RESUMO
A solution with 0.38 mM of the pesticide propoxur (PX) at pH 3.0 has been comparatively treated by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF), and photoelectro-Fenton (PEF). The trials were carried out with a 100-mL boron-doped diamond (BDD)/air-diffusion cell. The EO-H2O2 process had the lowest oxidation ability due to the slow reaction of intermediates with â¢OH produced from water discharge at the BDD anode. The EF treatment yielded quicker mineralization due to the additional â¢OH formed between added Fe2+ and electrogenerated H2O2. The PEF process was the most powerful since it led to total mineralization by the combined oxidative action of hydroxyl radicals and UVA irradiation. The PX decay agreed with a pseudo-first-order kinetics in EO-H2O2, whereas in EF and PEF, it obeyed a much faster pseudo-first-order kinetics followed by a much slower one, which are related to the oxidation of its Fe(II) and Fe(III) complexes, respectively. EO-H2O2 showed similar oxidation ability within the pH range 3.0-9.0. The effect of current density and Fe2+ and substrate contents on the performance of the EF process was examined. Two primary aromatic products were identified by LC-MS during PX degradation.
Assuntos
Boro/química , Diamante/química , Inseticidas , Propoxur , Poluentes Químicos da Água , Inseticidas/análise , Inseticidas/química , Oxirredução , Propoxur/análise , Propoxur/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Purificação da ÁguaRESUMO
In the present work a new application of third-order multivariate calibration algorithms is presented, in order to quantify carbaryl, naphthol and propoxur using kinetic spectroscopic data. The time evolution of fluorescence data matrices was measured, in order to follow the alkaline hydrolysis of the pesticides mentioned above. This experimental system has the additional complexity that one of the analytes is the reaction product of another analyte, and this fact generates linear dependency problems between concentration profiles. The data were analyzed by three different methods: parallel factor analysis (PARAFAC), unfolded partial least-squares (U-PLS) and multi-dimensional partial least-squares (N-PLS); these last two methods were assisted with residual trilinearization (RTL) to model the presence of unexpected signals not included in the calibration step. The ability of the different algorithms to predict analyte concentrations was checked with validation samples. Samples with unexpected components, tiabendazole and carbendazim, were prepared and spiked water samples of a natural stream were used to check the recovered concentrations. The best results were obtained with U-PLS/RTL and N-PLS/RTL with an average of the limits of detection of 0.035 for carbaryl, 0.025 for naphthol and 0.090 for propoxur (mg L(-1)), because these two methods are more flexible regarding the structure of the data.
Assuntos
Algoritmos , Carbaril/análise , Naftóis/análise , Propoxur/análise , Espectrometria de Fluorescência/métodos , Benzimidazóis/análise , Calibragem , Carbamatos/análise , Cinética , Análise dos Mínimos Quadrados , Análise Multivariada , Praguicidas/análise , Reprodutibilidade dos Testes , Rios/química , Poluentes Químicos da Água/análiseRESUMO
The insecticide propoxur was applied as 2 non-overlapping bands approximately 1 m wide to the interior of houses in El Salvador once every 35 days for a period of 9 months. Air samples were collected from the interior of the houses once every seventh day during the entire period. In the study area, air temperatures remain relatively constant, while rainfall varies seasonally. It was found that volatilization of propoxur, as determined by the amounts detectable in air, represented release of the chemical from the treated surface and that the volatilization process was most influenced by the amount of moisture present in the air. Higher air concentrations of propoxur occurred during periods of high relative humidity than in periods of low relative humidity. The principles involved in this process and its bearing on the value of propoxur in malaria control programmes are discussed.