Showing papers by "F. Javier Benitez published in 2004"

Oxidation of MCPA and 2,4-d by UV Radiation, Ozone, and the Combinations UV/H2O2 and O3/H2O2

Abstract: The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).

Modeling of photooxidation of acetamide herbicides in natural waters by UV radiation and the combinations UV/H2O2 and UV/O3

Abstract: The photooxidation of several herbicides belonging to the acetamides group (specifically propachlor, metolachlor and butachlor) by means of a monochromatic UV irradiation in ultrapure water was studied. In the case of propachlor, the quantum yield for its photolysis was evaluated directly, and a value 0.127 ± 0.01 mol Eins−1 was obtained independent of the pH. The quantum yields for the photolysis of metolachlor and butachlor were determined by using a competition kinetic model which used propachlor as reference compound, and values of 0.56 ± 0.05 and 0.78 ± 0.04 mol Eins−1 were deduced respectively for metolachlor and butachlor. In a second step, the elimination of the selected herbicides in some natural and mineral waters was studied by means of several oxidation systems: UV radiation alone, and UV radiation combined with hydrogen peroxide and ozone. The influence of the operating variables in these processes (acetamide type, presence or absence of tert-butyl alcohol and types of waters) are discussed as a consequence of the amounts of herbicides removed. Two different kinetic studies were carried out for the oxidation of the herbicides: the first one for UV radiation alone and UV radiation combined with H2O2; the second one for the combination UV radiation plus ozone. In these studies, the specific rate constants were evaluated in every process. Finally, kinetic models for the prediction of the elimination of these herbicides in the natural waters selected by the different oxidation systems are proposed. The values of concentrations predicted by these models agree well with the experimental results obtained. Copyright © 2004 Society of Chemical Industry

Chemical treatment of cork-processing wastewaters for potential reuse

Abstract: The chemical treatment of cork-processing wastewater by ozonation, alone and in combination with hydrogen peroxide and UV radiation was investigated. A reduction of the chemical oxygen demand (COD) ranging from 42% to 76% was obtained during ozonation after 3 h of reaction, depending on the experimental conditions. The additional presence of hydrogen peroxide and UV radiation enhanced the efficiency of the ozonation treatment due to the contribution of the OH radicals formed in the decomposition of ozone. Thus, final reductions of the COD higher than 90% and a complete elimination of phenolic compounds and absorbance at 254 nm were achieved in both Advanced Oxidation Processes (AOPs), O3/H2O2 and O3/UV. Therefore the effluent resulting from the ozonation treatments can be reused in the cork-processing industry. In a second step, the chemical treatment was conducted by means of UV radiation alone and by the action of hydroxyl radicals, which were generated by the following AOPs: UV/H2O2, Fenton's reagent, and photo-Fenton system. The single photochemical process resulted in 9% of the organic matter present being removed, while the AOPs significantly enhanced this reduction with values in the range 20–75%. Kinetic studies for both groups of treatments were performed, and apparent kinetic rate constants were evaluated. In the ozone-based experiments, the rate constants ranged from 1846 to 10922 dm3 mol−1 O3 h−1, depending on the operating conditions. In the oxidation experiments using oxidants other than ozone, the rate constants varied between 0.06 and 1.19 h−1. Copyright © 2004 Society of Chemical Industry