Widespread monitoring of chiral pharmaceuticals in urban rivers reveals stereospecific occurrence and transformation

•First study on enantiomeric occurrence of chiral drugs and metabolites in surface water in China.•NODDV and α-hydroxymetoprolol were for the first time confirmed in domestic water.•The transformation products contributed to 60% of the total load of 11 compounds.•TPs could be transported substantial distances along the river with limited attenuation.•R-venlafaxine was more readily biotransformed than the S-form. The present work aimed to discuss the enantiomeric occurrence of chiral pharmaceuticals including 5 parent compounds (PCs) metoprolol, propranolol, atenolol, venlafaxine and fluoxetine as well as 6 of their transformation products (TPs) in surface water in Beijing. Among which, 9 out of 11 were detected during the two sampling campaigns with N-O-Didesmethylvenlafaxine (NODDV) and α-hydroxymetoprolol confirmed in the catchment for the first time. Metoprolol acid (MTPA) was the most abundant up to 1508 ng L−1, followed by metoprolol and O-desmethylvenlafaxine (ODV). Most compounds showed 100% detection frequency or nearly, while norfluoxetine (the main metabolite of fluoxetine) and 4-hydroxypropranololone (one TP of propranolol) were not detected. Metoprolol (MTP) and venlafaxine (VFX) did not vary significantly between two sampling periods with mean concentrations of 280.7 and 22.9 ng L−1, respectively. Enantiomeric enrichment was observed for venlafaxine, metoprolol and NODDV, where R-venlafaxine was preferentially biotransformed than the S-form through O-desmethylation. Risk assessment indicated that fluoxetine and atenolol could pose harmful effects to aquatic organisms. This work provides enantiospecific profiles of pharmaceutically active compounds (PhACs), and extended the concept of applying the ratio of TPs vs. parent compound plus their enantiomeric traits for quantitative assessment of in situ biodegradation. Due to the considerable contribution by TPs (64% in present study) as well as the unexpected impacts from enantiomeric existence, the stereoselectivity of chiral pollutants during environmental process should be taken into account in future study. To the best of the authors’ knowledge, it is the first comprehensive evaluation of chiral pharmaceuticals and transformation products at enantiomeric level in aquatic environment in China, which would facilitate better understanding of their environmental fate.