Barite precipitation in porous media: Impact of pore structure and surface charge on ionic diffusion

Several scientific fields such as global carbon sequestration, deep geological radioactive waste disposal, and oil recovery/fracking encounter safety assessment issues originating from pore-scale processes such as mineral precipitation and dissolution. These processes occur in situations where the pore solution contains chemical complexity (such as pH, ionic strength, redox chemistry, etc.…) and the porous matrix contains physical complexity (such as pore size distribution, surface charge, surface roughness, etc.…). Thus, to comprehend the participation of each physicochemical phenomenon on governing mineral precipitation, it is essential to investigate the precipitation behavior of a given mineral in different confined volumes. In this study, a counter-diffusion approach was used to investigate barite precipitation in two porous materials: micritic chalk and compacted kaolinite. The two materials present similar water and anionic tracer diffusivities and total accessible porosities but distinct pore size distributions with pore throats of c.a. 660 nm in chalk versus c.a. 35 nm in kaolinite. X-ray tomography results obtained on the two materials showed a distinct distribution of barite precipitates: a 500 μm-thick homogeneous layer in chalk versus spherical clusters spread in a thickness of 2 mm in kaolinite. Mass balance calculations showed that barite precipitation led to a porosity decrease in the chalk reacted zone from 45% to 12% and in the kaolinite reacted zone from 36% to 34.5%. In contrast, water tracer diffusion experiments showed that diffusivity decreased by a factor of 28 in chalk and by a factor of 1000 in kaolinite. Such a discrepancy was attributed to the difference in the pore size distribution that would lead to the distinct barite precipitation patterns, capable of altering in a very different manner the connectivity within the reacted zone of the two selected porous media. Such local alterations in connectivity linked to pore volume reduction would also magnify surface charge effects on ionic transport, as indicated by chloride diffusion experiments and electrophoric tests using zeta potential measurements. Indeed, ³⁶Cl^- was strongly more hindered than water, when diffused in reacted materials, with a diffusivity decrease by a factor of 450 in chalk and a total restriction of ³⁶Cl^- in kaolinite. These experiments clearly provide an insight of how local pore structure properties combined with mineral reactivity could help in predicting the evolution of pore scale clogging and its impact on water and ionic diffusive transport.