Rivers host a myriad of invisible chemical solutes that define the baseline quality of life-sustaining flowing waters. River chemistry reflects the response of Earth's Critical Zone, the zone from the tree top to the bottom of groundwater, to external climate forcing and human perturbations (Brantley et al., 2017). River water originates from precipitation, most of which infiltrates and flows via subsurface and river corridors (Figure 1). Along its journey, water mobilizes solutes by interacting with roots, microbes, soils, sediments, and rocks. As it eventually exits at river outlets, it carries the chemical signature of its interactions along its flow paths, and reflect the relative magnitude of biogeochemical reactions that produce solutes and export processes that transport solutes (Li et al., 2021).River chemistry is essential in regulating carbon-climate feedbacks, water quality, and aquatic ecosystem health. Solutes such as dissolved organic and inorganic carbon (DOC and DIC) and nutrients readily transform in rivers and emit greenhouse gases including CO 2 , N 2 O, and CH 4 (

High-elevation mountain regions, central to global freshwater supply, are experiencing more rapid warming than low-elevation locations. High-elevation streams are therefore potentially critical indicators for earth system and water chemistry response to warming. Here we present concerted hydroclimatic and biogeochemical data from Coal Creek, Colorado in the central Rocky Mountains at elevations of 2700 to 3700 m, where air temperatures have increased by about 2 °C since 1980. We analyzed water chemistry every other day from 2016 to 2019. Water chemistry data indicate distinct responses of different solutes to inter-annual hydroclimatic variations. Specifically, the concentrations of solutes from rock weathering are stable inter-annually. Solutes that are active in soils, including dissolved organic carbon, vary dramatically, with double to triple peak concentrations occurring during snowmelt and in warm years. We advocate for consistent and persistent monitoring of high elevation streams to record early glimpse of earth surface response to warming.

Abstract. Watersheds are the fundamental Earth surface functioning units that connect the land to aquatic systems. Many watershed-scale models represent hydrological processes but not biogeochemical reactive transport processes. This has limited our capability to understand and predict solute export, water chemistry and quality, and Earth system response to changing climate and anthropogenic conditions. Here we present a recently developed BioRT-Flux-PIHM (BioRT hereafter) v1.0, a watershed-scale biogeochemical reactive transport model. The model augments the previously developed RT-Flux-PIHM that integrates land-surface interactions, surface hydrology, and abiotic geochemical reactions. It enables the simulation of (1) shallow and deep-water partitioning to represent surface runoff, shallow soil water, and deeper groundwater and of (2) biotic processes including plant uptake, soil respiration, and nutrient transformation. The reactive transport part of the code has been verified against the widely used reactive transport code CrunchTope. BioRT-Flux-PIHM v1.0 has recently been applied in multiple watersheds under diverse climate, vegetation, and geological conditions. This paper briefly introduces the governing equations and model structure with a focus on new aspects of the model. It also showcases one hydrology example that simulates shallow and deep-water interactions and two biogeochemical examples relevant to nitrate and dissolved organic carbon (DOC). These examples are illustrated in two simulation modes of complexity. One is the spatially lumped mode (i.e., two land cells connected by one river segment) that focuses on processes and average behavior of a watershed. Another is the spatially distributed mode (i.e., hundreds of cells) that includes details of topography, land cover, and soil properties. Whereas the spatially lumped mode represents averaged properties and processes and temporal variations, the spatially distributed mode can be used to understand the impacts of spatial structure and identify hot spots of biogeochemical reactions. The model can be used to mechanistically understand coupled hydrological and biogeochemical processes under gradients of climate, vegetation, geology, and land use conditions.

Warming in mountains is known to intensify aridity and threaten water availability globally. Its impacts on water quality, however, have remained poorly understood. Here we collate long-term (multi-year to decadal mean), baseline stream concentrations and fluxes of dissolved organic and inorganic carbon, two essential indicators of water quality and soil carbon response to warming, across more than 100 streams in the United States Rocky Mountains. Results show a universal pattern of higher mean concentrations in more arid mountain streams with lower mean discharge, a long-term climate measure. A watershed reactor model revealed less lateral export of dissolved carbon (via less water flow) out of the watersheds in more arid sites, leading to more accumulation and higher concentrations. Lower concentrations typically occur in cold, steep, and compact mountains with higher snow fraction and lower vegetation cover, which generally have higher discharge and carbon fluxes. Inferring from a space-for-time perspective, the results indicate that as warming intensifies, lateral fluxes of dissolved carbon will decrease but concentrations will increase in these mountain streams. This indicates deteriorating water quality and potentially elevated CO2 emission directly from the land (instead of streams) in the Rockies and other mountain areas in the future climate.

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