Influence of transient flow on contaminant biodegradation

The rate of biodegradation in contaminated aquifers depends to a large extent on dispersive mixing processes that are now generally accepted to result from spatial variations in the velocity field. It has been shown, however, that transient flow fields can also contribute to dispersive mixing. The influence of transient flow on biodegrading contaminants is particularly important since it can enhance mixing with electron acceptors, further promoting the reactive process. Using numerical simulations, the effect of transient flow on the behavior of a biodegradable contaminant is evaluated here both with respect to the development of apparently large horizontal transverse dispersion and also with respect to enhanced mixing between the substrate (electron donor) and electron acceptor. The numerical model BIO3D, which solves for advective-dispersive transport coupled with Monod-type biodegradation of substrates in the presence of an electron acceptor, was used for the simulations. The model was applied in a two-dimensional plan view mode considering a single substrate. Transient flow fields were found to yield larger apparent transverse dispersion because the longitudinal dispersivity also acts transverse to the mean flow direction. In the reactive case, the transient flow field increases substrate-oxygen mixing, which in turn enhances the overall rate of biodegradation. The results suggest that in the case of moderate changes of flow directions, a steady-state flow field can be justified, thereby avoiding the higher computational costs of a fully transient simulation. The use of a higher transverse horizontal dispersivity in a steady flow field can, under these conditions, adequately forecast plume development.     

A Critical Analysis of Transverse Dispersivity Field Data

Transverse dispersion, or tracer spreading orthogonal to the mean flow direction, which is relevant e.g, for quantifying bio-degradation of contaminant plumes or mixing of reactive solutes, has been studied in the literature less than the longitudinal one. Inferring transverse dispersion coefficients from field experiments is a difficult and error-prone task, requiring a spatial resolution of solute plumes which is not easily achievable in applications. In absence of field data, it is a questionable common practice to set transverse dispersivities as a fraction of the longitudinal one, with the ratio 1/10 being the most prevalent. We collected estimates of field-scale transverse dispersivities from existing publications and explored possible scale relationships as guidance criteria for applications. Our investigation showed that a large number of estimates available in the literature are of low reliability and should be discarded from further analysis. The remaining reliable estimates are formation-specific, span three orders of magnitude and do not show any clear scale-dependence on the plume traveled distance. The ratios with the longitudinal dispersivity are also site specific and vary widely. The reliability of transverse dispersivities depends significantly on the type of field experiment and method of data analysis. In applications where transverse dispersion plays a significant role, inference of transverse dispersivities should be part of site characterization with the transverse dispersivity estimated as an independent parameter rather than related heuristically to longitudinal dispersivity.     

Two-dimensional concentration distribution for mixing-controlled bioreactive transport in steady state

Under steady-state conditions, the degradation of contaminant plumes introduced continuously into an aquifer is controlled by transverse dispersion when the other reacting compound is provided from ambient groundwater. Given that the reaction is instantaneous and longitudinal dispersion can be neglected, the length of the plume is inversely proportional to the transverse dispersion coefficient. In typical scenarios of natural attenuation, however, the considered reaction is biotic and kinetic. The standard model of bioreactive transport relies on double-Monod kinetics and pseudo first-order biomass decay. Under these conditions, a fraction of the injected mass flux remains beyond the length of the plume determined for the instantaneous reaction. We present an analytical framework to derive the steady-state concentration distributions of the dissolved compounds and the biomass from the concentration distribution of a conservative compound, assuming double-Monod kinetics and two different models describing biomass decay. The first biomass-decay model assumes a constant first-order decay coefficient, while the second assumes that the decay coefficient depends upon the electron-acceptor concentration. We apply the method to the case of a line-injection in two-dimensional uniform flow. In general, the bioreactive concentration distributions are similar to the distributions computed for an instantaneous reaction. The similarity is greater when the biomass decay coefficient is assumed to depend on the electron-acceptor concentration rather than being constant.     

Simulation of Tidal Effects on Contaminant Transport in Porous Media

A one-dimensional numerical model is developed with oscillating velocities and dispersions to simulate the migration process of a contaminant plume within tidally influenced aquifers. Model simulations demonstrate that a major effect the tidal fluctuation has on the migration process of a contaminant plume is the exit concentration discharging to the tidal estuary. Tidal fluctuation causes the exit concentration levels to be significantly diluted by the surface-water body of the estuary. Sensitivity analyses demonstrate that tidal fluctuation hastens the rate of plume migration near the bank of the estuary because of the relatively high advective and dispersive fluxes induced by tides. However, tides affect the migration process only over a short distance from the tidal-water interface (about 40 ft for the parameters used in this study). If the contaminant plume is located far beyond the interface, tidal fluctuations will not affect the rate of plume migration until an existing regional ground-water flow velocity brings the plume to the tidally active zone. With or without tides, the rate of contaminant migration increases with higher regional hydraulic gradient. Furthermore, the effects of tidal fluctuations on the transport process become insignificant with higher regional hydraulic gradients.     

Solute transport in heterogeneous media: The impact of anisotropy and non-ergodicity in risk assessment

Conceptual model selection is a key issue in risk assessment studies. We analyze the effect of a number of conceptual aspects related to solute transport in two-dimensional heterogeneous media. The main issues addressed are non-ergodicity, anisotropy in the correlation structure of the transmissivity field, and dispersion at the local scale. In particular, we study the development of a solute plume when mean flow is oriented at an angle with respect to the principal directions of anisotropy. The study is carried out in a Lagrangian framework using Monte Carlo analysis. Of special interest is the evolution of individual plumes. A number of aspects are analyzed, namely the location of the center of mass for each plume and the different ways to compute the angles that the main axes of the plume develop with respect to the direction of the mean flow. Stochastic theories based upon ergodicity conclude that the plume gets oriented in the mean flow direction. In our non-ergodic simulations, the mean of the offset angles, for each individual plume in each particular realization, is offset from the mean flow direction towards the direction of maximum anisotropy. If, instead, the analysis is performed on the ensemble plume (superposition of all different simulations), it is then found oriented closer to the direction of the mean flow than the average offset angle for the different plumes considered separately. This last result adds an extra word of caution to the use of ensemble averaged values in solute transport studies. Serious implications for risk assessment follow from the conceptual model adopted. First, in any single realization there will a large uncertainty in locating the plume at any given time; second, real dilution would be less than what would be expected if the macrodispersion values obtained for ergodic conditions were applied; third, the volume that is affected by a non-zero concentration is smaller than that predicted from macrodispersion concepts; fourth, the orientation of the plume does not correspond to that of the mean flow; and fifth, accounting for local dispersion helps reducing uncertainty.     

Effective dispersion in conditioned transmissivity fields

We analyze the impact of conditioning to measurements of hydraulic transmissivity on the transport of a conservative solute. The effects of conditioning on solute transport are widely discussed in the literature, but most of the published works focuses on the reduction of the uncertainty in the prediction of the plume dispersion. In this study both ensemble and effective plume moments are considered for an instantaneous release of a solute through a linear source normal to the mean flow direction, by taking into account different sizes of the source. The analysis, involving a steady and spatially inhomogeneous velocity field, is developed by using the stochastic finite element method. Results show that conditioning reduces the ensemble moment in comparison with the unconditioned case, whereas the effective dispersion may increase because of the contribution of the spatial moments related to the lack of stationarity in the flow field. As the number of conditioning points increases, this effect increases and it is significant in both the longitudinal and transverse directions. Furthermore, we conclude that the moment derived from data collected in the field can be assessed by the conditioned second-order spatial moment only with a dense grid of measured data, and it is manifest for larger initial lengths of the plume. Nevertheless, it seems very likely that the actual dispersion of the plume may be underestimated in practical applications.     

Effect of tidal forcing on a subterranean estuary

Groundwater flow and chemical transport in subterranean estuaries are poorly understood despite their potentially important implications for chemical fluxes from aquifers to coastal waters. Here, a numerical study of the dynamics in a subterranean estuary subject to tidal forcing is presented. Simulations show that salt transport associated with tidally driven seawater recirculation leads to the formation of an upper saline plume in the intertidal region. Computed transit times and flow velocities indicate that this plume represents a more active zone for mixing and reaction than the dispersion zone of the lower, classical salt wedge. Proper conceptualisation of this surficial mixing zone extends our understanding of processes within the subterranean estuary. Numerical tracer simulations reveal that tidal forcing may reduce the threat of a land-derived contaminant discharging to the marine environment by modifying the subsurface transport pathway and local geochemical conditions. Mixing and stratification in the subterranean estuary are strongly affected by both inland and tidal forcing. Based on the estuarine analogy we present a systematic classification of subterranean estuaries.     

Micro-scale modelling in the study of plume evolution in heterogeneous media

The migration of contaminants in heterogeneous aquifers involves dispersive processes that act at different scales. The interaction of these processes as a plume evolves can be studied by micro-scale modelling whereby two scales, a local- or micro-scale and an aquifer- or macro-scale, are covered simultaneously. Local-scale dispersive processes are represented through the local dispersion coefficient in the transport equation, while large-scale dispersion due to heterogeneities is represented through the resolution of the flow field and the diffusive exchange between streamtubes. The micro-scale model provides both the high degree of resolution compatible with local-scale processes, and the extent required for the approach to asymptotic conditions, using grids of up to a million nodal points. The model is based on the dual potential-streamfunction formulation for flow, and the transport problem is formulated in a natural coordinate system provided by the flownet. Simulations can be used to verify stochastic theories of dispersion, without the restrictive assumptions inherent in the theory. For the two-dimensional case, results indicate convergence of the effective dispersivity to the theoretical macrodispersivity value. Convergence takes place within a travel distance of about 50 correlation lengths of the hydraulic conductivity field. However, the approach taken to asymptotic conditions, as well as the macrodispersivity value, may differ for different realizations of the same medium. The influence of early-time events such as plume splitting on the asymptotic convergence remains to be investigated.     

Effects of Process Control Changes on Aquifer Oxygenation Rates During In Situ Air Sparging in Homogeneous Aquifers

In situ air sparging is used to remediate petroleum fuels and chlorinated solvents present as submerged contaminant source /ones and dissolved contaminant plumes, or to provide barriers to dissolved contaminant plume migration. Contaminant removal occurs through a combination of volatilization and aerobic biodegradation: thus, the performance at any given site depends on the contaminant and oxygen mass transfer rates induced by the air injection. It has been hypothesized that these rates are sensitive to changes in process flow conditions and site lithology, but no data is available to identify trends or the magnitude of the changes. In this work, oxygenation rates were measured for a range of air injection rates, ground water flow rates, and pulsing frequencies using a laboratory-scale two-dimensional physical model constructed to simulate a homogeneous hydrogeologic setting. Experiments were conducted with water having low chemical and biochemical oxygen demand. Results suggest the following: that there is an optimum air injection rate: advective How of ground water can be a significant factor when ground water velocities are > 0.3 m/d: and pulsing the air injection had little effect on the oxygenation rate relative lo the continuous air injection case.     

Error analysis of finite difference methods for two-dimensional advection–dispersion–reaction equation

In this paper, the numerical errors associated with the finite difference solutions of two-dimensional advection–dispersion equation with linear sorption are obtained from a Taylor analysis and are removed from numerical solution. The error expressions are based on a general form of the corresponding difference equation. The variation of these numerical truncation errors is presented as a function of Peclet and Courant numbers in X and Y direction, a Sink/Source dimensionless number and new form of Peclet and Courant numbers in X–Y plane. It is shown that the Crank–Nicolson method is the most accurate scheme based on the truncation error analysis. The effects of these truncation errors on the numerical solution of a two-dimensional advection–dispersion equation with a first-order reaction or degradation are demonstrated by comparison with an analytical solution for predicting contaminant plume distribution in uniform flow field. Considering computational efficiency, an alternating direction implicit method is used for the numerical solution of governing equation. The results show that removing these errors improves numerical result and reduces differences between numerical and analytical solution.     

Determination of transverse dispersion coefficients from reactive plume lengths

With most existing methods, transverse dispersion coefficients are difficult to determine. We present a new, simple, and robust approach based on steady-state transport of a reacting agent, introduced over a certain height into the porous medium of interest. The agent reacts with compounds in the ambient water. In our application, we use an alkaline solution injected into acidic ambient water. Threshold values of pH are visualized by adding standard pH indicators. Since aqueous-phase acid-base reactions can be considered practically instantaneous and the only process leading to mixing of the reactants is transverse dispersion, the length of the plume is controlled by the ratio of transverse dispersion to advection. We use existing closed-form expressions for multidimensional steady-state transport of conservative compounds in order to evaluate the concentration distributions of the reacting compounds. Based on these results, we derive an easy-to-use expression for the length of the reactive plume; it is proportional to the injection height squared, times the velocity, and inversely proportional to the transverse dispersion coefficient. Solving this expression for the transverse dispersion coefficient, we can estimate its value from the length of the alkaline plume. We apply the method to two experimental setups of different dimension. The computed transverse dispersion coefficients are rather small. We conclude that at slow but realistic ground water velocities, the contribution of effective molecular diffusion to transverse dispersion cannot be neglected. This results in plume lengths that increase with increasing velocity.     

Monte Carlo evaluation of microbial-mediated contaminant reactions in heterogeneous aquifers

Monte Carlo simulations are conducted to evaluate microbial-mediated contaminant reactions in an aquifer comprised of spatially variable microbial biomass concentrations, aquifer hydraulic conductivities, and initial electron donor/acceptor concentrations. A finite element simulation model is used that incorporates advection, dispersion, and Monod kinetic expressions to describe biological processes. Comparisons between Monte Carlo simulations of heterogeneous systems and simulations using homogeneous formulation of the same two-dimensional transport problem are presented. For the assumed set of parameters, physical aquifer heterogeneity is found to have a minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system; however, it noticeably changes the dispersion, skewness, and peakness of contaminant concentration distributions. Similarly, for low microbial growth rate, given favorable microbial growth characteristics, biological heterogeneity has minor effect on the mass of contaminant biodegraded/transformed when compared to a homogeneous system. On the other hand, when higher effective growth rates are assumed, biological heterogeneity and spatial heterogeneities in essential electron donor/acceptors reduce the efficiency of biotic contaminant reactions; consequently, model simulations derived from heterogeneous biomass distributions predict remediation time scales that are longer than those simulated for homogeneous systems. When correlations between physical aquifer and biological heterogeneities are considered, the assumed correlation affects predicted mean and variance of contaminant concentration and biomass distributions. For example, an assumed negative correlation between hydraulic conductivity and the initial biomass distribution produces a plume where less efficient biotic contaminant reactions occur at the leading edge of the plume; this is consistent with less degradation/transformation occurring over regions of higher groundwater velocities. However, the presence and absence of these correlations do not appear to affect the efficiency of microbial-mediated contaminant attenuation.     

Reactive transport in stratified flow fields with idealized heterogeneity

A two-dimensional equation governing the steady state spatial concentration distribution of a reactive constituent within a heterogeneous advective–dispersive flow field is solved analytically. The solution which is developed for the case of a single point source can be generalized to represent analogous situations with any number of separate point sources. A limiting case of special interest has a line source of constant concentration spanning the domain’s upstream boundary. The work has relevance for improving understanding of reactive transport within various kinds of advection-dominated natural or engineered environments including rivers and streams, and bioreactors such as treatment wetlands. Simulations are used to examine quantitatively the impact that transverse dispersion (deviations from purely stochastic-convective flow) can have on mean concentration decline in the direction of flow. Results support the contention that transverse mixing serves to enhance the overall rate of reaction in such systems.     

Methodology for comparing source and plume remediation alternatives

It is often difficult at contaminated sites to decide whether remediation effort should be focused on the contaminant source, the dissolved plume, or on both zones. The decision process at these sites is hampered by a lack of quantitative tools for comparing remediation alternatives. A new screening-level mass balance approach is developed for simulating the transient effects of simultaneous ground water source and plume remediation. The contaminant source model is based on a power function relationship between source mass and source discharge, and it can consider partial source remediation at any time after the initial release. The source model serves as a time-dependent mass flux boundary condition to a new analytical plume model, where flow is assumed to be one dimensional, with three-dimensional dispersion. The plume model simulates first-order sequential decay and production of several species, and the decay rates and parent/daughter yield coefficients are variable functions of time and distance. This new method allows for flexible simulation of natural attenuation or remediation efforts that enhance plume degradation. The plume remediation effort may be temporary or delayed in time, limited in space, and it may have different chemical effects on different contaminant species in the decay chain.     

Capture and release zones of permeable reactive barriers under the influence of advective–dispersive transport in the aquifer

The problem of permeable reactive barrier (PRB) capture and release behavior is investigated by means of an approximate analytical approach exploring the invariance of steady-state solutions of the advection–dispersion equation to conformal mapping. PRB configurations considered are doubly-symmetric funnel-and-gate as well as less frequent drain-and-gate systems. The effect of aquifer heterogeneity on contaminant plume spreading is hereby incorporated through an effective transverse macro-dispersion coefficient, which has to be known. Results are normalized and graphically represented in terms of a relative capture efficiency M of contaminant mass or groundwater passing a control plane (transect) at a sufficient distance up-stream of a PRB as to comply with underlying assumptions. Factors of safety FS are given as the ratios of required capture width under advective–dispersive and purely advective transport for achieving equal capture efficiency M. It is found that M also applies to the release behavior down-stream of a PRB, i.e., it describes the spreading and dilution of PRB treated groundwater possibly containing incompletely remediated contamination and/or remediation reaction products. Hypothetical examples are given to demonstrate results.     

Modeling plume behavior for nonlinearly sorbing solutes in saturated homogeneous porous media

Transport of a sorbing solute in a two-dimensional steady and uniform flow field is modeled using a particle tracking random walk method. The solute is initially introduced from an instantaneous point source. Cases of linear and nonlinear sorption isotherms are considered. Local pore velocity and mechanical dispersion are used to describe the solute transport mechanisms at the local scale. The numerical simulation of solute particle transport yields the large scale behavior of the solute plume. Behavior of the plume is quantified in terms of the center-of-mass displacement distance, relative velocity of the center-of-mass, mass breakthrough curves, spread variance, and longitudinal skewness. The nonlinear sorption isotherm affects the plume behavior in the following way relative to the linear isotherm: (1) the plume velocity decreases exponentially with time; (2) the longitudinal variance increases nonlinearly with time; (3) the solute front is steepened and tailing is enhanced     

Computational issues in the determination of solute discharge moments and implications for comparison to analytical solutions

Solute discharge moments (mean and variance) are computed using numerical modeling of flow and advective transport in two-dimensional heterogeneous aquifers and are compared to theoretical results. The solute discharge quantifies the temporal evolution of the total contaminant mass crossing a certain compliance boundary. In addition to analyzing the solute discharge moments within a classical absolute dispersion framework, we also analyze relative dispersion formulation, whereby plume meandering (deviation from mean flow path caused by velocity variations at scales larger than plume size) is removed. This study addresses some important issues related to the computation of solute discharge moments from random walk particle tracking experiments, and highlights some of the important differences between absolute and relative dispersion frameworks. Relative dispersion formulation produces maximum uncertainty that coincides with the peak mean discharge. Absolute dispersion, however, results in earlier arrival of the uncertainty peak as compared to the first moment peak. Simulations show that the standard deviation of solute discharge in a relative dispersion framework requires increasingly large temporal sampling windows to smooth out some of the large fluctuations in breakthrough curves associated with advective transport. Using smoothing techniques in particle tracking to distribute the particle mass over a volume rather than at a point significantly reduces the noise in the numerical simulations and removes the need to use large temporal windows. Same effect can be obtained by adding a local dispersion process to the particle tracking experiments used to model advective transport. The effect of the temporal sampling window bears some relevance and important consequences for evaluating risk-related parameters. The expected value of peak solute discharge and its standard deviation are very sensitive to this sampling window and so will be the risk distribution relying on such numerical models.     

Determination of two‐dimensional laboratory‐scale dispersivities

A tracer test was conducted in a laboratory chamber representing a two‐dimensional aquifer to investigate the longitudinal dispersivity (α_L) and the ratio (α_T/α_L) of transverse to longitudinal dispersivity of sandy aquifer materials. Dispersive parameters were obtained by matching the observed chloride plumes at 9 hours and 16 hours after tracer injection with those simulated by a flow and transport model. The best match was found for α_L = 0·2 ? 0·25 cm and α_T/α_L = 0·2. The ratio of α_T/α_L = 0·2 was within the range of laboratory values reported in the literature. Sensitivity analysis revealed that the tracer plume concentration and shape were more sensitive to variations in longitudinal dispersivity than to the ratio of transverse to longitudinal dispersivity. This result contrasted with findings of others, showing that the dispersivity ratio greatly affects contaminant plume shape. However, our experimental boundary conditions restricted expansion of the plume normal to the direction of flow and thus affected the parameter estimation. Copyright © 2004 John Wiley & Sons, Ltd.