Reactivity of sandstone and siltstone samples from the Ketzin pilot CO₂ storage site-Laboratory experiments and reactive geochemical modeling

To evaluate mineralogical-geochemical changes within the reservoir of the Ketzin pilot CO₂ storage site in Brandenburg, Germany, two sets of laboratory experiments on sandstone and siltstone samples from the Stuttgart Formation have been performed. Samples were exposed to synthetic brine and pure CO₂ at experimental conditions and run durations of 5.5 MPa/40 °C/40 months for sandstone and 7.5 MPa/40 °C/6 months for siltstone samples, respectively. Mineralogical changes in both sets of experiments are generally minor making it difficult to differentiate natural variability of the whole rock samples from CO₂-induced alterations. Results of sandstone experiments suggest dissolution of the anorthite component of plagioclase, anhydrite, K-feldspar, analcime, hematite and chlorite + biotite. Dissolution of the anorthite component of plagioclase, anhydrite and K-feldspars is also observed in siltstone experiments. In an inverse modeling approach, an extensive set of equilibrium simulations was set up in order to reproduce the experimental observations of the sandstone experiments. Simulations generally show fairly good matches with the experimental observations. Best matches with measured brine data are obtained from mineral combinations of albite, analcime, anhydrite, dolomite, hematite, illite, and kaolinite. The major discrepancies during equilibrium modeling, however, are reactions involving Fe²⁺ and Al³⁺. The best matching subsets of the equilibrium models were finally run including kinetic rate laws. These simulations reveal that experimentally determined brine data was well matched, but reactions involving K⁺ and Fe²⁺ are not fully covered. The modeling results identified key primary minerals as well as key chemical processes, but also showed that the models are not capable of covering all possible contingencies.