A new methodology to assess the performance of AOPs in complex samples: Application to the degradation of phenolic compounds by O3 and O3/UV-A–Vis

A methodology combining experimental design methodology, liquid chromatography, excitation emission matrixes (EEM) and bioassays has been applied to study the performance of O3 and O3/UVA-vis in the treatment of a mixture of eight phenolic pollutants. An experimental design methodology based on Doehlert matrixes was employed to determine the effect of pH (between 3 and 12), ozone dosage (02–1.0 g/h) and initial concentration of the pollutants (1–6 mg/L each). The following conclusions were obtained: a) acidic pH and low O3 dosage resulted in an inefficient process, b) increasing pH and O3 amount produced an enhancement of the reaction, and c) interaction of basic pH and high amounts of ozone decreased the efficiency of the process. The combination of O3/UVA-vis was able to enhance ozonation in those experimental regions were this reagent was less efficient, namely low pH and low ozone dosages. The application of EEM-PARAFAC showed four components, corresponding to the parent pollutants and three different groups of reaction product and its evolution with time. Bioassays indicated important detoxification (from 100% to less than 30% after 1 min of treatment with initial pollutant concentration of 6 mg/L, pH = 9 and ozone dosage of 0.8 g/h) according to the studied methods (D. magna and P. subcapitata). Also estrogenic activity and dioxin-like behavior were significantly decreased.