Dégradation photochimique d'herbicides chlorophenoxyalcanoïques en milieux aqueux Photochemical degradation of chlorophenoxyalcanoic herbicides in aqueous media

Résumé

La dégradation photochimique de cinq herbicides appartenant à la famille des chlorophénoxyalcanoïques a été étudiée en solution aqueuse par irradiation à 254 nm selon trois systèmes : UV seul, UV/H₂O₂ et UV/H₂O₂/ Fe^III (photo-Fenton). Le procédé photochimique semble constituer une alternative prometteuse aux méthodes existantes de traitement chimique des eaux polluées; en effet il permet de détruire photochimiquement l'herbicide initial et d'obtenir, dans les conditions opératoires initiales, sa minéralisation complète en CO₂ et H₂O. Il s'agit d'un procédé d'oxydation avancé, utilisant comme agent oxydant, des radicaux OH. produits in situ photochimiquement. L'évolution de la composition chimique des solutions d'herbicides étudiés a été suivie par chromatographie liquide à haute performance (CLHP). La minéralisation a été évaluée par mesure de la demande chimique en oxygène (DCO) et par le dosage des ions chlorures libérés. La cinétique de photodégradation, la nature et l'évolution des produits formés ainsi que le rendement du procédé ont été déterminés.

Mots-clés:

• Herbicides chlorophénoxyalcanoïques,
• procédé photo-Fenton,
• radicaux hydroxyles,
• minéralisation,
• demande chimique en oxygène

Abstract

Contamination of surface and ground waters by persistent organic pollutants constitutes a serious environmental problem. A number of physical and biological methods have been proposed to remove these pollutants from industrial wastewater. However, many organic contaminants are not destroyed by these techniques. Various chemical treatment methods for polluted waters have been proposed. These methods are based on catalytic, electrochemical and photochemical reactions, known as advanced oxidation processes (AOPs). However, despite these treatments, there is presently no universal technique available. Because of their widespread agricultural use, chlorophenoxyacid herbicides contaminate waterways and ground waters in France and many other European countries.

In the present study, we have investigated the photochemical degradation of several chlorophenoxyacids in aqueous solution at room temperature, by ultraviolet (UV) irradiation at 254 nm. We compared the efficiency of three different systems: UV alone; assisted photochemistry (UV/H₂O₂); and photo-Fenton reaction (UV/H₂O₂/Fe^III). The latter photochemical system was found to represent a promising alternative approach, relative to existing methods of polluted water chemical treatment. The method photochemically destroyed the initial herbicides into CO₂ and H₂O. Also, it constitutes an AOP based on the in situ photochemical formation of OH· radicals. The evolution of the chemical composition of the herbicide samples studied was monitored by high performance liquid chromatography (HPLC). The mineralization of the initial herbicides was evaluated by the measurement of the chemical oxygen demand (COD) and the determination of chloride ions. The photodegradation kinetics, the nature and evolution of the photoproducts as well as the process yield were studied for the three photochemical systems for five different chlorophenoxyacid herbicides, including 2-(2-methyl-4-chlorophenoxy)propionic acid (MCPP), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D), 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T).

Photodegradation by UV alone was relatively slow and partial, taking place in 1 h for MCPA, 1.5 h for MCPP and 3 h for 2,4-D. This process did not completely destroy the photoproducts. The mineralization yields for the organic matter were 64 %, for MCPA, 69 % for MCPP, 42 % for 2,4-DP and 35 % for 2,4-D, following an irradiation time of 2 h. The technique based on the photolysis of hydrogen peroxide (UV/H₂O₂) produced a more rapid photodecomposition, occurring within about 30 min for MCPA and MCPP and more than 60 min for 2,4-D and 2,4,5-T. The corresponding mineralization yields for the organic matter were 79 % for MCPP and 2,4-DP and 56 % for 2,4-D. The absolute rate constants for the reaction with hydroxyl radicals were found to be1.5×10⁹, 1.6×10⁹, 3.2×10⁹ and 3.6×109 M^-1 s^-1 respectively for 2,4,5-T, 2,4-DP, MCPP and MCPA using this technique.

The photo-Fenton system significantly improved the kinetic performance and mineralization yield. The photodegradation times were 7 min for MCPA, 10 min for MCPP, 40 min for 2,4-D and 60 min for 2,4,5-T, whereas the mineralization yields reach respective values of 96 % for MCPP, 95 % for MCPA, 80 % for 2,4-D, 94 % for 2,4-DP and 89 % for 2,4,5-T.

Keywords:

• Chlorophenoxyacid herbicides,
• Photo-Fenton process,
• Hydroxyl radicals,
• Herbicide,
• Mineralization,
• Chemical oxygen demand