Chemistry of Zircon in Rare Metal Granitoids and Associated Rocks, Eastern Desert, Egypt

Typological study, including paragenic, morphological, textural, and chemical characteristics of zircon from nine rare metal granitic stocks and associated greisens, was carried out in order to identify the metallogenic processes of their host granitoids. The investigated zircon‐bearing granitoids and type occurrences can be categorized into magmatically and metasomatically specialized types. The magmatic type includes: (i) peralkaline, Zr + Nb‐enriched, A₁‐granite (e.g. Um Hibal); (ii) metaluminous, Nb + Zr + Y‐enriched, A₂‐type alkali granite (e.g. Hawashia and Ineigi); and (iii) peraluminous, Ta ≥ Nb + Sn + Be ± W‐enriched, Li‐albite granite (e.g. Nuweibi, Igla and Abu Dabbab). The metasomatized granites are Nb>>Ta + Sn + Zr + Y + U ± Be ± W‐enriched and hydrothermally altered alkali feldspar granite (i.e. apogranite; e.g. Um Ara, Abu Rusheid, and Um Naggat). Zircon of peralkaline granite is characteristically equant with well‐developed pyramidal faces and short prisms (i.e. pseudo‐octahedral form) with length/width ratios in the range of 2:1–1:1. It is of Zr_0.990Hf_0.007SiO₄ composition and is associated with hypersolvus assemblage consisting of alkali feldspar, quartz, aegirine and minor reibeckite. Zircon of metaluminous alkali granites is of Zr_0.99Hf_0.01SiO₄ composition and is associated with sub‐ to transolvus assemblage of K‐feldspar, quartz, plagioclase and annite‐siderophyllite mica. It is prismatic with length/width ratios in the range of 5:1–3:1, doubly terminated with small pyramidal faces. Compositionally, zircon of Li‐albite granite ranges between Zr_0.925Hf_0.075SiO₄ and Zr_0.705Hf_0.295SiO₄. It is idiomorphic with a simple combination of prism and bipyramidal terminations with a length/width ratio of 3:1–2:1. This zircon commonly exhibits a normal zoning with rims consistently higher in Hf than cores. The higher Hf content, of this zircon coupled with its association with topaz, tantalite and lithian micas (e.g. zinnwaldite and Li‐white mica), indicates a higher solubility of Hf‐fluoride complexes and their more stabilized state at lower temperature in Li‐ and F‐rich sodic melts. Zircon of apogranite association ranges in composition between Zr_0.967Hf_0.013SiO₄ in the lower unaltered alkali feldspar granite zone and Zr_0.805Hf_0.064(Y, U, Th, heavy rare‐earth elements) [HREE])_0.125SiO₄ in the apical metasomatized (i.e. microclinized, albitized, and greisenized) apogranite zones. This compositional change appears to reflect a roofward increasing in μ_KF, μ_NaF, and μ_HF of the exsolved fluids. Columbite, xenotime, thorite, cassiterite, beryl and fluorite are common associates of this zircon. This zircon is of bipyramidal to typical octahedral form with complete absence of prism concurrently with conspicuous development of pyramid, thus the zircon crystals have a length/width ratio of 1:1–0.5:1. The neoformed metasomatic zircon commonly exhibits either normal or reverse zoning with rims consistently different in Hf, U, Y, and HREE than cores, reflecting disequilibrium conditions (e.g. sudden change in P, T, salinity, and pH) between the growing crystals and the exsolved fluids.     

Genesis of the Proterozoic Mangabeira tin–indium mineralization,Central Brazil: Evidence from geology,petrology, fluid inclusion and stable isotope data

The Mangabeira deposit is the only known Brazilian tin mineralization with indium. It is hosted in the Paleo- to Mesoproterozoic Mangabeira within-plate granitic massif, which has geochemical characteristics of NYF fertile granites. The granitic massif is hosted in Archean to Paleoproterozoic metasedimentary rocks (Ticunzal formation), Paleoproterozoic peraluminous granites (Aurumina suite) and a granite–gneiss complex. The mineralized area comprises evolved Li-siderophyllite granite, topaz–albite granite, Li–F-rich mica greisens and a quartz–topaz rock, similar to topazite. Two types of greisens are recognized in the mineralized area: zinnwaldite greisen and Li-rich muscovite greisen, formed by metasomatism of topaz–albite granite and Li-siderophyllite granite, respectively. Cassiterite occurs in the quartz–topaz rock and in the greisens. Indium minerals, such as roquesite (CuInS₂), yanomamite (InAsO₄·2H₂O) and dzhalindite (In(OH₃)), and In-rich cassiterite, sphalerite, stannite group minerals and scorodite are more abundant in the quartz–topaz rock, and are also recognized in albitized biotite granite and in Li-rich muscovite greisen. The host rocks and mineralized zones were subsequently overprinted by the Brasiliano orogenic event.Primary widespread two-phase aqueous and rare coeval aqueous-carbonic fluid inclusions are preserved in quartz from the topaz–albite granite, in quartz and topaz from the quartz–topaz rock and in cassiterite from the Li-rich muscovite greisen. Eutectic temperatures are − 25 °C to − 23 °C, allowing modeling of the aqueous fluids in the system H₂O–NaCl(–KCl). Rare three-phase H₂O–NaCl fluid inclusions (45–50 wt.% NaCl equiv.) are restricted to the topaz–albite granite. Salinities and homogenization temperatures of the aqueous and aqueous-carbonic fluid inclusions decrease from the topaz–albite granite (15–20 wt.% NaCl equiv.; 400 °C–450 °C), to the quartz–topaz rock (10–15 wt.% NaCl equiv.; 250 °C–350 °C) and to the greisen (0–5 wt.% NaCl equiv.; 200 °C–250 °C). Secondary fluid inclusions have the same range of salinities as the primary fluid inclusions, and homogenize between 150 and 210 °C.The estimated equilibrium temperatures based on δ¹⁸O of quartz–mica pairs are 610–680 °C for the topaz–albite granite and 285–370 °C for the Li-rich muscovite greisens. These data are coherent with measured fluid inclusion homogenization temperatures. Temperatures estimated using arsenopyrite geothermometry yield crystallization temperatures of 490–530 °C for the quartz–topaz rock and 415–505 °C for the zinnwaldite greisens. The fluids in equilibrium with the topaz–albite granite have calculated δ¹⁸O and δD values of 5.6–7.5‰ and − 67 to − 58‰, respectively. Estimated δ¹⁸O and δD values are mainly 4.8–7.9‰ and − 60 to − 30‰, respectively, for the fluids in equilibrium with the quartz–topaz rock and zinnwaldite greisen; and 3.4–3.9‰ and − 25 to − 17‰, respectively, for the Li-rich muscovite greisen fluid. δ³⁴S data on arsenopyrite from the quartz–topaz rock vary from − 1.74 to − 0.74‰, consistent with a magmatic origin for the sulfur. The integration of fluid inclusion with oxygen isotopic data allows for estimation of the minimum crystallization pressure at ca. 770 bar for the host topaz–albite granite, which is consistent with its evolved signature.Based on petrological, fluid inclusion and isotope data it is proposed that the greisens and related Mangabeira Sn–In mineralization had a similar hydrothermal genesis, which involved exsolution of F-rich, Sn–In-bearing magmatic fluids from the topaz–albite granite, early formation of the quartz–topaz rock and zinnwaldite greisen, progressive cooling and Li-rich muscovite greisen formation due to interaction with meteoric water. The quartz–topaz rock is considered to have formed in the magmatic-hydrothermal transition. The mineralizing saline and CO₂-bearing fluids are interpreted to be of magmatic origin, based on the isotopic data and paragenesis, which has been documented as characteristic of the tin mineralization genetically related to Proterozoic within-plate granitic magmatism in the Goias Tin Province, Central Brazil.     

In situ analyses of micas in the Yashan granite,South China: Constraints on magmatic and hydrothermal evolutions of W and Ta–Nb bearing granites

Most rare-metal granites in South China host major W deposits with few or without Ta–Nb mineralization. However, the Yashan granitic pluton, located in the Yichun area of western Jiangxi province, South China, hosts a major Nb–Ta deposit with minor W mineralization. It is thus important for understanding the diversity of W and Nb–Ta mineralization associated with rare-metal granites. The Yashan pluton consists of multi-stage intrusive units, including the protolithionite (-muscovite) granite, Li-mica granite and topaz–lepidolite granite from the early to late stages. Bulk-rock REE contents and La/Yb ratios decrease from protolithionite granite to Li-mica granite to topaz–lepidolite granite, suggesting the dominant plagioclase fractionation. This variation, together with increasing Li, Rb, Cs and Ta but decreasing Nb/Ta and Zr/Hf ratios, is consistent with the magmatic evolution. In the Yashan pluton, micas are protolithionite, muscovite, Li-mica and lepidolite, and zircons show wide concentration ranges of ZrO₂, HfO₂, UO₂, ThO₂, Y₂O₃ and P₂O₅. Compositional variations of minerals, such as increasing F, Rb and Li in mica and increasing Hf, U and P in zircon are also in concert with the magmatic evolution from protolithionite granite to Li-mica granite to topaz–lepidolite granite. The most evolved topaz–lepidolite granite has the highest bulk-rock Li, Rb, Cs, F and P contents, consistent with the highest contents of these elements and the lowest Nb/Ta ratio in mica and the lowest Zr/Hf ratio in zircon. Ta–Nb enrichment was closely related to the enrichment of volatile elements (i.e. Li, F and P) in the melt during magmatic evolution, which raised the proportion of non-bridging oxygens (NBOs) in the melt. The rims of zoned micas in the Li-mica and topaz–lepidolite granites contain lower Rb, Cs, Nb and Ta and much lower F and W than the cores and/or mantles, indicating an exotic aqueous fluid during hydrothermal evolution. Some columbite-group minerals may have formed from exotic aqueous fluids which were originally depleted in F, Rb, Cs, Nb, Ta and W, but such fluids were not responsible for Ta–Nb enrichment in the Yashan granite. The interaction of hydrothermal fluids with previously existing micas may have played an important role in leaching, concentrating and transporting W, Fe and Ti. Ta–Nb enrichment was associated with highly evolved magmas, but W mineralization is closely related to hydrothermal fluid. Thus these magmatic and hydrothermal processes explain the diversity of W and Ta–Nb mineralizations in the rare-metal granites.     

Compositional characteristics and Existing Forms of Major,Trace and Rare—earth Elements in Cassiterite,Dupangling Tin Ore Field,Guangxi

Trace elements in cassiterite,including Ta,W,Fe,Mn,Ti,Zr,V,Sc,Si,Al,In,Ga,Ge,Be,Bi,Ag,Sb,As,Cu,Pb,Zn,Co and REE,have been studied by many workers (Shan Zhenhua etal.,1998;Huang Zhou Tianren et al.,1987;Wu Qingsheng et al.,1988;Hu Zening,1988,Li Zhong-qing 1988 Mingzhei et al.,1988;Wang Lihua et al.,1988;Liu Kanghuai,1990).Up to now,however,most of the previous studies are concerned with trace-element variations in cassiterites of different occurrences and colors from different types of ore deposits,Data concerning the modes of occurrence of these trace elements are rare,except for the contention that Nb-Ta,Fe^2 -Mn-Fe^3 and W-Fe^3 may substitute isomorphously for Sn as pointed out by Zhou Tianren et al.(1987) and Moller et al.(1988).In this paper we are concerned with the compositional characteristics as well as the modes of occurrence of trace elements in cassiterites from quartz veins and greisens in the Dupangling tin field,Guangxi,based on multivariate statistical analyses.Tin mineralization in the Dupangling area is found associated with the medium-to fine-grained protolithionite-albite granite(γ5^2b) and its outer contacts.Cassiterite occurs,with wolframite,both in quartz veins in the contact and in greisens within the granite.^1) Spatially,greisens become dominant over quartz veins in the contact andin greisens with the granite.^1)Spatialy,gresens become dominant over quartz veins in going from the contact to the interior of the granite and with increasing depth.The greisens are of various shapes.The vein-shaped and the sheet-shaped greisens at the top of the granie are rich in quartz and the chambered greiens always constitute rich ores and contain abundant topaz or mica.Genetically,Sn,W mineralizations associated with the protolithionite-albite granite(γ5^2b) are considered to have been formed from fluid melt derived from the ore-forming magma responsible for the granite(γ5^2b).     

Mineralogical and Geochemical Characterization of Beryl-Bearing Granitoids, Eastern Desert, Egypt: Metallogenic and Exploration Constraints

Mineral chemistry and geochemical characteristics of beryl-bearing granitoids in Eastern Desert of Egypt, were examined in order to identify the metallogenetic processes of the host granitoids. The investigated Be-bearing granitoids and type occurrences are classified into two groups: (i) peraluminous, Ta ≥ Nb + Sn + Be ± W-enriched, Li-albite granite (e.g. Nuweibi and Abu Dabbab); and (ii) metasomatized, Nb >> Ta + Sn + Be ± W ± Mo-enriched alkali feldspar granite (i.e. apogranite; e.g. Homr Akarem, Homr Mikpid and Qash Amir). In these two groups, beryl occurs as stockwork greisen veins, greisen bodies, beryl-bearing cassiterite ± wolframite quartz veins, dissemination, and miarolitic pegmatites. Beryl of the Be-granitoids, particularly those of miarolitic pegmatites, contains appreciable contents of Fe, Na, and H₂O. An important feature of the Be-apogranites is the occurrence of white mica as the sole mafic mineral in the unaltered alkali feldspar granite in lower zones. Presence of white mica as volatile-rich pockets suggests that the melt underwent disequilibrium crystallization, rapid nucleation rates, and exsolving and expulsion of volatiles.     

The late stages of evolution of the Kwandonkaya A-type granite complex,Nigeria, as deduced from mafic minerals

In the Kwandonkaya Complex, an A-type metaluminous to peraluminous granite complex in northern Nigeria, the presence of Fe²⁺-rich ferromagnesian phases (fayalite, hedenbergite and amphibole) at the initial and annite at final stages of crystallisation indicates relatively reduced melts throughout (⪯QFM). Annite and associated species in the biotite granites provide the best indication as to the nature of volatile loss, albitisation and greisen formation.From the mica chemistry, it is inferred that degassing was accompanied by preferential loss of Cl in the roof zones and margins of the plutonic rocks, with the resulting enrichment of F and inferred Li in mica from the drusy facies. During albitisation, the mica composition was rockbuffered with respect to major constituents like Fe. However, the F±(Li, REE, Y, Nb, Ta, Sn) contents were enhanced during albitisation to produce F-rich mica associated with disseminated-type typaz-columbite-cassiterite mineralisation. Greisen formation was accompanied by the buildup of Si, Al, Ti, F and possibly Li, which is in agreement with enhanced normative quartz and corundum, and increases in modal mica, quartz, topaz and fluorite. The mafic minerals and their alteration assemblages indicate that volatile loss, incipient subsolidus modifications, albitisation and greisen formation were associated with increases in f_HF and f_H2O). Both oxidation and preferential Cl loss promoted the deposition of cassiterite at post-magmatic stages.     

一种特殊类型的云英岩:湘南香花岭地区癞子岭云英岩成岩成矿特征

癞子岭岩体具有极好的垂向分带性,从下部到顶部包括了花岗岩、云英岩和伟晶岩,其中云英岩以其厚度巨大,云母类型属于铁锂云母,黄玉含量高,W-Sn-Nb-Ta含量高,而区别于其他地区云英岩。通过对癞子岭云英岩进行岩石学、地球化学和矿物学的研究,本文得出:癞子岭云英岩是高硅的强过铝质岩石类型,全碱含量低(3~4.3 wt%),富集挥发组分,全岩Zr/Hf(~8)和Nb/Ta(~1.7)比值低。造岩矿物铁锂云母中Nb(~74×10~(-6))、Ta(~66×10~(-6))、W(~23×10~(-6))、Sn(~75×10~(-6))等成矿元素含量较高。副矿物锆石自形且成分均一,含有HfO_2约10 wt%,Zr/Hf比值最低为5,与云英岩下部的癞子岭钠长花岗岩中的锆石成分有连续过渡的关系。这些特征与南岭地区高演化稀有金属花岗岩或伟晶岩相当,体现了相近的演化程度。癞子岭云英岩中有明显的Nb-Ta-W-Sn成矿作用发生,主要形成铌铁矿族矿物、锡石和黑钨矿,成分和结构均具有岩浆成因特征。花岗质熔体中含有大量挥发组分Li和F,结晶出黄玉和Li-F云母,F在稀有金属的成矿作用和云英岩的成岩过程中发挥了非常重要的作用,成矿作用发生在岩浆演化的晚期并伴随有流体作用。因此,云英岩可能是钠长花岗岩高度分异演化之后的特殊产物,这为研究花岗岩岩浆-热液体系成岩成矿过程提供了新的窗口。     

Behavior of iron,uranium, and thorium during formation of secondary quartzites

This paper presents data on the age, composition, and origin of rare-metal granites and associated tin tungsten mineralization in the region of the Tigrin deposit, in the Central Sikhote-Alin' mountain range (Primor'ye). These granites were formed in two successive subphases. The porphyritic protolithionite granites constituting the upper stock belong to the first, and the zinnwaldite granites of the lower (Main) stock belong to the second. The age of the granites of the lower and upper stocks (67 and 73.2 Ma, respectively) was determined for the first time, by the Rb-Sr method. The rare-metal granites crystallized from a magma enriched in fluids, rare alkalies, and ore elements. The tin-tungsten ores of the Tigrin deposit, related to these granites, are classified as deposits of the cassiterite-quartz association, but they differ from such deposits in other regions in the extensive development of stannite, the presence of a substantial amount of varlamoffite in the zone of oxidation, and an insignificant amount of sulfides in the presence of extensive development of topaz and lithium-iron micas. Sc-W-Nb minerals were found for the first time-scandium minerals proper, scandian ixiolite, and scandian-tungsten ixiolite occurring in the form of inclusions in wolframite and cassiterite.

In the Tigrin deposit, tin mineralization of the greisen association is genetically related to the rare-metal granites, and extensive vein-veinlet ore zones in hornfels and granites are paragenetically related to them.     

新疆白石头泉高铷氟花岗岩不同相带云母成分及其演化

白石头泉含黄玉花岗岩体在露头上显示很好的岩性分带,从下至上依次为:淡色花岗岩(a带)、含天河石花岗岩(b带)、天河石花岗岩(c带)、含黄玉天河石花岗岩(d带)和黄玉钠长花岗岩(e带).岩体组成矿物主要为石英、钾长石(部分富铷的为天河石)、钠长石、黄玉和云母,副矿物为锰铝榴石和萤石.总体说来,从a带到c带,云母的Al、Mn、F和Rb含量递增,Fe、Mg和Ti含量递减;Li含量从a带到b带和c带递增,但b带和c带之间变化不明显.从c带到e带,随着Fe、Mg和Ti的减少,总体上表现为Al、Li递增,F、Mn和Rb递减的演化方向,但Li、F、Mn和Rb在c带和d带之间变化不明显,d带和e带之间却表现出急剧的变化.e带中的次生云母与原生云母相比,前者F、Li高而Al低,从a带到e带,Na K变化不明显.云母成分的这些变化特征与岩体的演化趋势相一致.白石头泉岩体与世界上其他地方类似花岗岩相比,没有出现锂云母这种高度富锂矿物,这可能与岩体中锂含量较低有关.     

An Overview on the REE-Mineralized Alkaline Granites in Egypt, with Special Reference to the Abu Khruq and Gara El Hamra Bodies

Abstract. The REE-mineralized alkaline granites in Egypt are divided into the following three classes: (1) Mesozoic, anorogenic nepheline syenite ring complexes with REE amounting up to 1.3 %, particularly in their fenitized parts (e.g. Abu Khruq), (2) an orogenic peralkaline syenite-granite, composed of i) Zr, Nb, - REE, and Th-enriched peralkaline granite-syenite complexes with REE amounting up to 0.5 % (e.g. Um Hibal, Tarbite North and South, Gharib, and Zarget Naam) and ii) Y, Th, HREE, and P-enriched post-Cretaceous peralkaline complexes that intrude the Phanerozoic rocks of the Southwestern Desert with REE amounting up to 2 % (e.g. Gara El Hamra), and (3) upper Proterozoic, post-orogenic siderophyllite alkali feldspar granite with REE amounting up to 0.8 %, particularly in their apical miarolitic pegmatites and albitized zones (e.g. Kadabora-Abu Dob and Um Naggat). Special attention is given to the Abu Khruq and Gara El Hamra granitic bodies.     

Phosphorus-rich topaz from fractionated granites (Podlesí, Czech Republic)

Summary A detailed electron microprobe study of P, F, Ge and Ga-contents in rock-forming topaz was performed on a suite of Variscan granites at Podlesí in the western Kruné Hory Mts., Czech Republic. Topaz crystals from the relatively less evolved biotite- and protolithionite granites display homogeneous cathodo-luminescence (CL) intensities, whereas topaz from the marginal pegmatite, highly fractionated zinnwaldite granite and greisens show intense oscillatory zoning. Phosphorus contents reach 1.15wt% P₂O₅ in topaz from the zinnwaldite granite. Many topaz crystals are distinctly zoned with a maximum P content in the transition zone between core and rim. Phosphorus is incorporated into the topaz lattice by berlinite substitution: Al³⁺+P⁵⁺=Si⁴⁺+Si⁴⁺. The majority of analysed topazes are highly saturated in F, reaching 90–97% of the theoretical maximum saturation. Topaz from the marginal pegmatite only reaches 87–90% of F-saturation. There is a positive correlation between P_topaz and P_{whole rock}, but no correlation between F_topaz and F_{whole rock}. No difference has been found in P and F contents between magmatic and the hydrothermal (=greisen stage) topaz. Contents of Ge and Ga vary from around the detection limit (50ppm) up to 200ppm Ge and 100ppm Ga, respectively.     

Contrasting evolution of low-P rare metal granites from two different terranes in the Hoggar area, Algeria

Two mineralogically different rare metal granites located in two distinct terranes from the Tuareg area are compared: the Tin-Amzi granite in the north of the Laouni Terrane and the Ebelekan granite in the Assodé–Issalane Terrane.The Tin-Amzi granite is enclosed within Eburnean granulitic gneisses, and consists of albite, quartz, protolithionite, K-feldspar and topaz granite (PG). The accessory minerals include columbite tantalite, U- and Hf-rich zircon, Th-uraninite, wolframoixiolite and wolframite. This facies is characterised by a mineralogical evolution from the bottom to the top underlined by a strong resorption of K-feldspar and albite and the crystalliK-feldspar of more abundant topaz and protolithionite II which is further altered in muscovite and Mn-siderite. It is underlain by an albite, K-feldspar, F-rich topaz, quartz and muscovite granite (MG), with W–Nb–Ta oxides, wolframite, Nb-rutile, zircon and scarce uranothorite as accessories.The Ebelekan granite intrudes into a coarse-grained biotite granite enclosed within upper amphibolite-facies metasediments. It comprises a zinnwaldite, albite, topaz porphyritic granite (ZG) with “snow ball” quartz and K-feldspar. The accessories are zircon, monazite, uranothorite, Ta bearing cassiterite, columbite tantalite and wodginite. It is capped by a banded aplite-pegmatite (AP).The geochemistry of Tin-Amzi and Ebelekan granites is nearly comparable. Both are peraluminous (A/CNK=1.10–1.29; ASI=1.17–1.31), sodolithic and fluorine rich with high SiO₂, Al₂O₃, Na₂O+K₂O, Rb, Ga, Li, Ta, Nb, Sn and low FeO, MgO, TiO₂, Ba, Sr, Y, Zr and REE contents. These rare metal Ta bearing granites belong to the P-poor subclass, relating to their P₂O₅ content ( 0.03–0.15 wt.%). Nevertheless, they are distinguished by their concentration of W, Sn and Ta. The Tin-Amzi granite is W–Ta bearing with high W/Sn ratio whereas the Ebelekan granite is Ta–Sn bearing with insignificant W content.At Tin-Amzi the W–Nb–Ta minerals define a sequence formed by W-columbite tantalite followed by wolframoixiolite and finally wolframite showing the effect of hydrothermal overprinting with an extreme W enrichment of the fluids. At Ebelekan, the Sn–Nb–Ta oxides follow a Mn sequence: manganocolumbite→manganotantalite→wodginite+titanowodginite→cassiterite that represents a trend of primary crystallisation resulting from progressive substitution Fe→Mn and Nb→Ta during the magmatic fractionation.     

Phyllosilicate and rutile compositions as indicators of Sn specialization in some southeastern Australian granites

Biotites from unaltered Sn granites in southeastern Australia are highly ferroan, Fe/(Fe+Mg+Mn) >0.75, whereas biotites from barren granites are less Ferich, Fe/(Fe+Mg+Mn)<0.65. Similar distinctions between Sn-specialized and barren granites can be observed in the other phyllosilicates, especially chlorite. Biotites and muscovites from Sn granites have greater Be, Cs, (F), Li, Mo, Rb, Sc, Sn, Tl, (Y) and Zn and lesser Ba abundances than corresponding micas from barren granites in the same district. Alteration of barren granites also results in similar enrichments in micas. Of these elements, Sn and Zn, because of their abundance and retention during degradation of biotite to chlorite, are the best trace element discriminants between barren granites and Sn granites/altered granites, with the Sn content of phyllosilicates being a better indicator than Zn. Rutile inclusions within phyllosilicates from unaltered Sn granites have Nb₂O₅ contents up to 26%. The Ta content tends to increase with Nb content but especially high Ta contents occur in the rutile inclusions of granites that give rise to pegmatitic deposits. The rutile inclusions in Sn granites may also have substantial Sn and W contents. The rutiles of barren granites have low Nb, Ta, Sn and W contents but Sn and W increase with alteration. Together, the ratio Fe/(Fe+Mg+Mn) and Sn contents in phyllosilicates and rutile compositions can be used to identify the Sn mineralization potential of a granite.     

云母:花岗岩-伟晶岩稀有金属成矿作用的重要标志矿物

云母是花岗岩、伟晶岩中的重要造岩矿物,不仅是整个岩浆阶段的结晶产物,而且也是热液过程的参与者。作为层状硅酸盐矿物,层间或八面体位置上可容纳锂、铷铯、锡、铌钽等稀有金属。本文结合前人研究积累和作者近年来的研究成果,阐述了云母作为一个重要的稀有金属成矿标志矿物的矿物学特征。铁锂云母-锂云母是稀有金属成矿作用中重要的锂矿物,同时云母中锂含量可以反映花岗岩的分异程度。铷、铯可以置换云母层间钾,在高演化花岗岩、伟晶岩中可以形成铷、铯为主的云母(既可以是锂云母系列,也可以是黑云母系列)。黑云母是稀有金属花岗岩中一个特殊的矿物。准铝质含锡花岗岩中黑云母锡含量可达100×10~(-6),其锡含量可以指示其锡成矿能力。稀有金属花岗岩中,常见的是铌钽氧化物矿物。但是最近研究发现,黑云母中铌可以超常富集(超过1000×10~(-6)),成为稀有金属花岗岩中最重要、甚至唯一的铌矿物,形成一种以富铌黑云母为特色的新类型稀有金属花岗岩,并可能代表了一种新型的潜在铌资源。基于云母在花岗岩中的重要性和结构的特殊性,今后要利用微区成分和结构分析技术,加强对云母中稀有金属晶体化学的研究,以及进一步揭示云母对稀有金属成矿的特殊重要意义。     

A combined EMPA and LA-ICP-MS study of Li-bearing mica and Sn–Ti oxide minerals from the Qiguling topaz rhyolite (Qitianling District,China): The role of fluorine in origin of tin mineralization

The Sn-rich Qiguling topaz rhyolite dike intrudes the Qitianling biotite granite of the Nanling Range in southern China; the granite hosts the large Furong Sn deposit. The rhyolite dike is typically peraluminous, volatile-enriched, and highly evolved. Whole-rock F and Sn concentrations attain 1.9 wt.% and 2700 ppm, respectively. The rhyolite consists of a fine-grained matrix formed by quartz, feldspar, mica and topaz, enclosing phenocrysts of quartz, feldspar and mica; it is locally crosscut by quartz veinlets. Lithium-bearing micas in both phenocrysts and the groundmass can be classified as primary zinnwaldite, “Mus-Ann” (intermediate member between annite and muscovite), and secondary Fe-rich muscovite. Topaz is present in the groundmass only; common fluorite occurs in the groundmass and also in a specific cassiterite, rutile and fluorite (Sn–Ti–F) assemblage. Cassiterite and rutile are the only Sn and Ti minerals; both cassiterite and Nb-rich rutile are commonly included in the phenocrysts. The Sn–Ti–F assemblage is pervasive, and contains spongy cassiterite in some cases; cassiterite also occurs in quartz veinlets which cut the groundmass. Electron microprobe and LA-ICP-MS compositions were used to study the magmatic and hydrothermal processes and the role of F in Sn mineralization. The presence of zinnwaldite and “Mus-Ann”, which are respectively representative of early and late mica crystallization during magma differentiation, also suggests a significant decrease in f(HF)/f(H₂O) of the system. Cassiterite included in the zinnwaldite phenocrysts is suggested to have crystallized from the primary magma at high temperature. Within the Sn–Ti–F aggregates, rutile crystallized as the earliest mineral, followed by fluorite and cassiterite. Spongy cassiterite containing inclusions of the groundmass minerals indicate a low viscosity of the late fluid. The cassiterite in the quartz veinlets crystallized from low-temperature hydrothermal fluids, which possibly mixed with meteoric water. In general, cassiterite precipitated during both magmatic and hydrothermal stages, and over a range of temperatures. The original fluorine and tin enrichments, f(HF)/f(H₂O) change in the residual magma, formation of Ca,Sn,F-rich immiscible fluid, decrease of the f(HF) during groundmass crystallization, and mixing of magma-derived fluids with low-saline meteoric water during the late hydrothermal stage, are all factors independently or together responsible for the Sn mineralization in the Qiguling rhyolite.     

Chemical Features of White Micas from the Piemonte Calc-schists, Western Alps and Implications for K–Ar Ages of Metamorphism

Anomalously large chemical ranges in muscovite-paragonite and muscovite-celadonite systems are observed in white micas from the Piemonte calcschists in the Chisone valley area, internal western Alps. The petrographical and chemical observations on white mica strongly suggest that most mica crystals with high Na/K ratios in the chlorite zone are of detrital origin, and were derived from the pre-Alpine high-temperature metamorphic sequence such the Caledonian and/or Variscan. Submicroscopic muscovite (Ms) - paragonite (Pg) composite aggregates occur in the chlorite zone and their EPMA analyses give an apparent chemical composition range from Ms_0.6Pg_0.4 to Ms_0.2Pg_0.8. In the rutile zone, the paragonite content of the white micas is less than 20%, suggesting that the white micas have been homogenized during the Alpine metamorphism even if detrital white micas existed.Metamorphic mica is also very heterogeneous. The total range in Si content becomes wider with increasing of metamorphic grade: 3.22–3.39 pfu for the chlorite zone, 3.07–3.45 pfu for the chloritoid zone and 3.06–3.59 pfu for the rutile zone. This clearly indicates that the micas have experienced significant retrogressive chemical reactions during cooling and exhumations of the host schists.The detrital white mica in the chlorite zone has not reset well in its K-Ar system during the Alpine subduction-related metamorphism. The wide range of the white mica K-Ar ages from 115 to 41 Ma must be due to a mixture of various amounts of detrital white mica in the separates. This feature is also observed in the chloritoid zone though the age variation is not so large as that in the chlorite zone. In contrast, the mica in the rutile zone, which was higher than 450°C, has been reset completely during Alpine HP metamorphism.     

Implications from inclusions in topaz for greisenisation and mineralisation in the Hensbarrow topaz granite, Cornwall, England

Textural and geochemical studies of inclusions in topaz from greisens in the Hensbarrow topaz granite stock (St. Austell, Cornwall) are used to constrain the composition of fluids responsible for late stage greisening and mineralisation. The topaz contains an abundant and varied suite of inclusions including aqueous liquid + vapour (L + V), quartz, zinnwaldite, albite, K-feldspar, muscovite, ilmenorutile, apatite, columbite, zircon, varlamoffite [(Sn, Fe)(O, OH)₂] and qitianlingite [(Fe⁺²,Mn⁺²)₂(Nb,Ta)₂W⁺⁶O₁₀]. Primary L + V inclusions in topaz show relatively high T _h (mainly 300 to >500 °C) and a narrow range of salinities (23–30 wt % NaCl equivalent) compared with those in greisen quartz (150–450 °C, 0–50 wt % NaCl equivalent). Textures indicate that topaz formed earlier than quartz and the fluid inclusion data are interpreted as indicating a cooling of the hydrothermal fluids during greisenisation, mixing with meteoric waters and a decrease in pressure causing intermittent boiling. The presence of early-formed albite and K-feldspar as inclusions in the topaz is likely to indicate that the greisen-forming fluid became progressively more acid during greisenisation. The most distinctive inclusions in the topaz are wisp- and bleb-shaped quartz, < 50 μm in size, which show textural characteristics indicating former high degrees of plasticity. They often have multiple shrinkage bubbles at their margins rich in Sn, Fe, Mn, S and Cl and, more rarely, contain euhedral albite, K-feldspar, stannite or pyrrhotite crystals up to 40 μm in size. The quartz inclusions show similar morphologies to inclusions in topaz from quartz-topaz rocks elsewhere which have been interpreted as trapped “silicate melt”. Their compositions are, however, very different to those expected for late stage topaz-normative granitic melts. From their textural and chemical characteristics they are interpreted as representing crystallised silica colloid, probably trapped as a hydro gel during greisenisation. There is also evidence for the colloidal origin of inclusions of varlamoffite in the topaz. These occurrences offer the first reported evidence in natural systems for the formation of colloids in high temperature hydrothermal fluids. Their high ore carrying potential is suggested by the presence of varlamoffite and the occurrence of stannite, pyrrhotite and SnCl within the quartz inclusions. Received: 9 April 1996 / Accepted: 12 November 1996     

湖南尖峰岭稀有金属花岗岩地球化学特征及成矿作用

湖南尖峰岭矿床是一个典型的花岗岩型Li、Nb和Ta稀有金属矿床,为研究花岗岩成矿作用以及指导湘南地区稀有金属找矿工作,采用XRF、ICP-MS和ISE法分析了与成矿有关的黑云母花岗岩、钠长石花岗岩及云英岩的中主量、微量元素和挥发分。结果表明:钠长石花岗岩和云英岩中的SiO_2(70.6%~84.85%)和挥发分F(2.43%~3.74%)质量分数高,富Al_2O_3(9.36%~22.99%),且A/CNK1.0,为过铝质岩石,全碱(w(Na_2O+K_2O)=1.51%~7.52%)和w(CaO)(0.1%~3.44%)变化大,w(Fe_2O_3)、w(MgO)、w(TiO_2)、w(MnO)、w(P_2O_5)较低;稀土元素组成具显著的Eu负异常和"M"型四分组效应,强烈富集Rb、Th、U、Nb、Ta元素,亏损Ba、Sr、Ti元素。花岗岩地球化学特征显示在演化过程中经历了高程度分异演化作用和岩浆不混溶作用,其挥发分F对稀有元素有明显的富集作用,并制约着熔体/流体体系的地球化学行为及其成矿效应。钠长石花岗岩和云英岩的稀有金属富集成矿受到岩浆不混溶作用、水岩反应、风化淋滤作用的共同控制。     

松树岗钽铌钨锡矿床石英脉的矿物学研究——云母和黑钨矿成分对热液成矿过程的制约

矿石矿物和脉石矿物的成分演化蕴含了热液成矿过程的详细信息。本文基于岩相学观察,从云母和黑钨矿着手,利用电子探针和LA-ICP-MS分析技术,对赣东北松树岗Ta-Nb-W-Sn矿床的浅部热液成矿过程开展了研究。结果表明,松树岗矿床浅部的钨锡矿体的石英脉,从早到晚,由深至浅,可以划分为黑钨矿石英脉、锡石石英脉、硫化物石英脉和贫矿石英脉。4类石英脉中都含有早期的铁锂云母和晚期的白云母与铁的氧化物集合体,深部早期脉中的云母以铁锂云母为主,而浅部晚期脉中的云母以白云母为主。与早期铁锂云母相比,晚期白云母具有明显较低的Ti、Na、Rb、Cs、W、Nb、Zn、Li_2O含量和明显较高的Pb、Cu、B含量。从深部早期脉到浅部晚期脉,云母成分存在如下演化趋势:Ti、Na、W、Nb含量降低,Pb、Zn、Cu、Li_2O、B含量增高。不同深度的黑钨矿石英脉中含有两种不同成分的黑钨矿,属同一期演化早晚形成。相对于热液流体早期沉淀的黑钨矿,晚期黑钨矿具有明显较低的Nb、Ta、Zr、Hf、Ti、Sn、U、In、Sc含量和明显较高的Mo含量和Fe O/MnO值。云母和黑钨矿主微量元素成分的演化揭示了在松树岗矿床浅部的热液成矿早期以岩浆热液为主,晚期由于水岩反应的加强有较多围岩物质贡献。     

湖南香花岭地区花岗岩中锂对成岩成矿的制约

锂(Li)是一种战略关键金属,岩浆阶段主要在花岗质岩石中得到富集和结晶.由于具有不相容和富挥发性等性质,锂对花岗岩的成岩成矿具有重要的制约.文章利用电子探针、LA-ICP-MS等分析手段,对湖南香花岭地区癞子岭和尖峰岭花岗岩进行系统岩相学、主微量和矿物学研究,结果表明:(1)花岗质岩浆结晶分异过程中,Li含量逐渐升高,...