The role of H2O in rapid emplacement and crystallization of granite pegmatites: resolving the paradox of large crystals in highly undercooled melts

Granite pegmatite sheets in the continental crust are characterized by very large crystals. There has been a shift in viewing pegmatites as products of very slow cooling of granite melts to viewing them as products of crystal growth in undercooled liquids. With this shift there has been a renewed debate about the role of H₂O in the petrogenesis of pegmatites. Based on data on nucleation of minerals and new viscosity models for hydrous granite melts, it is argued that H₂O is the essential component in the petrogenesis of granite pegmatites. H₂O is key to reducing the viscosity of granite melts, which enhances their transport within the crust. It also dramatically reduces the glass transition temperature, which permits crystallization of melts at hundreds of degrees below the thermodynamic solidus, which has been demonstrated by fluid inclusion studies and other geothermometers. Published experimental data show that because H₂O drastically reduces the nucleation rates of silicate minerals, the minerals may not be able to nucleate until melt is substantially undercooled. In a rapidly cooling intrusion, nucleation starts at its highly undercooled margins, followed by inward crystal growth towards its slower-cooling, hotter core. Delay in nucleation may be caused by competition for crystallization by several minerals in the near-eutectic melts and by the very different structures of minerals and the highly hydrated melts. Once a mineral nucleates, however, it may grow rapidly to a size that is determined by the distance between the site of nucleation and the point in the magma at which the temperature is approximately that of the mineral’s liquidus, assuming components necessary for mineral growth are available along the growth path. Granite pegmatites are apparently able to retain H₂O during most of their crystallization histories within the confinement of their wall rocks. Pegmatitic texture is a consequence of delayed nucleation and rapid growth at large undercooling, both of which are facilitated by high H₂O (±Li, B, F and P) contents in granite pegmatite melts. Without retention of H₂O the conditions for pegmatitic textural growth may be difficult to achieve. Loss of H₂O due to decompression and venting leads to microcrystalline texture and potentially glass during rapid cooling as seen in rhyolites. In contrast, slow cooling within a large magma chamber promotes continuous exsolution of H₂O from crystallizing magma, growth of equant crystals, and final solidification at the thermodynamic solidus. These are the characteristics of normal granites that distinguish them from pegmatites.     

Vapor-undersaturated experiments with Macusani glass+H2O at 200 MPa,and the internal differentiation of granitic pegmatites

Vapor-undersaturated fractional crystallization experiments with Macusani glass (macusanite), a peraluminous rhyolite obsidian, at 200 MPa yield mineralogical fabrics and zonation, and melt fractionation trends that closely resemble those found in zoned granitic pegmatites and other granitoids of comparable composition (typically peraluminous, Li-Be-Ta-rich deposits). The zonation from the edge of charges inward is characterized by: (1) fine-grained sodic feldspar-quartz border zones; (2) a fringe of very coarse-grained graphic quartz-feldspar intergrowths that flair radially toward melt and terminate with nearly monophase K-feldspar; (3) cores of very coarse-grained, nearly monominerallic quartz or virgilite (LiAlSi₅O₁₂)±mica; and (4) late-stage, fine-grained albite+mica intergrowths that are deposited from alkaline, Na-rich interstitial melt at vapor saturation. Similar experimental products have been observed in compositionally simpler, less evolved systems. Liquid lines of descent from initially H₂O-undersaturated runs are marked by a decrease in SiO₂, and increases in Na/K, B, P, F, H₂O, and a variety of trace lithophile cations. These trends are believed to be governed by three factors: (1) disequilibrium growth of feldspars (±quartz) via metastable supersaturation; (2) fractionation of melt toward SiO₂-depleted, Na-rich compositions due to increases in B, P, and F; and (3) changes in nucleation and growth rates, mostly as a function of the H₂O content of melt (X _w ^m ). In contrast, experiments that are cooled below the liquidus from the field of melt+aqueous vapor (London et al. 1988) fail to replicate pegmatitic characteristics in most respects. On the basis of these and other experiments, we suggest that the formation of pegmatite fabrics stems primarily from fractional crystallization in volatile-rich melts, and that enrichments in normally trace lithophile elements result from melt differentiation trends toward increasingly alkaline, silica-depleted compositions. Although vapor saturation at near-solidus and subsolidus conditions may promote extensive recrystallization, an aqueous vapor phase does not appear to be necessary for the generation of most of the salient characteristics of pegmatites.     

Multistage Growth of a Rare-Element, Volatile-Rich Microgranite at Argemela (Portugal)

The small Argemela microgranite body in central Portugal displaysmany of the mineralogical and chemical features characteristicof peraluminous, Li, P-rich, rare-element pegmatites. Its mineralogyconsists predominantly of quartz, albite, white mica (partlyreplaced by lepidolite) and a phosphate of the amblygonite series.K-feldspar is noticeably absent or scarce. Cassiterite, beryland columbite are the main accessories. The microgranite showsextreme enrichment in incompatible elements such as F, P, Rb,Cs, Li, Sn and Be, and extreme depletion in Sr, Ba, Zr and REE.It is highly sodic and strongly peraluminous. The micrograniteoverall is interpreted as a mixture of two components: a crystalmush injected from below (seen in narrow dykes intersected duringdrilling, composed of quartz, albite and phengite) and interpretedas ‘feeders’, overprinted by a second highly evolvedcomponent dominated by Li, F, P (Rb, Cs, Be, Sn, Nb, Ta, etc.)considered as a ‘lubricant’ medium for the ascendingmush and occasionally quenched (quartz, albite, skeletal lepidoliteand amblygonite). This second component has the mineralogicaland chemical characteristics of rare-element pegmatites. Allthese petrological characteristics are magmatic. Only a fewnarrow cross-cutting veinlets with quartz, K-feld-spar and F-pooramblygonite are considered as fluid derived. A model of crystallizationin successive steps is proposed where concentration in fluxingagents (F, Li, P, etc.) is progressively enhanced up to saturationwith the crystallization of magmatic lepidolite and amblygonite. KEY WORDS: petrogenesis; microgranite; pegmatite; volatiles; Portugal ^*Corresponding author.     

Geochemistry and evolution of the South Platte granite-pegmatite system,Jefferson County,Colorado

The South Platte pegmatite district is well known for its significant enrichment in the rare earth elements (REE), Y, Nb, F, and for the exceptionally well-developed internal zonation of the complex pegmatites located within a reversely zoned portion of the Pikes Peak batholith. Chemical trends both within and between pegmatites define the behavior of major and trace elements and the role of F in the fractionation of the granitic magma and pegmatitic fluids, suggesting a new model for the evolution of the granite-pegmatite system.Whole-rock XRF and INAA analyses of the host Pikes Peak granite and quartz monzonite and pegmatite wall zones provide strong evidence that all three are related by differentiation. With increasing SiO₂, there is systematic enrichment in K₂O, Na₂O, and Rb, and depletion in CaO, MgO, FeO1, TiO₂, P₂O₅, Ba, Sr, and Sc. REE, Y, Zr, and Th were strongly partitioned out of the wall zone into the final residual fluids where they were concentrated up to an order of magnitude over levels in the granite.Within the district, there is also chemical zonation of F, Nb, Th, U, and REE between groups of pegmatites. Polyzonal quartz-core types typically contain more fluorite, samarskite, HREE-zircon, and yttrian-fluorite than their bizonal composite-core counterparts, which contain only sparse fluorite and allanite.The sequence of magmatic evolution involved: (1) a process of diffusive differentiation and fractional crystallization which produced a chemically stratified magma chamber with a hotter more mafic quartz monzonitic base and a more felsic, granitic top enriched in H₂O, F, HREE, Nb, and Y; (2) resurgence of the more mafic lower level crystal mush in to the upper more felsic part of the pluton; and (3) separation of pegmatitic fluids from the juxtaposed magmas giving rise to two compositionally distinct groups of pegmatites.     

我国东北小古里河-科洛-五大连池-二克山火山带钾质矿物成因及地质意义

东北黑龙江小古里河-科洛-五大连池-二克山火山岩带是我国近代保存最好的火山群之一,此带火山岩的岩石化学特点全都强碱富钾,K₂O/Na₂O>1.2,属于一套高钾过碱性火山岩。通过对东北钾质火山岩及金云母橄榄岩地幔捕虏体中钾质矿物金云母、白榴石的成分、结晶环境与岩浆成分及来源关系的研究,认为在岩石圈伸展构造背景下,地幔金云母橄榄岩的低度部分熔融形成钾质岩浆,钾质岩浆上升到地壳浅部经历了白榴石的结晶作用。岩浆演化晚期,因钾质矿物大量晶出导致岩浆相对富钠而出现他形霞石和方钠石等填隙矿物。火山岩及地幔捕虏体中富挥发分矿物金云母、白榴石、磷灰石、霞石和方钠石还提供了钾质岩浆富含H₂O、F、Cl、P等挥发分的证据。     

An experimental study of B-, P- and F-rich synthetic granite pegmatite at 0.1 and 0.2 GPa

Extreme enrichment in H₂O, B, P and F is characteristic of many evolved granites and pegmatites. We report experimental phase relations of a synthetic peraluminous pegmatite spiked with P₂O₅, B₂O₃ and F (5 wt% of each), Rb₂O, Cs₂O (1 wt% of each) and Li₂O (0.5 wt%). Experiments were carried out in H₂O-saturated conditions in cold-seal rapid-quench pressure vessels at 0.1-0.2 GPa. Crystallisation starts at about 820 °C with berlinite and topaz. Quartz appears at 700-750 °C. Topaz is replaced by muscovite at about 600 °C. At near-solidus temperatures (450-500 °C) amblygonite, lacroixite and a Cs-bearing aluminosilicate crystallise. In all charges aluminosilicate melt coexists with low-density hydrous fluid and hydrosaline melt. The latter is strongly enriched in Na₃AlF₆ and H₃BO₃ components. Experimental evidence of the liquid immiscibility and mineral reactions documented in our study offers new explanations of many enigmatic features of natural pegmatites.     

Mineral recorders of pegmatite internal evolution: REE contents of tourmaline from the Bob Ingersoll pegmatite,South Dakota

Trace rare earth elements (REE) have been determined by radiochemical neutron activation analysis for tourmaline samples from an internally zoned, rare-element, granitic pegmatite, located in the Black Hills, South Dakota. The total REE concentrations range from 40 ppm–0.2 ppm, and are highest in tourmaline from the exomorphic halo (country rock) and pegmatite border zone. Chondrite-normalized patterns are highly fractionated from light REE to heavy REE; and REE concentrations decrease in tourmaline from the outer wall zone and first intermediate zone, through the inner wall zone and third intermediate zone, to lowest levels in the pegmatite core. The REEs, as recorded by tourmaline, appear to behave compatibly in this pegmatite system due to early crystallization of apatite and other possible “REE-sink” minerals. The large range of REE concentrations and differences in slopes of chondrite-normalized patterns probably also reflect significant changes in the structural state of the pegmatite melt, caused by changes in pH₂O and other volatiles (B, F, P) as crystallization progressed. Tourmaline samples that appear to have been fluid-derived are HREE-depleted relative to coexisting silicate-melt-derived tourmaline. Tourmaline does not exhibit any strong preference for specific REEs, rather its REE content appears to reflect the REE content of the medium from which the tourmaline crystallized.     

The miarolitic pegmatites from the K?nigshain: a contribution to understanding the genesis of pegmatites

In this paper, we show that the crystallization of miarolitic pegmatites at K?nigshain started at about 700°C, in melts containing up to 30 mass% water. Such high water concentration at low pressures (1–3 kbar) is only possible if the melts are peralkaline. Such peralkaline melts are highly corrosive, and reacted with the wall rock—here the granite host—forming the graphic granite zone, in part via a magmatic–metasomatic reaction. With cooling, the water concentration in some melt fractions increased up to 50 mass% H₂O. The melt-dominated system ends below 600°C and passes into a fluid-dominated system, the beginning of which is characterized by strong pressure fluctuations, caused by the change of OH and CO₃ ²⁻ in the melt, to molecular water and CO₂. We note two generations of smoky quartz, one crystallized above the β–α-transition of quartz (≈573°C), and one below, both of which contain melt inclusions. This indicates that some melt fraction remains during at least the higher-temperature portion of the growth of minerals into the miarolitic cavity, contradicting the view that minerals growing into a pegmatite chamber only do so from aqueous fluids. We show that the K?nigshain miarolitic pegmatites are part of the broad spectrum of pegmatite types, and the processes active at K?nigshain are representative of processes found in most granitic pegmatites, and are thus instructive in the understanding of pegmatite formation in general, and constraining the composition and characteristics of pegmatite-forming melts. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Genesis of tin and tantalum mineralization in pegmatites from the Bynoe area,Pine Creek Geosyncline,Northern Territory

The tin‐ and tantalum‐bearing pegmatites of the Bynoe area are located in the western Pine Creek Geosyncline. They are emplaced within psammopelitic rocks in the contact aureole of the Two Sisters Granite. The latter is a Palaeoproterozoic, fractionated, granite with S‐type characteristics and comprises a syn‐ to late‐orogenic, variably foliated, medium‐grained biotite granite and a post‐orogenic, coarse‐grained biotite‐muscovite granite. The pegmatites comprise a border zone of fine grained muscovite + quartz followed inward by a wall zone of coarse grained muscovite + quartz which is in turn followed by an intermediate zone of quartz + feldspar + muscovite. A core zone of massive quartz is present in some occurrences. Feldspars in the intermediate zone are almost completely altered to kaolinite. This zone contains the bulk of cassiterite, tantalite and columbite mineralization. Fluid inclusions in pegmatitic quartz indicate that early Type A (CO₂ + H₂O ± CH₄) inclusions were trapped at the H₂O‐CO₂ solvus at P～100 MPa, T～300°C (range 240–328°C) and salinity ～6 wt% eq NaCl. Pressure‐salinity corrected temperatures on Type B (H₂O + ～20% vapour), C (H₂O + < 15% vapour) and D (H₂O + halite + vapour) inclusions also fall within the range of Type A inclusions. Oxygen and hydrogen isotope data show that kaolin was either formed in isotopic equilibrium with meteoric waters or subsequent to its formation, from hydrothermal fluid, underwent isotopic exchange with meteoric waters. Fluid inclusion waters from core zone quartz show enrichment in deuterium suggesting metamorphic influence. Isotope values on muscovite are consistent with a magmatic origin. It is suggested that the pegmatites were derived from the post‐orogenic phase of the Two Sisters Granite. Precipitation of cassiterite took place at about 300°C from an aqueous fluid largely as a result of increase in pH due to feldspar alteration.     

The competing models for the origin and internal evolution of granitic pegmatites in the light of melt and fluid inclusion research

In this paper we discuss the main petrogenetic models for granitic pegmatites and how these models have evolved over time. We suggest that the present state of knowledge requires that some aspects of these models to be modified, or absorbed into newer ones. Pegmatite formation and internal evolution have long supposed the need for highly water- and flux-enriched magmas to explain the differences between pegmatites and other intrusives of similar major element composition. Compositions and textural characteristics of fluid and melt inclusions in pegmatite minerals provide strong evidence for such magmas. Furthermore, we show that melt inclusion research has increased the number of potential flux components, which may include H₂O, OH^?, CO₂, HCO ₃ ^? , CO ₃ ^2? , SO ₄ ^2? , PO ₄ ^3? , H₃BO₃, F , and Cl, as well as the elements Li, Na, K, Rb, Cs, and Be, herein described as melt structure modifiers. In this paper we emphasize that the combined effect which these components have on the properties of pegmatite melts is difficult to deduce from experimental studies using only a limited number of these components. The combination and the amount of the different magmatic species, together with differences in the source region, and variations in pressure and temperature cause the great diversity of the pegmatites observed. Some volatile species, such as CO ₃ ^2? and alkalis, have the capacity to increase the solubility of H₂O in silicate melt to an extraordinary degree, to the extent that melt-melt-fluid immiscibility becomes inevitable. It is our view that the formation of pegmatites is connected with the complex interplay of many factors.     

Iron and titanium solution properties in peraluminous and peralkaline rhyolitic liquids

The saturation surface of pseudobrookite (Fe₂TiO₅) was determined for melts in the system SiO₂-Al₂O₃-K₂O-FeO-Fe₂O₃-TiO₂ at 1400° C and 1 atm. The variation in concentrations of Fe₂O₃, TiO₂ and Fe₂TiO₅ in liquids can be used to infer relative changes in activity coefficients of these components with changing K₂O/(K₂O+Al₂O₃) of the melts. Saturation concentrations of these components are low and relatively constant in the peraluminous melts and increase with increasing K₂O/(K₂O+Al₂O₃) in peralkaline liquids. The activity coefficients of Fe₂O₃ and TiO₂ and Fe₂TiO₅, therefore, are higher in peraluminous liquids than in peralkaline liquids in this system. In addition, the iron redox ratio was measured as a function of K₂O/(K₂O+Al₂O₃) for liquids just below the saturation surface; was fixed so all variations in redox ratio are entirely due to changes in melt composition. The redox ratio from unsaturated liquids was applied to saturated liquids where redox analysis of the glass is impossible. The homogeneous equilibrium experiments indicate that the activity coefficient of Fe₂O₃ relative to that of FeO is significantly greater in peraluminous melts than peralkaline melts. Both the heterogeneous and homogeneous equilibria suggest that in peralkaline liquids K⁺in excess of that required to charge balance tetrahedral Al⁺³ is used to stabilize both Fe⁺³ and Ti⁺⁴. Calculations show that ferric iron and titanium compete equally effectively for charge-balancing potassium but neither can outcompete aluminum. The observed changes in solution properties of Fe₂O₃ and TiO₂ in the synthetic melts are used to explain variations in Fe-Ti oxide stabilities in natural peraluminous and peralkaline rhyolites and granites. Since the activity coefficients of both ferric iron and titanium are significantly higher in peraluminous liquids than in peralkaline liquids, Fe-Ti oxides should occur earlier in the crystallization sequence in peraluminous rhyolites than in peralkaline rhyolites. In addition, iron will be reduced in peraluminous granites and rhyolites relative to peralkaline ones under comparable P, T, and . Finally, observed crystallization patterns for minerals containing highly charged cations other than ferric iron and titanium are evaluated in the context of this and other experimental studies.     

Perspectives for Li- and Ta-Mineralization in the Borborema Pegmatite Province,NE-Brazil: A review

The increasing strategic importance of Li- and Ta-ores during the last decades due to the strong consumption growth for rechargeable batteries and high temperature and corrosion resistant capacitors reactivated the interest of studies in pegmatite fields around the world, because these rocks supply respectively 25% and 100% of the world consumption in these elements. Research on petrogenetic issues and major and accessory mineral chemistry variations in rare element (REL)-pegmatites of the Borborema Pegmatite Province in Northeast Brazil were tested as tools for the diagnosis of the metallogenetic potential of rare metals in individual pegmatites and in the province as a whole along the last dozen of years. The results allowed to establish the nearly isobaric (3.8 kbar) crystallization conditions of the REL-pegmatites between approximately 580 °C (liquidus) and 400 °C (solidus) from a peraluminous melt saturated in an aquo-carbonic medium to low salinity volatile phase and an immiscible peralkaline flux-enriched (H₂O, CO₂, F, B, Li etc.) melt fraction, based on melt and fluid inclusion studies. Mineral-chemistry data from 30 selected REL-pegmatites in the province allowed to classify three of them as being of the complex-spodumene or -lepidolite subtype in Černý's classification. Both subtypes are supposed to be potentially fertile, (highly fractionated, and with good chances to bear Li- and Ta-ore concentrations). It was also possible to identify several pegmatitic granite intrusions with textural and lithogeochemical characteristics also found in source granites of REL-pegmatite provinces elsewhere. Preliminary chemical Pb/U/Th geochronological determinations in uraninite and xenotyme crystals of these granites indicate an age of 520 ± 10 Ma and match recently published Ar/Ar in mica and U/Pb ages in columbite-group minerals (CGM) of the REL-pegmatites between 509 and 525 Ma. Mineral-chemistry data from grains of the outer zones of the pegmatites do not allow to distinguish potentially fertile from barren pegmatites. This discrimination is possible only if samples of the inner intermediate zone, replacement pockets or quartz core are used. From the tested minerals trace-element determinations (mainly Li, Al, Ti, Ge, B among 14 tested elements) by LA-ICP-MS technique in quartz seem to be more efficient than the classical approach (of Rb, K, Cs, Ga, Sr Ta) in K-feldspar or micas, due to the susceptibility to hydrothermal or supergene alteration of the latter. Mineral-chemistry variations in CGM, tourmalines, garnet and gahnite turned out to be efficient discriminators but all of them have the disadvantage of an eventual and, if present, random distribution, typical for accessory minerals in pegmatites, not allowing a regular sampling in most cases. Additional tests are recommended to confirm respectively the preliminary results of mineral-chemistry as exploration tools on a larger number of pegmatites and geochronological data to confirm the existence of another, older, synorogenetic generation of REL-pegmatites in the BPP.     

Chemical variations and significance of phosphates from the Fregeneda-Almendra pegmatite field, Central Iberian Zone (Spain and Portugal)

Granitic pegmatites are widespread within a schist-metagreywacke complex in the Fregeneda-Almendra area (Central Iberian Zone). They intrude pre-Ordovician metasedimentary rocks and show a zonal distribution relative to the Meda-Penedono-Lumbrales granitic complex, from barren bodies to those enriched in Li, F, Sn, Nb>Ta, P and Be. Based on mineralogical criteria, these pegmatites are classified into three main categories: barren, intermediate and rare-element pegmatites, with each type including various subtypes. Phosphates are present in many pegmatites that usually occur as fine-grained accessory minerals. The most complex association of such minerals includes numerous Fe–Mn phosphates that occur in intermediate pegmatites. Al-phosphates are characteristic of Li-rich pegmatites. Electron microprobe analyses of representative phosphates reflect compositional differences depending on the pegmatite type. The Fe/(Fe+Mn) ratio of phosphates tends to decrease as the evolution degree of the pegmatites increases.     

The nature of fluids during pegmatite development in metamorphic terrains: Evidence from Hamadan complex,Sanandaj-Sirjan metamorphic zone,Iran

In the Sanandaj-Sirjan zone of metamorphic belt of Iran, the area south of Hamadan city comprises of metamorphic rocks, granitic batholith with pegmatites and quartz veins. Alvand batholith is emplaced into metasediments of early Mesozoic age. Fluid inclusions have been studied using microthermometry to evaluate the source of fluids from which quartz veins and pegmatites formed to investigate the possible relation between host rocks of pegmatites and the fluid inclusion types. Host minerals of fluid inclusions in pegmatites are quartz, andalusite and tourmaline. Fluid inclusions can be classified into four types. Type 1 inclusions are high salinity aqueous fluids (NaCl_eq >12 wt%). Type 2 inclusions are low to moderate salinity (NaCl_eq <12 wt%) aqueous fluids. Type 3 and 4 inclusions are carbonic and mixed CO₂-H₂O fluid inclusions. The distribution of fluid inclusions indicate that type 1 and type 2 inclusions are present in the pegmatites and quartz veins respectively in the Alvand batholith. This would imply that aqueous magmatic fluids with no detectable CO₂ were present during the crystallization of these pegmatites and quartz veins. Types 3 and 4 inclusions are common in quartz veins and pegmatites in metamorphic rocks and are more abundant in the hornfelses. The distribution of the different types of fluid inclusions suggests that CO₂ fluids generated during metamorphism and metamorphic fluids might also contribute to the formation of quartz veins and pegmatites in metamorphic terrains.     

青海祁漫塔格地区矽卡岩型矿床花岗质岩石矿物学及地质意义

青海祁漫塔格地区位于东昆仑造山带西段,是我国近些年来的重点找矿地区之一。本文对区内与虎头崖矿床I矿带(Fe)、野马泉矿床(Fe)、虎头崖矿床VI矿带(Zn)和卡而却卡矿床B区(Cu)有关的花岗质岩石开展了矿物学研究。结果显示,虎头崖矿床I矿带的斜长石以奥长石为主(An15.0-24.1);虎头崖矿床VI矿带的斜长石主要为钠长石和奥长石(An8.7-20.8);卡而却卡矿床B区的斜长石主要是中长石(An33.8-42.2);野马泉矿床的斜长石主要为奥长石和中长石(An26.2-48.4)。角闪石为典型的钙角闪石,其中,虎头崖矿床I矿带的角闪石属铁浅闪石;卡而却卡矿床B区的角闪石为镁角闪石和铁角闪石。各矿床(带)的黑云母普遍富Fe、Ti、F、Cl,属典型的铁黑云母。矿物学特征显示,各矿床(带)的黑云母结晶于相似的高氧逸度条件下,但在结晶温度和挥发份组成等方面存在差异。黑云母的结晶温度和氧逸度特征与各矿床类型之间未表现出明显的规律性特征。结合前人的研究成果可知,岩浆结晶的温度和氧逸度可能不是控制本区矽卡岩矿床成矿作用类型的主要因素。黑云母的挥发份组成与各成矿元素间表现出明显的规律性特征,其中,以Fe为主的虎头崖矿床I矿带和野马泉矿床的岩浆流体特征基本一致,表现出相对富Cl、贫H2O、F的特点;以Zn为主的虎头崖矿床VI矿带的岩浆流体相对富F贫H2O、Cl;以Cu为主的卡而却卡矿床B区的岩浆流体相对富Cl、H2O贫F,说明岩浆流体不同的挥发份组成可能与不同的矿床类型之间存在密切的联系。综合地质特征和矿物学特征可知,岩浆流体的挥发份组成可能是控制青海祁漫塔格地区矽卡岩矿床成矿作用类型多样性的重要因素之一。     

Petrogenesis and geochemical composition of biotites in rare-element granitic pegmatites in the southwestern Grenville Province,Canada

Summary Field, mineralogical, and chemical determinations of biotite from late-tectonic rare-element (U, Th, Mo, Nb, REE) Grenville pegmatites are used to characterize and evaluate their petrogenesis in part of the southwestern Grenville Province. These pegmatites occur within middle to upper amphibolite facies rocks along and adjacent to shear zones and have hybridized margins because of interaction with their host rocks. Endo- and exomorphic biotite forms by the mechanical incorporation or hydrothermal replacement of pre-existing biotite, hornblende, Ca pyroxene and/or feldspar; accompanied by chemical re-equilibration, an increase in grain size, and inherit some of the chemical characteristics of the pegmatite. In general, the Fe/(Fe + Mg) ratio ranges between 0.22 and 0.86. The most highly fractionated biotites have high Fe/(Fe + Mg), Al, Mn, Rb, Nb, and Zn and low Ba. The chemical compositions of biotite from unzoned, partially-zoned, and zoned pegmatites indicate a trend of increasing chemical fractionation based on LIL enrichment.Overlap in calculated log (3.2 to 4.7) and log (1.3 to 2.8) for biotite (@ 600°C) among the different pegmatites is extensive. Commonly, magnetite and microcline coexist with biotites having an Fe/(Fe + Mg) between 0.54 to 0.65. Volatile enrichment and vapor-phase saturation are probably responsible for the development of zonation in the pegmatites. The diffusive loss of H₂ at or near H₂O vapor saturation at high H₂O/Fe²⁺ may be responsible for the oxidized nature of some pegmatites.Rare-element enrichment due to pegmatite fractionation combined with partitioning of rare-elements from the pegmatite melt into the volatile phase and subsequent interaction with the host rocks is key to the formation of these rare-element mineral deposits.

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Petrogenese und geochemische Zusammensetzung von Biotiten in seltenen Element-führenden granitischen Pegmatiten der südwestlichen Grenville Provinz, Kanada

Zusammenfassung Die Ergebnisse von Geländearbeiten, sowie von mineralogischen und geochemischen Untersuchungen an Biotit aus spättektonischen seltenen Element-Pegmatiten (U, Th, Mo, Nb, REE) von Grenville-Alter bilden die Basis einer Diskussion ihrer Petrogenese in der südwestlichen Grenville Provinz. Diese Pegmatite kommen in Gesteinen der mittleren bis oberen Amphibolit-Fazies längs und in der Nähe von Shearzonen vor und haben hybridisierte Ränder, die auf Interaktion mit ihren Wirtsgesteinen zurückgehen. Endo- und exomorphe Biotite sind durch mechanische Einschließung oder durch hydrathermale Verdrängung von Biotiten, Hornblenden, Kalziumpyroxenen und/oder Feldspäten gebildet worden. Dies wird durch chemische Reequilibrierung, eine Zunahme der Korngröße und durch Übernahme einiger chemischer Charakteristika der Pegmatite begleitet. Im allgemeinen schwanken die Fe/(Fe + Mg) Verhältnisse von 0.22 bis 0.68, die am stärksten fraktionierten Biotite haben hohe Fe/(Fe + Mg), Al, Mn, Rb, Nb und Zn Gehalte und niedrige Ba Gehalte. Die chemische Zusammensetzung von Biotit aus nicht zonierten, teilweise zonierten und zonierten Pegmatiten zeigt einen Trend mit zunehmend chemischer Fraktionierung, die auf einer Anreicherung von LIL-Elementen basiert.Beträchtliche überschneidungen in den berechneten log (3.2 bis 4.7) und log (1.3 bis 2.8) für Biotit (600°C) von verschiedenen Pegmatiten sind zu erkennen. Im allgemeinen koexistiert Magnetit und Mikroklin mit Biotiten von Fe/ (Fe + Mg) Verhältnissen zwischen 0.54 und 0.65. Anreicherung von volatilen Phasen und eine Sättigung der Dampfphase sind wahrscheinlich für die Entwicklung der Zonierung der Pegmatite verantwortlich. Der Verlust von H₂ durch Diffusion im Bereich der H₂O Dampfsättigung bei hohen H₂O/Fe²⁺ Werten dürfte für die oxidierte Natur einiger Pegmatite verantwortlich sein.Wichtigster Faktor für die Bildung dieser Lagerstätten seltener Elemente ist die Anreicherung von seltenen Elementen durch Pegmatit-Fraktionierung, wobei diese von der Pegmatit-Schmelze in die volatile Phase gehen, und die anschließende Interaktion mit den Nebengesteinen.

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With 9 Figures     

Phase Relations of Peralkaline Silicic Magmas and Petrogenetic Implications

The phase relationships of three peralkaline rhyolites fromthe Kenya Rift have been established at 150 and 50 MPa, at oxygenfugacities of NNO - 1·6 and NNO + 3·6 (log fO₂relative to the Ni–NiO solid buffer), between 800 and660°C and for melt H₂O contents ranging between saturationand nominally anhydrous. The stability fields of fayalite, sodicamphiboles, chevkinite and fluorite in natural hydrous silicicmagmas are established. Additional phases include quartz, alkalifeldspar, ferrohedenbergite, biotite, aegirine, titanite, montdoriteand oxides. Ferrohedenbergite crystallization is restrictedto the least peralkaline rock, together with fayalite; it isreplaced at low melt water contents by ferrorichterite. Riebeckite–arfvedsoniteappears only in the more peralkaline rocks, at temperaturesbelow 750°C (dry) and below 670°C at H₂O saturation.Under oxidizing conditions, it breaks down to aegirine. In themore peralkaline rocks, biotite is restricted to temperaturesbelow 700°C and conditions close to H₂O saturation. At 50MPa, the tectosilicate liquidus temperatures are raised by 50–60°C,and that of amphibole by 30°C. Riebeckite–arfvedsonitestability extends down nearly to atmospheric pressure, as aresult of its F-rich character. The solidi of all three rocksare depressed by 40–100°C compared with the solidusof the metaluminous granite system, as a result of the abundanceof F and Cl. Low fO₂ lowers solidus temperatures by at least30°C. Comparison with studies of metaluminous and peraluminousfelsic magmas shows that plagioclase crystallization is suppressedas soon as the melt becomes peralkaline, whatever its CaO orvolatile contents. In contrast, at 100 MPa and H₂O saturation,the liquidus temperatures of quartz and alkali feldspar arenot significantly affected by changes in rock peralkalinity,showing that the incorporation of water in peralkaline meltsdiminishes the depression of liquidus temperatures in dry peralkalinesilicic melts compared with dry metaluminous or peraluminousvarieties. At 150 MPa, pre-eruptive melt H₂O contents rangefrom 4 wt % in the least peralkaline rock to nearly 6 wt % inthe two more peralkaline compositions, in broad agreement withprevious melt inclusion data. The experimental results implymagmatic fO₂ at or below the fayalite–quartz–magnetitesolid buffer, temperatures between 740 and 660°C, and meltevolution under near H₂O saturation conditions. KEY WORDS: peralkaline; rhyolite; phase equilibria     

The geochemical and genetic role of organic substances in postmagmatic derivatives of alkaline plutons

Solid bituminous substances (SBS) are common components of the late hydrothermal mineral assemblages of peralkaline pegmatites. SBS are formed in a reductive setting as a result of progressive sorption of minor carbon-bearing molecules (CO, CO₂, CH₄, C₂H₆, C₂H₄, etc.), their polymerization, transformation into aromatic compounds (reformation), and selective oxidation on microporous zeolite-like Ti-, Nb-, and Zrsilicates serving as sorbents and catalysts. The oxygen-bearing aromatic compounds with hydrophile functional groups (−OH, −C=O, −COOH, −COO) act as complexing agents with respect to Th, REE, U, Zr, Ti, Nb, Ba, Sr, Ca, resulting in transfer of these bitumenophile elements under low-temperature hydrothermal conditions in the form of water-soluble macroassociates of the micelle type. Th, REE, and to a lesser extent, U, Zr, Ti, and Nb concentrate at the late stage of the hydrothermal process as microphases impregnating SBS or macroscopic segregations of Th and REE minerals. At the final stage, homogeneous SBS break down into organic (partly together with Ca, Sr, Ba, and Pb) and mineral (with Th, Ln, Y, Ti, Nb, Ca, Na, K, Si) microphases.     

Behavior and effects of phosphorus in the system Na2O−K2O−Al2O3−SiO2−P2O5−H2O at 200 MPa(H2O)

The addition of phosphorus to H₂O-saturated and initially subaluminous haplogranitic (Qz–Ab–Or) compositions at 200 MPa(H₂O) promotes expansion of the liquidus field of quartz, a marked decrease of the solidus temperature, increased solubility limits of H₂O in melt at low phosphorus concentrations, and fractionation of melt out of the haplogranite plane (projected along an Or₂₈ isopleth) toward a peralkaline, silica-poor but quartz-saturated minimum composition. The partition coefficient for P₂O₅ between aqueous vapor and melt with an ASI (aluminum saturation index, mol Al/[mol Na+K])=1 is negligible (0.06), and consequently so are the effects of phosphorus on other melt-vapor relations involving major components. Phosphorus becomes more soluble in vapor, however, as the concentration of a NaPO₃ component increases via the fractionation of melt by crystallization of quartz and feldspar. The experimental results here corroborate existing concepts regarding the interaction of phosphorus with alkali aluminosilicate melt: phosphorus has an affinity for alkalis and Al, but not Si. Phosphorus is incorporated into alkali feldspars by the exchange component AlPSi_-2. For subaluminous compositions (ASI=1), the distribution coefficient of phosphorus between alkali feldspar and melt, D[P]Af/m, is 0.3. This value increases to D[P]Af/m=1.0 at a melt ASI value of 1.3. The increase in D[P]Af/m with ASI is expected from the fact that excess Al promotes the AlPSi_-2 exchange. With this experimental data, the P₂O₅ content of feldspars and whole rocks can reveal important facets of crystallization and phosphorus geochemistry in subaluminous to peraluminous granitic systems.     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。