Iron isotope fractionation between pyrite (FeS2), hematite (Fe2O3) and siderite (FeCO3): A first-principles density functional theory study

In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln alpha Fe-57/Fe-54 = 4.59 +/- 0.30 parts per thousand and 5.46 +/- 0.63 parts per thousand at 20 degrees C for theoretical and experimental data, respectively) while those for Fe(III)(aq)-hematite and Fe(II)(aq)-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions (beta-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mossbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mossbauer spectroscopy. Geochim. Cosmochim. Acta 71, 3833-3846], our iron beta-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived beta-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined. (C) 2009 Elsevier Ltd. All rights reserved.