A highly oxidized atmosphere–ocean system and oceanic molybdenum drawdown during the Paleoproterozoic

Abstract:

Multiple lines of evidence suggest that the first major oxidation of the atmosphere–ocean system occurred during the Paleoproterozoic. However, the course of this redox transition remains elusive. A number of large Mn deposits are distributed in Paleoproterozoic sedimentary successions. As Mn is a redox-sensitive element characterized by high redox potential, knowledge of the Mn cycle in Paleoproterozoic seawater may provide insight into redox evolution during this period.

Here, we investigate the Mn cycle in Paleoproterozoic seawater based on the Re–Os and Mo isotope compositions, and the abundance of major and trace elements, in Mn-rich sedimentary rocks from the Nsuta deposit of the Birimian Supergroup, Ghana. The Mn ore is composed mainly of rhodochrosite and is distributed at the boundaries between sedimentary rocks and tholeiitic volcanic rocks. The Re–Os isochron age (2217 ± 100 Ma) we obtained was consistent with U–Pb zircon ages of the volcanic rocks. The manganophile elements, except for Mo, show no enrichment, which is similar to modern hydrothermal Mn oxides. The PAAS-normalized REE compositions show positive Ce anomaly, indicative of Ce enrichment due to the oxidation of Ce(III) by Mn(IV). These findings suggest that Mn ore formed from primary precipitation of Mn oxides from hydrothermal fluids as they were mixed with bottom seawater at ~2.2 Ga. Thus, the bottom seawater would have been sufficiently oxygenated for the precipitation of Mn oxides at ~2.2 Ga.

 The Nsuta ore samples exhibit slight Mo enrichment, but Mo/Mn ratios are orders of magnitude lower than those in modern hydrothermal Mn oxides. We also found that the Mo isotopes in the Nsuta ore are ~0.7‰ heavier than those in modern hydrothermal and hydrogenous Mn oxides. As Mo in hydrothermal Mn oxides is sourced primarily from seawater (Goto et al., in prep), these results may reflect smaller oceanic Mo inventory and heavier seawater Mo isotope composition at 2.2 Ga than those of present-day. Our calculation using a simple mass balance model suggests that substantial removal of light Mo by Mn oxides may have caused such oceanic conditions.

Our findings are consistent with the recently proposed ‘oxygen overshoot’ model (Bekker and Holland, 2012) and low Mo contents in ~2.2-Ga black shales and sedimentary pyrites (e.g., Scott et al., 2008).