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In this paper, we evaluated the potentialities of Raman spectroscopy and electron backscattered diffraction (EBSD) in the microscopic characterization of Ca-REE fluorcarbonates (CRFC) belonging to the bastnäsite-synchysite series to provide a "road map" for further investigations with transmission electron microscopy (TEM). EBSD was efective in establishing the sample orientation, setting up the oriented cuts, and ascertaining the effective syntactic relationship among all the detected CRFC phases; however, it failed to distinguish between diferent polysomes. On samples with diferent orientations that were preventively ascertained by EBSD and characterized by scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS), micro-Raman spectroscopy allows for distinguishing between polysomes based on the diferences in intensity and position of the symmetric stretching vibration (v1) of the carbonate group C O 3 2 − in the region around 1080–1099 cm–1. However, as evidenced by TEM-EDS, what appears as a homogeneous polysome in backscattered electrons (BSE) images may be a disordered intergrowth of compositional faults with a bulk composition being matched with that of a real polysome only by accident. Therefore, we conclude that the Raman signal is sensitive to diferent Ca/(Ca+REE) ratios but not to any ordered distribution of Ca-poor and Ca-rich lamellae within the analyzed volume, making the unambiguous identification of a polysome tricky. Finally, several ordered polysomes were detected at the TEM scale, including a B2S and a long-range polytype with a 32 nm repeat distance along c. The possible implications of the detected microstructure for ore mineral formation are discussed. [ABSTRACT FROM AUTHOR]

Bastnäsite contains considerable amounts of U and Th and has been widely used for U-Th-Pb dating. Hydrothermal alteration of bastnäsite is common in nature but its effects on U-Th-Pb dating are not currently well constrained. Hence the significance of U-Th-Pb ages obtained from altered bastnäsite cannot be evaluated. Here, we present a detailed geochronologic as well as micro- and nano-scale mineralogical study of altered bastnäsite in a Mo-REE deposit, Central China. The original bastnäsite grains were confirmed to have crystalized at 208 Ma but were variably overprinted by a hydrothermal event at 150 Ma. They commonly exhibit typical replacement textures that appear to have formed from a coupled dissolution-reprecipitation process, i.e., a primary unaltered domain surrounded by a porous altered domain. Micro- and nano-scale mineralogical observations strongly suggest that during the coupled dissolution-reprecipitation process, non-radiogenic (common) Pb was incorporated into the altered domains in the form of nanoscale galena inclusions. Such incorporation (even minor) has significantly affected the 206Pb/238U and 207Pb/206Pb ratios due to the low contents of U and its daughter isotopes in bastnäsite, resulting in highly variable, discordant U-Pb dates for the altered domains. In contrast, incorporation of the non-radiogenic Pb has very limited effects (<5%) on the Th-Pb system due to the remarkably high contents of Th and radiogenic 208Pb in bastnäsite. Instead, the scattered 208Pb/232Th ages (208 to 150 Ma) of the altered domains were essentially affected by incomplete replacement, and thus can be used to approximate the lower age limit of the primary hydrothermal activity or the upper age limit of the secondary hydrothermal activity. The results from this study highlight that because of the different orders of magnitude between the U and Th contents in bastnäsite, the mobilization of radiogenic and non-radiogenic Pb during alteration may have significantly different impacts on the U-Pb and Th-Pb systems. Therefore, the two systems should be treated separately during the dating of bastnäsite resulting from secondary hydrothermal events. [ABSTRACT FROM AUTHOR]

The time and processes of hydrothermal mineralization are long-standing problems in geology. This work addresses these questions with reference to the Maoniuping giant rare earth elements (REE) deposit (southwest China), which has rare earth oxides (REO) reserves of 3.17 million tons with an average grade of 2.95 wt%. Bastnäsite is the dominant economic mineral, occurring as four distinct paragenetic types in the Maoniuping syenite–carbonatite complex: (1) primary euhedral bastnäsite (type-A) in syenite, with isolated melt inclusions; (2) macro-crystalline tabular euhedral bastnäsite (type-B) in pegmatitic dikes, with a diverse variety of fluid inclusions; (3) fine-grained, anhedral veinlet-disseminated bastnäsite (type-C) in syenite; and (4) coarse-grained anhedral bastnäsite (type-D) in carbonatite dikes, occurring as veinlets or interstitial to calcite, fluorite, and barite. From the paragenetic and compositional variations, it is inferred that type-A bastnäsite is of primary magmatic origin, whereas the other three types have characteristics of hydrothermal origins. In situ LA-ICP-MS U-Pb geochronology of the four types of bastnäsite results in lower intercept ages of 28.2 ± 0.5 Ma (n = 95, MSWD = 5.10), 27.8 ± 0.4 Ma (n = 43, MSWD = 0.73), 26.8 ± 0.7 Ma (n = 50, MSWD = 0.83), and 25.8 ± 0.7 Ma (n = 55, MSWD = 1.70), respectively, which are consistent with the weighted average 206Pb/238U and 208Pb/232Th ages by 207Pb-correction method. Compositional variations of clinopyroxene and apatite from the associated syenite, pegmatitic and carbonatitic dikes indicate a genetic relationship of the Maoniuping alkaline complex. The compositions of clinopyroxene range from Ae44–67Di14–18Hd17–41 in pegmatitic dikes, Ae43–66Di6–20Hd21–38 in carbonatitic dikes to Ae68–90Di0–3Hd10–30 in syenite. Apatites in the pegmatitic and carbonatitic dikes have similar compositions with higher F, total REE, and Sr, and lower CaO contents than those in the syenite, which suggests a cogenetic origin for the associated pegmatite and carbonatite. Clinopyroxene and apatite compositions suggest that the pegmatitic melt might differentiate directly from the initial carbonatitic melt rather than the syenitic magma. The bastnäsite U-Pb geochronology and minerals data indicate continuous magmatic-hydrothermal evolution for the REE mineralization in the Maoniuping alkaline complex. [ABSTRACT FROM AUTHOR]

Bastnäsite-(Ce), a rare earth element (REE) bearing carbonate (Ce,La,Y,Nd,Pr)CO3F, is one of the most common REE-bearing minerals and has importance from both economic and geologic perspectives due to its large REE concentration. It also provides an example of the structural interplay between carbonate groups and fluorine ions, as well as the complex bonding properties of rare earth elements. We report Raman vibrational and Nd3+ luminescence ( 4 F 3 / 2 → 4 I 9 / 2 , 4 F 3 / 2 → 4 I 11 / 2 , $\left(^{4}{{\text{F}}_{3/2}}{{\to }^{4}}{{\text{I}}_{9/2}}{{,}^{4}}{{\text{F}}_{3/2}}{{\to }^{4}}{{\text{I}}_{11/2}}, \right.$ and 4 F 5 / 2 + 2 H 9 / 2 → 4 I 9 / 2 ) $\left. ^{4}{{\text{F}}_{5/2}}{{+}^{2}}{{\text{H}}_{9/2}}{{\to }^{4}}{{\text{I}}_{9/2}} \right)$ spectra of natural bastnäsite-(Ce) to 50 GPa at 300 K. Two phase transitions are observed under compression. Bastnäsite-I remains the stable phase up to 25 GPa, where it undergoes a subtle phase transition to bastnäsite-II. This is likely produced by a change in symmetry of the carbonate ion. Bastnäsite-II transforms to bastnäsite-III at ~38 GPa, as demonstrated by changes in the luminescence spectra. This second transition is particularly evident within the 4 F 3 / 2 → 4 I 9 / 2 $^{4}{{\text{F}}_{3/2}}{{\to }^{4}}{{\text{I}}_{9/2}}$ luminescent transitions, and it appears that a new rare earth element site is generated at this phase change. This transition is also accompanied by modest changes in both the Raman spectra and two sets of luminescent transitions. Despite these transformations, the carbonate unit remains a stable, threefold-coordinated unit throughout this pressure range, with a possible increase in its distortion. Correspondingly, the rare-earth element site(s) appears to persist in quasi-ninefold coordination as well, implying that the general bonding configuration in bastnäsite is at least metastable over a ~30% compression range. All pressure-induced transitions are reversible, with some hysteresis, reverting to its ambient pressure phase on decompression. [ABSTRACT FROM AUTHOR]

The studied rock samples belong to the classic1615–1645 Ma Wiborg Rapakivi granite terrane of southeasternFinland. Geochemical studies show that the rapakivigranites and associated rocks form metaluminousto peraluminous A-type granites and plot in the "withinplate granites (WPG)" field on the tectonic discriminate diagramsfrom the Onkamaa, Suomenniemi and Luumäki.The rapakivi granite displays enrichment of light overheavy REE (LREE/HREE = 2-34) and usually negative Euanomalies (Eu/Eu* = 0.01 - 1.4). Enrichment in REE in somestudied samples is confined to highly fractionated portionsof the Rapakivi granite. Fractional crystallization ofthe evolving fluorite-rich peraluminous granitic magmawas accompanied, particularly at later stages by fluid fractionation,which plays an important role in the genesis ofthe REE-mineralization.The studied rapakivi granites host REE-minerals includingmonazite-(Ce), allanite (Ce), bastnäsite (Ce), xenotime,thorite and REE-bearing mineral apatite. Monazite and allaniteare the most important REE carriers in the studiedgranites and these minerals are strongly enriched in theLREE.Monazites are hosted in apatite, quartz, plagioclase,K-feldspar, and biotite. Grain size of monazite is variableranging from 50 to >100 μm.Monazite contains 48-68 wt%REE2O3, 24.3-29.3 wt% P2O5 and low Th

An understanding of the mineralogy and petrogenesis of rare earth element deposits has significant implications for their economic viability. Lanthanide-bearing compounds are known to produce sharp absorption features in the visible to short-wave infrared region (VIS-SWIR), however, a significant knowledge gap exists between the fields of hyperspectral reflectance spectroscopy and rare earth element mineralogy. Reflectance spectra were collected from four bastnäsite samples, two parisite samples, and one synchysite sample from the visible into the short-wave infrared. These REE fluorocarbonate mineral samples were characterized via scanning electron microscopy and electron probe microanalysis. Sharp absorptions of REE-bearing minerals are mostly the result of 4f-4f intraconfigurational electron transitions and for the light REE-enriched fluorocarbonates, the bulk of the features can be ascribed to Nd3+, Pr3+, Sm3+, and Eu3+. The lanthanide-related spectral responses of the REE fluorocarbonates are consistent across the group, supporting the notion that the REE cation site is very similar in each of these minerals. Carbonate-related spectral responses differed between these minerals, supporting the notion that the crystallographic sites for the carbonate radical differ between bastnäsite, synchysite, and parisite. Exploitable spectral differences include a distinct absorption band at 2243 nm that separates bastnäsite from synchysite and parisite. Similarly, for bastnäsite a dominantly Pr3+-related absorption band located is at 1968 nm, while in synchysite and parisite it occurs at 1961 nm. [ABSTRACT FROM AUTHOR]

Hydroxyl-bästnasite-(Ce), ideally CeCO3(OH), had been regarded isostructural with bästnasite-(Ce), CeCO3F, the dominant member of the bästnasite family that produces ~70% of the world's supply of rare-earth elements. Using single-crystal X-ray diffraction and Raman spectroscopy, our structural analysis on hydroxyl-bästnasite-(Ce) shows that the previous assumption is incorrect. The crystal structure of hydroxyl-bästnasite-(Ce) possesses P6̄ symmetry with unit-cell parameters a = 12.4112(2), c = 9.8511(3) Å, and V = 1314.2(1) ų, in contrast to the space group P6̄2c and a ≈ 7.10, c ≈ 9.76 Å, and V ≈ 430 ų for bästnasite-(Ce). Moreover, there are 6, 3, and 5 symmetrically-distinct CO3 groups, Ce cations, and (OH/F) ions, respectively, in hydroxyl-bästnasite-(Ce), but 1, 1, and 2 in bästnasite-(Ce). The two structures, nevertheless, are similarly characterized by the layers of CO3 groups alternating with the Ce-(OH/F) layers along the c direction. The Raman spectrum of hydroxyl-bästnasite-(Ce) is dominated by three strong bands at 1080, 1087, and 1098 cm-1 in the CO3 symmetrical stretching region, along with at least four bands in the OH stretching region. Our study further suggests that natural hydroxyl-bästnasite-(Nd) is most likely isotypic with hydroxyl-bästnasite-(Ce), rather than with bästnasite-(Ce), as previously proposed. [ABSTRACT FROM AUTHOR]