Reactive transport model of kinetically controlled celestite to barite replacement

Abstract

Abstract. Barite formation is of concern for many utilisations of the geological subsurface, ranging from oil and gas extraction to geothermal reservoirs. It also acts as a scavenger mineral for the retention of radium within nuclear waste repositories. The impact of its precipitation on flow properties has been shown to vary by many orders of magnitude, emphasising the need for robust prediction models. An experimental flow-through column setup on the laboratory scale investigating the replacement of celestite (SrSO4) with barite (BaSO4) for various input barium concentrations was taken as a basis for modelling. We provide here a comprehensive, geochemical modelling approach to simulate the experiments. Celestite dissolution kinetics, as well as subsequent barite nucleation and crystal growth were identified as the most relevant reactive processes, which were included explicitly in the coupling. A digital rock representation of the granular sample was used to derive the initial inner surface area. Medium (10 mM) and high (100 mM) barium input concentration resulted in a comparably strong initial surge of barite nuclei formation, followed by continuous grain overgrowth and finally passivation of celestite. At lower input concentrations (1 mM), nuclei formation was significantly less, resulting in fewer but larger barite crystals and a slow moving reaction front with complete mineral replacement. The modelled mole fractions of the solid phase and effluent chemistry match well with previous experimental results. The improvement compared to models using empirical relationships is that no a-priori knowledge on prevailing supersaturations in the system is needed. For subsurface applications utilising reservoirs or reactive barriers, where barite precipitation plays a role, the developed geochemical model is of great benefit as only solute concentrations are needed as input for quantified prediction of alterations.