RESUMEN
Previous studies along the banks of the tidal Meghna River of the Ganges-Brahmaputra-Meghna Delta demonstrated the active sequestration of dissolved arsenic (As) on newly formed iron oxide minerals (Fe(III)-oxides) within riverbank sands. The sand with high solid-phase As (>500 mg/kg) was located within the intertidal zone where robust mixing occurs with oxygen-rich river water. Here we present new evidence that upwelling groundwater through a buried silt layer generates the dissolved products of reductive dissolution of Fe(III)-oxides, including As, while mobilization of DOC by upwelling groundwater prevents their reconstitution in the intertidal zone by lowering the redox state. A three end-member conservative mixing model demonstrated mixing between riverbank groundwater above the silt layer, upwelling groundwater through the silt layer, and river water. An electrochemical mass balance model confirmed that Fe(III)-oxides were the primary electron acceptor driving the oxidation of DOC sourced from sediment organic carbon in the silt. Thus, the presence of an intercalating silt layer in the riverbanks of tidal rivers can represent a biogeochemical hotspot of As release while preventing its retention in the hyporheic zone.
RESUMEN
This note describes the development and testing of a novel, programmable reversing flow 1D (R1D) experimental column apparatus designed to investigate reaction, sorption, and transport of solutes in aquifers within dynamic reversing flow zones where waters with different chemistries mix. The motivation for constructing this apparatus was to understand the roles of mixing and reaction on arsenic discharging through a tidally fluctuating riverbank. The apparatus can simulate complex transient flux schedules similar to natural flow regimes The apparatus uses an Arduino microcontroller to control flux magnitude through two peristaltic pumps. Solenoid valves control flow direction from two separate reservoirs. In-line probes continually measure effluent electrical conductance, pH, oxidation-reduction potential, and temperature. To understand how sensitive physical solute transport is to deviations from the real hydrograph of the tidally fluctuating river, two experiments were performed using: (1) a simpler constant magnitude, reversing flux direction schedule (RCF); and (2) a more environmentally relevant variable magnitude, reversing flux direction schedule (RVF). Wherein, flux magnitude was ramped up and down according to a sine wave. Modeled breakthrough curves of chloride yielded nearly identical dispersivities under both flow regimes. For the RVF experiment, Peclet numbers captured the transition between diffusion and dispersion dominated transport in the intertidal interval. Therefore, the apparatus accurately simulated conservative, environmentally relevant mixing under transient, variable flux flow regimes. Accurately generating variable flux reversing flow regimes is important to simulate the interaction between flow velocity and chemical reactions where Brownian diffusion of solutes to solid-phase reaction sites is kinetically limited.
RESUMEN
Central Kentucky could be considered a critical source area of nutrients in water ways because of low permeability soils, fast groundwater flow through bedrock fractures, and pervasive agriculture and development. Of particular concern is rising development in rural areas, which creates mixed land cover (MLC) watersheds, i.e., watersheds with development, agriculture, and other land cover types. MLC watersheds add complexity to spatial and temporal releases of dissolved constituents, leading to less predictable water quality patterns. The goal of this research was to examine the export of dissolved substances from a small, upland MLC catchment in central Kentucky with a focus on how the interaction between discharges from developed agricultural land cover and groundwater influence base flow water quality. Our approach was to spatially sample a representative catchment monthly over 1 year, characterize the major dissolved constituents, and evaluate catchment processes with statistical analyses and Piper diagrams. Principal component analysis, factor analysis, and Piper diagrams indicate base flow was composed of groundwater influenced by two different host rocks and an outfall draining a developed region. Base flow nutrient export was dominated by mixing nitrate-sulfate rich groundwater with ammonium-phosphate-chloride rich outfall drainage. High nitrate groundwater dominated nitrogen export in the winter, whereas high ammonium outfall drainage dominated summer export. Spatial analysis revealed that ~ 10% of the basin may have similar land cover and hydrologic processes, suggesting that MLC catchments are small but collectively significant nitrogen sources to river networks due to development and agriculturally impacted groundwater.