The dissolution of minerals in contact with water plays a crucial role in geochemistry. However, obtaining molecular insight into interfacial chemistry is challenging. Dissolution typically involves the release of ions from the surface, giving rise to a charged mineral surface. This charge affects the interfacial water arrangement, which can be investigated by surface-specific vibrational Sum Frequency Generation (v-SFG) spectroscopy. For the fluorite-water interface, recent spectroscopic studies concluded that fluoride adsorption/desorption determines the surface charge, which contrasts zeta potential measurements assigning this role to the calcium ion. By combining v-SFG spectroscopy and flow experiments with systematically suppressed dissolution, we uncover the interplay of dominant fluoride and weak calcium adsorption/desorption, resolving the controversy in the literature. We infer the calcium contribution to be orders of magnitude smaller, emphasizing the sensitivity of our approach.