Fraction-specific rare earth elements enable the reconstruction of primary seawater signatures from iron formations

Rare earth element (REE) abundances in iron formations (IFs) provide key evidence to track the redox evolution of the Precambrian oceans. Deriving information about processes and sources from IFs is complicated by the variable roles of diagenetic dissolution and precipitation that modify primary depositional signals in the rocks. Iron formations are typically mineralogically heterogeneous with varying amounts of carbonate (ankerite + siderite), oxide (predominantly magnetite) and silicate (chert and Fe-silicates). To date, little is known about the respective contributions of these fractions to the bulk-rock REE signal, and which fraction most accurately records primary seawater signals. Here we evaluate an optimized sequential extraction scheme for REE analysis in the ca. 2.46 Ga Asbestos Hills IFs from the Griqualand-West Basin in South Africa. These rocks were deposited immediately before the Great Oxidation Event and are potentially an important archive for large-scale redox changes in the (near) surface environment. To fully evaluate our method, we measured lanthanide elements plus ytrrium (REY) in individual minerals, in bulk rock samples and in three separate fractions using acetate, oxalate and total digestion sequential extractions. The extraction techniques were then verified using a mass balance approach, the first time that this has been comprehensively applied to IFs. Similarities between the carbonate fraction data and modern seawater, coupled with strong measurement reproducibility and systematic stratigraphic variability suggests that carbonate most closely tracks the primary seawater composition. The Asbestos Hills IFs show distinctive REY signatures with strongly variable (Yb/Pr)SN ratios, positive La anomalies, positive and constant Y/Ho, weakly positive Eu anomalies and a lack of Ce anomalies in their carbonate fraction. Stratigraphic variations in these parameters suggest deposition in a stratified fully anoxic ocean, which became shallower over time. The silicate fraction was influenced by various amounts of allochthonous material (detrital and volcanic ash), although some minerals including greenalite, minnesotaite and stilpnomelane may have tracked seawater REE variability. The oxide fraction was found to be the most REY-depleted and therefore susceptible to allochthonous influences as well as diagenetic controls. It shows a systematic MREE enrichment that has not been described in IFs before, but has been seen in sub-oxic, ferrous environments. An increase in the ratio of carbonate to oxide minerals ongoing upwards through the Asbestos Hills IF, from deep to shallow water conditions, most likely reflected an increase in dissimilatory iron reduction close to the margin of the anoxic basin