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The geochemistry and strontium isotope data for Coal Creek Watershed, Colorado, consists of cation, anion, and 87Sr/87Sr isotope values from samples collected at 8 stream location along Coal Creek, samples from two groundwater springs within the watershed, and a shallow subsurface piezometer. All stream and spring samples were collected between June and October, 2021, and the shallow, near stream piezometer sample was collected in July of 2022. These data were collected to evaluate how groundwater contributions to Coal Creek originating from shallow vs deep flow paths respond seasonal drying. Understanding of groundwater-surface water interactions in montane systems in critical for the future of water availability in the Western US as groundwater contributions are expected to become more important for sustaining summer stream flows. This data package contains: (1) a csv of all cation samples; (2) a csv of all anion samples; (3) a csv of all 87Sr/87Sr isotope samples; and (4) a csv of locations for each sampling site. The dataset additionally includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata; and a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type. 

ABSTRACT Hydrologic connectivity is defined as the connection among stores of water within a watershed and controls the flux of water and solutes from the subsurface to the stream. Hydrologic connectivity is difficult to quantify because it is goverened by heterogeniety in subsurface storage and permeability and responds to seasonal changes in precipitation inputs and subsurface moisture conditions. How interannual climate variability impacts hydrologic connectivity, and thus stream flow generation and chemistry, remains unclear. Using a rare, four‐year synoptic stream chemistry dataset, we evaluated shifts in stream chemistry and stream flow source of Coal Creek, a montane, headwater tributary of the Upper Colorado River. We leveraged compositional principal component analysis and end‐member mixing to evaluate how seasonal and interannual variation in subsurface moisture conditions impacts stream chemistry. Overall, three main findings emerged from this work. First, three geochemically distinct end members were identified that constrained stream flow chemistry: reach inflows, and quick and slow flow groundwater contributions. Reach inflows were impacted by historic base and precious metal mine inputs. Bedrock fractures facilitated much of the transport of quick flow groundwater and higher‐storage subsurface features (e.g., alluvial fans) facilitated the transport of slow flow groundwater. Second, the contributions of different end members to the stream changed over the summer. In early summer, stream flow was composed of all three end members, while in late summer, it was composed predominantly of reach inflows and slow flow groundwater. Finally, we observed minimal differences in proportional composition in stream chemistry across all four years, indicating seasonal variability in subsurface moisture and spatial heterogeneity in landscape and geologic features had a greater influence than interannual climate fluctuation on hydrologic connectivity and stream water chemistry. These findings indicate that mechanisms controlling solute transport (e.g., hydrologic connectivity and flow path activation) may be resilient (i.e., able to rebound after perturbations) to predicted increases in climate variability. By establishing a framework for assessing compositional stream chemistry across variable hydrologic and subsurface moisture conditions, our study offers a method to evaluate watershed biogeochemical resilience to variations in hydrometeorological conditions. 

High elevation mountain watersheds are undergoing rapid warming and declining snow fractions worldwide, causing earlier and quicker snowmelt. Understanding how this hydrologic shift affects subsurface flow paths, biogeochemical reactions, and solute export has been challenging due to the entanglement of hydrological and biogeochemical processes. Coal Creek, a high-elevation catchment (2,700 3,700 m, 53 km2) in Colorado, is experiencing a higher rate of warming than surrounding low-lying areas. This warming corresponds with dynamic and increased responses from biogenic solutes and dissolved organic carbon (DOC), whereas the behavior of geogenic solutes and dissolved inorganic carbon (DIC) has remained relatively unchanged. DOC has experienced the largest concentration increase (>3x), with annual average flow weighted concentrations positively correlated to average annual temperature. This suggests temperature is the main driver of increasing DOC levels. Although DOC and DIC response to warming is influenced by many drivers, the relative contribution of each remains unknown. DOC and DIC were analyzed to incorporate both carbon component products of soil respiration (DOC and CO2) and to represent high solute concentrations transported by shallow (DOC) versus deep (DIC) subsurface flow. The contrasting behavior of these carbon solutes indicates climate change and warming are driving changes in organic matter decomposition and soil respiration. Modeling results from the process-based model HBV-BioRT show increased temperatures cause earlier snowmelt and streamflow generation and lower peak discharge. As stream flow generation occurs earlier, so do DOC flushing and DIC dilution events. Additionally, post-snowmelt periods show greater DOC production and concentrations under warming scenarios. Results indicated increased production of DOC in post-snowmelt periods. DOC is then flushed out by earlier snowmelt partitioned through the shallow soil zone. Most process-based studies lack a watershed-scale understanding of carbon transformation and flow path alterations. This work demonstrates complex hydrologic and biogeochemical coupling at the watershed scale to illustrate how water flow paths and chemistry are responding to a changing climate in highelevation mountain watersheds. 

Abstract Terrestrial production and export of dissolved organic and inorganic carbon (DOC and DIC) to streams depends on water flow and biogeochemical processes in and beneath soils. Yet, understanding of these processes in a rapidly changing climate is limited. Using the watershed‐scale reactive‐transport model BioRT‐HBV and stream data from a snow‐dominated catchment in the Rockies, we show deeper groundwater flow averaged about 20% of annual discharge, rising to ∼35% in drier years. DOC and DIC production and export peaked during snowmelt and wet years, driven more by hydrology than temperature. DOC was primarily produced in shallow soils (1.94 ± 1.45 gC/m²/year), stored via sorption, and flushed out during snowmelt. Some DOC was recharged to and further consumed in the deeper subsurface via respiration (−0.27 ± 0.02 gC/m²/year), therefore reducing concentrations in deeper groundwater and stream DOC concentrations at low discharge. Consequently, DOC was primarily exported from the shallow zone (1.62 ± 0.96 gC/m²/year, compared to 0.12 ± 0.02 gC/m²/year from the deeper zone). DIC was produced in both zones but at higher rates in shallow soils (1.34 ± 1.00 gC/m²/year) than in the deep subsurface (0.36 ± 0.02 gC/m²/year). Deep respiration elevated DIC concentrations in the deep zone and stream DIC concentrations at low discharge. In other words, deep respiration is responsible for the commonly‐observed increasing DOC concentrations (flushing) and decreasing DIC concentrations (dilution) with increasing discharge.  DIC export from the shallow zone was ~66% of annual export but can drop to ∼53% in drier years. Numerical experiments suggest lower carbon production and export in a warmer, drier future, and a higher proportion from deeper flow and respiration processes. These results underscore the often‐overlooked but growing importance of deeper processes in a warming climate. 

Abstract Summer streamflow predictions are critical for managing water resources; however, warming‐induced shifts from snow to rain regimes impact low‐flow predictive models. Additionally, reductions in snowpack drive earlier peak flows and lower summer flows across the western United States increasing reliance on groundwater for maintaining summer streamflow. However, it remains poorly understood how groundwater contributions vary interannually. We quantify recession limb groundwater (RLGW), defined as the proportional groundwater contribution to the stream during the period between peak stream flow and low flow, to predict summer low flows across three diverse western US watersheds. We ask (a) how do snow and rain dynamics influence interannual variations of RLGW contributions and summer low flows?; (b) which watershed attributes impact the effectiveness of RLGW as a predictor of summer low flows? Linear models reveal that RLGW is a strong predictor of low flows across all sites and drastically improves low‐flow prediction compared to snow metrics at a rain‐dominated site. Results suggest that strength of RLGW control on summer low flows may be mediated by subsurface storage. Subsurface storage can be divided into dynamic (i.e., variability saturated) and deep (i.e., permanently saturated) components, and we hypothesize that interannual variability in dynamic storage contribution to streamflow drives RLGW variability. In systems with a higher proportion of dynamic storage, RLGW is a better predictor of summer low flow because the stream is more responsive to dynamic storage contributions compared to deep‐storage‐dominated systems. Overall, including RLGW improved low‐flow prediction across diverse watersheds.