New insight into genesis of the Maojun laterite Fe–Mn deposit in the Lanshan area, Hunan Province, South China: Evidence from detailed mineralogical and geochemical studies

Abstract

Laterite Fe–Mn deposits are widespread in South China, with the majority of Fe–Mn ore being present in residual quaternary clay beds. However, detailed geological data on the lateritization of low-iron-content carbonate rocks are rare. In this study, we present new results on the mineralogy and geochemistry, as well as a genetic model, of the Maojun laterite Fe–Mn deposit in the Lanshan area, Hunan Province, South China. The profile sequence of laterite consists of an eroded bedrock horizon at its base, an intermediate black–brown clay layer containing earthy Fe–Mn ore, and a reddish-brown clay layer with nodular ferromanganese ore in contact with reddish-brown or yellowish-brown clay on top. Field evidence and chemical analysis indicated that during lateritization, the Mn-Fe-containing carbonate rocks of the Huanggongtang (D2h) and Shetianqiao formations (D3s) saw a more significant removal of mobile elements (Mg, Ca, and Na) whilst insoluble elements (Fe, Mn, Si, Al, Pb, and Zn) exhibited persistent enrichment in situ. Discriminative diagrams of Fe–Mn mineralization, as well as the assemblage-related enrichment of Y, U, Mo, Pb, and Zn and depletion of high-field-strength elements Zr, Nb, and Th, imply that subsequent hydrothermal circulation overprinted on the previously formed hydrogenous deposit. Mineralogical studies conducted using XRD, EPMA, HR-TEM, and TIMA indicated the predominance of iron and manganese oxides; hematite, goethite, limonite, and hollandite were identified as major oxide phases and cryptomelane, pyrolusite, and coronadite were present in minute quantities. Similar minerals constitute the upper ferromanganese nodule horizons, although they possess distinct textures and concentrations. The mineralogy, geochemical associations, and Ti mass balance show a continuous vertical evolution from top to bottom in the lateritic profile. Ferromanganese concretions from the drenching zone with poorly crystallized Al–goethite, Al–hematite, limonite, Fe–kaolinite, Fe–Mn oxides and hollandite predominate in shallow parts, and microcrystalline hematite, goethite and hollandite were found in deeper layers. Mn2+ can be rapidly oxidized and precipitated on the surface of hematite and limonite as high-valence-state (Mn4+) manganese oxides and binds strongly with mobile elements (Ba, K, Pb, Zn, Ca, and Ni). Petrographical, mineralogical, and geochemical studies show that three stages comprised the formation of the Maojun laterite Fe–Mn deposit.