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Woody encroachment is a widespread phenomenon in grassland ecosystems, driven by overgrazing, fire suppression, nitrogen deposition and climate change, among other environmental changes. The influence of woody encroachment on processes such as chemical weathering however is poorly understood. In particular, for fast reactions such as carbonate weathering, root traits associated with woody encroachment (e.g., coarser, deeper, and longer residence times) can potentially change fluxes of inorganic carbon into streams and back to the atmosphere, providing CO2-climate feedbacks. Here we examine the influence of deepening roots arising from woody encroachment on catchment water balance and carbonate weathering rates at Konza a tallgrass prairie within a carbonate terrain where woody encroachment is suspected to drive the groundwater alkalinity upwards. We use a watershed reactive transport model BioRT-Flux-PIHM to understand the ramifications of deepening roots. Stream discharge and evapotranspiration (ET) measurements were used to calibrate the hydrology model. The subsurface CO2 concentration, water quality data for groundwater, stream, soil water and precipitation were used to constrain the soil respiration and carbonate dissolution reaction rates. The hydrology model has a Nash-Sutcliffe Efficiency value of 0.88. Modelling results from numerical experiments indicate that woody encroachment results in overall lower stream flow due to higher ET, yet the groundwater recharge is higher due to deep macropore development from deepening roots. The deeper macropores enhance carbonate weathering rate as more acidic, CO2-rich water recharges the deeper calcite bedrock. Accounting for the change in inorganic carbon fluxes caused by such land use changes gives a better estimate of carbon fluxes in the biosphere. Such knowledge is essential for effective planning of climate change mitigation strategies. 

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. 

The evasion of CO₂from inland waters, a major carbon source to the atmosphere, depends on dissolved inorganic carbon (DIC) concentrations. Our understanding of DIC dynamics across gradients of climate, geology, and vegetation conditions however have remained elusive. To understand its large‐scale patterns and drivers, we collated instantaneous and mean (multiyear average) DIC concentrations from about 100 rivers draining minimally‐impacted watersheds in the contiguous United States. Within individual sites, instantaneous concentrations (C) measured at daily to seasonal scales exhibit a near‐universal response to changes in river discharge (Q) in a negative power law form. High concentrations occur at low discharge when DIC‐enriched groundwater dominates river discharge; low concentrations occur under high flow when relatively DIC‐poor shallow soil water predominates river discharge. Such patterns echo the widely observed increase of soil CO₂and DIC with depth and the shallow‐and‐deep hypothesis that emphasizes the importance of flow paths and source water chemistry. Across sites, mean concentrations (C_m) decrease with increasing mean discharge (Q_m), a long‐term climate measure, and reachs maxima at around 200 mm/yr. A parsimonious model reveals that high mean DIC arises from soil CO₂accumulation when rates of DIC‐generating reactions are relatively high compared to its export fluxes in arid climates. Although instantaneous and mean DIC concentrations similarly decrease with increasing discharge, results here highlight their distinct drivers: daily to seasonal‐scale instantaneous concentration variations (C) are controlled by subsurface CO₂distribution over depth (from below), whereas long‐term mean concentrations (C_m) are regulated by climate (from above). The results emphasize the significance of land‐river connectivity via subsurface flow paths. They also underscore the importance of characterizing subsurface CO₂distribution to illuminate belowground processes in order to project the future of water and carbon cycles in a warming climate.