Surrogate-Based Correlation Models in View of Real-Time Control of Ozonation of Secondary Treated Municipal WastewaterModel Development and Dynamic Validation

New robust correlation models for real-time monitoring and control of trace organic contaminant (TrOC) removal by ozonation are presented, based on UVA254 and fluorescence surrogates, and developed considering kinetic information. The abatement patterns of TrOCs had inflected shapes, controlled by the reactivity of TrOCs toward ozone and HO• radicals. These novel and generic correlation models will be of importance for WRRF operators to reduce operational costs and minimize byproduct formation. Both UVA254 and fluorescence surrogates could be used to control ΔTrOC, although fluorescence measurements indicated a slightly better reproducibility and an enlarged control range. The generic framework was validated for several WRRFs and correlations for any compound with known kinetic information could be developed solely using the second order reaction rate constant with ozone (k O3). Two distinct reaction phases were defined for which separate linear correlations were obtained. The first was mainly ozone controlled, while the second phase was more related to HO• reactions. Furthermore, parallel factor analysis of the fluorescence spectra enabled monitoring of multiple types of organic matter with different O3 and HO• reactivity. This knowledge is of value for kinetic modeling frameworks and for achieving a better understanding of the occurring changes of organic matter during ozonation.