Degradation of conazole fungicides in water by electrochemical oxidation.

The electrochemical oxidation (EO) treatment in water of three conazole fungicides, myclobutanil, triadimefon and propiconazole, has been carried out at constant current using a BDD/SS system. First, solutions of each fungicide were electrolyzed to assess the effect of the experimental parameters such as current, pH and fungicide concentration on the decay of each compound and total organic carbon abatement. Then a careful analysis of the degradation by-products was made by high performance liquid chromatography, ion chromatography and gas chromatography coupled with mass spectrometry in order to provide a detailed discussion on the original reaction pathways. Thus, during the degradation of conazole fungicides by the electrochemical oxidation process, aromatic intermediates, aliphatic carboxylic acids and Cl(-) were detected prior to their complete mineralization to CO2 while NO3(-) anions remained in the treated solution. This is an essential preliminary step towards the applicability of the EO processes for the treatment of wastewater containing conazole fungicides.

Mechanism of pyrogallol red oxidation induced by free radicals and reactive oxidant species. A kinetic and spectroelectrochemistry study.

Pyrogallol red (PGR) presents high reactivity toward reactive (radical and nonradical) species (RS). This property of PGR, together with its characteristic spectroscopic absorption in the visible region, has allowed developing methodologies aimed at evaluating the antioxidant capacity of foods, beverages, and human fluids. These methods are based on the evaluation of the consumption of PGR induced by RS and its inhibition by antioxidants. However, at present, there are no reports regarding the degradation mechanism of PGR, limiting the extrapolation to how antioxidants behave in different systems comprising different RS. In the present study, we evaluate the kinetics of PGR consumption promoted by different RS (peroxyl radicals, peroxynitrite, nitrogen dioxide, and hypochlorite) using spectroscopic techniques and detection of product by HPLC mass spectrometry. The same pattern of oxidation and spectroscopic properties of the products is observed, independently of the RS employed. Mass analysis indicates the formation of only one product identified as a quinone derivative, excluding the formation of peroxides or hydroperoxides and/or chlorinated compounds, in agreement with FOX's assays and oxygen consumption experiments. Cyclic voltammetry, carried out at different pH's, shows an irreversible oxidation of PGR, indicating the initial formation of a phenoxy radical and a second charge transfer reaction generating an ortho-quinone derivative. Spectroelectrochemical oxidation of PGR shows oxidation products with identical UV-visible absorption properties to those observed in RS-induced oxidation.