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.

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Published on 01/01/2009

DOI: 10.1029/2008WR006823
Licence: CC BY-NC-SA license

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