REE Contents Research Articles

The Raman spectrum of florencite‐(REE) [REEAl3(PO4)2(OH)6]: An integrated experimental and computational approach

AbstractFlorencite is a hydrous light rare‐earth elements (LREE) aluminium phosphate [REEAl3(PO4)2(OH)6], that amongst the REE‐rich minerals is quite common. The main end‐members are Ce‐, La‐ and Nd‐rich terms that were found in several genetic environments. Despite the large occurrence worldwide, to the authors' knowledge, florencite has attracted very few studies, particularly concerning the characterization of its Raman spectrum. We present a detailed study of the Raman spectrum of florencite, combining experimental measurements and theoretical calculations. Experimental Raman spectra (in the 100–1300 cm−1 spectral range) are measured on four florencite samples characterized by different chemical composition, that is, different REE abundance. The results highlight a remarkable coincidence between different Raman spectra measured on each sample, despite the significantly different chemical compositions in terms of their REE content. The same similarities were also observed in the computed spectra at the ab initio level; moreover, the calculations allowed the attributions of the different Raman signals to specific vibrational modes.

Characterization of complex micellar systems by Scattering techniques (SAXS and SANS) and wet-scanning transmission electron microscopy (wet-STEM)

The morphology of complex micellar assemblies is generally described using indirect methods such as small-angle X-ray scattering (SAXS) or small angle neutron scattering (SANS) that can yield to ambiguous descriptions of the nano-objects when the sample contains multiple structures or completely unknown structures. We herein propose to directly observe the nano-objects formed in P123 pluronic solutions (with and without rare-earth element - REE) using wet-Scanning Transmission Electron Microscopy (wet-STEM) and to compare the results with sample descriptions derived from SAXS and SANS measurements. The results obtained by the different analytical techniques are consistent. Each analytical method provides complementary information that allows the internal structure of the objects, their compositions and their mutual interactions to be described precisely. The main contributions of wet-STEM microscopy are to describe the nano-objects individually and, in particular, to show that the REE content can vary from 1 to 10 from one micelle to another, to observe the dynamics of the nano-objects in the liquid and to prove the co-existence of nano-objects with very different morphologies in the same system.

Apatite geochemical composition of Mesozoic granitoids in the eastern Jiangnan Orogen, S. China: insights into petrogenesis and intrinsic magmatic variables

ABSTRACT The geochemical compositions of apatite are commonly used to provide reliable constraints on the intrinsic magmatic variables of the parental magma. There is a widespread distribution of Mesozoic granitic rocks in the eastern Jiangnan Orogen (EJNO), which include I-type and A-type granitoids. This study aims to investigate the geochemical composition of apatite in 11 representative I-type and A-type granitic intrusions from the EJNO to understand their petrogenesis, intrinsic magmatic variables, and polymetallic mineralization potential. The results show that apatites in these granitoids were characterized by oscillatory zonation and homogeneous texture, and exhibited high F, and low Cl contents, as well as high REE, Y, and Th contents, indicating magmatic origin. These apatites were divided into two groups depending on their geochemical characteristics and original rock types. In Group I apatites (in the I-type granitoids), the absence of an abrupt change in major and trace element concentrations from the core to the rim of the apatite crystals, combined with their low levels of MgO, Sr, and HREY (HREE+Y), serves as evidence to classify the I-type granitoids as low Sr-Y adakitic granitoids with a low Mg#, which can be attributed to the partial melting of the thickened lower crust. In Group A apatites (in the A-type granites), the normal increase in incompatible elements from the core to the rim, as well as the presence of a flat REE pattern with pronounced Eu anomalies, can be attributed to crystal fractionation of plagioclase, allanite, and zircon. Furthermore, Group I apatites have higher SO3, Cl, and molar OH/F and Cl/F ratios compared to Group A apatites. Quantitative calculation by apatite-melt partitioning and modelling suggests that the I-type granitic magmas were more volatile-rich and more oxidized than A-type granitic magmas. Taken together, based on the relationship between the intrinsic magmatic variables and the behaviour of ore-forming elements, our study demonstrates that early I-type granitoids of the EJNO have a strong W-Mo-Cu polymetallic mineralization potential, while late A-type granites may possess rare metal mineralization potential.

Trace Elements of Multi‐stage Minerals and Titanite U‐Pb Dating for the Gneisses from Liansan Island, Sulu UHPM Belt

AbstractGneisses with anatectic characteristics from the Liansan island in the Sulu UHPM (ultra‐high pressure metamorphic) belt were studied for petrography, titanite U‐Pb dating and mineral geochemistry. Three origins of garnets are distinguished: metamorphic garnet, peritectic garnet and anatectic garnet, which are formed in the stages of peak metamorphism, retrograde anatexis and melt crystallization, respectively. The euhedral titanite has a high content of REE and high Th/U ratios, which is interpreted as indicating that it was newly‐formed from an anatectic melt. The LA‐ICP‐MS titanite U‐Pb dating yields 214–217 Ma ages for the titanite (melt) crystallization. The distribution of trace elements varies in response to the different host minerals at different stages. At the peak metamorphic stage, Y and HREE are mainly hosted by garnet, Ba and Rb by phengite, Sr, Nb, Ta, Pb, Th, U and LREE by allanite and Y, U and HREE by zircon. During partial melting, Y, Pb, Th, U and REE are released into the melt, which causes a dramatic decline of these element contents in the retrograde minerals. Finally, titanite absorbs most of the Nb, U, LREE and HREE from the melt. Therefore, the different stages of metamorphism have different mineral assemblages, which host different trace elements.

Geochronological Constraints on the Evolution and Petrogenesis of the Malwa Plateau Subprovince of the Deccan Traps

AbstractThe eruptive history of the Malwa Plateau Subprovince of the Deccan Traps is addressed by dating 21 lavas spanning the exposed stratigraphic extent, using the 40Ar/39Ar method applied to plagioclase separates. Major, minor, and trace element geochemistry was determined for each of the dated lavas and four additional ones. Dating results indicate that the eruptions began prior to 66.8 Ma, at least 400 ka before the oldest known lava in the more extensively studied Western Ghats, representative of the main Deccan province, to the south. Eruption rates peaked from 66.4 to 66.3 Ma and then diminished until 65.6 Ma. The peak in eruption rates coincides with the well‐documented Late Maastrichtian Warming event. Malwa lavas show some major and trace element affinities with geochemically defined lava flow formations of the Western Ghats, but are generally out of the stratigraphic sequence manifest in the Western Ghats. The distinct geochemical evolution of Malwa Plateau lavas compared with those of the Western Ghats is at least in part a consequence of differences in crustal composition between the two subprovinces. Modeling of REE concentration patterns of Malwa lavas suggests that they were derived by slightly lower degrees of partial melting, at lower mantle temperatures and depths, than those in the Western Ghats. The Malwa Plateau thus appears to record an earlier, cooler stage of the Deccan plume's evolution and continued to erupt through a large part of the lifetime of the main Deccan province.

Ecological and geochemical assessment of soil cover on the territory of Ufa city

The relevance. The need for constant monitoring of the state of natural environments because of Ufa increasing industrialization. This study is especially relevant due to the presence of enterprises of various industries (petrochemical, energy, metal construction, timber processing, chemical) located on a fairly small territory of the millionaire city. The aim. To determine the degree of technogenic pollution of the soil cover from industrial facilities in the study area. It is necessary to assess the impact of industrial emissions, as well as emissions from stationary and mobile sources for development of measures aimed at reducing the impact of chemical elements on the environment. Methods. Instrumental neutron activation analysis, atomic absorption spectroscopy, kappametry, mathematical statistics, mapping (spatial distribution of indicator geochemical indicators and content of the main pollutants). Results. The paper introduces the results of the analysis of the content of 29 chemical elements in the soil cover on the territory of Ufa according to the study of 104 samples. For each industrial area of the city, the priority elements-pollutants from the list of the analyzed ones were identified. Areas with high traffic congestion, as well as areas near oil refineries, are characterized by increased concentrations of As and LREE group (La, Ce, Nd). Elevated levels of Br and Sc are observed in areas near energy complexes. Increased concentrations of REE (Nd, Tb, Lu) were detected around the objects of the timber industry complex. A special situation is observed with the concentrations of some metals (Cr, Zn, Co). The entire territory of the city is characterized by increased concentrations of elements of the transition metal group due to the presence of a large metalworking complex and heavy automobile traffic. Using statistical methods of data interpretation, associations of chemical elements were identified and divided by possible genesis: mainly natural (Ca-Sr), mixed (Cs-Rb, Br-Ta-Na), mainly technogenic (Sb-Zn, Ba-As-Cr-Hg, Th-Lu-Hf-Yb, Ce-La-Nd). The constructed maps-schemes of spatial distribution, the total indicator of pollution and magnetic susceptibility determined that the territory of Ordzhonikidze district and the territory of the Dema railway station can be considered as the most susceptible to anthropogenic influence.

Tracing provenance of eolian sands in the northern Ulan Buh Desert, China: Evidence from the REE geochemical characteristics

Desertification is a primary threat to crop farming, the livestock industry, and the eco-environment in northwestern China. Through field research and satellite imagery, it has been discovered that there are 4–5 sand belts in the shape of handclasps connecting major deserts in the Alxa Plateau region of northern China. These sand belts have been expanding for several decades. However, eolian sand transport between major deserts through these expanding sand belts is still underestimated. Identifying the source areas of eolian sands in deserts provide essential knowledge to prevent desertification. In this study, we collected samples from the northern Ulan Buh Desert (UBD), the Yamalik Desert (YD), and the Langshan Mountains and analyzed their REE contents in the <125 μm fraction. We compared REE geochemical characteristics of fine-grained sands in the UBD with other recently published REE data for potential source areas. Our findings indicate that the primary origins of fine-grained sands in the northern UBD are from the Qilian Mountains (QM) and Badain Jaran Desert (BJD), which are transported through the YD. Contributions from the Gobi-Altay Mountains to the north are relatively minor. The Langshan Mountains and Hawula Mountains are not considered as the primary sources of fine-grained sands in the UBD. In contrast, surface sediments in the southern UBD have a local mixture of the paleo-lacustrine deposits, the Gobi sediments, and minor external inputs from the BJD and QM. Our findings demonstrate that sand belts connecting these deserts play a crucial role in the eolian transport of fine-grained sands. Therefore, both the Chinese government and scientists should pay close attention to them in future efforts to combat desertification.

Geochemical characteristics and implications of epidote in South Dulan and Vlaska exploration greenfield in north of Bor metallogenic zone, Serbia

The Bor metallogenic belt in Serbia is a promising region for copper-gold (Cu-Au) resources, hosting numerous porphyry copper deposits, epithermal gold deposits and metallogenic prospects, such as the South Dulan and Vlaska exploration greenfield. Epidote alteration is integral to the propylitic and sodic-calcic alteration assemblages within this region. It is distinguished by the extensive occurrence of two primary epidote types: disseminated (Ep1) and veined (Ep2) epidote. In this study, comprehensive petrographic analysis reveals that in the propylitic zone, epidote mainly replaced hornblende (Ep1a) and plagioclase phenocrysts (Ep1b), coexisting with chlorite, apatite and titanite. In proximity to the potassic zone, epidote (E1c) coexists with biotite, while epidote (Ep2), chlorite, pyrite and chalcopyrite veinlets are observed near the ore body. Notably, Ep1 exhibits lower Fe and higher Mn contents in comparison to Ep2. Additionally, elements such as Ca, Al and Fe in Ep1a, and Ca, Fe, Mg, Mn and Ti in Ep1b, as well as Ca, Al, Fe and Mn in Ep1c, are introduced into the epidote through hydrothermal fluid interactions. Variations in trace element characteristics are evident among different epidotes. Specifically, Ep1a exhibits elevated Mg content (324–6050 ppm), Ep1b is notable for its high Na (22–942 ppm) and Sr (523–3075 ppm) contents, while Ep1c contains elevated K (24–445 ppm) and Na (41–103 ppm). Which suggest that disseminated epidote (Ep1) inherits the geochemical features from its precursor minerals. In comparison to disseminated epidote, epidote in veinlet exhibits higher Fe3+, Cu, Sn and REEs, along with lower contents of Pb, Sb and Sc, suggesting that these elements have been integrated into epidote through isomorphism substitution and influenced by fluids compositions, physical factors (temperature, pressure, etc.) and chemical parameters (speciation, pH, fO2, etc.), as well as mineral assemblages. Therefore, the trace element contents of Pb, Sb, Sc, Cu, Sn and REEs in epidote could serve as more appropriate indicators for mineral geochemistry in porphyry deposit hydrothermal centers.

Petrogenesis and rare-metal mineralization of the Ririwai alkaline granitoids, north-central Nigeria: mineralogical and geochemical constraints

ABSTRACT The Ririwai anorogenic alkaline complex harbours extensive rare metal (Nb-Zr-Sn-Zn) mineralization. However, uncertainty still surrounds their origin and magmatic-hydrothermal processes responsible for their rare metal mineralization. The complex is composed of peralkaline arfvedsonite ± albite-bearing granites, mildly peralkaline fayalite-bearing granite porphyries, and weakly peraluminous biotite-bearing granites, all of which show diagnostic A1-type characteristics. Zircon U-Pb dating reveals emplacement ages between 181.4 ± 0.81 and 188.6 ± 7 Ma for the three rock units. Sm-Nd and Pb isotopes (εNd (t) = –0.6 to −5.4, 206Pb/204Pb = 17.68–17.93) constrained the Ririwai A-type granites to represent highly fractionated products of enriched mantle-derived magmas. Mass-balance modelling suggests that magma evolution was fuelled by extensive fractional crystallization of 50 ~ 60 vol.% K-feldspar, 30 ~ 35 vol% fayalite, 5 ~ 10 vol.% amphibole, and ~ 5 vol.% apatite under reduced and water-undersaturated (ΔFMQ = –1.55; logfo2 = –18.63; H2O = <2.0 wt.%) conditions and assimilation of ~ 50 vol.% crust. Whole rock and amphibole compositions revealed an increasing degree of fractionation from the fayalite-bearing granite porphyries through biotite-bearing granites to the arfvedsonite ± albite-bearing granites. This extended fractionation at the late stage of magma differentiation, facilitated by fluorine dissolution and concentration of excess HFSE and REE as alkali-fluorocomplexes in the fluorine-rich silicate melt, allowed the accumulation of economic rare metal pyrochlore and columbite mineralizations in the highly fractionated arfvedsonite± albite- and biotite-bearing granites, respectively. Nonetheless, the metasomatic reaction rim textures around the magmatic pyrochlore, coupled with the M-type lanthanide tetrad effect (TE1,3 >1.10) indicate the subsequent effect of hydrothermal processes. Tectonically, reactivated shear fractures and transcurrent faults following lithospheric stresses in a transtensional regime allowed magma uprising and emplacement of A-type granites in the Ririwai complex.

Cathodoluminescence and geochemical characteristics of Apatite: Implications for mineral exploration in the Xiongcun District, Tibet, China

Apatite grains from the No. 2 porphyry Cu–Au deposit in the Xiongcun district of Tibet, China, have a range of physical and compositional features. This study investigates the potential use of apatite associated with hydrothermal alteration as a tool for mineral exploration. In situ textural, cathodoluminescence (CL), and chemical analyses were performed on thin sections containing apatite from various alteration zones in the deposit. No clear variation was seen in apatite from rocks of the potassic, sodic–calcic, chlorite–sericite, phyllic, and propylitic alteration zones using visible light and scanning electron microscopy; however, distinct variations were observed in optical cathodoluminescence (OP-CL) (dark yellow to green, orange to green, yellow–brown to green, yellow-orange to brown, and light yellow–brown to green luminescence for the respective zones). The alteration-related differences in luminescence were a result of the interaction between Fe and Mn; the Na and Cl contents; and depletion in total heavy rare earth elements (ΣHREE) and Y. The variations in the REE contents of apatite from different types of altered rock record reactions with Cl- and F-rich fluids. The partitioning behavior of Cl between apatite and hydrothermal fluids is influenced by pressure, temperature, pH, and fluid composition, whereas the partitioning of F between apatite and fluids is dependent on the fluid composition and not the temperature. At high temperatures, Eu3+ is reduced to Eu2+, which results in negative Eu anomalies in apatite from the potassic-altered rocks and propylitic-altered rocks. Apatite grains in the sodic–calcic-altered rocks and chlorite–sericite-altered rocks show a similar enrichment in light REEs (LREEs) that resulted from REE and Y incorporation as follows: Na+ + (Y + REE)3+ = 2Ca2+. Apatite grains in the phyllic-altered rocks are enriched in the middle REEs. This study confirms that the luminescence, chemical composition (including Fe, Mn, Na, Cl, ΣHREE, and Y contents), and REE patterns of apatite can be affected by hydrothermal alteration; therefore, these results may be used to constrain the evolution of ore-forming hydrothermal fluids and may offer an effective tool for mineral exploration.

Geochemical and Mineralogical Characteristics of Ion-Adsorption Type REE Mineralization in the Mosuoying Granite, Panxi Area, Southwest China

The ion-adsorption rare earth deposit developed on the Mosuoying granite in the Panxi area of southwestern China represents a significant advancement in the exploration of ion-adsorption rare earth deposits in Sichuan. Being the first and currently the sole ion-adsorption rare earth deposit in Sichuan, studying its rare earth mineralization characteristics holds great importance. This paper aims to investigate the geochemical properties of the Mosuoying granite and its overlying weathered crust using rock geochemical methods based on field geological investigations. The findings reveal that the deposit belongs to the light rare earth type, with the ore-forming parent rock attributed to the high-potassium calc-alkaline series. It exhibits a high rock REE content ranging from 419 to 578 ppm, indicating favorable mineralization potential. Hydrothermal alteration reduces the REE content of the parent rock, leading to a notable increase in the LREE/HREE ratio, thus impacting the partitioning of rare earth elements and subsequent ore formation. The distribution characteristics of rare earth elements in each layer of the weathered crust are controlled by the parent rock and exhibit a light rare earth distribution pattern. The completely weathered layer is the main enrichment zone for rare earth elements, and the migration and enrichment patterns of rare earth elements in the weathered crust are evident. From the semi-weathered layer to the completely weathered layer, all REEs were gained, with a higher degree of migration for LREE. From the completely weathered layer to the clay layer, all REEs were lost, and the vertical distribution of rare earth content shows a “low-high-low” pattern.

Geochemistry of the Leatherwood coal in eastern Kentucky with an emphasis on enrichment and modes of occurrence of rare earth elements

The Middle Pennsylvanian (Bolsovian) Leatherwood coal in the central part of eastern Kentucky is a moderately thick, moderate-S seam that has been one of the major energy resources in the region. Much of the seam profile consists of clarain, dull clarain, and durain with some brighter lithologies at the base of the seam and in the upper portion of the coal at one site. A previous study emphasized petrographic trends. In this investigation, the geochemistry of the coal is examined. Some elements, such as Ge and Ga, are enriched at 2× and 5× the World hard coal averages in the coal lithotypes adjacent to rock (roof, floor, partings). Arsenic and other chalcophile elements (Zn, Co, Ni) tend to be concentrated at the top and bottom of the seam profiles and below partings, generally in the coals with the highest pyritic sulfur content. Manganese enrichments occur in bright clarain lithologies at one site. No coal lithology reaches a 5× the World hard coal average, but samples between the 2× and 5× World hard coal averages tend to be at the top and bottom of the coal seam. Most coal samples tend to have a light rare earth element (LREE) enrichment. The basal lithotype at all sites, though, has a heavy REE enrichment and, via inference from the Zr and TiO2 concentrations, a smaller influx of detrital minerals than the basal lithotypes in many Appalachian coals. While the nature of REE associations is complicated by the high volatile A bituminous coal rank, the relatively high concentrations of the heavy REE suggest an original, albeit possibly not exclusive, organic association for those elements.

Geochemical characteristics and ecological risks of rare earth elements in river sediments of coal-grain composite area in eastern China.

Coal and grain complex areas influence the geochemical characterization of REEs through coal mining activities and agricultural production. However, there is a lack of relevant studies. In this study, we investigated the geochemical characterization and risk assessment of REEs in river sediments of the northern Anhui plain, a typical coal-grain composite area. The results showed that the average concentrations of ∑REE in the sediments ranged from 134.7 to 220.3 μg/g, and LREE was significantly enriched. Among the 14 REEs, Gd and Eu were the most enriched, with enrichment factors of 1.792 and 1.764, respectively. In addition, the differences in REEs content and enrichment between different rivers were related to the location of coal mines and the degree of population concentration. The average values of δCe and δEu in the sediments were 0.990 and 1.080, respectively, and most of the sampling sites showed a weak positive Ce, Eu anomaly. The results of Pearson's correlation and RDA redundancy analyses showed that Fe, Al, Mn and sand contributed more to the enrichment of REEs. The river sediments in the whole area had a slight potential ecological risk, with Eu (Er=13.05) and Lu (Er=14.07) having the highest potential risk. The ADD results also showed that the average daily dose of REEs by children was around 2.000 (μg/(kg·day)), which was significantly higher than that of adults. The results of this study can be used as a basis for the prevention and control of REEs in rivers in northern Anhui Province.

Multi-Phase Hydrothermal Fluid Events in the Giant Lannigou Gold Deposit, SW China: Insights from Calcite Sm–Nd Age, Trace Elements, and C-O-Sr Isotopes

The Nanpanjiang basin hosts the world’s second-largest concentration of Carlin-type gold deposits. To decipher the origin and evolution of hydrothermal fluid, this study conducted Sm–Nd dating, in-situ trace element, and C-O-Sr isotopic analyses on three types of calcite samples from the giant Lannigou gold deposit in the Nanpanjiang basin, SW China. The type-I calcite, intergrown with Au-bearing arsenian pyrite, has an Sm–Nd isochron age of 213 ± 7 Ma (MSWD = 0.81), indicating that gold mineralization occurred in Late Triassic. The type-II calcite, which coexists with high-maturity bitumens and cut through the main-stage gold orebodies, yields an Sm–Nd age of 188 ± 14 Ma (MSWD = 0.34), representing a post-ore hydrocarbon accumulation event. The type-I and type-II calcite samples have low REE contents (5.28–51.6 ppm) and exhibit MREE-enriched and LREE-/HREE-depleted patterns. Combined with their identical C-O-Sr isotopes, we suggest that hydrothermal fluids responsible for the precipitation of type-I and type-II calcite samples were derived from a mixed metamorphic fluid and meteoric water source. In contrast, the type-III calcite samples, associated with realgar and orpiment, have distinct Mn, Sr, and As contents, REE patterns, and C-O-Sr isotopic composition from the type-I and II calcites, suggestive of different fluid sources. Based on our and previously published data, we propose that the fluid evolution, gold mineralization, and hydrocarbon accumulation in the Nanpanjiang basin are closely related to the Indosinian and Yanshanian orogenies in South China.

Apatite trace elements and O-Sr isotopes reveal different magmatic sources of Fe-Ti oxide deposits in the eastern Tianshan, NW China

Magmatic Fe-Ti oxide deposits are one of the most important iron deposit in eastern Tianshan, NW China, and their ore-forming mechanism remains obscure. Here, we use trace elements and O-Sr isotopes of apatite from two representative magmatic Fe-Ti oxide deposits (Niumaoquan and Weiya) in the eastern Tianshan to constrain the genesis of ore formation. The apatites from the Niumaoquan Fe-Ti oxide ores exhibit higher Eu/Eu* values, lower Mn contents, and larger REE variations than those from the Weiya Fe-Ti oxide ores, indicating a protracted evolution process of the Niumaoquan ore-forming magmas under a relatively reduced condition. Specifically, the apatites from the Niumaoquan Fe-Ti oxide ores can be divided into two groups: Group 1 with relatively low REE contents, low 87Sr/86Sr ratios (0.70574–0.70641) and high δ18O values (5.1–5.6‰), and Group 2 with relatively high REE contents, high 87Sr/86Sr ratios (0.70703–0.70792) and low δ18O values (2.8–3.3‰). The Group 1 apatites formed by early crystallization in the mantle, while the Group 2 apatites formed by assimilation of low δ18O-high 87Sr/86Sr altered rocks during magmas emplacement en route to the continental crust. Unlike the Niumaoquan apatites, the apatites from the Weiya Fe-Ti oxide ores have relatively homogeneous, high δ18O values (8.3‰-9.1‰) and 87Sr/86Sr ratios (0.70798–0.70848), indicating involvement of continental crustal materials in their mantle sources. Combined with previous studies, we suggest that the Niumaoquan and the Weiya Fe-Ti oxide deposits formed in a non-plume tectonic setting but they originated from different magmatic sources. Our study highlights that trace elements and O-Sr isotopes of apatite can be used as powerful tools to constrain the source characteristics and ore-forming processes of magmatic Fe-Ti oxide deposits.

Significant mobilization of REE from calc-alkaline melt into fluid during fluid exsolution: Insights from magmatic amphibole composition from Tieshan skarn Fe-Cu deposit (Hubei Province, China)

Hydrothermal fluids associated with carbonatites and peralkaline silicate rocks typically exhibit high REE content, but this is generally not the case for calc-alkaline rocks. However, the Tieshan skarn Fe-Cu deposit in the Edong district of Hubei Province in China demonstrates economic REE mineralization potential linked to calc-alkaline rocks. To investigate the presence of REE enrichment in the fluid, we present textural and compositional data of rock-forming mineral amphibole from the quartz diorite in the Tieshan deposit. Three distinct types of amphibole are identified in the Tieshan quartz diorite, namely Early amphibole, Main-stage amphibole, and Late amphibole, following the crystallization sequence. Early amphibole (813–864 °C, 115–152 MPa) crystallized when the magma was emplaced at a depth of approximately 4.8 km. Main-stage amphibole (741–806 °C, 58–103 MPa) crystallized at a depth of roughly 3 km. Between the early and main-stage amphibole crystallization, the magma experienced fractional crystallization of pyroxene, amphibole, and plagioclase, resulting in a REE enrichment in the residual melt. Late amphibole crystallized subsequent to the transition from lithostatic to hydrostatic stress states (656–729 °C, 27–52 MPa). Significantly, the transport of REE from the magma system initiated towards the end of Main-stage amphibole crystallization. A comparison with the Tonglvshan granitic rocks in the same district indicates an elevated F content and extended fractional crystallization history in the Tieshan magma, contributing to REE enrichment in its melt. Furthermore, the high F content lowered the solidus temperature of the Tieshan magma, thereby facilitating the more efficient removal of REE into the fluid. The assimilation of evaporate into the magma possibly led to heightened sulfur and chlorine levels in the fluid, enabling the transport of a significant amount of REE.

Rare earth elements into the aqueous phase of mud volcanoes of the Kerch-Taman region

This article presents original data on the content and distribution of major and rare earth elements into the waters phases from 26 mud volcanoes within the Kerch-Taman region. According to the chemical composition of the studied mud volcanic waters are represented by Na-Cl and Na-HCO3-Cl types, and the Cl/Br, Na/Cl, and Y/Ho ratios specify three main genetic groups of volcanoes. It was found that the rare-earth element contents in the aqueous phase of mud volcanoes are low (fractions of μg/L) and are distinguished by negative cerium anomalies and positive europium and holmium anomalies. The highest REE concentrations are observed in mud volcanoes located within the oldest Cretaceous sediments in the area of fault influence. As the distance from the Mesozoic source ΣREE sharply decreases. It has found that the free CO2 content in the aqueous phase regulates the REE content in waters and the value of cerium and europium anomalies.

Study on the complex magmatic and hydrothermal metallogenic processes in the giant Huayangchuan uranium (U)-polymetallic ore district: Constraints from geochemical and geochronological evidences

The supergiant Huayangchuan uranium (U)-polymetallic deposit is situated in the west part of Lesser Qinling Orogen, Central China, which is renowned for its unique metallogenic type and complex mineralization processes. This newly-discovered deposit contains economic endowments of U, Nb, Pb, Se, Sr, Ba and REEs. The genesis of this deposit remains hugely controversial and the related magmatic and metallogenic framework have not been well established. In our study, we present newly obtained zircon U-Pb age data, whole-rock trace elements, detailed SEM observation, carbon and oxygen isotope determination and titanite U-Pb age result to provide geochemical and geochronological constraints on the magmatic and hydrothermal metallogenic processes in Huayangchuan ore district and give insight into the REE, Nb and U mineralization and remobilization mechanism. Carbonatite in Huayangchuan deposit is rich in Ba, Sr, Nb, U and REE and the δ18OSMOW and δ13CPDB (‰) values of carbonatite vary between + 7.30 ‰ to + 9.80 ‰ and − 6.00 ‰ to − 7.20 ‰, respectively, which is the unique characteristic of igneous carbonatite. The total REE contents of carbonatite range from 1319.5 to 2535.8 ppm, significantly higher than that of the granite pegmatite dykes and Taihua Group granitic gneiss. Two zircon grains from the Huayangchuan carbonatite yield the 206 Pb / 238 U age of 223 ± 5.6 Ma and 217 ± 8.6 Ma. Uranium and niobium are mainly hosted in the primary mineral of betafite, minorly in uraninite and fergusonite. REE are remained in various REE carbonates, phosphates and silicates, e.g. allanite, parite, monazite, apatite, yttrialite and xenotime. Betafite contains numerous mineral inclusions of calcite, allanite and apatite, which displays as vermicular relicts with metasomatic corrosion texture. The intimate relationship between betafite, calcite, apatite, allanite and REE carbonates implies that U and Nb mineralization occurred during carbonatite-related magmatic stage. Late Triassic carbonatite magmatism (∼220 Ma) was responsible for the world-class U-Nb-Mo-REE mineralization in the Qinling Orogen. Whereas, LA-ICP-MS U-Pb data of titanite collected from Huayangchuan carbonatite reveal two sets of ages in the Huayangchuan deposit: during the Late Triassic and the Early Cretaceous. LA-ICP-MS data of the Triassic titanite and Cretaceous titanite in Huayangchuan deposit yield the lower intercept age of 223.1 ± 9.4 Ma and 141.9 ± 4.7 Ma respectively in the Tera-Wasserburg (238U/206Pb - 207Pb/206Pb) diagram. Cretaceous hydrothermal titanites show enrichment in Y, HREEs and depletion in TiO2 and LREEs relative to the Triassic magmatic titanites. Primary betafite and titanite were subjected to later hydrothermal alteration. The close genetic relation between altered titanite and Ti-Fe-Nb-Pb-U mineral inclusions demonstrates that Early Cretaceous hydrothermal fluids contributed to the Nb, U and Ti remobilization. Early Cretaceous regional granitic magmatic activity brought hydrothermal fluids to alter the early carbonatite magmatic pyrochlore and titanite. U, Nb, Ti, Y, Pb and HREEs were transferred and subsequently re-precipitated into uraninite, and hydrothermal titanite.

Magmatic-hydrothermal evolution of the aquamarine-bearing Yamrang Pegmatite, Eastern Nepal: Insights from beryl, garnet, and tourmaline mineral chemistry

The Ikhabu Pegmatite Field (IPF) in the Nepal Himalaya is a newly discovered rare-element (REL) pegmatite field that hosts the Yamrang pegmatite, the primary source of the famous Nepalese aquamarines. In this contribution, we provide a comprehensive description of the geology of both the IPF and the Yamrang pegmatite, offering insights into the evolutionary stages of the Yamrang pegmatite based on its internal texture and the mineral chemistry of beryl, garnet, and tourmaline. The Yamrang pegmatite is classified as a beryl-columbite subtype of REL pegmatite, exhibiting axial symmetric zonation and is differentiated into five mineralogical-textural zones during magmatic and hydrothermal stages. The magmatic stage involves undercooling, disequilibrium crystallization, and fractional crystallization whereas the hydrothermal stage comprises alkali-enriched fluid exsolution, the formation of miarolitic cavities, and the crystallization of aquamarine. Yamrang aquamarines are enriched in FeO, up to 1.1 wt%, with Fe2+ as the primary chromophore, resulting in their blue color. Two types of beryl have been identified: magmatic beryl in zones 3 and 4 and hydrothermal beryl in miarolitic cavities (zone 5). Magmatic beryls are characterized by their alkali-poor to sodic composition, prismatic to columnar habit, homogeneous texture, and the presence of Fe-Al octahedral substitution. In contrast, hydrothermal beryls belong to the sodic to Li-Cs beryl group, with tabular to acicular habit, weak compositional zoning, and channel-tetrahedral substitution. Yamrang garnet belongs to the almandine-spessartine series, while the tourmalines are Mg-Ca rich dravite-schorl to Fe-Mn rich schorl variety. Alkali-poor to Li-Cs beryl with low REE contents, spessartine garnet (spessartine component, Xsps ∼ 52) with high HREE, and schorl with high Ti but low Li, Pb, and REE contents suggests that the Yamrang Pegmatite is an intermediate-fractionated REL pegmatite. Potential pegmatite evolution indicators for IPF include high alkali, Fe, Mn, and Rb contents in beryl, high Xsps in garnet, and an increase in Li, Fe, Mn, Zn, Ga, and Nb, alongside depletion of Mg, Ca, Ti, and Ta in schorl. The identification of a rare metal pegmatite field in the Nepalese Himalaya reinforces the general rare metal mineralization potential of the entire Himalaya region.

Катодолюминесценция конодонтовых элементов

Conodont elements are used as a geochemical archive of seawater. Some compositional features of conodont elements reflect conodont ecology and trophic structure of Palaeozoic pelagic ecosystems. However, the screening of conodont elements prior to geochemical and/or isotopic studies is a real problem. This study evaluates SEM cathodoluminescence (SEM-CL), which is very sensitive to the REE and Mn content of apatite, for the detection of traces of secondary transformation in the composition of conodont bioapatite. The SEM-CL of conodont elements is similar to that of unaltered shark teeth (blue-violet), but differs significantly from that of fossil vertebrate teeth (orange-red). Thermal alteration has little effect on the SEM-CL. Elements with a CAI of 1—1.5 show a redder and more intense CL than elements with a CAI of 5. In the case of corrosion of the conodont element surface in carbonate host rocks, the CL of the outer parts of the conodont element become reddish due to invasion of the carbonate material. Conodont elements from the clay host rock show deep purple SEM-CL. Thus, SEM-CL allows detection of the results of secondary processes in conodont mineralised tissues, including enrichment by REE and/or Mn, corrosion and contamination by carbonate material. This method can be used to screen significantly altered samples prior to chemical and isotopic analyses.