Mountainous watersheds are characterized by variability in functional traits, including vegetation, topography, geology, and geomorphology, which together determine nitrogen (N) retention, and release. Coal Creek and East River are two contrasting catchments within the Upper Colorado River Basin that differ markedly in total nitrate (NO3-) export. The East River has a diverse vegetation cover, sinuous floodplains, and is underlain by N-rich marine shale, resulting in a three to twelve times greater total NO3- export relative to the conifer-dominated Coal Creek. While this can partly be explained by the larger size of the East River, the distinct watershed traits of these two catchments imply different mechanisms controlling the aggregate N-export signal. A causality analysis shows biogenic and geogenic processes were critical in determining NO3- export from the East River catchment. Stable isotope ratios of NO3- (δ15NNO3 and δ18ONO3) show the East River catchment is a strong hotspot for biogeochemical processing of NO3- at the soil-saprolite interface and within the floodplain prior to export. By contrast, the conifer-dominated Coal Creek retained nearly all (~97 %) atmospherically-deposited NO3-, and its export was controlled by catchment hydrological traits (i.e., snowmelt periods and water table depth). The conservative N-cycle within Coal Creek is likely due to the abundance of conifer trees, and a smaller riparian region, retaining more NO3- overall and reduced processing prior to export. This study highlights the value of integrating isotope systematics to link watershed functional traits to mechanisms of watershed element retention and release.

Understanding the partitioning of snow and rain contributing to either catchment streamflow or evapotranspiration (ET) is of critical relevance for water management in response to climate change. To investigate this partitioning, we use endmember splitting and mixing analyses based on stable isotope (18O) data from nine headwater catchments in the East River, Colorado. Our results show that one third of the snow partitions to ET and 13% of the snowmelt sustains summer streamflow. Only 8% of the rainfall contributes to the summer streamflow, because most of the rain (67%) partitions to ET. The spatial variability of precipitation partitioning is mainly driven by aspect and tree density across the sub-catchments. Catchments with higher tree density have a higher share of snow becoming ET, resulting in less snow in summer streamflow. Summer streamflow did not contain more rain with higher rainfall sums, but more rain was taken up in ET.

Quantifying flow and transport from hillslopes is vital for understanding surface water quality, but remains obscure because of limited subsurface measurements. A recent combination of water mass balance over a single year with the transmissivity feedback model for a lower montane hillslope in the East River watershed (Colorado) left large uncertainties in transmissivities and predicted fluxes. Because snowmelt drives subsurface flow on this hillslope, improved constraints on the transmissivity profile were obtained by optimizing flux predictions over years having large differences in precipitation minus evapotranspiration. The optimized field-scale hydraulic properties combined with water table elevations predict groundwater discharges that are consistent with wide ranges of snowmelt. As snowmelt rapidly raises the water table, solutes released primarily through bedrock weathering are largely transported out of the hillslope via its highly transmissive soil. Such pulsed water and solute exports along the soil are minimized during snow drought years. Although solute concentrations generally are lower in soils relative to the underlying weathering zone, solute exports during high recharge occur predominantly via soil because of its enlarged transmissivities under snowmelt-saturated conditions. In contrast, this shallow pathway is negligible when recharge and water table elevations are low. The multiyear calibrated subsurface properties combined with updated pore water chemistry continue to show that the weathering zone is the primary source of base cations and reactive nitrogen released from the hillslope. Subsurface export predictions can now be obtained for wide ranges of snowmelt based on measurements of water table elevation and profiles of pore water chemistry.

Stable isotopes of water are important tracers in hydrologic research for understanding water partitioning between vegetation, groundwater, and runoff, but are rarely applied to large watersheds with persistent snowpack and complex topography. We combined an extensive isotope dataset with a coupled hydrologic and snow isotope fractionation model to assess mechanisms of isotopic inputs into the soil zone and implications on recharge dynamics within a large, snow-dominated watershed of the Upper Colorado River Basin. Results indicate seasonal isotopic variability and isotope lapse rates of net precipitation are the dominant control on isotopic inputs to the basin. Snowpack fractionation processes account for <5% annual isotope influx variability. Isotopic fractionation processes are most important in the shrub-dominated upper montane. Effects of isotopic fractionation are less important in the low-density conifer forests of the upper subalpine due to vegetative shading, low aridity, and a deep, persistent snowpack that buffers small sublimation losses. Melt fractionation can have sub-seasonal effects on snowmelt isotope ratios with initial snowmelt depleted but later snowmelt relatively enriched in heavy isotopes through the isotopic mass balance of the remaining snowpack, with the efficiency of isotopic exchange between ice and liquid water declining as snow ablation progresses. Hydrologic analysis indicates maximum recharge in the upper subalpine with wet years producing more isotopically depleted snowmelt (1-2‰ reduction in d18O) through reduced aridity when energy-limited. The five-year volume-weighted d18O in this zone (18.2±0.4‰) matches groundwater observations from multiple deep wells, providing evidence that the upper subalpine is a preferential recharge zone in mountain systems.

A coupled hydrologic and snowpack stable water isotope model assesses controls on isotopic inputs across a large, mountainous basin. The most depleted isotope conditions occur in the upper subalpine where snow accumulation is high and rainfall is low. Snowmelt evolution over time indicates isotopic enrichment is not dictated by melt fractionation but is determined by elevation which controls the amount, phase and isotopic mass of spring precipitation coincident with the ablation period. With respect to snowpack kinetic fractionation, its effect on snowmelt is a balance between energy and snow-availability. It is highest above treeline and in the shrub-dominated upper montane where vegetation shading is low, while deep snowpack and conifer forests limit the influence of kinetic fractionation in the subalpine. Wet years reduce the effects of snowpack fraction on snowmelt across the basin, except in the lower montane where added snowfall bolsters water-limited conditions.