Abstract
Organic micropollutants (OMPs) represent an anthropogenic stressor on stream ecosystems. In this work, we combined passive sampling with suspect and nontarget screening enabled by liquid chromatography-high-resolution mass spectrometry to characterize complex mixtures of OMPs in streams draining mixed-use watersheds. Suspect screening identified 122 unique OMPs for target quantification in polar organic chemical integrative samplers (POCIS) and grab samples collected from 20 stream sites in upstate New York over two sampling seasons. Hierarchical clustering established the co-occurrence profiles of OMPs in connection with watershed attributes indicative of anthropogenic influences. Nontarget screening leveraging the time-integrative nature of POCIS and the cross-site variability in watershed attributes prioritized and confirmed 11 additional compounds that were ubiquitously present in monitored streams. Field sampling rates for 37 OMPs that simultaneously occurred in POCIS and grab samples spanned the range of 0.02 to 0.22 L/d with a median value of 0.07 L/d. Comparative analyses of the daily average loads, cumulative exposure-activity ratios, and multi-substance potentially affected fractions supported the feasibility of complementing grab sampling with POCIS for OMP load estimation and screening-level risk assessments. Overall, this work demonstrated a multi-watershed sampling and screening approach that can be adapted to assess OMP contamination in streams across landscapes.