Crystallization Pathways of Iron Formations: Insights From Magnetic Properties and High-Resolution Imaging of the 2.7 Ga Carajás Formation, Brazil.

Banded iron formations (BIFs) are chemical sedimentary rocks commonly utilized for exploring the chemistry and redox state of the Precambrian ocean. Despite their significance, many aspects regarding the crystallization pathways of iron oxides in BIFs remain loosely constrained. In this study, we combine magnetic properties characterization with high-resolution optical and electron imaging of finely laminated BIFs from the 2.7 Ga Carajás Formation, Brazil, to investigate their nature and potential for preserving ancient environmental conditions. Our findings reveal that magnetite, in the form of large 0.1-0.5 mm crystals, is the main iron oxide, with an overall averaged saturation magnetization (M) of 25 Am/kg (corresponding to ~27 wt% of magnetite) over the studied 230 m of the sequence. Nevertheless, the non-negligible contribution of minerals with higher coercivity suggests variable proportions of hematite along the core. Additionally, we observe non-uniform behavior in magnetite grains, with distinct populations identified through low-temperature measurements of the Verwey transition. Petrographic observations indicate that the original sediment was an Fe-Si mud consisting of a ferrihydrite-silica mixture formed in the water column. This assemblage was rapidly transformed into nano-scale hematite embedded in silica as indicated by a honeycomb structure composed of Si-spherules distributed in a microscale hematite matrix. Textural relationships show that the nucleation of magnetite started during or soon after the formation of hematite, as indicated by the preservation of the Si-spherules within magnetite cores. Further magnetite overgrowth stages are characterized by inclusion-free rims, associated with continuous Si supply during the evolving diagenetic or early metamorphic stages. These findings, combined with existing literature, suggest that ferrihydrite precipitated alongside Si and organic material, later crystallizing as hematite on the seafloor. Anaerobic respiration by Fe(III)-reducing microorganisms likely contributed to early magnetite formation in a fluid-saturated, unconsolidated sediment. Subsequent low-grade metamorphism and Si mobilization led to palisade quartz precipitation and a second stage of magnetite growth likely formed at the expense of matrix hematite through thermochemical Fe(III) reduction. Low-temperature magnetic analyses revealed that the two generations of magnetite core and rim are associated with specific stoichiometry.