Occurrence and modeling of pharmaceuticals on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions

The occurrence of 73 representative pharmacologically active compounds (PhACs) was assessed in a sewage-impacted section of the Llobregat River (NE Catalonia, Spain). This Mediterranean river is characterized by flow rate fluctuations strongly influenced by seasonal rainfall. River flow variations increase the potential environmental risk posed by organic micro-pollutants as their concentrations may increase substantially under low flow conditions. Little is known about the transport behavior of emerging contaminants in surface waters once they are discharged from waste water treatment plants (WWTP) into rivers. This research aimed to study the presence and fate of emerging contaminants under different hydrological conditions by sampling two different sites along the river in different seasons. The highest levels of pharmaceuticals were determined during cold and dry periods. The impact of the flow changes on the concentration of the pharmaceuticals in the river was assessed with the relative sensitive coefficients. Due to expected dilution effects, the response of pharmaceuticals to river flow was negative. Only in a few cases, positive relationships between drug concentrations and flow were detected, suggesting an important role of other hydrological phenomena like sediment re-suspension as well as the source of pollutants. To evaluate the role of other factors influencing PhAC concentrations, a plug-flow model was applied to obtain disappearance constants “k” for a set of selected compounds. Erythromycin presented k values of − 0.15 h− 1 in both sites being the compound more efficiently removed from the water column. The k values for ibuprofen, furosemide, enrofloxacin, enalapril, acetaminophen, diclofenac and Ketoprofen were between − 0.04 and − 0.10 h− 1 showing less disappearance than erythromycin in the water column. However, other compounds presented k values < 0.06, which suggested conservative behavior of these compounds in the water column. This study supports the reliability of the calculated k values for the disappearance of compounds in river waters.

► The occurrence of pharmacological compounds in a Mediterranean river at variable hydrological conditions was studied.
► The impact of the flow changes on the concentrations was assessed using relative sensitivity coefficients.
► A plug-flow model was developed to explain the observed variations in the load of the most relevant compounds analyzed.
► The model takes into consideration the circulating flow, the average upstream emissions and an overall decay constant.