Sectoral zoning in natural fluorites from carbonatite rocks of Ambadongar,Gujarat

In this article, we want to examine the presence of various types of zoning and spatial distribution of luminescence activating trace elements including REEs in natural fluorites from carbonatite rocks of Ambadongar, Gujarat. At Ambadongar, fluorite occurs as veins and vugs in different colours e.g. blue, yellow, green and purple associated with carbonatite and alkaline rocks. Cathodoluminescence microscopy was used to study the internal morphology including growth sectors, growth bands and concentric zoning patterns in fluorite crystals.     

The Laal-Kan fluorite deposit,Zanjan Province,NW Iran: constraints on REE geochemistry and fluid inclusions

The Laal-Kan fluorite deposit (west of Zanjan city, NW Iran) mainly occurred as some open-space filling and vein/veinlet in the schist of the Paleozoic age. Mineralogically, calcite, fluorite types (white, smoky, and violet), and quartz are the principal constituents accompanied by a number of minor accessory minerals such as hemimorphite, hematite, barite, and clays. Based on chemical analyses, fluorites of various colors were found to have low rare earth element (REE) concentrations (4.16–25.67 ppm). The chondrite-normalized REE patterns indicated that early fluorites were enriched in LREE, relative to HREE, whereas late fluorites were enriched in HREE relative to LREE. This study, therefore, indicated that fugacity of oxygen likely played a significant role in the occurrence of positive Ce and negative anomaly in the late fluorite. Furthermore, the Gd behavior of the fluorite samples could be attributed to the Gd-F complex in ore-forming fluids. On the other hand, low pH hydrothermal fluids under alkaline conditions were probably the main mechanism responsible for the deposition of the early fluorites in this district. Fluorite-hosted fluid inclusion analyses also indicated that fluorite-forming fluids consisted of NaCl, MgCl₂, CaCl₂, and LiCl with a narrow T_H (118–151 °C) and high salinities (18.96–23.47 wt.% NaCl equiv.). Further, the diagram of Tb/La-Tb/Ca ratios revealed that fluorites were predominantly deposited in the hydrothermal environment and the late stage fluorites could be considered as the product of the secondary mineralization of the early fluorites due to the interaction of the fluid with the early fluorites.     

俄罗斯高温高压处理钻石特征

采用显微观察、红外光谱、可见吸收光谱和低温光致发光谱等分析方法,对9颗俄罗斯高温高压处理钻石样品进行了研究。结果表明,该类钻石样品的内部多见石墨化现象,尤以彩色钻石样品更明显;金黄色、紫红色、黄绿色样品为ⅠaAB型,浅黄色样品为ⅠaB型,近无色样品为Ⅱa型;样品的可见吸收光谱因颜色不同而差异显著,其中金黄色样品可见475 nm处的吸收宽带,紫红色样品可见638,614,595 nm处的吸收峰,黄绿色和浅黄色样品可见415,475,503 nm处的吸收峰,近无色样品则为较光滑的平直曲线。此外,该类样品在低温光致发光谱中可见575 nm与637 nm处强发光峰。这些特征为探讨该类钻石的晶格缺陷与呈色机理提供了一定的科学依据。     

河北省丰宁银矿萤石特征及找矿意义

萤石是丰宁银矿最重要的标志性脉石矿物之一,对其产出的地质地球化学特征研究认为,银成矿与萤石具有极其相似的地球化学行为,空间上可密切伴生产出.紫色萤石于热液活动早期酸性介质中沉淀而成,距矿体最近;绿色、白色萤石在热液活动中-晚期于中性介质中沉淀而成,距矿体较远;无色萤石在热液活动晚期于碱性介质中析出,距离矿液活动中心最远.     

Trace and REE element geochemistry of fluorite and its relation to uranium mineralizations,Gabal Gattar Area,Northern Eastern Desert,Egypt

Uranium mineralizations occur and form in a broad range of geologic setting and age, including magmatic to surfacial conditions, and there are numerous controls on their transportation and deposition, such as redox, pH, ligand concentration, complexation, and temperature. These temporal and spatial variations have caused a range of ore deposit mineral assemblages. Consequently, understanding their conditions of formation is still in its infancy. This research reports rare earth elements (REE) and trace elements of fluorite associated with hexavalent uranium mineralizations and tests of genetic models for the deposits. These data contribute to a better understanding of the variables controlling fluorite formation and uranium ore composition through understanding the evolution of these ore-forming hydrothermal systems. Fluorite in Gabal Gattar granite occurs as disseminations and/or thin veinlets and encrustations filling some uranium mineralized fissures and fractures along the northern margin of host granite mass. In the U-poor samples, fluorite forms well-developed large crystals that are commonly zoned. The zones are represented by alternating colorless and violet zones, and the outer zones are frequently dark violet. In the U-rich samples, fluorite is usually anhedral, unzoned, and has a dark violet color. The results of analysis of REE and trace element contents of fluorites using laser ablation inductively coupled plasma mass spectrometry indicate that total REE in the anhedral unzoned fluorite are elevated compared to the well developed zoned fluorite, and also total REE in dark violet zones of zoned fluorite are elevated with respect to the colorless zones. The fluorites and host granite are generally characterized by strongly negative Eu anomalies and slightly negative or chondritic Ce anomalies. Accordingly, REE patterns of the fluorite and host granite are roughly alike, indicating that the source of REE and trace elements of hydrothermal fluids is the host granite leached by fluids. Y/Y*, Ce/Ce,* and Eu/Eu* patterns show that fluorite clearly records the compositional evolution of the hydrothermal solutions that have transferred trace and REE from host granite during the fluid–wall rocks interactions. The high uranium contents of fluorite in Gabal Gattar granite suggest that parent fluids bearing fluorine have interacted with host granite to leach uranium from the accessory minerals of granite and tetravalent uranium minerals in reduced or weakly oxidized zones.     

Trace-element and Sr–Nd isotopic evidence for the origin of the Sardinian fluorite mineralization (Italy)

The fluorite-bearing hydrothermal mineralization in Sardinia mainly occurs within Paleozoic volcanic and metasedimentary rocks. Only 3 occurrences are located in volcanic and siliciclastic Cenozoic rocks. Most Sardinian fluorites exhibit relatively high rare earth and Y (REY) contents, strong positive Y anomalies, slightly negative Ce and generally positive Eu anomalies. These features indicate that the REY were mobilized mainly from non-carbonate rocks. Neither Sr nor Nd isotopes can be used to date radiometrically the Sardinian fluorites. However, the measured Sr-isotope ratios of the fluorites hosted by Paleozoic rocks fit mixing lines in the 1000/Sr versus ⁸⁷Sr/⁸⁶Sr plot once recalculated at 280 Ma, suggesting that the age inferred for the correction probably represents that of the formation of the fluorite mineralization. Mixing likely occurred between diluted surficial waters and brines circulating mainly through the Lower Paleozoic metasedimentary basement. The Cenozoic fluorites exhibit chemical and isotopic features similar to those of the Paleozoic fluorites, except the Nuraghe Onigu fluorite displaying a possible contribution of Sr from Cenozoic magmatic rocks. The initial ε_Nd values of the Paleozoic fluorites fit the age proposed for the formation of the deposits. Moreover, the values suggest that radiogenic Nd was provided to the fluids from the Ordovician siliciclastic basement, except for 3 deposits where the potential source rocks of Nd were mainly Ordovician acidic magmatic rocks. The initial ε_Nd values of the Cenozoic fluorites suggest a provenance of Nd essentially from the leaching of Variscan granitoids.     

Thermodynamic modeling of the REE distribution between fluorite and ore-forming fluid in postmagmatic deposits in western Transbaikalia

The factors determining the REE distribution in natural hydrothermal systems are studied by a numerical experiment. The behavior of REE is examined based on the composition of ore-bearing hydrothermal solutions and the parameters of ore formation processes at different fluorite deposits. These data were obtained in studies of fluid inclusions. Some regularities of the REE behavior during the formation of fluorite deposits have been revealed. It is shown that the REE distribution in fluorites is related mainly to changes in the composition of mineral-producing fluid solution.     

Geochemistry and Nd,Sr isotopes of the Pohrenk fluorites (Kırsehir-Turkey)

The Pohrenk fluorite mineralisation which makes up Central Anatolia’s most extensive fluorite region is Lutetian aged, and hosted in carbonate rocks that have undergone occasional karstification and silicification along a N–S fault trend. Fluid inclusion values and the position of fluorites in the Tb/La–Tb/Ca diagram show that mineralisation occurred in a hydrothermal environment with homogenisation temperatures ranging from 78.1–363°C. The presence of fluorite as a space filler in carbonate rocks and its association with silicification indicates that the solutions contained considerable amounts of Si alongside F (fluorine). The Pohrenk fluorite samples have ¹⁴³Nd/¹⁴⁴Nd values of between 0.512349 and 0.512497, whilst ⁸⁷Sr/⁸⁶Sr values vary between 0.708161 and 0.708772. These values indicate a mantle origin where continental contamination could occur. When the Nd–Sr values are compared to magmatic and young volcanics, the Pohrenk fluorites are seen to be enriched and exhibit similar isotopic signatures to Upper Cretaceous aged magmatics, Early-Middle Miocene volcanics and Mio-Quaternary volcanics.     

碳酸盐岩中地开石的分布特征及其成因

塔里木盆地巴楚-麦盖提地区石炭系小海子组碳酸盐岩中存在大量地开石,利用X射线粉晶衍射对该矿物进行了鉴定,利用阴极发光显微镜和扫描电镜对地开石的形态与分布进行了研究。地开石晶体为短柱状,晶体大小约3~13 μm,分布在溶蚀孔、白云石晶间孔和缝合线的溶解段中。经岩石薄片和阴极发光观察,发现在地开石出现的岩样中存在萤石。地开石与萤石组合的出现,表明该地区小海子组存在着热液活动。经统计,地开石和萤石通常富集于某一层,可追踪热液流体来源的深度。由于地层中未见地开石的前身矿物,并且在温度低于100℃的地层中也出现了地开石,推断该区地开石为热液成因。热液流体不仅为地开石形成创造了条件,还导致了小海子组碳酸盐岩产生大量溶蚀孔隙。热液与岩石间的水岩反应导致萤石交代白云石,溶孔壁白云石重结晶。通过对储层物性数据的分析,表明热液溶蚀能明显增加孔隙度,但萤石和地开石的形成对孔隙度起破坏作用。热液溶蚀是小海子组碳酸盐岩储层形成的重要机理,对指导该区油气勘探具有实际意义。     

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。     

塔里木盆地顺南501井鹰山组白云岩储层特征与成因

塔里木盆地顺南地区多口钻井揭示在白云岩储层中天然气富集成藏,但白云岩储层的成因存在争议。顺南501井鹰山组取芯段发育白云岩储层,为研究该地区白云岩储层成因提供了条件。通过岩芯观察与描述、显微岩石学、成岩作用与序列研究、基于铸体薄片的孔隙图像分析、计算机断层扫描、电子探针背散射成像与微量元素Fe、Mn定量、流体包裹体等技术手段,研究了白云岩储层特征与成因。结果表明,白云岩储层类型为裂缝-孔隙型,主要储集空间为裂缝-扩溶缝、晶间孔-晶间溶孔,孔隙发育与裂缝具有明显相关关系。热液矿物萤石与方解石呈共生关系充填于裂缝与孔隙空间。裂缝与孔隙附近的白云石、白云石环边以及与萤石共生的方解石均具有较高的FeO、MnO含量。萤石发育成群无色透明盐水包裹体,均一温度为165℃~175℃、盐度为15.5~17.5 wt.% NaCl equiv.。热液流体活动对围岩的改造导致局部方解石、白云石富Fe2+、Mn2+,同时提供了萤石结晶所需要的F-。一方面热液流体改造白云岩形成储集空间,另一方面以萤石与方解石为代表的热液矿物则充填裂缝与孔隙。因此,构造-热液流体活动在一定程度上影响了白云岩储集空间的形成。     

辽西义县萤石矿床Sr同位素组成及成因

辽西义县是辽宁省主要的萤石矿床产地,萤石产于中元古界长城系-蓟县系碳酸盐岩中.为了研究成矿物质来源及矿床成因,对该矿床进行了Sr同位素研究.萤石的Sr同位素N(87Sr)/N(86Sr)比值为0.708 476～0.708 533,该比值介于赋矿碳酸盐岩Sr同位素比值(0.708 926～0.722 043)和中侏罗统髫髻山组火山岩Sr同位素比值(0.707 584～0.710 382)之间,表明成矿物质主要来源于赋矿围岩和髫髻山组火山岩,结合Sr同位素图解认为其矿床类型属于热液充填交代型.     

On the presence of hydrous defects in differently coloured wulfenites (PbMoO4): an infrared and optical spectroscopic study

Several samples of wulfenite, PbMoO₄, varying in colour from colourless to yellow, orange and red, have been characterised by means of IR and optical absorption spectroscopy and by microprobe analyses. A distinct pleochroic band group with absorption maxima centred at 3,380 and 3,150 cm^?1 can be seen in the IR spectra of wulfenite single-crystals, indicating the presence of hydroxyl groups. The pleochroic and thermal behaviour of the OH stretching bands along with deuteration experiments, as well as results obtained from synthetic flux-grown samples, exclude the presence of submicroscopic hydrous mineral inclusions as their primary origin. The pleochroic scheme and the band positions were used to postulate a model for the OH incorporation mode, based on the assumption of vacancies on Mo and Pb sites in the structure of this ‘nominally anhydrous mineral’. Optical absorption spectra of coloured natural samples show a broad and polarised band around 23,000–24,000 cm^?1, preceding the fundamental UV absorption edge, which has been identified as the reason for the colour of the mineral. The comparison with synthetic PbMoO₄ single-crystals, doped with variable amounts of Cr⁶⁺, yielded conclusive evidence that trace amounts of the CrO₄ ^2? anion group, substituting for MoO₄ ^2?, determine the variable colour. Besides, in one sample, trace amounts of Nd³⁺ have been spectroscopically identified.     

Comparative study of yttrium and rare-earth element behaviours in fluorine-rich hydrothermal fluids

The mineral fluorite is utilized as a probe to investigate the behaviour of the pseudolanthanide yttrium with respect to the lanthanides (rare-earth elements, REE) in fluorine-rich hydrothermal solutions. Hydrothermal vein fluorites are characterized by the close association of Y and REE, but in contrast to igneous and clastic rocks they show variable and nonchondritic Y/Ho ratios of up to 200. This suggests that Y and Ho, although similar in charge and size, may be fractionated in fluorine-rich medium-temperature aqueous fluids. In such solutions Y acts as a pseudolanthanide heavier than Lu. Y/Ho ratios of hydrothermal siderites are slightly below those of chondrites, suggesting that in (bi)carbonate-rich siderite-precipitating solutions Y may act as a Sm-like light pseudolanthanide. This indicates that Y-Ho fractionation is not a sourcerelated phenomenon but depends on fluid composition. Based on these results it is strongly recommended that discussions of normalized REE patterns in general should be extended to normalized Rare-Earth-and-Yttrium (REY) patterns (Y inserted between Dy and Ho), because the slightly variable behaviour of the pseudolanthanide yttrium with respect to the REE may provide additional geochemical information. Available thermodynamic data suggest a negative correlation between Y/Ho and La/Ho during migration of a fluoriteprecipitating hydrothermal solution. Cogenetic fluorites, therefore, should display either similar Y/Ho and similar La/Ho ratios, or a negative correlation between these ratios. This criterion may help to choose samples suitable for Sm-Nd isotopic studies prior to isotope analysis. However, in cogenetic hydrothermal vein fluorites the range of Y/Ho ratios is often almost negligible compared to the range of La/Ho ratios. This may be explained by modification of REE distributions by post-precipitation processes involving (partial) loss of a separate LREE-enriched phase. The presence of variable amounts of such an accessory phase in most fluorite samples is revealed by experiments employing stepwise incomplete fluorite decomposition. Fluorites derived from and deposited near to igneous rocks apparently display chondritic Y/Ho ratios close to those of their igneous source-rocks. However, a positive Y_SN anomaly is likely to develop as the distance between sites of REY mobilization and deposition increases.     

晴隆锑矿床中萤石的稀土元素特征及其指示意义

本文系统地研究了黔西南晴隆锑矿床中萤石的稀土元素地球化学,表明不同颜色、不同矿物组合的萤石的稀土元素含量变化较大,但具有固定的REE分配模式,以明显的负Ce异常、富MREE、分配曲线相对平缓为特征;这种配分模式主要是受其晶体化学因素的控制,而与溶液中REE络合物的稳定性关系不大。萤石的稀土元素组成与其矿物共生组合关系不大,但与其颜色关系较密切。萤石的Ce、Eu异常主要是受氧逸度的控制,流体源区的氧逸度较高,矿物沉淀场所的氧逸度相对较低,从而导致该矿中萤石呈明显的负Ce异常,或正或负的Eu异常。晴隆锑矿床形成于开放体系条件下,水/岩反应很可能是导致萤石发生沉淀的主要机制。萤石中的Ca部分来自茅口组灰岩,部分来自大厂层玄武岩;而矿化剂F可能主要来自外部。     

河南省萤石矿床地质特征、成矿规律及找矿方向

萤石是我国战略性矿种之一,提高其资源储备对国民经济发展具有重要意义。本研究对河南省萤石矿床的地质特征、时空分布、成矿物质来源等进行分析,系统总结萤石矿床的成矿规律,并提出河南省萤石找矿方向。结果表明：（1）河南省萤石矿床类型以热液充填型为主,全省可划分为三个萤石成矿带;（2）河南省萤石矿床主要分布于中生代花岗质侵入岩体的内部或其周边地层的北西向、北东向断裂构造带中,方城地区萤石矿床主要赋存于岩体附近的地层中;（3）萤石矿床的成矿年龄在120 Ma左右,方城地区萤石矿床可能形成于新元古代;（4）中生代花岗质岩浆作用或其期后热液活动为萤石成矿提供重要的物质和驱动热;地层岩石为萤石成矿提供重要的氟,其丰富钙源很可能是巨量萤石富集的关键;（5）萤石主成矿阶段的成矿流体应属低温、低盐度、低密度的流体系统,大气降水对萤石成矿具有重要作用;（6）河南省萤石找矿重点地区应在太华群地层岩石和中生代花岗质侵入岩体广泛发育的北带和中带,特别是合峪、太山庙、天目山、铜山等岩体的内部或其周围。     

Water solubility in nominally anhydrous minerals measured by FTIR and 1H MAS NMR: the effect of sample preparation

Samples of enstatite and forsterite were crystallized in the presence of a hydrous fluid at 15 kbar and 1100 °C. Water contents in quenched samples were measured by ¹H MAS NMR and by FTIR. If the samples were prepared in the same way, similar water concentrations were obtained by both methods. There is no evidence that one or the other method would severely over or underestimate water contents in nominally anhydrous minerals. However, measured water contents vary by orders of magnitude depending on sample preparation. The lowest water contents are measured by polarized FTIR spectroscopy on clear, inclusion-free single crystals. These water contents probably reflect the real point defect solubility in the crystals. Polycrystalline material shows much higher total water concentrations, presumably due to hydrous species on grain boundaries, growth defects, and in submicroscopic fluid inclusions. Grinding the sample in air further increases water concentration. This effect is even more pronounced if the sample is ground in water and subsequently dried at 150 °C. Polarized FTIR measurements on clear single crystals of enstatite saturated at 15 kbar and 1100 °C give 199 ± 25 ppm by weight of water. The spectra show sharp and strongly polarized bands. These bands are also present in spectra measured through turbid, polycrystalline aggregates of enstatite. However, in these spectra, they are superimposed on much broader, nearly isotropic bands resulting from hydrous species in grain boundaries, growth defects, and submicroscopic fluid or melt inclusions. Total water contents for these polycrystalline aggregates are between 2000 and 4000 ppm. Water contents measured by FTIR on enstatite powders are 5300 ppm after grinding in air and 12 600 ppm after grinding under water und subsequent drying at 150 °C. Received: 25 June 1999 / Revised, accepted: 4 October 1999     

Calibration of Infrared Absorption Coefficients for Structural Hydroxyl in Garnet by a Combined Study of Isotope Ratio Spectrometry and Vibrational Spectroscopy

An accurate determination of water content in garnet is critical to quantify the transport of water to the deep mantle by the subducted oceanic crust beyond the breakdown of hydrous phases. Fourier transform infrared spectroscopy (FTIR) is the most widely used approach to determine the species and contents of water in garnet. Accurate quantification of OH in garnet requires independent calibration using an external method, as OH absorbance is mineral and composition specific. To obtain the infrared absorption coefficients of structural hydroxyl in garnet, a combined study of spectrometric analyses by FTIR and a method combining a thermal conversion elemental analyser with isotope ratio mass spectrometry (TC/EA-MS) was carried out for fourteen gem-quality natural garnet crystals with variable compositions. The obtained molar absorption coefficients were 9322 ± 338 and 240 ± 26 l mol⁻¹ cm⁻² for grossular- and spessartine-rich garnet and pyrope-almandine garnet, respectively. These results are within the range of previous studies. A new molar absorption coefficient of 689 ± 177 l mol⁻¹ cm⁻² was obtained for pyrope-spessartine garnet. The large variation in the absorption coefficient indicates it is controlled by both garnet composition and OH-absorption bands. The obtained absorption coefficients are only appropriate for certain types of eclogitic garnet, and more studies should be carried out on eclogitic garnets.     

次生萤石的特征及其成因

本文探讨了次生萤石的成因。由于成矿后的断裂活动,使原生萤石脉受压破碎,形成了空洞。细末状萤石在地下水作用下形成胶体溶液搬运、沉淀和再结晶。另外,随着成矿后构造断裂而来的热液,引起萤石的新的溶解和结晶。     

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