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The rare earth elements (REEs) have unique and diverse properties that make them function as an “industrial vitamin” and thus, many countries consider them as strategically important resources. China, responsible for more than 60% of the world’s REE production, is one of the REE-rich countries in the world. Most REE (especially light rare earth elements (LREE)) deposits are closely related to carbonatite in China. Such a type of deposit may also contain appreciable amounts of industrially critical metals, such as Nb, Th and Sc. According to the genesis, the carbonatite-related REE deposits can be divided into three types: primary magmatic type, hydrothermal type and carbonatite weathering-crust type. This paper provides an overview of the carbonatite-related endogenetic REE deposits, i.e., primary magmatic type and hydrothermal type. The carbonatite-related endogenetic REE deposits are mainly distributed in continental margin depression or rift belts, e.g., Bayan Obo REE-Nb-Fe deposit, and orogenic belts on the margin of craton such as the Miaoya Nb-REE deposit. The genesis of carbonatite-related endogenetic REE deposits is still debated. It is generally believed that the carbonatite magma is originated from the low-degree partial melting of the mantle. During the evolution process, the carbonatite rocks or dykes rich in REE were formed through the immiscibility of carbonate-silicate magma and fractional crystallization of carbonate minerals from carbonatite magma. The ore-forming elements are mainly sourced from primitive mantle, with possible contribution of crustal materials that carry a large amount of REE. In the magmatic-hydrothermal system, REEs migrate in the form of complexes, and precipitate corresponding to changes of temperature, pressure, pH and composition of the fluids. A simple magmatic evolution process cannot ensure massive enrichment of REE to economic values. Fractional crystallization of carbonate minerals and immiscibility of melts and hydrothermal fluids in the hydrothermal evolution stage play an important role in upgrading the REE mineralization. Future work of experimental petrology will be fundamental to understand the partitioning behaviors of REE in magmatic-hydrothermal system through simulation of the metallogenic geological environment. Applying “comparative metallogeny” methods to investigate both REE fertile and barren carbonatites will enhance the understanding of factors controlling the fertility.

The giant Bayan Obo REE deposit bears a large amount of iron resources as well. However, the genesis of iron mineralization is still highly controversial with limited research. In this study, new data of trace elements of magnetite from Bayan Obo ores, Eastern contact zone skarn and Heinaobao BIF are obtained by Laser ablation (LA) ICP-MS analyses, revealing the genesis of Bayan Obo iron resources through comparing study. The Bayan Obo deposit contains disseminated, banded and massive ores, and in which magnetite is associated with REE minerals, fluorite, aegirine, riebeckite, and biotite. Euhedral magnetite in the skarn of Eastern contact zone is usually associated with pyrite, biotite, fluorite, and bastnaesite. There are two types of magnetite in the Heinaobao BIF: (1) euhedral to subhedral magnetite associated with quartz and a small amount of amphibole; (2) anhedral magnetite associated with quartz, garnet, plagioclase, amphibole and biotite. Magnetite in the Bayan Obo is enriched in Ni, but depleted in Mg, Al, Ti, Ge, Mn, Ga and Zn, showing low and variable concentrations, which is similar to the hydrothermal magnetite. The contents of some trace elements (e.g. Ti, Mn, Sc, Zn, Nb and REE) of magnetite from the skarn ores are generally higher, indicating a relatively high formation temperature. Magnetite in the Heinaobao BIF is generally characterized by low and uniform trace element contents, except for the abnormal values of Ti, Al, Cr and Mn, suggesting the involvement of terrigenous clastic materials. Compared with Bayan Obo magnetite, the skarn magnetite has the highest Sn/Ga, Co/Ni, Nb/Ta, La/Yb, Ti/V and Ti/Al ratios, while magnetite in the BIF has the highest Al/Co and lowest Nb/Ta ratios. The significant difference in mineralogical and trace element characteristics among the three types of magnetite indicates that the iron resources in Bayan Obo deposit are unlikely to be a skarn Fe deposit nor a BIF deposit. However, the Bayan Obo magnetite shows similar geochemical characteristics to hydrothermal magnetite related to carbonatite, both of which are depleted in high field strength elements, such as Zr, Hf and Ta, and show strong positive anomalies of Mn and Zn and negative anomalies of Co and Ga. In addition, in the diagrams of Ti vs. Nb + Ta and Ti vs. Zr + Hf, the Bayan Obo magnetite falls into the field of hydrothermal magnetite associated with carbonatite. In conclusion, it is recommended that the Bayan Obo iron deposit is a typical hydrothermal deposit related to carbonatite. In this contribution, the skarn magnetite formed at high temperature and the BIF magnetite was contaminated by terrigenous materials deviating from the expected region in discriminant diagrams. It is therefore proposed that the validity of these diagrams depends on a full understanding of mineralogical characteristics of samples and magnetite precipitation environment, and that multiple discrimination diagrams should be used in combination.

The Bayan Obo REE-Nb-Fe deposit with giant rare earth reserves, still has no unified understanding of the REE and Nb-bearing mineral evolution and the division of mineralization stages, due to the complicated metallogenic process and the huge controversy on the important issues such as the origin of ore-hosting dolomite. In this work, the whole process of carbonatite magma solidification and mineralization is divided into six stages: coarse dolomitic facies, fine dolomitic facies, disseminated mineralization, banded mineralization, massive mineralization and vein mineralization. The mineralogical composition and paragenesis of various types of rocks and ores have been systematically studied using the automatic mineral analysis technology-Advanced Mineral Identification and Characterization System (AMICS), supplemented by optical microscopy and cathodoluminescence. In order to establish the internal relationship between different stages, trace elements of six kinds of rocks and ores were analyzed. The mineralogical studies show that the rare earth minerals appear in the order of transition from the phosphate minerals in the brine-melt stage (fine dolomitic facies), through the fluorcarbonate minerals in the hydrothermal stage (disseminated, banded and massive mineralization), to the Ba-fluorcarbonate minerals in the Paleozoic vein mineralization, and all of these are generally associated with apatite, baryte, fluorite, aegirine and quartz. The distribution of niobium minerals in all kinds of ores is in the form of disseminated grains, and there is no obvious paragenetic relationship with other minerals, which indicate that niobium mineralization may only be related to the content of niobium in hydrothermal solution. The geochemical data show that all types of rocks and ores have positive anomalies of Ba and Nb, negative anomalies of U, Ta, Sr, Zr and Y. From coarse dolomitic facies to massive mineralization, the content of REE, Nb and Th increases, the content of Sr decreases, and the ratio of (La/Yb)N and (La/Nd)N increases, all of which change continuously. Vein mineralization has similar (La/Nd)N and (La + Ce + Pr)N/REE ratios compared with coarse dolomitic facies and has a wide range of Sr, Th, Nb and REE compositions, and elemental ratio and content of vein mineralization are within the distribution range of ore-hosting dolomite and different types of mineralization. Based on the above, it is considered that the main mineralization body at Bayan Obo was formed in the process of auto-metasomatism of Mesoproterozoic igneous carbonatite, while vein mineralization was the product of homogenization and re-precipitation of early ore-forming material by the Paleozoic fluids, without the addition of exogenous metallogenic materials.

The Bayan Obo REE-Nb-Fe deposit, which reserves the current largest REE resources globally, also hosts over 70% of China’s Nb resources. Unlike many world-class carbonatite-related Nb deposits (e.g. Morro dos Seis Lagos and Araxa, Brazil) with igneous or secondary origin, Nb was mainly stored in Nb-bearing minerals (aeschynite, ilmenorutile, baotite, fergusonite etc.) of hydrothermal origin at Bayan Obo, supported by evidence from petrography, element and isotopic geochemistry. Although igneous fersmite and columbite were occasionally discovered in local carbonatite dykes, the Mesoproterozoic and Paleozoic hydrothermal metasomatism occurred in the ore-hosting dolomite, related to carbonatite intrusion and the closure of Paleo-Asian Ocean respectively, has played a more significant role during the ultimate Nb enrichment. REE, however, was significantly enriched during both the carbonatite-related magmatic and hydrothermal processes. Consequently, there was differentiated mineralization between REE and Nb in the carbonatite dykes and the ores. Niobium mineralization at Bayan Obo is rather limited in Mesoproterozoic carbonatite, whereas more extensive in the metasomatized ore-hosting dolomite, and generally postdating the REE mineralization at the same stage. According to mineral geochemistry, Bayan Obo aeschynite was classified into 3 groups: aeschynite-(Nd) with convex REE patterns (Group 1); aeschynite-(Ce) (Group 2) and nioboaeschynite (Group 3) with nearly flat REE patterns. Aeschynite (Group 1), ilmenorutile and fergusonite precipitated from Paleozoic hydrothermal fluids with advanced fractionation of Ce-rich REE minerals. The Mesoproterozoic hydrothermal Nb mineralization, represented by aeschynite (Group 3) and baotite, occurred postdating REE mineralization at same stage. Besides, fersmite and aeschynite (Group 2) precipitated from the Mesoproterozoic REE-unfractionated melt and hydrothermal fluids, respectively. All above Nb-bearing minerals exhibit extreme Nb-Ta fractionation as a primary geochemical characteristic of mantle-derived carbonatite. The forming age of the aeschynite megacrysts (Group 1) has not been accurately determined. However, the potential age was constrained to ~430 Ma or alternatively ~270–280 Ma subjected to subduction and granite activity, respectively. These aeschynite crystals inherited REEs from multiphase former REE mineralization, with an intermediate apparent Sm-Nd isochron age between the Mesoproterozoic and the Paleozoic REE mineralization events.