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A solution with 0.38 mM of the pesticide propoxur (PX) at pH 3.0 has been comparatively treated by electrochemical oxidation with electrogenerated HO (EO-HO), 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-HO process had the lowest oxidation ability due to the slow reaction of intermediates with OH produced from water discharge at the BDD anode. The EF treatment yielded quicker mineralization due to the additional OH formed between added Fe and electrogenerated HO. 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-HO, 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-HO showed similar oxidation ability within the pH range 3.0-9.0. The effect of current density and Fe and substrate contents on the performance of the EF process was examined. Two primary aromatic products were identified by LC-MS during PX degradation. [ABSTRACT FROM AUTHOR]

BACKGROUND Due to contamination of the environment by pesticides and their mishandling, there is the need for treatment of contaminated sites and correct disposal of materials containing them. Thus, studies with advanced oxidation processes are expanding and can determine the rate constant of the hydroxyl radical with organic compounds of great importance in environmental contamination. In this context, the use of laser flash photolysis has been shown to be viable for the determination of these constants. RESULTS The reaction rate constants of different pesticides with HO• in degassed acetonitrile have been determined. They were 1.6 × 109 M−1 s−1, 0.6 × 109 M−1 s−1, 1.2 × 109 M−1 s−1, 2.4 × 109 M−1 s−1 and 2.2 × 109 M−1 s−1 for the pesticides carbaryl, propoxur, fenoxycarb, ethoxysulfuron and chlorimuron-ethyl, respectively. These values are about an order of magnitude smaller than the diffusion controlled rate and correlate with the relative rates of disappearance of the pesticides in the photo-Fenton reaction in water. CONCLUSION The correlation of the relative rate constants determined by laser flash photolysis with the relative rates of photo-Fenton degradation of the pesticides is compelling evidence for the participation of the hydroxyl radical in the degradation of these pesticides in the latter system. © 2015 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

The intensive use and irregular disposal of pesticides in agriculture has caused serious environmental and health problems. In this work was evaluated the efficiency of UV and some advanced oxidation processes involving photo-Fenton reaction, O3 and O3/UV for the treatment of aqueous solutions containing commercial and standard pesticides. The results showed that the combination of UV radiation in alkaline means with O3 significantly increased the efficiency of the process of degradation and the photo-Fenton system is a promising alternative for the treatment of effluents containing pesticides. [ABSTRACT FROM AUTHOR]

CuO nanostructured thin films supported on silicon with 6.5 cm 2 area (geometric area greater than the studies reported in the literature) were synthesized by a chemical bath deposition technique. The electrodes were characterized by MEV, XRD, XPS, contact angle, cyclic voltammetry and electrochemical impedance spectroscopy analyses. To evaluate the photoelectrochemical properties of the CuO films, photocurrent-voltage measurements were performed using linear voltammetry. The catalytic activities of CuO nanostructures were evaluated by monitoring photodegradation of Mitoxantrone (MTX) under UV-A light irradiation. The method of photoelectrocatalysis (PEC), applying a voltage of 1.5 V and assisted by adding H 2 O 2 , was undertaken. To the best of our knowledge, no studies on the degradation of anticancer agents using PEC process have been found in the literature. For comparison purposes, experiments were performed under the same conditions by assisted photocatalysis (PC) with H 2 O 2 and direct photolysis. CuO deposits consist of a needle-like morphology. The presence of CuO in the tenorite phase was evidenced by XRD and the XPS spectra showed the presence of copper(II) oxide. The increase in current under illumination shows that CuO exhibits photoactivity. The PEC system showed a 75% level of MTX degradation, while the level achieved using PC was 50%. Under UV-A light alone only 3% removal was obtained after 180 min. Up to 10 by-products were identified by chromatography-mass spectrometry (LC-MS) with m/z values ranging between 521 and 285 and a plausible degradation route has been proposed. It is worth mentioning that 9 by-products identified in this work, were not found in the literature in other studies of degradation or products generated as metabolites. The toxicity tests of MTX before and after PEC treatment with Artemia Salina and Allium cepa showed a decrease in the acute toxicity of the medium as the antineoplastic was degraded., (Copyright © 2018. Published by Elsevier B.V.)

This study employed direct UV-ABC photolysis and the UV-ABC/H 2 O 2 process to investigate the degradation of tolfenamic acid (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 2 3 factorial design with added center point was used to evaluate the effect of three independent variables-namely, H 2 O 2 concentration ([H 2 O 2 ]), TA concentration ([TA]), and experiment time (time)-on TA degradation and H 2 O 2 photolysis during UV-ABC/H 2 O 2 treatment using a high-pressure mercury vapor lamp (photon flux of 2.6307 × 10 4 J s -1 ) as the UV irradiation source. The responses yielded similar values, revealing a linear behavior, with correlation coefficients R = 0.9968 and R adj = 0.9921 for TA degradation and R = 0.9828 and R adj = 0.9570 for H 2 O 2 photolysis. The most efficient combination of variables was [H 2 O 2 ] = 255 mg L -1 and [TA] = 25 mg L -1 , resulting in 100% TA degradation and 98.87% H 2 O 2 photolysis by 90 min of treatment. Additionally, the second-order kinetic constant of the reaction between TA and HO ● was determined using a competitive kinetic model, employing 2,4-dichlorophenoxyacetic acid (2,4D) as the reference compound. The kinetic constant was 1.9 × 10 10 M -1 s -1 in alkaline medium. TA degradation by direct photolysis generated quinone imines as by-products, responsible for the formation of a dark red "internal filter" that increased the value of acute toxicity to Artemia salina. The UV-ABC/H 2 O 2 process did not promote formation of quinone imines by 90 min of treatment and therefore did not increase acute toxicity values. Several by-products generated during TA degradation were identified and possible degradation pathways for the UV-ABC and UV-ABC/H 2 O 2 processes were proposed., (Copyright © 2016 Elsevier B.V. All rights reserved.)