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.

As weather and climate extremes continue to set new records (WMO, 2017), it is becoming increasingly important to study the effects of these extremes on hydrologic cycles (Bates et al., 2008) as well as our ability to simulate these changes within hydrologic models (Nijssen et al., 2001; Xu, 1999). In the United States, Cal-Abstract Climate change impacts on hydroclimatology are becoming increasingly apparent around the world. It is unknown how annual variations in precipitation and air temperature alter the modelinferred importance of hydrological processes and how this varies across watersheds. To examine this, we used parsimonious rainfall-runoff model and applied time-varying sensitivity analysis across 30 Californian watersheds for a 33-year period (1981-2014). We calculated annual total order sensitivity indices for five performance metrics: Kling-Gupta Efficiency (KGE) and model error in simulating hydrologic signatures (runoff ratio, slope of flow duration curve, baseflow index, and timing of streamflow centroid). Sensitivity of hydrological signatures to the parameters differed by signature, while parameter importance with respect to KGE was much more spatially and temporally variable. Variations in parameter sensitivity with respect to KGE were either correlated with air temperature (snow-dominated sites in the Sierra Nevada) or precipitation (lower elevation sites < 1,300 m). Across error metrics and signatures, parameter sensitivity strongly differed between wet and dry years for a subset of our study sites. While parameter importance varied through time, parameter sensitivity variations across watersheds were much more pronounced. This suggests that parameter controls on model performance are much more a reflection of watershed properties as opposed to being dominantly shaped by shifts in precipitation and air temperature. These findings emphasize the importance of understanding simulated watershed responses to fluctuating annual conditions, as this conceptual knowledge is necessary to anticipate similarities and differences in response across even relatively proximal watersheds in the face of growing extreme conditions. Plain Language Summary Computer models are useful tools that can be used to analyze what inputs matter most to ensuring that model output is similar to observed conditions. In order to understand how very wet years versus very dry years impact which model inputs (called parameters) are most important to matching good predictions, we simulated streamflow using a simple mathematical model many thousands of times. We used these outputs to determine how variations in predictions of streamflow (output from the model) are related to variations in model parameters, to identify which parameters are most important for ensuring reasonable model predictions. We focused on watersheds that are close together, but that may experience different average conditions and interannual variability. We found that which parameters are important varied across different watersheds and also varied with total a...

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