Sorption processes that occur during reactive solute movement through porous media can be modeled using either an equilibrium or kinetic approach. Because of the resulting conceptual and mathematical simplification, many transport models assume local chemical equilibrium is valid for describing sorption reactions. This paper presents quantitative criteria to assess the validity of the local equilibrium assumption for one-dimensional, steady flow through homogeneous soils. A method is described whereby formulas for solute breakthrough curve time moments can be determined without knowledge of the analytical solution to the mass transport model. This method is applied to several commonly used nonequilibrium formulations as well as the standard linear equilibrium model. The formulations considered include both the physical nonequilibrium models where the sorption rate is controlled by diffusive solute transfer between mobile and stagnant fluid zones and the chemical nonequilibrium models where the overall sorption rate is governed by the rate of reaction at the soil-solution interfaces. Criteria for local equilibrium to be valid are derived by comparing the time moment formulas for the nonequilibrium and equilibrium models. These criteria explicitly show that basic system parameters (e.g., seepage velocity, dispersion coefficient, distribution coefficient, sorption rate, boundary conditions) have a significant influence on the attainment of local equilibrium.Considering the large number of transport models that have been formulated utilizing either equilibrium or kinetic reaction submodels, it is surprising that there have been so few investigations into the conditions under which LEA breaks down. In an interesting study, James and Rubin [1979] performed laboratory column experiments over a range of seepage velocities and found that the equilibrium theory failed at the higher fluxes (see Table 1). By using the model of Glueckauf •1955], James and Rubin concluded that the local equilibrium assumption applies when the ratio of the hydrodynamic dispersion coefficient to the molecular diffusion coefficient is "near unity." However, Table 1 does indicate several investigations where equilibrium models proved successful under conditions where hydrodynamic dispersion was significantly greater than molecular diffusion (10 -• cm2/s is a typical value of molecular diffusivity). Bolt [1979] studied the criterion for LEA validity by performing a theoretical analysis of solute movement through an aggregated soil; however, his analysis neglected the effect of hydrodynamic dispersion. Palciauskas and Domenico [1976] studied only steady state conditions in their theoretical examination of diffusion-controlled carbonate dissolu-

Over the last two decades, lattice Boltzmann methods have become an increasingly popular tool to compute the flow in complex geometries such as porous media. In addition to single phase simulations allowing, for example, a precise quantification of the permeability of a porous sample, a number of extensions to the lattice Boltzmann method are available which allow to study multiphase and multicomponent flows on a pore scale level. In this article, we give an extensive overview on a number of these diffuse interface models and discuss their advantages and disadvantages. Furthermore, we shortly report on multiphase flows containing solid particles, as well as implementation details and optimization issues.

The objectives of this work were to determine if a pore-scale model could accurately capture the physical and chemical processes that control transverse mixing and reaction in microfluidic pore structures (i.e., micromodels), and to directly evaluate the effects of porous media geometry on a transverse mixing-limited chemical reaction. We directly compare pore-scale numerical simulations using a lattice-Boltzmann finite volume model (LB-FVM) with micromodel experiments using identical pore structures and flow rates, and we examine the effects of grain size, grain orientation, and intraparticle porosity upon the extent of a fast bimolecular reaction. For both the micromodel experiments and LB-FVM simulations, two reactive substrates are introduced into a network of pores via two separate and parallel fluid streams. The substrates mix within the porous media transverse to flow and undergo instantaneous reaction. Results indicate that (i) the LB-FVM simulations accurately captured the physical and chemical process in the micromodel experiments, (ii) grain size alone is not sufficient to quantify mixing at the pore scale, (iii) interfacial contact area between reactive species plumes is a controlling factor for mixing and extent of chemical reaction, (iv) at steady state, mixing and chemical reaction can occur within aggregates due to interconnected intra-aggregate porosity, (v) grain orientation significantly affects mixing and extent of reaction, and (vi) flow focusing enhances transverse mixing by bringing stream lines which were initially distal into close proximity thereby enhancing transverse concentration gradients. This study suggests that subcontinuum effects can play an important role in the overall extent of mixing and reaction in groundwater, and hence may need to be considered when evaluating reactive transport.

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