Progressive ocean oxygenation at ~2.2 Ga inferred from geochemistry and molybdenum isotopes of the Nsuta Mn deposit, Ghana

Recent geochemical data suggest the occurrence of an O2 overshoot during the mid-Paleoproterozoic (~2.3–2.0 Ga). This O2 overshoot appears to be consistent with carbon isotope records that suggest high burial rates of organic carbon during that period, the so-called Lomagundi Event. However, little is known about the changes in the ocean redox conditions associated with the O2 overshoot. To better understand the mid-Paleoproterozoic ocean chemistry, we investigated the microstructures, major and trace element concentrations, Re-Os and Mo (δ98/95Mo) isotopes, and total organic carbon contents of Mn-ore and phyllite samples from the Nsuta Mn deposit in the Birimian Supergroup of Ghana which were deposited during the O2 overshoot (at ~2.2 Ga). The Mn-ore samples contain early diagenetic rhodochrosite (Mn carbonate). The trace element compositions and Re-Os isotopes of the Mn-ore samples suggest that the rhodochrosite originated from primary manganese oxides (MnO2) deposited at ~2.2-Ga. The δ98/95Mo values of the least-altered Mn-ore samples range between −1.10‰ and −0.55‰ (relative to NIST3134), suggesting seawater δ98/95Mo values of 1.85 ± 0.18‰ (1SD) during the O2 overshoot. Such high seawater δ98/95Mo values can be best explained by enhanced removal of isotopically light Mo through adsorption onto Mn oxides. To form extensive Mn-oxide deposits, bottom seawater with O2 concentrations of > 10 μM would have expanded at ~2.2 Ga. The oxidizing conditions might have supported the emergence of stem group eukaryotes during the mid-Paleoproterozoic.