Robert L. Runkel

A new metric for determining the importance of transient storage

A review of various metrics used to characterize transient storage indicates that none of the existing measures successfully integrate the interaction between advective velocity and the transient storage parameters (storage zone area, storage zone exchange coefficient). Further, 2 existing metrics are related to mean travel time, a quantity that is independent of the storage zone exchange coefficient, α. This interaction and the effect of α on travel time are important considerations when determining the mass of solute entering the storage zone within a given reach. A new metric based on median reach travel time is therefore proposed. Median reach travel time due to advection–dispersion and transient storage, and median reach travel time due solely to advection–dispersion are computed based on numerical simulations. These 2 travel times are used to determine Fmed, the fraction of median travel time due to transient storage. Application of the new metric to 53 existing parameter sets indicates that transient storage accounts for 0.12% to 68.0% of total reach travel time. Rankings of storage zone importance based on the new metric are substantially different from rankings based on storage zone residence time, storage exchange flux, and the hydrological retention factor. These differences result from the ability of the new metric to characterize the interaction between advective velocity and transient storage, and the resultant effects on reach travel time and mass transport.

Assessment of metal loads in watersheds affected by acid mine drainage by using tracer injection and synoptic sampling: Cement Creek, colorado, USA

Watersheds in mineralized zones may contain many mines, each of which can contribute to acidity and the metal load of a stream. In this study the authors delineate hydrogeologic characteristics determining the transport of metals from the watershed to the stream in the watershed of Cement Creek, Colorado. Combining the injection of a chemical tracer, to determine a discharge, with synoptic sampling, to obtain chemistry of major ions and metals, spatially detailed load profiles are quantified. Using the discharge and load profiles, the authors (1) identified sampled inflow sources which emanate from undisturbed as well as previously mined areas; (2) demonstrate, based on simple hydrologic balance, that unsampled, likely dispersed subsurface, inflows are significant; and (3) estimate attenuation. For example, along the 12-km study reach, 108 kg per day of Zn were added to Cement Creek. Almost half of this load came from 10 well-defined areas that included both mined and non-mined parts of the watershed. However, the combined effect of many smaller inflows also contributed a substantial load that could limit the effectiveness of remediation. Of the total Zn load, 58.3 kg/day came from stream segments with no visible inflow, indicating the importance of contributions from dispersed subsurface inflow. The subsurface inflow mostly occurred in areas with substantial fracturing of the bedrock or in areas downstream from tributaries with large alluvial fans. Despite a pH generally less than 4.5, there was 58.4 kg/day of Zn attenuation that occurred in mixing zones downstream from inflows with high pH. Mixing zones can have local areas of pH that are high enough for sorption and precipitation reactions to have an effect. Principal component analysis classified inflows into 7 groups with distinct chemical signatures that represent water-rock interaction with different mineral-alteration suites in the watershed. The present approach provides a detailed snapshot of metal load for the watershed to support remediation decisions, and quantifies processes affecting metal transport.

Analysis of Transient Storage Subject to Unsteady Flow: Diel Flow Variation in an Antarctic Stream

Transport of dissolved material in streams and small rivers may be characterized using tracer-dilution methods and solute transport models. Recent studies have quantified stream/substream interactions using models of transient storage. These studies are based on tracer-dilution data obtained during periods of steady flow. We present a modeling framework for the analysis of transient storage in stream systems with unsteady flows. The framework couples a kinematic wave routing model with a solute transport model that includes transient storage. The routing model provides time-varying flows and cross-sectional areas that are used as input to the solute transport model. The modeling framework was used to quantify stream/substream interaction in Huey Creek, an Antarctic stream fed exclusively by glacial meltwater. Analysis of tracer-dilution data indicates that there was substantial interaction between the flowing surface water and the hyporheic (substream) zone. The ratio of storage zone area to stream cross-sectional area (As/A) was >1 in all stream reaches, indicating that the substream area contributing to hyporheic exchange was large relative to stream cross-sectional area. The rate of exchange, as governed by the transient storage exchange coefficient (α), was rapid because of a high stream gradient and porous alluvial materials. Estimates of α generally exceed those determined for other small streams. The high degree of hyporheic exchange supports the hypothesis that weathering reactions within the hyporheos account for observed increases in solute concentration with stream length, as noted in other studies of Antarctic streams.

Inorganic N and P dynamics of Antarctic glacial meltwater streams as controlled by hyporheic exchange and benthic autotrophic communities

Abstract The McMurdo Dry Valleys of South Victoria Land, Antarctica, contain numerous glacial meltwater streams that drain into lakes on the valley floors. Many of the streams have abundant perennial mats of filamentous cyanobacteria. The algal mats grow during streamflow in the austral summer and are in a dormant freeze-dried state during the rest of the year. NO3 and soluble reactive P (SRP) concentrations were lower in streams with abundant algal mats than in streams with sparse algal mats. NO3 and SRP concentrations were higher in the hyporheic zone of a stream with abundant algal mats than in the stream itself. An experimental injection of LiCl, NaNO3, and K3PO4 was conducted in Green Creek, which has abundant algal mats. Substantial hyporheic exchange occurred. The NO3 and PO4 concentrations at 50 m below the injection were 55 μM and 18 μM, respectively, during the experiment. NO3 and PO4 concentrations were below the detection limit of 1 to 2 μM at a site 497 m below the injection during the Cl tracer arrival, indicating a high capacity for nutrient uptake by algal communities. NO2 and NH4 were present at sites 226 and 327 m below the injection, indicating that, in addition to denitrification and algal uptake, dissimilatory NO3 reduction to NO2 and NH4 may be a NO3 sink during transport. Transport modelling with nutrient uptake represented as a 1st-order process yielded reach-scale parameters of 4.3 × 10−5 to 3.9 × 10−4/s and 1.4 × 10−4 to 3.8 × 10−4/s for uptake of NO3 and PO4, respectively. The best match with the observed data was a model in which PO4 uptake occurred only in the main channel and NO3 uptake occurred in the main channel and in the hyporheic zone. Hyporheic NO3 uptake was 7 to 16% of the total uptake for the different stream reaches. These results demonstrate that nutrient flux to the lakes is controlled by hyporheic exchange and nutrient uptake by algal mats in dry valley streams. Streams without algal mats contribute more nutrients to the lakes than streams with algal mats.

Conservative and reactive solute transport in constructed wetlands

[1] The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater-dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first-order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%). INDEX TERMS: 1890 Hydrology: Wetlands; 1871 Hydrology: Surface water quality; 3230 Mathematical Geophysics: Numerical solutions; KEYWORDS: constructed wetlands, OTIS, transient storage

Modeling hyporheic zone processes

Stream biogeochemistry is influenced by the physical and chemical processes that occur in the surrounding watershed. These processes include the mass loading of solutes from terrestrial and atmospheric sources, the physical transport of solutes within the watershed, and the transformation of solutes due to biogeochemical reactions. Research over the last two decades has identified the hyporheic zone as an important part of the stream system in which these processes occur. The hyporheic zone may be loosely defined as the porous areas of the stream bed and stream bank in which stream water mixes with shallow groundwater. Exchange of water and solutes between the stream proper and the hyporheic zone has many biogeochemical implications, due to differences in the chemical composition of surface and groundwater. For example, surface waters are typically oxidized environments with relatively high dissolved oxygen concentrations. In contrast, reducing conditions are often present in groundwater systems leading to low dissolved oxygen concentrations. Further, microbial oxidation of organic materials in groundwater leads to supersaturated concentrations of dissolved carbon dioxide relative to the atmosphere. Differences in surface and groundwater pH and temperature are also common. The hyporheic zone is therefore a mixing zone in which there are gradients in the concentrations of dissolved gasses, the concentrations of oxidized and reduced species, pH, and temperature. These gradients lead to biogeochemical reactions that ultimately affect stream water quality. Due to the complexity of these natural systems, modeling techniques are frequently employed to quantify process dynamics. This special issue of Advances in Water Resources presents recent research on the modeling of hyporheic zone processes. To begin this preface, a brief history on modeling hyporheic zone processes is presented. This background information is by no means complete; additional information may be found in Streams and Groundwaters [17] and the references therein. The preface concludes with an overview of current re-

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The models ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Reactive Solute Transport in Streams: 1. Development of an Equilibrium‐Based Model

An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

Automated calibration of a stream solute transport model: implications for interpretation of biogeochemical parameters

The hydrologic processes of advection, dispersion, and transient storage are the primary physical mechanisms affecting solute transport in streams. The estimation of parameters for a conservative solute transport model is an essential step to characterize transient storage and other physical features that cannot be directly measured, and often is a preliminary step in the study of reactive solutes. Our study used inverse modeling to estimate parameters of the transient storage model OTIS (One dimensional Transport with Inflow and Storage). Observations from a tracer injection experiment performed on Uvas Creek, California, USA, are used to illustrate the application of automated solute transport model calibration to conservative and nonconservative stream solute transport. A computer code for universal inverse modeling (UCODE) is used for the calibrations. Results of this procedure are compared with a previous study that used a trial-and-error parameter estimation approach. The results demonstrated 1) importance of the proper estimation of discharge and lateral inflow within the stream system; 2) that although the fit of the observations is not much better when transient storage is invoked, a more randomly distributed set of residuals resulted (suggesting nonsystematic error), indicating that transient storage is occurring; 3) that inclusion of transient storage for a reactive solute (Sr2+) provided a better fit to the observations, highlighting the importance of robust model parameterization; and 4) that applying an automated calibration inverse modeling estimation approach resulted in a comprehensive understanding of the model results and the limitation of input data.

Reactive Solute Transport in Streams: 2. Simulation of a pH Modification Experiment

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.