Interfacial energy effects and the evolution of pore size distributions during quartz precipitation in sandstone

Pore size is usually thought to control the rate of crystal growth in porous geological media by determining the ratio of mineral surface area to fluid volume. However, theory suggests that in micron-scale to nanometer scale pores, interfacial energy (surface energy) effects can also become important. Interfacial energy typically increases the solubility of very small crystals growing in tiny pores, and when the fluid is close to equilibrium - as is often the case in geological systems - mineral precipitation could occur in relatively large pores, while in very small adjacent pores crystal growth might be suppressed. Such a mechanism would effectively restrict the reactive surface area of the porous medium, thereby reducing the bulk reaction rate. We investigated the pore size distributions in naturally cemented sandstone adjacent to an isolated stylolite and found that quartz precipitation was inhibited in pores smaller than 10 μm in diameter. Furthermore, we demonstrate that kinetic formulations which assume constant solubility cannot reproduce the observed pore size patterns in mineralized samples; by contrast, excellent fits with the data are obtained when interfacial energy effects are taken into account. Reaction rates in geological media determined in field studies can be orders of magnitude lower than those measured in laboratory experiments, and we propose that reduced reaction rates in porous media with micron and submicron-scale porosity could account for much of the apparent paradox.