Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb²⁺ Solutions

Abstract

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 Pb 2+ 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 Pb 2+ concentrations ([Pb 2+ ] = 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 [Pb 2+ ]. 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 [Pb 2+ ] ≥ 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.