Effects of Al/Si ordering on feldspar dissolution: Part II. The pH dependence of plagioclases’ dissolution rates

The rate of mineral dissolution in an aquatic environment is sensitive to the pH of the contacting solution. The pH dependence of mineral dissolution rate has been interpreted by the Transition State Theory-Surface Complexation Model (TST-SCM) formalism in terms of pH-sensitive variability in surface chemistry. In this study, we provide an alternative interpretation for the experimentally observed nonlinear pH dependence of feldspar dissolution rates. The interpretation is based on a new formalism for feldspar dissolution which, while compatible with the TST-SCM formalism, incorporates the effects of both surface chemistry and bulk chemistry on feldspar dissolution into the quantification of dissolution rate. The pH dependence of dissolution rate varies from one feldspar specimen to another because different TOT linkages within one solid matrix can respond differently to the attack of proton. Our results suggest that the pH dependence of feldspar dissolution rate is not a constant in general, and could be affected by pH, substitutional Al/Si ordering, chemical composition of the specimen, and the relative rapidness of linkage hydrolysis according to different mechanisms. The rate law proposed in this study is able to capture the experimentally observed pH dependence of the dissolution rates of a series of plagioclases, including albite, andesine, labradorite, bytownite, and anorthite. The effectiveness of the newly proposed formalism for feldspar dissolution, hence, suggests that dissolution reactions of minerals are combinations of surface renewal and heterogeneous chemical reactions. The currently widely used TST-SCM-based rate laws can be further improved by taking into account the effects of bulk chemistry and surface renewal in the prediction of mineral dissolution rates. An improved formalism for mineral dissolution will be mineral-specific, and will reflect the effects of the temporal decay in the availability of reactive surface sites as well as the interconnectivities of atoms within the solid matrix of a mineral.