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Sodium chloride has long been used for winter deicing, although its legacy use has resulted in rising chloride concentrations in urban watersheds. Persistently high chloride levels impair drinking water resources and threaten the health of aquatic life and vegetation. In urban areas, chloride fate and transport is impacted by human modification of the environment, including increased impervious surface cover and disconnection of stream corridors from riparian groundwater. We couple continuous streamflow records with weekly chloride concentration data over two water years to create continuous chloride load estimates at three locations along a degraded, urban stream in upstate New York with contrasting channelized and intact reaches. Our results show that degraded reaches characterized by channelized, armored banks and minimal groundwater connection deliver chloride loads closer to chloride application rates in the surrounding watershed. In contrast, stream–groundwater interactions in intact reaches adjacent to riparian floodplains, including surface water losses to subsurface flow paths, result in stream chloride loads that are 50% less than those delivered from upstream channelized reaches. These findings show that longitudinal chloride load estimates along a stream channel can be valuable in identifying the timing and magnitude of chloride sources and sinks, which may be common but less apparent in urban environments.

Urbanization negatively impacts water quality in streams by reducing stream‐groundwater interactions, which can reduce a stream's capacity to naturally attenuate nitrate. Meadowbrook Creek, a first order urban stream in Syracuse, New York, has an inverse urbanization gradient, with heavily urbanized headwaters that are disconnected from the floodplain and downstream reaches that have intact riparian floodplains and connection to riparian aquifers. This system allows assessment of how stream‐groundwater interactions in urban streams impact the net sources and sinks of nitrate at the reach scale. We used continuous (15‐min) streamflow measurements and weekly grab samples at three gauging stations positioned longitudinally along the creek to develop continuous nitrate load estimates at the inlet and outlet of two contrasting reaches. Nitrate load estimates were determined using a USGS linear regression model, RLOADEST, and differences between loads at the inlet and outlet of contrasting reaches were used to quantify nitrate sink and source behaviour year‐round. We observed a nitrate load of 1.4 × 10⁴ kg NO₃⁻per water year, on average, at the outlet of the urbanized reach while the nitrate load at the outlet of the downstream, connected reach was 1.0 × 10⁴ kg NO₃⁻per water year, on average. We found the more heavily urbanized, hydrologically‐disconnected reach was a net source of nitrate regardless of season. In contrast, stream‐groundwater exchange caused the hydrologically connected reach to be both a source and sink for nitrate, depending on time of year. Both reaches alter nitrate source and sink behaviour at various spatiotemporal scales. Groundwater connection in the downstream, connected reach reduces annual nitrate loads and provides more opportunities for sources and sinks of nitrate year‐round than the hydrologically disconnected stream reach. Mechanisms include groundwater discharge into the stream with variable nitrate concentrations, surface‐water groundwater interactions that foster denitrification, and stream load loss to surrounding near‐stream aquifers. This study emphasizes how loads are important in understanding how stream‐groundwater interactions impact reach scale nitrate export in urban streams.

Although stream temperature energy balance models are useful to predict temperature through time and space, a major unresolved question is whether fluctuations in stream discharge reduce model accuracy when not exactly represented. However, high‐frequency (e.g., subdaily) discharge observations are often unavailable for such simulations, and therefore, diurnal streamflow fluctuations are not typically represented in energy balance models. These fluctuations are common due to evapotranspiration, snow pack or glacial melt, tidal influences within estuaries, and regulated river flows. In this work, we show when to account for diurnally fluctuating streamflow. To investigate how diurnal streamflow fluctuations affect predicted stream temperatures, we used a deterministic stream temperature model to simulate stream temperature along a reach in the Quilcayhuanca Valley, Peru, where discharge varies diurnally due to glacial melt. Diurnally fluctuating streamflow was varied alongside groundwater contributions via a series of computational experiments to assess how uncertainty in reach hydrology may impact simulated stream temperature. Results indicated that stream temperatures were more sensitive to the rate of groundwater inflow to the reach compared with the timing and amplitude of diurnal fluctuations in streamflow. Although incorporating observed diurnal fluctuations in discharge resulted in a small improvement in model RMSE, we also assessed other diurnal discharge signals and found that high amplitude signals were more influential on modelled stream temperatures when the discharge peaked at specific times. Results also showed that regardless of the diurnal discharge signal, the estimated groundwater flux to the reach only varied from 1.7% to 11.7% of the upstream discharge. However, diurnal discharge fluctuations likely have a stronger influence over longer reaches and in streams where the daily range in discharge is larger, indicating that diurnal fluctuations in stream discharge should be considered in certain settings.

A myriad of downstream communities and industries rely on streams fed by both groundwater discharge and glacier meltwater draining the Cordillera Blanca, Northern Peruvian Andes, which contains the highest density of glaciers in the tropics. During the dry season, approximately half the discharge in the region's proglacial streams comes from groundwater. However, because of the remote and difficult access to the region, there are few field methods that are effective at the reach scale to identify the spatial distribution of groundwater discharge. An energy balance model, Rhodamine WT dye tracing, and high‐definition kite‐borne imagery were used to determine gross and net groundwater inputs to a 4‐km reach of the Quilcay River in Huascaran National Park, Peru. The HFLUX computer programme (http://hydrology.syr.edu/hflux.html) was used to simulate the Quilcay River's energy balance using stream temperature observations, meteorological measurements, and kite‐borne areal photography. Inference from the model indicates 29% of stream discharge at the reach outlet was contributed by groundwater discharge over the study section. Rhodamine WT dye tracing results, coupled with the energy balance, show that approximately 49% of stream water is exchanged (no net gain) with the subsurface as gross gains and losses. The results suggest that gross gains from groundwater are largest in a moraine subreach but because of large gross losses, net gains are larger in the meadow subreaches. These insights into pathways of groundwater–surface water interaction can be applied to improve hydrological modelling in proglacial catchments throughout South America. Copyright © 2016 John Wiley & Sons, Ltd.