RESUMEN
Within the context of environmentally friendly methods for the elimination of surface-water pollutants, the photodegradation of the phenolic pesticides bromoxynil (BXN) and dichlorophen (DCP) under simulated natural conditions has been studied. The work was done in the presence of the visible-light absorber photosensitizer riboflavin (Rf), usually present in trace quantities in natural waters. Under aerobic conditions, an efficient photooxidation of both pesticides was observed. The relatively intricate photochemical mechanism involves pesticide and oxygen consumption and, to a lesser extent, Rf degradation. The kinetic and mechanistic study supports that both H(2)O(2) and singlet molecular oxygen, O(2)((1)Δ(g)), are involved in the process. Kinetic data for the O(2)((1)Δ(g))-mediated oxidation indicate that BXN and DCP are photodegraded with this species faster than the parent compound phenol, very frequently employed as a model for aquatic contaminants, likely due to their lower pK(a) values. This observation allows the design of phenolic pesticides with different photodegradation rates under environmental conditions.
Asunto(s)
Diclorofeno/química , Nitrilos/química , Plaguicidas/química , Fenoles/química , Cinética , Oxígeno/química , Fotoquímica , Análisis Espectral/métodosRESUMEN
The acaricide abamectin is a mixture of two colorless homologues in a molar ratio of at least 4:1 with the same structure of macrocyclic lactone. The kinetics of its degradation under direct (254 nm) and dye-sensitized (>400 nm) photoirradiation in methanol solution has been studied by UV-vis spectrophotometry, potentiometric detection of dissolved oxygen, stationary fluorescence, laser flash photolysis, and time-resolved detection of singlet molecular oxygen (O2((1)Delta(g))) phosphorescence. The results indicate that the degradation is very efficient under direct irradiation with UV light (254 nm), with a quantum yield of 0.23. On the contrary, under visible-light irradiation, using the natural pigment riboflavin or the synthetic dye rose bengal as sensitizers, the degradation is very inefficient and proceeds through a O2((1)Delta(g))-mediated mechanism, with a bimolecular rate constant for the overall O2((1)Delta(g)) quenching (the sum of physical and chemical quenching) of 5.5 x 10(5) M(-1) s(-1). This value is similar to those reported for the rate constants of the reactions of O2((1)Delta(g)) with isolated double bonds or conjugated dienes and points to similar processes in the case of abamectin.
Asunto(s)
Antihelmínticos/química , Ivermectina/análogos & derivados , Luz , Ivermectina/química , Cinética , Oxidación-Reducción , Oxígeno/química , Fotoquímica , Fotólisis , Rosa Bengala , Espectrofotometría Ultravioleta , Rayos UltravioletaRESUMEN
The present work studies the visible-light-promoted photodegradation of the colorless fungicide carbendazim (methyl 2-benzimidazolecarbamate) and several 2-substituted benzimidazoles (SBZ's), in water or water-methanol solution, in the presence of air and, as a photosensitizer, the synthetic xanthene dye Rose Bengal (RB) or the natural pigment riboflavin (Rf). The results indicate that the degradation of each particular SBZ depends on its chemical structure and on the sensitizer employed. In the presence of RB, the degradation always operates via a singlet molecular oxygen (O(2)((1)Delta(g)))-mediated mechanism, through a highly efficient process, as deduced from the comparison of the rate constants for physical and chemical quenching of O(2)((1)Delta(g)). In the presence of Rf, the visible-light irradiation of any of the studied SBZ's produces a series of competitive processes that depend on the relative concentrations of Rf and SBZ. These processes include the quenching of excited singlet and triplet Rf states by the SBZ and the generation of both O(2)((1)Delta(g)) and superoxide radical anion (O(2)(-)), the latter generated by electron transfer from excited Rf species to the dissolved oxygen. The overall result is the photodegradation of the SBZ and the photoprotection of the sensitizer.