Several groups of popular antibacterial agents (i.e., phenols, fluoroquinolones, aromatic N-oxides, and tetracyclines) were demonstrated in earlier studies to be highly susceptible to oxidation by manganese oxides, a common oxidant in soils. However, because of the high complexity, the reaction kinetics were not fully characterized. A mechanism-based kinetic model has now been developed to successfully describe the entire range of kinetic data for a total of 21 compounds of varying structural characteristics (with R2 > 0.93). The model characterizes the reaction kinetics by two independent parameters, the reaction rate constant (k) and total reactive surface sites (S(rxn)). The model fitting indicates that the reaction kinetics of antibacterials with MnO2 are controlled by either the rate of surface precursor complex formation (for tetracyclines) or by the rate of electron transfer within the precursor complex (for phenols, fluoroquinolones, and aromatic N-oxides). The effect of reactant concentration, pH, and cosolutes on the reaction kinetics was evaluated and correlated to kand S(rxn). All the trends are consistent with the proposed rate-limiting steps. This new model improves the ability to quantitatively evaluate the kinetics of oxidative transformation of organic contaminants by manganese oxides in well-defined systems.

No abstract

Complexation of tetracyclines (TCs) with dissolved Mn(II) and Cu(II) ions were found to significantly enhance the transformation of these antibiotics in the presence of oxygen at pH 8-9.5 and pH 4-6, respectively. In the TC-Mn(II)-O2 system, oxidation of the TC-complexed Mn(II) to Mn(III) by oxygen occurs, followed by oxidation of TC by Mn(III) to regenerate Mn(II). In the TC-Cu(II)-O2 system, Cu(II) oxidizes TC within the complex and the yielded Cu(I) is reoxidized by the present oxygen. Opposite reactivity trends were observed with the two metals: OTC (oxytetracycline) > TTC (tetracycline) >> iso-CTC (iso-chlorotetracycline) for the Mn(II)-mediated reaction, whereas CTC > TTC > OTC > epimers for the Cu(II)-mediated reaction. The reactivity results and examination of TC-metal ion complexation and transformation products suggest that the BCD-ring and A-ring of TC are crucial to interact with Mn(II) and Cu(II), respectively. This study highlights that the fate of TCs in aquatic environments may differ significantly by their strong interactions with different metal species present in the systems.

No abstract

No abstract