nm-Range forces acting between calcite surfaces in water affect macroscopic properties of carbonate rocks and calcite-based granular materials and are significantly influenced by calcite surface recrystallization. We suggest that the repulsive mechanical effects related to nm-scale surface recrystallization of calcite in water could be partially responsible for the observed decrease of cohesion in calcitic rocks saturated with water. Using the surface forces apparatus, we simultaneously followed the calcite reactivity and measured the forces in water in two surface configurations: between two rough calcite surfaces (CC) and between rough calcite and a smooth mica surface (CM). We used nm-scale rough, polycrystalline calcite films prepared by atomic layer deposition. We measured only repulsive forces in CC in CaCO-saturated water, which was related to roughness and possibly to repulsive hydration effects. Adhesive or repulsive forces were measured in CM in CaCO-saturated water depending on calcite roughness, and the adhesion was likely enhanced by electrostatic effects. The pull-off adhesive force in CM became stronger with time, and this increase was correlated with a decrease of roughness at contacts, the parameter which could be estimated from the measured force-distance curves. That suggested a progressive increase of real contact areas between the surfaces, caused by gradual pressure-driven deformation of calcite surface asperities during repeated loading-unloading cycles. Reactivity of calcite was affected by mass transport across nm- to μm-thick gaps between the surfaces. Major roughening was observed only for the smoothest calcite films, where gaps between two opposing surfaces were nm-thick over μm-sized areas and led to force of crystallization that could overcome confining pressures of the order of MPa. Any substantial roughening of calcite caused a significant increase of the repulsive mechanical force contribution.

Fluid-induced alteration of rocks and mineral-based materials often starts at confined mineral interfaces where nm-thick water films can persist even at high overburden pressures and at low vapor pressures. These films enable transport of reactants and affect forces acting between mineral surfaces. However, the feedback between the surface forces and reactivity of confined solids is not fully understood. We used the surface forces apparatus (SFA) to follow surface reactivity in confinement and measure nm-range forces between two rough calcite surfaces in NaCl, CaCl 2 , or MgCl 2 solutions with ionic strength of 0.01, 0.1 or 1 M. We observed long-range repulsion that could not be explained by changes in calcite surface roughness, surface damage, or by electrostatic or hydration repulsion, but was correlated with precipitation events which started at µm-thick separations. We observed a submicron-sized precipitate that formed in the confined solution. This liquid-like viscous precipitate did not undergo any spontaneous ripening into larger crystals, which suggested that confinement prevented its dehydration. Nucleation was significantly postponed in the presence of Mg 2+ . The long-range repulsion generated by nucleation between confined mineral surfaces can have a crucial influence on evolution of the microstructure and therefore the macroscopic strength of rocks and materials.

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The stability of organomineral aggregates in soils has a key influence on nutrient cycling, erosion, and soil productivity. Both clay minerals with distinct basal and edge surfaces and organic molecules with reactive functional groups offer rich bonding environments. While clay edges often promote strong inner-sphere bonding of −COOH-laden organics, we explore typically weaker, outer-sphere bonding of such molecules onto basal planes and its significance in organomineral interactions. In this surface force apparatus study, we probed face-specific interactions of negatively charged mica basal surfaces in solutions containing carboxyl-bearing, low-molecular-weight dicarboxylic acids (DAs). Our experiments provide distance-resolved, nanometer-range measurements of forces acting between two (001) mica surfaces and simultaneously probe DA adsorption. We show that background inorganic ions display crucial importance in nanoscale forces acting between basal mica surfaces and in DA adsorption: Na+ contributes to strong repulsion and little binding of dicarboxylic anions, while small amounts of Ca2+ are sufficient to screen the basal surface charge of mica, facilitate strong adhesion, and enhance dicarboxylic anion adsorption by acting as cationic bridges. Despite reversible and weak adsorption of DAs, we resolve their multilayer binding via assembly of hydrophobic chains in the presence of Ca2+, pointing the importance of abundant, less reactive basal clay surfaces in organomineral interactions.