Magmatic evolution of Li–F, rare-metal granites: a case study of melt inclusions in the Khangilay complex, Eastern Transbaikalia (Russia)

We report compositions of homogenized quartz-hosted melt inclusions from a layered sequence of Li-, F-rich granites in the Khangilay complex that document the range of melt evolution from barren biotite granites to Ta-rich, lepidolite–amazonite–albite granites. The melt inclusions are crystalline at room temperature and were homogenized in a rapid-quench hydrothermal apparatus at 200 MPa before analysis. Homogenization runs determined solidus temperatures near 550 °C and full homogenization between 650 and 750 °C. The compositions of inclusions, determined by electron microprobe and Raman spectroscopy (for H₂O), show regular overall trends of increasing differentiation from the least-evolved Khangilay units to apical units in the Orlovka intrusion. Total volatile contents in the most-evolved melts reach over 11 wt.% (H₂O: 8.6 wt.%, F: 1.6 wt.%, B₂O₃: 1.5 wt.%). Concentrations of Rb range from about 1000 to 3600 ppm but other trace elements could not be measured reliably by electron microprobe. The resulting trends of melt evolution are similar to those described by the whole-rock samples, despite petrographic evidence for albite- and mica-rich segregations previously taken as evidence for post-magmatic metasomatism.

Melt variation trends in most samples are consistent with fractional crystallization as the main process of magma evolution and residual melt compositions plot at the granite minimum in the normative Qz–Ab–Or system. However, melts trapped in the highly evolved pegmatitic samples from Orlovka deviate from the minimum melt composition and show compositional variations in Al, Na and K that requires a different explanation. We suggest that unmixing of the late-stage residual melt into an aluminosilicate melt and a salt-rich dense aqueous fluid (hydrosaline melt) occurred. Experimental data show the effectiveness of this process to separate K (aluminosilicate melt) from Na (hydrosaline melt) and high mobility of the latter due to its low viscosity and relatively low density may explain local zones of albitization in the upper parts of the granite.     

Parental melts of melilitolite and origin of alkaline carbonatite: evidence from crystallised melt inclusions, Gardiner complex

Perovskite and melilite crystals from melilitolites of the ultramafic alkaline Gardiner complex (East Greenland) contain crystallised melt inclusions derived from: (1) melilitite; (2) low-alkali carbonatite; (3) natrocarbonatite. The melilitite inclusion (1) homogenisation temperature of 1060 °C is similar to liquidus temperatures of experimentally investigated natural melilitites. The compositions are peralkaline, low in MgO (ca.␣5 wt%), Ni and Cr, and they are low-pressure fractionates of more magnesian larnite-normative ultramafic lamprophyre-type melts of primary mantle origin. Low-alkali carbonatite compositions (2) homogenise at 1060–1030 °C and are compositionally similar to immiscible calcite carbonatite dykes derived from the melilitolite magma. Natrocarbonatite inclusions (3) homogenise between 1030 and 900 °C and are compositionally similar to natrocarbonatite lava from Oldoinyo Lengai. Nephelinitic to phonolitic dykes which are related to the calcite carbonatite dykes, are very Zr-rich and agpaitic (molecular Na₂O + K₂O/Al₂O₃ > 1.2) and resemble nephelinites of Oldoinyo Lengai. The petrographic, geochemical and temporal relationships indicate unmixing of carbonatite compositions (ca. 10% alkalies) from evolving melilitite melt and continued fractionation of melilitite to nephelinite. It is suggested that the natrocarbonatite compositions represent degassed supercritical high temperature fluid formed in a cooling body of strongly larnite-normative nephelinite or evolved melilitite. The Gardiner complex and similar melilitolite and carbonatite-bearing ultramafic alkaline complexes are believed to represent subvolcanic complexes formed beneath volcanoes comparable to Oldoinyo Lengai and that the suggested origin of natrocarbonatite may be applied to natrocarbonatites of Oldoinyo Lengai. Received: 18 January 1996 / Accepted: 2 September 1996     

A Synthetic Germanium-Bismuth Glass for the Coarse Mass Calibration of SIMS Instruments

This short technical note describes a simple technique for synthesising an optimised binary glass for performing coarse mass table calibrations of secondary ion mass spectrometers. A Ge-Bi glass doped with five selected trace elements was used to anchor the entire mass table up to m/z ≥ 209 at an accuracy of < 0.5 dalton. Using this material it has been possible to calibrate coarsely the mass table of a Cameca ims 6f instrument in less than five minutes, thereby greatly simplifying the switch from low mass range to high mass range measurements. Although not suitable for the quantification of geological materials, the ease of synthesis and its utility for rapidly performing what is an otherwise time consuming process makes this material a useful tool for SIMS instruments which offer a multiple mass range capability.     

Partitioning of Mg, Ca, and Na between carbonatite melt and hydrous fluid at 0.1–0.2 GPa

Experimental studies of the element distribution between carbonatite melts and hydrous fluids are hampered by the fact that neither the fluid nor the melt can be isochemically quenched in conventional high-pressure vessels. In order to overcome this problem, we used a double-capsule technique to separate immiscible fluid and melt phases during and after the runs. The inner platinum capsules were charged with carbonate mixtures (CaCO₃, MgCO₃ and Na₂CO₃) and placed inside the outer capsules charged with distilled water and diamond powder. The latter was used as an inert trap for solids precipitating from the fluid on quenching. Carbonate melt and hydrous fluid equilibrated through a small hole left in the upper end of the inner capsule. The runs were performed in rapid-quench cold-seal pressure vessels at 0.1–0.2 GPa and 700–900 °C in the two-phase (fluid + melt) stability region. Both quenched melt and quenched fluid were dissolved in dilute HCl and analysed by inductively coupled plasma atomic emission spectroscopy. The results show that under all conditions investigated, fluid/melt partition coefficients for Ca and Mg are similar and several times smaller than those for Na. At 0.1 GPa and a water/carbonatite ratio of 1 (by weight), the partition coefficients are D_Na = 0.35 ± 0.02, D_Ca = 0.09 ± 0.02, and D_Mg = 0.13 ± 0.01. Between 700 and 900 °C, the effect of temperature on partitioning is negligible. However, D_Na increases significantly with decreasing water/carbonatite ratio in the system. Our data show that the release of a hydrous fluid enriched in sodium and simultaneous crystallisation of calcite can transform an alkaline, vapour-saturated carbonatite melt into a body of pure calcite surrounded by zones of sodium metasomatism. Thus, it is quite possible that carbonate magmas with substantial amounts of alkalies were common parental liquids of plutonic carbonatites. Received: 6 May 1999 / Accepted: 31 August 1999     

Liquid immiscibility and its role at the magmatic–hydrothermal transition: a summary of experimental studies

Several types of fluid immiscibility may affect the evolution of volatile-rich magmatic systems at the magmatic–hydrothermal transition. The topology of silicate–salt–H₂O systems implies that three-fluid immiscibility (silicate melt+hydrosaline melt+vapour) should be stable in a broad range of compositions and P–T conditions. The most important factor controlling the immiscibility appears to be the Coulombic properties (electric charges Z and ionic radii r) of the main network-modifying cations and the capacity for immiscibility appears to decrease in the following sequence: Mg>Ca>Sr>Ba>Li>Na>K. Liquid immiscibility is enhanced in peralkaline compositions and in the presence of nonsilicate anions such as F⁻, Cl⁻, CO₃²⁻ and BO₃³⁻. In volatile-rich magmatic systems, the H₂O is likely to react with the chloride, fluoride, borate and carbonate species and the chemical effects of high-temperature hydrolysis may be greatly enhanced by phase separation in systems with multiple immiscible fluid phases. Natural granitic magmas can thus exsolve a range of chemically and physically diverse hydrosaline liquids and the role of these fluid phases is likely to be especially significant in pegmatites and Li–F rare-metal granites.     

Immiscible silicate liquid partition coefficients: implications for crystal-melt element partitioning and basalt petrogenesis

This study investigates partitioning of elements between immiscible aluminosilicate and borosilicate liquids using three synthetic mixtures doped with 32 trace elements. In order to get a good spatial separation of immiscible liquids, we employed a high-temperature centrifuge. Experiments were performed at 1,050–1,150°C, 1 atm, in sealed Fe and Pt containers. Quenched products were analysed by electron microprobe and LA ICP-MS. Nernst partition coefficients (D’s) between the Fe-rich and Si-rich aluminosilicate immiscible liquids are the highest for Zn (3.3) and Fe (2.6) and the lowest for Rb and K (0.4–0.5). The plots of D values against ionic potential Z/r in all the compositions show a convex upward trend, which is typical also for element partitioning between immiscible silicate and salt melts. The results bear upon the speciation and structural position of elements in multicomponent silicate liquids. The ferrobasalt–rhyolite liquid immiscibility is observed in evolved basaltic magmas, and may play an important role in large gabbroic intrusions, such as Skaergaard, and during the generation of unusual lavas, such as ferropicrites.     

Is natrocarbonatite a cognate fluid condensate?

Natrocarbonatite flows in the crater of the volcano Oldoinyo Lengai (Tanzania) are the only carbonatite magmas observed to erupt and have provided strong arguments in favor of a magmatic origin for carbonatite. The currently favored explanation for the genesis of these carbonatites by liquid immiscibility between a silicate and a carbonatite melt is questioned based on the extremely low eruption temperatures of 544-593 °C and compositional and mineralogical characteristics not in agreement with experimental constraints. Experimental investigations of the relationship between Oldoinyo Lengai natrocarbonatite and related silicate rock compositions do indicate that alkali-bearing peralkaline carbonatite with liquidus calcite can form by liquid immiscibility. At the same time, these experiments result in evidence which speaks against a liquid immiscibility origin for the highly alkaline and peralkaline Oldoinyo Lengai natrocarbonatite. On the carbonatite side of the miscibility gap, fractional crystallization cannot account for a liquid evolution from alkali-bearing peralkaline carbonatite to highly alkaline natrocarbonatite. Such an evolution does not seem to be compatible with the liquidus mineral assemblages and the chemistry of Oldoinyo Lengai natrocarbonatite. No natural silicate magma is known to produce natrocarbonatite compositions by liquid immiscibility. The best interpretation of the Oldoinyo Lengai natrocarbonatite flows involves expulsion of a cognate, mobile, alkaline, and CO₂-rich fluid condensate. This conclusion is supported by recent studies of silicate and carbonatite melt inclusions in minerals of ultramafic alkaline complexes, trace element partitioning, isotopic constraints, and by experimental data on major element partitioning between coexisting H₂O-CO₂-rich fluid and carbonatitic melt. In contrast to all other suggested modes of formation, an origin of Oldoinyo Lengai natrocarbonatite from cognate fluid appears best to be in agreement with the field observations, the petrography, mineralogy, and geochemistry of Oldoinyo Lengai natrocarbonatite and the dynamics of the Oldoinyo Lengai natrocarbonatite extrusion.     

Phase equilibria in the silica-undersaturated part of the KAlSiO4– Mg2SiO4– Ca2SiO4– SiO2– F system at 1 atm and the larnite-normative trend of melt evolution

The evolution of nephelinitic melts in equilibrium with mica-bearing liquidus assemblages and melting relations have been studied on two silica-undersaturated joins of the KAlSiO₄– Mg₂SiO₄– Ca₂SiO₄– SiO₂– F system at atmospheric pressure by quench runs in sealed platinum capsules. Fluorine has been added to the batch compositions by the direct exchange of fluorine for oxygen (2F⁻ = O²⁻). The first join is the pseudo-ternary Forsterite – Diopside – KAlSiO₃F₂ system. Forsterite, diopside, F-phlogopite and leucite crystallisation fields and a fluoride-silicate liquid immiscibility solvus are present on the liquidus surface of the join. Sub-liquidus and sub-solidus phases include akermanite, cuspidine, spinel, fluorite and some other minor fluorine phases. The second system is the pseudo-binary Akermanite – F-phlogopite join that intersects the Forsterite – Diopside – KAlSiO₃F₂ join. Akermanite, forsterite, diopside, F-phlogopite, leucite and cuspidine are found to crystallise on the join. Forsterite (fo) and leucite (lc) are related to F-phlogopite (phl) by a reaction with the fluorine-bearing liquid: fo + lc + l = phl, and the reaction proceeds until forsterite or leucite are completely consumed. The reaction temperature and resulting phase association depend on batch composition. Thus, leucite is not stable in the sub-solidus of the Akermanite – F-phlogopite join, but is preserved in a part of the Forsterite – Diopside – KAlSiO₃F₂ system where forsterite reacts out, or does not crystallise at all. The phlogopite-in reaction has an important effect on the composition of the coexisting liquid. The liquids initially saturated in forsterite evolve to extremely Ca rich, larnite-normative residuals. The experimental data show that larnite-normative melilitolites can crystallise from evolved melilititic melts generated from “normal” melanephelinitic parental magmas with no normative larnite. The evolution towards melilitites requires fractionation of phlogopite-bearing assemblages under volatile pressure. Received: 3 June 1997 / Accepted: 5 January 1998     

Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks

Some F-rich granitic rocks show anomalous, nonchondritic ratios of Y/Ho, extreme negative Eu anomalies, and unusual, discontinuous, segmented chondrite-normalised plots of rare earth elements (REE). The effects of F-rich fluids have been proposed as one of the explanations for the geochemical anomalies in the evolved granitic systems, as the stability of nonsilicate complexes of individual rare earths may affect the fluid-melt element partitioning. The lanthanide tetrad effect, related to different configurations of 4f-electron subshells of the lanthanide elements, is one of the factors affecting such complexing behaviour. We present the first experimental demonstration of the decoupling of Y and Ho, and the tetrad effect in the partitioning of rare earths between immiscible silicate and fluoride melts. Two types of experiments were performed: dry runs at atmospheric pressure in a high-temperature centrifuge at 1100 to 1200°C, and experiments with the addition of H₂O at 700 to 800°C and 100 MPa in rapid-quench cold-seal pressure vessels. Run products were analysed by electron microprobe (major components), solution-based inductively coupled plasma mass spectrometry (ICP-MS) (REE in the centrifuged runs), and laser ablation ICP-MS (REE and Li in the products of rapid-quench runs). All the dry centrifuge runs were performed at super-liquidus, two-phase conditions. In the experiments with water-bearing mixtures, minor amounts of aqueous vapour were present in addition to the melts. We found that lanthanides and Y concentrated strongly in the fluoride liquids, with two-melt partition coefficients reaching values as high as 100-220 in water-bearing compositions. In all the experimental samples, two-melt partition coefficients of lanthanides show subtle periodicity consistent with the tetrad effect, and the partition coefficient of Y is greater than that of Ho. One of the mixtures also produced abundant fluorite (CaF₂) and cryolite (Na₃AlF₆) crystals, which enabled us to study fluorite-melt and cryolite-melt REE partitioning. REE concentrations in fluorite are high and comparable to those in the fluoride melt. However, fluorite-melt partition coefficients appear to depend mostly on ionic radii and show neither significant tetrad anomalies, nor differences in Y and Ho partitioning. In contrast, REE concentrations in cryolite are low (∼5-10 times lower than in the silicate melt), and cryolite-melt REE partitioning shows very strong tetrad and Y-Ho anomalies. Our results imply that Y-Ho and lanthanide tetrad anomalies are likely to be caused mainly by aluminofluoride complexes, and the tetrad REE patterns in natural igneous rocks can result from fractionation of F-rich magmatic fluids.