Asymptotic Analysis of Solute Transport with Linear Nonequilibrium Sorption in Porous Media

We analysed the asymptotic behaviour of breakthrough curves (BTCs) obtained after a single pulse injection in a 1D flow domain. Five different types of solute transport with nonequilibrium sorption were considered. The properties of the porous medium were assumed to be spatially constant. For long times, the concentration at a fixed position in time was found to decay like exp(–t) where depends on both the transport parameters and the parameters describing the nonequilibrium process. The results from the asymptotic analysis were compared with 1D numerical transport calculations. For all cases examined a good agreement between numerical calculations and the asymptotic analysis was found. The results from the asymptotic analysis provide an alternative way to determine transport and sorption related parameters from BTCs. The derived relationships between and the model parameters are however only valid for large times. This requires that the very low concentrations need to be measured and not only the bulk mass, too. By either increasing or decreasing the velocity during BTC experiments additional asymptotic equations are obtained which can be used to determine the value of the model parameters. The results from the asymptotic analysis can also be used in standard inverse modelling techniques to either obtain good initial guesses or to reduce the parameter space. The fact that linear nonequilibrium processes decay like exp(–t) can be used to qualitatively evaluate observed BTCs. The asymptotic analysis can also be easily extended to a larger class of transport problems (e.g. transport of solutes with microbial decay) provided that the overall transport problem remains linear in the concentration.     

Analytical Solution for the Effect of Viscous Dissipation on Mixed Convection in Saturated Porous Media

A new analytical solution is introduced for the effect of viscous dissipation on mixed convection flow and heat transfer about an isothermal vertical wall embedded in Darcy and non-Darcy porous media with uniform free stream velocity. The effect of viscous dissipation on mixed convection in both regimes has been analyzed for both the aiding and opposing flows using Gebhart number, Ge _x =gx/c _p. The governing parameters are Re, Ra, Pe and Ge _x . The case of Re=0 corresponds to Darcy mixed convection region and Re/Pe is identified as the mixed convection governing parameter, Ra=0 leading to pure forced convection. A good agreement was found between the numerical and analytical solutions. It was found from the Nusselt number results that viscous dissipation lowers the heat transfer rate in both Darcy and Forchheimer flow regimes for aiding as well as opposing flows.     

Comparison of Kinetic and Hybrid-Equilibrium Models Simulating Colloid-Facilitated Contaminant Transport in Porous Media

The presence of colloidal particles in groundwater can enhance contaminant transport by reducing retardation effects and carrying them to distances further than predicted by a conventional advective/dispersive equation with normal retardation values. When colloids exist in porous media and affect contaminant migration, the system can best be simulated as a three-phase medium. Mechanisms of mass transfer from one phase to another by colloids and contaminants can be kinetic or equilibrium-based, depending on the sorption–desorption reaction rate between the aqueous and solid phases. When the rate of sorption between the water phase and the solid phase(s) is not much greater than the rate of change in contaminant concentration in the water phase, kinetic sorption models may better describe the phenomenon. In some cases of modeling one or more mass transfer processes, a useful simplification may be to introduce the local equilibrium assumption. In this study, the local equilibrium assumption for sorption processes on colloidal surfaces (hybrid equilibrium model) was compared with kinetic-based models. Sensitivity analyses were conducted to deduce the effect of major parameters on contaminant transport. The results obtained from the hybrid equilibrium model in predicting the transport of colloid-facilitated groundwater contaminant are very similar to those of the kinetic model, when the point of interest is not at contaminant and colloid source vicinities and the time of interest is sufficiently long for imposed sources.     

Delay Model for a Cycling Transport Through Porous Medium

A solute transport through a porous medium is examined provided that the fluid leaving the porous sample returns back in a continuous way. The porous medium is thus included into a closed hydrodynamic circuit. This cycling process is suggested as an experimental tool to determine porous medium parameters describing transport. In the present paper the mathematical theory of this method is developed. For the advective type of transport with solute retention and degradation in porous medium, the system of transport equations in a closed circuit is transformed to a delay differential equation. The exact analytical solution to this equation is obtained. The solute concentration manifests both the oscillatory and monotonous behaviors depending on system parameters. The number of oscillation splashes is shown to be always finite. The maximum/minimum points are determined as solutions of a polynomial equation whose degree depends on the unknown solution itself. The cyclic methods to determine porous medium parameters as porosity and retention rate are developed.     

An Analytical Solution to the One-Dimensional Solute Advection-Dispersion Equation in Multi-Layer Porous Media

An analytical solution to the one-dimensional solute advection-dispersion equation in multi-layer porous media is derived using a generalized integral transform method. The solution was derived under conditions of steady-state flow and arbitrary initial and inlet boundary conditions. The results obtained by this solution agree well with the results obtained by numerically inverting Laplace transform-generated solutions previously published in the literature. The analytical solution presented in this paper provides more flexibility with regard to the inlet conditions. The numerical evaluation of eigenvalues and matrix exponentials required in this solution technique can be accurately and efficiently computed using the sign-count method and eigenvalue evaluation methods commonly available. The illustrative calculations presented herein have shown how an analytical solution can provide insight into contaminant distribution and breakthrough in transport through well defined layered column systems. We also note that the method described here is readily adaptable to two and three-dimensional transport problems.     

Transport of Viruses Through Saturated and Unsaturated Columns Packed with Sand

Laboratory-scale virus transport experiments were conducted in columns packed with sand under saturated and unsaturated conditions. The viruses employed were the male-specific RNA coliphage, MS2, and the Salmonella typhimurium phage, PRD1. The mathematical model developed by Sim and Chrysikopoulos (Water Resour Res 36:173–179, 2000) that accounts for processes responsible for removal of viruses during vertical transport in one-dimensional, unsaturated porous media was used to fit the data collected from the laboratory experiments. The liquid to liquid–solid and liquid to air–liquid interface mass transfer rate coefficients were shown to increase for both bacteriophage as saturation levels were reduced. The experimental results indicate that even for unfavorable attachment conditions within a sand column (e.g., phosphate-buffered saline solution; pH = 7.5; ionic strength = 2 mM), saturation levels can affect virus transport through porous media.     

Experiments on Solute Transport in Aggregated Porous Media: Are Diffusions Within Aggregates and Hydrodynamic Dispersion Independent?

Two region models for solute transport in porous media assume that hydrodynamic dispersion in mobile water and solute diffusion within immobile water regions are independent. Experimental and theoretical results for transport through a macropore indicate that hydrodynamic dispersion and solute exchange are interdependent. Experiments were carried out to investigate this problem for a column packed with spherical porous aggregates. The effective diffusion coefficient of a tracer within the agreggates was determined from specific experiments. The dispersivity of the bed was determined from experiments carried out with a column filled with nonporous beads. We took advantage of the dependence of hydrodynamic dispersion on density ratios between the invading and displaced solutions to obtain a set of breakthrough curves corresponding to situations where the diffusion coefficient remains constant, whereas the dispersivity varies. Simulations reproduce correctly the experiments. Small discrepancies are noted that can be corrected either by increasing the dispersion coefficient or by fitting the external mass transfer coefficient. Increased dispersion coefficients probably reveal a modification of Taylor dispersion due to solute exchange. The fitted external mass transfer coefficients are close to the values obtained with classical correlations of the chemical engineering literature.     

Upscaling of Nonwetting Phase Residual Transport in Porous Media: A Network Approach

Based on the volume averaging method, a macroscopic model is developed for the upscaling of NAPL transport in a porous medium idealised by a network model. Under the assumption of local mass non-equilibrium, a macroscopic equation involving a dispersion tensor, additional convective terms and a linear form for the interfacial mass flux is obtained. The resolution of the two local closure problems obtained allow the determination of the local properties without adjustable parmeters. These problems are solved in a semi-analytical, semi-numerical manner on the network. The originality of this work is the association of the upscaling by volume averaging method with the network approach. The local properties, including the dispersion tensor and the mass exchange coefficient, can therefore be calculated over a large number of pore-bodies and pore-throats in a computationaly tractable manner, thus leading to more significant results. Results are presented for 3D, spatially periodic models of porous media.     

The Role of Biofilm Growth in Bacteria-Facilitated Contaminant Transport in Porous Media

Groundwater contaminants adhered to colloid surfaces may migrate to greater distances than predicted by using the conventional advective-dispersive transport equation. Introduction of exogenous bacteria in a bioremediation operation or mobilization of indigenous bacteria in groundwater aquifers can enhance the transport of contaminants in groundwater by reducing the retardation effects. Because of their colloidal size and favorable surface conditions, bacteria can be efficient contaminant carriers. In cases where contaminants have low mobility because of their high partition with aquifer solids, facilitated contaminant transport by mobile bacteria can create high contaminant fluxes. In this paper, we developed a methodology to describe the bacteria-facilitated contaminant transport in a subsurface environment using the biofilm theory. The model is based on mass balance equations for bacteria and contaminant. The contaminant is utilized as a substrate for bacterial growth. Bacteria are attached to solid surfaces as a biofilm. We investigate the role of the contaminant adsorption on both biofilm and mobile bacteria on groundwater contaminant transport. Also, the effect of bacterial injection on the contaminant transport is evaluated in the presence of indigenous bacteria in porous media. The model was solved numerically and validated by experimental data reported in the literature. Sensitivity analyses were conducted to deduce the effect of critical model parameters. Results show that biofilm grows rapidly near the top of the column where the bacteria and contaminant are injected, and is detached by increasing fluid shear stress and re-attach downstream. The adsorption of contaminant on bacterial surfaces reduces contaminant mobility remarkably in the presence of a biofilm. The contaminant concentration decreases significantly along the biofilm when contaminant partition into bacteria. Bacterial injection and migration in subsurface environments can be important in bioremediation operations regardless of the presence of indigenous bacteria.     

Analytical Solutions for Solute Transport in a Spherically Symmetric Divergent Flow Field

Exact analytical solutions for an equation describing advection, dispersion, first-order decay, and rate-limited sorption of a solute in a steady, hemispherical or spherically symmetric, divergent flow field are presented for constant concentration and constant flux boundary conditions in a porous medium. The partial differential equation describing transport is a confluent hypergeometric equation that may be solved with variable substitution and Laplace transform, and the solutions are expressed by parabolic cylindrical functions. The novel solutions derived here may be applied to predict concentration distributions in space and time for porous media transport in a spherically symmetric flow field or for the special case where injection is just below a confining layer (hemispherical flow). The analytical solutions can be used to simulate wastewater injection from short-screened wells into thick formations or to analyze tracer tests that use short-screened wells to create approximately spherical flow fields in thick formations.     

Free-Boundary Problems for Nonlinear Models of Fluid Filtration in Inhomogeneous Porous Media

Existence theorems are proved for solutions of problems of nonlinear gravity fluid filtration in regions with specified boundaries of complex geometry. The theory developed can be used to design the underground flow net of a hydraulic structure with specified filtration characteristics.     

Stochastic Simulations of NAPL Mass Transport in Variably Saturated Heterogeneous Porous Media

A multiphase flow and transport numerical model is developed to study the effects of porous media heterogeneities on residual NAPL mass partitioning and transport of dissolved and/or volatilized NAPL mass in variably saturated media. The results indicate the significance of porous media heterogeneity in influencing the mass transfer processes and NAPL transport in the subsurface. Among the parameters investigated in this study, the heterogeneity of the permeability field has the most significant influence on the NAPL mass partitioning and transport. In general, the heterogeneity of the porous media properties enhances the NAPL mass plume spreading in both the water phase and the gas phase while the influence on the water phase is much more significant. Overall, the porous media property heterogeneities tend to increase the accumulation of NAPL mass in the water phase. The nonequilibrium mass transfer processes result in the expected trend of decreasing the NAPL mass dissipation rate and causing long-term groundwater contamination.     

Local Mass Transfer Correlations for Nonaqueous Phase Liquid Pool Dissolution in Saturated Porous Media

Local mass transfer correlations are developed to describe the rate of interface mass transfer of single component nonaqueous phase liquid (NAPL) pools in saturated subsurface formations. A threedimensional solute transport model is employed to compute local mass transfer coefficients from concentration gradients at the NAPL–water interface, assuming that the aqueous phase concentration along the NAPL–water interface is constant and equal to the solubility concentration. Furthermore, it is assumed that the porous medium is homogeneous, the interstitial fluid velocity steady and the dissolved solute may undergo firstorder decay or may sorb under local equilibrium conditions. Powerlaw expressions relating the local Sherwood number to appropriate local Peclet numbers are developed for both rectangular and elliptic/circular source geometries. The proposed power law correlations are fitted to numerically generated data and the correlation coefficients are determined using nonlinear least squares regression. The estimated correlation coefficients are found to be direct functions of the interstitial fluid velocity, pool dimensions, and pool geometry.     

Conservative Solute Versus Heat Transport in Porous Media During Push-pull Tests

Both heat and solute transport in porous media are described by partial differential equations of similar form. Nevertheless, observing these phenomena in the field on the scale of well tests clearly indicates dissimilar behaviour. This article studies the aforementioned transport processes by interpreting two push-pull tests of different duration. In both tests, chloride is applied as a conservative tracer and lower temperature water is injected in higher temperature pristine water at different flow rates. Simulation and interpretation of the tests are performed by means of ReacTrans, a two-dimensional, axially symmetric, finite-difference, solute and heat transport model. Since conflicting views exist in literature on the relation between solute and thermal dispersivity, analysis of field observations focuses on parameters which describe aquifer characteristics affecting these processes. Parameter estimation is conducted through sensitivity analysis and collinear diagnosis in order to identify derivable parameters. It is concluded that longitudinal solute dispersivity and thermal diffusivity could be inferred accurately from chloride and temperature data sampled from the injection/extraction well respectively. Involving supplementary data sampled from an observation well enables derivation of effective porosity from chloride data and thermal retardation from temperature data. Moreover, it is inferred that longitudinal solute dispersivity is scale dependent. Thermal diffusivity, however, seems not to be. This points to dissimilar development of transition zones during solute and heat transport. It is concluded that conductive transport of heat is much more important than effects of velocity variations through the pore space.     

Comments on ‘Analytical Solution for the Effect of Viscous Dissipation on Mixed Convection in Saturated Porous Media’, Transport in Porous Media 41, 197–209, 2000

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Thermodynamic Correction for Salts in Variably Saturated Porous Media

Using thermodynamic principles, the general relationship describing the equilibrium vapor content in the gas phase above a saline liquid and across a curved liquid–gas interface is developed. Since high salt concentration affects the intensive and extensive liquid properties, it is also necessary to account for these effects in liquid water content/liquid water pressure relationship curves so that experimentally derived curves for pure water may be useful for elevated salt concentrations. The appropriate thermodynamic relationships are derived to describe the salt effects on liquid and vapor properties. The resulting equations are valid for salt concentrations between zero and saturation, and for any temperatures that nominally occur in nearsurface geologic materials.     

Laboratory Investigation of Variable-Density Flow and Solute Transport in Unsaturated–Saturated Porous Media

In many groundwater systems, fluid density and viscosity may vary in space and time as a function of changes in concentration and temperature of the fluid. When dense groundwater plumes interact with less dense ambient groundwater, these density variations can significantly affect flow and transport processes. Under certain conditions, gravitational instabilities in the form of lobe-shaped fingers can occur. This process is significant because it can lead to more rapid and spatially extensive solute transport. This paper presents new experiments carried out in a sand filled glass flow container under both fully saturated and variably-saturated conditions and focuses upon the processes that occur at the capillary fringe and below the water table, as affected by a dense contaminant plumes migration through the unsaturated zone. Source fluids stained with Rhodamine-WT were introduced at the upper boundary of the tank at a range of low and high densities. In addition to the fluid density gradients and porous medium permeability that determine the onset conditions for instabilities in fully saturated experiments, volumetric water content appears critical in the variably-saturated laboratory runs. Plume behaviour at the water table appears dependent upon the density of the fluid that accumulates there. For neutral and low density fluids, plumes accumulate at the water table and then spread laterally above it and the water table forms a barrier to further vertical flow as pore water velocities reduce with increasing water content. For medium and high density fluids, vertical movement continues as instabilities form at the capillary fringe and fingers begin to grow at the water table boundary and move downwards into the saturated zone. In these cases, lateral spreading of the plume is small. Despite these more qualitative observations, the exact nature of the relevant stability criteria for the onset and growth of instabilities in variably-saturated porous media presently remain unclear. All experimental results suggest, however, that the unsaturated zone and position of the water table must be considered in contaminant studies in order to predict the migration pathways, rates and ultimate fate of dense contaminant plumes. It is possible that the results of experiments presented in this paper could form a useful basis for the testing of variable-density (and variably-saturated) groundwater flow and solute transport numerical codes because they offer controlled physical laboratory analogs for comparison. They also provide a strong basis for the development of more rigorous mathematical formulations that are likely to be either developed or tested using numerical flow and solute transport simulators.     

Analytical Solutions for Reactive Transport of Multiple Volatile Contaminants in the Vadose Zone

Groundwater contamination usually originates from surface contamination. Contaminants then move downward through the vadose zone and finally reach the groundwater table. To date, however, analytical solutions of multi-species reactive transport are limited to transport only in the saturated zone. The motivation of this work is to utilize analytical solutions, which were previously derived for single-phase transport, to describe the reactive transport of multiple volatile contaminants in the unsaturated zone. A mathematical model is derived for describing transport with phase partitioning of sequentially reactive species in the vadose zone with constant flow velocity. Linear reaction kinetics and linear equilibrium partitioning between vapor, liquid, and solid phases are assumed in this model.