Oxidation kinetics of cyclophosphamide and methotrexate by ozone in drinking water

This study investigates the aqueous degradation by ozone of two target cytostatic drugs, cyclophosphamide and methotrexate. A column switching technique for on-line solid phase extraction (SPE) coupled to electro-spray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was used for the simultaneous detection of the trace contaminants. The second-order kinetic rate constants for the reaction of cyclophosphamide with molecular ozone and hydroxyl radicals were determined in bench-scale experiments at pH 8.10. The molecular ozone oxidation kinetics was studied in buffered ultrapure water and compared to the oxidation kinetics in natural water from a municipal drinking water treatment plant in the province of Quebec (Canada). For cyclophosphamide, the degradation rate constant with molecular ozone in ultrapure water was low (ko(3) = 3.3 +/- 0.2 M-1 s(-1)) and the extent of oxidation was linearly correlated to the ozone exposure. The impact of water quality matrix on oxidation efficacy was not significant during direct ozone reaction (ko(3) = 2.9 +/- 0.3 M-1 s(-1)). The rate constant with hydroxyl radicals was higher at 2.0 x 10(9) M-1 s(-1). Methotrexate reacted quickly with molecular ozone at dosages typically applied in drinking water treatment (ko(3) > 3.6 x 10(3) M-1 s(-1)). Overall, the results confirmed that organic compounds reactivity with ozone was dependent of their chemical structure. Ozone was very effective against methotrexate but high oxidant concentration x contact time (CT) values were required to completely remove cyclophosphamide from drinking water. Further studies should be conducted in order to identify the ozonation by-products and explore the impact of ozone on their degradation and toxicity. (C) 2010 Elsevier Ltd. All rights reserved.