Influence of water matrix components on the UV/chlorine process and its reactions mechanism

The UV/chlorine system has become an attractive alternative Advanced Oxidation Process (AOP) for the removal of recalcitrant pollutants in the last decade due to the simultaneous formation of chlorine and hydroxyl radicals. However, there is no consensus regarding the results and trends obtained in previous micropollutant removal studies by AOPs, highlighting the complexity of the UV/chlorine process and the need for further research. This study investigates the degradation of acetaminophen (ACTP) by UV/chlorine and the effects of the water matrix in the reaction kinetics. In particular, the effects of natural organic matter (NOM), alkalinity and mineral salts on the kinetics and reactive species were elucidated. The complexity of the system was revealed by the analysis of the radical generation and transformation in different water matrices, applying the kinetic modelling approach to complement the scavenger tests. The higher kinetic rates of ACTP at alkaline pH provided new insights into the chlorine reactions under UV radiation, where secondary and tertiary reactive oxygen species including ozone were proven to play the major role in degradation. On the contrary, at acidic pH, reaction kinetic modelling demonstrated that ClO^• radical occurs at high concentrations in the order of 10^-10 M, being therefore the main oxidant, followed by other chlorine radicals. It is noteworthy that at alkaline pH the presence of typical inorganic ions such as carbonate had little impact on ACTP degradation, contrary to the observed reduction of degradation rates at acidic pH. The expected detrimental effect of the NOM in AOPs was also evidenced, although the use of chlorine as radical source reduces the relevance of the inner filter effect in comparison to UV/H₂O₂.