A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Analytical solutions for multiple species reactive transport in multiple dimensions

Many numerical computer codes used to simulate multi-species reactive transport and biodegradation have been developed in recent years. Such numerical codes must be validated by comparison of the numerical solutions with an analytical solution. In this paper, a method for deriving analytical solutions of the partial differential equations describing multiple species multi-dimensional transport with first-order sequential reactions is presented. Although others have developed specific solutions of multi-species transport equations, here a more general analytical approach, capable of describing any number of reactive species in multiple dimensions is derived. A substitution method is used to transform the multi-species reactive transport problem to one that can be solved using previously published single-species solutions for various initial and boundary conditions. One- and three-dimensional examples are presented to illustrate the steps involved in extending single-species solutions to a four-species system with sequential first-order reactions.     

Numerical modeling of coupled variably saturated fluid flow and reactive transport with fast and slow chemical reactions

The couplings among chemical reaction rates, advective and diffusive transport in fractured media or soils, and changes in hydraulic properties due to precipitation and dissolution within fractures and in rock matrix are important for both nuclear waste disposal and remediation of contaminated sites. This paper describes the development and application of LEHGC2.0, a mechanistically based numerical model for simulation of coupled fluid flow and reactive chemical transport, including both fast and slow reactions in variably saturated media. Theoretical bases and numerical implementations are summarized, and two example problems are demonstrated. The first example deals with the effect of precipitation/dissolution on fluid flow and matrix diffusion in a two-dimensional fractured media. Because of the precipitation and decreased diffusion of solute from the fracture into the matrix, retardation in the fractured medium is not as large as the case wherein interactions between chemical reactions and transport are not considered. The second example focuses on a complicated but realistic advective-dispersive-reactive transport problem. This example exemplifies the need for innovative numerical algorithms to solve problems involving stiff geochemical reactions.     

Transport of reactive colloids and contaminants in groundwater: effect of nonlinear kinetic interactions

Transport of reactive colloids in groundwater may enhance the transport of contaminants in groundwater. Often, the interpretation of results of transport experiments is not a simple task as both reactions of colloids with the solid matrix and reactions of contaminants with the solid matrix and mobile and immobile colloids may be time dependent and nonlinear. Further colloid transport properties may differ from solute transport properties. In this paper, a one-dimensional model for coupled and contaminant in a porous medium (COLTRAP) is presented together with simulation results. Calculated breakthrough curves (BTC's) during contamination and decontamination show systematically the effect of nonlinear and kinetic interactions on contaminant transport in the presence of reactive colloids, and the effect of colloid transport properties that differ from solute transport properties. It is shown that in case of linear kinetic reactions, the rate of exchange of mobile and immobile colloids have a large impact on the shape of BTC's even if the solid matrix is saturated with respect to colloids. BTC's during the contamination and decontamination phase have identical shapes in this case. Moreover, the slow reactions of contaminants and colloids may lead to unretarded breakthrough of contaminants. Independent of reaction rates, nonlinear reactions lead to BTC's that are steeper during contamination than in the linear case. A characteristic aspect of nonlinear sorption is that shapes of BTC's differ during the contamination and decontamination phase. It has been observed that shapes of some of the simulated adsorption and desorption curves are similar as shapes found in experiments reported in literature. This stresses the importance of incorporating both kinetics and nonlinearity in models for coupled colloid and contaminant transport and the capability of COLTRAP to interpret experimental results. Finally, to figure out whether nonlinear processes play a role, it is very important to consider both contamination and decontamination in transport experiments.     

Development and analysis of an adaptive transport scheme

An approach to solving the advection dominated atmospheric mass transport problem which adaptively constructs and updates the computational mesh is implemented and analyzed. The formulation of the mesh adaptation algorithm allows for information from other model processes as well as transport to influence mesh refinement. Comparisons to other methods are limited to a pure advection test problem. The scheme is based on a Petrov–Galerkin finite element method using quadratic interpolating polynomials over triangular elements. The temporal component of the transport equation is discretized using the Crank–Nicolson method. A single time step is applied to the entire domain regardless of mesh refinement levels. Two means of upwind biasing the solution via modification of the finite element weighting functions are investigated. Criteria for refining and unrefining the mesh based on advective flux and an estimate of the error are proposed and compared. The effects of varying the number of time steps taken between mesh refinements are analyzed. Results for adapted mesh solutions of a test problem are shown to be superior to corresponding uniform mesh finite element solutions. Comparisons to several other popular uniform mesh advection schemes indicate either equal or improved accuracy for the adapted mesh solutions.     

Operator-splitting errors in coupled reactive transport codes for transient variably saturated flow and contaminant transport in layered soil profiles

One possible way of integrating subsurface flow and transport processes with (bio)geochemical reactions is to couple by means of an operator-splitting approach two completely separate codes, one for variably-saturated flow and solute transport and one for equilibrium and kinetic biogeochemical reactions. This paper evaluates the accuracy of the operator-splitting approach for multicomponent systems for typical soil environmental problems involving transient atmospheric boundary conditions (precipitation, evapotranspiration) and layered soil profiles. The recently developed HP1 code was used to solve the coupled transport and chemical equations. For steady-state flow conditions, the accuracy was found to be mainly a function of the adopted spatial discretization and to a lesser extent of the temporal discretization. For transient flow situations, the accuracy depended in a complex manner on grid discretization, time stepping and the main flow conditions (infiltration versus evaporation). Whereas a finer grid size reduced the numerical errors during steady-state flow or the main infiltration periods, the errors sometimes slightly increased (generally less than 50%) when a finer grid size was used during periods with a high evapotranspiration demand (leading to high pressure head gradients near the soil surface). This indicates that operator-splitting errors are most significant during periods with high evaporative boundary conditions. The operator-splitting errors could be decreased by constraining the time step using the performance index (the product of the grid Peclet and Courant numbers) during infiltration, or the maximum time step during evapotranspiration. Several test problems were used to provide guidance for optimal spatial and temporal discretization.     

Stochastic-convective transport with nonlinear reactions and mixing: finite streamtube ensemble formulation for multicomponent reaction systems with intra-streamtube dispersion

An effective streamtube ensemble method is developed to upscale convective-dispersive transport with multicomponent nonlinear reactions in steady nonuniform flow. The transport is cast in terms of a finite ensemble of independent discrete streamtubes that approximate convective transport along macroscopically averaged pathlines and dispersive transport longitudinally as microscopic mixing within streamtubes. The representation of fate and transport via a finite ensemble of effective linear streamtubes, allows the treatment of arbitrarily complex reaction systems involving both homogeneous and heterogeneous reactions, and longitudinal dispersive/diffusive mixing within streamtubes. This allows the use of reactive-transport codes designed to solve such problems in an Eulerian framework, as opposed to reliance on closed-form (convolutional or canonical) expressions for reactive transport in exclusively convective streamtubes. The approach requires both reactive-transport solutions for a representative ensemble of one-dimensional convective-dispersive-reactive streamtubes and the distribution of flux over the streamtube ensemble variants, and it does not allow for lateral mixing between streamtubes. Here, the only ensemble variant is travel time. The discussion details the way that the conventional Eulerian fate and transport model is converted first into an ensemble of transports along three-dimensional streamtubes of unknown geometry, and then to approximate one-dimensional streamtubes that are designed to honor the important global properties of the transport. Conditions under which such an 'equivalent' ensemble of one-dimensional streamtubes are described. The breakthrough curve of a nonreactive tracer in the ensemble is expressed as a combined Volterra-Fredholm integral equation, which serves as the basis for estimation of the distribution of flux over the variant of the ensemble, travel time. Transient convective speed and the effects of errors in flux distributions are described, and the method is applied to a demonstration problem involving nonlinear multicomponent reaction kinetics and strongly nonuniform flow.     

A model for contaminant mass flux in capped sediment under consolidation

The paper presents a model for contaminant transport and flux through a consolidating subaqueous sediment and overlying cap. The formulation is based on the effect of consolidation and excess pore pressure dissipation on transient, nonlinear advective component of transport through sediment and the cap. The consolidation is induced by the buoyant weight of the cap when it is placed on the contaminated sediments. One equation is presented for advective-diffusive transport through the sediment that is dependent upon soil/contaminant properties and transient advective velocity, which is calculated from a second equation based on the Terzaghi consolidation theory. A third equation is provided to describe the transport of contaminants in the cap. The parameters, including advective velocity, and boundary conditions used for contaminant transport through the cap are derived from the solution of the first two equations. The finite difference method is used to solve the system of equations for consolidation and contaminant transport. A hypothetical case is analyzed to demonstrate the formulation, and the results show that advection due to consolidation can accelerate breakthrough of contaminant through the cap by orders of magnitude. The derivation and results show that consolidation should be included for cap design, and that reactive caps are essential for delaying and reducing dissolved contaminant flux.     

Numerical validation of a Eulerian hydrochemical code using a 1D multisolute mass transport system involving heterogeneous kinetically controlled reactions

It is demonstrated that at steady state, the 1D thermo-kinetic hydrochemical Eulerian mass balance equations in pure advective mode are indeed identical to the governing mass balance equations of a single reaction path (or geochemical) code in open system mode. Thus, both calculated reaction paths should be theoretically identical whatever the chemical complexity of the water-rock system (i.e., multicomponent, multireaction zones kinetically and equilibrium-controlled). We propose to use this property to numerically test the thermo-kinetic hydrochemical Eulerian codes and we employ it to verify the algorithm of the 1D finite difference code KIRMAT. Compared to the other methods to perform such numerical tests (i.e., comparisons with analytical, semi-analytical solutions, between two Eulerian hydrochemical codes), the advantage of this new method is the absence of constraints on the chemical complexity of the modelled water-rock systems. Moreover, the same thermo-kinetic databases and geochemical functions can be easily and mechanically used in both calculations, when the numerical reference comes from the Eulerian code with no transport terms (u and D = 0) and modify to be consistent with the definition of the open system mode in geochemical modelling. The ability of KIRMAT to treat multicomponent pure advective transport, subjected to several kinetically equilibrium-controlled dissolution and precipitation reactions, and to track their boundaries has been successfully verified with the property of interest. The required numerical validation of the reference calculations is bypassed in developing the Eulerian code from an already checked single reaction path code. A forward time-upstream weighting scheme (a mixing cell scheme) is used in this study. An appropriate choice of grid spacing allows to calculate within the grid size uncertainty the correct mineral reaction zone boundaries, despite the presence of numerical dispersion. Its correction enables us to improve the convergence and to extend the numerical test to mixed advective-dispersive mass transport. However, the skewness factor involves numerical oscillations that prevent to compute different grid spacing. The use of a different chemically controlled time step constraint in both calculations induces some inconsistencies into the validation tests. This numerical validation method may be applied as well as to check a thermo-kinetic hydrochemical finite element based code, from a 1D heterogeneous systems, and 2D-3D systems provided that they are designed so as to be 1D equivalent. A one-step algorithm and the use of a numerical reference coming from the Eulerian code to be tested ensure the potential success (accuracy) of the numerical validation method.     

A numerical model for transient-hysteretic flow and solute transport in unsaturated porous media

A two-dimensional flow and transport model was developed for simulating transient water flow and nonreactive solute transport in heterogeneous, unsaturated porous media containing air and water. The model is composed of a unique combination of robust and accurate numerical algorithms for solving the Richards', Darcy flux, and advection-dispersion equations. The mixed form of Richards' equation is solved using a finite-element formulation and a modified Picard iteration scheme. Mass lumping is employed to improve solution convergence and stability behavior. The flow algorithm accounts for hysteresis in the pressure head-water content relationship. Darcy fluxes are approximated with a Galerkin and Petrov-Galerkin finite-element method developed for random heterogeneous porous media. The transport equation is solved using an Eulerian-Lagrangian method. A multi-step, fourth-order Runge-Kutta, reverse particle tracking technique and a quadratic-linear interpolation scheme are shown to be superior for determining the advective concentration. A Galerkin finite-element method is used for approximating the dispersive flux. The unsaturated flow and transport model was applied to a variety of rigorous problems and was found to produce accurate, mass-conserving solutions when compared to analytical solutions and published numerical results.     

Evaluating the sensitivity of a subsurface multicomponent reactive transport model with respect to transport and reaction parameters.

The input variables for a numerical model of reactive solute transport in groundwater include both transport parameters, such as hydraulic conductivity and infiltration, and reaction parameters that describe the important chemical and biological processes in the system. These parameters are subject to uncertainty due to measurement error and due to the spatial variability of properties in the subsurface environment. This paper compares the relative effects of uncertainty in the transport and reaction parameters on the results of a solute transport model. This question is addressed by comparing the magnitudes of the local sensitivity coefficients for transport and reaction parameters. General sensitivity equations are presented for transport parameters, reaction parameters, and the initial (background) concentrations in the problem domain. Parameter sensitivity coefficients are then calculated for an example problem in which uranium(VI) hydrolysis species are transported through a two-dimensional domain with a spatially variable pattern of surface complexation sites. In this example, the reaction model includes equilibrium speciation reactions and mass transfer-limited non-electrostatic surface complexation reactions. The set of parameters to which the model is most sensitive includes the initial concentration of one of the surface sites, the formation constant (Kf) of one of the surface complexes and the hydraulic conductivity within the reactive zone. For this example problem, the sensitivity analysis demonstrates that transport and reaction parameters are equally important in terms of how their variability affects the model results.     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.     

Numerical simulation of reactive processes in an experiment with partially saturated bentonite

Bentonites are preferred materials for use as engineered barriers for high-level nuclear waste repositories. Simulation of geochemical processes in bentonite is therefore important for long-term safety assessment of those repositories. In this work, the porewater chemistry of a bentonite sample subject to simultaneous heating and hydration, as studied by Cuevas et al. [Cuevas, J., Villar, M., Fernández, A., Gómez, P., Martín, P., 1997. Porewaters extracted from compacted bentonite subjected to simultaneous heating and hydration. Applied Geochemistry 12, 473-481.], was assessed with a non-isothermal reactive transport model by coupling the geochemical software PHREEQC2 with the object-oriented FEM simulator GeoSys/RockFlow. Reactive transport modelling includes heat transport, two-phase flow, multicomponent transport and geochemical reactions in the liquid phase, i.e. ion exchange, mineral dissolution/precipitation and equilibrium reactions. Simulations show that the easily soluble minerals in bentonite determine the porewater chemistry. Temperature affects both two-phase flow and geochemical reactions. Porosity change due to dissolution/precipitation is low during the experiment. However, changes of the effective porosity caused by bentonite swelling can be very large. The simulated results agree well with the experimental data.     

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO₄). Both the high density (1025 gL^− 1) and reactivity of the treatment solution influence the fate of permanganate (MnO₄) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO₄ utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer–aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO₄ have a negligible effect on solution density and MnO₄ delivery.     

Operator-splitting procedures for reactive transport and comparison of mass balance errors

Operator-splitting (OS) techniques are very attractive for numerical modelling of reactive transport, but they induce some errors. Considering reactive mass transport with reversible and irreversible reactions governed by a first-order rate law, we develop analytical solutions of the mass balance for the following operator-splitting schemes: standard sequential non-iterative (SNI), Strang-splitting SNI, standard sequential iterative (SI), extrapolating SI, and symmetric SI approaches. From these analytical solutions, the operator-splitting methods are compared with respect to mass balance errors and convergence rates independently of the techniques used for solving each operator. Dimensionless times, NOS, are defined. They control mass balance errors and convergence rates. The following order in terms of decreasing efficiency is proposed: symmetric SI, Strang-splitting SNI, standard SNI, extrapolating SI and standard SI schemes. The symmetric SI scheme does not induce any operator-splitting errors, the Strang-splitting SNI appears to be O(N2OS) accurate, and the other schemes are first-order accurate.     

Reactive solute transport in macroscopically homogeneous porous media: analytical solutions for the temporal moments

In this work, we investigate one-dimensional solute transport affected by rate-limited sorption, first-order mass transfer, and first-order transformation. Analytical expressions are obtained for the temporal moments of the solute in the solution phase. The effect of various rate coefficients on the temporal moments is examined. It was found that, in the presence of transformation reactions, the mean arrival time, and the spread and skewness of the breakthrough curves, are not monotonic functions of the rate coefficients. These solutions will be useful as a preliminary analysis tool for ascertaining the relative importance of various processes under given conditions. They may also be used to analyze the accuracy of various numerical techniques used for simulation of reactive transport.     

An application of the theory of kinematics of mixing to the study of tropospheric dispersion

The most common technique used for numerical simulations of tracer mixing is that of the numerical solution of the advection–diffusion equation with the unresolved fluxes parameterized using the similarity theory. Despite correct predictions of the overall directions of transport, models based on a numerical solution of the advection–diffusion equation lack sufficient accuracy to correctly reproduce the coupling of mixing with small scale processes which are sensitive to the microstructure of the tracer distribution. The objective of this paper is to revisit the basic formalism employed in numerical models used to investigate atmospheric tracers. The main mathematical method proposed here is the theory of kinematics of mixing which could be applied effectively for simulations of atmospheric transport processes. At the beginning of the paper, we introduce simple mathematical transformations in order to demonstrate how complex topological structures are created by mixing processes. These idealistic flow systems are essential to explain transport properties of much more complex three-dimensional geophysical flows. An example of the application of the kinematics of mixing to the analysis of tracer transport on a planetary scale is presented in the following sections. The complex filamentary structures simulated in the numerical experiment are evaluated using some commonly applied statistical measures in order to compare the results with the data published in the literature. The results of the experiment are also analysed with the help of simple conceptual models of fluid filaments. The microstructure of the tracer distribution introduced in the paper is essential to increase our understanding of atmospheric transport and to develop more realistic parameterizations of small-scale mixing. The presented results could also be used to improve calculations of the coupling between microphysical processes and tracer mixing.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.