Karst-bauxite formation during the Great Oxidation Event indicated by dating of authigenic rutile and its thorium content.

Aluminium (Al)-rich palaeosols-i.e., palaeobauxite deposits-should have formed in karst depressions in carbonate sequences as a result of acidic solutions from oxidative weathering of sulfide minerals during the Great Oxidation Event (GOE), but no GOE-related karst-palaeobauxite deposits have so far been recorded. Here, we report results of in situ uranium-lead (U-Pb) dating of detrital zircon and spatially associated rutile from a metamorphosed Al-rich rock within a dolomite sequence in the Quadrilátero Ferrífero (QF) of Minas Gerais, Brazil, known as the Gandarela Formation. Rutile grains are highly enriched in thorium (Th = 3-46 ppm; Th/U ratio = 0.3-3.7) and yielded an isochron, lower-intercept age of ca. 2.12 Ga, which coincides with the final phase of the GOE-i.e., the Lomagundi event. The rutile age represents either authigenic growth of TiO2 enriched in Th, U and Pb during bauxite formation, or subsequent rutile crystallisation during metamorphic overprint. Both cases require an authigenic origin for the rutile. Its high Th contents can be used as a palaeoenvironmental indicator for decreased soil pH during the GOE. Our results also have implications for iron (Fe)-ore genesis in the QF. This study demonstrates that in situ U-Th-Pb-isotope analyses of rutile can place tight constraints on the age and nature of palaeosols.

Molybdenum-isotope signals and cerium anomalies in Palaeoproterozoic manganese ore survive high-grade metamorphism.

Molybdenum (Mo) and its isotopes have been used to retrieve palaeoenvironmental information on the ocean-atmosphere system through geological time. Their application has so far been restricted to rocks least affected by severe metamorphism and deformation, which may erase or alter palaeoenvironmental signals. Environmental Mo-isotope signatures can be retrieved if the more manganese (Mn)-enriched rocks are isotopically depleted and the maximum range of δ98Mo values is close to the ~2.7‰ Mo-isotope fractionation known from Mo sorption onto Mn oxides at low temperature. Here, we show that the Morro da Mina Mn-ore deposit in Minas Gerais, Brazil, contains Mn-silicate-carbonate ore and associated graphitic schist that likely preserve δ98Mo of Palaeoproterozoic seawater, despite a metamorphic overprint of at least 600 °C. The extent of Mo-isotope fractionation between the Mn-silicate-carbonate ore and the graphitic schist is similar to modern Mn-oxide precipitates and seawater. Differences in δ98Mo signals are broadly reflected in cerium (Ce) anomalies, which suggest an oxic-anoxic-stratified Palaeoproterozoic ocean.