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Photocatalytic degradation of dichlorvos in aqueous TiO₂ suspensions
Introduction In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO₂ photocatalysis at pH 4 and 9, and the formation of degradation intermediates and final products under specific experimental conditions. Experimen...
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Published in: | Environmental science and pollution research international 2010-06, Vol.17 (5), p.1158-1166 |
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Main Authors: | , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Introduction In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO₂ photocatalysis at pH 4 and 9, and the formation of degradation intermediates and final products under specific experimental conditions. Experimental observations and theoretical considerations allowed us to suggest the degradation mechanism of DDVP by the UV/TiO₂ process in aqueous solution. Methods The irradiation experiments were carried out in a photoreactor using a 228-W medium-pressure Hg vapor lamp. The concentration of DDVP, phosphate ion and formaldehyde as reaction intermediate, are determined spectrophotometrically. Chloride ion concentration was measured potentiometrically. Results The photocatalytic degradation rate of dichlorvos (DDVP) under UV irradiation (360-380 nm) was optimized with respect to the flow rate of O₂ gas sparged into the solution and photocatalyst concentration for a constant dichlorvos concentration (1.66×10⁻⁴ M) at pH 4. Kinetic data were obtained at pH 4 and pH 9 for dichlorvos and the inorganic species released through its photo-induced degradation. The proposed mechanism which assumes the formation of some toxic intermediates resistant to mineralization is supported by theoretical calculations and the observed inorganic mass balances. Conclusions The calculated pseudo-first-order rate constants were dependent on the dissolved oxygen level at low O₂ flow rate, but somewhat independent on the initial pH. The decrease of pH during the irradiation suggests the formation of organic acids. The presence of organic intermediates was confirmed also by TOC measurements. A plausible reaction mechanism of DDVP degradation through the UV-A/TiO₂ process was proposed. |
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ISSN: | 0944-1344 1614-7499 |
DOI: | 10.1007/s11356-009-0292-4 |