Early Archean biogeochemical iron cycling and nutrient availability: New insights from a 3.5 Ga land-sea transition

The chemical and isotopic compositions of Precambrian Fe-rich chemical sedimentary rocks have figured prominently in discussions on the Fe biogeochemical cycle and redox conditions in the early Earth. Broad trends of decreasing δ56Fe values for Eoarchean to Paleoproterozoic iron formations (IFs) and jaspilites (hematite-chert) with decreasing age reflect a general increase in extent of oxidation of aqueous Fe(II) (Fe(II)aq) in marine environments, consistent with increasing oxygenation of surface environments, particularly since the Mesoarchean. Such trends may record a shift from anaerobic to aerobic oxidation, in part reflecting increasing nutrient abundances that follow increased emergence of continental crust. It is commonly proposed that the size of the biosphere in the early Archean was largely nutrient limited, specifically P limited. Highly positive δ56Fe values for Fe oxides in chemical sedimentary rocks deposited in open marine environments at this time are consistent with excess Fe(II)aq.