Xavier Sanchez-Vila

A procedure for the solution of multicomponent reactive transport problems

[1] Modeling transport of reactive solutes is a challenging problem, necessary for understanding the fate of pollutants and geochemical processes occurring in aquifers, rivers, estuaries, and oceans. Geochemical processesinvolving multiple reactive species are generally analyzed using advanced numerical codes. The resulting complexity has inhibited the development of analytical solutions for multicomponent heterogeneous reactions such as precipitation/dissolution. We present a procedure to solve groundwater reactive transport in the case of homogeneous and classical heterogeneous equilibrium reactions induced by mixing different waters. The methodology consists of four steps: (1) defining conservative components to decouple the solution of chemical equilibrium equations from species mass balances, (2) solving the transport equations for the conservative components, (3) performing speciation calculations to obtain concentrations of aqueous species, and (4) substituting the latter into the transport equations to evaluate reaction rates. We then obtain the space-time distribution of concentrations and reaction rates. The key result is that when the equilibrium constant does not vary in space or time, the reaction rate is proportional to the rate of mixing, * T u D Vu, where u is the vector of conservative components concentrations and D is the dispersion tensor. The methodology can be used to test numerical codes by setting benchmark problems but also to derive closed-form analytical solutions whenever steps 2 and 3 are simple, as illustrated by the application to a binary system. This application clearly elucidates that in a three-dimensional problem both chemical and transport parameters are equally important in controlling the process.

Multicomponent reactive transport in multicontinuum media

Multicomponent reactive transport in aquifers is a highly complex process, owing to a combination of variability in the processes involved and the inherent heterogeneity of nature. To date, the most common approach is to model reactive transport by incorporating reaction terms into advection-dispersion equations (ADEs). Over the last several years, a large body of literature has emerged criticizing the validity of the ADE for transport in real media, and alternative models have been presented. One such approach is that of multirate mass transfer (MRMT). In this work, we propose a model that introduces reactive terms into the MRMT governing equations for conservative species. This model conceptualizes the medium as a multiple continuum of one mobile region and multiple immobile regions, which are related by kinetic mass transfer processes. Reactants in both the mobile and immobile regions are assumed to always be in chemical equilibrium. However, the combination of local dispersion in the mobile region and the various mass transfer rates induce a global chemical nonequilibrium. Assuming this model properly accounts for transport of reactive species, we derive explicit expressions for the reaction rates in the mobile and immobile regions, and we study the impact of mass transfer on reactive transport. Within this framework, we observe that the resulting reaction rates can be very different from those that arise in a system governed by an ADE-type equation.

Coupling of mass transfer and reactive transport for nonlinear reactions in heterogeneous media

Fast chemical reactions are driven by mixing‐induced chemical disequilibrium. Mixing is poorly represented by the advection‐dispersion equation. Instead, effective dynamics models, such as multirate mass transfer (MRMT), have been successful in reproducing observed field‐scale transport, notably, breakthrough curves (BTCs) of conservative solutes. The objective of this work is to test whether such effective models, derived from conservative transport observations, can be used to describe effective multicomponent reactive transport in heterogeneous media. We use a localized formulation of the MRMT model that allows us to solve general reactive transport problems. We test this formulation on a simple three‐species mineral precipitation problem at equilibrium. We first simulate the spatial and temporal distribution of mineral precipitation rates in synthetic hydraulically heterogeneous aquifers. We then compare these reaction rates to those corresponding to an equivalent (i.e., same conservative BTC) homogenized medium with transport characterized by a nonlocal in time equation involving a memory function. We find an excellent agreement between the two models in terms of cumulative precipitated mass for a broad range of generally stationary heterogeneity structures. These results indicate that mass transfer models can be considered to represent quite accurately the large‐scale effective dynamics of mixing controlled reactive transport at least for the cases tested here, where individual transport paths sample the full range of heterogeneities represented by the BTC.

Variable-density flow in porous media

Steady-state distributions of water potential and salt concentration in coastal aquifers are typically modelled by the Henry problem, which consists of a fully coupled system of flow and transport equations. Coupling arises from the dependence of water density on salt concentration. The physical behaviour of the system is fully described by two dimensionless groups: (i) the coupling parameter

Optimal reconstruction of concentrations, gradients and reaction rates from particle distributions

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Formation of diclofenac and sulfamethoxazole reversible transformation products in aquifer material under denitrifying conditions: batch experiments.

, which encapsulates the relative importance of buoyancy and viscous forces, and (ii) the Peclet number

Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

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Microcosm experiments to control anaerobic redox conditions when studying the fate of organic micropollutants in aquifer material.

, which quantifies the relative importance of purely convective and dispersive transport mechanisms. We provide a systematic analytical analysis of the Henry problem for a full range of the Peclet number. For moderate

Assessing and forecasting the impacts of global change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins

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Apparent directional mass-transfer capacity coefficients in three-dimensional anisotropic heterogeneous aquifers under radial convergent transport

, analytical solutions are obtained through perturbation expansions in