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Decomposition of antibiotic ornidazole by gamma irradiation in aqueous solution: kinetics and its removal mechanism.

An efficient gamma radiolytic decomposition of one of the extensively used pharmaceutical ornidazole (ORZ) was explored under different experimental conditions by varying initial concentrations, solution pHs, and doses and concentrations of inorganic ([Formula: see text]) and organic (t-BuOH) additives. The results showed that low ORZ concentrations could be efficiently decomposed using gamma irradiation. The decomposition was followed by pseudo first-order reaction kinetics with rate constant values of 2.34, 1.48, 1.11, and 0.80 kGy-1 for the following initial concentrations: 25, 50, 75, and 100 mg L-1 with their corresponding (G(-ORZ)) values of 1.004, 1.683, 2.237, and 2.273, respectively. Decomposition rate of ORZ was remarkably improved under acidic condition when compared to neutral or alkaline medium. It was also observed that the decomposition was primarily caused by the reaction of ORZ with radiolytically generated reactive HO• radicals. The addition of H2 O2 had a synergistic effect on the decomposition and mineralization extent of ORZ. However, the removal of total organic carbon (TOC) was not as effective as the decomposition of ORZ. Finally, the quantum chemical calculations were employed to optimize the geometry structure of ORZ and liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) was used to identify the decomposition intermediates. On the basis of Gaussian calculations and analysis of LC-QTOF-MS, it can be inferred that ORZ radiolytic decomposition was mainly attributed to oxidative HO• radicals and the direct cleavage of ORZ molecules. Possible pathways for ORZ decomposition using gamma irradiation in aqueous medium were proposed.

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