Fluid-rock interaction: A reactive transport approach

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

Solid phase evolution in the Biosphere 2 hillslope experiment as predicted by modeling of hydrologic and geochemical fluxes

A reactive transport geochemical modeling study was conducted to help predict the mineral transformations occurring over a ten year time-scale that are expected to impact soil hydraulic properties in the Biosphere 2 (B2) synthetic hillslope experiment. The modeling sought to predict the rate and extent of weathering of a granular basalt (selected for hillslope construction) as a function of climatic drivers, and to assess the feedback effects of such weathering processes on the hydraulic properties of the hillslope. Flow vectors were imported from HYDRUS into a reactive transport code, CrunchFlow2007, which was then used to model mineral weathering coupled to reactive solute transport. Associated particle size evolution was translated into changes in saturated hydraulic conductivity using Rosetta software. We found that flow characteristics, including velocity and saturation, strongly influenced the predicted extent of incongruent mineral weathering and neo-phase precipitation on the hillslope. Results were also highly sensitive to specific surface areas of the soil media, consistent with surface reaction controls on dissolution. Effects of fluid flow on weathering resulted in significant differences in the prediction of soil particle size distributions, which should feedback to alter hillslope hydraulic conductivities

Approaches to Modeling Coupled Flow and Reaction in a 2-D Cementation Experiment

Porosity evolution at reactive interfaces is a key process that governs the evolution and performances of many engineered systems that have important applications in earth and environmental sciences. This is the case, for example, at the interface between cement structures and clays in deep geological nuclear waste disposals. Although in a different transport regime, similar questions arise for permeable reactive barriers used for biogeochemical remediation in surface environments. The COMEDIE project aims at investigating the coupling between transport, hydrodynamics and chemistry when significant variations of porosity occur. The present work focuses on a numerical benchmark used as a design exercise for the future COMEDIE-2D experiment. The use of reactive transport simulation tools like Hytec and Crunch provides predictions of the physico-chemical evolutions that are expected during the future experiments in laboratory. Focus is given in this paper on the evolution during the simulated experiment of precipitate, permeability and porosity fields. A first case is considered in which the porosity is constant. Results obtained with Crunch and Hytec are in relatively good agreement. Differences are attributable to the models of reactive surface area taken into account for dissolution/precipitation processes. Crunch and Hytec simulations taking into account porosity variations are then presented and compared. Results given by the two codes are in qualitative agreement, with differences attributable in part to the models of reactive surface area for dissolution/precipitation processes. As a consequence, the localization of secondary precipitates predicted by Crunch leads to lower local porosities than for predictions obtained by Hytec and thus to a stronger coupling between flow and chemistry. This benchmark highlights the importance of the surface area model employed to describe systems in which strong porosity variations occur as a result of dissolution/precipitation. The simulation of highly non-linear reactive transport systems is also shown to be partly dependent on specific numerical approaches

Basalt weathering rates on Earth and the duration of liquid water on the plains of Gusev Crater, Mars

Where Martian rocks have been exposed to liquid water, chemistry versus depth profiles could elucidate both Martian climate history and potential for life. The persistence of primary minerals in weathered profiles constrains the exposure time to liquid water: on Earth, mineral persistence times range from {approx}10 ka (olivine) to {approx}250 ka (glass) to {approx}1Ma (pyroxene) to {approx}5Ma (plagioclase). Such persistence times suggest mineral persistence minima on Mars. However, Martian solutions may have been more acidic than on Earth. Relative mineral weathering rates observed for basalt in Svalbard (Norway) and Costa Rica demonstrate that laboratory pH trends can be used to estimate exposure to liquid water both qualitatively (mineral absence or presence) and quantitatively (using reactive transport models). Qualitatively, if the Martian solution pH > {approx}2, glass should persist longer than olivine; therefore, persistence of glass may be a pH-indicator. With evidence for the pH of weathering, the reactive transport code CrunchFlow can quantitatively calculate the minimum duration of exposure to liquid water consistent with a chemical profile. For the profile measured on the surface of Humphrey in Gusev Crater, the minimum exposure time is 22 ka. If correct, this estimate is consistent with short-term, episodic alteration accompanied by ongoing surface erosion. More of these depth profiles should be measured to illuminate the weathering history of Mars

Biogeochemical Coupling of Fe and Tc Speciation in Subsurface Sediments: Implications to Long-Term Tc Immobilization

The project has been focused on biochemical processes in subsurface sediments involving Fe that control the valence state, solubility, and effective mobility of 99Tc. Our goal has been to understand the Tc biogeochemistry as it may occur in suboxic and biostimulated subsurface environments. Two objectives have been pursued: (1) To determine the relative reaction rates of 99Tc(VII)O2(aq) with metal reducing bacteria and biogenic Fe(II); and to characterize the identity, structure, and molecular speciation of Tc(IV) products formed through reaction with both biotic and abiotic reductants. (2) To quantify the biogeochemical factors controlling the reaction rate of O2 with Tc(IV)O2?nH2O in sediment resulting from the direct enzymatic reduction of Tc(VII) by DIRB and/or the reaction of Tc(VII) with the various types of biogenic Fe(II) produced by DIRB