Linking chemical weathering, evolution of preferential flow paths and transport self-organization in porous media using non-equilibrium thermodynamics

Chemical weathering of soil and rock is a complex geophysical process during which the reaction and transport processes in the porous medium interact, causing erosion of the medium. This process is ubiquitous in geophysical systems and can be encountered, among others, in formation of karst systems, subsurface carbon sequestration and surface weathering of river beds. A common outcome of chemical weathering is the emergence and intensification of preferential flow paths, where the weathering alters the transport properties of the rock, thus introducing coupling between transport and reaction. While numerous approaches have been undertaken to simulate this complex interaction, still a need exists for a unified framework able to correlate the emergence of preferential flow paths due to reaction-transport interaction with the associated dissipative dynamics. Here we propose such a framework considering the case of subsurface chemical weathering of calcite porous rock undergoing reversible dissolution-precipitation reaction, and apply non-equilibrium thermodynamics to analyze the ensuing reaction-transport interaction in this geophysical scenario. ... mehrWe identify the entropy generation sources, attributed to the dissipative processes inherent to this physical scenario and show a clear correlation between the emergence and intensification of preferential flow paths and the accompanying dissipative dynamics, where the evolution of the emerging paths leads to a decrease in the free-energy dissipation rate due to flow percolation, mixing of chemical constituents and reaction. This indicates that the emergence of preferential flow paths due to chemical weathering in geophysical systems represents an energetically-preferred state of the system that can be considered a manifestation of the minimum energy dissipation principle. Our analysis implies that, for a given pressure head, a more homogeneous porous matrix will result in less pronounced preferential flow paths, along with lower flow and higher mineralization rates. On the other hand, for a highly heterogeneous matrix dominant preferential flow paths will be obtained, along with higher flow and lower mineralization rates. Considering these aspects for carbon sequestration where acidified brine leads to carbon mineralization, we conclude that, for a given pressure head, an injection into a more heterogeneous matrix will result in a higher injection rate, while a more homogeneous domain will yield a higher mineralization rate, thus exemplifying the resulting trade-off in the injection strategy.