Many challenges related to carbon-dioxide ($$\hbox {CO}_2$$ CO 2 ) sequestration in subsurface rock are linked to the injection of fluids through induced or existing fracture networks and how these fluids are altered through geochemical interactions. Here, we demonstrate that fluid mixing and carbonate mineral distributions in fractures are controlled by gravity-driven chemical dynamics. Using optical imaging and numerical simulations, we show that a density contrast between two miscible fluids causes the formation of a low-density fluid runlet that increases in areal extent as the fracture inclination decreases from 90$$^\circ$$ ∘ (vertical fracture plane) to 30$$^\circ$$ ∘ . The runlet is sustained over time and the stability of the runlet is controlled by the gravity-driven formation of 3D vortices that arise in a laminar flow regime. When homogeneous precipitation was induced, calcium carbonate covered the entire surface for horizontal fractures (0$$^\circ$$ ∘ ). However, for fracture inclinations greater than 10$$^\circ$$ ∘ , the runlet formation limited the areal extent of the precipitation to less than 15% of the fracture surface. These insights suggest that the ability to sequester $$\hbox {CO}_2$$ CO 2 through mineralization along fractures will depend on the fracture orientation relative to gravity, with horizontal fractures more likely to seal uniformly.

Fluids with different densities often coexist in subsurface fractures and lead to variable-density flows that control subsurface processes such as seawater intrusion, contaminant transport, and geologic carbon sequestration. In nature, fractures have dip angles relative to gravity, and density effects are maximized in vertical fractures. However, most studies on flow and transport through fractures are often limited to horizontal fractures. Here, we study the mixing and transport of variable density fluids in vertical fractures by combining three-dimensional (3D) pore-scale numerical simulations and visual laboratory experiments. Two miscible fluids with different densities are injected through two inlets at the bottom of a fracture and exit from an outlet at the top of the fracture. Laboratory experiments show the emergence of an unstable focused flow path, which we term a “runlet.” We successfully reproduce an unstable runlet using 3D numerical simulations, and elucidate the underlying mechanisms triggering the runlet. Dimensionless number analysis shows that the runlet instability arises due to the Rayleigh-Taylor instability, and flow topology analysis is applied to identify 3D vortices that are caused by the Rayleigh-Taylor instability. Even under laminar flow regimes, fluid inertia is shown to control the runlet instability by affecting the size and movement of vortices. Finally, we confirm the emergence of a runlet in rough-walled fractures. Since a runlet dramatically affects fluid distribution, residence time, and mixing, the findings in this study have direct implications for the management of groundwater resources and subsurface applications.