BACKGROUND: Large amounts of pharmaceutical compounds are consumed throughout the world, and after being metabolized in humans are discharged into water streams. Some of them are not completely removed in wastewater treatment plants and, as a result, they are found in some effluents as well as in surface and ground waters. RESULTS: Four pharmaceutical compounds (metoprolol, naproxen, amoxicillin and phenacetin) frequently found in wastewaters were selected to be individually photo-oxidized in ultra-pure water by monochromatic UV radiation. The influence of independent variables (pH, temperature, and additional presence of hydrogen peroxide) was established, and first-order rate constants and quantum yields evaluated. The compounds were also oxidized using Fenton's reagent and, after establishing the influence of the operating conditions (ferrous ions and hydrogen peroxide concentrations, pH and additional presence of UV radiation), the rate constants for the radical reaction between each pharmaceutical and hydroxyl radicals were determined. Finally, the simultaneous photo-oxidation of mixtures of the selected pharmaceuticals in several types of water (commercial mineral water, groundwater and reservoir water) was performed by means of UV radiation alone and by the combination UV/H2O2. The influence of the independent variables in these processes was discussed, and the kinetic study allowed the determination of various rate constants for each compound. CONCLUSION: As the pharmaceutical concentrations theoretically calculated by the proposed kinetic model agree well with the experimental results obtained, this model constitutes an excellent tool to predict the elimination of these compounds when they are present in different natural waters. (C) 2009 Society of Chemical Industry