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Published: 2009
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Fluid-rock interaction (or water-rock interaction, as it was more commonly known) is a subject that has evolved considerably in its scope over the years. Initially its focus was primarily on interactions between subsurface fluids of various temperatures and mostly crystalline rocks, but the scope has broadened now to include fluid interaction with all forms of subsurface materials, whether they are unconsolidated or crystalline ('fluid-solid interaction' is perhaps less euphonious). Disciplines that previously carried their own distinct names, for example, basin diagenesis, early diagenesis, metamorphic petrology, reactive contaminant transport, chemical weathering, are now considered to fall under the broader rubric of fluid-rock interaction, although certainly some of the key research questions differ depending on the environment considered. Beyond the broadening of the environments considered in the study of fluid-rock interaction, the discipline has evolved in perhaps an even more important way. The study of water-rock interaction began by focusing on geochemical interactions in the absence of transport processes, although a few notable exceptions exist (Thompson 1959; Weare et al. 1976). Moreover, these analyses began by adopting a primarily thermodynamic approach, with the implicit or explicit assumption of equilibrium between the fluid and rock. As a result, these early models were fundamentally static rather than dynamic in nature. This all changed with the seminal papers by Helgeson and his co-workers (Helgeson 1968; Helgeson et al. 1969) wherein the concept of an irreversible reaction path was formally introduced into the geochemical literature. In addition to treating the reaction network as a dynamically evolving system, the Helgeson studies introduced an approach that allowed for the consideration of a multicomponent geochemical system, with multiple minerals and species appearing as both reactants and products, at least one of which could be irreversible. Helgeson's pioneering approach was given a more formal kinetic basis (including the introduction of real time rather than reaction progress as the independent variable) in subsequent studies (Lasaga 1981; Aagaard and Helgeson 1982; Lasaga 1984). The reaction path approach can be used to describe chemical processes in a batch or closed system (e.g., a laboratory beaker), but such systems are of limited interest in the Earth sciences where the driving force for most reactions is transport. Lichtner (1988) clarified the application of the reaction path models to water-rock interaction involving transport by demonstrating that they could be used to describe pure advective transport through porous media. By adopting a reference frame which followed the fluid packet as it moved through the medium, the reaction progress variable could be thought of as travel time instead. Multi-component reactive transport models that could treat any combination of transport and biogeochemical processes date back to the early 1980s. Berner and his students applied continuum reactive transport models to describe processes taking place during the early diagenesis of marine sediments (Berner 1980). Lichtner (1985) outlined much of the basic theory for a continuum model for multicomponent reactive transport. Yeh and Tripathi (1989) also presented the theoretical and numerical basis for the treatment of reactive contaminant transport. Steefel and Lasaga (1994) presented a reactive flow and transport model for nonisothermal, kinetically-controlled water-rock interaction and fracture sealing in hydrothermal systems based on simultaneous numerical solution of both reaction and transport This chapter begins with a review of the important transport processes that affect or even control fluid-rock interaction. This is followed by a general introduction to the governing equations for reactive transport, which are broadly applicable to both qualitative and quantitative interpretations of fluid-rock interactions. This framework is expanded through a discussion of specific topics that are the focus of current research, or are either incompletely understood or not fully appreciated. At this point, the focus shifts to a brief discussion of the three major approaches to modeling multi-scale porous media (1) continuum models, (2) pore scale and pore network models, and (3) hybrid or multi-continuum models. From here, the chapter proceeds to investigate some case studies which illuminate the power of modern numerical reactive transport modeling in deciphering fluid-rock interaction.
