A Statistical Model and DFT Study of the Fragmentation Mechanisms of Metronidazole by Advanced Oxidation Processes

The degradation pathway of the antibiotic metronidazole (MNZ) in wastewater was investigated computationally with a physical statistical method and a quantum chemical approach. In both cases, density functional theory (DFT) at the M06-2X/6-311+G(d,p) level was used to calculate the structures and property parameters of all molecules. On one hand, decay of the isolated MNZ molecule excited at a given excitation energy was studied using the statistical molecular fragmentation (SMF) model. On the other hand, the reaction mechanisms of MNZ oxidized by hydroxyl radicals (^•OH) in advanced oxidation processes (AOPs) were analyzed. Both studies show that the main reaction sites in MNZ are, by decreasing importance, -NO₂, -CH₂OH, and -CH₂CH₂OH. The main degradation reactions are (i) alcohol group oxidation including the abstraction of hydrogen on C in the -CH₂OH group and oxidation of the hydroxyl group to the aldehyde and further to the carboxylic acid and (ii) addition-elimination reactions happening on the imidazole ring which finally replace the nitro by hydroxyl radicals. The results gained are in a good agreement with the available experimental data on MNZ degradation by AOPs. The structures of intermediates, transition states, and free energy surfaces are helpful in elucidating the details of the elimination mechanism, supplementing current experimental knowledge.