In this study, the degradation mechanism of 1,4-dioxane using zero-valent iron (Fe-0) in the presence of UV light was investigated kinetically. The degradation of 1,4-dioxane in Fe-0-only, photolysis, and combined Fe-0 and UV reactions followed the kinetics of a pseudo-first-order model. The degradation rate constant (19 x 10(-4) min(-1)) in the combined reaction with UV-C (4.2 mW cm (2)) and Fe-0 (5 mg L-1) was significantly enhanced compared to Fe-0-only (4.8 x 10(-4) min(-1)) and photolytic reactions (2.25 x 10(-4) min(-1)), respectively. The removal efficiency of 1,4-dioxane in combined reaction with Fe-0 and UV within 4 h was enhanced by increasing UV intensity at UV-C region (34% at 4.2 mW cm(-2) and 89% at 16.9 mW cm(-2)) comparing with the removal in the combined reaction with Fe-0 and UV-A (29% at 2.1 mW cm(-2), and 33% at 12.6 mW cm(-2)). It indicates that 1,4-dioxane was degraded mostly by OH radicals in the combined reaction. The degradation patterns in both Fe-o-only and combined reactions were well fitted to the Langmuir-Hinshelwood model, implying that adsorption as well as the chemical reaction occurred. The transformation of Fe-0 to Fe2+ and Fe3+ was observed in the Fe-0-only and combined reactions, and the transformation rate of Fe-0 was improved by UV irradiation. Furthermore, the reduction of Fe3+ was identified in the combined reaction, and the reduction rate was enhanced by an increase of UV energy. Our study demonstrated that the enhancement of 1,4-dioxane removal rate occurred via an increased supply of OH radicals from the Fenton-like reaction induced by the photolysis of Fe-0 and H2O, and with producing less sludge. (C) 2008 Elsevier Ltd. All rights reserved.