Post-treatment of real municipal wastewater effluents by means of granular activated carbon (GAC) based catalytic processes: A focus on abatement of pharmaceutically active compounds.

Pharmaceutically active compounds (PhACs) widely present in urban wastewater effluents pose a threat to ecosystems in the receiving aquatic environment. In this work, efficiency of granular activated carbon (GAC) - based catalytic processes, namely catalytic wet peroxide oxidation (CWPO), peroxymonosulfate oxidation (PMS/GAC) and peroxydisulfate oxidation (PDS/GAC) at ambient temperature and pressure were studied for removal of 22 PhACs (ng L level) that were present in secondary effluents of real urban wastewater. Concentrations of PhACs were measured using Ultra Performance Liquid Chromatography - Triple Quadrupole Mass Spectrometry (UPLC-QqQ-MS/MS). Catalytic experiments were conducted in discontinuous mode using up-flow fixed bed reactors with granular activated carbon (GAC) as a catalyst. The catalyst was characterized by means of N adsorption-desorption isotherm, mercury intrusion porosimetry (MIP), elemental analysis, X-ray fluorescence spectroscopy (WDXRF), X-ray diffraction (XRD), thermal gravimetry and differential temperature analyses coupled mass spectrometry (TGA-DTA-MS). Results indicate that the highest efficiency in terms of TOC removal was achieved during CWPO performed at optimal operational conditions (stoichiometric dose of HO; TOC removal ~ 82%) followed by PMS/GAC (initial PMS concentration 100 mg L; TOC removal ~73.7%) and PDS/GAC (initial PDS concentration 100 mg L; TOC removal ~ 67.9%) after 5 min of contact time. Full consumption of oxidants was observed in all cases for CWPO and PDS/GAC at contact times of 2.5 min, while for PMS/GAC it was 1.5 min. In general, for 18 out of 22 target PhACs, very high removal efficiencies (> 92%) were achieved in all tested processes (including adsorption) performed at optimal operational conditions during 5 min of contact time. However, moderate (40 - 70%) and poor (< 40%) removal efficiencies were achieved for salicylic acid, ofloxacin, norfloxacin and ciprofloxacin, which can be possibly attributed to insufficient contact time. Despite high efficiency of all studied processes for PhACs elimination from urban wastewater effluent, CWPO seems to be more promising for continuous operation.