Advanced Oxidation Processes (AOPs) promoted by ultraviolet light are innovative and potentially cost-effective solutions for treating persistent pollutants recalcitrant to conventional water and wastewater treatment. While several studies have been performed during the past decade to improve the fundamental understanding of the UV-H(2)O(2) AOP and its kinetic modeling, Computational Fluid Dynamics (CFD) has only recently emerged as a powerful tool that allows a deeper understanding of complex photochemical processes in environmental and reactor engineering applications. In this paper, a comprehensive kinetic model of UV-H(2)O(2) AOP was coupled with the Reynolds averaged Navier-Stokes (RANS) equations using CFD to predict the oxidation of tributyl phosphate (TBP) and tri(2-chloroethtyl) phosphate (TCEP) in two different photoreactors: a parallel- and a cross-flow UV device employing a UV lamp emitting primarily 253.7 nm radiation. CFD simulations, obtained for both turbulent and laminar flow regimes and compared with experimental data over a wide range of UV doses, enabled the spatial visualization of hydrogen peroxide and hydroxyl radical distributions in the photoreactor. The annular photoreactor displayed consistently better oxidation performance than the cross-flow system due to the absence of recirculation zones, as confirmed by the hydroxyl radical dose distributions. Notably, such discrepancy was found to be strongly dependent on and directly correlated with the hydroxyl radical rate constant becoming relevant for conditions approaching diffusion-controlled reaction regimes (k(C,OH) > 10(9) M(-1) s(-1)).

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