Profiling emerging micropollutants in urban stormwater runoff using suspect and non-target screening via high-resolution mass spectrometry

Urban surface runoff contains chemicals that can negatively affect water quality. Urban runoff studies have determined the transport dynamics of many legacy pollutants. However, less attention has been paid to determining the first-flush effects (FFE) of emerging micropollutants using suspect and non-target screening (SNTS). Therefore, this study employed suspect and non-target analyses using liquid chromatography-high resolution mass spectrometry to detect emerging pollutants in urban receiving waters during stormwater events. Time-interval sampling was used to determine occurrence trends during stormwater events. Suspect screening tentatively identified 65 substances, then, their occurrence trend was grouped using correlation analysis. Non-target peaks were prioritized through hierarchical cluster analysis, focusing on the first flush-concentrated peaks. This approach revealed 38 substances using in silico identification. Simultaneously, substances identified through homologous series observation were evaluated for their observed trends in individual events using network analysis. The results of SNTS were normalized through internal standards to assess the FFE, and the most of tentatively identified substances showed observed FFE. Our findings suggested that diverse pollutants that could not be covered by target screening alone entered urban water through stormwater runoff during the first flush. This study showcases the applicability of the SNTS in evaluating the FFE of urban pollutants, offering insights for first-flush stormwater monitoring and management.