Microbial metallogenesis of Cryogenian manganese ore deposits in South China

The Datangpo Formation manganese deposits (DFMnD) in South China formed during the interglacial stage between the Sturtian and Marinoan glaciations of the Cryogenian period. These black shale-hosted deposits are composed of massive Mn-carbonates with microscopic laminae/laminations and cherty veins. To date, it has been thought that the DFMnD formed through inorganic processes, which were controlled by redox changes in the post-Sturtian Nanhua Rift Basin, South China. However, in this study, systematic petrographic, mineralogical, and geochemical analyses indicate a microbially mediated origin of the Mn ore deposits. Mineralized microbial woven micro-textures (observed at the pm scale) and microbial fossils are common in the laminated Mn-carbonate ores. We infer that microbial enzyme activity formed poorly crystallized Mn oxide/hydroxides and carbonaceous material, which transformed to rhodochrosite, kutnohorite, ankerite/dolomite, framboidal pyrite, and apatite via diagenesis. Some micro-scale quartz and K-feldspar may be detrital but most appears to have formed during diagenesis or through hydrothermal activity. A micro-mineralogical profile determined by 2500 spectra via high-resolution in situ micro-Raman spectroscopy also revealed cyclic laminations of Ca-rhodochrosite as microbialite (ankerite/dolomite) and quartz, indicating a mineralized biomat system. Ca-rhodochrosite transformed to kutnohorite under elevated temperatures, as indicated by the maturation level of organic matter (determined via Raman spectroscopy). Alternating micro-laminae denote cyclic changes in microbial groups (Mn- and Fe-oxidizing microbes versus cyanobacteria) during the formation of the Mn ore deposits. Our proposed model for the microbially mediated metallogenesis of Mn-carbonate deposits begins with enzymatic multi-copper oxidase processes associated with autotrophic microbial activity under obligatory oxic conditions, which results in the precipitation of Mn bio-oxides. Following their burial in organic-rich sediments, the Mn(IV) oxides and hydroxides are reduced, producing soluble Mn(II) via processes mediated by heterotrophic microbes under suboxic conditions, which in turn form the Mn-carbonates. This microbial metallogenesis model for the Cryogenian DFMnD in South China is similar to that proposed for the Jurassic Urkut Mn deposit in Hungary, indicating that a two-step microbially mediated process of Mn ore formation might be common throughout geological history.