Study on the photocatalytic degradation of metronidazole antibiotic in aqueous media with TiO2 under lab and pilot scale

Abstract

Nowadays, the increased consumption of antibiotics, such as metronidazole (MTZ), leads to their introduction in wastewater as well as in the receiving surface waters due to their incomplete removal by conventional wastewater treatment plants. Heterogeneous photocatalysis is a versatile technology that can efficiently degrade such organic contaminants. In the present research, the photocatalytic degradation of MTZ with TiO₂ P25 was studied under lab and pilot (CPC reactor) conditions. The antibiotic was efficiently removed at high rates in both cases (100 % and 91 %) following pseudo-first order kinetics with rate constants equal to 0.0452 min^-1 (±RSD% = 0.68 % - 2.57 %) and 0.0462 L KJ^-1 (±RSD% = 8.94 % - 21.64 %) respectively. Also, by scavenging lab scale experiments, the contribution of the generated reactive species was investigated and hydroxy radicals (HO^•) were proposed as the predominant species. By applying high resolution mass spectrometry techniques, the transformation products (TPs) were identified and possible transformation pathways were proposed. The ecotoxicity of the TPs was assessed in silico using the ECOSAR software with the results revealing that most of them were less toxic than the parent compound. Similarly, the mutagenicity, developmental toxicity and bioconcentration factors of the TPs were predicted by utilizing the T.E.S.T. software and in their majority, were found to be less mutagenic and developmentally toxic than MTZ. The ecotoxicity monitoring with the Vibrio fischeri bioassay in both laboratory and pilot scale experiments indicated that through heterogeneous photocatalysis it is possible to reduce the toxicity of wastewater containing MTZ. Finally, the stability and reusability of the photocatalyst was investigated through three consecutive catalytic cycles with the results showing that the performance of TiO₂ decreased after each use. For the heterogeneous photocatalysis with TiO₂ to be a "real life" applicable technique, further studies focusing on catalyst regeneration and optimization of the catalytic conditions must be conducted.

Keywords: AOPs; CPC reactor; Pilot plant; TiO(2); Toxicity assessment; Transformation products.