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Abstract Winters in snow-covered regions have warmed, likely shifting the timing and magnitude of nutrient export, leading to unquantified changes in water quality. Intermittent, seasonal, and permanent snow covers more than half of the global land surface. Warming has reduced the cold conditions that limit winter runoff and nutrient transport, while cold season snowmelt, the amount of winter precipitation falling as rain, and rain-on-snow have increased. We used existing geospatial datasets (rain-on-snow frequency overlain on nitrogen and phosphorous inventories) to identify areas of the contiguous United States (US) where water quality could be threatened by this change. Next, to illustrate the potential export impacts of these events, we examined flow and turbidity data from a large regional rain-on-snow event in the United States’ largest river basin, the Mississippi River Basin. We show that rain-on-snow, a major flood-generating mechanism for large areas of the globe (Berghuijs et al 2019 Water Resour. Res. 55 4582–93; Berghuijs et al 2016 Geophys. Res. Lett. 43 4382–90), affects 53% of the contiguous US and puts 50% of US nitrogen and phosphorus pools (43% of the contiguous US) at risk of export to groundwater and surface water. Further, the 2019 rain-on-snow event in the Mississippi River Basin demonstrates that these events could have large, cascading impacts on winter nutrient transport. We suggest that the assumption of low wintertime discharge and nutrient transport in historically snow-covered regions no longer holds. Critically, however, we lack sufficient data to accurately measure and predict these episodic and potentially large wintertime nutrient export events at regional to continental scales. 

Current understanding of the dynamic and slow flow paths that support streamflow in mountain headwater catchments is inhibited by the lack of long-term hydrogeochemical data and the frequent use of short residence time age tracers. To address this, the current study combined the traditional mean transit time and the state-of-the-art fraction of young water ( F yw ) metrics with stable water isotopes and tritium tracers to characterize the dynamic and slow flow paths at Marshall Gulch, a sub-humid headwater catchment in the Santa Catalina Mountains, Arizona, USA. The results show that F yw varied significantly with period when using sinusoidal curve fitting methods (e.g., iteratively re-weighted least squares or IRLS), but not when using the transit time distribution (TTD)-based method. Therefore, F yw estimates from TTD-based methods may be particularly useful for intercomparison of dynamic flow behavior between catchments. However, the utility of 3 H to determine F yw in deeper groundwater was limited due to both data quality and inconsistent seasonal cyclicity of the precipitation 3 H time series data. Although a Gamma-type TTD was appropriate to characterize deep groundwater, there were large uncertainties in the estimated Gamma TTD shape parameter arising from the short record length of 3 H in deep groundwater. This work demonstrates how co-application of multiple metrics and tracers can yield a more complete understanding of the dynamic and slow flow paths and observable deep groundwater storage volumes that contribute to streamflow in mountain headwater catchments. 

High‐elevation mountain catchments are often subject to large climatic and topographic gradients. Therefore, high‐density hydrogeochemical observations are needed to understand water sources to streamflow and the temporal and spatial behaviour of flow paths. These sources and flow paths vary seasonally, which dictates short‐term storage and the flux of water in the critical zone (CZ) and affect long‐term CZ evolution. This study utilizes multiyear observations of chemical compositions and water residence times from the Santa Catalina Mountains Critical Zone Observatory, Tucson, Arizona to develop and evaluate competing conceptual models of seasonal streamflow generation. These models were tested using endmember mixing analysis, baseflow recession analysis, and tritium model “ages” of various catchment water sources. A conceptual model involving four endmembers (precipitation, soil water, shallow, and deep groundwater) provided the best match to observations. On average, precipitation contributes 39–69% (55 ± 16%), soil water contributes 25–56% (41 ± 16%), shallow groundwater contributes 1–5% (3 ± 2%), and deep groundwater contributes ~0–3% (1 ± 1%) towards annual streamflow. The mixing space comprised two principal planes formed by (a) precipitation‐soil water‐deep groundwater (dry and summer monsoon season samples) and (b) precipitation‐soil water‐shallow groundwater (winter season samples). Groundwater contribution was most important during the wet winter season. During periods of high dynamic groundwater storage and increased hydrologic connectivity (i.e., spring snowmelt), stream water was more geochemically heterogeneous, that is, geochemical heterogeneity of stream water is storage‐dependent. Endmember mixing analysis and³H model age results indicate that only 1.4 ± 0.3% of the long‐term annual precipitation becomes deep CZ groundwater flux that influences long‐term deep CZ development through both intercatchment and intracatchment deep groundwater flows.

 

Catchment‐scale response functions, such as transit time distribution (TTD) and evapotranspiration time distribution (ETTD), are considered fundamental descriptors of a catchment's hydrologic and ecohydrologic responses to spatially and temporally varying precipitation inputs. Yet, estimating these functions is challenging, especially in headwater catchments where data collection is complicated by rugged terrain, or in semi‐arid or sub‐humid areas where precipitation is infrequent. Hence, we developed practical approaches for estimating both TTD and ETTD from commonly available tracer flux data in hydrologic inflows and outflows without requiring continuous observations. Using the weighted wavelet spectral analysis method of Kirchner and Neal [2013] for δ¹⁸O in precipitation and stream water, we calculated TTDs that contribute to streamflow via spatially and temporally variable flow paths in a sub‐humid mountain headwater catchment in Arizona, United States. Our results indicate that composite TTDs (a combination of Piston Flow and Gamma TTDs) most accurately represented this system for periods up to approximately 1 month, and that a Gamma TTD was most appropriate thereafter during both winter and summer seasons and for the overall time‐weighted TTD; a Gamma TTD type was applicable for all periods during the dry season. The TTD results also suggested that old waters, i.e., beyond the applicable tracer range, represented approximately 3% of subsurface contributions to streamflow. For ETTD and using δ¹⁸O as a tracer in precipitation and xylem waters, a Gamma ETTD type best matched the observations for all seasons and for the overall time‐weighted pattern, and stable water isotopes were effective tracers for the majority of vegetation source waters. This study addresses a fundamental question in mountain catchment hydrology; namely, how do the spatially and temporally varying subsurface flow paths that support catchment evapotranspiration and streamflow modulate water quantity and quality over space and time.