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Groundwater flow paths and processes that govern metal mobility and transport are difficult to characterize in mountainous bedrock watersheds. Despite the difficulty in holistic characterization, conceptual understanding of subsurface hydrologic and geochemical processes is key to developing remediation plans for locations affected by acid mine drainage, such as the Upper Animas River watershed in southwestern Colorado, USA. Stable isotopes of water and rare earth elements were utilized to evaluate groundwater flow and metal sources within this complex catchment. Stable isotope samples collected from draining mine adits and springs display systematic spatial variation wherein sample sites at higher elevations have greater seasonal variability than sites at lower elevations. The Upper Cement Creek watershed, where multiple draining mines are present, displays the lowest seasonal variation in stable isotopic signatures, potentially indicating the presence of a large, well-mixed volume of groundwater storage or interbasin groundwater flow. Rare earth elements display statistically significant variation between different alteration styles in the catchment. Overprinting of regional propylitic alteration is evident based on enrichment of middle rare earth elements in acidic springs and mines that are not spatially associated with surficial exposures of acid generating alteration styles. Europium anomaly and middle rare earth enrichment signatures from two flooded mine tunnels on opposite sides of a watershed divide indicate connections to the same subsurface flooded mine workings. 

Streams impacted by historic mining activity are characterized by acidic pH, unique microbial communities, and abundant metal-oxide precipitation, all of which can influence groundwater-surface water exchange. We investigate how metal-oxide precipitates and hyporheic mixing mediate the composition of microbial communities in two streams receiving acid-rock and mine drainage near Silverton, Colorado, USA. A large, neutral pH hyporheic zone facilitated the precipitation of metal particles/colloids in hyporheic porewaters. A small, low pH hyporheic zone, limited by the presence of a low-permeability, iron-oxyhydroxide layer known as ferricrete, led to the formation of steep geochemical gradients and high dissolved-metal concentrations. To determine how these two hyporheic systems influence microbiome composition, we installed well clusters and deployed in situ microcosms in each stream to sample porewaters and sediments for 16S rRNA gene sequencing. Results indicated that distinct hydrogeochemical conditions were present above and below the ferricrete in the low pH system. A positive feedback loop may be present in the low pH stream where microbially-mediated precipitation of iron-oxides contribute to additional clogging of hyporheic pore spaces, separating abundant, iron-oxidizing bacteria (Gallionella spp.) above the ferricrete from rare, low-abundance bacteria below the ferricrete. Metal precipitates and colloids that formed in the neutral pH hyporheic zone were associated with a more diverse phylogenetic community of nonmotile, nutrient-cycling bacteria that may be transported through hyporheic pore spaces. In summary, biogeochemical conditions influence, and are influenced by, hyporheic mixing, which mediates the distribution of micro-organisms and thus the cycling of metals in streams receiving acid-rock and mine drainage. 

Abstract The western U.S. is experiencing shifts in recharge due to climate change, and it is currently unclear how hydrologic shifts will impact geochemical weathering and stream concentration–discharge (C–Q) patterns. Hydrologists often useC–Qanalyses to assess feedbacks between stream discharge and geochemistry, given abundant stream discharge and chemistry data. Chemostasis is commonly observed, indicating that geochemical controls, rather than changes in discharge, are shaping streamC–Qpatterns. However, fewC–Qstudies investigate how geochemical reactions evolve along groundwater flowpaths before groundwater contributes to streamflow, resulting in potential omission of importantC–Qcontrols such as coupled mineral dissolution and clay precipitation and subsequent cation exchange. Here, we use field observations—including groundwater age, stream discharge, and stream and groundwater chemistry—to analyseC–Qrelations in the Manitou Experimental Forest in the Colorado Front Range, USA, a site where chemostasis is observed. We combine field data with laboratory analyses of whole rock and clay x‐ray diffraction and soil cation‐extraction experiments to investigate the role that clays play in influencing stream chemistry. We use Geochemist's Workbench to identify geochemical reactions driving stream chemistry and subsequently suggest how climate change will impact streamC–Qtrends. We show that as groundwater age increases,C–Qslope and stream solute response are not impacted. Instead, primary mineral dissolution and subsequent clay precipitation drive strong chemostasis for silica and aluminium and enable cation exchange that buffers calcium and magnesium concentrations, leading to weak chemostatic behaviour for divalent cations. The influence of clays on streamC–Qhighlights the importance of delineating geochemical controls along flowpaths, as upgradient mineral dissolution and clay precipitation enable downgradient cation exchange. Our results suggest that geochemical reactions will not be impacted by future decreasing flows, and thus where chemostasis currently exists, it will continue to persist despite changes in recharge. 

High concentrations of trace metal(loid)s exported from abandoned mine wastes and acid rock drainage pose a risk to the health of aquatic ecosystems. To determine if and when the hyporheic zone mediates metal(loid) export, we investigated the relationship between streamflow, groundwater–stream connectivity, and subsurface metal(loid) concentrations in two ~1-km stream reaches within the Bonita Peak Mining District, a US Environmental Protection Agency Superfund site located near Silverton, Colorado, USA. The hyporheic zones of reaches in two streams—Mineral Creek and Cement Creek—were characterized using a combination of salt-tracer injection tests, transient-storage modeling, and geochemical sampling of the shallow streambed (<0.7 m). Based on these data, we present two conceptual models for subsurface metal(loid) behavior in the hyporheic zones, including (1) well-connected systems characterized by strong hyporheic mixing of infiltrating stream water and upwelling groundwater and (2) poorly connected systems delineated by physical barriers that limit hyporheic mixing. The comparatively large hyporheic zone and high hydraulic conductivities of Mineral Creek created a connected stream–groundwater system, where mixing of oxygen-rich stream water and metal-rich groundwater facilitated the precipitation of metal colloids in the shallow subsurface. In Cement Creek, the precipitation of iron oxides at depth (~0.4 m) created a low-hydraulic-conductivity barrier between surface water and groundwater. Cemented iron oxides were an important regulator of metal(loid) concentrations in this poorly connected stream–groundwater system due to the formation of strong redox gradients induced by a relatively small hyporheic zone and high fluid residence times. A comparison of conceptual models to stream concentration–discharge relationships exhibited a clear link between geochemical processes occurring within the hyporheic zone of the well-connected system and export of particulate Al, Cu, Fe, and Mn, while the poorly connected system did not have a notable influence on metal concentration–discharge trends. Mineral Creek is an example of a hyporheic system that serves as a natural dissolved metal(loid) sink, whereas poorly connected systems such as Cement Creek may require a combination of subsurface remediation of sediments and mitigation of upstream, iron-rich mine drainages to reduce metal export.