Comparative study on heterogeneous and homogeneous catalytic ozonation efficiency in micropollutants' removal

Catalytic ozonation was applied for the removal of small concentrations (4 μM) of micropollutants benzotriazole, carbamazepine, p-CBA from aqueous solutions at pH 7. These compounds present different physicochemical characteristics and different kinetic rate constants, when reacting with ozone or hydroxyl radicals in the ranges of ,0.15-3× 105, 5.2× 109, and 8.8× 109 M-1s-1, respectively. Calcite was used as heterogeneous catalyst and its catalytic activity evaluated, by applying (and optimized) different experimental conditions (i.e., pH, temperature, ozone concentration), concerning the removal efficiency of p-CBA. Study of micropollutants' removal showed all examined organic compounds can be sufficiently removed by application of catalytic ozonation either by use of calcite, or by presence of Co(II) or Fe(II) (applied as homogeneous catalysts), while the optimum catalyst between them was found to be calcite. Carbamazepine with kO3 =3 × 105 M-1s-1 can be easily removed, even by application of single ozonation, while benzotriazole and p-CBA resulted in 50% and 68.2% higher removal after application of catalytic ozonation within 3 min of oxidation reaction, due to acceleration of hydroxyl radicals' production by presence of calcite in the ozonation system. The contribution of hydroxyl radicals in removal of all three micropollutants was evaluated by extraction of Rct and f OH parameters.