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.     

Fluid inclusion and cathodoluminescence studies on fluorite from the Kerio valley, Kenya

The Kerio valley lies between the Elgeyo escarpment and the Tugen hills which mark the western margin of the Kenya rift valley. The main fluorite deposits are located in the southern part of the valley at Kimwarer, Choff and Kamnaon.Three types of inclusion fillings were identified: Liquid+Vapour, Liquid+Daughter Minerals and Liquid. The L+V type is dominant. Inclusions occur as clusters, trails along the crystal growth zones and as isolated ones. Low salinities, apparently lower than the 5% wt. NaCl equivalent, were established. Homogenization temperatures suggest that fluorite mineralization took place at different stages and at temperatures between 120 and 180 °C. Isolated readings above 180°C may be referring to the original inclusions in limestone. These measurements and the absence of CO₂ in the inclusions, as well as the occurrence of vugs and crustifications with fluorite, suggest that mineralization took place at relatively shallow depths.Emission spectrum lines representing Eu²⁺, Dy³⁺, Tb³⁺ and Sm³⁺ in fluorite were identified. Sm³⁺ was detected only in the pinkish luminescence of veined fluorite, whereas the pinkish zone in banded fluorite contains Tb³⁺. Eu²⁺ which gives the strongest emission lines in the blue part of the visible spectrum, apparently is responsible for the strong blue cathodoluminescence (CL) in fluorite. The dominance of Eu²⁺ peaks further points to the fact that fluorite mineralization in the Kerio valley took place in an environment that was enriched in Lanthanide Rare Earth Elements (LREE). The presence of rare earths and radioactive elements in fluorite points towards their enrichment in the environment of fluorite mineralization. A juvenile origin of mineral forming solutions is proposed.Two generations of fluorite were established: allotriomorphic fluorite, forming the matrix, and the idiomorphic variety, occurring either in barite or in druzes in early fluorite. Barite in turn forms idiomorphic crystals in allotriomorphic fluorite. Relics of calcite occur in both K-feldspars and in early fluorite. Oxides and hydroxides of Fe, Mn, Ti and Al commonly occur in open spaces in fluorite. Of significance is the presence of gold in fluorite. Fluorite mineralization is of hydrothermal origin in the post-Miocene era and was formed as a result of metasomatic replacement of marble and open space fillings.     

辽宁岫岩县桑皮峪透闪石玉成矿年龄研究

运用偏光显微镜、电子探针对辽宁岫岩县桑皮峪透闪石玉的岩石学特征进行了研究,并运用二次离子质谱仪测定从桑皮峪透闪石玉中分离的锆石和榍石的年龄。结果表明：桑皮峪透闪石玉主要由透闪石组成,次要矿物包括磷灰石、方解石、绿泥石、石墨、褐铁矿、锆石、榍石等。偏光显微镜下桑皮峪透闪石玉的主要结构是毛毡状纤维交织结构、显微细晶质结构和纤维变晶结构;主要构造为块状构造。主要化学成分为SiO₂、MgO和CaO,Mg²⁺/（Mg²⁺+Fe²⁺）值为0.964~0.971。桑皮峪透闪石玉的锆石U-Pb谐和年龄为1 851±7 Ma,榍石的²⁰⁷Pb/²⁰⁶Pb年龄为1 848±17 Ma,表明桑皮峪透闪石玉矿形成于古元古代白云岩的区域变质时期。     

The luminescence properties of rare-earth ions in natural fluorite

For the first time, the luminescence properties of Pr³⁺, Nd³⁺ and Tm³⁺ and Yb³⁺ ions in fluorite crystal have been obtained by steady-state measurements. In addition, the luminescence spectra of Ce³⁺, Sm²⁺, Sm³⁺, Dy³⁺, Er³⁺ and Yb³⁺ were measured. It was pointed out that λ_exc.?=?415?nm is most suitable for measuring the Ho³⁺ emission beside the Er³⁺. The emission of trivalent holmium and erbium ions was measured independently using time-resolved measurements and tentative assignment of luminescence lines to C _3v and C _4v symmetry sites was proposed. Besides for natural fluorite crystal, the transitions between Stark energy levels of lanthanide ions were presented.     

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     

Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995     

Geochemical assessment of groundwater contamination with special emphasis on fluoride concentration, North Jordan

The concentrations of fluorine in groundwater of North Jordan range from 0.009 to 0.055 mg/l. Other chemical parameters, e.g. pH, EC, TDS, Cl, TH, HCO₃, PO₄, SO₄, NO₃, NH₄, K, Ca, Mg, and NO₃ have been studied and showed higher concentrations in HCO₃⁻ and NO₃⁻ of 307 and 51 mg/l, respectively. Thermodynamic considerations show that almost all the analyzed samples are undersaturated with respect to calcite and fluorite. This undersaturation is probably due to their low availability in the locations. Fluoride concentration shows a positive relation to pH and HCO₃, whereas Cl, Mg, Ca, and Na initially increase and then decrease with increasing fluoride in the water. Saturation indexes of fluorite and calcite are estimated. The chemistry of the groundwater is controlled by the fluorite and calcite solubility. The topography of the area has exerted control on the aerial extent of fluoride concentration.     

Energy transfer among Pb, Ce and Mn in fluorescent calcite from Kuerle, Xinjiang, China

Natural calcite from Kuerle, Xinjiang, China, shows orange-red fluorescence when exposed to short-wave ultraviolet (UV) light (Hg 253.7 nm). Photoluminescence (PL) emission and excitation spectra of the calcite are observed at room temperature in detail. The PL emission spectrum under 208 nm excitation consists of three bands: two UV bands at 325 and 355 nm and an orange-red band at 620 nm. The three bands are ascribed to Pb²⁺, Ce³⁺ and Mn²⁺, respectively, as activators. The Pb²⁺ excitation band is observed at 243 nm, and the Ce³⁺ excitation band at 295 nm. The Pb²⁺ excitation band is also observed by monitoring the Ce³⁺ fluorescence, and the Pb²⁺ and Ce³⁺ excitation bands, in addition to six Mn²⁺ excitation bands, are also observed by monitoring the Mn²⁺ fluorescence. These indicate that four types of the energy transfer can occur in calcite through the following processes: (1) Pb²⁺ → Ce³⁺, (2) Pb²⁺ → Mn²⁺, (3) Ce³⁺ → Mn²⁺ and (4) Pb²⁺ → Ce³⁺ → Mn²⁺.     

Laser-induced time-resolved luminescence of tugtupite,sodalite and hackmanite

We have interpreted a number of luminescence centers in natural tugtupite Na₈Al₂Be₂Si₈O₂₄Cl₂, sodalite Na₈Al₆Si₆O₂₄C₂ and hackmanite Na₈Al₆Si₆O₂₄(Cl₂,S) by use of laser-induced time-resolved luminescence spectroscopy. The main new results are the following: Fe³⁺, Mn²⁺, Eu²⁺, Ce³⁺, mercury type (potentially Pb²⁺, Tl⁺, Sn²⁺ and/or Sb³⁺), radiation induced luminescence centers; several types of S₂ ⁻ centers. Spectral shift connected with the presence of luminescence centers, which are detected together with S₂ ⁻ centers and impossible to resolve with continuous wave luminescence spectroscopy, is the possible reason for spectral diversity of S₂ ⁻ luminescence centers presented in different publications.     

Origin and granite alteration effects of hydrothermal fluid: isotopic evidence from fluorite veins, Co. Galway, Ireland

The Costelloe Murvey Granite is a chemically evolved, high heat production, leucocratic component of the 400 Ma old Galway Granite batholith and is host to hydrothermal fluorite-quartz-calcite veins. A previously reported clinopyroxene ⁴⁰Ar-³⁹Ar age of 231±4 Ma obtained from a pre-mineralization dolerite dyke is reinterpreted as dating this mineralization. The hydrothermal fluid extensively altered its granite wallrocks, leading to lower Sm and Nd and higher Rb concentrations in altered granite, disturbing both its Rb-Sr and Sm-Nd isotopic systems. The ⁸⁷Sr/⁸⁶Sr ratio of the hydrothermal fluid from which fluorite and calcite precipitated ranged from 0.7101 to 0.7139. These ratios are very much lower than in the Costelloe Murvey Granite at the time of mineralization, precluding the granite as a source for more than 2% of the hydrothermal Sr. The initial ¹⁴³Nd/¹⁴⁴Nd ratio varies between fluorite in different veins due to Nd derivation from local wallrocks, and between fluorite of petrographically distinct growth phases within a single hand specimen, highlighting the difficulty of Sm-Nd isochron dating of fluorite in cases where there are multiple sources of hydrothermal Nd. It is proposed that fluorite and calcite precipitated where hot, dilute fluids rising through the granite mixed with cooler, more saline fluids of basinal origin migrating through Lower Carboniferous limestone which then overlay the granite. Received: 3 August 1995 / Accepted: 11 April 1996     

Experimental reconstruction of sodic dolomitic carbonatite melts from metasomatised lithosphere

 Investigations of peridotite xenolith suites have identified a compositional trend from lherzolite to magnesian wehrlite in which clinopyroxene increases at the expense of orthopyroxene and aluminous spinel, and in which apatite may be a minor phase. Previous studies have shown that this trend in mineralogy and chemical composition may result from reaction between sodic dolomitic carbonatite melt and lherzolite at pressures around 1.7 to 2 GPa. This reaction results in decarbonation of the carbonatite melt, releasing CO₂-rich fluid. In this study, we have experimentally reversed the decarbonation reaction by taking two natural wehrlite compositions and reacting them with CO₂ at a pressure of 2.2 GPa and temperatures from 900 to 1150° C. Starting materials were pargasite-bearing wehrlites, one with minor apatite (composition 71001^*) and one without apatite (composition 70965^*). At lower temperatures (900° C) the products were apatite+pargasite+magnesite harzburgite for runs using composition 71001^*, and pargasite+dolomite lherzolite for runs using composition 70965^*. At and above 1000° C, carbonatite melt with harzburgite residue (olivine+orthopyroxene+spinel) and with lherzolite residue (olivine+orthopyroxene+clinopyroxene+ spinel) were produced respectively. Phase compositions in reactants and products are consistent with the documented carbonatite/lherzolite reactions, and also permit estimation of the carbonatite melt compositions. In both cases the melts are sodic dolomitic carbonatites. The study supports the hypothesis of a significant role for ephemeral, sodic dolomitic melts in causing metasomatic changes in the lithosphere at P≤2 GPa. The compositions of wehrlites imply fluxes of CO₂, released by metasomatic reactions, which are locally very large at around 5 wt% CO₂. Received: 15 December 1995/Accepted: 14 February 1996     

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.     

A late Triassic 40Ar/39Ar age for the El Hammam high-REE fluorite deposit (Morocco): mineralization related to the Central Atlantic Magmatic Province?

El Hammam is the only fluorite mine in Morocco (production 100,000 t/year). The fluorite mineralization is in an array of fluorite–calcite veins and is characterized by unusually high REE content in carbonate minerals (1,400 ppm in calcite; up to 2,000 ppm in siderite) and in fluorite (about 600 ppm). Since the 1960s, the genesis of the deposit has been attributed to a mesothermal hydrothermal event connected with late-Variscan granitic intrusions. Precise ⁴⁰Ar/³⁹Ar dating of hydrothermal K-feldspar yields an age of formation of the El Hammam deposit at 205 ± 1 Ma. Its genesis is therefore associated in time and space with the development of the Triassic–Jurassic basins and the associated anorogenic continental flood basalts of the Moroccan Mesetian Middle Atlas. The source of the hydrothermal mineralization (magmatic and/or metamorphic) is discussed.     

Hydrogeochemistry of mine, surface and groundwaters from the Sanggok mine creek in the upper Chungju Lake, Republic of Korea

 The Sanggok mine used to be one of the largest lead-zinc mines in the Hwanggangri mining district, Republic of Korea. The present study characterizes the heavy metal contamination in the abandoned Sanggok mine creek on the basis of physico-chemical properties of various kinds of water samples (mine, surface and groundwater). Hydrochemistry of the water samples is characterized by the relatively significant enrichment of Ca²⁺, HCO₃ ^–, NO₃ ^– and Cl^– in the surface and groundwaters, whereas the mine water is relatively enriched in Ca²⁺, Mg²⁺, heavy metals, and HCO₃ ^– and SO₄ ^2–. The more polluted mine water has a lower pH and higher Eh, conductivity and TDS values. The concentrations of some toxic elements (Al, As, Cd, Cu, Fe, Mn, Pb, Se, Sr, Pb and Zn) are tens to hundreds of times higher in the mine water than in the unpolluted surface and groundwaters. However, most immobile toxic pollutants from the mine drainage were quickly removed from the surface water by the precipitation of Al and Fe oxyhydroxides. Geochemical modeling showed that potentially toxic heavy metals might exist largely in the forms of MSO₄ ^2– and M²⁺ in the mine water. These metals in the surface and groundwaters could form M²⁺, CO₃ ^2– and OH^– complex ions. Computer simulation indicates that the saturation indices of albite, alunite, anhydrite, chlorite, fluorite, gypsum, halloysite and strontianite in the water samples are undersaturated and have progressively evolved toward the saturation condition. However, barite, calcite, chalcedony, dolomite, gibbsite, illite and quartz were in equilibrium, and only clay minerals were supersaturated. Ground and mine waters seemed to be in equilibrium with kaolinite field, but some surface water were in equilibrium with gibbsite and seceded from the stability field of quartz. This indicates that surface water samples in reaction with carbonate rocks would first equilibrate with carbonate minerals, then gibbsite to kaolinite. Investigations on water quality and environmental improvement of the severely polluted Sanggok creek, as well as remediation methods on the possible future pollution of the groundwater by the acid mine drainage from the abandoned metal mines, are urgently required. Received: 4 February 2000 · Accepted: 9 May 2000     

Isotopic composition of strontium in the Valle de Tena (Spanish Central Pyrenees) fluorite deposits: relevance for the source of elements and genetic significance

The fluorite deposits of the Valle de Tena, Central Pyrenees, include stratabound (Portalet) and vein (Lanuza and Tebarray) deposits the formation of which are linked to a Namurian-Westfalian emersion episode and to post-Hercynian hydrothermal systems similar to those occurring elsewhere in Hercynian Europe. In this study, strontium isotopes were used to determine the source(s) of strontium, and by inference calcium, of the fluorite mineralizations, as well as the nature of the ore-forming fluids. Fluorite and calcite from each deposit have similar ⁸⁷Sr/⁸⁶Sr ratios (Portalet 0.7085–0.7108; Lanuza 0.7086–0.7104 and Tebarray 0.7086–0.7101). In all deposits, the Sr isotope composition of most of the Ca-minerals is more radiogenic than that of the host limestones. This indicates that the Ca-minerals contain a mixture of Sr derived locally from the host limestones and ⁸⁷ Sr-enriched Sr leached from silicate minerals in the siliciclastic portion of the basement sequence and in granites from the study area. Volcanic rocks are ruled out as a significant Sr source for the fluorite deposits. The observed trend in ⁸⁷Sr/⁸⁶Sr versus 1/Sr support a fluid-rock interaction model which satisfactorily reproduces the marked ⁸⁷Sr-enrichment in the fluorites and calcites from the deposits. Received: 19 February 1997 / Accepted: 22 July 1997     

Fluoride ion contamination in the groundwater of Mithi sub-district, the Thar Desert, Pakistan

Groundwater samples were collected from various localities of Mithi sub-district of the Thar Desert of Pakistan and analysed for fluoride ion along with other chemical parameters. The area is mainly covered by sand dunes and kaolin/granite at variable depths. Results showed that collected water samples were severely contaminated by the presence of fluoride ion and most of the samples have higher concentration than prescribed WHO standards (1.5 mg/l) for drinking water. Fluoride ion concentrations ranged between 0.09 and 11.63 mg/l with mean and median values of 3.64 and 3.44 mg/l, respectively, in this area whereas, distribution pattern showed high concentrations in the vicinity of Islamkot and Mithi towns. The content of F⁻ has also been correlated with other major ions found in the groundwater of the study area. The positive correlation of F⁻ with Na⁺ and HCO₃ ⁻ showed that the water with high Na⁺ and HCO₃ ⁻ stabilizes F⁻ ions in the groundwater of the Thar Desert. The pH versus F⁻ plots signifies high fluoride concentration at higher pH values, implying that alkaline environment favours the replacement of exchangeable OH⁻ with F⁻ in the groundwater of Mithi area. The saturation indices (SI) of fluorite (CaF₂) and calcite (CaCO₃) in the groundwater samples showed that most of the samples are oversaturated with respect to calcite whereas majority of samples have been found under saturated with respect to fluorite. The log TDS and Na/Na+Ca ratio reflected supremacy of weathering of rocks, which promotes the availability of fluoride ions in the groundwater. Piper diagram has been used to classify the hydrofacies. In the cation triangle, all samples are Na-type, while the anion triangle reflects major dominance of Cl-type with a minor influence of HCO₃ ⁻ and SO₄ ⁻.     

Geochemical evidence on the origin of the epithermal fluorite deposit at Monte Delle Fate near Cerveteri (Latium,Central Italy)

Sr content was measured in 6 fluorite and 7 calcite samples from an epithermal deposit of fluorite at Monte delle Fate near Cerveteri (Latium, Italy). Sr isotope ratios were obtained from two selected samples. Sr contents of calcite range from 1,200 to 2,620 ppm and of fluorite from 10 to 360 ppm. ⁸⁷Sr/⁸⁶Sr values of calcite and fluorite are 0.7087 and 0.7091, respectively. Such isotope ratios clearly indicate that the bulk of strontium present in both minerals was provided by marine sedimentary reservoirs. According to the Sr distribution coefficient, the low contents measured in fluorite, which formed after calcite, clearly prove that the mineral was not deposited by the same kind of waters from which calcite originated. The high Sr contents of calcite suggest that the bicarbonate-bearing waters have largely interacted with Ca-sulphate evaporites of Upper Triassic age. On the contrary, the waters from which fluorite precipitated were apparently involved in a more superficial circulation through post-Triassic sedimentary formations.

---

Résumé On a determiné la teneur de strontium dans 6 échantillons de fluorite et 7 échantillons de calcite d'un gisement à fluorite près de Monte delle Fate, Cerveteri (Latium; Italie centrale). De plus les rapports isotopiques du même élément ont été mésurés pour deux échantillons choisis. Les teneurs du strontium dans la calcite et la fluorite varient de 1 200 à 2 620 ppm et de 10 à 360 ppm, respectivement. La valeur du rapport ⁸⁷Sr/⁸⁶Sr est pour la calcite 0,7087 et pour la fluorite 0,7091. Ces rapports indiquent que les sédiments marins ont été la source de la plupart du strontium dans les deux minéraux. Selon le coefficient de distribution du strontium, la fluorite, de déposition postérieure à la calcite, n'a pas pu précipiter de la même eau de la calcite. Les teneurs élevées de l'élément dans la calcite sont la conséquence de l'interaction des eaux bicarbonatées avec les sédiments sulfate-évaporitiques du Triassique supérieur. Au contraire les eaux primaires de la fluorite ont circulé dans les sédiments post-Triassiques.

     

Sr and Nd isotope data of apatite,calcite and dolomite as indicators of source,and the relationships of phoscorites and carbonatites from the Kovdor massif,Kola peninsula,Russia

A detailed Sr−Nd isotopic study of primary apatite, calcite and dolomite from phoscorites and carbonatites of the Kovdor massif (380 Ma), Kola peninsula, Russia, reveals a complicated evolutionary history. At least six types of phoscorites and five types of carbonatite have been identified from Kovdor by previous investigators based on relative ages and their major and accessory minerals. Isotopic data from apatite define at least two distinct groups of phoscorite and carbonatite. Apatite from the earlier phoscorites and carbonatites (group 1) are characterized by relatively low⁸⁷Sr/⁸⁶Sr (0.70330–0.70349) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51230–0.51240) with F=2.01–2.23 wt%, Sr=2185–2975 ppm, Nd=275–660 ppm and Sm=31.7–96.2 ppm. Apatite from the second group has higher⁸⁷Sr/⁸⁶Sr (0.70350–0.70363) and¹⁴³Nd/¹⁴⁴Nd initial ratios (0.51240–0.51247) and higher F (2.63–3.16 wt%), Sr (4790–7500 ppm), Nd (457–1074 ppm) and Sm (68.7–147.6 ppm) contents. This group corresponds to the later phoscorites and carbonatites. One apatite sample from a carbonatite from the earlier group fits into neither of the two groups and is characterized by the highest initial⁸⁷Sr/⁸⁶Sr (0.70385) and lowest¹⁴³Nd/¹⁴⁴Nd (0.51229) of any of the apatites. Within both groups initial⁸⁷Sr/⁸⁶Sr and¹⁴³Nd/¹⁴⁴Nd ratios show negative correlations. Strontium isotope data from coexisting calcite and dolomite support the findings from the apatite study. The Sr and Nd isotopic similarities between carbonatites and phoscorites indicate a genetic relationship between the two rock types. Wide variations in Sr and Nd isotopic composition within some of the earlier carbonatites indicate several distinct intrusive phases. Oxygen isotopic data from calcite and dolomite (δ¹⁸O=+7.2 to +7.7‰ SMOW) indicate the absence of any low-temerature secondary processes in phoscorites and carbonatites, and are consistent with a mantle origin for their parental melts. Apatite data from both groups of phoscorite plot in the depleted quadrant of an ε_Nd versus ε_Sr diagram. Data for the earlier group lie along the Kola Carbonatite Line (KCL) as defined by Kramm (1993) and data from the later group plot above the KCL. The evolution of the phoscorites and carbonatites cannot be explained by simple magmatic differentiation assuming closed system conditions. The Sr−Nd data can best be explained by the mixing of three components. Two of these are similar to the end-members that define the Kola Carbonatite Line and these were involved in the genesis of the early phoscorites and carbonatites. An additional component is needed to explain the isotopic characteristics of the later group. Our study shows that apatite from rocks of different mineralogy and age is ideal for placing constraints on mantle sources and for monitoring the Sr−Nd evolution of carbonatites. Editorial responsibility: W. Schreyer     

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⁺.     

Natural fluorite emitting yellow fluorescence under UV light

Many mineralogists believe that fluorite emits violet fluorescence under UV light, but a special fluorite from Japan emits yellow fluorescence under UV light. The analysis by inductively coupled plasma-mass spectrometry (ICP-MS) shows that this fluorite includes high concentrations of Dy together with various rare-earth (RE) impurities other than Pm and Eu. Photoluminescence (PL) emission and excitation spectra of the fluorite are investigated at 10, 80 and 300 K. The origin of yellow fluorescence is attributed to the electronic transition within Dy³⁺. Profiles of the PL and excitation spectra depend on the excitation wavelength and on the observation wavelength, respectively. The obtained spectra are ascribed to the RE ions Ce³⁺, Sm³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Sm²⁺ and Yb²⁺ in the fluorite. In natural fluorite, the low concentration of Eu enables us to observe the bright fluorescence characteristic of trivalent RE ions, instead of the bluish violet fluorescence due to Eu²⁺.