Estimates of chlorine isotope fractionation factors using density functional theory: Applications to ore-forming systems

Chloride is the most important anion in ore-forming hydrothermal fluids, and chlorine isotopes are therefore potentially sensitive tracers of the origin and evolution of ore-forming fluids. However, they remain a relatively under-utilized tool in ore deposit geochemistry due to the lack of knowledge of chlorine isotope fractionation during ore-forming processes. Using first-principles density functional theory, this study estimates chlorine isotope fractionation factors for various ore-forming processes. All metal-Cl complexes in hydrothermal fluids are enriched in Cl-37 compared to chloride ions, but the change in delta Cl-37 of the fluid trapped in ore minerals is small after the destabilization of metal-chloride complexes during ore mineral deposition. In the precipitation of evaporite minerals from brine, the sequence of enrichment of the heavy Cl isotope (Cl-37) is halite > carnallite > aqueous chloride > kainite > sylvite > bischofite. The results of this study agree with the experimental observations that progressive precipitation of halite from brine lowers the delta Cl-37 value of the residual fluid until the formation of K-Mg chlorides. In low-temperature deposits, delta Cl-37 values for fluid inclusions and minerals reflect those of the hydrothermal fluid provenance and the mixing of this fluids with saltwater or basinal brines. In high-temperature magmatic-hydrothermal ore deposits that undergo liquid-vapour phase separation, chlorine isotopes fractionate among phases of silicate melt, vapour and chloride-rich liquid. The considerable range in delta Cl-37 in fluid inclusions may also reflect fluid mixing and hydrothermal alteration. At ambient temperature, the delta Cl-37 values may reflect evaporative processes and, in the case of chemical weathering of metallic mineral deposits, may record the supergene enrichment of the metals. This study highlights the use of chlorine isotopes as a new tool for interpreting ore-forming processes.