Modelling natural attenuation is crucial to managing pharmaceuticals. However, little is known about the mechanism behind their in-stream sorption. To better understand the in-stream attenuation of the highly sorptive antibiotics azithromycin (AZM) and levofloxacin (LVF), we monitored them in a 2.1-km stretch of the Asano River under diverse flow conditions. This stretch receives effluent directly from a sewage treatment plant (STP), which was a dominant source of the pharmaceuticals. Average distribution coefficients between dissolved and particulate phases (Kd,SPM) in the outflow river water were 6.3×105 L/kg for AZM and 7.5×104 L/kg for LVF, while those in the STP effluent were 1-2 orders of magnitude lower. Mass balances in the river stretch calculated by considering only dissolved phase (MBw) and both dissolved and particulate phases (MBs) were 8%-52% and 58%-102%, respectively, for AZM, and 58%-71% and 60%-105% for LVF. MBw<MBs is attributed to an increase in suspended particulate matter (SPM)-mediated mass flows in the river stretch, i.e., in-stream sorption to SPM, which was caused mainly by their much higher river Kd,SPM values than those in the effluent. Their river Kd,SPM values increased on higher-flow days with decreasing effluent content in the river water, resulting in the increase of their in-stream SPM sorption. Their in-stream loss from the entire water column (i.e., 100-MBs), which was attributable to their mass transfer from the overlying water to sediment through sorption, was decreased on higher-flow days by hydrological factors. A key finding is that AZM and LVF mostly entered the river stretch in the dissolved phase of STP effluent, whereas they existed substantially in the particulate phase in the outflow river water, especially on high-flow days.
Keywords: Flow rate; Natural attenuation; Pharmaceuticals; Sediment; Suspended particulate matter.
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