矿床地球化学国家重点实验室知识库

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃⁻ from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.