Two-stage fluid pathways generated by volume expansion reactions: insights from the replacement of pyrite by chalcopyrite

Volume expansion reactions involved in mineral-fluid interactions are linked to a number of geological processes, including silicate weathering, retrograde metamorphism, and mineralization. However, the effect of volume expansion on replacement reactions remains unclear. Here, we demonstrate that reactions associated with volume expansion during the replacement of pyrite by chalcopyrite involve two competing processes. The reaction is initially augmented because of the development of reaction-induced fractures in the pyrite. However, these fractures are subsequently filled by compacted products, which ultimately disrupts the contact and interaction between bulk fluids and the pristine pyrite surface. These competing processes indicate that replacement reactions are both augmented and inhibited by volume expansion reactions during pyrite replacement.