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Fluorite of various occurrences could portray the hydrothermal metasomatism occurred in the giant Bayan Obo REE-Nb-Fe ore deposit. Two Mesoproterozoic and Paleozoic hydrothermal events with distinguished fluid origin and geochemical properties have been studied. In Mesoproterozoic, discrete fluorite from the dolomite-dominating REE-Nb ores and banded fluorite aggregates from the banded REE-Nb-Fe ores are extremely enriched in LREE and depleted in HFSE compared with the primitive mantle. In Paleozoic, fluorite from veined-breccia REE-Nb ores varies significantly in trace element components, ranging from LREE-enriched HFSE-depleted fluorite to fluorite with “flat” REE pattern and extremely depletion of Zr. The veined fluorites have variable and higher radiogenic Sr isotopic components (initial 87 Sr/ 86 Sr ratios: 0.703464–0.708208) than the discrete and banded fluorite (0.703183–0.705047), indicating crustal contamination in the Paleozoic hydrothermal fluids from Precambrian basement rocks and Bayan Obo Group. Fluorites of different occurrences and associated bastnäsite and monazite have similar Nd isotopic components and Nd evolution history, which is mostly consistent with whole rock of the ore-hosting dolomite. The Sm-Nd system of some fluorite and bastnäsite were reset during the Paleozoic alteration triggered by the closure of Paleo-Asian Ocean. In such geological setting, according to the δ 34 S of the dominating sulfur-bearing mineral, Paleozoic veined sulfides (∼0 ± 3‰), the prime sulfur source was oceanic crust/MORB. Relatively high δ 34 S of barite (∼13–14‰) was caused by fractionation of sulfur isotopes at an equilibrium temperature of 400–430 °C, rather than contribution from ancient seawater. The trace element, Sr-Nd isotope of fluorite and sulfur isotope characters of sulfides indicate carbonatitic origin of the Mesoproterozoic hydrothermal fluids, while the Paleozoic fluids, derived from subducted Paleo-Asian oceanic crust, carried sulfur components from MORB, scavenged high radiogenic Sr components from Precambrian basement rocks or Bayan Obo group, may leached a deep-seated carbonatite stock and finally altered the Mesoproterozoic mineralized ore-hosting dolomite. Both the Mesoproterozoic and Paleozoic hydrothermal fluids had initial temperature of ∼400–500 °C, and gangue minerals (fluorite, sulfide and sulfate) precipitated at the temperature of ∼320–440 °C. Preliminary thermodynamic calculations of the REE-F-C-Ca system constrained that the pressure of both fluids would not exceed 2 kbar. The drop of temperature and increase of pH are two critical factors to REE mineralization. Paragenesis of Fe-bearing minerals indicates an increase of fO 2 in the Mesoproterozoic hydrothermal fluids and a drop of fS 2 in the Paleozoic fluids in the Fe-O-S system. Furthermore, in the Ca-F-C-O system, the Mesoproterozoic hydrothermal fluids evolved with increasing aCa 2+ and decreasing aF − , while the Paleozoic fluids present characteristic of mixing origin again with significantly variable aCa 2+ and aF − . [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]

The origin of dolomite that hosts the Bayan Obo REE-Nb-Fe deposit (57.4 Mt.@6% REE 2 O 3 , 2.16 Mt.@0.13% Nb 2 O 5 , and >1500 Mt.@35% iron oxides) has been controversial for decades, but it is integral to understanding of the genesis of this giant deposit. In this study, based on the textures and in situ major and trace element composition of its carbonates, the dolomite was proved to be initially generated from magnesio-ferro‑carbonatite melts. It subsequently experienced magmatic-hydrothermal alteration and recrystallization in a low strain environment, caused by calcio‑carbonatitic fluids, with formation of finer-grained dolomite, interstitial calcite and increasing amounts of associated fluorocarbonates. Available stable isotope analyses indicate that the recrystallized ore-hosting dolomite has higher δ13C and δ18O ratios compared to its igneous coarse-grained precursor. Rayleigh fractionation during the recrystallization process, rather than crustal contamination, played a major role in the highly-variable stable isotope composition of carbonates in the dolomite. Low-T alteration increased variability with apparently random increases in δ18O within carbonates. The REE, Ba and Sr were added simultaneously with the elevated (La/Yb) cn from magnesio-ferro‑carbonatite melts to calcio‑carbonatitic fluids, and to carbonatite-derived aqueous fluids, through which extensive fluorine metasomatism and alkali alteration overlapped the recrystallization of the ore-hosting dolomite. Therefore, the multi-stage REE mineralization at Bayan Obo is closely related to metasomatism by calcio‑carbonatitic fluids of previously-emplaced intrusive magnesio-ferro‑carbonatite bodies during late evolution of the Bayan Obo carbonatite complex. Then, the ore-hosting dolomitic carbonatite was subjected to compressive tectonics during a Paleozoic subduction event, and suffered intense, largely brittle, deformation, which partially obscured the earlier recrystallization process. The complex, multi-stage evolution of the ore-hosting dolomite is responsible for the uniqueness, high grade and giant size of the Bayan Obo deposit, the world's largest single REE resource with million tonnes of REE oxides. Unlabelled Image • Portrait evolution of Bayan Obo dolomite with petrography-based geochemistry. • Hydrothermal process playing dominating role in Bayan Obo REE enrichment. • Potential of Mg-Fe‑carbonatite melts carrying REE have been overestimated. • Systematic petrographic-geochemical comparison of carbonates with diverse origins. [ABSTRACT FROM AUTHOR]