In situ iron isotope analyses of pyrite and organic carbon isotope ratios in the Fortescue Group: Metabolic variations of a Late Archean ecosystem

The biogeochemical cycle of the Late Archean ocean is important for understanding the relationships between biological activity and oxygenation of the atmosphere and ocean. Based on the detailed geological survey of the Fortescue Group in the Redmont area in Pilbara Craton, Western Australia, we carefully selected 44 samples for iron isotope analyses, which consist of sandstones, stromatolitic carbonate rocks, alternating mudstone/sandstone rocks, mudstones and cherts. Our in situ analyses of δ56Fe values of 210 pyrite grains in these samples show a large variation from −4.2‰ to +3.0‰. We also analyzed 128 and 40 carbon isotope compositions of organic (δ13Corg: −51.8 to −10.3‰) and inorganic (δ13Ccarb: −6.1 to 0.6‰) carbons, respectively.Microscopic observations show obvious relationships between pyrite grain morphology and iron isotope ratio. Most pyrite grains with positive δ56Fe values show hexagonal, rectangular, and parallelogram shapes, which may replace former iron-oxide crystal systems: hematite, magnetite, and goethite, respectively. In contrast, more than half the pyrite grains with negative δ56Fe values show irregular forms. The correlation allows the possibility to solve the origin and the formation process of each grain of pyrite. The positive δ56Fe values suggest the partial oxidation of iron in an oxygen-limited environment. Some pyrites show very lower δ56Fe values below −2.2‰ suggesting a biological origin, probably due to microbial iron reduction.On the other hand, the pyrite is accompanied by isotopically very light organic carbon (δ13Corg: −51.8‰ to −40‰), which indicates aerobic or anaerobic methanotrophy. The coexistence of the low δ56Fe values and low δ13C values in the some rocks suggests anoxic oxidation of methane by iron-reduction (AOM/IR). The iron and carbon isotopes demonstrate the metabolic variations of microorganisms in a Late Archean shallow marine environment.

► We present in situ Fe isotope analyses of each pyrite grain in the Fortescue Group.
► Carbon isotope analyses of organic and inorganic carbon are also given.
► Good correlation of the morphologies with Fe isotope values of the pyrite grains.
► Quite low δ56Fe values, −4.18‰, indicate activity of iron-reducing bacteria (IRB).
► Extremely low δ56Fe and δ13Corg values are the oldest evidence for AOM/IR coupling.