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.