation of benzotriazone which photodegrades in its turn into anthranillic acid. In the case of cyanophos, another organophosphorus pesticide, the degradation involves both singlet and triplet excited state. Several chemical processes were present: homolytic cleavage, hydrolysis. 4-cyanophenol, cyanophos-oxon and [(dimethoxyphosphorothiolyl) oxy] benzoïc acid represent the main observed photoproducts. The study of azinphos-methyl degradation upon direct irradiation has been also studied at the surface of clays (kaolinite, bentonite) and iron oxide (goethite). Adsorption of the pesticide on clays leads to an enhancement of its spectroscopic features permitting a better solar light absorption. Moreover, the photodegradation of AZM appears to be efficient, in Suntest device, on all the studied clays. The efficiency of the reaction depend on the type of clay, thickness, water content, and iron(III) concentration. The degradation of azinphos-methyl involves both direct photochemical reactions and clay photoinduced processes. The involvement of hydroxyl radical was demonstrated by ESR and fluorescence measurements. Among several other products, azinphos-methyl oxon was found to be formed and to accumulate in the medium inducing an increase of the toxicity.
Le pesticide organophosphoré azinphos-méthyle (AZM) voit son efficacité de photodégradation augmenter avec l'énergie d'excitation, vraisemblablement dû à des différences de réactivité entre états excités. Sa dégradation sous excitation directe conduit à la formation de benzotrione qui se dégrade en l'acide anthranilique. Un autre organophosphoré, le cyanophos, se dégrade sous excitation directe en faisant intervenir les états excités triplet et singulet pour former : le 4-cyanophénol, le cyanophos-oxon et un dérivé de l'acide benzoïque. Le dépot de l'AZM dans l'argile conduit à une meilleur absorption de la lumière solaire. Sa photodégradation sur argiles et oxyde de fer est efficace, avec une vitesse dépendant essentiellement de la nature et de l'épaisseur du solide du taux d'humidité et de fer(III). L'AZM se dégrade par des processus issus d'une excitation directe et d'autres photoinduits par le support. La formation de radicaux hydroxyles a également été mise en évidence
Domaines
Chimie analytique
Loading...