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

Paragenetic, textural, and chemical characteristics of micas from 10 rare-metal granitic stocks and the associated greisens were examined in order to identify the metallogenetic processes of the host granitoids. The investigated granitoids and type occurrences can be categorized as: (1) metaluminous, Nb + Zr + Y-enriched alkali granite (e.g., Hawashia, Ineigi, and a stock northwest of Um Naggat); (2) peraluminous, Ta > Nb + Sn ± W + Be-enriched Li-albite granites (e.g., Nuweibi, Igla, and Abu Dabbab); and (3) metasomatized, Nb » Ta + Sn + Zr + Y + U ± Be ± W-enriched apogranites (e.g., Um Ara, Abu Rusheid, Mueilha, and Homr Akarem).

Mica of the alkali granite is of the annite-siderophyllite series, and is characterized by an average FeO? of 28.14, low MgO of 0.05, a mean Fe?/(Fe? + Mg)_atom. value of 0.996, TiO₂ of 0.69, enhanced Al₂O₃ of 14.91, MnO of 0.58, Li₂O of 0.26, and moderate to low F of 0.86. These characteristics are representative of the relatively highly evolved nature of the annite-siderophyllite-bearing magmas. The micas closely resemble those of the anorogenic pegmatites and A-type granites.

Primary mica of the Li-albite granites is compositionally constrained between zinnwaldite in the lower zones, and white mica in the apical, more evolved zone, and is associated with columbite-tantalite, topaz, and fluorite. The occurrence of zinnwaldite with high contents of Mn and F indicates its stabilization at rather low temperatures in Li- and F-rich sodic melts. The restriction of white mica with lower Mn, F, and Li contents to the apical zones can be attributed to either volatile degassing or to the beginning of topaz crystallization. These two factors brought about an evolutionary trend for micas, which contrasts with the documented trends of Li-micas in other Li-granites (i.e., from Li-siderophyllite or Li-muscovite to lepidolite).

Micas range in composition between white mica in the lower unaltered zones of the apogranites and Li-siderophyllite-zinnwaldite in the apical microclinized and albitized zones; this systematic compositional change appears to reflect roofward increasing in μ_KF and μ_LiF of the exsolved fluids. Columbite, cassiterite, zircon, xenotime, beryl, and fluorite are common associates of the zinnwaldites. However, white micas from the greisenized apogranite and endogreisen veins have diminishing Li contents. The subsolidus formation of zinnwaldite and Li-siderophyllite in the apogranites, and white mica in the associated greisens, represent transitions from magmatic to hydrothermal environments under the influence of decreasing P, T, salinity, and alkalinity of the exsolved fluids.     

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

Late Paleozoic rare-metal granitoid magmatism of the Southern Baikal region

The Late Paleozoic intraplate magmatism of the Selenga-Vitim structural zone of the Baikal region (Khamar-Daban Range) produced granitoids of different geochemical types: palingenic calc-alkaline granitoids, subalkaline monzogranites, and rare-metal Li-F granitoids and their subvolcanic analogues. Subalkaline and rare-metal granitoids occur in the periphery of the Late Paleozoic magmatic zone. Rare metal granite magmatism is manifested in this region as nearly N-S trending intrusive-dike belts comprising multiphase intrusions (Kharagul, Urugudei, and Bitu-Dzhida massifs) with an exposed area of ∼10 km² and an age of formation from 311 to 321 Ma and series of accompanying dikes. The early phases of the intrusions are made up of biotite granites usually with fluorite, which are changed during the late stage by typical topazbearing rare-metal amazonite-albite granites. In the subvolcanic facies, thicker subalkaline dikes of monzonite porphyry, granite porphyry, and elvan are changed by ongonites, topaz rhyolites, and topazites, which occasionally serve as cement in eruptive and fluid-explosive breccias. The development of multiphase intrusions from early biotite granites to late amazonite-albite granites with Li-F mica was accompanied by an increase in SiO₂ and, especially, Na₂O contents, whereas the level of (FeO + Fe₂O₃), CaO, and K₂O declined. Geochemical evolution includes an increase in the same direction in the contents of F, Li, Rb, Cs, Sn, Be, Ta, and Pb and a decrease in Ba, Sr, Zn, Zr, Th, and U. Similar evolution is also characteristic of the subvolcanic rocks, which emphasizes the genetic relation of the whole intrusive-dike complex of the Khamar-Daban province. Significant differences were detected in the distribution of K, Ba, Sr, and Zr between the calc-alkaline granitoids and rare-metal Li-F granites. The continental crust-normalized patterns of the raremetal granites show positive anomalies for Li, Rb, Nb, and Pb. The rare-metal Li-F granites could not be produced by palingenesis only, and their formation required specific conditions causing extensive accumulation of characteristic trace elements. During the evolution of granite melts, Li, Rb, Ta, Nb, Sn, W, and F are extensively accumulated in late intrusive phases, which indicates an important role of the processes of magmatic and fluid-magmatic differentiation during their formation. The composition and isotope geochemical characteristics of the supposed magma source material correspond to the ancient Precambrian continental crust with a mean model age of more than 1200 Ma.     

WALL ROCK ALTERATIONS OF HYDROTHERMAL PNEUMATOLYTIC DEPOSITS OF RARE ELEMENTS

The geochemical features of hydrothermal-pneumatolytic rare element deposits are discussed on the basis of a natural connection between high temperature metasomatism phenomena and concentration processes of some rare elements. Two kinds of metasomatic processes are most interesting from the view-point of rare elements (albitization and greisenization). Li and Rb are concentrated in zinnwaldite-bearingalbitized granites and greisens. Nb, Ta (in columbite, pyrochlore, microlite, hatchettolite), Zr (in malacone zyrtolite), Be (beryl) are concentrated in albitized and greisenized granites. The beryllium deposits are closely connected with greisens of different composition, and quartz-greisen veins. The fluorite-bearing metasomatic rocks among carbonate rocks are characterizedby accumulations of Be (chrysoberyl, phenacite, taateite, sianhualite), Li (Li - margarite), Sn (cassiterite). The character of postmagmatic alterations of intrusive and wall rocks is a valuable indicator of the possibility of concentration of different rare elements.—Auth. English Summary.     

Tetrad effects in the rare earth element patterns of granitoid rocks as an indicator of fluoride-silicate liquid immiscibility in magmatic systems

This paper focuses on reasons for the appearance of tetrad effects in chondrite-normalized REE distribution patterns of granitoids (Li-F granites, peralklaine granites, ongonites, fluorine-rich rhyolites, and granitic pegmatites). The analysis of published data showed that the alteration of such rocks by high- and/or low-temperature metasomatic processes does not result in most cases in the appearance or enhancement of M-type tetrad effects in REE patterns. These processes are accompanied by the removal or addition of lanthanides, a W-type sag appears between Gd and Ho, and negative or positive Ce anomalies develop sometimes in REE patterns. The formation conditions of peculiar rocks enriched in Ca and F from the Ary Bulak ongonite massif (eastern Transbaikalia) and the character of REE distribution in these rocks and melt inclusion glasses were discussed. Based on the obtained data and the analysis of numerous publications, it was concluded that REE tetrad effects in rare-metal granitoids are caused by fluoride-silicate liquid immiscibility and extensive melt differentiation in the accumulation chambers of fluorine-rich magmas. A considerable increase in fluorine content in a homogeneous granitoid melt can cause its heterogenization (liquation) and formation of fluoride melts of various compositions. The redistribution of lanthanides between the immiscible liquid phases of granitoid magma will result in the formation of M-type tetrad effects in the silicate melts, because the REE patterns of fluoride melts exhibit pronounced W-type tetrad effects. The maximum M-type tetrad effect between La and Nd, which is observed in many rare-metal granitoids, is related to the character of REE partitioning between fluoride and silicate melts and F- and Cl-rich magmatic fluids. The low non-chondritic Y/Ho ratio (<15) of many rare-metal granitoids may be indicative of a contribution of fluoride melts to the differentiation of F-rich silicic magmas, from which these rocks were formed. The influence of high-temperature F-Cl-bearing fluids on melts and/or granitoid rocks results in an increase in Y/Ho ratio owing to the elevated solubility of Ho in such fluids.     

Geology,geochemistry and petrogenesis of late Precambrian granitoids in the Central Hijaz Region of the Arabian Shield

Late Precambrian granitoid rocks occurring within a 44,000 km² area of the western Arabian Shield are subdivided on the basis of geology and petrology into older (820 to 715 Ma) and younger (686 to 517 Ma) assemblages. The older assemblage contains major complexes which can be assigned to either one of a granodioritic or trondhjemitic petrologic association. The earliest granitoid rocks are trondhjemitic tonalites (trondhjemite association), depleted in Ba, Ce, F, La, Li, Nb, Rb, Y and Zr compared to granitoids of the slightly younger granodiorite association, which are related to a calcic, calc-alkaline suite of rocks ranging in composition from gabbro through monzogranite. The plutonic rocks of the older assemblage were probably emplaced in the cores of contemporary island arcs.The younger plutonic assemblage is dominated by three, geochemically distinct, coeval granitic associations: the alkali granite, alkali-feldspar granite and monzogranite associations. The alkali granite association is composed of perthite granites (alkali granites and genetically related alkali-feldspar granites). Rocks of this association are marginally peralkaline or metaluminous and are characterized by low contents of Ba, Co, Li, Rb, Sc and Sr, and high contents of Be, Cu, F, REE, Nb, Sn, Y, Zn and Zr. The alkali-feldspar granite association is mainly composed of alkali-feldspar granites and syenogranites. Rocks of this association are marginally peraluminous or metaluminous and contain low Ba, Sr, and high F, Rb, Sn, Th and U. The monzogranite association consists mainly of monzogranites and granodiorites. Rocks of this association are peraluminous or marginally metaluminous and have the highest contents of Ba, Cu, Co, Li, Sc, Sr, Ta, and V, and the lowest contents of REE, Nb, Rb, Sn, Th, U, Y, Zn and Zr of the three granitic associations.These voluminous granitic magmas, together with the felsic component of a coeval sequence of bimodal volcanic rocks, are partial melts of the earlier island arc terrain produce during a prolonged fusion event. Subsolvus, highca granites of the monzogranite association have I-type features and represent partial melts of previously unfused crust, while low-Ca perthite granites of the alkali granite and alkali-feldspar granite associations have A-type features and represent partial melts of previously fused crust.This type of petrogenetic model can account for much of the petrologic diversity of the Pan-African granitic terrain of the Arabian Shield.     

Abdar-Khoshutula intrusive-dike series: Evolution and origin of granitoids in Early Mesozoic magmatic area (Central Mongolia)

The dike belt and separate intrusive bodies of the Abdar–Khoshutula series were formed in the NE-trending linear zone, southwest of the Daurian–Khentei batholith, in the peripheral part of the Early Mesozoic magmatic area, on the western termination of the Mongol–Okhotsk belt. The granitoids of this series are subdivided into following geochemical types: anatectic granitoids of the calc-alkaline and subalkaline series, alkaline rocks, and plumasite rare-metal leucogranites (Li–F granites). The entire series was formed within approximately 12–15 Ma. Its geochemical evolution follows two trends, which correspond to two stages of the granitoid magmatism. The early stage was responsible for the formation of granitoids of two phases of the Khoshutulinsky Pluton and alkaline syenites with similar trace element distribution patterns. However, syenites, as agpaitic rocks, are significantly enriched in Ba, Zr, and Hf. The late stage of the intrusive- dike series resulted in the formation of the dike belt and Abdar Massif of rare-metal granites. These rocks show enrichment in Li, Rb, Cs, Nb, Ta, Sn, and Y, and deep negative anomalies of Ba, Sr, La, and Ce, which are best expressed in the late amazonite–albite granites of the Abdar intrusion and ongonites of the dike belt. The intrusive-dike series in the magmatic areas of different age of Mongolia and Baikal region are characterized by the wide compositional variations, serve as important indicators of mantle-crustal interaction and differentiation of granitoid magmas, and could highlight the nature of zonal areas within the Central Asian Fold Belt. Obtained geochemical data indicate a potential opportunity to concentrate trace and ore components during long-term evolution of the intrusive-subvolcanic complexes, which could be indicators of the evolution of the ore-magmatic systems bearing rare-metal mineralization.     

Exhalative Sn and W deposits associated with mafic volcanism as precursors to Sn and W deposits associated with granites

Precambrian and Early Palaeozoic submarine exhalative Sn and W deposits are most commonly present in thick deep water sequences comprising pelites, carbonate, calcsilicate and cherty rocks, mafic volcanics and quartz-tourmaline rocks. The exhalative deposits are commonly low grade and, in places, the sequence is transgressed by granites with economic Sn or W mineralisation. These thick deep water sequences as components of sinking trenches are more likely than most other rocks to undergo high grade metamorphism and anatexis. Thus elements such as Sn, W, B, F, Mo, Bi, Li, Be and base metals associated with the exhalites rapidly partition into the anatectic melt, lower the liquidus and solidus, and are concentrated in the late stage aqueous fluids and residual melt fractions to form Sn or W deposits associated with highly fractionated granitic rocks.     

Trace elements and evolution of granite melt as exemplified by the Raumid Pluton,Southern Pamirs

New trace element data were obtained by ICP-MS for 58 samples representing eight intrusive phases of the Raumid granite Pluton. All of the rocks, except for one sample that was deliberately taken from a greisenized zone, were not affected by postmagmatic fluid alteration. The sequential accumulation of incompatible trace elements (Rb, Ta, Nb, Pb, U, and others) in the Raumid Pluton from the early to late phases coupled with a decrease in incompatible element contents (Sr, Eu, Ba, and others) indicates a genetic link between the granites of all phases via fractional crystallization of a granite melt. The REE distribution patterns of final granite phases are typical of rare-metal granites. The Ta content in the granites of phase 8 is only slightly lower than that of typical rare-metal granites. Greisenization disturbed the systematic variations in trace element distribution formed during the magmatic stage. The ranges of trace element contents (Rb, Sr, Ta, Nb, and others) and ratios (Rb/Sr, La/Lu, Eu/Eu*, and others) in the Raumid granite overlap almost entirely the ranges of granitic rocks of various compositions, from the least differentiated with ordinary trace element contents to rare-metal granites. This indicates that the geochemical signature of rare-metal granites can develop at the magmatic stage owing to fractional crystallization of melts, which is the case for the melt of the Raumid granite.     

富锂氟含稀有矿化花岗质岩石的对比和成因思考

Li-F花岗质岩石以超酸性、过铝、富含H2O、F、B、P等挥发性组分和富含Li、Rb、Cs、Be、Ta、Nb、Sn、W等亲石稀有金属元素为主要特征，以黄玉－锂云母－钠长石花岗岩为典型代表。从该类岩石地质产状的多样性和可对比性、空间分布的规律性、矿物岩石的结构构造、硅酸盐－熔体包裹体特征以及实验岩石学的研究成果等方面，综合论证该类岩石主要是从经过分异演化而形成的残余熔浆中直接结晶而在的；充分的分离结晶作用，是产生这种残余熔浆的主要机制；岩体的空间分带特征和各带之间的渐变过渡关系，为分离结晶作用的途径和演化方向提供了重要信息；熔体中挥发性组分的大量存在，是分离结晶作用能充分进行的关键因素；亲石稀有金属元素在流／熔配分中倾向于进入熔体相，是残余熔体中逐步富集这些稀有金属元素的主要原因；岩浆－热液过渡阶段出溶的流体相与已晶出的共存固相之间的相互作用，造成了广泛的交代蚀变现象；残余熔浆在不同地质和物理化学环境中的侵位、结晶和演化，造成了Li-F花岗质岩石在产状、结构构造和矿物组合等方面的多样性。     

Experimental partitioning of Be,Cs, and other trace elements between cordierite and felsic melt,and the chemical signature of S-type granite

The trace-element signature that cordierite (Crd) imparts to silicic magmas was evaluated by experiment using metapelite mineral mixtures to produce cordierite-bearing peraluminous granitic melts at 200 MPa (P_H2O), from 700 to 850 °C. Most elemental partition coefficients vary with T. Beryllium is strongly compatible, with D_Be^Crd/melt values decreasing linearly from 202.0 to 6.7 as T rises from 700 to 850 °C. Manganese is compatible (D_Mn^Crd/melt=7.67 to 1.92 over the same range of T), and shows similar values to those reported for biotite in silicic melts. Incompatible components include Li, Rb, B, F and P, although Cs is nearly compatible in cordierite, especially at higher T (D_Cs^Crd/melt=~0.19 to 0.60) where the large alkalis are better accommodated structurally. Cordierite appears to be the most effective crystalline reservoir of Be and Cs in metapelites and their anatectic melts. Natural data support the hypothesis that Crd, when present in granitic melts, sequesters Be, Cs and, in the absence of garnet, Mn. S-type granitic rocks containing Crd show consistently low Be contents (mean=0.8 ppm Be with an average range of <1 to 1.20) whereas Crd-free granites (e.g., containing accessory garnet) exhibit distinctly higher Be contents (mean=6 ppm Be with an average range of 3 to 12). These values increase further in evolved facies (mean=69 ppm Be with a an average range of 11 to 145) which commonly give rise to beryl-bearing pegmatites. Whole-rock signatures of Be discriminate source environments of silicic magmas at a resolution equal to the boundaries of the cordierite stability field - e.g., at the P-T-X conditions where cordierite gives rise to garnet+aluminum silicate. Cordierite-bearing granitic rocks contain low Cs contents (mean=1.8 ppm Cs) compared to the Crd-free equivalents (mean=18 ppm Cs). Mn contents also correlate with the presence (mean=0.01 wt% MnO) or absence of Crd (mean=0.09 wt% MnO). Depending on its contribution to anatexis, cordierite may either give or take S-type chemical character from granitic liquids, resulting in a distinctive Crd-associated group of S-type elements. This signature is different from that of micas (high Li, F and, to a lesser degree, Be and Mn). Whole-rock compositions of granites, coupled with notable absences of beryl in their associated pegmatites, indicate that a sizable population of S-type granites originated from Crd-bearing sources. The normative Crd component of silicic peraluminous melts is Д wt% to 850 °C. Higher modal contents of cordierite reflect either restite entrainment or peritectic reactions which produce Crd after magma ascent to shallow depths. The distinctive trace-element signature of cordierite now provides improved resolution of the source mineralogy for S-type magmas.     

Rare-metal pegmatoid granites,markers of the beginning of the Hercynian within-plate stage in the Ol’khon region of the Baikal area

On the background of Early Paleozoic precollisional, syncollisional, and late collisional igneous rocks prevailing in the region (Khaidai and Shara-Nur granitoids and Birkhin gabbroid complex), rare-metal pegmatoid granite bodies and pegmatites along the southern edge of the Ol’khon region are of particular interest. They have a Middle Paleozoic age (390-391 Ma), cut the Caledonides, and belong to different geochemical types. The Anga unit includes amazonite-containing Li-F-B pegmatites, which are also enriched in Ta, Nb, and W. In the Ol’khon Group, only one K-feldspathic body rich in Rb, Be, Nb, W, Sn, Sc, U, and Th, with large crystals of aquamarine, has been found. The compositions of granite-pegmatite bodies and accessory rare-metal minerals have been studied. The rare-metal granite-pegmatites probably form a peripheral zone of the Hercynian within-plate setting widespread in the eastern Baikal area and related to the influence of the Siberian hot spot.     

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。     

Hydrosilicate liquids in the system rare-metal granite–Na<Subscript>2</Subscript>O–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O as accumulators of ore components at high pressure and temperature

Experimental investigations in the system rare-metal granite–Na₂O–SiO₂–H₂O with the addition of aqueous solutions containing Rb, Cs, Sn, W, Mo, and Zn at 600°C and 1.5 kbar showed that the typical elements of rare-metal granites (Li, Rb, Cs, Be, Nb, and Ta) are preferentially concentrated in hydrosilicate liquids coexisting with aqueous fluid. The same behavior is characteristic of Zn and Sn, the minerals of which are usually formed under hydrothermal conditions. In contrast, Mo and W are weakly extracted by hydrosilicate liquids and almost equally distributed between them and aqueous fluids. Liquids similar to those described in this paper are formed during the final stages of magmatic crystallization in granite and granitepegmatite systems. The formation of hydrosilicate liquids in late magmatic and postmagmatic processes will be an important factor controlling the redistribution of metal components between residual magmatic melts, minerals, and aqueous fluids and, consequently, the mobility of these components in fluid-saturated magmatic systems enriched in rare metals.     

Geochemical Exploration on the Stream Sediments of Gabal El Mueilha Area, Central Eastern Desert, Egypt: An Overview on the Rare Metals

Abstract: El Mueilha area consists of post-collision granitic rocks intruding Pan-African metasediments, metavolcanics and granodiorites. Tin mineralization in Gabal El Mueilha is either of vein type or disseminated in the greisenized and albitized parts of the granitic rocks. Cassiterite and wolframite-bearing quartz veins also characterize a small intrusion of muscovite granite at El Mueilha tin mine area. Detailed geochemical prospecting for the rare metals Sn, Nb, Be, Li, U, Th and some other trace elements was carried out at Gabal El Mueilha area using stream sediments survey. Sixty-seven stream sediment samples were collected from the main drainage patterns of the study area. Statistical parameters were calculated for the analyzed elements. The sought elements Sn, Nb, Be and Li have relatively high background values in the studied sediments. This may reflect the role of the pathfinder elements (Nb, Be and Li) during secondary dispersion survey for Sn mineralization.
Geochemical maps were constructed to delineate anomalous areas with abnormally high rare metal contents. The anomalous Sn, Nb and Be areas are mainly encountered in the main stream draining the mineralized zones of El Mueilha tin mine and near the SW albitized parts of the post-collision granite. Correlation coefficient matrices show significant positive relation between Sn and the rare metals group (Nb, Rb and Li) at 99 % significant level. R-mode factor analysis for the concerned elements yields five factor–model.     

Geochemistry, geochronology and mineralisation potential of the granites in the Central Iberian Zone: The Jalama batholith

The Jalama batholith (Spain and Portugal) is one of the numerous granites of the Central Iberian Zone with Sn- and W-associated mineralisation. On the basis of petrographical and geochemical characterisation three types of granite have been distinguished: inhomogeneous granitoids, porphyrytic granites and leucogranites, all of these being peraluminous and subalkaline. All the granites correspond to S-type granites. The field data, the petrography and lack of geochemical affinity relationships of the leucogranites with the remaining granites indicate that their geneses correspond to an independent magma batch and superimposed fractional crystallisation process. The granitic units show subparallel REE patterns. There is a decrease in total REE and an increase in the negative Eu anomaly from the inhomogeneous granitoids to leucogranites. Some leucogranites show relatively low contents of Sn and W almost certainly due to segregation in the magma of a melt rich in water carrying Sn-W. These elements are concentrated in the water phase, which eventually gives rise to Sn-W-associated mineralisation.The ages obtained by means of a whole-rock Rb-Sr isochron for the granites mainly indicate an early intrusion of the inhomogeneous granitoids (319±10 Ma), followed in time by porphyrytic granites (279±9 Ma), which can be associated to the late-post-kinematic granites within the third Variscan deformation phase (D₃).Apart from the average Sn content, the variations of trace elements, principally Sr, Ba, Rb, Th and P, establish that the porphyritic granites and the inhomogeneous granitoids will be barren granites while the leucogranites and the subfacies at the margin of the porphyritic granites correspond to granites with mineralisation potential. It is precisely in these granites of the Jálama batholith that the Sn-W mineralisation is located, for which the criteria utilised has been demonstrated to be effective.     

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.     

Zr/Hf ratio as an indicator of fractionation of rare-metal granites by the example of the Kukulbei complex,eastern Transbaikalia

The concept of granitic melt fractionation as the main process in the concentration of rare elements in granites calls for the development of a reliable method to determine the evolutionary sequences of granite series. We propose to use for this purpose a zirconium-hafnium indicator, the Zr/Hf weight ratio in granitic rocks (Zaraisky et al., 1999, 2000). By the example of three classic regions of rare-metal deposits, eastern Transbaikalia, central Kazakhstan, and Erzgebirge (Czech Republic and Germany), it was empirically shown that the Zr/Hf ratio of granites decreases during the fractional crystallization of granite magmas in the sequence granodiorite → biotite granite → leucogranite → lithium-fluorine granite. The reason is the higher affinity of Hf compared with Zr to a granite melt. This implies that the crystallization and settling of accessory zircon will cause the progressive enrichment of Hf relative to Zr in the residual melt. As a result, the Zr/Hf ratio decreases regularly in the series of sequential phases of granite intrusion related to a single magma chamber from granodiorite to biotite granite, leucogranite, and Li-F granite (from 45-30 to 10-2). Our experimental investigations supported the preferential enrichment of haplogranite melt in Hf and zircon crystals in equilibrium with melt in Zr (T= 800°C and P = 1 kbar). The Zr/Hf indicator was tested by the example of the wellknown Kukulbei rare-metal granite complex of eastern Transbaikalia (J3), which is unique in the degree of fractionation of initial granite melt with the formation of three phases of granite emplacement and vein derivatives. An important feature of the complex is its “short” differentiation trend. It was supposed that the granite magma of the first phase is parental, and the later phases forming small intrusive bodies in large massifs of biotite granites of the first phase are sequential products of its crystallization differentiation in a magma chamber. The biotite granites of the first phase are barren. The leucocratic granites of the second phase are accompanied by tin-tungsten greisen deposits (e.g., Spokoininskoe), and the upper part of cupola-like stocks of Li-F amazonite granites of the third phase host apogranite-type tantalum deposits (Orlovka, Etyka, and Achikan). In addition to three granite phases, the Kukulbei complex includes dikes of ongonites, elvans, amazonite granites, and chamber miarolitic pegmatites. All of the granitic rocks of the complex have similar isotopic ages of 142± 0.6 Ma. The Zr/Hf ratio decreases systematically from phase 1 (40–25), to phase 2 (20–10), and phase 3 (10–2). The ongonites, elvans, and pegmatites have similar Zr/Hf ratios (15-5), falling between the ranges of leucocratic muscovite granites and Li-F granites. Compared with other granite series, the granitic rocks of the Kukulbei complex show specific petrographic and geochemical features: they are strongly enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From the early to late intrusion phases, the degree of enrichment and depletion in these element groups increases regularly. This is accompanied by a significant decrease (from 40 to 2) in Zr/Hf, which can be used as a reliable indicator of genetic relations, degree of fractionation, and rare-metal potential of granites. Granites with Zr/Hf values lower than 25 are promising for prospecting for Sn, W, Mo, and Be greisen deposits, whereas the formation of Ta deposits requires Zr/Hf values lower than 10.     

Textural and chemical evolution of a fractionated granitic system: the Podlesí stock, Czech Republic

The Podlesí granite stock (Czech Republic) is a fractionated, peraluminous, F-, Li- and P-rich, and Sn, W, Nb, Ta-bearing rare-metal granite system. Its magmatic evolution involved processes typical of intrusions related to porphyry type deposits (explosive breccia, comb layers), rare-metal granites (stockscheider), and rare metal pegmatites (extreme F–P–Li enrichment, Nb–Ta–Sn minerals, layering). Geological, textural and mineralogical data suggest that the Podlesí granites evolved from fractionated granitic melt progressively enriched in H₂O, F, P, Li, etc. Quartz, K-feldspar, Fe–Li mica and topaz bear evidence of multistage crystallization that alternated with episodes of resorption. Changes in chemical composition between individual crystal zones and/or populations provide evidence of chemical evolution of the melt. Variations in rock textures mirror changes in the pressure and temperature conditions of crystallization. Equilibrium crystallization was interrupted several times by opening of the system and the consequent adiabatic decrease of pressure and temperature resulted in episodes of nonequilibrium crystallization. The Podlesí granites demonstrate that adiabatic fluctuation of pressure (“swinging eutectic”) and boundary-layer crystallization of undercooled melt can explain magmatic layering and unidirectional solidification textures (USTs) in highly fractionated granites.     

Les Quartzites à Silicates Calciques et Scheelite: Préconcentrations Familières ou Pièges pour un Tungstène Etranger lié à L'Hydrothermalisme Périgranitique? Exemple du Nord-Est Transmontain (Portugal)

Three groups of Sn-W veins occur in the contact aureole of composite granitic plutons South of Bragança (Trás-os-Montes, Portugal). Thin layers of calcic quartzites with or without scheelite are interbedded in the Ordovician and Silurian metamorphic country-rocks. Could they represent synsedimentary preconcentrations and a likely source for the W-deposits? The geologic features and the trace-elements distribution (W, Sn, Be, B, Li, F, Rb) in the metasedimentary and granitic rocks support the following conclusions: 1) the scheelite-bearing calcic quartzites are tactites, that occur only in the contact aureole of the granites; 2) the dynamo-metamorphic country-rocks are weakly enriched in W and impoverished in Sn compared to the "clarke" values; 3) the trace-elements concentration is higher in the contact aureole (X 2) than outwards; 4) the quartzites are scheelite-bearing only in the vicinity of the wolframite veins. Thus, scheelite appears related to mineralizing hydrothermal processes. Through their chemical composition and their mechanical properties, the calcic quartzites appear as traps for a tungsten mainly foreign to the metamorphic rocks close to the granites. Thus, the source of W lies deeper in lower crust levels or in the upper-mantle.