Fluorite Samples Research Articles

Optically Stimulated Luminescence (OSL) characteristics of four fluorite samples under green light stimulation

This study investigates the OSL properties of four natural fluorite color varieties (green, purple, blue-yellow banded and yellow) under green light stimulation. Thermoluminescence reveals two peaks, with the green sample showing the strongest glow. OSL exhibits a fast initial decay followed by a slower one, with phototransfer observed in purple and yellow. OSL intensity is linear with dose (1-30 Gy) for most samples, except yellow. Curve fitting using a first order kinetics model suggests multiple OSL components (between 3 and 5). Preheat treatment at 100°C increases the very fast components (thermal transfer). Anomalous fading shows rapid initial decay followed by a slower one.

Spectroscopic characterization of fluorite of Amba Dongar, Gujarat, India: Linking chemical composition with color

This work addresses the long-standing debate surrounding the origin of color variation in fluorite (CaF2) through a novel quantitative approach. By examining eight carefully selected fluorite samples having different hue of colors from the Amba Dongar mine in Gujarat, India, a rigorous quantitative analysis was conducted. This approach combined chemical compositional data and optical spectroscopic features to elucidate the relationship between elemental composition, concentration, and color variation in fluorite. Precise elemental concentration data for trace transition metals, alkali metals, and rare earth elements (REEs) were obtained through inductively coupled plasma mass spectroscopy (ICP-MS) analysis of powdered fluorite samples. Optical spectroscopic techniques, including UV–visible absorption, emission (photoluminescence and fluorescence), and Raman spectroscopy, were employed to capture characteristic spectral signatures for specific color of the study sample. The work unveils a strong correlation between specific elemental concentrations and observed spectral features, particularly influenced by alkaline metals, transition group elements, and REEs. Fluorite’s optical absorption behavior lacks a clear pattern in UV and infrared wavelength ranges but correlates well with transition metal, alkaline element, and REE concentrations in visible wavelength regions, influencing coloration. Luminescent centers in the study fluorite samples correspond to specific REE concentrations, indicating a strong linkage between emission wavelengths with the presence of specific REE. UV–visible and fluorescence in fluorite result from trivalent REE or Eu2+ ions, with emission intensity affected by REE concentration and specific REE or combinations thereof. Raman spectroscopy identifies characteristic modes related to F-substitution and REE impurities, providing insights into fluorite’s structural composition. This quantitative correlation between elemental composition and spectroscopic characteristics represents a novel contribution for understanding color variation mechanisms in fluorite. The comprehensive analysis of this present work underscores the intricate interplay of mineral composition, and element concentration particularly alkaline metals, transition group elements, and REEs, for variation in spectral signatures with variation in fluorite’s visual attributes.

Case study of fluorite mineralization using traditional and laser spectroscopic techniques, homret akarem area south eastern desert, Egypt

Green fluorite samples from Homret Akarem, eastern desert Egypt, were investigated by laser-based Raman spectroscopy to study the effect of rare earth elements (REEs) and natural radiation from the surrounding environment on their physico-chemical properties, taking into consideration the geological setting. Geochemical data of trace elements display fluorite enrichment with Y, Pb, Sr, Sn, and other REEs. XRD showed lattice parameters with values higher than those for synthetic fluorite due to the substitution of Ca by Sr and less likely by radiation from U. A considerable shift in the binding energy (BE) for Ca and F obtained from the XPS spectrum indicates that U carried by the hydrothermal solutions formed a discontinuous thin film on the surface of fluorite. Laser-Raman spectroscopy showed strong peaks below 500 cm−1 and both shallow and weak peaks above 500 cm−1. The strong peaks indicate that the substitution of Ca by Sr, point defects, and natural radiation caused by U have a stronger effect on the crystal structure than REEs. Raman spectroscopy supported the initial reports of uranium minerals like Rutherfordine, Kasolite, Soddyite, and Uranophane-alpha.

Fluid Evolution of Greisens from Krupka Sn-W Ore District, Bohemian Massif (Czech Republic)

The Sn-W ore deposits in the Krupka surroundings are associated with greisens, which occur in the upper parts of Late Variscan granitoid intrusions. Fluid inclusions were studied in samples of quartz, cassiterite, apatite, fluorite, and topaz in greisenized granites, greisens, and hydrothermal veins with Sn-W mineralization. The greisenization process took place at temperatures 370–490 °C and pressures 155–371 bars, and associated fluids had predominantly low salinity and a low gas (CO2, N2 and CH4) content. The post-greisenization stage was connected with the formation of (i) low-salinity (0–8 wt. % NaCl eq.) fluid inclusions with homogenization temperatures <120–295 °C and (ii) high-salinity (18 to >35 wt. % NaCl eq.) fluid inclusions with homogenization temperatures 140–370 °C, often containing trapped crystals of quartz, topaz, and sulfides, or daughter crystals of salts and carbonates, which were identified by microthermometric measurements, electron microprobe analysis, and Raman spectroscopy. Analyses of fluid inclusion leachates have shown that Na and Ca chlorides predominate in fluids. According to hydrogen stable isotopes, the source of greisenizing and post-greisenizing fluids was not only magmatogenic but also meteoric water or fluids derived from sedimentary rocks.

Geochemical and Isotopic Compositions of Fluorites from the Yama Fluorite Deposit in the Qilian Orogen in Northwest China, and Their Metallogenic Implications

The Yama area is characterized by numerous large-scale fluorite–quartz veins that are located along faults within the widespread Late Devonian–Late Silurian syenogranites in the Tataleng granitic batholith, Qilian Orogen, Northwest China. These fluorite–quartz veins contribute to an important fluorite reserve, but their ore genesis remains unresolved so far. In this study, trace elements, rare earth elements (REEs), and hydrogen, oxygen, and strontium isotopic compositions of fluorites are analyzed. The studied fluorite samples have similar chondrite-normalized REEs, including Y patterns, with relatively strong enrichment in heavy REEs, negative Eu anomalies, strongly positive Y anomalies, and comparably invariable Y/Ho ratios of 41.43–73.79, suggesting a unique hydrothermal genesis. The relatively variable values of δD and δ18O are −77.4‰ to −102.4‰ and −12.7‰ to −4.3‰, respectively, close to the meteoric water line. These fluorites yield relatively invariable analytical 87Sr/86Sr ratios of 0.749089−0.756628 (except for an anomalously high ratio), and their calculated initial 87Sr/86Sr ratios, based on the ore-forming ages provided, are apparently higher than the calculated initial 87Sr/86Sr ratios of syenogranite wall rocks. Collectively, the geochemistry of trace elements, REEs, and stable isotopes (H, O, and Sr) suggests that the ore-forming fluids were of meteoric origin and that the Sr sources were directly derived from the ore-forming fluids themselves rather than syenogranite wall rocks. Finally, it was considered that the Yama fluorite deposit is a fault-controlled hydrothermal vein-type deposit which was possibly related to the evolution of the Paleo-Tethys Ocean in the Permian–Triassic.

Uranium in Fluorite, a Case Study: The La Azul Fluorspar Deposit, Taxco, Guerrero, Mexico

Uranium can be found in the Earth’s crust in different reservoirs, with igneous rocks being the primary source of this element from which many types of secondary deposits are formed. Fluorspar deposits generally do not contain uranium, but in some cases, fluorite can carry both uranium in solid solutions and inclusions of uranium minerals. We studied the concentration (ICP-MS), composition (electronic microprobe), and spatial distribution (microscopy and auto-radiography) of elemental uranium and uranium minerals at different scales (microscopy and auto-radiography in fluorite from the La Azul fluorspar deposit (Taxco, Mexico) to assess the origin of uranium and its significance in this ore deposit. Auto-radiography images with the CR-39 detector were found to be impressive in their ability to elucidate uranium distribution at the millimeter scale. The limit between the solid solution of elemental uranium in natural fluorite and the appearance of uranium oxides as inclusions appeared to be between 20 μg g−1 and 40 μg g−1 bulk uranium concentration in this fluorspar ore. The maximum concentration of U in fluorite from the La Azul deposit was about 100 μg g−1. Using Raman spectroscopy and microprobe analysis, we identified the micro-inclusions of uranium minerals as uraninite (of the pitchblende variety); its composition suggested a hydrothermal origin for this fluorspar deposit. We also calculated a chemical age that can be compared with the previously published regional geology and isotopic (U-Th-Sm)/He ages in fluorite. Micro-thermometric studies of fluid inclusions were carried out in different samples of uranium-rich fluorite to identify the nature and origin of the mineralizing fluid and the precipitation mechanisms of uranium minerals. We concluded that the uranium-rich fluorite precipitated in the initial phases of mineralization from a reducing fluid, with low salinity (<8% NaCl eq.) and an intermediate temperature (110–230 °C), and that the presence of organic compounds and sulfides (mainly pyrite) favored the simultaneous precipitation of uraninite (pitchblende variety) and fluorite.

Laser-Induced breakdown spectroscopy and Energy-Dispersive X-ray analyses for green mineral fluorite (CaF2)

Laser-induced breakdown spectroscopy (LIBS) technique was utilized to investigate the green mineral fluorite (CaF2) samples. The LIBS experiment was implemented by using Nd: YAG Laser system and a linear array CCD detector coupled with an Avantes spectrometer in an air atmosphere. The emission spectra of ten various fluorite samples were studied. The molecular bands correspond to the green B2Σ+-X2Σ+ and orange A2Π-X2Σ systems of diatomic CaF-molecule, specifically at Δν = -1, 0, +1 sequences and the CaO diatomic molecule between 618 nm and 630 nm were detected. It was observed that the CaF-diatomic molecular emission bands exhibited stronger optical emission compared to the fluorine (F) atomic lines. Chemical composition (wt.%) analysis was acquired using CF-LIBS methodology under optically thin and local thermodynamic equilibrium (LTE) conditions. Our CF-LIBS studies revealed that Ca (50–60%) and F (30–40%) were the major elements, while C (3–5%) and O (2–5%) were minor elements present in all samples. For comparison, we employed energy-dispersive X-ray (EDX) technique to study the essential elemental composition (wt.%). The results achieved from CF-LIBS were found to be in good agreement to that obtained from the EDX technique. To validate CF-LIBS results, the calibration curve method was employed using the validated samples (S3, S5, and S7). Furthermore, we utilized a principal component analysis (PCA) technique on the LIBS spectral data to classify the fluorite samples.

Infrared emission from calcium fluoride anion defects observed in synthetic material and natural fluorites

Fluorine-based defect structures in calcium fluoride have previously been shown to emit visible-spectrum fluorescence when excited by UV light. This work shows the behaviour of a new fluorescence centre emitting in the near infrared at 1100–1200 nm when excited by visible light. This emission was most readily observed in natural fluorite samples, which have structural defects due to a long term exposure to environmental radiation, but was also induced in a synthetic calcium fluoride sample using intense UV light. Excitation of the near infrared emission reaches a maximum near the previously reported F-centre aggregate absorption peak. Emission is also “recharged” when excited by photons matching the fluorine interstitial migration energy. The measurement of this fluorescence could be used to monitor defects in optical grade fluorite caused by high power lasers and could also have applications in fluorite mineral detection during mining operations. Potential resetting of these optical defects is additionally discussed.

Fluid Inclusions and REE Geochemistry of White and Purple Fluorite: Implications for Physico-Chemical Conditions of Mineralization; an Example from the Pinavand F Deposit, Central Iran

The Pinavand fluorite deposit is hosted by lower Cretaceous carbonate rocks in the structural-geological transitional zone of Central Iran. The purple and white fluorite occur, respectively, as early replacement masses and late cross-cutting veins. Both fluorites have different and distinct physicochemical characteristics. The purple fluorite has higher homogenization temperatures of fluid inclusions (170–260 °C) and lower ∑REE (1.6 ppm) and Y (1.3 ppm) than the white variety (90–150 °C, 11.12 ppm, and 21.3 ppm, respectively). All fluorite samples show positive Y anomalies (Y/Y*) in the range of 1.15–3.5. The average values of La/Ho in the purple and white fluorites are 23.1 and 3.4, respectively. The purple fluorite samples have lower Y/Ho values (an average of 63.45) than the white fluorite samples (an average of 87.64). The Tb/Ca ratio in the Pinavand fluorites ranges between 0.0000000348 and 0.00000105, and the Tb/La ratio varies between 0.01 and 0.4; these values suggest that both fluorite types are “hydrothermal” in origin. The purple fluorites have a lower Sr and a negative Eu anomaly. These differences in concentrations and ratios of various REE suggest that the physico–chemical conditions of mineralization changed during fluorite deposition at the Pinavand. These changes correspond to an increase in oxygen fugacity and pH, which occurred during white fluorite mineralization at lower temperatures. The δ34S values of the Pinavand barite samples (an average of 23.25‰) are similar to those of seawater sulfate in the upper Proterozoic. The δ34S values of galena range from −0.2‰ to −3.7‰, compatible with bacterial sulfate reduction (BSR). These features are similar to those in the hydrothermal and magmatic deposits.

Lanthanide and yttrium substitution in natural fluorite

Fluorite is one of the most common minerals in the crust and is of widespread economic importance. It shows strong UV-excited luminescence, variously attributed to defects within the fluorite structure and lanthanide substitutions. We present here a detailed chemical characterisation of a suite of natural fluorite samples, chosen to represent the range of compositions observed in nature. We perform X-ray excited luminescence spectroscopy on the samples as a function of temperature (20–673 K) in the wavelength range 250–800 nm to provide insights into physical defects in the lattice and their interactions with lanthanide substituents in natural fluorite. Most broad bands in the UV are attributed to electronic defects in the fluorite lattice, whereas sharp emissions are attributed to intra-ion energy cascades in trivalent lanthanides. Lanthanides are accommodated in fluorite by substitution for Ca2+ coupled with interstitial F−, O2− (substituting for F−) and a variety of electronic defect structures which provide local charge balance. The chondrite-normalised lanthanide profiles show that fluorite accommodates a greater proportion of heavy lanthanides (and Y) as the total Rare Earth Element (REE) concentration increases; whereas cell parameters decrease and then increase as substitution continues. Luminescence intensity also goes through a maximum and then decreases as a function of REE concentration. All three datasets are consistent with a model whereby lanthanides initially act as isolated centres, but, beyond a critical threshold (~ 1000 ppm), cluster into lanthanide-rich domains. Clustering results in shorter REE-O bond distances (favouring smaller heavier ions), a larger unit cell but more efficient energy transfer between lanthanides, thereby promoting non-radiative energy loss and a drop in the intensity of lanthanide emission.

Mineralogical and Structural Analyses of Natural Fluorite from Yantuwaru Mining Site, Nigeria

Experimental studies of natural fluorite have been reported. In this study, combined X-Ray Fluorescence, FTIR and UV-Vis analyses were performed to give mineralogical information about natural fluorspar. The X-ray diffraction technique was also used to determine the crystallographic parameters and structure of the mineral. Results show a variation of Ca contents and low concentration of F, through all fluorite samples due to Ba and Br contents in the samples, causing replacements of impurity ions in the fluorite lattice. REEs in the fluorite samples were to be found responsible for colour. UV-Visible absorption results showed peaks between 209 to 368 nm, which did not affect the fluorite colour. The 224 nm and 365 nm peaks were caused by the electrons and holes trapped in the Ca2+ interstitial and vacancy, respectively. The absorption bands in the visible range relate to the corresponding fluorite samples. The FTIR results showed absorptions causing CO2 and CO32-stretching vibration due to the CaCO3 and OH stretching vibration due to water in the samples. The structural configuration, the lattice parameters, and the planes confirmed a cubic structure. Obtained results confirmed them to be Calcium Fluorite, as expected.

Implications for the contribution of Pacific plate subduction to fluorite mineralization in southeast China: Evidence from Nanzhou large fluorite deposit, Fujian province

In SE China, there are numerous Mesozoic igneous rocks and a tectonically active area known as the Wuyi Fluorite Mineralization Belt. The Nanzhou fluorite deposit can effectively represent most hydrothermally filled fluorite deposits strictly controlled by the fault zones. These were mainly trending NE, NNE, followed by NW, and nearly EW. It is the epitome of fluorite mineralization in the Wuyi fluorite metallogenic belt, which can provide clues for the subduction of the Mesozoic Pacific plate to the Eurasian plate. As the surrounding rocks of the Nanzhou fluorite ore bodies, the zircon U-Pb isotopic age of the Anjiang syenogranite is 147±1 Ma, while the biotite plagioclase granulite of the Xiafeng Formation in the Wanquan group is 817±3 Ma and 811±3 Ma. However, fluorite is of hydrothermal origin. It yields an Sm-Nd isochron age of 103.8±5.0 Ma and an Rb-Sr isochron age of 106±15.0 Ma, more than c.a. 40 Ma younger than the Anjiang Syenogranite, indicating fluorite is a product of late hydrothermal mineralization. The right-leaning REE distribution curves of most fluorite samples are similar to those of Yanshanian Anjiang syenogranite and biotite plagioclase granulite of the Xiafeng Formation, which indicates that fluorite is closely related to the surrounding rocks. Most fluid inclusions in fluorite have salinities of 0.5–2.24 wt% NaCl eqv and low homogenization temperatures of 140–200 °C. The inclusions include a NaCl-H2O system with δDV-SMOW between −79.7 to −77.6‰ and δ18OV-SMOW values range from 0.4 to 2.1‰. The (87Sr/86Sr)i ratios of the fluorite, which are between 0.717427 and 0.719482, are characteristic of a crustal contribution. Based on the above description, the mineralized fluid of Nanzhou fluorite deposit belongs to the NaCl-H2O system with medium-low temperature and low salinity, which is obviously different from the magmatic hydrothermal fluid. In addition, the age of fluorite mineralization is younger than that of igneous rocks by ca. 40 Ma, so they are not correlated. It is proposed that the ore-forming fluid may be involved in atmospheric precipitation and circulate within the northeastward fault with increasing geothermal gradient to form Nanzhou-fluorite deposit. The Nanzhou-fluorite deposit was formed in 103.8±5.0 Ma and 106±15.0 Ma, which corresponds to the plate subduction and rollback period of the Late Cretaceous (in ca. 110–70 Ma). The formation of the Nanzhou deposit has important implications for the subduction of the Pacific plate to the Eurasian plate.

Ultra-fast high-temperature sintering (UHS) of Ce0.2Zr0.2Y0.2Gd0.2La0.2O2−δ fluorite-structured entropy-stabilized oxide (F-ESO)

Single-phase high entropy fluorite (Ce0.2Zr0.2Y0.2Gd0.2La0.2O2−δ) samples were synthesized by co-precipitation and consolidated by ultrafast high-temperature sintering (UHS) in less than 2 min. The chemical homogeneity of the sintered materials was confirmed by X-Ray Diffraction (XRD), Energy Dispersive X-ray Spectroscopy (EDXS), high-resolution EDXS using Transmission Electron Microscopy (TEM), and Raman spectroscopy. Compared to conventional sintering, UHS of high entropy ceramics was a hundred times faster and it resulted in highly dense microstructures (relative density > 93%) with nanometric grains. Ce0.2Zr0.2Y0.2Gd0.2La0.2O2−δ densified under an UHS current of 20–25 A. An optimized step-wise UHS schedule was proposed to obtain dense, single-phase pellets with a reduced amount of defects. The extreme heating rates were found beneficial to limit grain coarsening and to obtain a single phase.

불소 오염토양의 기원별 오염특성을 파악하기 위한 광물학적 특성분석 및 세척효율평가

In this study, mineralogical characteristics analysis and extraction characteristics evaluation were performed to identify the contamination characteristics by origin of fluoride-contaminated samples of natural origin by granite mica and artificial fluoride-contaminated samples by waste gypsum fluoride of making fertilizer process. In samples of natural origin, mica, quartz, feldspar, fluorite, and amphibole showed the high mineral content in the order. Among them, mica, which is expected to be the causative mineral of fluorine contamination, consisted of muscovite, biotite, and lithium mica. In artificial fluoride-contaminated samples, quartz, plagioclase, illite, gypsum, sulfur, and wollastonite showed the highest mineral content in the order. Compared to the total mica content and fluorine concentration of the natural origin contaminated sample, a proportional linear relationship(R2=0.68) was shown, and this result is estimated to be the influence of natural origin by minerals in badlock not artificial contamination. When compared with the gypsum content and fluorine concentration of the artificially contaminated samples, a proportional linear relationship(R2=0.79) was shown, and the fluoride concentration was found to exceed the standard in all samples with a gypsum content of about 20 % or more. As a result of the washing efficiency test for each mica fluoride-contaminated sample, it was confirmed that the washing efficiency was relatively low with all washing agents less than 10 %, and hydrochloric acid(HCl) had the highest washing efficiency. In addition, the optimal hydrochloric acid(HCl) concentration was confirmed to be 1 M. As a result of the washing efficiency test for each washing agent for the fluorine-contaminated sample of a fertilizer factory, sodium hydroxide(NaOH) was confirmed to have the highest washing efficiency and showed about 1.5 times higher than hydrochloric acid(HCl). In addition, the optimal concentration of sodium hydroxide(NaOH) is judged to be suitable at 0.5 M, which showed a washing efficiency of 65.6 %. Based on the results of this study, it is intended to be used as a basic data for the development of soil remediation technology considering the method of proving the cause of fluoride-contaminated soil and the characteristics of contamination by origin.

Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Bismuth oxide kinetically stabilized by doping with a metastable structure of disordered fluorite ?-Bi2O3 has a unique conductivity. Oxygen selective membranes at intermediate temperatures ~550?C, on the base of cermet ?-Bi2O3/Ag, have the highest potential for air separation and can be used to produce oxygen for distributed multigeneration by burning fossil carbon fuels. When searching for the optimal composition of ?-Bi2O3, the degradation of fluorite into a new tetragonal phase was discovered in ceramics synthesized using mechanical activation. The tetragonal phase is formed and exists in a topotaxial composite with the fluorite structure. For a relatively stable over a wide temperature range tetragonal phase with a = 0.3854, c = 0.88905 nm, S.G. P-4, crystal structure and atomic coordinates have been proposed. In samples of fluorite and topotaxial composite, the Raman and M?ssbauer spectra were recorded and discussed. The discovery of a new tetragonal phase of doped bismuth oxide and its existence area makes it possible to optimize the composition and the synthesis of a more stable solid electrolyte ?-Bi2O3 with high conductivity.

Magnetic properties of doped CaF2 powders

Room-temperature “ferromagnetism” found last decades in nonmagnetic nanoparticles is a puzzle that is not solved yet. In this work we report about the observation of room-temperature magnetism in powders of CaF2 doped with CeO2 as well as in the undoped powder but containing small amount impurity. The studied powders were obtained by grinding of bulk crystals using a sapphire mortar with a pestle. Magnetization dependences on magnetic field for the studied powder samples resemble the dependences observed in nonmagnetic oxide nanoparticles like CeO2. The comparative study of bulk and powder fluorite samples unambiguously confirms the key role of surface defects in the observed features. XRD and TEM measurements show that powder samples have particles of different sizes from the micro down to the submicron scale. The undoped bulk fluorite as well as doped with 0.5at.% (two differently grown crystals), 2at.%, 10at.% of CeO2 revealed only diamagnetic or paramagnetic contribution to magnetization curve whereas the powders of the same samples have ferromagnetic-like contribution on M−H curve. This work may help to get new insight in room-temperature “ferromagnetism” phenomenon of nonmagnetic nanoparticles.

Tailoring of thermoluminescent properties and assessment of trapping parameters of natural fluorite samples from Dogargaon fluorite mines, India.

Mineral fluorite or fluorspar (CaF2 ) can host significant quantities of trivalent REE3+ (rare earth element) by substitution with divalent Ca2+ . The fluorites associated with carbonatites are often REE-rich compared to those derived from sedimentary, hydrothermal, or Mississippi Valley-type (MVT) fluorites. The naturally occurring fluorites have several industrial applications one of which is for luminescence. Whether or not REE enriched, the fluorite makes an ideal host for REEs, which are very important phosphors. The naturally occurring fluorites are available in sufficient quantities to cater to the industrial demand. Investigations have been carried out on the fluorites from active fluorite mines at Dongargaon in central India. Thermoluminescence behavior of a natural fluorite sample was investigated using a Nucleonix TL 1009I thermoluminescence reader. Multiple traps formed in the broad thermoluminescent (TL) glow curve were found by TL anal deconvolution software. Trapping parameters for all multiple traps formed on deconvoluting broad TL glow curve were found by different methods like Initial rise method, Chen's Peak shape method and Ilich method.

Microanalysis and signature of rare earth elements in geochemical samples using neutron activation analysis

Abstract Nuclear techniques are applied for exploration and efficient tapping of natural resources in finding promising resources of mining and mineral processing industries. The rare earth elements (REEs) in four fluorite samples, collected from Nuba Mountains are determined using neutron activation analysis (NAA) technique. The concentration of 11 REEs (Sc, La, Ce, Nd, Sm, Eu, Gd, Dy, Tb, Yb, Lu) was measured and found within ranges between 685 and 1747 ppm. The Ca is a major element in the four samples. The Fe, Al, Na, Ba and Sr are found as minor elements in the investigated samples. In addition, tracer levels of U, Th, Cs, V and Sc are also detected. The signature of Ce, La and Nd as light REEs is characterized in all samples under this study. The enrichment types of light-REEs (L-type), medium-REEs (M-type) and several distinct features of some REEs e.g., Ce and Eu anomalies are identified and described as the signature of REEs in the geochemical samples. These results have demonstrated promising materials that could be used for hydrometallurgy processing to get significant amounts of REEs.

Sm–Nd Isochron Age Constraints of Au and Sb Mineralization in Southwestern Guizhou Province, China

Southwestern Guizhou, China, is famous for hosting clusters of Carlin-type Au, Sb, and Hg-Tl deposits. These deposits are thought to be the products of a low-temperature hydrothermal metallogenic event. Calcite and fluorite are common and widespread gangue minerals in Au and Sb deposits, respectively. Ore-related calcite commonly coexists with stibnite, realgar, and orpiment at the periphery of high-grade orebodies in Au deposits, while ore-related fluorite is generally intergrown with stibnite in Sb deposits. In this study, ore-related calcite and fluorite samples from representative Au (Zimudang) and Sb (Dachang) deposits, respectively, were separated, and the rare earth element (REE) concentrations, Sm/Nd isotope ratios, and Sm–Nd isochron ages were analyzed. This study aims to determine the formation ages of the calcite and fluorite and to constrain the age of low-temperature metallogenic event in Southwestern Guizhou. The calcite and fluorite samples contain relatively high total concentrations of REEs (8.21–22.5 μg/g for calcite, 21.7–36.6 μg/g for fluorite), exhibit variable Sm/Nd ratios (0.51–1.01 for calcite, 0.35–0.49 for fluorite), and yield Sm–Nd isochron ages of 148.4 ± 4.8 and 141 ± 20 Ma, respectively. These ages are consistent with the age range constrained by the low-temperature thermochronology of zircon (132–160 Ma), crosscutting relationships of stratigraphy or intrusions (96–160 Ma), and previous dating results (135–150 Ma) in Southwestern Guizhou. Collectively, the ages obtained in this study add new evidence to previous geochronology studies, such that the low-temperature hydrothermal mineralization in Southwestern Guizhou can be constrained to 135–150 Ma, corresponding to the Yanshanian orogeny, which was associated with a weak extensional tectonic environment.

Upconversion Fluorescence in Naturally Occurring Calcium Fluoride.

Fluorine can negatively interfere with leach and smelting processes during mineral processing. Real-time knowledge of the concentration and mineral hosts of fluorine in a mineral processing ore stream is important to protect process line equipment and product. Currently only offline methods of detection are available. Online sensors that determine specific fluorine-bearing mineral concentration in real-time would enable improved efficiency in processing decisions during mine production. Common excitation wavelengths used for fluorescence studies in minerals frequently provide signals that are not clearly host-specific, and hence of limited utility for mineral identification. We show that upconversion fluorescence, a process in which two or more photons are absorbed and one higher-energy photon is emitted, provides a more host-specific fluorescence output, minimizing spurious signals in complex environments and therefore greatly improving detection thresholds. Natural samples of fluorite (CaF2), a major fluorine host at many mine sites, have been analyzed by near-infrared excitation and have revealed upconversion fluorescence from rare earth inclusions. Upconversion fluorescence was detected in samples with rare earth concentrations as low as one part per million and is therefore considered a potential new sensing modality for real-time fluorite monitoring.