Unusual manganese enrichment in the Mesoarchean Mozaan Group, Pongola Supergroup, South Africa

An unusual sediment-hosted manganese deposit is described from the Mesoarchean Mozaan Group, Pongola Supergroup, South Africa. MnO contents up to 15 wt.% were observed in marine clastic and chemical sedimentary rocks. Mn enrichment is interpreted to have resulted from the hydrothermal alteration of manganiferous shale and BIF parent rocks, the primary MnO contents of which are as high as 8.5 wt.%. A detailed mineralogical and petrographic study shows that these parent rocks are characterized by manganoan siderite, ferroan rhodochrosite and other Mn-Fe-rich mineral phases, such as kutnohorite and Fe-Mn-chlorite. Their hypogene alteration gave rise to a diversification of mineral assemblages where ferroan tephroite, calcian rhodochrosite, rhodochrosite, pyrochroite, pyrophanite, cronstedtite, manganoan Fe-rich chlorite and manganoan phlogopite partially or totally replaced the previous mineral assemblage. Thermodynamic modeling performed on chlorite phases associated with the described mineral assemblages illustrates a decrease of average crystallization temperatures from ca. 310 °C during early metamorphic stages to ca. 250 °C during a hydrothermal stage. Mineral transformation processes were thus related to retrograde metamorphism and/or hydrothermal alteration post-dating metamorphism and gave rise to progressive Mn enrichment from unaltered parent to altered rocks. The timing of hypogene alteration was constrained by 40Ar/39Ar dating to between about 1500 and 1100 Ma ago, reflecting tectonic processes associated with the Namaqua-Natal orogeny along the southern Kaapvaal Craton margin. Manganiferous shale and BIF of the Mozaan Group may represent the oldest known examples of primary sedimentary Mn deposition, related to oxidation of dissolved Mn(II) by free oxygen in a shallow marine environment. Oxygenic photosynthesis would have acted as a first-order control during Mn precipitation. This hypothesis opens a new perspective for better constraining secular evolution of sediment-hosted mineral deposits linked to oxygen levels in the atmosphere-hydrosphere system during the Archean Eon.