Oxidation processes and me.

This publication summarizes my journey in the field of chemical oxidation processes for water treatment over the last 30+ years. Initially, the efficiency of the application of chemical oxidants for micropollutant abatement was assessed by the abatement of the target compounds only. This is controlled by reaction kinetics and therefore, second-order rate constant for these reactions are the pre-requisite to assess the efficiency and feasibility of such processes. Due to the tremendous efforts in this area, we currently have a good experimental data base for second-order rate constants for many chemical oxidants, including radicals. Based on this, predictions can be made for compounds without experimental data with Quantitative Structure Activity Relationships with Hammet/Taft constants or energies of highest occupied molecular orbitals from quantum chemical computations. Chemical oxidation in water treatment has to be economically feasible and therefore, the extent of transformation of micropollutants is often limited and mineralization of target compounds cannot be achieved under realistic conditions. The formation of transformation products from the reactions of the target compounds with chemical oxidants is inherent to oxidation processes and the following questions have evolved over the years: Are the formed transformation products biologically less active than the target compounds? Is there a new toxicity associated with transformation products? Are transformation products more biodegradable than the corresponding target compounds? In addition to the positive effects on water quality related to abatement of micropollutants, chemical oxidants react mainly with water matrix components such as the dissolved organic matter (DOM), bromide and iodide. As a matter of fact, the fraction of oxidants consumed by the DOM is typically > 99%, which makes such processes inherently inefficient. The consequences are loss of oxidation capacity and the formation of organic and inorganic disinfection byproducts also involving bromide and iodide, which can be oxidized to reactive bromine and iodine with their ensuing reactions with DOM. Overall, it has turned out in the last three decades, that chemical oxidation processes are complex to understand and to manage. However, the tremendous research efforts have led to a good understanding of the underlying processes and allow a widespread and optimized application of such processes in water treatment practice such as drinking water, municipal and industrial wastewater and water reuse systems.