Tatiana Oncescu1, Mihaela I Stefan, Petruta Oancea. 1. Department of Physical Chemistry, University of Bucharest, Bd. Regina Elisabeta, no. 4-12, 030018, Bucharest, Romania. toncesc@gw-chimie.math.unibuc.ro
Abstract
INTRODUCTION: In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO(2) 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/TiO(2) 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 O(2) gas sparged into the solution and photocatalyst concentration for a constant dichlorvos concentration (1.66 x 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 O(2) 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/TiO(2) process was proposed.
INTRODUCTION: In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO(2) 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/TiO(2) 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 O(2) gas sparged into the solution and photocatalyst concentration for a constant dichlorvos concentration (1.66 x 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 O(2) 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/TiO(2) process was proposed.