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The carbon dioxide (CO2) fluxes from headwater streams are not well quantified and could be a source of significant carbon, particularly in systems underlain by carbonate lithology. Also, the sensitivity of carbonate systems to changes in temperature will make these fluxes even more significant as climate changes. This study quantifies small-scale CO2 efflux and estimates annual CO2 emission from a headwater stream at the Konza Prairie Long-Term Ecological Research Site and Biological Station (Konza), in a complex terrain of horizontal, alternating limestones and shales with small-scale karst features. CO2 effluxes ranged from 2.2 to 214 g CO2 m−2 day−1 (mean: 20.9 CO2 m−2 day−1). Downstream of point groundwater discharge sources, CO2 efflux decreased, over 2 m, to 3–40% of the point-source flux, while δ13C-CO2 increased, ranging from −9.8 ‰ to −23.2 ‰ V-PDB. The δ13C-CO2 increase was not strictly proportional to the CO2 flux but related to the origin of vadose zone CO2. The high spatial and temporal variability of CO2 efflux from this headwater stream informs those doing similar measurements and those working on upscaling stream data, that local variability should be assessed to estimate the impact of headwater stream CO2 efflux on the global carbon cycle.

 

Biogeochemical properties of soils play a crucial role in soil and stream chemistry throughout a watershed. How water interacts with soils during subsurface flow can have impacts on water quality, thus, it is fundamental to understand where and how certain soil water chemical processes occur within a catchment. In this study, ~200 soil samples were evaluated throughout a small catchment in the Front Range of Colorado, USA to examine spatial and vertical patterns in major soil solutes among different landscape units: riparian areas, alluvial/colluvial fans, and steep hillslopes. Solutes were extracted from the soil samples in the laboratory and analyzed for major cation (Li, K, Mg, Br, and Ca) and anion (F, Cl, NO 2 , NO 3 , PO 4 , and SO 4 ) concentrations using ion chromatography. Concentrations of most solutes were greater in near surface soils (10 cm) than in deeper soils (100 cm) across all landscape units, except for F which increased with depth, suggestive of surface accumulation processes such as dust deposition or enrichment due to biotic cycling. Potassium had the highest variation between depths, ranging from 1.04 mg/l (100 cm) to 3.13 mg/l (10 cm) sampled from riparian landscape units. Nearly every solute was found to be enriched in riparian areas where vegetation was visibly denser, with higher mean concentrations than the hillslopes and fans, except for NO 3 which had higher concentrations in the fans. Br, NO 2 , and PO 4 concentrations were often below the detectable limit, and Li and Na were not variable between depths or landscape units. Ratioed stream water concentrations (K:Na, Ca:Mg, and NO 3 :Cl) vs. discharge relationships compared to the soil solute ratios indicated a hydraulic disconnection between the shallow soils (<100 cm) and the stream. Based on the comparisons among depths and landscape units, our findings suggest that K, Ca, F, and NO 3 solutes may serve as valuable tracers to identify subsurface flowpaths as they are distinct among landscape units and depth within this catchment. However, interflow and/or shallow groundwater flow likely have little direct connection to streamflow generation. 

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. 

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. 

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.

 

Soil biota generate CO2 that can vertically export to the atmosphere, and dissolved organic and inorganic carbon (DOC and DIC) that can laterally export to streams and accelerate weathering. These processes are regulated by external hydroclimate forcing and internal structures (permeability distribution), the relative influences of which are rarely studied. Understanding these interactions is essential a hydrological extremes intensify in the future. Here we explore the question: How and to what extent do hydrological and permeability distribution conditions regulate soil carbon transformations and chemical weathering? We address the questions using a hillslope reactive transport model constrained by data from the Fitch Forest (Kansas, United States). Numerical experiments were used to mimic hydrological extremes and variable shallow-versus-deep permeability contrasts. Results demonstrate that under dry conditions (0.08 mm/day), long water transit times led to more mineralization of organic carbon (OC) into inorganic carbon (IC) form (>98\%). Of the IC produced, ~ 75\% was emitted upward as CO2 gas and ~ 25\% was exported laterally as DIC into the stream. Wet conditions (8.0 mm/day) resulted in less mineralization (~88\%), more DOC production (~12\%), and more lateral fluxes of IC (~50\% of produced IC). Carbonate precipitated under dry conditions and dissolved under wet conditions as the fast flow rapidly droves the reaction to disequilibrium. The results depict a conceptual hillslope model that prompts four hypotheses for our community to test. H1: Droughts enhance carbon mineralization and vertical upward carbon fluxes, whereas large hydrological events such as storms and flooding enhance subsurface vertical connectivity, reduce transit times, and promote lateral export. H2: The role of weathering as a net carbon sink or source to the atmosphere depends on the interaction between hydrologic flows and lithology: transition from droughts to storms can shift carbonate from a carbon sink (mineral precipitation) to carbon source (dissolution). H3: Permeability contrasts regulate the lateral flow partitioning via shallow flow paths versus deeper groundwater though this alter reaction rates negligibly. H4: Stream chemistry reflect flow paths and can potentially quantify water transit times: solutes enriched in shallow soils have a younger water signature; solutes abundant at depth carry older water signature. 

Riverine exports of silicon (Si) influence global carbon cycling through the growth of marine diatoms, which account for ∼25% of global primary production. Climate change will likely alter river Si exports in biome‐specific ways due to interacting shifts in chemical weathering rates, hydrologic connectivity, and metabolic processes in aquatic and terrestrial systems. Nonetheless, factors driving long‐term changes in Si exports remain unexplored at local, regional, and global scales. We evaluated how concentrations and yields of dissolved Si (DSi) changed over the last several decades of rapid climate warming using long‐term data sets from 60 rivers and streams spanning the globe (e.g., Antarctic, tropical, temperate, boreal, alpine, Arctic systems). We show that widespread changes in river DSi concentration and yield have occurred, with the most substantial shifts occurring in alpine and polar regions. The magnitude and direction of trends varied within and among biomes, were most strongly associated with differences in land cover, and were often independent of changes in river discharge. These findings indicate that there are likely diverse mechanisms driving change in river Si biogeochemistry that span the land‐water interface, which may include glacial melt, changes in terrestrial vegetation, and river productivity. Finally, trends were often stronger in months outside of the growing season, particularly in temperate and boreal systems, demonstrating a potentially important role of shifting seasonality for the flux of Si from rivers. Our results have implications for the timing and magnitude of silica processing in rivers and its delivery to global oceans.