Iron and sulphur isotopes from the Carajás mining province (Pará, Brazil): Implications for the oxidation of the ocean and the atmosphere across the Archaean–Proterozoic transition

Abstract

Mineralogical analyses and major and trace element geochemistry combined with iron and sulfur isotopes were applied to banded iron formations (BIFs) and pyrite-bearing sandstones from the Carajás mineral province, Brazil. The BIFs belong to the 2.7 Ga old Grão Pará Group and show a rather simple mineralogy (hematite and quartz or cryptocrystalline silica). Their REE + Y patterns suggest deposition under marine sub-oxic conditions. Fe isotopes show highly positive values (δ 57Fe IRMM-14 = 2.06 ± 0.34‰ in average) which can be explained by the partial oxidation of Fe 2+ aq in the surface ocean, subsequent to the upwelling of deep anoxic seawater. The resulting iron oxy-hydroxides likely formed in the shallow photic zone as a seasonal process and acquired highly positive iron isotope signature values consistent with a Rayleigh distillation model. The pyrite-bearing sandstones belong to the Aguas Claras Formation of (Palaeoproterozoic) younger age and were cored at the base of the giant Azul manganese deposit. Diagenetic pyrite is characterized by positive δ 57Fe IRMM-14 = 1.02 ± 0.2‰ and δ 34S VCTD (11.97 ± 0.12‰) average values, that are different from values of modern marine biogenic pyrite. Results likely indicate that dissolved sulfate was the limiting factor controlling biogenic pyrite formation at that time. Near-zero Δ 33S values (0.013 ± 0.003‰) indicate minimal mass-independent sulfur isotope fractionation (MIF-S), consistent with the 2.1 Ga age previously obtained from the Aguas Claras pyrites. This result suggests deposition at a time when the oxygen partial pressure in the atmosphere was already high enough (10 − 5 to 10 − 2 PAL- or Present Atmospheric Level-) to hinder MIF-S by photochemical reactions. Incidentally, this also confirms that the giant Mn deposit of Carajás is in the same age range (2.1 ± 0.2 Ga) as other Mn ores in Gabon and South Africa, pointing to the importance of Mn precipitation in Paleoproterozoic times.