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AbstractCritical zone influences on hydrologic partitioning, subsurface flow paths and reactions along these flow paths dictate the timing and magnitude of groundwater and solute flux to streams. To isolate first‐order controls on seasonal streamflow generation within highly heterogeneous, snow‐dominated basins of the Colorado River, we employ a multivariate statistical approach of end‐member mixing analysis using a suite of daily chemical and isotopic observations. Mixing models are developed across 11 nested basins (0.4 to 85 km2) spanning a gradient of climatological, physical, and geological characteristics. Hydrograph separation using rain, snow, and groundwater as end‐members indicates that seasonal contributions of groundwater to streams is significant. Mean annual groundwater flux ranges from 12% to 33% whereas maximum groundwater contributions of 17% to 50% occur during baseflow. The direct relationship between snow water equivalent and groundwater flux to streams is scale dependent with a trend toward self‐similarity when basins exceed 5.5 km2. We find groundwater recharge increases in basins of high relief and within the upper subalpine where maximum snow accumulation is coincident with reduced conifer cover and lower canopy densities. The mixing model developed for the furthest downstream site did not transfer to upstream basins. The resulting error in predicted stream concentrations points toward weathering reactions as a function of source rock and seasonal shifts in flow path. Additionally, the potential for microbial sulfate reduction in floodplain sediments along a low‐gradient, meandering portion of the river is sufficient to modify hillslope contributions and alter mixing ratios in the analysis. Soil flushing in response to snowmelt is not included as an end‐member but is identified as an important mechanism for release of solutes from these mountainous watersheds. End‐member mixing analysis used in combination with high‐frequency observations reveals important aspects of catchment hydrodynamics across scale.
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