New data on equilibrium iron isotope fractionation among sulfides: Constraints on mechanisms of sulfide formation in hydrothermal and igneous systems

Abstract

Fe, S, and Cu reduced partition function ratios (β-factors) allow calculation of equilibrium isotope fractionation factors. β-Factors for chalcopyrite are calculated from experimental and theoretical partial phonon densities of state states ( Kobayashi et al., 2007). The Fe β-factors for mackinawite are calculated from Mössbauer spectroscopy data ( Bertaut et al., 1965). Excellent agreement exists between Fe β-factors for chalcopyrite calculated from the experimental and theoretical 57Fe phonon densities of states, supporting the reliability of the Fe β-factors for chalcopyrite. The 34S β-factor for chalcopyrite is consistent with experimental data on equilibrium sulfur isotope fractionation factors among sulfides and theoretical 34S β-factors, except those recently calculated by a DFT approach. Up-to-date experimental isotope-exchange data on equilibrium Fe isotope fractionation factors between minerals and aqueous Fe were critically reevaluated in conjunction with Fe β-factors for minerals, and the following expressions for β-factors for aqueous Fe 2+ and Fe 3+ were obtained: 10 3 ln β Fe aq 3 + = 1.0063 10 6 T 2 ; T > 273 K 10 3 ln β Fe aq 2 + = 0.6537 10 6 T 2 ; T > 273 K. .Application of these new β-factors to Fe and S isotope fractionation at seafloor hydrothermal conditions shows that chalcopyrite may precipitate in equilibrium with Fe in hydrothermal fluids. In contrast, Fe and S isotope compositions of pyrite are may not be controlled by isotope equilibration with Fe in the hydrothermal fluid. Previously reported data on Fe isotope fractionation between pyrite and chalcopyrite in intrusions in the Grasberg Igneous Complex seem to be reasonable, and are in general agreement with previous “non-isotopic” estimates. Fe isotope fractionation between pyrite and chalcopyrite appear to reflect equilibrium in the intrusions of the Grasberg Igneous Complex, and Fe isotopes may therefore be considered as a potential geothermometer. The pyrite–chalcopyrite Fe isotope geothermometer, however, cannot be applied to the skarn facies of the Grasberg complex, where the initial Fe isotope compositions may have been disturbed by subsequent processes related to skarn formation.