Photocatalytic degradation of thiocarbamate herbicide active ingredients in water

It has been shown that a wide range of organic compounds in aqueous solutions is photocatalytically oxidized to carbon dioxide in the presence of titanium dioxide with near-UV radiation. The photocatalytic mineralization of thiocarbamate derivative pesticides (EPTC, butylate, molinate, vernolate and cycloate) in water by illuminated TiO2 has been studied. The determination of the effects of various kinetic factors on the photocatalytic degradation and the determination of the nature of the principal intermediates form part of the focus of this study. The degradation rate of these thiocarbamates in a continuous recirculation mode approximates first-order kinetics. It was demonstrated that photocatalyzed degradation of thiocarbamate active ingredients does not occur instantaneously to form carbon dioxide, but through the formation of long-lived intermediate species. Photocatalytic intermediates detected during the degradation of thiocarbamates were identified by GC/MS techniques. Intermediates detected in the photocatalytic oxidation of thiocarbamates in water solutions are in excellent agreement with products identified from the atmospherically important reactions of OH radical with thiocarbamates. Particular attention will be paid to the carbon dioxide formed from the illuminated suspension in order to demonstrate not only apparent destruction but also complete mineralization. The degradation of a two-component mixture was carried out and compared to results obtained with single-component studies.

[1]  S. McEvoy,et al.  Formation of ammonium and nitrate ions from photocatalytic oxidation of ring nitrogenous compounds over titanium dioxide , 1989 .

[2]  S. Martin,et al.  Environmental Applications of Semiconductor Photocatalysis , 1995 .

[3]  William H. Glaze,et al.  Advanced Oxidation Processes for Treating Groundwater Contaminated With TCE and PCE: Laboratory Studies , 1988 .

[4]  D. Ollis Contaminant degradation in water. , 1985, Environmental science & technology.

[5]  A. Mills,et al.  PHOTOMINERALIZATION OF 4-CHLOROPHENOL SENSITIZED BY TITANIUM-DIOXIDE - A STUDY OF THE INITIAL KINETICS OF CARBON-DIOXIDE PHOTOGENERATION , 1993 .

[6]  C. Minero,et al.  Metal Oxides as Photocatalysts for Environmental Detoxification , 1994 .

[7]  A. Vidal,et al.  Developments in solar photocatalysis for water purification. , 1998, Chemosphere.

[8]  David F. Ollis,et al.  Mixed reactant photocatalysis: Intermediates and mutual rate inhibition , 1989 .

[9]  S. Martin,et al.  Surface Structures of 4-Chlorocatechol Adsorbed on Titanium Dioxide , 1996 .

[10]  C. Yao,et al.  Rate constants for reaction of hydroxyl radicals with several drinking water contaminants , 1992 .

[11]  David F. Ollis,et al.  Photocatalytic degradation of organic water contaminants: Mechanisms involving hydroxyl radical attack , 1990 .

[12]  D. Weichgrebe,et al.  Photocatalytic detoxification with the thin-film fixed-bed reactor (TFFBR): Clean-up of highly polluted landfill effluents using a novel TiO2-photocatalyst , 1996 .

[13]  André M. Braun,et al.  Photochemical processes for water treatment , 1993 .

[14]  M. Romero,et al.  Heterogeneous photocatalysis: degradation of ethylbenzene in TiO2 aqueous suspensions , 1994 .

[15]  S. M. Aschmann,et al.  Rate constants for the gas-phase reactions of the OH radical with selected carbamates and lactates , 1996 .

[16]  S. McEvoy,et al.  Formation of nitrate and ammonium ions in titanium dioxide mediated photocatalytic degradation of organic compounds containing nitrogen atoms , 1991 .

[17]  John C. Crittenden,et al.  Photocatalytic oxidation of chlorinated hydrocarbons in water , 1997 .

[18]  S. Srijaranai,et al.  Sensitized photo-oxidations of dissolved alcohols in homogenous and heterogeneous systems Part 2. TiO2-sensitized photodehydrogenations of benzyl alcohol , 1991 .

[19]  C. Minero A rigorous kinetic approach to model primary oxidative steps of photocatalytic degradations , 1995 .

[20]  C. Minero,et al.  Photocatalytic degradation of phenol in aqueous titanium dioxide dispersions , 1988 .