Sensitivity analysis of conservative and reactive stream transient storage models applied to field data from multiple-reach experiments

The transient storage model (TSM) has been widely used in studies of stream solute transport and fate, with an increasing emphasis on reactive solute transport. In this study we perform sensitivity analyses of a conservative TSM and two different reactive solute transport models (RSTM), one that includes first-order decay in the stream and the storage zone, and a second that considers sorption of a reactive solute on streambed sediments. Two previously analyzed data sets are examined with a focus on the reliability of these RSTMs in characterizing stream and storage zone solute reactions. Sensitivities of simulations to parameters within and among reaches, parameter coefficients of variation, and correlation coefficients are computed and analyzed. Our results indicate that (1) simulated values have the greatest sensitivity to parameters within the same reach, (2) simulated values are also sensitive to parameters in reaches immediately upstream and downstream (inter-reach sensitivity), (3) simulated values have decreasing sensitivity to parameters in reaches farther downstream, and (4) in-stream reactive solute data provide adequate data to resolve effective storage zone reaction parameters, given the model formulations. Simulations of reactive solutes are shown to be equally sensitive to transport parameters and effective reaction parameters of the model, evidence of the control of physical transport on reactive solute dynamics. Similar to conservative transport analysis, reactive solute simulations appear to be most sensitive to data collected during the rising and falling limb of the concentration breakthrough curve.     

Modeling the Impact of Stream Discharge Events on Riparian Solute Dynamics

The biogeochemical composition of stream water and the surrounding riparian water is mainly defined by the exchange of water and solutes between the stream and the riparian zone. Short-term fluctuations in near stream hydraulic head gradients (e.g., during stream flow events) can significantly influence the extent and rate of exchange processes. In this study, we simulate exchanges between streams and their riparian zone driven by stream stage fluctuations during single stream discharge events of varying peak height and duration. Simulated results show that strong stream flow events can trigger solute mobilization in riparian soils and subsequent export to the stream. The timing and amount of solute export is linked to the shape of the discharge event. Higher peaks and increased durations significantly enhance solute export, however, peak height is found to be the dominant control for overall mass export. Mobilized solutes are transported to the stream in two stages (1) by return flow of stream water that was stored in the riparian zone during the event and (2) by vertical movement to the groundwater under gravity drainage from the unsaturated parts of the riparian zone, which lasts for significantly longer time (> 400 days) resulting in long tailing of bank outflows and solute mass outfluxes. We conclude that strong stream discharge events can mobilize and transport solutes from near stream riparian soils into the stream. The impact of short-term stream discharge variations on solute exchange may last for long times after the flow event.     

Microtopographical and hydrophysical controls on subsurface flow and solute transport: A continuous solute release experiment in a subarctic bog

Resource extraction and transportation activities in subarctic Canada can result in the unintentional release of contaminants into the surrounding peatlands. In the event of a release, a thorough understanding of solute transport within the saturated zone is necessary to predict plume fate and the potential impacts on peatland ecosystems. To better characterize contaminant transport in these systems, approximately 13,000 L/day of sodium chloride tracer (200 mg/L) was released into a bog in the James Bay Lowland. The tracer was pumped into a fully penetrating well (1.5 m) between July 5 and August 18, 2015. Horizontal and vertical plume development was measured via in situ specific conductance and water table depth from an adaptive monitoring network. Over the spill period, the bulk of the plume travelled a lateral distance of 100 m in the direction of the slight regional groundwater and topographical slope. The plume shape was irregular and followed the hollows, indicating preferential flow paths due to the site microtopography. Saturated transport of the tracer occurred primarily at ~25 cm below ground surface (bgs), and at a discontinuous high hydraulic conductivity layer ~125 cm bgs due to a complex and heterogeneous vertical hydraulic conductivity profile. Plume measurement was confounded by a large amount of precipitation (233 mm over the study period) that temporarily diluted the tracer in the highly conductive upper peat layer. Longitudinal solute advection can be approximated using local water table information (i.e., depth and gradient); microtopography; and meteorological conditions. Vertical distribution of solute within the peat profile is far more complex due to the heterogeneous subsurface; characterization would be aided by a detailed understanding of the site‐specific peat profile; the degree of decomposition; and the type of contaminant (e.g., reactive/nonreactive). The results of this research highlight the difficulty of tracking a contaminant spill in bogs and provide a benchmark for the characterization of the short‐term fate of a plume in these complex systems.     

Finite-element analysis of the transport of water and solutes in title-drained soils

The finite-element method based on a Galerkin technique was used to formulate the problem of simulating the two-dimensional (cross-sectional) transient movement of water and solute in saturated or partially saturated nonuniform porous media. The numerical model utilizes linear triangular elements. Nonreactive, as well as reactive solutes whose behaviour can be described by a distribution coefficient or first-order reaction term were considered. The flow portion of the model was tested by comparison of the model results with experimental and finite-difference results for transient flow in an unsaturated sand column and the solute transport portion of the model was tested by comparison with analytical solution results. The model was applied to a hypothetical case involving movement of water and solutes in tile-drained soils. The simulation results showed the development of distinct solute leaching patterns in the soil as drainage proceeded. Although applied to a tile drainage problem in this study, the model should be equally useful in the study of a wide range of two-dimensional water and solute migration problems.     

Effects of compound-specific dilution on transient transport and solute breakthrough: A pore-scale analysis

This pore-scale modeling study in saturated porous media shows that compound-specific effects are important not only at steady-state and for the lateral displacement of solutes with different diffusivities but also for transient transport and solute breakthrough. We performed flow and transport simulations in two-dimensional pore-scale domains with different arrangement of the solid grains leading to distinct characteristics of flow variability and connectivity, representing mildly and highly heterogeneous porous media, respectively. The results obtained for a range of average velocities representative of groundwater flow (0.1–10 m/day), show significant effects of aqueous diffusion on solute breakthrough curves. However, the magnitude of such effects can be masked by the flux-averaging approach used to measure solute breakthrough and can hinder the correct interpretation of the true dilution of different solutes. We propose, as a metric of mixing, a transient flux-related dilution index that allows quantifying the evolution of solute dilution at a given position along the main flow direction. For the different solute transport scenarios we obtained dilution breakthrough curves that complement and add important information to traditional solute breakthrough curves. Such dilution breakthrough curves allow capturing the compound-specific mixing of the different solutes and provide useful insights on the interplay between advective and diffusive processes, mass transfer limitations, and incomplete mixing in the heterogeneous pore-scale domains. The quantification of dilution for conservative solutes is in good agreement with the outcomes of mixing-controlled reactive transport simulations, in which the mass and concentration breakthrough curves of the product of an instantaneous transformation of two initially segregated reactants were used as measures of reactive mixing.     

Concentration–discharge relationships describe solute and sediment mobilization,reaction, and transport at event and longer timescales

Concentration–discharge (C‐Q) relationships reflect material sources, storage, reaction, proximity, and transport in catchments. Differences in hydrologic pathways and connectivity influence observed C‐Q patterns at the catchment outlet. We examined solute and sediment C‐Q relationships at event and interannual timescales in a small mid‐Atlantic (USA) catchment. We found systematic differences in the C‐Q behaviour of geogenic/exogenous solutes (e.g., calcium and nitrate), biologically associated solutes (e.g., dissolved organic carbon), and particulate materials (e.g., total suspended solids). Negative log(C)–log(Q) regression slopes, indicating dilution, were common for geogenic solutes whereas positive slopes, indicating concentration increase, were common for biologically associated solutes. Biologically associated solutes often exhibited counterclockwise hysteresis during events whereas geogenic solutes exhibited clockwise hysteresis. Across event and interannual timescales, solute C‐Q patterns are linked to the spatial distribution of hydrologic sources and the timing and sequence of hydro‐biogeochemical source contributions to the stream. Groundwater is the primary source of stormflow during the earliest and latest stages of events, whereas precipitation and soil water become increasingly connected to the stream near peakflow. This sequence and timing of flowpath connectivity results in dilution and clockwise hysteresis for geogenic/exogenous solutes and concentration increase and counterclockwise hysteresis for biologically associated solutes. Particulate materials demonstrated positive C‐Q slopes over the long‐term and clockwise hysteresis during individual events. Drivers of particulate and solute C‐Q relationships differ, based on longitudinal and lateral expansion of active channels and changing shear stresses with increasing flows. Although important distinctions exist between the drivers of solute and sediment C‐Q relationships, overall solute and sediment C‐Q patterns at event and interannual timescales reflect consistent catchment hydro‐biogeochemical processes.     

Transport of nonsorbing solutes in a streambed with periodic bedforms

Previous studies of hyporheic zone focused largely on the net mass transfer of solutes between stream and streambed. Solute transport within the bed has attracted less attention. In this study, we combined flume experiments and numerical simulations to examine solute transport processes in a streambed with periodic bedforms. Solute originating from the stream was subjected to advective transport driven by pore water circulation due to current–bedform interactions as well as hydrodynamic dispersion in the porous bed. The experimental and numerical results showed that advection played a dominant role at the early stage of solute transport, which took place in the hyporheic zone. Downward solute transfer to the deep ambient flow zone was controlled by transverse dispersion at the later stage when the elapsed time exceeded the advective transport characteristic time t_c (= L/u_c with L being the bedform length and u_c the characteristic pore water velocity). The advection-based pumping exchange model was found to predict reasonably well solute transfer between the overlying water and streambed at the early stage but its performance deteriorated at the later stage. With dispersion neglected, the pumping exchange model underestimated the long-term rate and total mass of solute transfer from the overlying water to the bed. Therefore both advective and dispersive transport components are essential for quantification of hyporheic exchange processes.     

Complex patterns of catchment solute–discharge relationships for coastal plain rivers

Riverine solute versus discharge (C–Q) relationships provide information about the magnitude and dynamics of material fluxes from landscapes. We analysed long‐term patterns of C–Q relationships for 44 rivers in Florida across a suite of geogenic, nutrient, and organic solutes and investigated land cover, watershed size, and surficial geology as controls on these patterns. Solute concentrations generally exhibited far less variability than did discharge, with coherent solute‐specific behaviours repeated across watersheds. Geogenic solutes generally diluted with increasing discharge, whereas organic solutes generally enriched; patterns for nutrients were highly variable across watersheds, but on average exhibited chemostasis. Despite strong evidence of both geologic and land cover controls on solute flow‐weighted concentrations, these variables were poor predictors of C–Q slopes (β) or relative coefficients of variation (CV_C:CV_Q). CV_C:CV_Q generally increased with watershed size, and wetland area appeared to influence C–Q patterns for base cations and organic solutes. Perhaps most importantly, we observed significant slope breaks in C–Q association in approximately half of our observations, challenging the generality of using single power functions to describe catchment solute export patterns. For all solutes except phosphorus (P), C–Q slopes decreased above statistically identified breaks (slopes for P increased), with breaks consistently at or near median flow (i.e., 50% flow exceedance probability). This common pattern significantly impacts solute load estimates; failing to account for slope breaks overestimates nitrate and total organic carbon loads as much as 125% and underestimates P loads as much as 35%. In addition to challenging generic power‐law characterization of C–Q relationships for these coastal plain rivers, and exploring the load estimate consequences thereof, our study supports emerging insights about watershed hydrochemical behaviours across a wide array of solutes.     

Characterizing hyporheic transport processes — Interpretation of electrical geophysical data in coupled stream–hyporheic zone systems during solute tracer studies

Quantifying hyporheic solute dynamics has been limited by our ability to assess the magnitude and extent of stream interactions with multiple domains: mobile subsurface storage (MSS, e.g., freely flowing pore water) and immobile subsurface storage (ISS, e.g., poorly connected pore water). Stream-tracer experiments coupled with solute transport modeling are frequently used to characterize lumped MSS and ISS dynamics, but are limited by the ability to sample only “mobile” water and by window of detection issues. Here, we couple simulations of near-surface electrical resistivity (ER) methods with conservative solute transport to directly compare solute transport with ER interpretations, and to determine the ability of ER to predict spatial and temporal trends of solute distribution and transport in stream–hyporheic systems. Results show that temporal moments from both ER and solute transport data are well correlated for locations where advection is not the dominant solute transport process. Mean arrival time and variance are especially well-predicted by ER interpretation, providing the potential to estimate rate-limited mass transport (i.e. diffusive) parameters from these data in a distributed domain, substantially increasing our knowledge of the fate and transport of subsurface solutes.     

Modelling soil solute release and transport in run‐off on a loessial slope with and without surface stones

Stone covers on loessial slopes can increase the time of infiltration by slowing the velocity of the overland flow, which reduces the transport of solutes, but few mechanistic models have been tested under water‐scouring conditions. We carried out field experiments to test a previously proposed, physically based model of water and solute transport. The area of soil infiltration was calculated from the uncovered surface area, and Richards' equation and the kinematic wave equation were used to describe water infiltration and flow along slopes with stone covers. The transport of chemicals into the run‐off from the surface soil, presumably by diffusion, and their movement in the soil profile could be described by the convection–diffusion equations of the model. The simulated and measured data correlated well. The stones on the soil surface reduced the area available for infiltration but increased the Manning coefficient, eventually leading to increased water infiltration and decreased solute loss with run‐off. Our results indicated that the traditional model of water movement and solute migration could be used to simulate water transport and solute migration for stone‐covered soil on loessial slopes.     

Does pore water velocity affect the reaction rates of adsorptive solute transport in soils? Demonstration with pore-scale modelling

Modelling adsorptive solute transport in soils needs a number of parameters to describe its reaction kinetics and the values of these parameters are usually determined from batch and displacement experiments. Some experimental results reveal that when describing the adsorption as first-order kinetics, its associated reaction rates are not constants but vary with pore water velocity. Explanation of this varies but an independent verification of each explanation is difficult because simultaneously measuring the spatiotemporal distributions of dissolved and adsorbed solutes in soils is formidable. Pore-scale modelling could play an important role to address this gap and has received increased attention over the past few years. This paper investigated the transport of adsorptive solute in a simple porous medium using pore-scale modelling. Fluid flow through the void space of the medium was assumed to be laminar and in saturated condition, and solute transport consisted of advection and molecular diffusion; the sorption and desorption occurring at the fluid–solid interface were modelled as linear first-order kinetics. Based on the simulated spatiotemporal distribution of dissolved and adsorbed solutes at pore scale, volumetric-average reaction kinetics at macroscopic scale and its associated reactive parameters were measured. Both homogeneous adsorption where the reaction rates at microscopic scale are constant, and heterogeneous adsorption where the reaction rates vary from site to site, were investigated. The results indicate that, in contrast to previously thought, the macroscopic reaction rates directly measured from the pore-scale simulations do not change with pore velocity under both homogeneous and heterogeneous adsorptions. In particular, we found that for the homogeneous adsorption, the macroscopic adsorption remains first-order kinetic and can be described by constant reaction rates, regardless of flow rate; whilst for the heterogeneous adsorption, the macroscopic adsorption kinetics continues not to be affected by flow rate but is no longer first-order kinetics that can be described by constant reaction rates. We discuss how these findings could help explain some contrary literature reports over the dependence of reaction rates on pore water velocity.     

Catchment chemostasis revisited: Water quality responds differently to variations in weather and climate

Solute concentrations in streamflow typically vary systematically with stream discharge, and the resulting concentration–discharge relationships are important signatures of catchment biogeochemical processes. Solutes derived from mineral weathering often exhibit decreasing concentrations with increasing flows, suggesting dilution of a kinetically limited weathering flux by a variable flux of water. However, previous work showed that concentration–discharge relationships of weathering‐derived solutes in 59 headwater catchments were much weaker than this simple dilution model would predict. Instead, catchments behaved as chemostats, with rates of solute production and/or mobilization that were nearly proportional to water fluxes, on both event and interannual timescales. Here, we re‐examine these findings using data for a wider range of solutes from 2,186 catchments, ranging from ~10 to >1,000,000 km² in drainage area and spanning a wide range of lithologic and climatic settings. Concentration–discharge relationships among this much larger set of larger catchments are broadly consistent with the previously described chemostatic behaviour, at least on event and interannual timescales for weathering‐derived solutes. Among these same catchments, however, site‐to‐site variations in mean concentrations of weathering‐derived solutes exhibit strong negative correlations with long‐term average precipitation and discharge, reflecting strong climatic control on long‐term leaching of the critical zone. We use multiple regression of site characteristics including discharge to identify potential controls on long‐term mean concentrations and find that lithologic and land cover controls are significant predictors for many analytes. The picture that emerges is one in which, on event and interannual timescales, weathering‐derived stream solute concentrations are chemostatically buffered by groundwater storage and fast chemical reactions, but each catchment's chemostatic “set point” reflects site‐to‐site differences in climatically driven evolution of the critical zone. In contrast to these weathering products, some nutrients and particulates are often near‐chemostatic across all timescales, and their long‐term mean concentrations correlate more strongly with land use than climatic characteristics.     

Simulation of less‐mobile porosity dynamics in contrasting sediment water interface porous media

Considering heterogeneity in porous media pore size and connectivity is essential to predicting reactive solute transport across interfaces. However, exchange with less‐mobile porosity is rarely considered in surface water/groundwater recharge studies. Previous research indicates that a combination of pore‐fluid sampling and geoelectrical measurements can be used to quantify less‐mobile porosity exchange dynamics using the time‐varying relation between fluid and bulk electrical conductivity. For this study, we use macro‐scale (10 s of cm) advection–dispersion solute transport models linked with electrical conduction in COMSOL Multiphysics to explore less‐mobile porosity dynamics in two different types of observed sediment water interface porous media. Modeled sediment textures contrast from strongly layered streambed deposits to poorly sorted lakebed sands and cobbles. During simulated ionic tracer perturbations, a lag between fluid and bulk electrical conductivity, and the resultant hysteresis, is observed for all simulations indicating differential loading of pore spaces with tracer. Less‐mobile exchange parameters are determined graphically from these tracer time series data without the need for inverse numerical model simulation. In both sediment types, effective less‐mobile porosity exchange parameters are variable in response to changes in flow direction and fluid flux. These observed flow‐dependent effects directly impact local less‐mobile residence times and associated contact time for biogeochemical reaction. The simulations indicate that for the sediment textures explored here, less‐mobile porosity exchange is dominated by variable rates of advection through the domain, rather than diffusion of solute, for typical low‐to‐moderate rate (approximately 3–40 cm/day) hyporheic fluid fluxes. Overall, our model‐based results show that less‐mobile porosity may be expected in a range of natural hyporheic sediments and that changes in flowpath orientation and magnitude will impact less‐mobile exchange parameters. These temporal dynamics can be assessed with the geoelectrical experimental tracer method applied at laboratory and field scales.     

Residence time of bedform-driven hyporheic exchange

Biogeochemical and ecological transformations in hyporheic zones are dependent on the timing of hyporheic exchange. We show through linked modeling of open channel turbulent flow, groundwater flow, and solute transport that the residence time distributions of solutes advected by hyporheic flow induced by current–bedform interaction follow power-laws. This tailing behavior of solutes exiting the sediments is explained by the presence of multiple path lengths coupled with very large variability in Darcy flow velocity, both occurring without heterogeneity in sediment permeability. Hyporheic exchange through bedforms will result in short-time fractal scaling of stream water chemistry.     

Modeling the effects of nonlinear equilibrium sorption on the transport of solute plumes in saturated heterogeneous porous media

Transport of sorbing solutes in 2D steady and heterogeneous flow fields is modeled using a particle tracking random walk technique. The solute is injected as an instantaneous pulse over a finite area. Cases of linear and Freundlich sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. This paper addresses the impact of the degree of heterogeneity and correlation lengths of the log-hydraulic conductivity field as well as negative correlation between the log-hydraulic conductivity field and the log-sorption affinity field on the behavior of the plume of a sorbing chemical. Behavior of the plume is quantified in terms of longitudinal spatial moments: center-of-mass displacement, variance, 95% range, and skewness. The range appears to be a better measure of the spread in the plumes with Freundlich sorption because of plume asymmetry. It has been found that the range varied linearly with the travelled distance, regardless of the sorption isotherm. This linear relationship is important for extrapolation of results to predict behavior beyond simulated times and distances. It was observed that the flow domain heterogeneity slightly enhanced the spreading of nonlinearly sorbing solutes in comparison to that which occurred for the homogeneous flow domain, whereas the spreading enhancement in the case of linear sorption was much more pronounced. In the case of Freundlich sorption, this enhancement led to further deceleration of the solute plume movement as a result of increased retardation coefficients produced by smaller concentrations. It was also observed that, except for plumes with linear sorption, correlation between the hydraulic conductivity and the sorption affinity fields had minimal effect on the spatial moments of solute plumes with nonlinear sorption.     

Analytical solutions for transport of decaying solutes in rivers with transient storage

Analytical solutions are presented for solute transport in rivers including the effects of transient storage and first order decay. The solute transport model considers an advection–dispersion equation for transport in the main channel linked to a first order mass exchange between the main channel and the transient storage zones. In case of a conservative tracer, it is shown that different analytical solutions presented in the literature are mathematically identical. For non-conservative solutes, first order decay reactions are considered with different reaction rate coefficients in the main river channel and in the dead zones. New analytical solutions are presented for different boundary conditions, i.e. instantaneous injection in an infinite river reach, and variable concentration time series input in a semi-infinite river reach. The correctness and accuracy of the analytical solutions is verified by comparison with the OTIS numerical model. The results of analytical and numerical approaches compare favourably and small differences can be attributed to the influence of boundary conditions. It is concluded that the presented analytical solutions for solute transport in rivers with transient storage and solute decay are accurate and correct, and can be usefully applied for analyses of tracer experiments and transport characteristics in rivers with mass exchange in dead zones.     

Variable nitrate concentration–discharge relationships in a forested watershed

The relationship between solute concentrations and discharge can inform an integrated understanding of hydrological and biogeochemical processes at watershed scales. Recent work from multiple catchments has shown that there is typically little variation in concentration relative to large variations in discharge. This pattern has been described as chemostatic behavior. Pond Branch, a forested headwater catchment in Maryland, has been monitored for stream nitrate (NO₃^?) concentrations at weekly intervals for 14 years. In the growing season and autumn of 2011 a high‐frequency optical NO₃^? sensor was used to supplement the long‐term weekly data. In this watershed, long‐term weekly data show that NO₃^? concentrations decrease with increasing discharge whereas 6 months of 15‐minute sensor observed concentrations reveal a more chemostatic behavior. High‐frequency NO₃^? concentrations from the sensor collected during different storm events reveal variable concentration–discharge patterns highlighting the importance of high resolution data and ecohydrological drivers in controlling solute export for biologically reactive solutes such as NO₃^?.     

Simulations of water movement and solute transport through different soil texture configurations under negative‐pressure irrigation

This study examined the effects of different soil texture configurations on water movement and solute transport to provide a reliable scientific basis for the application of negative‐pressure irrigation (NPI) technology. HYDRUS‐2D was used to analyse water movement and solute transport under NPI. The main results are as follows: (a) HYDRUS‐2D can be used to simulate water movement and solute transport under NPI, as there was good agreement between the simulated and measured values for water contents, NaCl concentrations, cumulative water infiltration, and wetting distances in the horizontal and vertical directions; the Nash–Sutcliffe efficiency coefficients were in the range of 0.94–0.97. (b) Layered soils have obvious effects on water movement under NPI. With the emitter position in the loam layer, when a coarse texture of loamy sand was present below the loam layer (namely, L‐LS), irrigation water accumulated in the topsoil, and this led to an increase in evaporation compared with the homogeneous loam profile. However, fine texture silty loam or silty clay loam layers beneath the loam layer (namely, L‐SiL or L‐SiCL, respectively) was more conducive to water infiltration into the lower layer, and this increased the amount of water infiltration and simultaneously reduced the surface evaporation effectively. (c) Layered soils have obvious effects on solute transport under NPI, and salt accumulation will readily occur in the clay‐rich soil layer at the interface. The maximum soil salt accumulation of L‐LS occurred above the soil interface between the two soil layers with a value of 21.80 g/kg; however, for L‐SiCL and L‐SiL, the maximum salt accumulation occurred below the soil interface between the two soil layers, with values of 23.80 g/kg and 20.08 g/kg, respectively. (d) Interlayered soils showed remarkable changes in the water infiltration characteristics and salt‐leaching intensities under NPI, and the properties for the soil profile with a silty loam interlayer were better than those for the soil profile with a silty clay loam interlayer. The soil profile with a loamy sand interlayer had the lowest amount of water infiltration, which resulted in reductions of the salt‐leaching intensities. Thus, NPI is clearly not suitable for loamy sand soil. Overall, the results demonstrated that soil texture configurations affected water movement and solute transport under NPI. Therefore, careful consideration should be given to the use of NPI to achieve target soil water and solution conditions and reduce water loss.     

Effects of suspended sediment characteristics and bed sediment transport on streambed clogging

Fine sediment deposition in streambeds can reduce pore water fluxes and the overall rate of hyporheic exchange, producing deleterious effects on benthic and hyporheic ecological communities. To increase understanding of the factors that control the reduction of hyporheic exchange by fine sediment deposition, we conducted experiments in a laboratory flume to observe changes in the rates of solute exchange and kaolinite clay deposition as substantial amounts of kaolinite accumulated in the streambed. Two long‐term experiments were conducted, with durations of 14 days and 29 days. Use of a laboratory flume system allowed steady stream flow conditions to be maintained throughout both experiments, and alternating injections of known quantities of kaolinite and a sodium chloride tracer were used to assess the effect of clay accumulation on hyporheic exchange directly. In the first experiment, there was no bed sediment transport and kaolinite deposition formed a highly clogged near‐surface layer that greatly reduced hyporheic exchange. Application of a fundamental model for advective hyporheic exchange indicated that the effective permeability and porosity of the streambed decreased substantially during the course of the experiment. In the second experiment, the kaolinite was prepared with different surface properties to be more mobile, and the experiment was conducted with a small degree of bed sediment transport. As a result, no distinct clogged layer developed, and the rate of hyporheic exchange was found to remain approximately constant throughout the experiment (29 days). These results indicate that increasing fine sediment loads, e.g. those that occur from changes in land use, can have substantially different impacts on hyporheic exchange and associated ecological processes depending on the stream flow conditions, the rate and frequency of bed sediment transport, and the extent of interaction of the introduced fines with bed sediments. Copyright © 2004 John Wiley & Sons, Ltd.