No abstract

Extreme weather, fires, and land use and climate change are significantly reshaping interactions within watersheds throughout the world. Although hydrological-biogeochemical interactions within watersheds can impact many services valued by society, uncertainty associated with predicting hydrologydriven biogeochemical watershed dynamics remains high. With an aim to reduce this uncertainty, an approximately 300-km 2 mountainous headwater observatory has been developed at the East River, CO, watershed of the Upper Colorado River Basin. The site is being used as a testbed for the Department of Energy supported Watershed Function Project and collaborative efforts. Building on insights gained from research at the "sister" Rifle, CO, site, coordinated studies are underway at the East River site to gain a predictive understanding of how the mountainous watershed retains and releases water, nutrients, carbon, and metals. In particular, the project is exploring how early snowmelt, drought, and other disturbances influence hydrological-biogeochemical watershed dynamics at seasonal to decadal timescales. A system-of-systems perspective and a scale-adaptive simulation approach, involving the combined use of archetypal watershed subsystem "intensive sites" are being tested at the site to inform aggregated watershed predictions of downgradient exports. Complementing intensive site hydrological, geochemical, geophysical, microbiological, geological, and vegetation datasets are long-term, distributed measurement stations and specialized experimental and observational campaigns. Several recent research advances provide insights about the intensive sites as well as aggregated watershed behavior. The East River "community testbed" is currently hosting scientists from more than 30 institutions to advance mountainous watershed methods and understanding.

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high‐elevation shale‐dominated catchment in the Rocky Mountains, using concentration‐discharge (C‐Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C‐Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flow paths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyrite oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during base flow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flow paths. Differential C‐Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. Future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C‐Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.

Three-dimensional variably saturated flow and multicomponent biogeochemical reactive transport modeling, based on published and newly generated data, is used to better understand the interplay of hydrology, geochemistry, and biology controlling the cycling of carbon, nitrogen, oxygen, iron, sulfur, and uranium in a shallow floodplain. In this system, aerobic respiration generally maintains anoxic groundwater below an oxic vadose zone until seasonal snowmelt-driven water table peaking transports dissolved oxygen (DO) and nitrate from the vadose zone into the alluvial aquifer. The response to this perturbation is localized due to distinct physico-biogeochemical environments and relatively long time scales for transport through the floodplain aquifer and vadose zone. Naturally reduced zones (NRZs) containing sediments higher in organic matter, iron sulfides, and non-crystalline U(IV) rapidly consume DO and nitrate to maintain anoxic conditions, yielding Fe(II) from FeS oxidative dissolution, nitrite from denitrification, and U(VI) from nitrite-promoted U(IV) oxidation. Redox cycling is a key factor for sustaining the observed aquifer behaviors despite continuous oxygen influx and the annual hydrologically induced oxidation event. Depth-dependent activity of fermenters, aerobes, nitrate reducers, sulfate reducers, and chemolithoautotrophs (e.g., oxidizing Fe(II), S compounds, and ammonium) is linked to the presence of DO, which has higher concentrations near the water table.

To understand how redox processes influence carbon, nitrogen, and iron cycling within the intrameander hyporheic zone, we developed a biotic and abiotic reaction network and incorporated it into the reactive transport simulator PFLOTRAN. Two‐dimensional reactive flow and transport simulations were performed (1) to evaluate how transient hydrological conditions control the lateral redox zonation within an intrameander region of the East River in Colorado and (2) to quantify the impact of a single meander on subsurface exports of carbon and other geochemical species to the river. The meander's overall contribution to the river was quantified by integrating geochemical outfluxes along the outside of the meander bend. The model was able to capture the field‐observed trends of dissolved oxygen, nitrate, iron, pH, and total inorganic carbon along a 2‐D transect. Consistent with field observations, simulated dissolved oxygen and nitrate decreased along the intrameander flow paths while iron (Fe2+) concentration increased. The simulation results further demonstrated that the reductive potential of the lateral redox zonation was controlled by groundwater velocities resulting from river stage fluctuations, with low‐water conditions promoting reducing conditions. The sensitivity analysis results showed that permeability had a more significant impact on biogeochemical zonation compared to the reaction pathways under transient hydrologic conditions. The simulation results further indicated that the meander acted as a sink for organic and inorganic carbon as well as iron during the extended baseflow and high‐water conditions; however, these geochemical species were released into the river during the falling limb of the hydrograph.

Although bedrock weathering strongly influences water quality and global carbon and nitrogen budgets, the weathering depths and rates within subsurface are not well understood nor predictable. Determination of both porewater chemistry and subsurface water flow are needed in order to develop more complete understanding and obtain weathering rates. In a long-term field study, we applied a multiphase approach along a mountainous watershed hillslope transect underlain by marine shale. Here we report three findings. First, the deepest extent of the water table determines the weathering front, and the range of annually water table oscillations determines the thickness of the weathering zone. Below the lowest water table, permanently water-saturated bedrock remains reducing, preventing deeper pyrite oxidation. Secondly, carbonate minerals and potentially rock organic matter share the same weathering front depth with pyrite, contrary to models where weathering fronts are stratified. Thirdly, the measurements-based weathering rates from subsurface shale are high, amounting to base cation exports of about 70 kmolc ha−1 y−1, yet consistent with weathering of marine shale. Finally, by integrating geochemical and hydrological data we present a new conceptual model that can be applied in other settings to predict weathering and water quality responses to climate change.

Floodplains, heavily used for water supplies, housing, agriculture, mining, and industry, are important repositories of organic carbon, nutrients, and metal contaminants. The accumulation and release of these species is often mediated by redox processes. Understanding the physicochemical, hydrological, and biogeochemical controls on the distribution and variability of sediment redox conditions is therefore critical to developing conceptual and numerical models of contaminant transport within floodplains. The Upper Colorado River Basin (UCRB) is impacted by former uranium and vanadium ore processing, resulting in contamination by V, Cr, Mn, As, Se, Mo and U. Previous authors have suggested that sediment redox activity occurring within organic carbon-enriched bodies located below the groundwater level may be regionally important to the maintenance and release of contaminant inventories, particularly uranium. To help assess this hypothesis, vertical distributions of Fe and S redox states and sulfide mineralogy were assessed in sediment cores from three floodplain sites spanning a 250km transect of the central UCRB. The results of this study support the hypothesis that organic-enriched reduced sediments are important zones of biogeochemical activity within UCRB floodplains. We found that the presence of organic carbon, together with pore saturation, are the key requirements for maintaining reducing conditions, which were dominated by sulfate-reduction products. Sediment texture was found to be of secondary importance and to moderate the response of the system to external forcing, such as oxidant diffusion. Consequently, fine-grain sediments are relatively resistant to oxidation in comparison to coarser-grained sediments. Exposure to oxidants consumes precipitated sulfides, with a disproportionate loss of mackinawite (FeS) as compared to the more stable pyrite. The accompanying loss of redox buffering capacity creates the potential for release of sequestered radionuclides and metals. Because of their redox reactivity and stores of metals, C, and N, organic-enriched sediments are likely to be important to nutrient and contaminant mobility within UCRB floodplain aquifers.

The commonly held assumption that photodependent processes dominate HO production in natural waters has been recently questioned. Here, we present evidence for the unrecognized and light-independent generation of HO in groundwater of an alluvial aquifer adjacent to the Colorado River near Rifle, CO. In situ detection using a sensitive chemiluminescent method suggests HO concentrations ranging from lower than the detection limit (<1 nM) to 54 nM along the vertical profiles obtained at various locations across the aquifer. Our results also suggest dark formation of HO is more likely to occur in transitional redox environments where reduced elements (e.g., reduced metals and NOM) meet oxygen, such as oxic-anoxic interfaces. A simplified kinetic model involving interactions among iron, reduced NOM, and oxygen was able to reproduce roughly many, but not all, of the features in our detected HO profiles, and therefore there are other minor biological and/or chemical controls on HO steady-state concentrations in such aquifer. Because of its transient nature, the widespread presence of HO in groundwater suggests the existence of a balance between HO sources and sinks, which potentially involves a cascade of various biogeochemically important processes that could have significant impacts on metal/nutrient cycling in groundwater-dependent ecosystems, such as wetlands and springs. More importantly, our results demonstrate that reactive oxygen species are not only widespread in oceanic and atmospheric systems but also in the subsurface domain, possibly the least understood component of biogeochemical cycles.