Xenobiotic removal efficiencies in wastewater treatment plants: Residence time distributions as a guiding principle for sampling strategies

The effect of mixing regimes and residence time distribution (RTD) on solute transport in wastewater treatment plants (WWTPs) is well understood in environmental engineering. Nevertheless, it is frequently neglected in sampling design and data analysis for the investigation of polar xenobiotic removal efficiencies in WWTPs. Most studies on the latter use 24-h composite samples in influent and effluent. The effluent sampling period is often shifted by the mean hydraulic retention time assuming that this allows a total coverage of the influent load. However, this assumption disregards mixing regime characteristics as well as flow and concentration variability in evaluating xenobiotic removal performances and may consequently lead to biased estimates or even negative elimination efficiencies. The present study aims at developing a modeling approach to estimate xenobiotic removal efficiencies from monitoring data taking the hydraulic RTD in WWTPs into consideration. For this purpose, completely mixed tanks-in-series were applied to address hydraulic mixing regimes in a Luxembourg WWTP. Hydraulic calibration for this WWTP was performed using wastewater conductivity as a tracer. The RTD mixing approach was coupled with first-order biodegradation kinetics for xenobiotics covering three classes of biodegradability during aerobic treatment. Model simulations showed that a daily influent load is distributed over more than one day in the effluent. A 24-h sampling period with an optimal time offset between influent and effluent covers less than the half of the influent load in a dry weather scenario. According to RTD calculations, an optimized sampling strategy covering four consecutive measuring days in the influent would be necessary to estimate the full-scale elimination efficiencies with sufficient accuracy. Daily variations of influent flow and concentrations can substantially affect the reliability of these sampling results. Commonly reported negative removal efficiencies for xenobiotics might therefore be a consequence of biased sampling schemes. In this regard, the present study aims at contributing to bridge the gap between environmental chemistry and engineering practices.