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  1. Abstract

    Unsteady transit time distribution (TTD) theory is a promising new approach for merging hydrologic and water quality models at the catchment scale. A major obstacle to widespread adoption of the theory, however, has been the specification of the StorAge Selection (SAS) function, which describes how the selection of water for outflow is biased by age. In this paper we hypothesize that some unsteady hydrologic systems of practical interest can be described, to first‐order, by a “shifted‐uniform” SAS that falls along a continuum between plug flow sampling (for which only the oldest water in storage is sampled for outflow) and uniform sampling (for which water in storage is sampled randomly for outflow). For this choice of SAS function, explicit formulae are derived for the evolving: (a) age distribution of water in storage; (b) age distribution of water in outflow; and (c) breakthrough concentration of a conservative solute under either continuous or impulsive addition. Model predictions conform closely to chloride and deuterium breakthrough curves measured previously in a sloping lysimeter subject to periodic wetting, although refinements of the model are needed to account for the reconfiguration of flow paths at high storage levels (the so‐called inverse storage effect). The analytical results derived in this paper should lower the barrier to applying TTD theory in practice, ease the computational demands associated with simulating solute transport through complex hydrologic systems, and provide physical insights that might not be apparent from traditional numerical solutions of the governing equations.

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  2. Abstract

    Storm direction modulates a hydrograph's magnitude and duration, thus having a potentially large effect on local flood risk. However, how changes in the preferential storm direction affect the probability distribution of peak flows remains unknown. We address this question with a novel Monte Carlo approach where stochastically transposed storms drive hydrologic simulations over medium and mesoscale watersheds in the Midwestern United States. Systematic rotations of these watersheds are used to emulate changes in the preferential storm direction. We found that the peak flow distribution impacts are scale‐dependent, with larger changes observed in the mesoscale watershed than in the medium‐scale watershed. We attribute this to the high diversity of storm patterns and the storms' scale relative to watershed size. This study highlights the potential of the proposed stochastic framework to address fundamental questions about hydrologic extremes when our ability to observe these events in nature is hindered by technical constraints and short time records.

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  3. Abstract

    Increasing trends in base cations, pH, and salinity of freshwaters have been documented in US streams over 50 years. These patterns, collectively known as freshwater salinization syndrome (FSS), are driven by multiple processes, including applications of road salt and human-accelerated weathering of impervious surfaces, reductions in acid rain, and other anthropogenic legacies of change. FSS mobilizes chemical cocktails of distinct elemental mixtures via ion exchange, and other biogeochemical processes. We analyzed impacts of FSS on streamwater chemistry across five urban watersheds in the Baltimore-Washington, USA metropolitan region. Through combined grab-sampling and high-frequency monitoring by USGS sensors, regression relationships were developed among specific conductance and major ion and trace metal concentrations. These linear relationships were statistically significant in most of the urban streams (e.g.R2= 0.62 and 0.43 for Mn and Cu, respectively), and showed that specific conductance could be used as a proxy to predict concentrations of major ions and trace metals. Major ions and trace metals analyzed via linear regression and principal component analysis showed co-mobilization (i.e. correlations among combinations of specific conductance (SC), Mn, Cu, Sr2+, and all base cations during certain times of year and hydrologic conditions). Co-mobilization of metals and base cations was strongest during peak snow events but could continue over 24 h after SC peaked, suggesting ongoing cation exchange in soils and stream sediments. Mn and Cu concentrations predicted from SC as a proxy indicated acceptable goodness of fit for predictedvs.observed values (Nash–Sutcliffe efficiency > 0.28). Metals concentrations remained elevated for days after SC decreased following snowstorms, suggesting lag times and continued mobilization after road salt use. High-frequency sensor monitoring and proxies associated with FSS may help better predict contaminant pulses and contaminant exceedances in response to salinization and impacts on aquatic life, infrastructure, and drinking water.

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  4. Abstract

    In this paper, we develop and validate a rigorous modeling framework, based on Duhamel's Theorem, for the unsteady one‐dimensional vertical transport of a solute across a flat sediment‐water interface (SWI) and through the benthic biolayer of a turbulent stream. The modeling framework is novel in capturing the two‐way coupling between evolving solute concentrations above and below the SWI and in allowing for a depth‐varying diffusivity. Three diffusivity profiles within the sediment (constant, exponentially decaying, and a hybrid model) are evaluated against an extensive set of previously published laboratory measurements of turbulent mass transfer across the SWI. The exponential diffusivity profile best represents experimental observations and its reference diffusivity scales with the permeability Reynolds number, a dimensionless measure of turbulence at the SWI. The depth over which turbulence‐enhanced diffusivity decays is of the order of centimeters and comparable to the thickness of the benthic biolayer. Thus, turbulent mixing across the SWI may serve as a universal transport mechanism, supplying the nutrient and energy fluxes needed to sustain microbial growth, and nutrient processing, in the benthic biolayer of stream and coastal sediments.

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  5. Abstract

    Factors driving freshwater salinization syndrome (FSS) influence the severity of impacts and chances for recovery. We hypothesize that spread of FSS across ecosystems is a function of interactions among five state factors:human activities,geology,flowpaths,climate, andtime. (1)Human activitiesdrive pulsed or chronic inputs of salt ions and mobilization of chemical contaminants. (2)Geologydrives rates of erosion, weathering, ion exchange, and acidification‐alkalinization. (3)Flowpathsdrive salinization and contaminant mobilization along hydrologic cycles. (4)Climatedrives rising water temperatures, salt stress, and evaporative concentration of ions and saltwater intrusion. (5)Timeinfluences consequences, thresholds, and potentials for ecosystem recovery. We hypothesize that state factors advance FSS in distinct stages, which eventually contribute to failures in systems‐level functions (supporting drinking water, crops, biodiversity, infrastructure, etc.). We present future research directions for protecting freshwaters at risk based on five state factors and stages from diagnosis to prognosis to cure.

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  6. Abstract

    Many water quality and ecosystem functions performed by streams occur in the benthic biolayer, the biologically active upper (~5 cm) layer of the streambed. Solute transport through the benthic biolayer is facilitated by bedform pumping, a physical process in which dynamic and static pressure variations over the surface of stationary bedforms (e.g., ripples and dunes) drive flow across the sediment‐water interface. In this paper we derive two predictive modeling frameworks, one advective and the other diffusive, for solute transport through the benthic biolayer by bedform pumping. Both frameworks closely reproduce patterns and rates of bedform pumping previously measured in the laboratory, provided that the diffusion model's dispersion coefficient declines exponentially with depth. They are also functionally equivalent, such that parameter sets inferred from the 2D advective model can be applied to the 1D diffusive model, and vice versa. The functional equivalence and complementary strengths of these two models expand the range of questions that can be answered, for example, by adopting the 2D advective model to study the effects of geomorphic processes (such as bedform adjustments to land use change) on flow‐dependent processes and the 1D diffusive model to study problems where multiple transport mechanisms combine (such as bedform pumping and turbulent diffusion). By unifying 2D advective and 1D diffusive descriptions of bedform pumping, our analytical results provide a straightforward and computationally efficient approach for predicting, and better understanding, solute transport in the benthic biolayer of streams and coastal sediments.

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  7. Abstract

    Freshwater salinization is an emerging global problem impacting safe drinking water, ecosystem health and biodiversity, infrastructure corrosion, and food production. Freshwater salinization originates from diverse anthropogenic and geologic sources including road salts, human-accelerated weathering, sewage, urban construction, fertilizer, mine drainage, resource extraction, water softeners, saltwater intrusion, and evaporative concentration of ions due to hydrologic alterations and climate change. The complex interrelationships between salt ions and chemical, biological, and geologic parameters and consequences on the natural, social, and built environment are called Freshwater Salinization Syndrome (FSS). Here, we provide a comprehensive overview of salinization issues (past, present, and future), and we investigate drivers and solutions. We analyze the expanding global magnitude and scope of FSS including its discovery in humid regions, connections to human-accelerated weathering and mobilization of ‘chemical cocktails.’ We also present data illustrating: (1) increasing trends in salt ion concentrations in some of the world’s major freshwaters, including critical drinking water supplies; (2) decreasing trends in nutrient concentrations in rivers due to regulations but increasing trends in salinization, which have been due to lack of adequate management and regulations; (3) regional trends in atmospheric deposition of salt ions and storage of salt ions in soils and groundwater, and (4) applications of specific conductance as a proxy for tracking sources and concentrations of groups of elements in freshwaters. We prioritize FSS research needs related to better understanding: (1) effects of saltwater intrusion on ecosystem processes, (2) potential health risks from groundwater contamination of home wells, (3) potential risks to clean and safe drinking water sources, (4) economic and safety impacts of infrastructure corrosion, (5) alteration of biodiversity and ecosystem functions, and (6) application of high-frequency sensors in state-of-the art monitoring and management. We evaluate management solutions using a watershed approach spanning air, land, and water to explore variations in sources, fate and transport of different salt ions (e.g.monitoring of atmospheric deposition of ions, stormwater management, groundwater remediation, and managing road runoff). We also identify tradeoffs in management approaches such as unanticipated retention and release of chemical cocktails from urban stormwater management best management practices (BMPs) and unintended consequences of alternative deicers on water quality. Overall, we show that FSS has direct and indirect effects on mobilization of diverse chemical cocktails of ions, metals, nutrients, organics, and radionuclides in freshwaters with mounting impacts. Our comprehensive review suggests what could happen if FSS were not managed into the future and evaluates strategies for reducing increasing risks to clean and safe drinking water, human health, costly infrastructure, biodiversity, and critical ecosystem services.

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  8. Abstract

    In this study, we explore the use of unsteady transit time distribution (TTD) theory to model solute transport in biofilters, a popular form of nature‐based or “green” storm water infrastructure (GSI). TTD theory has the potential to address many unresolved challenges associated with predicting pollutant fate and transport through these systems, including unsteadiness in the water balance (time‐varying inflows, outflows, and storage), unsteadiness in pollutant loading, time‐dependent reactions, and scale‐up to GSI networks and urban catchments. From a solution to the unsteady age conservation equation under uniform sampling, we derive an explicit expression for solute breakthrough during and after one or more storm events. The solution is calibrated and validated with breakthrough data from 17 simulated storms at a field‐scale biofilter test facility in Southern California, using bromide as a conservative tracer. TTD theory closely reproduces bromide breakthrough concentrations, provided that lateral exchange with the surrounding soil is accounted for. At any given time, according to theory, more than half of the water in storage is from the most recent storm, while the rest is a mixture of penultimate and earlier storms. Thus, key management endpoints, such as the pollutant treatment credit attributable to GSI, are likely to depend on the evolving age distribution of water stored and released by these systems.

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  9. There are challenges in monitoring and managing water quality due to spatial and temporal heterogeneity in contaminant sources, transport, and transformations. We demonstrate the importance of longitudinal stream synoptic (LSS) monitoring, which can track combinations of water quality parameters along flowpaths across space and time. Specifically, we analyze longitudinal patterns of chemical mixtures of carbon, nutrients, greenhouse gasses, salts, and metals concentrations along 10 flowpaths draining 1,765 km 2 of the Chesapeake Bay region. These 10 longitudinal stream flowpaths are drained by watersheds experiencing either urban degradation, forest and wetland conservation, or stream and floodplain restoration. Along the 10 longitudinal stream flowpaths, we monitored over 300 total sampling sites along a combined stream length of 337 km. Synoptic monitoring along longitudinal flowpaths revealed: (1) increasing, decreasing, piecewise, or no trends and transitions in water quality with increasing distance downstream, which provide insights into water quality processes along flowpaths; (2) longitudinal trends and transitions in water quality along flowpaths can be quantified and compared using simple linear and non-linear statistical relationships with distance downstream and/or land use/land cover attributes, (3) attenuation and transformation of chemical cocktails along flowpaths depend on: spatial scales, pollution sources, and transitions in land use and management, hydrology, and restoration. We compared our LSS patterns with others from the global literature to synthesize a typology of longitudinal water quality trends and transitions in streams and rivers based on hydrological, biological, and geochemical processes. Applications of LSS monitoring along flowpaths from our results and the literature reveal: (1) if there are shifts in pollution sources, trends, and transitions along flowpaths, (2) which pollution sources can spread further downstream to sensitive receiving waters such as drinking water supplies and coastal zones, and (3) if transitions in land use, conservation, management, or restoration can attenuate downstream transport of pollution sources. Our typology of longitudinal water quality responses along flowpaths combines many observations across suites of chemicals that can follow predictable patterns based on watershed characteristics. Our typology of longitudinal water quality responses also provides a foundation for future studies, watershed assessments, evaluating watershed management and stream restoration, and comparing watershed responses to non-point and point pollution sources along streams and rivers. LSS monitoring, which integrates both spatial and temporal dimensions and considers multiple contaminants together (a chemical cocktail approach), can be a comprehensive strategy for tracking sources, fate, and transport of pollutants along stream flowpaths and making comparisons of water quality patterns across different watersheds and regions. 
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    Free, publicly-accessible full text available June 9, 2024