Isotopic Constraints on the Nature of Primary Precipitates in Archean–Early Paleoproterozoic Iron Formations from Determinations of the Iron Phonon Density of States of Greenalite and 2L- and 6L-Ferrihydrite

Abstract

Iron formations (IFs) are chemical sedimentary rocks that were widely deposited before the Great Oxidation Event (GOE) around 2.4–2.2 Ga. It is generally thought that IFs precipitated as hydrated Fe3+ oxides (HFOs) such as ferrihydrite following surface oxidation of Fe2+-rich, anoxic deep waters. This model often implicates biological oxidation and underpins reconstructions of marine nutrient concentrations. However, nanoscale petrography indicates that an Fe2+ silicate, greenalite, is a common primary mineral in well-preserved IFs, motivating an alternative depositional model of anoxic ferrous silicate precipitation. It is unclear, however, if Fe2+-rich silicates can produce the Fe isotopic variations in IFs that are well explained by Fe2+ oxidation. To address this question, we constrain the equilibrium Fe isotopic (56Fe/54Fe) fractionation of greenalite and ferrihydrite by determining the iron phonon densities of states for those minerals. We use ab initio density functional theory (DFT + U) calculations and nuclear resonant inelastic X-ray scattering spectroscopy to show that ferrous greenalite should be isotopically lighter than ferrihydrite by ∼1–1.2‰ at equilibrium, and fractionation should scale linearly with increasing Fe3+ content in greenalite. By anchoring ferrihydrite–greenalite mineral pair fractionations to published experimental Fe isotopic fractionations between HFOs and aqueous Fe2+, we show that ferrous greenalite may produce all but the heaviest pre-GOE Fe isotopic compositions and mixed valence greenalites can produce the entire record. Our results suggest that heavy Fe isotope enrichments alone are not diagnostic of primary IF mineralogies, and ferrihydrite and partially oxidized or even purely ferrous greenalite are all viable primary IF mineralogies.

Equilibrium Sn Isotope Fractionation among Sn-Bearing Minerals

“…The underestimation of force constants by the PBE functional relative to NRIXS measurements has also been found in minerals of other Mössbauer-active elements such as Fe and Eu. Nie et al and Heard et al summarized the average Fe force constants in minerals (i.e., hematite, goethite, ferrihydrite, almandine, ilmenite, annite, schorl, fayalite, and greenalite) obtained from the PBE­(+U) calculations and NRIXS measurements in their and previous studies (DFT: refs , . NRIXS: refs , .…”

“…relative to NRIXS measurements has also been found in minerals of other Mossbauer-active elements such as Fe and Eu. Nie et al 9 and Heard et al 84 89 also compared their computational results of magnetite, forsterite, and enstatite (at the PBE level) with the previous NRIXS data. 87,90−92 The average Eu force constants in EuPO 4 , EuO, EuS, and EuSe obtained from the PBE+U calculations are lower than those from the NRIXS measurements.…”