Suspect and non-target screening of contaminants of emerging concern in streams in agricultural watersheds

Highlights: • HRMS-based screening was applied to agricultural runoff. • 58 contaminants were identified, 36 of them confirmed with standards. • Pesticides were detected in both agricultural and non-agricultural sites. • 3 fungicides, 1 herbicide and 1 insecticide had high risk quotients (RQ > 1). Surface water runoff is an important source of water contamination affecting nearby rivers and streams. Many rural creeks are documented habitats for important aquatic species and the focus of restoration activities. In this study, we collected creek water samples in watersheds with a range of commercial-to-agricultural land use during rain events, and applied suspect and non-target screening with high-resolution mass spectrometry (HRMS) to characterize the occurrence of contaminants of emerging concern (CECs). In total, 58 CECs were identified, and 36 of them were confirmed and semi-quantified with reference standards. Pesticides were detected in all land use, including urban/commercial areas. Some pesticides were observed at concentrations of >10,000 ng/L demonstrating the strong contamination input during rain events. Five pesticides (azoxystrobin, fludioxonil, 4-hydroxy-chlorothalonil, imidacloprid, 2-methyl-4-chlorophenoxyacetic acid) were prioritized based on their risk quotients. HRMS chemical profiles demonstrated the wide range of chemical exposures in a given stream system and that compounds associated with specific land uses occur across land uses. Temporal trends suggested that some CECs remain present in creek water for months, resulting in chronic exposures across the life stages of aquatic species. These findings highlight the potential for contamination from agricultural runoff and the associated ecological risk to aquatic species.