pH-dependent control of feldspar dissolution rate by altered surface layers

• Dissolution rate of feldspar minerals decreases due to ageing of reactive surfaces.
• An amorphous surface layer forms during labradorite dissolution in acidic conditions.
• pH controls the layer's properties and thus the dissolution rate of the mineral
• The ageing process depends on crystallographic orientation.
• Passivation of mineral surfaces under field-relevant conditions

Relevant modeling of mass and energy fluxes involved in pedogenesis, sequestration of atmospheric CO2 or geochemical cycling of elements partly relies on kinetic rate laws of mineral dissolution obtained in the laboratory. Deriving an accurate and unified description of mineral dissolution has therefore become a prerequisite of crucial importance. However, the impact of amorphous silica-rich surface layers on the dissolution kinetics of silicate minerals remains poorly understood, and ignored in most reactive transport codes. In the present study, the dissolution of oriented cleavage surfaces and powders of labradorite feldspar was investigated as a function of pH and time at 80 °C in batch reactors. Electron microscopy observations confirmed the formation of silica-rich surface layers on all samples. At pH = 1.5, the dissolution rate of labradorite remained constant over time. In contrast, at pH = 3, both the dissolution rates at the external layer/solution interface and the internal layer/mineral interface dramatically decreased over time. The dissolution rate at the external interface was hardly measurable after 4 weeks of reaction, and decreased by an order of magnitude at the internal interface. In another set of experiments conducted in aqueous silica-rich solutions, the stabilization of silica-rich surface layers controlled the dissolution rate of labradorite at pH = 3. The reduction of labradorite dissolution rate may result from a gradual modification of the textural properties of the amorphous surface layer at the fluid/mineral interface. The passivation of the main cleavage of labradorite feldspar was consistent with that observed on powders. Overall, our results demonstrate that the nature of the fluid/mineral interface to be considered in the rate limiting step of the process, as well as the properties of the interfacial layer (i.e. its chemical composition, structure and texture) to be taken into account for an accurate determination of the dissolution kinetics may depend on several parameters, such as pH or time. The dramatic impact of the stabilization of surface layers with increasing pH implies that the formation and the role of surface layers on dissolving feldspar minerals should be accounted for in the future.