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[Display omitted] • S-isotope and trace element of Bayan Obo pyrites are first reported systematically. • H 8 dolomite was derived from the upper mantle contaminated by oceanic crust. • The banded ore was heterogeneously contaminated by K-rich H 9 slate. • The Paleozoic thermal events contributed little to the enormous REE resources. The genesis of the Bayan Obo REEs deposit has been debated for a century. The most outstanding issue concerns the genesis of the ore-hosting dolomite and the contribution of the Paleozoic overprint events in the rare earth budget. Pyrite offers a unique window into those debates in that it is the only common fingerprinting mineral shared by both events. In this contribution, LA-ICP-MS trace element mapping, in-situ elemental and sulfur isotopic analyses on pyrite are integrated in order to constrain the genesis of ore-hosting dolomite and evaluate the contribution of the Paleozoic thermal events to enormous REEs resources. Five types of pyrite were distinguished in ore-hosting dolomites, various types of ore and skarns based on mineral paragenesis and geochemical signatures. The dolomites contain early euhedral pyrite (Py-1) overgrown by magnetite and euhedral pyrite (Py-2w in the West Open Pit and Py-2d in the deep boreholes) associated with pyrrhotite, monazite, dolomite and apatite. By contrast, pyrite in the banded ores (Py-3b) and the massive ores (Py-3 m) was co-precipitated with magnetite, aegirine, fluorite, riebeckite, REEs minerals and apatite. Pyrite in the vein ores (Py-4) usually coexists with barite, quartz, aegirine and calcite, and those (Py-5) in skarns associated with biotite and amphibole. Py-1 is enriched in Ti, Ni, Nb, Hf and REEs, with high Co/Ni and Y/Ho ratios (ca. 66), and high δ34S values from +8.6‰ to +13.8‰. In comparison, Py-2w and Py-2d have higher Co/Ni yet lower Y/Ho (ca. 11) ratios, but exhibit magmatic δ34S values (-1.0‰ to +3.0‰; −1.0‰ to +3.7‰). Py-3b and Py-3 m are relatively enriched in Cr, Mn, Zn and LREEs, and possess intermediate δ34S values (+5.7‰ to +7.7‰, and +0.2‰ to +2.4‰, respectively). Py-4 is generally depleted in trace elements with magmatic δ34S values (-2.0‰ to +2.7‰). Compared with Py-3 m and Py-3b, Py-5 is characterized by high Co yet low Ti, Cr, Mn, Cu and Zn with variable REEs, and is enriched in 34S (δ34S: +9.1‰ to +10.8‰). The high δ34S value and Y/Ho ratio in Py-1 indicate that the ore-hosting dolomite is an igneous carbonatite originated from partial melting of upper mantle contaminated by altered and subducted oceanic crust. The marked difference in trace elements and sulfur isotopes between Py-3, Py-4 and Py-5 implies that the Paleozoic thermal events contributed little to the primary REEs mineralization except remobilizing preexisting ore metals. [ABSTRACT FROM AUTHOR]

[Display omitted] • The Bayan Obo deposit has notable differences with skarn/BIF in mineralogy and magnetite geochemistry. • Trace element contents in Bayan Obo magnetite controlled by coexisting mineral, f O 2 and T. • Bayan Obo iron deposit was a hydrothermal deposit related to igneous carbonatite. 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. [ABSTRACT FROM AUTHOR]

[Display omitted] • The mineralizing process of carbonatite system can be divided into six stages. • The associated behaviors of REE and Nb are different in migration and deposition. • The sequence of REE minerals is phosphate, fluorcarbonate, Ba-fluorocarbonate. • The main body of the deposit was formed in the autometasomatism of carbonatite. 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. [ABSTRACT FROM AUTHOR]