Hyper-localized carbon mineralization in diffusion-limited basalt fractures

Basalt formations could enable secure carbon sequestration through mineral trapping. CO2 injection acidifies formation brines and drives dissolution of the host rock, which releases divalent metal cations that combine with dissolved carbonate ions to form stable carbonate minerals. Here, a series of high-pressure flow-through experiments was conducted to evaluate how transport limitations and geochemical gradients drive microscale carbonation reactions in fractured basalts. To isolate advection- and diffusion-controlled zones, surfaces of saw-cut basalt cores were milled to create one primary flow channel adjoined by four dead-end fracture pathways. In the first experiment, a representative basalt brine (6.3 mM NaHCO3) equilibrated with CO2 (100ºC, 10 MPa) was injected at 1 mL/h under 20 MPa confining stress. The second experiment was conducted under the same physical conditions but [NaHCO3] was elevated to 640 mM, and in the third, temperature was also raised to 150ºC. Effluent chemistry was monitored via ICP-MS to infer dissolution trends and calibrate reactive transport models. Reacted cores were characterized using x-ray computed tomography (xCT), optical microscopy, scanning electron microscopy, and Raman spectroscopy. Carbonation occurred in all experiments but increased in experiments with higher alkalinity and higher temperature. At low [NaHCO3], secondary precipitate coatings formed distinct reaction fronts that varied with distance into dead-end fractures. Reactive transport modeling demonstrated that these reactions fronts were due to sharp gradients in pH and dissolved inorganic carbon. Carbonation was restricted to transport-limited vugs and pores between the confined core surfaces and was highly localized on reactive primary mineral grains (e.g. pyroxene) that contributed major divalent cations. Increasing [NaHCO3] by two orders of magnitude significantly enhanced carbonation and promoted Mg and Fe uptake into carbonates. While xCT scans revealed clays filling the advective path, no permeability changes were measured. Our coupled experiment-modeling approach further elucidates the geochemical conditions controlling carbonation reactions and extends unique microstructural observations to implications for long-term CO2 mineralization in basalt reservoirs.