Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb²⁺ Solutions

Reactions of mineral surfaces with dissolved metal ions at far-from-equilibrium conditions can deviate significantly from those in near-equilibrium systems due to steep concentration gradients, ion-surface interactions, and reactant transport effects that can lead to emergent behavior. We explored the effect of dissolved Pb²⁺ on the dissolution rate and topographic evolution of calcite (104) surfaces under far-from-equilibrium acidic conditions (pH 3.7) in a confined single-pass laminar-flow geometry. Operando measurements by digital holographic microscopy were conducted over a range of Pb²⁺ concentrations ([Pb²⁺] = 0 to 5 × 10^-2 M) and flow velocities (v = 1.67-53.3 mm s^-1). Calcite (104) surface dissolution rates decreased with increasing [Pb²⁺]. The inhibition of dissolution and the emergence of unique topographic features, including micropyramids, variable etch pit shapes, and larger scale topographic patterns, became increasingly apparent at [Pb²⁺] ≥ 5 × 10^-3 M. A better understanding of such dynamic reactivity could be crucial for constructing accurate models of geochemical transport in aqueous carbonate systems.