Abstract

Analysis of the space‐time evolution of reactive solutes in porous systems is complex owing to the presence of different types of chemical reactions. The complete description of a reactive transport scenario entails calculating the spatial and temporal distribution of species concentrations and reaction rates. Here we develop an exact explicit expression for the space‐time distribution of reaction rates for a scenario where the geochemical system can be described by an arbitrary number of equilibrium (fast) reactions and one kinetic (slow) reaction, in the absence of non‐constant‐activity immobile species. The key result is that the equilibrium reaction rate is the sum of two terms representing the availability of reactants. One term involves diffusion and dispersion and represents the contribution of mixing. The other term includes the contribution of the kinetic reaction. The approach also yields the local concentrations of all dissolved species. Yet the latter are not needed for the direct computation of equilibrium reaction rates. We illustrate the approach by means of a simple reactive transport scenario, involving a common ion effect in the presence of a kinetic and an equilibrium reaction leading to precipitation and dissolution processes within a one‐dimensional fully saturated porous medium. The example highlights the highly nonlinear and nonmonotonic response of the system to the controlling input parameters

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Published on 01/01/2010

DOI: 10.1029/2009WR008439
Licence: CC BY-NC-SA license

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