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The genesis of Earth’s largest rare earth element (REE) deposit, Bayan Obo (China), has been intensely debated, in particular whether the host dolomite marble is of sedimentary or igneous origin. The protracted (Mesoproterozoic to Paleozoic) and intricate (magmatic to metasomatic) geological processes complicate geochemical interpretations. In this study, we present a comprehensive petrographic and in situ, high-spatial resolution Sr-Pb isotopic and geochemical investigation of the host dolomite from the Bayan Obo marble. Based on petrographic evidence, the dolomite marble is divided into three facies including coarse-grained (CM), fine-grained (FM), and heterogeneous marble (HM). All carbonates are ferroan dolomite with high SrO and MnO contents (> 0.15 wt.%), consistent with an igneous origin. Trace element compositions of these dolomites are highly variable both among and within individual samples, with CM dolomite displaying the strongest LREE enrichment. In situ 206Pb/204Pb and 207Pb/204Pb ratios of the dolomite are generally consistent with mantle values. However, initial 208Pb/204Pb ratios define a large range from 35.45 to 39.75, which may result from the incorporation of radiogenic Pb released from decomposition of monazite and/or bastnasite during Early Paleozoic metasomatism. Moreover, in situ Sr isotope compositions of dolomite indicate a large range (87Sr/86Sr = 0.70292–0.71363). CM dolomite is characterized by a relatively consistent, unradiogenic Sr isotope composition (87Sr/86Sr = 0.70295–0.70314), which is typical for Mesoproterozoic mantle. The variation of 87Sr/86Sr ratios together with radiogenic 206Pb/204Pb signatures for dolomite within FM and HM possibly represents recrystallization during Early Paleozoic metasomatism with the contribution of radiogenic Sr and Pb from surrounding host rocks. Therefore, our in situ geochemical data support a Mesoproterozoic igneous origin for the ore-bearing dolomite marble in the Bayan Obo deposit, which subsequently underwent intensive metasomatism during the Early Paleozoic.

Recent exploration revealed a number of rare earth element (REE) deposits that are distributed along the Qinling Orogenic Belt, Central China. These deposits have an estimated total reserve of about 2 Mt. REE2O3, thus making this belt a world-class REE metallogenic province. Understanding the metallogenesis of the belt requires direct dating of REE minerals. In this study, LA-ICP-MS U-Th-Pb dating on bastnasite and monazite from the Huangshuian, Taipingzhen, and Miaoya deposits in different units of the belt was used to precisely determine the timing of the REE mineralization. The Huangshuian deposit in the north is a carbonatite-related Mo-(REE) deposit in which the REE minerals are closely associated with molybdenite. After correction for common Pb and excessed 206Pb decayed from 230Th, a weighted average 206Pb/238U age of 207 ± 4 Ma (n = 17; MSWD = 1.9) is obtained for bastnasite grains from this deposit. Such an age is slightly younger than that of the final collision (peak at 230–220 Ma) of the Qinling Orogenic Belt, thus indicating that the Mo-REE mineralization is likely related to a post-collisional extension setting. The Taipingzhen REE deposit in the middle contains sheet-like ore bodies composed of veins where bastnasite, the dominant REE mineral, is closely associated with quartz, fluorite, and barite. In situ bastnasite U-Th-Pb dating shows that the REE mineralization in this deposit has formed at 421 ± 7 Ma (n = 17; MSWD = 1.5), synchronous with extension-related magmatism in the region. The Miaoya deposit in the south is the largest one in the belt, and it is essentially a REE-mineralized syenite-carbonatite complex. In this deposit, the monazite grains are closely associated with major minerals of the syenites or carbonatites (e.g., K-feldspar or calcite), but commonly exhibit complex internal textures. Different domains of monazite yield two groups of U-Pb ages at 414 ± 11 Ma (n = 5; MSWD = 0.91) and 231 ± 2 Ma (n = 21; MSWD = 3.1), whereas the bastnasite has an age of 206 ± 4 Ma (n = 14; MSWD = 1.5). The early age of 414 Ma is obtained from homogenous monazite grains and in good agreement with zircon U-Pb ages of the Miaoya syenite-carbonatite complex, and thus is considered to represent the timing of the major REE mineralization in the deposit. The younger ages of 231–206 Ma are obtained from monazite grains with complex internal textures and bastnasite in late veinlets, thus recording secondary, consecutive REE remobilization events likely related to the compression process during formation of the Qinling Orogenic Belt. Our new U-Th-Pb ages, in combination with previously geochronological data, demonstrate that there are two episodes of REE mineralization at 440–410 Ma and 220–200 Ma in the Qinling Orogenic Belt.

Carbonate gangue in historically important post-Variscan polymetallic Pb-Zn-Cu-Ag vein systems in the Upper Harz Mountains has elevated rare earth element contents (ΣREE+Y, 1500 ± 340 ppm; n = 16) in bulk samples. This enrichment is due to the occurrence of abundant micrometer-sized synchysite inclusions in calcite, identified via Raman spectroscopy. Calcite bulk analyses have roof-shaped PAAS-normalized REE patterns with a Eu peak but without Ce or Y anomalies and with a steeply dipping HREE pattern. Microbeam analysis (electron microprobe and LA-ICPMS) identifies these patterns as dominated by synchysite-(Ce–Nd) with strong Eu enrichment in the weight percent range and LREE/HREE fractionation (La/Lu ~ 100, PAAS-normalized). The synchysite component in calcite gangue is detected in polymetallic veins all over the Harz Mountains, which seems to be a diagnostic feature of the region and suggests a large-scale Mesozoic fluid system. However, the Upper (western) Harz systems with no fluorite have more elevated REE content, compared with the Lower (eastern) Harz fluorite-rich systems with less REE content. Carbonate gangue in the Upper Harz systems has homogeneous 87Sr/86Sri around 0.714 and eNdi of ~ − 9, while carbonate gangue in the Lower Harz systems has 87Sr/86Sri around 0.716 and eNdi of − 2 to − 5. Fluorite in the Lower Harz Mountains has strong positive Y anomalies and variable Eu anomalies at generally low REE abundances and no REE-mineral inclusions. Both Sr and Nd isotope compositions in the fluorite are very variable and indicate an open system (87Sr/86Sri, 0.710–0.718; eNdi, − 3 to − 17). The synchysite MREE enrichment in calcite gangue in the Upper Harz Mountains compares favorably with carbonatite-related LREE-dominated bastnasite from China and elsewhere and allows an interesting perspective as a by-product of Pb–Zn mining.

Rare-earth deposits associated with intrusive carbonatite complexes are the world’s most important source of these elements (REE). One of the largest deposits of this type is Maoniuping in the Mianning-Dechang metallogenic belt of eastern Tibet (Sichuan, China). In the currently mined central part of the deposit (Dagudao section), REE mineralization is hosted by a structurally and mineralogically complex Late Oligocene (26.4 ± 1.2 Ma, 40Ar/39Ar age of fluorphlogopite associated with bastnasite) hydrothermal vein system developed in a coeval syenite intrusion. Low-grade stockworks of multiple veinlets and breccias in the lower part of the orebody grade upwards into progressively thicker veins (up to 12 m in width) that are typically zoned and comprise ferromagnesian micas (biotite to fluorphlogopite), sodium clinopyroxenes (aegirine to aegirine-augite), sodium amphiboles (magnesio-arfvedsonite to fluororichterite), K-feldspar, fluorite, barite, calcite, and bastnasite. The latter four minerals are most common in the uppermost 80 m of the Dagudao section and represent the climax of hydrothermal activity. Systematic variations in the fluid inclusion data indicate a continuous hydrothermal evolution from about 230–400 °C (fluid inclusions in feldspar, clinopyroxene, and amphibole) to 140–240 °C (fluid inclusions in bastnasite, fluorite, calcite). Hydrothermal REE transport was probably controlled by F−, (SO4)2−, Cl−, and (CO3)2− as complexing ligands. We propose that at Dagudao, silicate magmas produced orthomagmatic fluids that explored and expanded a fissure system generated by strike-slip faulting. Initially, the fluids had appreciable capacity to transport REE and, consequently, no major mineralization developed. The earliest minerals to precipitate were alkali- and Fe-rich silicates containing low levels of F, which caused progressive enrichment of the fluid in Ca, Mg, F, Cl, REE, (SO4)2−, and (CO3)2−, leading to the crystallization of aegirine-augite, fluororichterite, fluorphlogopite, fluorite, barite, calcite, and bastnasite gradually. Barite, fluorite, calcite, and bastnasite are the most common minerals in typical ores, and bastnasite generally postdates these gangue minerals. Thus, it is very probable that fluid cooling and formation of large amount of fluorite, barite, and calcite triggered bastnasite precipitation in the waning stage of hydrothermal activity.

The Bastnas-type deposits, with mineral assemblages of Fe oxides, Ca-Mg silicates, rare earth element (REE) silicates, REE fluorocarbonates, and Cu-Fe-Mo-Bi sulfides, are associated with marble horizons in a strongly Na, K, and/or Mg altered, metavolcanic succession, over a distance of at least 80 km in a SW-NE trending zone in western Bergslagen. Two subtypes occur: (1) enriched (relative to the other type) in light REE (LREE) and Fe, exemplified by the Bastnas and Rodbergsgruvan deposits, and (2) enriched in heavy REE (HREE), Y, Mg, Ca, and F, represented by deposits in the Norberg district. Bastnasite hosts primary fluid H2O-CO2 inclusions with salinities of 6–29 eq. wt% CaCl2 and with total homogenization temperatures (Th tot) of ca. 300–400 °C. Subtype 2 has late-stage fluorite with fluid inclusions that show 1–16 eq. wt% NaCl and Th tot of ca. 90–150 °C. Molybdenite Re-Os ages obtained from three deposits are 1,904 ± 6, 1,863 ± 4, and 1,842 ± 4 Ma. Nd isotopic data from five different REE minerals yielded no defined isochron, but a range in eNd (1.88 Ga) of +0.2 to +1.6. The oxygen isotope values (δ18OSMOW) of dolomite and calcite from the associated REE-mineralized skarn and recrystallized carbonate assemblages lie in the range 6.1–8.6 ‰, overlapping with those of the host marbles. Carbon isotope values (δ13CPDB) show typical magmatic signatures of −6.7 to −4.4 ‰, while the host marbles group around ca. −2.4 ‰. The sulfur isotope (δ34SCDT) values of associated sulfides range between −10.8 and +0.2 ‰. The combined evidence suggests REE mineralization, beginning at 1.9 Ga, from mainly Svecofennian, juvenile magmatic (>400 °C) fluids carrying Si, F, Cl, S, CO2, and the REE in addition to other metals; mineralization occurred through reactions with dolomitic layers in the supracrustal units coevally with regional metasomatic alteration associated with fluid circulation through an extensive active volcano–plutonic complex.