Mechanistic Considerations for the Advanced Oxidation Treatment of Fluoroquinolone Pharmaceutical Compounds using TiO2 Heterogeneous Catalysis

Pharmaceutical compounds and metabolites are being found in Surface and ground waters which is indicative of inefficient removal by conventional wastewater treatment technologies. Advanced oxidation processes (AOPs), which utilize free-radical reactions to degrade chemical contaminates, are an alternative to traditional water treatment. Three fluoroquinolone pharmaceutical compounds were studied and the absolute rate constants for hydroxyl radical (center dot OH) and hydrated electron (e(aq)(-)) are reported. For norfloxacin, levofloxacin, and lomefloxacin, the bimolecular reaction rate constants with center dot OH were determined as (6.18 +/- 0.18) x 10(9), (7.59 +/- 0.16) x 10(9) and (8.04 +/- 0.62) x 10(9) M-1 s(-1), and with e(aq)(-) were (1.18 +/- 0.10) x 10(10), (2.46 +/- 0.05) x 10(10) and (2.79 +/- 0.05) x 10(10) M-1 s(-1), respectively. To provide insights into the chemistry of destruction of these three tat-get pharmaceuticals, transient spectra were obtained for the reaction of hydroxyl radicals with the three compounds. Photocatalysis was chosen as a representative advanced oxidation technology to degrade these three fluoroquinolones and their degradation pathways were proposed. Elimination of piperazynilic ring in fluoroquinolone molecules, addition of hydroxyl radical to quinolone ring, and ipso attack at the F atoms on the aromatic ring by hydroxyl radicals occurred. These results indicate that AOPs involving production of center dot OH radicals are efficiently alternative treatment technologies for degradation of fluoroquinolones in aqueous Solution.