Ketoprofen removal by O₃ and O₃/UV processes: kinetics, transformation products and ecotoxicity

Abstract

Ozonation (O3) and its combination with ultraviolet radiation (O3/UV) were used to decompose ketoprofen (KET). Depending on the initial KET concentration, fourteen to fifty time's faster KET degradation was achieved using combined O3/UV method compared to simple ozonation. Using both methods, formation of four major aromatic transformation products were observed: 3-(1-hydroxyethyl)benzophenone, 3-(1-hydroperoxyethyl) benzophenone, 1-(3-benzoylphenyl) ethanone and 3-ethylbenzophenone. In the combined treatment the degradation was mainly due to the direct effect of UV light, however, towards the end of the treatment, O3 highly contributed to the mineralization of small carboxylic acids. High (~90%) mineralization degree was achieved using the O3/UV method. Toxicity tests performed using representatives of three trophic levels of the aquatic ecosystems (producers, consumers and decomposers) Pseudokirchneriella subcapitata green algae, Daphnia magna zooplanktons and Vibrio fischeri bacteria showed that under the used experimental conditions the transformation products have significantly higher toxicity towards all the test organisms, than KET itself. The bacteria and the zooplanktons showed higher tolerance to the formed products than algae. The measured toxicity correlates well with the concentration of the aromatic transformation products, therefore longer treatments than needed for complete degradation of KET are strongly suggested, in order to avoid possible impact of aromatic transformation products on the aquatic ecosystem.

Keywords: AOP; AOPs; COD; DOC; Daphnia magna; EC50; HPLC; KET; Ketoprofen; MS; NSAID; Ozonation; PNEC; PPCP; Predicted No Effect Concentration; Pseudokirchneriella subcapitata; STP; Sewage Treatment Plant; TOC; Total Organic Carbon; UV; VUV; Vibrio fischeri; Vis; advanced oxidation processes; chemical oxygen demand; dissolved organic carbon; effective concentration for 50% inhibition; high-performance liquid chromatography; ketoprofen; mass spectrometry; non-steroidal anti-inflammatory drug; pharmaceuticals and personal care products; ultraviolet; vacuum-ultraviolet; visible.