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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 Understanding soil organic carbon (SOC) response to global change has been hindered by an inability to map SOC at horizon scales relevant to coupled hydrologic and biogeochemical processes. Standard SOC measurements rely on homogenized samples taken from distinct depth intervals. Such sampling prevents an examination of fine‐scale SOC distribution within a soil horizon. Visible near‐infrared hyperspectral imaging (HSI) has been applied to intact monoliths and split cores surfaces to overcome this limitation. However, the roughness of these surfaces can influence HSI spectra by scattering reflected light in different directions posing challenges to fine‐scale SOC mapping. Here, we examine the influence of prescribed surface orientation on reflected spectra, develop a method for correcting topographic effects, and calibrate a partial least squares regression (PLSR) model for SOC prediction. Two empirical models that account for surface slope, aspect, and wavelength and two theoretical models that account for the geometry of the spectrometer were compared using 681 homogenized soil samples from across the United States that were packed into sample wells and presented to the spectrometer at 91 orientations. The empirical approach outperformed the more complex geometric models in correcting spectra taken at non‐flat configurations. Topographically corrected spectra reduced bias and error in SOC predicted by PLSR, particularly at slope angles greater than 30°. Our approach clears the way for investigating the spatial distributions of multiple soil properties on rough intact soil samples. 

Abstract. Carbonate weathering is essential in regulating atmosphericCO2 and carbon cycle at the century timescale. Plant roots accelerateweathering by elevating soil CO2 via respiration. It however remainspoorly understood how and how much rooting characteristics (e.g., depth anddensity distribution) modify flow paths and weathering. We address thisknowledge gap using field data from and reactive transport numericalexperiments at the Konza Prairie Biological Station (Konza), Kansas (USA), asite where woody encroachment into grasslands is surmised to deepen roots. Results indicate that deepening roots can enhance weathering in two ways.First, deepening roots can control thermodynamic limits of carbonatedissolution by regulating how much CO2 transports vertical downward tothe deeper carbonate-rich zone. The base-case data and model from Konzareveal that concentrations of Ca and dissolved inorganic carbon (DIC) areregulated by soil pCO2 driven by the seasonal soil respiration. Thisrelationship can be encapsulated in equations derived in this workdescribing the dependence of Ca and DIC on temperature and soil CO2. The relationship can explain spring water Ca and DIC concentrations from multiple carbonate-dominated catchments. Second, numericalexperiments show that roots control weathering rates by regulating recharge(or vertical water fluxes) into the deeper carbonate zone and exportreaction products at dissolution equilibrium. The numerical experimentsexplored the potential effects of partitioning 40 % of infiltrated waterto depth in woodlands compared to 5 % in grasslands. Soil CO2 datasuggest relatively similar soil CO2distribution over depth, which in woodlands and grasslands leads only to 1 % to∼ 12 % difference inweathering rates if flow partitioning was kept the same between the two landcovers. In contrast, deepening roots can enhance weathering by ∼ 17 % to200 % as infiltration rates increased from 3.7 × 10−2 to 3.7 m/a. Weathering rates in these cases however are more than an order of magnitude higher than a case without roots atall, underscoring the essential role of roots in general. Numericalexperiments also indicate that weathering fronts in woodlands propagated> 2 times deeper compared to grasslands after 300 years at aninfiltration rate of 0.37 m/a. These differences in weathering fronts areultimately caused by the differences in the contact times of CO2-charged water with carbonate in the deep subsurface. Within the limitation of modeling exercises, these data and numerical experiments prompt the hypothesis that (1) deepening roots in woodlands can enhance carbonate weathering by promotingrecharge and CO2–carbonate contact in the deepsubsurface and (2) the hydrological impacts of rooting characteristics canbe more influential than those of soil CO2 distribution in modulatingweathering rates. We call for colocated characterizations of roots,subsurface structure, and soil CO2 levels, as well as their linkage to waterand water chemistry. These measurements will be essential to illuminatefeedback mechanisms of land cover changes, chemical weathering, globalcarbon cycle, and climate.