Oxidation of diclofenac with chlorine dioxide in aquatic environments: influences of different nitrogenous species

Abstract

The oxidation of diclofenac (DCF), a non-steroidal anti-inflammatory drug and emerging water pollutant, with chlorine dioxide was investigated under simulated water disinfection conditions. The reaction kinetics as functions of the initial concentrations of DCF, different nitrogenous species, and different pE values were experimentally determined. The results demonstrated that DCF reacted rapidly with ClO₂, where more than 75 % of DCF (≤3.00 μM) was removed by 18.94 μM ClO₂ within 60 s. All of the reactions followed pseudo first-order kinetics with respect to DCF, and the rate constant, k _obs, exhibited a significant decrease from 4.21 × 10⁻² to 8.09 × 10⁻³ s⁻¹, as the initial DCF concentration was increased from 1.00 to 5.00 μM. Furthermore, the degradation kinetics of DCF was clearly dependent on nitrogen-containing ion concentrations in the reaction solution. Ammonium and nitrite ions inhibited the DCF degradation by ClO₂, whereas nitrate ion clearly initiated its promotion. In contrast, the inhibitory effect of NO₂ ⁻ was more robust than that of NH₄ ⁺. When the values of pE were gradually increased, the transformation of NH₄ ⁺ to NO₂ ⁻, and subsequently to NO₃ ⁻, would occur, the rate constants were initially decreased, and then increased. When NH₄ ⁺ and NO₂ ⁻ coexisted, the inhibitory effect on the DCF degradation was less than the sum of the partial inhibitory effect. However, when NO₂ ⁻ and NO₃ ⁻ coexisted, the actual inhibition rate was greater than the theoretical estimate. These results indicated that the interaction of NH₄ ⁺ and NO₂ ⁻ was antagonistic, while the coexistence of NO₂ ⁻ and NO₃ ⁻ was observed to have a synergistic effect in aqueous environments.