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The rare-earth elements (REEs, La–Lu, Y) are essential for the development of renewable technologies. Bastnäsite (REECO3F) is a common REE ore mineral that is often subject to hydrothermal alteration at all crustal levels. Mechanisms of hydrothermal bastnäsite alteration therefore govern the evolution of REE deposits, though these mechanisms remain poorly understood. This experimental work investigates the hydrothermal replacement of bastnäsite by rhabdophane (REEPO4∙xH2O, x = 0–1) and monazite (REEPO4) in phosphatic fluids. Two temperature-dependent alteration pathways were identified; both follow the coupled dissolution-reprecipitation (CDR) mechanism. At 90 °C, bastnäsite was replaced by highly-porous metastable rhabdophane which was then replaced by monazite, forming an inner layer of rhabdophane and an outer layer of monazite. At 220 °C, bastnäsite was replaced directly by monazite. Although replacement initiated more quickly at 220 °C, greater overall replacement occurred at 90 °C (~ 61 wt.% after 500 h, compared to ~ 13 wt.% at 220 °C) due to surface passivation by monazite at 220 °C. Geochemical analyses showed REE fractionation during bastnäsite alteration. At 90 °C, rhabdophane was enriched in heavy REEs (Eu–Lu, Y), likely due to the evolving fluid chemistry, while at 220 °C secondary monazite was enriched in Sm and Ho compared to bastnäsite. These results indicate that: 1) the hydrothermal alteration of bastnäsite by rhabdophane and monazite in ore deposits leads to REE immobilisation, with little net loss of REEs to solution; 2) rhabdophane is metastable relative to monazite at 90 °C, and; 3) variable temperatures can cause different mineral textures and REE fractionation trends during hydrothermal alteration and mineral replacement. [ABSTRACT FROM AUTHOR]

Objective The Chishan rare earth deposit in Weishan County, Shandong Province is located on the southeastern edge of the North China Plate. It is a magmatic hydrothermal rare earth deposit mainly composed of light rare earths, and is currently the third largest light rare earth deposit in China. There is still controversy over its mineralization age. Methods Therefore, taking the latest exploration borehole ore samples from Chishan rare earth deposit as the research object, the mineralization age of Chishan rare earth deposit was accurately determined through field investigation, mineralogy, and chronology research, using Th-Pb isotope dating of fluorocarbon cerium ore. Results The Th-Pb isotope dating results of 5 fluorocarbon cerium deposits indicate that the mineralization age of the Chishan rare earth deposit can be divided into two periods: the early period is (125.5±0.5)-(122.2±0.5)Ma, and the late period is (112.3±0.6) Ma. Conclusion The early age is basically consistent with the mineralization age of the deposit determined by previous studies, while the late mineralization age is the first report, indicating that there may be two periods of mineralization activity in the Chishan rare earth deposit, which is worthy of attention and further work.

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]

Fluocerite has been shown experimentally and by thermodynamic modeling to be an important phase for the evolution of magmatic-hydrothermal REE mineralizing systems, but one that is rarely observed in nature. The reason for the latter is poorly understood. The newly discovered Taipingzhen REE deposit in Henan province, Central China, is unique for containing abundant fluocerite and thus provides a great opportunity to explore the role of fluocerite in REE mineralization. Fluocerite was the earliest REE mineral to crystallize in this deposit and was replaced extensively by bastnäsite. It has a higher La/Nd ratio than the later-depositing REE minerals, e.g., bastnäsite and monazite. This decrease in the La/Nd ratio with time is interpreted to have resulted from the fluocerite-mediated fractionation of REE (fluocerite prefers the lightest REE during its deposition from a high temperature, sulfate-rich hydrothermal fluid, in which the REE were transported as sulfate complexes). This study provides compelling evidence that fluocerite is, indeed, an important, early crystallizing mineral in magmatic-hydrothermal REE systems, which elsewhere was replaced entirely by bastnäsite during subsequent fluid evolution. Moreover, the study shows that the bastnäsite, which replaced fluocerite, inherited its high La/Nd ratio, suggesting that this ratio could be used as a tool with which to identify the former presence of fluocerite. The preservation of fluocerite in the Taipingzhen deposit is interpreted to have been due to the lack of significant cooling until a late stage of mineralization, at which time most of the fluid was lost from the system. [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 interaction between rare earth element (REE)‐rich (La, Pr, Nd, Dy) aqueous solutions, dolomite (CaMg(CO3)2), and aragonite (CaCO3) at low temperature hydrothermal conditions (25–220 °C) is studied. The experiments result in the solvent‐mediated surface precipitation and subsequent pseudomorphic mineral replacement of the dolomite and aragonite seeds by newly formed REE‐carbonates. The host grains are replaced from periphery inward. The newly formed REE‐bearing carbonates in La‐, Pr‐, and Nd‐doped systems follow the crystallization sequence: lanthanite [REE2(CO3)3·8H2O] → kozoite [orthorhombic REECO3(OH)] → hydroxylbastnasite [hexagonal REECO3(OH)]. The interaction of Dy‐bearing solutions with dolomite results only in the crystallization of kozoite [orthorhombic DyCO3(OH)]. However, experiments with aragonite reveal a two‐step crystallization pathway: tengerite [Dy2(CO3)3·2‐3(H2O)] → kozoite [orthorhombic DyCO3(OH)]. The temperature, the dissolution rate of the host mineral, and the ionic radii of the REE3+ in question are found to control the kinetics of the replacement reaction, the polymorph selection, and the crystallization pathways toward bastnasite. The findings allow to gain a more in‐depth understanding of the formation REE‐bearing carbonates, particularly the mineral bastnasite, which is the main source of REEs for industry. This knowledge can be used to improve REE separation, exploration, exploitation methods, as well to produce carbonate minerals with tailored structures. [ABSTRACT FROM AUTHOR]

The rapid depletion of high-grade rare earth elements (REE) resources implies that future supplies may be augmented with low-grade ores, tailings, and other unconventional resources to meet cut-off grades and, subsequently, supply demands. This paper presents an amalgamation of studies conducted on selected complex low-grade iron-oxide-silicate-rich tailings, with the overall aim of developing efficacious methods and associated process mineralogy characterization for enhanced REE minerals recovery and upgrade. To this end, a summary of the overarching key results from froth flotation, magnetic separation, and gravity separation studies of the tailings and their implications are presented in this review. Reconciliation of all the findings reveals lucid links between feed ore properties, mainly mineralogy and particle size distribution, as the key influential factors that affect the beneficiation of real complex low-grade tailings, although distinct differences in physicochemical properties of the valuable and gangue minerals may exist. It is clearly established that the unliberated association between REE and gangue minerals within the ore can lead to either synergistic or antagonistic effects on the quality of concentrates produced. Furthermore, the limitations presented by the poorly liberated minerals are exacerbated by their “fine” nature. With appreciable recoveries obtained using such readily available conventional separation methods, the tailings provide additional REE value to the primary commodities; hence, such material could be considered a potential resource for REE beneficiation. The learnings from the respective beneficiation studies are significantly important as they provide the knowledge base and greater understanding of the mineralogical characteristics and beneficiation response of REE minerals in typical complex, low-grade tailings.

Abstract The interaction between rare earth element (REE)‐rich (La, Pr, Nd, Dy) aqueous solutions, dolomite (CaMg(CO3)2), and aragonite (CaCO3) at low temperature hydrothermal conditions (25–220 °C) is studied. The experiments result in the solvent‐mediated surface precipitation and subsequent pseudomorphic mineral replacement of the dolomite and aragonite seeds by newly formed REE‐carbonates. The host grains are replaced from periphery inward. The newly formed REE‐bearing carbonates in La‐, Pr‐, and Nd‐doped systems follow the crystallization sequence: lanthanite [REE2(CO3)3·8H2O] → kozoite [orthorhombic REECO3(OH)] → hydroxylbastnasite [hexagonal REECO3(OH)]. The interaction of Dy‐bearing solutions with dolomite results only in the crystallization of kozoite [orthorhombic DyCO3(OH)]. However, experiments with aragonite reveal a two‐step crystallization pathway: tengerite [Dy2(CO3)3·2‐3(H2O)] → kozoite [orthorhombic DyCO3(OH)]. The temperature, the dissolution rate of the host mineral, and the ionic radii of the REE3+ in question are found to control the kinetics of the replacement reaction, the polymorph selection, and the crystallization pathways toward bastnasite. The findings allow to gain a more in‐depth understanding of the formation REE‐bearing carbonates, particularly the mineral bastnasite, which is the main source of REEs for industry. This knowledge can be used to improve REE separation, exploration, exploitation methods, as well to produce carbonate minerals with tailored structures.

Rare earth element (REE) fluorcarbonates are found for the first time in the ore-hosting sequence of the Saf’yanovka Cu–Zn massive sulfide deposit, Middle Urals: bastnäsite, synchysite-(Ce), and synchysite-(Y) in an assemblage with fluorite, calcite, barite, pyrite, and sphalerite. Samples with fluorcarbonates were found at a depth of 262 m in quartz veinlets of an altered zone of pyrite–carbonate–kaolinite–sericite–quartz rocks at the contact with massive pyrite–chalcopyrite and pyrite–sphalerite ores. It is suggested that the REE fluorcarbonates formed from a hydrothermal fluid synchronously with fluorite and calcite. This event can be related to hydrothermal activity at the postcollision stage of the evolution of the Urals fold system. [ABSTRACT FROM AUTHOR]

This study presented the first in a series of investigations currently underway to develop efficacious, cost-effective, and benign processing opportunities to produce rare earth elements (REE)–rich concentrate from an Australian complex low–grade saprolite ore [1.14% total rare earth oxides (TREO) grade], which is primarily exploited for its gold and copper values. This work specifically presented a preliminary flotation investigation carried out on the ore using sodium oleate as a collector. The relative effects of pulp pH, desliming, and depressants were investigated to ascertain any chance of recovering and upgrading REE minerals in saprolite ore using three different processing configurations. Based on the experimental results, flotation processes carried out on raw feed allowed the recovery of the majority of REE minerals (>50%), but the process was unselective, where clay and silicate gangue minerals reported into the flotation concentrate along with the REE minerals. However, desliming before flotation in the presence of depressants (starch and sodium silicate) improved REE minerals flotation selectivity, which produced concentrates assaying 5.87% and 4.22% TREO grades, with corresponding recoveries of 45% and 50% at pulp pH 9 and 10.5, respectively. Mineralogical analysis conducted on selected flotation concentrate indicated that silicate and clay gauge minerals were recovered via the synergistic act of surface activation and entrainment due to their fine to ultrafine nature. A comparison of all the test results revealed a haphazard grade–recovery relationship suggesting that there is an opportunity to further maximize both REE recovery and grade through further flotation studies where other process parameters may be investigated and optimized. The prospect of using magnetic separation has also been suggested. [ABSTRACT FROM AUTHOR]

The rapid depletion of high-grade rare earth elements (REE) resources implies that future supplies may be augmented with low-grade ores, mining tailings and other unconventional resources to meet cutoff grades and subsequently supply demands. In this work, detailed characterization of tailings from a copper processing plant was carried out to expand the knowledge of their chemical and mineralogical characteristics for REE recovery. The results showed that the REE are mainly mineralized as bastnäsite, monazite, and stetindite, along with uncommon minerals, such as brannerite, stillwellite, and florencite, for which there is limited processing data. In a preliminary effort to recover the REE, the tailings were subjected to gravity, magnetic, and froth flotation separation. Over 90% REE recovery was achieved via froth flotation, whereas magnetic and gravity separation tests recovered up to 86% and 54% REE, respectively. The results from this study suggest that, with systematic optimization studies, REE recovery and upgrade could be enhanced, with significant efforts of minimizing the recovery of key gangue minerals, such as goethite, hematite, and quartz. Overall, the study confirms that the tailings used in this work could be regarded as unconventional REE resources subject to tactical development and optimization of beneficiation methods. [ABSTRACT FROM AUTHOR]

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Bauxite deposits are an important source of Al and also host a variety of critical metals, including rare earth elements (REEs). However, the parent rocks of bauxite deposits generally have low REE contents, leading to uncertainty over the REE sources and enrichment mechanisms. In this study, we report high REE (2095 ppm; Ce = 1340 ppm) contents in the Lijiatian bauxite deposit in Luxi County, western Hunan Province, South China. The Lijiatian bauxite deposit is the largest deposit in Hunan Province, with a total Al resources exceeding 7 × 106 tons. The ore-bearing strata in the lower Permian Liangshan Formation (ca. 275 Ma) are comprised a 3–5-m-thick bauxite layer (bauxite ore/clay) and an underlying 4–8-m-thick Fe layer (Fe ore/Fe-rich clay). The high REE contents in the bauxites can be attributed to the widespread presence of bastnäsite. The bastnäsite commonly coexists with authigenic chlorite, which formed at temperatures of 221–285 °C, indicative of a hydrothermal origin. Uranium–Pb dating of the bastnäsite yielded an age of 141.4 ± 7.0 Ma, indicating a hydrothermal overprint occurred during the Early Cretaceous, which resulted in the enrichment of REEs in the bauxites. The high contents of REEs, Ba, and P in the Cambrian Niutitang Formation black shales indicate it was a potential source of these elements for bastnäsite and coexisting barite and apatite. The deep-seated hydrothermal fluids (enriched in HF, CO 2 , and H 2 S) associated with the late Yanshanian extensional tectonic event in South China (155–123 Ma) ascended along fractures. The ascending fluids interacted with the black shales, extracting REEs, Ba, and P. When the fluids reached a certain depth, they mixed with the infiltrating basinal waters to form a mineralising fluid. The fluid then migrated towards the bauxite layers, underwent cooling and depressurisation, and precipitated bastnäsite, barite, apatite, and chlorite. We propose that a hydrothermal event led to the enrichment of REEs in the bauxites in Hunan Province. Considering the scarcity of REEs in the parent rocks of bauxites worldwide, hydrothermal activity likely has a key role in REE enrichment in bauxites. [Display omitted] • The main mineral hosting REE (Ce) in Permian bauxite from southern China is Bastnäsite. • The bastnäsite formed during the Cretaceous period due to hydrothermal fluid activity. • The REEs are source from the basement black shale. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bastnäsite formed in the Vuoriyarvi carbonatites during Triassic at ca. 235 Ma. • Bastnäsite is not related to the magmatic event that formed the Vuoriyarvi complex. • Bastnäsite of the Vuoriyarvi is not supergene. The Vuoriyarvi massif is a Devonian multistage alkaline-ultrabasic carbonatite complex within the Kola alkaline province. Dolomite carbonatites of the Vuoriyarvi massif contain abundant rare-earth mineralization mainly represented by ancylite-(Ce) and bastnäsite-(Ce). Ancylite was previously shown to have probably formed in the Devonian (ca. 365 Ma) during an early postmagmatic overprint. Previous geological observations have revealed a much later crystallization of bastnäsite but have not been able to specify the exact age of the mineralization. The in situ U-Pb dating of bastnäsite allowed us to constrain its genesis. Bastnäsite for this study was extracted from two varieties of dolomite carbonatite breccias cemented by (1) quartz-bastnäsite and (2) strontianite aggregates (hereafter bastnäsite-rich and strontianite-rich carbonatites – BRC and SRC, respectively). The obtained age estimations (237.7 ± 9.8 Ma and 239.9 ± 4.1 Ma, respectively) indicate that both studied rocks were formed during a single event. The revealed age difference (∼125 Ma) excludes the genetic link between the bastnäsite origin and regional alkaline magmatism, pointing out an additional source for the Vuoriyarvi bastnäsite-bearing rocks. Moreover, the obtained U-Pb ages provide strong evidence that a Triassic event is responsible for the occurrence of bastnäsite mineralization due to hydrothermal REE redistribution from the Devonian ancylite-rich carbonatites. Most of the REEs released during this process via dissolution of ancylite were precipitated in situ as bastnäsite, while strontium was transported and incorporated into strontianite. The Pb isotopic characteristics of bastnäsite (206Pb/204Pb = 18.1 ± 0.1, 207Pb/204Pb = 15.3 ± 0.1, and 207Pb/206Pb = 0.84 ± 0.01) are most probably inherited from the Devonian host rocks of the Vuoriyarvi massif involved in the Triassic overprint. Isotopic signatures of Pb, Sr, and Nd show that the depleted mantle and lower crust played the leading role in formation of the Vuoriyarvi alkaline complex. Taken together, the results of the present study negate the supergene origin of the Vuoriyarvi bastnäsite, implying that the bastnäsite mineralization is not confined to near-surface layers and, therefore, may be dispersed more broadly throughout the complex. These findings raise the question on underestimation of the probable REE reserves and lay the groundwork for a reassessment of the economic potential of the Vuoriyarvi complex. [ABSTRACT FROM AUTHOR]

The rapid depletion of high-grade rare earth elements (REE) resources implies that future supplies may be augmented with low-grade ores, tailings, and other unconventional resources to meet cut-off grades and, subsequently, supply demands. This paper presents an amalgamation of studies conducted on selected complex low-grade iron-oxide-silicate-rich tailings, with the overall aim of developing efficacious methods and associated process mineralogy characterization for enhanced REE minerals recovery and upgrade. To this end, a summary of the overarching key results from froth flotation, magnetic separation, and gravity separation studies of the tailings and their implications are presented in this review. Reconciliation of all the findings reveals lucid links between feed ore properties, mainly mineralogy and particle size distribution, as the key influential factors that affect the beneficiation of real complex low-grade tailings, although distinct differences in physicochemical properties of the valuable and gangue minerals may exist. It is clearly established that the unliberated association between REE and gangue minerals within the ore can lead to either synergistic or antagonistic effects on the quality of concentrates produced. Furthermore, the limitations presented by the poorly liberated minerals are exacerbated by their "fine" nature. With appreciable recoveries obtained using such readily available conventional separation methods, the tailings provide additional REE value to the primary commodities; hence, such material could be considered a potential resource for REE beneficiation. The learnings from the respective beneficiation studies are significantly important as they provide the knowledge base and greater understanding of the mineralogical characteristics and beneficiation response of REE minerals in typical complex, low-grade tailings. [ABSTRACT FROM AUTHOR]

Rare earth elements (REEs) are considered critical elements in modern society due to their irreplaceable role in new innovative and energy technologies. The giant carbonatite-related Bayan Obo deposit contributes most REE resources in the world's market, while its origin is still unclear because of the complicated and diverse REE ore mineralogy and texture. Thescanning electron mircroscopy SEM)-based automated mineralogy allows for the numeric assessment of rocks and ores' compositional and textural properties. Here, we use TIMA (TESCAN Integrated Mineral Analyzer) to quantitatively characterize REE ore mineralogy from the deep drill core within the H8 unit ("dolomite marble") to better understand the deposit. The mineral composition, occurrence, and Ce elemental deportment of the borehole ores at different depths (i.e., 1107 m, 1246 m, 1406 m, 1546 m, and 1682 m) were obtained. The results show that the main types of ores in the investigated samples can be divided into banded REE-Fe ores, banded REE ores, disseminated REE-Fe ores, and veined REE ores. REE and gangue minerals vary significantly in abundance and occurrence. Monazite-(Ce) and bastnäsite-(Ce) are the primary REE host minerals, and both contribute the most to the REE budget. Other REE minerals, such as parisite-(Ce)/synchysite-(Ce), cerite-(Ce), huanghoite-(Ce)/cebaite-(Ce), and aeschynite-(Ce), are significant contributors. The gangue minerals generally include fluorite, barite, magnetite, pyrite, quartz, magnesio-arfvedsonite, and minerals of the biotite and apatite groups, among others. Combined with the newly published mineral-scale chronological and isotopic geochemical analyses, it is reasonable to conclude that the later hydrothermal fluids remobilized and redistributed the original Mesoproterozoic carbonatitic REE minerals and formed a high variable ore mineral assemblage. Furthermore, it is demonstrated that the mineralogical study using TIMA can provide accurate and reliable mineralogy data for the comprehensive interpretation of the complex REE ores, and extend our understanding of the deposit. [ABSTRACT FROM AUTHOR]

The stability relations of cerium and its species in the hydrometallurgical processing of bastnasite were studied using Pourbaix diagrams. Different systems of Ce-(F)-(CO3)-(SO4)-(C2O4)-H2O were constructed using HSC Chemistry software with the necessary thermodynamic data. The Ce-F-H2O system exhibits a large stability region for CeF3 (pH∼ −1.5 – 12). The stability domain of was determined by Ce-CO3-H2 system in the pH of 4.5 – 12. The decomposition behaviours of CeFCO3 were studied by Ce-F-CO3-H2O system which shows the stability domain of CeFCO3 from neutral to basic media. The treatment of CeFCO3 with H2SO4 was investigated by depicting diagrams of Ce-F-CO3-SO4-H2O system. According to this system, CeFCO3 can be decomposed to produce soluble Ce sulphates at around pH 6.2. In contrast, alkaline treatment of CeFCO3 converts it to Ce(OH)3 at pH 11. Finally, the recovery of Ce by oxalate precipitation was studied by Ce-C2O4-H2O system which showed the domain of Ce oxalate decahydrate. [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]

Thermodynamic calculations on the impact of carbonate–bicarbonate fluids cooling from 500 to 100°C on a monazite + calcite association with a simultaneous decrease in pressure from 2000 to 125 bar are performed. It is shown that the REE carbonate–bicarbonate complexes gain importance only at low temperatures. In this case, the total concentration of lanthanides in the fluid turns out to be rather low. This indicates that, in the presence of even insignificant amounts of fluorine and calcium in the hydrothermal system, carbonate–bicarbonate fluids do not lead to the removal of REEs but contribute to their accumulation in the form of precipitating fluorocarbonates. Thus, the role of carbonate-bicarbonate hydrothermal fluids in the transport and deposition of rare earth elements has been assessed for the first time for a wide range of TP-parameters and for the entire series of lanthanides. [ABSTRACT FROM AUTHOR]

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[Display omitted] • Monazite and bastnäsite U-Th-Pb dating demonstrate that the Boziguoer deposit formed at ∼ 290–280 Ma. • Post-magmatic hydrothermal processes play a significant role in the mineralization process at Boziguoer deposit. • The alkaline rocks and associated Nb-Ta-Rb-Zr-REE mineralization of the South Tianshan formed in a Tarim mantle plume setting. The Boziguoer alkaline intrusion is located in the South Tianshan Orogenic Belt on the northern margin of the Tarim Craton. The intrusion is entirely mineralized and forms a super-large rare metal (RM) and rare-earth element (REE) deposit dominated by Nb-Ta-Rb, accompanied by Zr-REE. The primary RM minerals include pyrochlore, astrophyllite, and zircon, while the main REE minerals consist of fluocerite, monazite, xenotime, and bastnäsite, which are commonly present as granular aggregates or singularly filling the interstices between gangue minerals. Through a combination of geochronological and geochemical analyses of different types of monazite and bastnäsite in the mineralized alkaline rocks, this study elucidates the role of magmatic-hydrothermal evolution on the Boziguoer RM-REE mineralization and reconstructs the geochronological framework of alkalic magmatic-hydrothermal evolution and mineralization processes, as well as establishing mechanisms responsible for RM-REE enrichment. Petrographic observations and back-scattered electron (BSE) imaging revealed several types of monazite and bastnäsite with different characteristics as follows: (1) type Ia monazite (Mnz-Ia) experienced intense hydrothermal alteration, forming residual cores of monazite mantled by apatite and allanite coronas; (2) type Ib monazite (Mnz-Ib) was partially eroded, forming concentric zoning patterns with a core of monazite, a mantle of apatite, and an outer rim of allanite coronas; (3) type II monazite (Mnz-II) is slightly modified, and commonly associated with fluorite; (4) bastnäsite and fluocerite exhibit a core-rim structure, with the core of fluocerite being brighter than the rim of bastnäsite in BSE images. According to the paragenetic relationships and compositional variations, all two types of monazite are of primary magmatic origin, while bastnäsite is of hydrothermal origin. In addition, principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) results indicate that Mnz-Ia and Mnz-Ib belong to the same group, different from Mnz-II. The latter has higher (Ce/Gd) N and (Th/U) N ratios, indicating relatively low-temperature crystallization of Mnz-II at late stages. In-situ LA-ICP-MS U-Th-Pb dating of monazite and bastnäsite show that Mnz-Ia and Mnz-Ib have ages of ca. 290 Ma, consistent with the zircon age of the intrusion, whereas the Mnz-II and bastnäsite have younger ages of ca. 280 Ma, representing a post-magmatic hydrothermal mineralization event at Boziguoer. These new ages indicate that both magmatic and subsequent hydrothermal processes played critical roles in the RM-REE mineralization in this deposit. The latest findings also support the model that the formation of the alkaline belt where the Boziguoer ore-bearing intrusion was temporally and spatially linked to the Tarim Large Igneous Province that is genetically related to a mantle plume. [ABSTRACT FROM AUTHOR]

Dissolution of rare earth elements from bastnasite ore was studied using different leaching agents such as sulfuric acid, hydrochloric acid, acetic acid, citric acid and sodium hydroxide at 70°C, with 1mol/L, solid/liquid ratio of 0.05 between 30 and 180 min. The one-step direct leaching strategy was applied under atmospheric pressure aiming at selective leaching of rare earth elements from a matrix of iron oxides in which the rare earth elements – carbonates & flourides – are embedded. / При исследовании процесса растворения редкоземельных рудных пород, содержащих фторкарбонат применялись различные виды выщелачивания: серной кислотой, соляной кислотой, уксусной кислотой, лимонной кислотой и гидроксидом натрия, при температуре 70° C, концентрация: 1 моль / л, соотношение твердость/жидкость: 0,05, в промежутке времени от 30 до 180 минут. Одностадийное выщелачивание проводилось с целью селективного выщелачивания редкоземельных элементов, в виде фторидов и хлоридов, находящихся в матрице оксида железа. / Rastvaranje elemenata retkih zemalja iz ruda koje sadrže fluorokarbonatni mineral proučavano je korišćenjem raznih reagenasa za luženje, kao što su sumporna, hlorovodonična, sirćetna i limunska kiselina i natrijumhidroksid, koncentracije 1 mol/l, na 70°C u vremenu od 30 do 120 minuta i odnosom čvrsto/tečno od 0,05. Direktno luženje u jednom koraku izvođeno je sa ciljem selektivnog luženja elemenata retkih zemalja u obliku fluorida i hlorida, koji su zarobljeni u matrici gvožđe oksida.

Isotopic dating studies have revealed that many carbonatite-related REE ore systems have protracted and complex temporal evolution histories. The mechanisms that cause these complex dating results remain poorly understood. Here, we present an in-situ Sm-Nd and Th-Pb isotopic investigation of monazite and bastnäsite from a geologically-complicated deposit, the world-class Bayan Obo REE deposit of China, with the aim of defining the general mechanisms accounting for the protracted age spread observed in this and many other REE deposits. Monazite and bastnäsite are two principle REE ore minerals in the Bayan Obo deposit. Most of the studied monazite and bastnäsite grains have experienced fluid-aided modification. The modified grains have generally homogeneous Sm and Nd contents and Sm-Nd isotopic compositions, implying low mobility of Sm and Nd during the modification process. Thus, the Sm-Nd chronometer can be used to constrain the primary crystallization timing of the REE minerals at 1293 ± 48 Ma. However, altered REE minerals have apparent 208Pb-232Th ages (1248–261 Ma) that are variably younger than the primary crystallization age. In most samples, Th contents have no correlations with 208Pb-232Th ages, while Pb contents tend to decrease along with the younging trend of 208Pb-232Th ages. NanoSIMS mapping shows that 208Pb and 208Pb/232Th are heterogeneous, and irregularly distributed in the altered grains. Such results are indicative of variable Pb loss during the fluid-aided modification process. Thus, many Th-Pb ages represent partial isotopic resetting and, hence, are geologically meaningless. Completely reset ages cluster at 450–400 Ma or 280–260 Ma, representing two discrete episodes of post-ore hydrothermal activity. Small amounts of monazite and bastnäsite that were newly crystallized during these two overprinting episodes have initial Nd isotopic signatures approaching the time-evolved isotopic compositions of primary ores, which suggests insignificant REE input to the primary ores during these events. This study provides critical evidence to resolve complex dating results and disparate ore genesis models for the giant Bayan Obo deposit. Moreover, our results indicate the resistance of Sm-Nd isotopes, but the susceptibility of Th-(U)-Pb isotopes, to fluid-aided modification. Therefore, younger Th-U-Pb dates in geologically-complicated deposits should be treated with caution as they may represent partial resetting results and/or may not represent events of increased metal tenor. [ABSTRACT FROM AUTHOR]

Bastnäsite is widespread in alkali granite, carbonatite and REE ore deposits. The U-Th-Pb ages of bastnäsite can constrain the mineralization age. Currently, the lack of suitable in situ analysis reference material is the major obstacle of bastnäsite U-Th-Pb geochronology. In this study, the matrix effects of U-Pb and Th-Pb age determination in bastnäsite using glass NIST 610 as the external calibration reference were evaluated with the 193-nm excimer LA-ICP-MS analysis in normal and additional gases laser ablation modes. The obtained U-Th-Pb ages of bastnäsite were approximately 7–11% lower than their reference values in the normal analytical mode (without additional gas). Fortunately, the determined systematic age biases in U-Th-Pb dating were significantly reduced (less than 1–2%) with the addition of water vapor within the ablation chamber. This reduction may be attributed to the observed significant suppression of 206Pb/238U and 208Pb/232Th downhole fractionation in both NIST 610 glass and bastnäsite by introducing a small quantity of water vapor in the ablation chamber. In addition, the obtained 206Pb/238U and 208Pb/232Th ages of bastnäsite K-9, LZ1384, and MAD809 showed great consistency with their corresponding recommended values. The obtained results show that accurate and precise U-Th-Pb ages of bastnäsite can be simultaneously obtained by using glass NIST 610 as the primary calibration standard in 193-nm LA-ICP-MS with the water vapor-assisted method. This simple and effective water vapor-assisted non-matrix-matched laser ablation method helps to promote the geological application of bastnäsite U-Th-Pb geochronology. [ABSTRACT FROM AUTHOR]

Dissolution of rare earth elements from bastnasite ores was studied using sulfuric acid at the atmospheric pressure. The one step strategy with sulfuric acid was studied further and the results showed that filtering difficulties do not happen for the chosen parameter combinations. Furthermore, the best parameter combinations were those with low temperatures and low acid concentrations. All in all, direct leaching is a simple process that uses the cheapest acid on the market and offers good leaching recoveries. Attention should be given to the formation of gel, especially when taking the process to the large scale, and the subsequent elimination of Ca from the leachate. / В данной работе представлены результаты исследований по растворению редкоземельных элементов из руд, содержащих фторкарбонаты, с помощью серной кислоты, при атмосферном давлении. Результаты выщелачивания с помощью серной кислоты показали, что фильтрование в процессе выбора различных параметров не влечет за собой негативных последствий. Наилучшие показатели были при комбинировании параметров с наиболее низкими температурами и наименьшей концентрацией кислоты. Прямое выщелачивание представляет собой весьма простой процесс, в осуществлении которого используется самая дешевая кислота на рынке сбыта. Особое внимание следует уделять образованию геля, особенно если в течение процесса использовался большой объем раствора, а также на последующее удаление кальция из раствора. / Ispitivano je rastvaranje elemenata retkih zemalja iz ruda koje sadrže fluorokarbonatni mineral pomoću sumporne kiseline pri atmosferskom pritisku. Rezultati rastvaranja u jednom koraku pomoću sumporne kiseline pokazuju da ne dolazi do problema prilikom filtriranja pri izboru raznih parametara. Najbolje su se pokazale kombinacije parametara s niskim temperaturama i malim koncentracijama kiseline. Direktno rastvaranje je jednostavan proces u kojem se koristi najjeftinija kiselina na tržištu. Posebnu pažnju treba obratiti na formiranje gela, naročito tokom procesa s većim zapreminama rastvora, kao i na naknadno uklanjanje kalcijuma iz rastvora.

The test results of the automated mineral identification and characterization system (AMICS), including the mineral composition, particle size distribution, dissemination state and degree of liberation of the target minerals, could be used to improve the beneficiation process. Taking the Dalucao rare earth ore located in Dechang, Sichuan Province, China (with an average content of 2.40 wt%) as the research object in this paper, the chemical composition, phase composition and dissemination state of the minerals were tested by AMICS, and the minerals of different fineness were ground. The concentrate yield, grade and recovery rate of the minerals of different fineness were compared through flotation tests. When the grinding lasted for 5 min and 82.60% of mineral grains passed through the − 74-μm sieve, the yield, grade and recovery rate could reach 20.19%, 8.75% and 73.64%, respectively (as the best grinding fineness), under the same flotation conditions. [ABSTRACT FROM AUTHOR]

Strongly carbonatized alkaline rocks and a carbonatite s. s. (xenolith) were discovered in the R-2 drillcore in the Roztoky Intrusive Complex (Figs 1, 2, 7; Rapprich et al. 2017). Both carbonate-rich rock types contain minerals of critical elements reported for the first time in the alkaline volcanic rocks of the České středohoří Mts. These include (Ca)-REE fluorocarbonates, minerals of Zr (zircon, baddeleyite; Fig. 3) and columbite. Chemical composition of these minerals was determined using SEM and EMP and the crystalchemical formulae were calculated. Columbite was classified as columbite-(Mn) (Tab. 3). (Ca)-REE fluorocarbonates were detected in two different samples and rock types. Ca-poor bastnäsite-(Ce) represents the only REE mineral present in carbonatized trachyte at the depth of 156.5 m. Synchysite-(Ce), bastnäsite-(Ce) and parisite-(Ce) were found in dolomite carbonatite at 286.5 m. These minerals form epitactic intergrowths up to 30 µm in size (Fig. 5, 8), which is, according to Armbrustmacher (1979), typical for primary (magmatic) REE minerals. (Ca)-REE fluorocarbonates are Ce-dominant (0.5 apfu), containing significant amounts of La (0.3 apfu) and Nd (0.2 apfu) (Tab. 1). The REE minerals show a typical Y3+?REE3+ substitution, which is especially significant in Ce-poor phases represented by analyses e3 and e4, where Ce is substituted by Y (0.1 apfu) and minor Sm, Eu, Gd and Th (Tab. 1). [ABSTRACT FROM AUTHOR]

The Vuoriyarvi Devonian carbonatite-ijolite-pyroxenite-olivinite complex comprises several carbonatite fields: Neske Vara, Tukhta-Vara, and Petyayan-Vara. The most common carbonatites in the Tukhta-Vara and Neske-Vara fields are calciocarbonatites, which host several P, Fe, Nb, and Ta deposits. This paper focuses on the Petyayan-Vara field, in which the primary magmatic carbonatites are magnesian. The least altered magnesiocarbonatites are composed of dolomite with burbankite and are rich in REE (up to 2.0 wt. %), Sr (up to 1.2 wt. %), and Ba (up to 0.8 wt. %). These carbonatites underwent several stages of metasomatism. Each metasomatic event produced a new rock type with specific mineralization. The introduction of K, Si, Al, Fe, Ti, and Nb by a F-rich fluid (or fluid-saturated melt) resulted in the formation of high-Ti magnesiocarbonatites and silicocarbonatites, composed of dolomite, microcline, Ti-rich phlogopite, and Fe-Ti oxides. Alteration by a phosphate-fluoride fluid caused the crystallization of apatite in the carbonatites. A sulfate-rich Ba-Sr-rare-earth elements (REE) fluid (probably brine-melt) promoted the massive precipitation of ancylite and baryte and, to a lesser extent, strontianite, bastnäsite, and synchysite. Varieties of carbonatite that contain the highest concentrations of REE are ancylite-dominant. The influence of sulfate-rich Ba-Sr-REE fluid on the apatite-bearing rocks resulted in the dissolution and reprecipitation of apatite in situ. The newly formed apatite generation is rich in HREE, Sr, and S. During late-stage transformations, breccias of magnesiocarbonatites with quartz-bastnäsite matrixes were formed. Simultaneously, strontianite, quartz, calcite, monazite, HREE-rich thorite, and Fe-hydroxides were deposited. Breccias with quartz-bastnäsite matrix are poorer in REE (up to 4.5 wt. % total REE) than the ancylite-dominant rocks (up to 11 wt. % total REE). [ABSTRACT FROM AUTHOR]

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO3F·CaCO3. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research. [ABSTRACT FROM AUTHOR]

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 bastnäsite 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 bastnäsite 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 bastnäsite, the dominant REE mineral, is closely associated with quartz, fluorite, and barite. In situ bastnäsite 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 bastnäsite 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 bastnäsite 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. [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 French Creek Granite, New Zealand, is an alkaline intrusion with enrichment in rare earth elements (REE). Petrography and whole-rock geochemical signatures demonstrate that the c. 82–84-Ma French Creek Granite is a composite granitoid, dominated by a ferroan, weakly peraluminous biotite alkali feldspar granite to syenogranite, with subordinate quartz-alkali feldspar (QAF) syenite. Maximum total REE + Y contents are higher in the granite and felsic dikes relative to the marginal QAF syenite, cogenetic mafic Hohonu Dike Swarm, and pegmatites. Our findings suggest that REE and high-field-strength element enrichment in the unaltered French Creek Granite is a function of partial melting from an enriched HIMU-like lithospheric mantle source, minor crustal assimilation, and extensive magmatic differentiation. Primary (magmatic) REE enrichment is defined by the occurrence of allanite, zircon, apatite, fergusonite, monazite, perrierite, and loparite, which are commonly associated with interstitial biotite. French Creek Granite samples from a phyllic-sericitic alteration zone in the Eastern Hohonu River are strongly elevated in REE relative to unaltered French Creek Granite, indicating remobilization and secondary REE enrichment by hydrothermal fluids. The REE are hosted in bastnäsite group minerals, monazite, xenotime, and zircon. Quartz protuberances, dilatational microfractures, and dike emplacement indicate that this alteration is structurally controlled. The δ13C and δ18O values of secondary carbonate veinlets are consistent with mixed low-temperature (~ 250–260 °C) magmatic hydrothermal fluids containing mantle-derived carbon. These fluids were likely part of a late-stage porphyry-type system operating during the same mantle degassing and extensional episode that was associated with the emplacement of the French Creek Granite and lamprophyric dikes of the Hohonu Dike Swarm, and initial Tasman Sea spreading. Results from this study provide an important insight into the complex processes responsible for REE enrichment in alkaline igneous systems. [ABSTRACT FROM AUTHOR]

Surface nanobubbles have been identified to play an important role in a range of industries from mineral processing to food science. The formation of surface nanobubbles is of importance for mineral processing in the extraction of complex ores, such as those containing rare earth elements. This is due to the way minerals are extracted utilising froth flotation. In this study, surface nanobubbles were imaged using non-contact atomic force microscopy on a polished cross section containing rare earth minerals. Nanobubbles were found on synchysite under reagent conditions expected to induce hydrophobicity in rare earth minerals, which is required for efficient processing. Synchysite –(Ce) is a rare earth fluorcarbonate mineral containing over 30% rare earth elements. Relatively little research has been conducted on synchysite, with only a few papers on its surface behaviour and flotation. The resulting nanobubbles were analysed and showed an average contact angle of 24° ± 8. These are in line with contact angles found on dolomite and galena by previous studies. [ABSTRACT FROM AUTHOR]

• Iron-oxide-silicate rich tailings was investigated as unconventional REE resource. • Major REE minerals were bastnäsite, monazite, brannerite, and stetindite. • Hematite and quartz were the major gangue minerals. • Magnetic separation was studied as preconcentration method. • Mineralogical and particle characteristics affected selective REE minerals recovery. This work is part of an ongoing investigation being conducted to recover and upgrade rare earth elements (REE) minerals from iron oxide and silicate rich tailings generated at a South Australian mining operation. Detailed mineralogical characterisation via Quantitative Evaluation of Minerals by Scanning electron microscopy (QEMSCAN) of the tailings established the presence of low grade (<1 wt% REE), fine-sized REE minerals. The REE minerals (bastnäsite, monazite, florencite, stillwellite, brannerite, and stetindite) identified were in intimate associations with weakly ferromagnetic/strongly paramagnetic iron oxides (mainly hematite and goethite) and diamagnetic silicate (quartz, illite, and annite) minerals. Chemical analysis showed the tailings comprised 26.2% Fe, 18.6% Si, 3.9% Al, and 1.07% total rare earth oxides (TREO). A rougher–scavenger–cleaner magnetic separation process was deployed to produce two useful streams of REE minerals concentrate and tails using a wet high-intensity magnetic separator (WHIMS). Typical metallurgical results indicated the rejection of 25% of the iron oxides at 0.11 T, whilst producing a magnetic concentrate with TREO recovery of 51% at a grade of 1.25% and non-magnetic tails with TREO recovery of 41% at a grade of 1.08%, both at 1.74 T. Bastnäsite, monazite, florencite, and stillwellite minerals were confirmed to be paramagnetic, whilst stetindite and brannerite were found to be diamagnetic. Whilst the applied magnetic field intensity was the most important factor in the minerals' magnetic separation efficacy, particle size distribution and mineralogical characteristics of ores also had significant effect. The findings exemplify both the challenges and opportunities for the beneficiation of complex, low grade REE-bearing iron oxide silicate rich tailings using WHIMS. They indicate that magnetic separation may be used to achieve modest preconcentration, the success of which is limited by the complex nature of the tailings and its concomitant magnetic properties, and thus warranting the need for further downstream processing (e.g., froth flotation) to produce cleaner, higher grade REE minerals concentrates for subsequent values extraction. [ABSTRACT FROM AUTHOR]

Simplified geological map showing the location of carbonatites, carbonatite-related REE deposits, and bastnäsite-dominated carbonatite-related REE deposits (i.e., where bastnäsite is among the three most abundant REE minerals; Weng et al., 2015; Smith et al., 2016). Map modified after Tang et al. (2013). • Ba, Sr, Ca, Th, U, and Sc commonly replace La and Ce in bastnäsite. • Large-scale bastnäsite crystallization occurred at the later stage of the hydrothermal system. • The process of REE enrichment in the Mianing-Dechang deposits is established. • The barite–calcite–fluorite assemblage can be regarded as a valuable guide in exploration for REE deposits. Bastnäsite is the main ore mineral in many carbonatite-related rare earth element (REE) deposits, which account for ∼51% of rare-earth oxide reserves worldwide. However, the occurrence, geochemistry, and genetic significance of bastnäsite has not been methodically investigated. The Cenozoic Mianning–Dechang (MD) REE belt in Sichuan Province, SW China, contains the Maoniuping, Dalucao, Lizhuang, and Muluozhai deposits as well as numerous smaller REE occurrences. Individual deposits within the belt contain different types of bastnäsite-bearing ore, which provides a unique opportunity to explore in detail the common mechanisms controlling the formation of bastnäsite-rich REE deposits. Here, we present detailed results from field observations and petrographic, geochemical, and fluid inclusion studies of bastnäsite from the main MD deposits. Calcite, fluorite, and barite form stable mineral assemblages that are commonly overprinted by bastnäsite. Homogenization temperatures of fluid inclusions in bastnäsite of ∼150–270 °C (Dalucao and Lizhuang deposits) and 155–210 °C (Maoniuping deposit) are systematically lower than those of fluid inclusions in gangue minerals. Therefore, the petrographic studies and homogenization temperatures both show that large-scale crystallization of bastnäsite took place during the later stage of the hydrothermal system. The bastnäsite, relatively geochemically homogeneous within all of the MD deposits, is enriched in Ba (293–8425 ppm), Th (16.4–2527 ppm), and U (4.19–92.7 ppm), and relatively depleted in high field strength elements such as Nb (0.15–17.4 ppm), Ta (0.06–6.48 ppm), Zr (0.71–31.1 ppm), Hf (0.62–5.65 ppm), and Ti (<60 ppm), the same to carbonatite, and ore veins. In comparison, the samples from the study area show an increase in average REE contents from syenites to carbonatites to ore veins (i.e., bastnäsite-bearing ores) and finally to bastnäsite. Lanthanum and Ce were commonly substituted by Th, U, Sc, Ba, and Sr supplied by more evolved hydrothermal fluids. Combining the present results with existing data, we present a three-stage model for the formation of carbonatite-related REE deposits. First, partial melting of metasomatized sub-continental lithospheric mantle, fluxed by REE- and CO 2 -rich fluids, forms the parental carbonatite–syenite magma. Second, Sr, Ba, and REEs are strongly partitioned into carbonatite melts during liquid immiscibility in the carbonatite–syenite magmatic system. Third, hydrothermal fluids exsolved from the crystalizing syenite and carbonatite magmas form ore veins with early gangue minerals and later bastnäsite overgrowths. Consequently, barite, calcite, and fluorite assemblages are a valuable guide in REE exploration. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The effect of EDTA on the separation of bastnaesite from fluorite by flotation was investigated. • Fluorite can be selectively depressed in bastnaesite flotation by EDTA. • Chemically adsorbed OHA on fluorite can be dissolved into soluble metal-EDTA complexes. • Chemically adsorbed OHA on bastnaesite is still stable after the addition of EDTA. Abstract Bastnäsite is an important mineral resource in the production of rare earth materials and is usually beneficiated by flotation. The flotation of bastnäsite is problematic due to the competitive adsorption of hydroxamate collector on bastnäsite and its associated calcium-bearing gangue minerals such as fluorite. One strategy to solve this problem is to use effective depressants to depress the gangue minerals. However, the current depressants all have some drawbacks. In this study, the effect of ethylenediamine tetraacetic acid (EDTA) as a depressant was tested in the flotation of single mineral of bastnäsite and fluorite and their mixture. The mechanism underpinning the role of EDTA was investigated through theoretical thermodynamic calculation, zeta potential and X-ray photoelectron spectroscopy (XPS) measurements. The results show that fluorite was significantly depressed, while the flotation of bastnäsite was almost unaffected when EDTA was present. The separation index between bastnäsite and fluorite increased from 1.18 to 12.66 with the increase of EDTA concentration from 0 to 7.79 kg/t. It was found that EDTA could dissolve the chemically adsorbed octyl hydroxamic acid (OHA) on fluorite through the formation of soluble Ca-EDTA complexes, whereas the chemically adsorbed OHA on bastnäsite was more stable and could not be transformed into Ce-EDTA spontaneously. Therefore, the flotation of fluorite was selectively depressed by EDTA. The results show that EDTA was a promising depressant for fluorite gangue mineral in bastnäsite flotation. [ABSTRACT FROM AUTHOR]

Dissolution of rare earth elements from bastnasite ore was studied using different leaching agents such as sulfuric acid, hydrochloric acid, acetic acid, citric acid and sodium hydroxide at 70°C, with 1mol/L, solid/liquid ratio of 0.05 between 30 and 180 min. The one-step direct leaching strategy was applied under atmospheric pressure aiming at selective leaching of rare earth elements from a matrix of iron oxides in which the rare earth elements - carbonates & flourides - are embedded. [ABSTRACT FROM AUTHOR]

Abstract A number of gravity separation techniques for rare earth elements (REE) minerals have been investigated and reported in the literature. These include the use of dense/heavy media, Falcon concentrators, Knelson concentrators, spiral concentrators, laboratory scale jigs, and shaking tables. Most of these methods have provided considerable REE minerals recovery and upgrade; but remain at the laboratory testing stage. There are vast quantities of iron-oxide-silicate rich tailings (IST) containing low grade REE in Australia. This work is part of research and development studies currently underway at the University of South Australia to develop economically viable methods to exploit selected IST for their REE contents. In this investigation, the feasibility of exploiting the differences in specific gravity to concentrate REE minerals from a typical IST sample was studied using two gravity separation units, a Knelson concentrator (KC) and Wilfley shaking table. The feed sample and gravity separation products were characterised using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Quantitative Evaluation of Minerals by Scanning Electron Microscopy (QEMSCAN) to study and compare the performance of the KC and shaking table as gravity preconcentration methods. The results indicated that the performance of both the KC and shaking table are significantly dependent on the mineralogical and particle size characteristics of the feed, however, the tabling was found to be the preferred choice over the KC, due to its greater selectivity. Tabling of >38 μm feed samples produced the desired split between the iron oxides and silicate minerals. The results suggest that desliming of the feed to remove fine/ultrafine particles (<38 μm) prior to tabling is key to attaining the desired results with the shaking table. Overall, tabling produced appreciable REE minerals upgrade, with iron oxides occupying the bulk of the concentrates. The test results confirm the complex mineralogy of the IST, which compromised REE minerals upgrade. A modified concentration criterion expression which considers the liberation characteristics of minerals is proposed, which provides a better idea on the feasibility of gravity separation. Graphical abstract Enrichment ratio of major mineral phases after KC and tabling separation of unclassified IST. Unlabelled Image Highlights • KC and shaking table were tested as gravity separation methods. • Particle and mineralogical characteristics affect gravity separation efficiency. • A modified concentration criterion expression is proposed. • Bastnäsite and monazite were upgraded using both KC and tabling. [ABSTRACT FROM AUTHOR]

Highlights • REE fluorcarbonates most widespread minerals in REE ore deposits. • Magnetic properties of parisite, röntgenite, synchysite determined for first time. • Magnetic behaviour varies from paramagnetic to diamagnetic according to REE:Ca ratio. Abstract Rare earth elements (REE) are considered as critical metals for electronics and green technology. The REE fluorcarbonates are one of the main REE ore minerals, common in many different types of REE deposit and yet some of their fundamental properties have still not been determined. This study measured the magnetic properties of pure REE fluorcarbonate single crystal minerals using a vibrating sample magnetometer (VSM) and determined their elemental compositions using electron probe microanalysis (EPMA). The results provide the first measurements of the magnetic behaviour and susceptibility of REE fluorcarbonates other than bastnäsite-(Ce). The magnetic susceptibility of REE fluorcarbonates varies systematically from one mineral to another and is highly dependent on the mineral chemistry. It is positive (paramagnetic) for bastnäsite-(Ce) and gradually decreases as the amount of Ca increases in parisite-(Ce), becoming negative (diamagnetic) for the Ca-rich member of the series, röntgenite. Synchysite-(Ce) is difficult to measure, generate good signal and acquire accurate readings because it practically always occurs as <5 mg crystals. Its magnetic susceptibility in samples from a REE ore deposit was experimentally determined by magnetic separation and checked by an associated study using a SQUID magnetometer, synchysite-(Ce) behaved as a diamagnetic mineral. This can be explained by the increase of Ca content and decrease of REE content, in addition to the variations in the layered structure common to the REE fluorcarbonate series minerals. Given the wide range of magnetic susceptibility of REE fluorcarbonates, it is important that the mineralogy is determined carefully before setting up a mineral processing flow sheet. [ABSTRACT FROM AUTHOR]

Graphical abstract Metallurgical balance of TREO distribution in flowsheets for flotation of REO using (a) sodium oleate and (b) hydroxamic acid in the presence of sodium silicate and starch. Highlights • Flotation was tested as separation method for rare earth oxides (REO). • Sodium oleate and hydroxamic acid were used as collectors. • Sodium silicate and starch were used as depressants. • Particle and mineralogical characteristics affect REO upgrade. Abstract To investigate the recovery of rare earth elements (REE) as a by-product from iron-oxide silicate rich tailings generated from the extraction of other primary commodities, bench scale flotation tests, in rougher-scavenger-cleaner configuration were studied. Preliminary mineralogical characterisation identified bastnäsite, monazite, stetindite, brannerite, florencite, and stillwellite as the REE minerals, with hematite and quartz being the major gangue minerals in the tailings material. The flotation response of the rare earth oxides (REO) and major gangue phases was investigated using sodium oleate and hydroxamic acid as collectors; and sodium silicate and starch as depressants. Generally, sodium oleate displayed relatively better selectivity for REO than hydroxamic acid in the presence of the depressants. The rougher-scavenger-cleaner flotation configuration using sodium oleate and the depressants produced a final concentrate recovering 63% REO at a grade of 2.25%. This investigation shows that both collectors may be used for REO recovery but the use of depressants is key, in tandem with cleaning of the rougher and scavenger concentrates. The pulp pH also had a strong impact on the flotation recovery of REO, with the selectivity deteriorating with increasing collector dosage. Furthermore, the high proportion of gangue minerals reporting to the concentrates, even with the use of depressants, affected the quality of concentrates grade. This study has shown that particle size distribution and mineralogical characteristics of feed significantly affect the upgrade and recovery of REO. [ABSTRACT FROM AUTHOR]

Dissolution of rare earth elements from bastnasite ores was studied using sulfuric acid at the atmospheric pressure. The one step strategy with sulfuric acid was studied further and the results showed that filtering difficulties do not happen for the chosen parameter combinations. Furthermore, the best parameter combinations were those with low temperatures and low acid concentrations. All in all, direct leaching is a simple process that uses the cheapest acid on the market and offers good leaching recoveries. Attention should be given to the formation of gel, especially when taking the process to the large scale, and the subsequent elimination of Ca from the leachate. [ABSTRACT FROM AUTHOR]

Carboxylates, hydroxamates and organic phosphoric acids are typical collectors used for rare earth mineral flotation. Carboxylates are not selective, while hydroxamates, though selective, require high concentrations to recover a significant amount of rare earth minerals. Other collectors such as organic phosphoric acids, which showed promising rare earth minerals collecting potential, have recently been explored. However, the mechanism of organic phosphoric acid adsorption on the surface of rare earth minerals has not been very well investigated. In this study, zeta potential measurements were conducted to study the surface property of dolomite, monazite and bastnäsite in the presence of benzohydroxamate (hydroxamate), sodium oleate (carboxylate) and Flotinor 1682 (phosphoric acid ester). These measurements, complemented with ATR-FTIR spectroscopy, evaluated the adsorption of the collectors at the surface of the minerals. The adsorption of the collectors was found to be highly influenced by the mineral cations present at the mineral/solution interface and in the solution. Possible adsorption mechanisms are proposed and discussed; some of which agree with those presented in the literature, while others provided different perspective. Although benzohydroxamate was the most selective, potential flotation processes to recover rare earth minerals using sodium oleate and Flotinor 1682 were also suggested. [ABSTRACT FROM AUTHOR]

Rare earth elements (REE) are critical to a wide range of technologies ranging from mobile phones to wind turbines. Processing and extraction of REE minerals from ore bodies is, however, both challenging and relatively poorly understood, as the majority of deposits contain only limited enrichment of REEs. An improved understanding of the surface properties of the minerals is important in informing and optimising their processing, in particular for separation by froth flotation. The measurement of zeta potential can be used to extract information regarding the electrical double layer, and hence surface properties of these minerals. There are over 34 REE fluorcarbonate minerals currently identified, however bastnäsite, synchysite and parisite are of most economic importance. Bastnäsite–(Ce), the most common REE fluorcarbonate, supplies over 50% of the world's REE. Previous studies of bastnäsite have showed a wide range of surface behaviour, with the iso-electric point (IEP), being measured between pH values of 4.6 and 9.3. In contrast, no values of IEP have been reported for parisite or synchysite. In this work, we review previous studies of the zeta potentials of bastnäsite to investigate the effects of different methodologies and sample preparation. In addition, measurements of zeta potentials of parisite under water, collector and supernatant conditions were conducted, the first to be reported. These results showed an iso-electric point for parisite of 5.6 under water, with a shift to a more negative zeta potential with both collector (hydroxamic and fatty acids) and supernatant conditions. The IEP with collectors and supernatant was <3.5. As zeta potential measurements in the presence of reagents and supernatants are the most rigorous way of determining the efficiency of a flotation reagent, the agreement between parisite zeta potentials obtained here and previous work on bastnäsite suggests that parisite may be processed using similar reagent schemes to bastnäsite. This is important for future processing of REE deposits, comprising of more complex REE mineralogy. [ABSTRACT FROM AUTHOR]

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