The photocatalytic degradation of a model azo-dye (Acid Orange, AO7) in aerated aqueous TiO2 dispersion has been studied under visible light (lambda > 400 nm) irradiation. The presence and role of oxidative species, such as singlet oxygen (O-1(2)), superoxide (O-2(-.)) and hydroperoxy (HO2.) radicals was examined with the use of appropriate quenchers of these species. The reaction pathway of dye degradation was also investigated by monitoring the temporal evolution of intermediates and final products on both the photocatalyst surface and in solution, with the use of a variety of techniques, including GC-MS, FTIR and UV-Vis spectroscopies. It has been found that complete decolorization of the solution may be achieved, accompanied by a substantial decrease of the chemical oxygen demand (COD) of the solution. Evidence is presented that the main oxidative species is O-2(-.) (or HO2.), while singlet oxygen, when formed, is also active. The adsorbed dye molecule is initially cleaved in the vicinity of the azo-bond and the resulting fragments are oxidized toward compounds of progressively lower molecular weight and, eventually, to CO2 and inorganic ions. However, when the solution is bleached, formation of active oxidative species does not take place, oxidation reactions cease and the concentrations of the dye intermediates remain practically stable upon further exposure to visible light irradiation. Formation of photoinduced hydrogen peroxide, which is also generated under the present conditions, also stops when the dye concentration in solution drops to very low levels. This behavior has been explained evoking the photosensitization mechanism of wide band-gap semiconductors, according to which the reaction is triggered by excitation of the dye molecule by visible light photons, followed by charge injection to the conduction band of the semiconductor and subsequent production of active oxygen radicals. Formation of the latter oxidizing species is possible only in the presence of visible light-absorbing compounds and cannot take place after fragmentation of the parent AO7 molecule in the vicinity of the azo-bond and decolorization. (C) 2003 Elsevier B.V. All fights reserved.