Analysis of chemical degradation of caffeine in aqueous solution using an advanced oxidation process: Fenton's reagent and UV radiation

The present study is aimed to analyse the degradation of caffeine in water employing an advanced oxidation process, the photo-Fenton reaction (H2O2/Fe2+/UV). Different concentrations of H2O2 and Fe2+ are used to evaluate the effects of the two reagents on the quality of the water after the reaction and on the kinetics of degradation. The quality of the water is estimated in terms of conductivity, turbidity, colour and aromaticity. These quantities were found to be not dependent on H2O2 concentrations, whereas the Fe2+ concentration affects them in a proportional way. Compared to the limits of European Directives, the resulting conductivity is acceptable. Turbidity and colour exceed the limits, and the observed influence of the catalyst suggests that they are due to iron species, not to reaction products. Finally, the method employed to evaluate the aromaticity, based on absorbance at 254 nm, does not seem to be reliable. The kinetics of degradation are elaborated through measurements of the absorbance at 272 nm as a function of time. The dependence of the reaction rate on H2O2 concentration observed here is small, but even the lowest concentration employed is 16 times larger than that of caffeine. When the H2O2 concentration is kept constant, a nearly direct proportionality results between reaction rates and Fe2+ doses. Further analyses have shown that caffeine can also be degraded only under UV-visible irradiation (no reagents), but the reaction would need a very long time (6% in 45 minutes). With the addition of Fe2+ (without H2O2) the reaction rate was found somewhat higher, while with the addition of only H2O2 (without Fe2+) the photo-degradation rate was found to be 2/3 of that measured using both reagents. Therefore, the Fe2+ catalyst contributes to the degradation, but dissociation of the perossidic O-O bond of H2O2 to give OH• radicals can also be directly caused by UV irradiation.