Leucocratic magmatic melts with the maximum fluorine concentrations: Experiment and relations in nature

Experimental data indicate that high F concentrations in leucocratic aluminosilicate melts (of granite and nepheline syenite composition) bring about the crystallization of F-rich minerals (topaz, villiaumite, and cryolite) on the liquidus. The crystallization of the minerals is controlled by the silicity, agpaitic coefficient, and proportions of alkalis in the system SiO₂-Al₂O₃-Na₂O-K₂O-F-H₂O. Our earlier experimental data on this system are compared with petrographic and petrochemical data on granites and nepheline syenites containing accessory topaz, cryolite, and villiaumite. The composition of topaz- and cryolite-bearing rocks is proved to correspond to the experimentally established equilibrium fields of F-rich aluminosilicate melt with these minerals. It is proved that the high-F minerals can crystallize from melt. The partial substitution of K and Na for Li modifies phase relations in the system, first of all, significantly expands the equilibrium field of aluminosilicate melt and alkaline aluminofluoride melts. The two melts are proved to be immiscible within broad compositional ranges in the SiO₂-Al₂O₃-Na₂O-Li₂O-F-H₂O system at 800–650°C and 1 kbar. Experimental data indicate that fluoride brine can coexist with aluminosilicate melts in nature. This finds support data on melt inclusions in granites and alkaline rocks whose contents of major components, water and fluorine are close to those in the experimental glasses. Our data lend support to the hypothesis that large cryolite bodies at the Ivigtut, Pitinga, Ulog-Tanzek, and other deposits were formed by fluoride salt melts that separated from F-rich aluminosilicate magmas late in the course of their differentiation. It is experimentally established that fluoride salt melts are able to concentrate valuable trace elements, such as Li, W, Nb, Hf, Sc, U, Th, and REE, which suggests that such melts can play an important role in the origin of rare-metal deposits genetically related to rocks that crystallize from magmas rich in F.     

Trace element constraints on pegmatite genesis: Tin Mountain pegmatite,Black Hills,South Dakota

The Tin Mountain pegmatite is a small, zoned granitic body that is extremely enriched in Rb and Li, but has moderate concentrations of Sr and Ba. These trace elements are modelled using granitic distribution coefficients in order to test the potentials of partial melting of metasedimentary rocks and fractionation of a less-evolved granitic melt to have produced the parental liquid to the Tin Mountain pegmatite. Batch melting of any reasonable metasedimentary source rock would likely have yielded melts that were either insufficiently enriched in Rb and Li to be the parental liquid, or that had Sr and Ba concentrations that were much higher than those estimated for the parental liquid. The modelling of simple fractional crystallization and equilibrium crystallization of a granitic melt within the compositional range of the spatially associated Harney Peak Granite gives calculated melt compositions with either lower Sr and Ba concentrations or inadequate Rb and Li enrichments, to be the parent liquid of the pegmatite. At least two variants from simple crystal-liquid fractionation models can, however, successfully account for the derivation of the parent liquid: 1) generation of a Rb-, Li-, Ba- and Sr-rich granitic melt (outside of the compositional range of the sampled portions of the Harney Peak Granite complex) by low degrees of partial melting of metasedimentary rocks found in the Black Hills, followed by moderate extents of fractional or equilibrium crystallization, 2) derivation from Harney Peak granite via a complex, multi-stage crystal-liquid fractionation process, such as progressive equilibrium crystallization.     

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.     

Zonation des éléments en traces au cours de la croissance des cristaux dans les bains silicatés: l'exemple de Rb,Cs, Sr et Ba dans le système Qz-Ab-Or-H2O

An indirect method was used to study Na, K, Rb, Cs, Sr and Ba partition coefficients between crystals and silicate melt. Equilibria between a hydrothermal solution and the melt at 800°C and 2 kb and between a hydrothermal solution and crystals at 750°C and 2 kb were separately achieved.For major element partitioning (Na and K), the results obtained here are in good agreement with those of Tuttle and Bowen (1958) which allow us to follow crystal evolution during a fractional crystallization process where the growth of zoned crystals takes place.For minor elements Rb, Cs, Sr, Ba, melt/aqueous solution partition coefficients depend on Na/K as well as the silica content of the melt. These effects are rather small for Rb and Cs, but are much more important for the alkaline earths. The feldspar/aqueous solution partition coefficients also depend on Na/K.The variations of the partition coefficients feldspar/melt are complex in the part of the Qz-Ab-Or diagram located below the cotectic line.During fractional crystallization following the Rayleigh law (assuming that there are no kinetic phenomena) Sr (D > 10) is almost totally removed from the melt in the early stages whereas Cs (D < 0.1) remains in the melt during the whole process. Rb and Ba have partition coefficients closer to unity. The variation of these coefficients, due to changes in bulk composition of liquid and crystals during fractional crystallization, can lead to complex zoning with possible concentration maxima at some stages. Similar phenomena can be expected in non-ideal natural solid solutions, even if no discontinuities can be detected in the physicochemical evolution of the parent magma.     

Trace element distribution patterns and their relationship to the crystallization of granitic melts

The distribution of Ba, Rb and Sr during crystallization of a granitic melt is examined in a number of theoretical models. The modes of crystallization considered are perfect fractional crystallization, perfect equilibrium crystallization, and an intermediate mode, incremental equilibrium crystallization. The effect of the degree of separation of cumulus minerals from melt during crystallization is also considered. Perfect fractional and incremental equilibrium crystallization (with small increments) are broadly similar, but differ in the final stages of crystallization in that the latter mode defines a finite trace element composition for the last solid. The effect of intercumulus melt in both modes of crystallization imparts a ‘liquid’ character to the solids, and suppresses the degree of enrichment of Rb and depletion of Ba and Sr in late solids and melts.Examination of trace element data for the Acid Phase of the Bushveld Igneous Complex in the light of these models suggests that these granites represent a suite of cumulate rocks, containing relatively large amounts of intercumulus melt.     

Trace element modelling of pelite-derived granites

The presence or absence of a vapour phase during incongruent-melt reactions of muscovite and biotite together with the composition of the protolith determines the trace-element characteristics of the resulting melt, provided that equilibrium melting occurs for those phases that host the tracc elements of interest. For granitic melts, Rb, Sr and Ba provide critical constraints on the conditions that prevailed during melting, whereas REE are primarily controlled by accessory phase behaviour. Mass-balance constraints for eutectic granites that are formed by the incongruent melting of muscovite in pelites indicate that melting in the presence of a vapour phase will result in a large melt fraction, and deplete the restite in feldspar. Hence the melt will be characterized by low Rb/Sr and high Sr/Ba ratios. In contrast, vapour-absent melting will result in a smaller melt fraction, and an increase in the restitic feldspar. Consequently high Rb/Sr and low Sr/Ba ratios are predicted. Vapour-absent melting will also enhance the negative Eu anomaly in the melt. Granites that result from the incongruent melting of biotite in the source will be characterized by higher Rb concentrations than those that result from the incongruent melting of muscovite. The Himalayan leucogranites provide an example of unfractionated, crustally derived eutectic melts that are enriched in Rb but depleted in Sr and Ba relative to their metasedimentary protoliths. These compositions may be generated by the incongruent melting of muscovite as a low melt fraction (F0.1) from a pelitic source under vapour-absent conditions.     

Can trace element distributions in migmatites be used as analogues in understanding petrogenesis of anatectic granites

Trace element concentrations in leucosomes of migmatites in the Black Hills, South Dakota, USA, were examined to determine if their compositions are analogous to those of pelite-derived granites. Melanosomes in the migmatites are dominated by biotite, sillimanite, and quartz. Leucosomes have constant Si/Al that corresponds to a peraluminous granite; however, they have variable proportions of (sil+qtz)/alkali feldspar that are attributed to instability of feldspar relative to sillimanite due to high a_HF in partial melts. There are strong positive correlations of Sr, Ba, Rb, and Cs concentrations with the proportion of feldspar in the leucosomes. The average concentrations of Sr and Ba are higher and of Rb and Cs lower in the leucosomes than in pelite-derived leucogranites. A reaction progress method is used to demonstrate that partitioning of these trace elements between melanosomes and leucosomes represent mineral-mineral equilibrium rather than residue-melt equilibrium. This implies that leucosomes in migmatites may crystallize while maintaining equilibrium with melanosomes and the resulting trace element compositions may not be analogous to those of partial melts.     

Fluid and magmatic processes in the formation of the Ary-Bulak ongonite massif (eastern Transbaikalia)

The paper discusses the formation conditions of the Ary-Bulak ongonite massif (eastern Transbaikalia). Studies of melt and fluid inclusions have shown that, along with crystalline phases and a silicate melt, ongonitic magma contained aqueous–saline fluids of different types, fluoride melts compositionally similar to fluorite, sellaite, cryolite, chiolite, and more complex aluminum fluorides as well as silicate melts with abnormal Cs and As contents. An ongonite melt crystallized with the participation of P–Q fluids as vapor solutions, presumably NaF-containing and slightly admixed with chlorides. We studied the properties and composition of brine inclusions from Ca- and F-rich rocks on the margin of the massif. Depending on the thermophysical properties of the host rocks and ongonite melt, the duration of its crystallization has been estimated for a magma chamber of the size and shape of the Ary-Bulak massif. Magma chamber cooling has been modeled, and the density, viscosity, and Rayleigh number of the ongonite melt have been estimated from the composition of silicate glasses in melt inclusions. These data strongly suggest intense convection in the residual magma chamber lasting for centuries. We have calculated possible fluid overpressure during the crystallization and degassing of the ongonite melt in a closed magma chamber.Calcium- and fluorine-rich aphyric and porphyritic rocks on the southwestern margin of the massif might have formed by the following mechanism. Local decompression in the magma chamber quenched an oxygen-containing calcium fluoride melt accumulated at the crystallization front, and then these rocks altered during the interaction with fluids. When penetrating the marginal zone, a P–Q magmatic fluid which coexisted with the melt in the residual chamber cooled and changed its composition and properties. This caused the fluid to boil and segregate into immiscible phases: a vapor solution and a brine extremely rich in Cl, F, K, Cs, Mn, Fe, and Al. The fluoride and silicate liquids were immiscible; the silicate melts had abnormal Cs and As contents; changes in the composition and properties of the magmatic fluids caused them to boil and produce brines. All this is evidence for complex fluid–magma interaction and heterogeneous ongonitic magma during the crystallization of the Ary-Bulak rocks. These processes were favored by the low viscosity and high mobility of the F- and water-rich ongonite melt, intense melt convection in the residual chamber, and rising fluid pressure during its degassing.     

Geochemistry of Sc in the magmatic process: Experimental evidence

Data on Sc distribution between aluminosilicate melt and fluoride phases (cryolite in the Na-K parts of the system and fluoride melt in its Li-bearing parts) were experimentally obtained for the Si-Al-Na-K-O-H-F system at 800, 750, and 700°C and $ P_{H_2 O} Data on Sc distribution between aluminosilicate melt and fluoride phases (cryolite in the Na-K parts of the system and fluoride melt in its Li-bearing parts) were experimentally obtained for the Si-Al-Na-K-O-H-F system at 800, 750, and 700°C and = 1000 bar, at the saturation of the aluminosilicate melt with respect to H₂O and F. The Sc partition coefficients between aluminosilicate melt and fluoride phases vary from 0.005 to 1.6 depending on phase relations in the system, which are, in turn, controlled by its bulk composition and experimental conditions. At 800°C, the Sc partition coefficients between aluminosilicate melt and fluoride phases are lower than 1 in all of the examined parts of the system; i.e., Sc is preferably distributed into the fluoride phase regardless of whether it is crystals of (Na, K-Na, or K)-cryolite or alkali-aluminofluoride melt. This is the fundamental difference of Sc behavior from those of REE, and most other elements, under the same conditions. A temperature decrease to 700°C and the transition from quartz-normative to nepheline-normative melts, as well as an increase in their agpaitic coefficient, leads to an increase in the Sc partition coefficients to values greater than 1. This tendency is related to an increase in the degree of depolymerization of the aluminosilicate melt. Sc is demonstrated to be characterized by strong affinity to F and can substitute up to half of Al atoms in the cryolite structure, and Sc is even more significantly incorporated into Li-bearing aluminofluoride melts. The high chemical affinity of Sc to F and the ability of the former to produce fluoride complexes in residual magmatic melts is one of the main reasons for Sc enrichment in pegmatites and high-temperature postmagmatic metasomatic rocks: greisens, skarns, and albitized granites. The data obtained on Sc behavior in the sequence of zones of reaction column developing during the interaction of dolerite with granitic melt do not validate the idea that Sc is selectively extracted during the migmatization and assimilation of host rocks. Original Russian Text ? T.I. Shchekina, E.N. Gramenitskii, 2008, published in Geokhimiya, 2008, No. 4, pp. 387–402.     

Comendites and pantellerites of Nemrut volcano,eastern Turkey: Genesis and relations between the trachyte-comenditic,comenditic, and pantelleritic melts

The paper reports data on the mineralogy, geochemistry, phase composition of comendites and pantellerites from Nemrut volcano, eastern Turkey; estimates of the crystallization conditions of minerals, composition of matrix glasses and melt inclusions in anorthoclase, fayalite, hedenbergite phenocrysts. LA-ICP-MS was applied to analyze the matrix glasses and phenocryst minerals. The distribution coefficients between phases and glass were calculated for P, B, Li, Rb, Cs, Ba, Sr, Zr, Hf, Ta, Nb, Sc, V, Cr, Ni, Cu, Pb, Th, U, Y, REE. Mass balance simulations of the comenditic and pantelleritic compositions, experimental data, data on melt inclusions are utilized to analyze the processes responsible for the derivation of the magmas, accumulation of components in them and to elucidate genetic links between the trachyte-comenditic, comenditic and pantelleritic melts. The origin of the residual comenditic and pantelleritic melts is explained by variations in the crystallization conditions of anorthoclase (dominant phase), hedenbergite, fayalite, Fe and Ti oxides in the parental trachyte-comenditic magma depending on the pressure and concentration of water dissolved in the melts. The accessory phases (REEand Sr-bearing fluorapatite and zircon) were likely involved in the fractionation of the melts. The following crystallization parameters were obtained by QUILF calculations for the hedenbergite, fayalite, and ilmenite phenocrysts (minimum values for quartz-free melts): 3 kbar, 763°C, ΔFMQ = ?1.27 for the Fe-comendites; 3.3–3.8 kbar, 715°C, ΔFMQ = ?1.8 for the pantellerites; 2.3 kbar, 748°C, ΔFMQ = ?1.16 for the low-Fe comendites. The equilibrium crystallization of anorthoclase phenocrysts in the comenditic melts proceeded at temperature ～750°C. Data on glasses of melt inclusions indicate that the comenditic and pantelleritic melts contained 1–3 wt % H₂O. Analysis of literature data and estimates of the conditions under which the Nemrut magmas were derived suggest that the local chambers with H₂O-undersaturated comenditic and pantelleritic melts could occur at centers of alkaline volcanism at depths within the range of 5 to 10–15 km (lithostatic pressure of 1–4 kbar), at temperatures <750°C and oxygen fugacity below the FMQ buffer.     

Experimental study of phase relations in a lithium-bearing fluorine-rich haplogranite and nepheline syenite system

Phase relations were investigated in the model water-saturated system Si-Al-Na-Li-F-O at high fluorine contents, a temperature of 800°C, and a pressure of 1 kbar. The obtained aluminosilicate melts are widely variable from quartz- to nepheline-normative compositions with agpaitic indexes both higher and lower than one. Various fluoride, aluminofluoride, and oxide phases were observed in the equilibrium assemblage depending on the melt composition: quartz and cryolite associate with the silica richest aluminosilicate melts, topaz and corundum coexist with peraluminous melts, and villiaumite was observed in highly peralkaline melts. Extensive immiscibility between aluminosilicate and aluminofluoride melts was observed in the system. Aluminofluoride melt coexists with quartz- and nepheline-normative aluminosilicate melts with agpaitic indexes (K _a) of 0.7–1.4. The composition of aluminosilicate melt in equilibrium with aluminofluoride melt ranges from 33 to 70 wt % SiO₂, from 12 to 24 wt % Al₂O₃, and from 5 to 16 wt % alkalis. The aluminofluoride melt is variable in composition, its Al/Na ratio ranges from 20/80 to 40/60 depending on the composition of the equilibrium aluminosilicate melt. The experimental aluminosilicate melts equilibrated with cryolite, topaz, and aluminofluoride melt coincide in major component proportions with the bulk compositions of cryolite- and topaz-bearing granites and melt inclusions in minerals.     

Petrology and geochemistry of Jurassic basalt dykes from Vestfjella, Dronning Maud Land, Antarctica

Mineral and whole rocks analyses of 12 Jurassic basalt dykes from Vestfjella, Dronning Maud Land, Antarctica, are presented, and their genesis discussed. On the basis of major oxides and norms the basalts may be classified as olivine and quartz tholeiites. Plotted in the Plag---Cpx---(Opx + 4Q) and Ol---Plag---Q projections, the compositions are most compatible with fractional crystallization of olivine, clinopyroxene and plagioclase from a basalt liquid at very low pressure. The ratios between strongly incompatible elements such as Rb, Cs, Zr, Hf, Ta and Th vary considerably, and petrographic mixing calculations give poor fits with respect to Rb, Cs, Ta, Th and light REE. Initial ⁸⁷Sr/⁸⁶ Sr ratios range between 0.70347 and 0.70687, and show no correlation with Rb/Sr or any other SIE ratios. The trace element and Sr isotope data thus do not suggest any simple cogenetic petrogenetic model. It is concluded that the basalt melts most plausibly have been contaminated by, or mixed with anatectic melts of crustal material, rather than reflecting mantle heterogeneity.     

The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions

Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H₂O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.     

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.     

Fractional crystallization and the origin of tin deposits in granitoids

A comparison between tin-bearing granitoids in an anorogenic setting (Bushveld Complex) and an orogenic setting (Blue Tier Batholith, Tasmania) reveals a number of genetically important similarities. These include: in situ fractional crystallization characterised by marked decrease in Ba and Sr and increase in Rb; the accumulation of late melt in a sheet-like form near the roof zone; the association of barren pegmatites overlying the ore; and of aplites; and the occurrence of conformable tin-bearing sheets, often exhibiting greisenization. These features allow the formulation of the following genetic model. A crustally-derived granitoid magma is emplaced and undergoes fractional crystallization from the margins inwards, with bottom crystallization dominating. Disruption of earlier formed solids by rest liquid commonly occurs. Continued fractional crystallization causes enrichment in volatiles and incompatible elements in the late rest melts, which have a sheet-like habit. The efficiency of enrichment of incompatible elements is critically dependant on the degree of separation of melt from solids throughout crystallization. An early, tin-poor vapour may separate after initial water-saturation of the magma is achieved, and this collects under the roof, commonly forming an impermeable barrier to later tin-bearing fluids. Continued fractional crystallization on the floor further enriches incompatible elements, and at a very late stage a Sn-rich vapour separates within the intercumulus phase and becomes concentrated by progressive crystallization of the intercumulus melt. At a late stage of solidification, this vapour loses equilibrium with the earlier formed feldspars and greisenization ensues, accompanied by the crystallization of cassiterite and other ore minerals. The nature of the mineralization changes if through-going fractures tap the late fluids. This model predicts systematic changes in trace element geochemistry with crystallization which provide useful tools for assessing the tin potential of a granitoid, and for indicating the direction of crystallization of the magma, and hence the location of possible ore.     

Experimental Study of REEs,Ba, and Sr Interphase Partitioning in Fluid–Magmatic Silicate Systems at T = 1250°C and P = 2 kbar

The results of study of the alkaline silicate melt–hydrous saline (carbonate, sulfate, and fluoride) fluid system, as well as partitioning of ore metals (Ba, Sr, and REEs) between coexisting phases at T = 1250°C and P = 2 kbar are reported. It is shown that aqueous solutions with the compositions studied cannot be effective concentrators and transporters of ore elements such as REEs, Sr, and Ba. The sulfate melt accumulates Sr and Ba in the alkaline silicate melt–hydrous sulfate fluid system, which provides evidence for the efficiency of sulfate ore extraction of Sr and Ba from the melt. The results obtained support the important oregenerating role of dense saline phases formed upon the development of liquid heterogeneity in fluid–magmatic systems.

     

Magmatic Evolution of Changbaishan Tianchi Volcano,China–North Korea: Evidence from Mineral-Hosted Melt and Fluid Inclusions

Data on mineral-hosted melt, fluid, and crystalline inclusions were used to study the composition and evolution of melts that produced rocks of Changbaishan Tianchi volcano, China–North Korea, and estimate their crystallization parameters. The melts crystallized within broad ranges of temperature (1220–700°C) and pressure (3100–1000 bar), at a drastic change in the redox potential: Δ log \(f_{O_2}\) from NNO + 0.92 to +1.42 for the basalt melts, NNO –1.61 to –2.09 for the trachybasaltic andesite melts, NNO –2.63 to –1.89 for the comendite melts, and NNO –1.55 to –3.15 for the pantellerite melts. The paper reports estimates of the compositions of melts that produced the continuous rock series from trachybasalt to comendite and pantellerite. In terms of trace-element concentrations, all of the mafic melts are comparable with OIB magmas. The silicic melts are strongly enriched in trace elements and REE. The most strongly enriched melts contain concentrations of certain elements almost as high as in ores of these elements. The paper reports data on H2O concentrations in melts of different composition. It is demonstrated that the variations in the H₂O concentrations were controlled by magma degassing. Data are reported on the Sr and Nd composition of the rocks. The deviations in the Sr isotopic composition are proportional to the ⁸⁷Sr/⁸⁶Sr ratio and could be produced in a melt with a high enough ⁸⁷Sr/⁸⁶Sr ratio during a geologically fairly brief time period. The evolution of melts that produced rocks of the volcano was controlled by crystallization differentiation of the parental basalt magmas at insignificant involvement of melt mixing and liquid immiscibility of silicate and sulfide melts. The alkaline salic rocks were generated in shallow-sitting (13–3.5 km) magmatic chambers in which the melts underwent profound differentiation that gave rise to pantellerites and comendites strongly enriched in trace elements (Th, Nb, Ta, Zr, and REE). Data on the composition of the magmas and parameters of their derivation are used to develop a generalized petrologic–geodynamic model for the origin of Changbaishan Tianchi volcano.     

In Situ Multi-Element Analysis of the Mount Pinatubo Quartz-Hosted Melt Inclusions by NIR Femtosecond Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

Microscopic melt inclusions found in magmatic minerals are undoubtedly one of the most important sources of information on the chemical composition of melts. This paper reports on the successful application of near-infrared (NIR) femtosecond laser ablation (LA) - inductively coupled plasma-mass spectrometry to in situ determination of incompatible trace elements (Li, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Ta, Th, U) and ore metals (As, Mo, Pb) in individual melt inclusions hosted in quartz from the Mount Pinatubo dacites, Philippines. The determined elements cover a concentration range of five orders of magnitude. Femtosecond LA-ICP-MS analyses of twenty-eight individual melt inclusions demonstrate the efficiency of the microanalytical technique and suggests a spectacular homogeneity of the entrapped melt, at least with respect to the following incompatible trace elements: Rb, Sr, Nb, Cs, Ba, La, Ce, Pr, Nd, Pb, Th. The analytical precision (1s) for Na, Ca, Rb, Sr, Y, Nb, Ba and LREE ranged from 3 to 20%. Comparison of trace element concentrations in Mt. Pinatubo melt inclusions determined by femtosecond LA-ICP-MS with those of melt inclusions previously analysed by secondary ion mass spectrometry analysis (SIMS) and those of matrix glasses previously determined by nanosecond LA-ICP-MS showed an agreement typically within 30–40%. The homogeneity of trace element concentrations of the Mt. Pinatubo melt inclusions and the matrix glasses is consistent with the melt inclusion origin as homogeneous rhyolitic melt that was trapped in quartz phenocrysts at the final crystallisation stages of the host adakite (dacite) magma.     

Rb and Sr partitioning between haplogranitic melts and aqueous solutions

Rubidium and strontium partitioning experiments between haplogranitic melts and aqueous fluids (water or 1.16-3.56 m (NaCl + KCl) ± HCl) were conducted at 750-950 °C and 0.2-1.4 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. In addition, we studied if the applied technique (rapid and slow quench, and in-situ determination of trace element concentration in the fluid) has a bearing on the obtained data. There is good agreement of the data from different techniques for chloridic solutions, whereas back reactions between fluid and melt upon cooling have a significant effect on results from the experiments with water.The Rb fluid-melt partition coefficient shows no recognizable dependence on melt composition and temperature.For chloridic solutions, it is ∼0.4, independent of pressure. In experiments with water, it is one to two orders of magnitude lower and increases with pressure. The strontium fluid-melt partition coefficient does not depend on temperature. It increases slightly with pressure in Cl free experiments. In chloridic fluids, there is a sharp increase in the Sr partition coefficient with the alumina saturation index (ASI) from 0.003 at an ASI of 0.8 to a maximum of 0.3 at an ASI of 1.05. At higher ASI, it decreases slightly to 0.2 at an ASI of 1.6. It is one to two orders of magnitude higher in chloridic fluids compared to those found in H₂O experiments. The Rb/Sr ratio in non-chloridic solutions in equilibrium with metaluminous melts increases with pressure, whereas the Rb/Sr ratio in chloridic fluids is independent of pressure and decreases with fluid salinity.The obtained fluid-melt partition coefficients are in good agreement with data from natural cogenetic fluid and melt inclusions. Numerical modeling shows that although the Rb/Sr ratio in the residual melt is particularly sensitive to the degree of fractional crystallization, exsolution of a fluid phase, and associated fluid-melt partitioning is not a significant factor controlling Rb and Sr concentrations in the residual melt during crystallization of most granitoids.     

Trace element geochemistry of Amba Dongar carbonatite complex,India: Evidence for fractional crystallization and silicate-carbonate melt immiscibility

Carbonatites are believed to have crystallized either from mantle-derived primary carbonate magmas or from secondary melts derived from carbonated silicate magmas through liquid immiscibility or from residual melts of fractional crystallization of silicate magmas. Although the observed coexistence of carbonatites and alkaline silicate rocks in most complexes, their coeval emplacement in many, and overlapping initial⁸⁷Sr/⁸⁶Sr and¹⁴³Nd/¹⁴⁴Nd ratios are supportive of their cogenesis; there have been few efforts to devise a quantitative method to identify the magmatic processes. In the present study we have made an attempt to accomplish this by modeling the trace element contents of carbonatites and coeval alkaline silicate rocks of Amba Dongar complex, India. Trace element data suggest that the carbonatites and alkaline silicate rocks of this complex are products of fractional crystallization of two separate parental melts. Using the available silicate melt-carbonate melt partition coefficients for various trace elements, and the observed data from carbonatites, we have tried to simulate trace element distribution pattern for the parental silicate melt. The results of the modeling not only support the hypothesis of silicate-carbonate melt immiscibility for the evolution of Amba Dongar but also establish a procedure to test the above hypothesis in such complexes.