The optimal dose of oxidants in UV-based advanced oxidation processes with respect to primary radical concentrations

UV-based advanced oxidation processes (AOPs) via photolysis of precursor chemical oxidants have been of interest to numerous researchers over the past several decades due to their capacity to generate highly active radical species and interesting radical chemistry. However, applications of UV-based AOPs have been commonly optimized case by case, due to the lack of theoretical investigations on process optimization, especially on oxidant doses. In this study, a simple equation for UV/H2O2 (.OH as the sole primary reactive species (PRS)) to obtain the theoretical optimal concentration (Copt-theoretical) for H2O2 was derived (Copt-theoretical = root Ab.Sc/epsilon.k). The equation was then validated for its accuracy in the calculation of Copt-theoretical for H2O2 in the UV/H2O2 AOP using a well-established comprehensive kinetic model. A competition kinetics method for the measurement of scavenging capacity (Sc, the unknown parameter for the simple equation) was designed, for which nitrobenzene was employed as the probe compound and tert-butyl alcohol was introduced as the standard compound. Based on this simple equation, we calculated the Copt-theoretical of 77 environmental water samples and introduced the concept of a practical optimal oxidants dose for the UV/H2O2 AOP, while minimizing the operation costs in engineering applications. Moreover, this study mathematically proved that the simple equation obtained from UV/H2O2 could be successfully extended to other UV-based AOPs, including UV/chlorine, UV/NH2Cl, UV/S2O82-, and UV/ peracetic acid. The simple equation of Copt-theoretical derived in this study may not only help to provide instructions for engineering applications, but also point out the ultimate treatment capability of each UV-based AOPs.

Automated summary

This study derived a simple equation for theoretical optimal concentration of H2O2 in the UV/H2O2 AOP, which was validated using a comprehensive kinetic model. The equation was applied to 77 environmental water samples, introducing the concept of practical optimal oxidant dose while minimizing operation costs. The study also showed the potential extension of the simple equation to other UV-based AOPs.