Photolytic and photocatalytic transformation of methadone in aqueous solutions under solar irradiation: kinetics, characterization of major intermediate products and toxicity evaluation.

The present manuscript describes the transformation and mineralization of methadone (MET) in aqueous solutions (demineralized water (DW) and synthetic municipal wastewater effluent (SWeff)) by natural solar irradiation and two solar photocatalytic processes: heterogeneous photocatalysis with titanium dioxide (TiO2) and homogeneous photocatalysis by photo-Fenton. Direct solar irradiation resulted in almost complete transformation of MET in the investigated matrices after 20 h of normalized irradiation time. MET photocatalytic transformation required shorter illumination times in DW compared to SWeff. Only 16 and 36 min of solar illumination were required during photo-Fenton and photocatalysis with TiO2, respectively, to transform MET completely in SWeff. Mineralization of the dissolved organic carbon took place only during photocatalytic treatments. Kinetics parameters were calculated for processes comparison. Additionally, phototransformation intermediates generated during each treatment were investigated and characterized by means of ultra-performance liquid chromatography coupled to quadrupole-time of flight tandem mass spectrometry (UPLC-QqTOF-MS/MS). The main MET phototransformation pathways were observed to be hydroxylation, and fragmentation and cyclization. According to the Vibrio fischeri bioassay, the acute toxicity of the generated phototransformation products was not relevant, since the observed inhibition percentages of bacterial bioluminescence were always below 30% after 30 min of sample contact.