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 (kO3). 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.

Municipal wastewater effluent characterization and variability analysis in view of an ozone dose control strategy during tertiary treatment: The status in Belgium.

Ozonation is known for removing trace organic contaminants (TrOCs) from secondary wastewater effluent. However, its implementation and overall efficiency on a broad scale depends on effluent characteristics, which can differ both in time as well as between different treatment plants (nowadays referred to as water resource recovery facilities (WRRFs)). Therefore, water quality was assessed over time at 15 different Belgian sampling locations to increase the understanding of effluent variability in view of online control of the tertiary ozonation step. Conventional and surrogate parameters as well as those specifically related to tertiary ozonation (e.g. instantaneous ozone demand) were assessed. Little differences between the different locations were found for spectral measurements (e.g. UVA254 or fluorescence). The small amount of observed outliers was clearly site or event dependent. A lower variability (for spectral measurements) is advantageous in simplifying the development and application of a generic control framework based on these spectral measurements. In addition, also variations in TrOC concentration levels seemed to be small, as the concentration of most individual compounds resided within one order of magnitude over multiple sampling events at two different WRRFs. The combination of this low variability in TrOC levels in the effluent before ozonation with a control strategy using a TrOC removal efficiency set-point, allows to indicatively assess absolute TrOC levels after ozonation. In contrast, significant variations between different plants (especially smaller sized plants) were observed and could be related to the conventional water quality parameters alkalinity (correlated with the electrical conductivity) and pH which are both known to have an influence on the ozonation process. This confirms that a differential dosing control strategy (i.e. accounting for the matrix reactivity) should be applied instead of one solely based on the (organic) effluent load before ozonation.

Dynamic validation of online applied and surrogate-based models for tertiary ozonation on pilot-scale.

New robust correlation models for ozonation, based on UVA254 and fluorescence surrogate parameters and developed considering kinetic information, have been applied at pilot-scale. This model framework is validated with the aim for operators to control the ozone dose for the removal of trace organic contaminants (TrOCs) in effluents from full-scale municipal wastewater treatment plants. The inflected correlation model between ΔTrOCs and the surrogates predicts the removal of TrOCs (based on statistical evidence) solely using the 2nd order reaction rate constant with ozone (kO3) and in a more adequate manner than similar single correlation models. This allows the use of this new model for current and future TrOCs under investigation which is highly interesting when imposed discharge limits might include more and other TrOCs in future. The use of UVA254 might be preferable at the current timing for online monitoring of TrOC abatement as the model showed a good predictive power (based on statistical evidence and visual confirmation). Reliable online sensors are more widespread (and commercially) available compared to fluorescence sensors which are still under development, with the exception of a few examples. Nevertheless, the data processing of the fluorescence signals, isolating the different intensities associated with moieties reacting similarly to ozone might even increase the predictive power, given the lower degree of interference (i.e. less scattering).

A comparative study on the efficiency of ozonation and coagulation-flocculation as pretreatment to activated carbon adsorption of biologically stabilized landfill leachate.

The present work investigates the potential of coagulation-flocculation and ozonation to pretreat biologically stabilized landfill leachate before granular activated carbon (GAC) adsorption. Both iron (III) chloride (FeCl3) and polyaluminium chloride (PACl) are investigated as coagulants. Better organic matter removal is observed when leachate was treated with FeCl3. At a dose of 1mg FeCl3/mg CODo (CODo: initial COD content), the COD and α254 removal was 66% and 88%, respectively. Dosing 1mg PACl/mg CODo resulted in 44% COD and 72% α254 removal. The settle-ability of sludge generated by PACl leveled off at 252mL/g, while a better settle-ability of 154mL/g was obtained for FeCl3 after dosing 1mg coagulant/mg CODo. For ozonation, the percentage of COD and α254 removal increased as the initial COD concentration decreased. Respectively 44% COD and 77% α254 removal was observed at 112mg COD/L compared to 5% COD and 26% α254 removal at 1846mg COD/L. Subsequent activated carbon adsorption of ozonated, coagulated and untreated leachate resulted in 77%, 53% and 8% total COD removal after treatment of 6 bed volumes. Clearly showing the benefit of treating the leachate before GAC adsorption. Mathematical modeling of the experimental GAC adsorption data with Thomas and Yoon-Nelson models show that ozonation increases the adsorption capacity and breakthrough time of GAC by a factor of 2.5 compared to coagulation-flocculation.