The dissolution kinetics of natural gypsum: a case study of Eocene facies in the north-eastern suburbs of Paris

Abstract

The dissolution kinetics of different varieties of natural gypsum samples with different porosity and content of insoluble impurities are experimentally investigated under unsaturated conditions. The main goal of this work is to verify whether and how the petrophysical and petrographic nature of gypsum influence its dissolution rate. Gypsum samples were taken from Priabonian (Ludian) and Lutetian formations located in the north-eastern suburbs of Paris, where the development of sinkholes due to gypsum dissolution is a common phenomenon. Experiments using the rotating disk technique allow us to determine the kinetic rate model parameters of each sample in pure water following the empirical rate expression derived from mixed kinetic theory. The kinetic order n shows a dispersion around a mean value $n=1.2$ and k, the pure dissolution rate coefficient varies according to the facies and the experimental conditions (k $\approx \,1\times 10^{-6}$ to 8$\times 10^{-6}$ mmol/$\hbox {cm}^2/\hbox {s}$). These results are adjusted according to the specific roughness and texture of each sample, for the results to be more representative of in situ conditions. Batch experiments are also performed to evaluate the extremely low dissolution rates when the solution is close to equilibrium. The results reveal a double kinetics: far from equilibrium, the dissolution rates show that the linear behavior and the kinetic parameters are relatively close with the values found using the rotating disk method. For concentrations greater than 0.94 ± 0.02 of the equilibrium concentration $C_\mathrm{{ref}}$, the dissolution rates show a linear behavior but with greater slope depending on the texture of the mineral. No changes of the dissolution rates were observed on pure gypsum crystals when non soluble solid impurities are added. However, a small degree of uncertainty around the value of $C_\mathrm{{ref}}$ show a significant effect on the parameters of the second kinetics.