Microscale heterogeneity of Fe isotopes in >3.71 Ga banded iron formation from the Isua Greenstone Belt, Southwest Greenland

We present Fe isotope compositions for magnetite crystals from > 3.7 Ga banded iron formation (BIF) from the Isua Greenstone Belt and younger, spatially related pyrite obtained in situ by secondary ion mass spectrometry (SIMS). Across a distance of several millimeters, individual magnetite crystals of BIF show delta Fe-56 values up to 2%, and within single magnetite-rich layers, there is a > 2% range in delta Fe-56. The highest positive delta Fe-56 values are consistent with those predicted by the equilibrium fractionation factor for oxidation of ferrous to ferric Fe in aqueous solution at a likely Early Archean ocean temperature of similar to 70 degrees C, and further suggest that subsequent precipitation of ferric oxides was sufficiently slow that kinetic fractionation effects were minimal. These high values also imply that the supply of oxidant was limited. Heterogeneity in delta Fe-56 values is attributed to diagenetic reactions occurring in limited-volume pore waters, isolated from the bulk ocean (delta(56) Fe = (0%), with development of isotope reservoir effects. Secondary pyrite in BIF and a conglomerate also show a distinct enrichment in heavy Fe isotopes, interpreted as redistribution and/or fractionation during postformational events.