Ozonation of pharmaceutical compounds: Rate constants and elimination in various water matrices

The ozonation of four pharmaceuticals (metoprolol, naproxen, amoxicillin, and phenacetin) in ultra-pure (UP) water was studied in the pH range between 2.5 and 9. The experiments allowed the determination of the apparent rate constants for the reactions between ozone and the selected compounds. The values obtained varied depending on the pH, and ranged between 239 and 1.27 × 104 M−1 s−1 for metoprolol; 2.62 × 104 and 2.97 × 105 M−1 s−1 for naproxen; 2.31 × 103 and 1.21 × 107 M−1 s−1 for amoxicillin; and 215 and 1.57 × 103 M−1 s−1 for phenacetin. Due to the acidic nature of these substances, the degree of dissociation of each pharmaceutical was determined at every pH of work, and the specific rate constants of the neutral and ionic species formed were evaluated. Additionally, the simultaneous ozonation of the pharmaceuticals in different water matrices was carried out by considering a groundwater, a surface water from a public reservoir, and three secondary effluents from municipal wastewater treatment plants. The influence of the operating conditions (initial ozone dose, nature of pharmaceuticals and type of water) on the pharmaceuticals elimination efficiency was established, and a kinetic model was proposed for the evaluation of the partial contribution to the global oxidation of both, the direct ozonation reaction and the radical pathway.