The monitoring of micropollutants in water compartments, in particular pharmaceuticals and personal care products, has become an issue of increasing concern over the last decade. Their occurrence in surface and groundwater, raw wastewater and treated effluents, along with the removal efficiency achieved by different technologies, have been the subjects of many studies published recently. The concentrations of these contaminants may vary widely over a given time period (day, week, month, or year). In this context, this paper investigates the average concentration and removal efficiency obtained by adopting four different sampling modes: grab sampling, 24-h time proportional, flow proportional and volume proportional composite sampling. This analysis is carried out by considering three ideal micropollutants presenting different concentration curves versus time (day). It compares the percentage deviations between the ideal concentration (and removal efficiencies) and the differently measured concentrations (removal efficiencies) and provides hints as to the best sampling mode to adopt when planning a monitoring campaign depending on the substances under study. It concludes that the flow proportional composite sampling mode is, in general, the approach which leads to the most reliable measurement of concentrations and removal efficiencies even though, in specific cases, the other modes can also be correctly adopted.
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