Color centers,associated rare-earth ions and the origin of coloration in natural fluorites

Natural colored fluorites were studied by means of optical absorption and electron paramagnetic resonance (EPR). Complex centers involving rare-earth ions and/or oxygen give rise to the various colors observed. These include yttrium-associated F centers (blue), coexisting yttrium and cerium-associated F centers (yellowish-green), the (YO₂) center (rose) and the O ₃ ^? molecule ion (yellow). Divalent rare-earth ions also contribute to the colorations, as for instance Sm³⁺ (green fluorites), or they are at the origin of strong fluorescence observed (Eu²⁺). Strong irradiation of the crystals with ionizing radiation leads to coagulation of color centers, and to precipitation of metallic calcium colloids. There is probably no simple relation connecting the coloration and the growth process of the crystal. Thermal stability studies, however, have allowed to partially classify the colors as being of primary or secondary origin.     

Stabilisation of divalent rare earth elements in natural fluorite

Summary ?The occurrence of divalent rare earth elements (Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺) in natural fluorite is evaluated using a suite of 37 samples deriving mainly from Sn–W deposits in the Erzgebirge (Germany), Central Kazakhstan, and the Mongolian Altai. Trace element composition was determined by ICP-AES and ICP-MS. The defect structure of the samples was studied by cathodoluminescence (CL), electron paramagnetic resonance (EPR), and optical absorption spectroscopy. Reduction of cubic Sm³⁺, Yb³⁺, Tm³⁺, and Ho³⁺ under radioactive irradiation produces the corresponding divalent centres. Our data suggest a preferable formation of Sm²⁺ and Yb²⁺ under thorium and of Tm²⁺ and Ho²⁺ under uranium irradiation. Irradiation (indicated by intense brownish (thorium) and deep purple (uranium) coloration of fluorite) gives rise to a population of divalent centres in equilibrium with their decay. However, sporadic radioactive irradiation and stabilisation of the divalent state of the REE by other electron defects were found in most cases. Three models of stabilisation of Sm²⁺, Yb²⁺, Tm²⁺, and Ho²⁺ are discussed. The most effective mechanism for Sm, Yb, Tm, and Ho is coupling with Fe³⁺ centres (REE³⁺+Fe²⁺ → REE²⁺+Fe³⁺). Accordingly, the occurrence of Fe³⁺ centres in natural fluorite is regarded to indicate not an oxidising, but rather a reducing environment during fluorite precipitation. Originally incorporated in the divalent form, Fe²⁺ was converted to Fe³⁺ by radioactive irradiation. Such a conclusion is in agreement with the finding of high contents of interstitial fluorine providing tetragonal local compensation of trivalent REE centres in crystals with high Fe³⁺. If Fe is not present, compensation of divalent Sm, Yb, and Tm is achieved by radiogenic oxidation of Ce(Pr, Tb)³⁺ accompanied by charge transfer (REE³⁺+Ce(Pr, Tb)³⁺ → REE²⁺+ Ce(Pr, Tb)⁴⁺). Ho²⁺ is sometimes stabilised by a hole trapped by an electron localised on a F vacancy (Ho³⁺+e⁻ on □_F → REE²⁺+ self-trapped exciton). Because Sm²⁺ is optically active, the stabilisation by Fe³⁺ (stable up to temperatures above 350 °C) or Ce(Pr, Tb)⁴⁺ (unstable even under visible light) in samples may be determined by careful observations in the field. Institut für Geotechnik, ETH Zürich, ETH-H?nggerberg, Zürich, Switzerland Stanford Linear Accelerator Center, Menlo Park, CA, USA Received January 8, 2002; revised version accepted June 10, 2002     

Temperature dependence of photoluminescence emission characteristics in a natural fluorite

Summary The temperature dependence of photoluminescence emission of a natural fluorite has been studied in the wavelength region of 380–500 nm and in the temperature range of 17.5–300 K. The emission spectra of the sample show a broad emission band between 380 and 500 nm for temperatures above 100 K. At 100 K and below, vibronic lines appear on the emission band at approximately 413.3, 418.1, 419.3, 420.2, 423.9 and 427.1 nm. This broad emission band and the vibronic lines in fluorite are usually associated with phonon-coupled electronic transitions from 4f⁶5d to 4f⁷ in the Eu²⁺ ion. Temperature dependences of the peak energy, intensity and full-width at half-maximum of the broad emission band are discussed, and the behaviour explained in terms of a configurational coordinate model. The excited state vibrational energy was obtained to be 0.023 ± 0.001 eV and this is lower than the LO phonon energy of 0.062 eV in pure fluorite. The activation energy of thermal quenching of the photoluminescence intensity was found to be 0.022 ± 0.002 eV.     

Photoluminescence properties of green and red luminescence from natural and heat-treated sodalite

The sodalite sample used in this investigation did not exhibit the characteristic orange-yellow luminescence due to the $ {\text{S}}_{ 2}^{ - } $ center, because there was no trace of sulfur impurity. The heat-treated samples exhibited green and red luminescence with maximum intensity at 496 and 687 nm, respectively, under 264 nm excitation at room temperature. Their luminescence intensities were extensively dependent on the treatment temperature. The green luminescence efficiency of the sample heat-treated at 900 °C was 6.5 times higher than that of unheated natural sodalite. At 8.5 K, the green luminescence showed a vibronic structure. After heating at 1,300 °C, the crystal structure of sodalite was transformed to NaAlSiO₄ (carnegieite), and the intense red luminescence was exhibited in the NaAlSiO₄ sample. The peak wavelength of the red luminescence shifted from 687 nm at 300 K to 726 nm at 8.5 K. The luminescence lifetimes of the green and red luminescence at room temperature were 2.1 and 5.1 ms, respectively. It was proposed that the origin of the green luminescence is Mn²⁺ replacing Na⁺, and that of the red luminescence is Fe³⁺ replacing Al³⁺ in sodalite or NaAlSiO₄ (carnegieite).     

FTIR spectroscpy of natural fluorite from Ambadongar, Gujarat

The principal aim of this study is to examine the presence of structural water in the form of a hydrous ion (OH-) in fluorites of Ambadongar, Gujarat. Several recent spectroscopic studies indicate that in addition to molecular water in fluid inclusions of fluorite, structurally bound water may occur as H₂O and OH species in hydrothermal fluorite. To further clarify this effect, a FTIR study has been carried on hydrothermal fluorite samples from Ambadongar. The analysis were carried out at room temperature as well as 250°C on powdered samples of yellow, blue-green, blue and colourless fluorites. FTIR spectroscopic measurements of all the fluorites show a broad absorption band between 3439–3410 cm^?1 corresponding to bond of O-H stretching vibration indicating the presence of structurally bound water in all fluorites. This structural water in variable amount as different hydrous species associated with other impurity may act as an energy absorbent in the crystal and production of colour in fluorites. From field study of fluorite veins the colour was determined as blue and purple, which, are commonly inter layered, followed by white, finally yellow and colourless varieties.     

Synchrotron-excited luminescence of natural zircon

The luminescence properties of two single zircon crystals from kimberlite of Yakutia have been studied, excited by the DORIS HASYLAB synchrotron, Germany, within energy range from the visible to the soft X-ray region (5–25, 50–200, and 500–620 eV) at temperatures of 300 and 10 K. The luminescence spectra in the range of 2.5 to 6.0 eV and excitation spectra of the main bands have been examined, the physical nature of the luminescence centers has been discussed, and the luminescence properties of a crystal containing growth (radiation) structural defects and a crystal with the same impurities but annealed in air at 1200°C are compared. The zoned structure of the mineral has been considered and the value of the energy gap (E _g) in the mineral has been estimated at 7.1 eV. Two groups of luminescence bands caused by impurities of intrinsic (growth, radiation) nature (E _max = 2.1, 2.7–2.8, and 3.2–3.3 eV) and matrix luminescence (E _max = 4.4−4.7 and 5.4 eV) probably with the participation of excitons were distinguished on the basis of selective excitation of zircon with different synchrotron energies relative to the gap value (E _excit < E _g, E _excit ∼ E _g, and E _excit ≫ E _g). The short-lived component with a response time of 4 ns has been revealed in the afterglow of zircon in the region of 5.4 eV.     

Laser-induced time-resolved luminescence as a tool for rare-earth element identification in minerals

 We have determined and distinguished a number of rare-earth elements in several minerals by use of laser-induced time-resolved luminescence spectroscopy. Unlike the conventional measurement of steady-state luminescence, the method allows discrimination between ions that emit in the same spectral range but have different decay times. The main new results are the following: decay time data for all REE luminescence centers; Tm³⁺, Pr³⁺, Er³⁺, Ho³⁺ luminescence in apatite, scheelite, zircon, calcite, and fluorite; Eu³⁺ luminescence in apatite, zircon, fluorite, calcite, danburite, and datolite. Received: 17 April 2000 / Accepted: 4 January 2001     

Luminescence properties of Pr3+ and Sm3+ ions in natural apatites

The luminescence spectra of Pr³⁺ and Sm³⁺ ions in apatite Ca₅[F∣(PO₄)₃] crystals from Spain and Russia have been compared with those for phosphate glasses doped with Pr³⁺, Sm³⁺ and Pr³⁺, Sm³⁺ ions. Time-resolved spectra measurements confirm that, in apatites, samarium ions occupy two non-equivalent crystal sites; the same is assumed for praseodymium ions. For the first time in minerals, the Stark splitting energy levels ΔE for ³H₆ and ¹D₂ of Pr³⁺ ion and ⁶H_7/2 of Sm³⁺ ion were determined. Some small differences in ΔE values for the Spanish and Russian apatite are discussed. The decay times of the excited levels of Pr³⁺, Sm³⁺ and Pr³⁺, Sm³⁺ doped in phosphate glass were measured at room temperature and at 77 K. The energy transfer process between samarium and praseodymium ions was observed and the energy transfer rate was calculated.     

萤石中氟化钙的测定

应用电感耦合等离子体发射光谱法(ICP-OES)测定萤石中钙的含量,经标准物质验证,方法准确度和精密度较高,萤石矿物标准物质中氟化钙的测定值与认定值相符,相对标准偏差小于1%。与传统EDTA滴定的分析方法相比,本法操作简单、快速,适合萤石矿中氟化钙含量的测定。     

The nature of red luminescence of natural benitoite BaTiSi3O9

Summary This work examines the red luminescence of benitoite studied by laser-induced time-resolved luminescence spectroscopy. This method allows the differentiation between luminescence centers of similar emission wavelengths, but different decay times. We have also examined the luminescence intensity and decay time as a function of temperature. We found that the red emission of benitoite consists of two individual bands and one line and suggest that the activators of luminescence in benitoite system are Ti³⁺ and a d³ element, namely Cr³⁺ or Mn⁴⁺.     

中国萤石矿床分类

通过对中国萤石矿床的成矿作用研究,综合考虑萤石矿床的成因类型和工业类型,将中国萤石矿床划分为沉积改造型、热液充填型和伴生型3种矿床类型。在全面分析萤石矿典型矿床的成矿条件、控矿因素和成矿作用的基础上,总结成矿要素,以相同或相似的二级成矿必要要素组合确定沉积改造型、热液充填型萤石矿床的亚类型,沉积改造型进一步划分出2个矿床式,热液充填型划分出5个矿床式,伴生型按伴生主矿种划分出4个矿床式。文章分析了每一个矿床式的成矿地质背景,成矿条件、矿床特征、控矿因素和成矿作用,总结了每一个矿床式的二级成矿必要要素。     

浙江青田县万山萤石矿矿床地质特征及成因

浙江青田县万山萤石矿成矿作用主要由地热水浅循环伴含氟成矿流体,在特定的物理化学条件下,沿有利的构造空间富集成矿,属低温热液充填型脉状矿床.矿体矿石、矿物组分比较简单,矿石矿物为萤石,脉石矿物以石英为主,次为蛋白石、高岭石、黄铁矿、方解石、绿泥石等.矿石主要化学成分为CaF2和SiO2,矿石中SiO2、CaF2二者总量约占97％～99％.随着CaF2含量的增加,SiO2含量减少.     

萤石矿自然重砂矿物组合规律及其找矿意义

为探究不同类型的萤石矿所反映的自然重砂矿物组合所携带的对各类型萤石矿的指示特征,统计了浙江、湖南、湖北、青海、广西、福建、安徽、新疆、甘肃、河北共计10个地区23个典型萤石矿床的自然重砂矿物报出情况,计算各重砂矿物报出率,分析得出热液型矿、后期热液型及热液充填型3种类型萤石矿床各自对应的自然重砂矿物组合和标型矿物组合。结果显示,各类型矿床自然重砂矿物组合既有相同之处也有显示各自的特点。因此,按照矿床类型建立的自然重砂矿物组合及其含量变化,对于新一轮的矿产资源勘查具有重要的意义。     

The significance of metamorphic fluorite in the Adirondacks

Thermodynamic calculations for selected silicate-oxide-fluorite assemblages indicate that several commonly occurring fluorite-bearing assemblages are restricted to relatively narrow fields at constant P?T. The presence of fayalite-ferrohedenbergite-fluorite-quartz ± magnetite and ferrosalite-fluorite-quartz-magnetite assemblages in orthogneisses from Au Sable Forks, Wanakena and Lake Pleasant, New York, buffered fluorine and oxygen fugacities during the granulite facies metamorphism in the Adirondack Highlands. These buffering assemblages restrict$\text{?}{}_{\mathrm{F}}{}_2$ to 10^{?29 ± 1} bar and $\text{?}{}_0{}_2$ to 10^{?16 ± 1} bar at the estimated metamorphic temperature of 1000K and pressure of 7 kbar. The assemblage biotite-magnetite-ilmenite-K-feldspar, found in the same Au Sable Forks outcrop as the fayalite-fluorite-ferrohedenbergite-quartz-magnetitie assemblage, restricts H₂O fugacities to less than 10^3·3 bar. These fugacities limit H₂ and HF fugacities to less than 10¹ bar for the Au Sable outcrop. The data indicate that relative to H₂O, O₂, H₂, F₂ and HF are not major species in the fluid equilibrated with Adirondack orthogneisses. The calculated F₂ fugacilies are similar to the upper limits possible for plagioclase-bearing rocks and probably represent the upper $\text{?}{}_{\mathrm{F}}{}_2$ limit for metamorphism in the Adirondacks and in other granulite facies terranes.     

Physicomechanical properties of cryptocrystalline fluorite from the Suran deposit, southern Urals

Microhardness (H) and fracture toughness (K _1C) have been studied for the main varieties of shock-resistant cryptocrystalline fluorite, a natural ceramic widespread at the Suran deposit. Suran cryptocrystalline fluorite (SCF) is characterized by high fracture toughness (K _1C), which is 2–5 times higher than K _1C of common fluorite monocrystals. The relationship between K _1C and microhardness H is complex and nonlinear. The SCF varieties from the sellaite-fluorite orebody are distinguished by the highest K _1C = 1.9–2.3 MPa m^1/2, which exceeds K _1C = 0.84 MPa m^1/2 of porcelain-like fluorite from the main fluorite orebody. Qualitative and quantitative variations of structural point defects in the studied samples exert a much stronger effect on microhardness than on fracture toughness, which mainly depends on the size of crystallites, their mutual crystallographic orientation, and the structure of intergranular boundaries, i.e., on the parameters seemingly related to recrystallization and/or twinning of fluorite. In general, the nature of the Suran deposit of fluorite ceramic with unusual physicomechanical properties remains a geological puzzle in many respects.     

A study of inclusions in fluorite from the Shuangjiangkou-Jiangjunmiao fluorite ore deposit in Hunan Province

The Shuangjiangkuo-Jiangjunmiao fluorite ore deposit occurs in Early Yenshanian granites in the fold system of south China. The average homogenization temperature of inclusions in fluorite is 250°C. The contents of CO₂ and CH₄ in the inclusions tend to increase from southeast to northwest as well as in the vertical direction. Liquid in the inclusions is composed mainly of CaO, F and Cl with minor SO ₄ ² . All this has contributed a lot to the formation of fluorite as well as to wall-rock alteration. This ore deposit is evidenced to be mesothermal in origin.     

湖南省萤石矿成矿地质特征及成矿带划分

萤石矿是湖南省优势矿种,资源丰富,类型齐全,开发历史悠久,找矿潜力巨大。为满足国内外对萤石矿日益增长的消费需求,深入研究湖南省萤石矿的控矿因素和富集规律具有重要的现实意义。介绍了湖南省萤石矿的成矿地质背景、资源特征、控矿因素及矿石类型; 结合实际地质资料, 综合分析湖南省萤石矿的成矿分布特征,总结萤石矿的成矿地质特征,划分了矿床成矿系列。研究认为,湖南省萤石找矿,需进一步开展矿产资源潜力评价、矿产资源调查及勘查工作。     

The Ribeira fluorite district,southern Brazil

The origin and evolution of different ore deposits grouped in the same district are often complex and may involve inheritance from crustal or mantle geochemical anomalies, remobilization of former ore deposits and a polyphase hydrothermal history. Localized in a Proterozoic basement in the Parana state, the Ribeira fluorite district is such an example composed of three deposit types with distinct geological and geochemical characters. Emplaced at different periods from the late Proterozoic to the Cretaceous, they are roughly aligned along a belt nearly 10 km in width and 50 km in length, the southern boundary of which is a transcurrent fault. Two main ore facies are present: (1) microcrystalline ore (< 0.1 mm grains) and (2) macrocrystalline ore (with a grain size of several millimetres). The former results from the replacement of metalimestones or internal karstic sediments and the latter from microcrystalline ore dissolution and pore precipitation or recrystallization. At least two different groups of source rocks can be proposed for the trapped REE in CaF₂: (1) fluorite samples associated with the Mato Preto carbonatitic rocks display a slightly negative ɛNd compatible with a mantle source and a REE pattern with the higher ΣREE and La/Yb ratio in the district; (2) other fluorites have a strongly negative ɛNd (− 14 to − 20) which indicates a crustal source. That fluorine and REE have the same source is possible in strata-bound and fracture-filling deposits, but is doubtful at Mato Preto, the only economic fluorite deposit associated with carbonatite rocks in Brazil. This occurrence within a Precambrian fluorite belt suggests that remobilization of a former strata-bound deposit was a more significant metallogenic process than magmatic differentiation. Editorial handling: DR     

义县萤石矿床稀土元素地球化学特征及其指示意义

为了研究辽西义县萤石矿床的成矿机理及成矿流体来源,文章对矿区萤石稀土元素进行了分析。结果表明:2种类型的萤石为同源不同阶段的产物,从成矿早期至晚期,LREE逐渐减少,Ce负异常由弱变强,Eu则均显明显的正异常;矿床成矿流体主要来源于中侏罗世髫髻山旋回岩浆热液;成矿过程为岩浆热液与围岩(主要为白云质灰岩和灰岩)的相互作用,并有天水的混入;成矿环境相对氧化。