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.     

Using dispersivity values to quantify the effects of pore-scale flow focusing on enhanced reaction along a transverse mixing zone

A key challenge for predictive modeling of transverse mixing and reaction of solutes in groundwater is to determine values of transverse dispersivity (_αT)$({\alpha }_T)$ in heterogeneous flow fields that accurately describe mixing and reaction at the pore scale. We evaluated the effects of flow focusing in high permeability zones on mixing enhancement using experimental micromodel flow cells and pore-scale lattice-Boltzmann-finite-volume model (LB-FVM) simulations. Micromodel results were directly compared to LB-FVM simulations using two different pore structures, and excellent agreement was obtained. Six different flow focusing pore structures were then systematically tested using LB-FVM, and both analytical solutions and a two-dimensional (2D) continuum-scale model were used to fit _αT${\alpha }_T$ values to pore-scale results. Pore-scale results indicate that the overall rate of mixing-limited reaction increased by up to 40% when flow focusing occurred, and it was greater in pore structures with longer flow focusing regions and greater porosity contrast. For each pore structure, _αT${\alpha }_T$ values from analytical solutions of transverse concentration profiles or total product at a given longitudinal location showed good agreement for nonreactive and reactive solutes, and values determined in flow focusing zones were always smaller than those downgradient after the flow focusing zone. Transverse dispersivity values from the 2D continuum model were between values within and downgradient from the flow focusing zone determined from analytical solutions. Also, total product and transverse concentration profiles along the entire pore structure from the 2D continuum model matched pore scale results. These results indicate that accurate quantification of pore-scale flow focusing with transverse dispersion coefficients is possible only when the entire flow and concentration fields are considered.     

Roughness scale dependence of the relationship between tracer longitudinal dispersion and Peclet number in variable‐aperture fractures

The relationship between the longitudinal dispersion (D_L) and Peclet number (Pe) is crucial for predicting and simulating tracer through the variable‐aperture fracture. In this study, the roughness of the self‐affine fracture wall was decomposed into primary roughness (relatively large‐scale waviness) and secondary roughness (relatively small‐scale waviness) by a multiscaled wavelet analysis technique. Based on the complete dispersion mechanism (diffusion, macrodispersion, and Taylor dispersion) in the variable‐aperture fracture, three relationships (second‐order, power‐law, and linear relationships) between the D_L and Pe were investigated at large and small scales, respectively. Our results showed that the primary roughness mostly controlled the Taylor dispersion mechanism, whereas the secondary roughness was a dominant factor for the macrodispersion mechanism. Increasing the Hurst exponent and removing the secondary roughness led to the decreasing range of Pe where macrodispersion mechanism dominated the solute transport. It was found that estimating the D_L from the power‐law relationship based on Taylor dispersion theory resulted in considerable errors, even in the range of Pe where the Taylor dispersion mechanism dominated. The exponent of the power‐law relationship increased as the secondary roughness was removed. Analysing the linear relationship between the D_L and Pe revealed that the longitudinal dispersivity α_L increased linearly. However, this linear increase became weak as the Taylor dispersion mechanism dominated. In the range of Pe where the macrodispersion mechanism dominated, increasing the Hurst exponent caused the increase of α_L and the secondary roughness played a significant role in enhancing the α_L. As the Taylor dispersion mechanism dominated, the α_L was insensitive to the influence of multiscale roughness in variable‐aperture fractures.     

Multicomponent competitive monovalent cation exchange in hierarchical porous media with multimodal reactive mineral facies

This paper presents a stochastic model for multicomponent competitive monovalent cation exchange in hierarchical porous media. Reactive transport in porous media is highly sensitive to heterogeneities in physical and chemical properties, such as hydraulic conductivity (K), and cation exchange capacity (CEC). We use a conceptual model for multimodal reactive mineral facies and develop a Eulerian-based stochastic theory to analyze the transport of multiple cations in heterogeneous media with a hierarchical organization of reactive minerals. Numerical examples investigate the retardation factors and dispersivities in a chemical system made of three monovalent cations (Na⁺, K⁺, and Cs⁺). The results demonstrate how heterogeneity influences the transport of competitive monovalent cations, and highlight the importance of correlations between K and CEC. Further sensitivity analyses are presented investigating how the dispersion and retardation of each cation are affected by the means, variances, and integral scales of K and CEC. The volume fraction of organic matter is shown to be another important parameter. The Eulerian stochastic framework presented in this work clarifies the importance of each system parameters on the migration of cation plumes in formations with hierarchical organization of facies types. Our stochastic approach could be used as an alternative to numerical simulations for 3D reactive transport in hierarchical porous media, which become prohibitively expensive for the multicomponent applications considered in this work.     

Upscaling geochemical reaction rates using pore-scale network modeling

Geochemical reaction rate laws are often measured using crushed minerals in well-mixed laboratory systems that are designed to eliminate mass transport limitations. Such rate laws are often used directly in reactive transport models to predict the reaction and transport of chemical species in consolidated porous media found in subsurface environments. Due to the inherent heterogeneities of porous media, such use of lab-measured rate laws may introduce errors, leading to a need to develop methods for upscaling reaction rates. In this work, we present a methodology for using pore-scale network modeling to investigate scaling effects in geochemical reaction rates. The reactive transport processes are simulated at the pore scale, accounting for heterogeneities of both physical and mineral properties. Mass balance principles are then used to calculate reaction rates at the continuum scale. To examine the scaling behavior of reaction kinetics, these continuum-scale rates from the network model are compared to the rates calculated by directly using laboratory-measured reaction rate laws and ignoring pore-scale heterogeneities. In this work, this methodology is demonstrated by upscaling anorthite and kaolinite reaction rates under simulation conditions relevant to geological CO₂ sequestration. Simulation results show that under conditions with CO₂ present at high concentrations, pore-scale concentrations of reactive species and reaction rates vary spatially by orders of magnitude, and the scaling effect is significant. With a much smaller CO₂ concentration, the scaling effect is relatively small. These results indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. This work demonstrates the use of pore-scale network modeling as a valuable research tool for examining upscaling of geochemical kinetics. The pore-scale model allows the effects of pore-scale heterogeneities to be integrated into system behavior at multiple scales, thereby identifying important factors that contribute to the scaling effect.     

Comparison of continuum and pore-scale models of nutrient biodegradation under transverse mixing conditions

Recent studies indicate that during in situ bioremediation of contaminated groundwater, degradation occurs primarily along transverse mixing zones. Classical reactive-transport models overpredict the amount of degradation because solute spreading and mixing are not distinguished. Efforts to correct this have focused on modifying both dispersion and reaction terms, but no consensus on the best approach has emerged. In this work, a pore-scale model was used to simulate degradation along a transverse mixing zone between two required nutrients, and a continuum model with fitted parameters was used to match degradation rates from the pore-scale model. The pore-scale model solves for the flow field, concentration field, and biomass development within pore spaces of porous medium. For the continuum model, the flow field and biomass distributions are assumed to be homogeneous, and the fitting parameters are the transverse dispersion coefficient (D_T) and maximum substrate utilization rate (k_S,c). Results from the pore-scale model show that degradation rates near the system inlet are limited by the reaction rate, while degradation rates downgradient are limited by transverse mixing. For the continuum model, the value of D_T may be adjusted so that the degradation rate with distance matches that from the pore-scale model in the mixing-limited region. However, adjusting the value of k_S only improves the fit to pore-scale results within the reaction-limited region. Comparison with field and laboratory experiments suggests that the length of the reaction rate-limited region is small compared to the length scale over which degradation occurs. This indicates that along transverse mixing zones in the field, values of k_S are unimportant and only the value of D_T must be accurately fit.     

Reactive transport in disordered media: Role of fluctuations in interpretation of laboratory experiments

We review the analysis of the dynamics of reactive transport in disordered media, emphasizing the nature of the chemical reactions and the role of small-scale fluctuations induced by the structure of the porous medium. We are motivated by results and interpretations of laboratory-scale experiments, for which detailed characterization of the system is possible. Modeling approaches based on continuum and particle tracking (PT) schemes are examined critically, highlighting how fluctuations are incorporated. The continuum approach spans a large literature. Traditional formats of reactive transport equations, such as the advection–dispersion–reaction equation (ADRE), are based on a series of assumptions related mainly to scale separation and relative magnitude of time scales involved in the reactive transport setting. These assumptions as well as further developments are assessed in depth. PT methods offer an alternative means of accounting for pore-scale dynamics, wherein space–time transitions are drawn from appropriate probability distributions that have been tested to account for anomalous transport. While PT methods have been employed for many years to describe conservative transport, their application to laboratory-scale reactive transport problems in the context of both Fickian and non-Fickian regimes is relatively recent. We concentrate on experimental observations of different types of reactions in disordered media: (1) the dynamics of a bimolecular reactive transport (A + B → C) in passive (non-reactive) media, and (2) a multi-step chemical reaction, as exemplified in the process of dedolomitization involving both dissolution and precipitation. The fluctuations in a number of the key variables controlling the processes prove to have a dominant role; elucidation of this role forms the basis of the present study and the comparison of methods.     

Diapirism in the earth's mantle: Experiments on the motion of a hot sphere in a fluid with temperature-dependent viscosity

The ascent of magma diapirs through the earth's mantle is modelled experimentally by the motion of a hot metal sphere through a fluid whose viscosity varies strongly with temperature. The dimensionless drag on the sphere (drag number D) and the heat transfer from it (Nusselt number Nu) are found as functions of the dimensionless velocity of the sphere (Peclet number Pe) and the viscosity contrast μ_∞/μ₀ = 10^γ, where μ_∞ and μ₀ are the viscosities of the fluid far from the sphere and at its surface. The drag D = D(Pe, γ) has two limits. For large Pe and small γ (“Stokes” limit), the drag approaches the Stokes' Law result. For small Pe and large γ (“lubrication” limit), the drag is orders of magnitude less than that predicted by Stokes' Law. Nu is a function of Pe alone. For reasonable values of the diapir radius and the viscosity contrast, the dimensionless scale height Pe/3 Nu may exceed a critical value, resulting in progressive melting during ascent. This suggests that diapirs may ascend great distances through the mantle while remaining largely molten. Lamont-Doherty Geological Observatory Contribution No. 3414.     

Intercomparison of 3D pore-scale flow and solute transport simulation methods

Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include 1) methods that explicitly model the three-dimensional geometry of pore spaces and 2) methods that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of the first type, using computational fluid dynamics (CFD) codes employing a standard finite volume method (FVM), against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of the first type based on the lattice Boltzmann method (LBM) and smoothed particle hydrodynamics (SPH), as well as a model of the second type, a pore-network model (PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (FVM-based CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and (for capable codes) nonreactive solute transport, and intercompare the model results. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations). Generally good agreement was achieved among the various approaches, but some differences were observed depending on the model context. The intercomparison work was challenging because of variable capabilities of the codes, and inspired some code enhancements to allow consistent comparison of flow and transport simulations across the full suite of methods. This study provides support for confidence in a variety of pore-scale modeling methods and motivates further development and application of pore-scale simulation methods.     

Simulating dispersion in porous media and the influence of segmentation on stagnancy in carbonates

Understanding the transport of chemical components in porous media is fundamentally important to many reservoir processes such as contaminant transport and reactive flows involved in CO₂ sequestration. Carbonate rocks in particular present difficulties for pore-scale simulations because they contain large amounts of sub-micron porosity. In this work, we introduce a new hybrid simulation model to calculate hydrodynamic dispersion in pore-scale images of real porous media and use this to elucidate the origins and behaviour of stagnant zones arising in transport simulations using micro-CT images of carbonates. For this purpose a stochastic particle model for simulating the transport of a solute is coupled to a Lattice-Boltzmann algorithm to calculate the flow field. The particle method incorporates second order spatial and temporal resolution to resolve finer features of the domain. We demonstrate how dispersion coefficients can be accurately obtained in capillaries, where corresponding analytical solutions are available, even when these are resolved to just a few lattice units. Then we compute molecular displacement distributions for pore-spaces of varying complexity: a pack of beads; a Bentheimer sandstone; and a Portland carbonate. Our calculated propagator distributions are compared directly with recent experimental PFG-NMR propagator distributions (Scheven et al., 2005; Mitchell et al., 2008), the latter excluding spin relaxation mechanisms. We observe that the calculated transport propagators can be quantitatively compared with the experimental distribution, provided that spin relaxations in the experiment are excluded, and good agreement is found for both the sandstone and the carbonate. However, due to the absence of explicit micro-porosity from the carbonate pore space image used for flow field simulations we note that there are fundamental differences in the physical origins of the stagnant zones for micro-porous rocks between simulation and experiment. We show that for a given micro-CT image of a carbonate, small variations in the parameters chosen for the segmentation process lead to different amounts of stagnancy which diffuse away at different rates. Finally, we use a filtering method to show that this is due to the presence of spurious isolated pores which arise from the segmentation process and suggest an approach to overcome this limitation.     

Quantification of longitudinal dispersion by upscaling Brownian motion of tracer displacement in a 3D pore-scale network model

We present a 3D network model with particle tracking to upscale 3D Brownian motion of non-reactive tracer particles subjected to a velocity field in the network bonds, representing both local diffusion and convection. At the intersections of the bonds (nodes) various jump conditions are implemented. Within the bonds, two different velocity profiles are used. At the network scale the longitudinal dispersion of the particles is quantified through the coefficient D_L, for which we evaluate a number of methods already known in the literature. Additionally, we introduce a new method for derivation of D_L based on the first-arrival times distribution (FTD). To validate our particle tracking method, we simulate Taylor’s classical experiments in a single tube. Subsequently, we carry out network simulations for a wide range of the characteristic Péclet number Pe_? to assess the various methods for obtaining D_L. Using the new method, additional simulations have been carried out to evaluate the choice of nodal jump conditions and velocity profile, in combination with varying network heterogeneity. In general, we conclude that the presented network model with particle tracking is a robust tool to obtain the macroscopic longitudinal dispersion coefficient. The new method to determine D_L from the FTD statistics works for the full range of Pe_?, provided that for large Pe_? a sufficiently large number of particles is used. Nodal jump conditions should include molecular diffusion and allow jumps in the upstream direction, and a parabolic velocity profile in the tubes must be implemented. Then, good agreement with experimental evidence is found for the full range of Pe_?, including increased D_L for increased porous medium heterogeneity.