Theoretical models and experimental determination methods for equations of state of silicate melts: A review

Silicate melts are very active in the interior of the Earth and other terrestrial planets, and are important carriers for the transport of material and energy. The determination of the equation of state(EOS) for silicate melts and the acquisition of a precise quantitative relationship between molar volume(or density) and temperature, pressure, and composition is essential for simulating the generation, migration, and eruption processes of magmas and the evolution of the magma ocean stage during the early formation of the Earth and other terrestrial planets, for calculating and modeling the phase equilibria involving silicate melts, and for revealing the variation of the microstructure of silicate melts with pressure. However, it is experimentally challenging to determine the volumetric properties of silicate melts and the accumulated density data at high pressure are still very limited due to a series of problems such as: the high liquidus temperature of silicate rocks; proneness for silicate melts to react with sample capsules to change the melt composition; and proneness for melts to flow and leak during the high pressure and high temperature experiments. In recent years, there is rapid progress in the high pressure and high temperature experimental techniques, in terms of not only the extension of temperature and pressure ranges but also the improvement on the accuracy of measurements, and the emergence of new methods for in-situ measurements. Here, we review the widely-used theoretical models of ambient-pressure and high-pressure EOS for silicate melts, and illustrate some problems that need to be solved urgently:(1) the room pressure EOS for iron-and titanium-bearing silicate melts needs to be improved;(2) the partial molar properties of the H2 O and CO2 components in silicate melts containing volatile components may vary markedly with the melt composition, which need to be addressed in high-pressure EOS;(3) how the formulation and applicable range of EOS correspond to changes in melt structure and compression mechanism requires further study. We highlight the basic principle and applicable range of various methods for determining the EOS for silicate melts, and compare the advantages and disadvantages of doublebob Archimedes method, fusion curve analysis, shock compression experiments, sink-float method, X-ray absorption, X-ray diffraction and ultrasonic interferometry. Future trends in this field are to develop experimental techniques for in situ measurements on melt density or sound velocity at high temperature and high pressure and to accumulate more experimental data,and on the other hand, to improve the theoretical models of the EOS for silicate melts by a combination of research on the microstructure and compression mechanisms of silicate melts.     

碳酸盐化橄榄岩的电性研究

为进一步探讨上地幔的高导层成因,了解碳酸盐在上地幔电性方面的作用并估算上地幔高导层的碳酸盐含量,本文对不同碳酸盐含量的橄榄岩及玄武岩样品在2~3 GPa、300~1300℃的条件下进行了电性实验研究.研究初步发现:碳酸盐熔体显著增强橄榄岩、玄武岩样品的导电能力;单纯用含硅酸盐熔体的橄榄岩或单纯用含水橄榄岩可能难以解释上地幔某些区域的异常高导现象;同样,单纯用碳酸盐化的橄榄岩可能也难以解释上地幔某些区域的高导现象;上地幔的高导区很可能是碳酸盐熔体、硅酸盐熔体及水的共存区域.     

Electrical conductivity of a spinel lherzolite and a garnet peridotite to 1550°C: relevance to the effects of partial melting

Electrical conductivity σ of two ultramafic rocks (a spinel lherzolite and a garnet peridotite) has been investigated to melting temperature at 1 bar under known oxygen fugacity environment. The electrical conductivity of the two rocks is found to increase with degree of partial melting and an ～ 15% melt fraction is necessary for the electrical conductivity to increase by ～ 1 order of magnitude. For a given melt fraction electrical conductivity of a spinel lherzolite is lower than that of a garnet peridotite and may be attributed to the differences in the composition of the melts formed.     

Electrical properties and geochemistry of carbonate rocks from the Qasr El‐Sagha Formation,El‐Faiyum,Egypt

Understanding petrographical, geochemical and electrical properties of rocks is essential for investigating minerals. This paper presents a study of the petrographical, geochemical and A.C. electrical properties of carbonate rock samples. The samples collected show six lithostratigraphic rock units. Electrical properties were measured using a non‐polarizing electrode at room temperature (～20°C) and a relative atmospheric humidity of ～50% by weight in the frequency range from 42 Hz to 5 MHz. The difference in electrical properties between the samples was attributed to the change in composition and texture between the samples. Electrical properties generally change with many factors (grain size, chemical composition, grain shape and facies). The dielectric constant decreases with frequency and increases with conductor composition. The conductivity increases with the increase of conductor paths between electrodes. Many parameters can contribute to the same result of the electrical properties. The main objective of the present study is to shed more light on the relation between the texture and geochemical composition of measured samples (carbonates that contain clays and quartz grains) through electrical laboratory measurements (conductivity and dielectric constant as a function of frequency).     

高温高压下碳酸盐熔体对地幔岩电导率的影响

为了观测含碳酸盐地幔岩部分熔融过程中电导率的变化,厘清碳酸盐熔体在金伯利岩岩浆形成过程中所起的作用,并探讨Slave克拉通中部Lac de Gras地区约80～120km深处的高导成因,我们利用DS 3600t六面顶压机和Solartron 1260阻抗/增益-相位分析仪在1.0～3.0GPa、673～1873K温压条件下分别测量了含碳酸钠(Na_2CO_3)、碳酸钙(CaCO_3)和大洋中脊玄武岩(MORB)的地幔岩样品的电导率.实验结果表明,地幔岩样品的电导率主要受到温度和组分的影响,而压力对其影响较小.在温度低于1023K时,含Na_2CO_3地幔岩样品的电导率明显高于含同比重CaCO_3和MORB的;温度达到1023K时,含Na_2CO_3地幔岩样品开始熔融;但在之后的200K温度区间内,该部分熔融样品的电导率随温度的增加几乎不发生变化.这一现象或许揭示:地幔深部的碳酸质岩浆在快速上升过程中会同化吸收岩石圈地幔中的斜方辉石(Opx),进而形成金伯利岩岩浆,期间岩浆的电导率几乎不发生变化.含CaCO_3和MORB的地幔岩样品分别在1723K和1423K开始熔融,其部分熔融样品的电导率随温度的增加而快速增加.依据前人的研究结果和我们的实验结果,我们认为可以用含碳酸盐的部分熔融样品来解释Slave克拉通中部Lac de Gras地区约80～120km深处的异常高导现象,并推测熔体中碳酸盐的熔体比例小于2wt.%.     

Electrical conductivity of magmatic liquids: effects of temperature,oxygen fugacity and composition

The effects of temperature, f_O2 and composition on the electrical conductivity of silicate liquids have been experimentally determined from 1200 to 1550°C under a range of f_O2 conditions sufficient to change the oxidation state of Fe from predominantly Fe²⁺ to Fe³⁺. Oxidation of ferrous to ferric iron in the melt has no measurable effect on the conductivity of melts with relatively low ratios of divalent to univalent cations. Under strongly oxidizing conditions a minor decrease of conductivity is detected inth highΣM²/ΣM⁺ ratios. It is concluded that for purposes of estimating the conductivity of magmatic liquids, f_O2 may be ignored to a first approximation. Both univalent and divalent cation transport is involved in electrical conduction. Melts relying heavily on divalent cations for conduction, i.e. melts with relatively large ΣM²⁺/ΣM⁺ ratios, show strong departures from Arrheenius temperature dependence with the apparent activation energies decreasing steadily as the temperature increases. Conductivities dominated by the univalent cations, in melts with relatively small ΣM²⁺/ΣM⁺ ratios, show classical Arrhenius temperature dependence. These observations are discussed in terms of the general characteristics of the melt structure.Compositional variations within the magmatic range account for much less than an order of magnitude variation in electrical conductivity at a fixed temperature. This observation, combined with previous measurements of the conductivity of olivine (A. Duba, H.C. Heard and R. Schock, 1974) make it possible to state with reasonable confidence that melts occurring within the mantle will be more conductive by 3–4 orders of magnitude than their refractory residues. Potential applications to geothermometry are discussed.     

Gold solubility in silicate melts and fluids: Advances from high-pressure and high-temperature experiments

The solubility of Au in silicate melts and fluids governs the enrichment and migration of Au during the formation of magmatic-hydrothermal Au deposits. Large Au deposits require vast amounts of Au to migrate from the upper mantle-lower crust to the shallow crust, and high Au solubility in magma and hydrothermal fluid facilitates the formation of Au-rich magma and fluid in the crust and mantle source and efficient transport. This paper reviews recent high-pressure and high-temperature experimental studies on Au species in magmas and hydrothermal fluids, the partitioning behavior of Au between silicate melts and fluids, and the effects of temperature, pressure, oxygen fugacity, sulfur fugacity, silicate melt composition, and volatiles(H_2O, CO_2, chlorine, and sulfur) on the solubility of Au in magma. We show that the solubility of Au in magma is largely controlled by the volatiles in the magma: the higher the content of reduced sulfur(S~(2-) and HS~-) in the magma, the higher the solubility of Au. Under high-temperature, high-pressure, H_2O-rich, and intermediate oxygen fugacity conditions, magma can dissolve more reduced sulfur species, thus enhancing the ability of the magma to transport Au. If the ore-forming elements of the Au deposits in the North China Craton originate from mantle-derived magmas and fluids, we can conclude, in terms of massive Au migration, that these deep Au-rich magmas might have been generated under H2 O-rich and moderately oxidized conditions(S~(2-) coexists with S~(6+)). The big mantle wedge beneath East Asia was metasomatized by melts and fluids from the dehydration of the Early Cretaceous paleo-Pacific stagnant slab, which not only caused thinning of the North China Craton, but also created physicochemical conditions favorable for massive Au migration.     

Correlations between electrical and elastic properties of solid–liquid composites with interfacial energy-controlled equilibrium microstructures

Electrical conductivity and seismic velocity are studied for plausible pore geometries in the Earth's interior for reliable quantitative analysis of experimental data such as seismic tomography and magnetotelluric explorations. Electrical conductivity of a two-phase system with equilibrium, interfacial energy-controlled phase geometry is calculated for the dihedral angles θ = 40°–100° that are typical for rock–aqueous fluid and θ = 20°–60° for rock–melt systems of lower crust and upper mantle for the case of tetrakaidecahedral grains. Electrical conductivity vs. seismic velocity correlations are acquired by combining of the simulated electrical conductivities with the seismic velocity calculated with the help of equilibrium geometry model Takei [Takei, Y., Effect of pore geometry on V_P/V_S: From equilibrium geometry to crack. J. Geophys. Res. 107 (2002): 10.1029/2001JB000522.] for the same pore geometries. The results show that electrical conductivity gradually decreases reaching zero when seismic velocities reach seismic velocities of intact rock for rock–melt systems, while for rock–aqueous fluid systems with θ ≥ 60° conductivity drops to zero at velocities up to 10% smaller. This can explain the seeming discrepancy of the low seismic velocity region, attributed to the high fluid fraction, and the low electrical conductivity of the same region, which is sometimes faced at collocated electromagnetic and seismic experiments.     

Beyond KTB - electrical conductivity of the deep continental crust

Great strides have been made in understanding the upper part of the crust by in-situ logging in, and laboratory experiments on core recovered from super-deep bore-holes such as the KTB. These boreholes do not extend into the lower crust, and can contribute little to the elucidation of mechanisms that produce the high electrical conductivities that are commonly observed therein by magneto-telluric (MT) methods. Laboratory studies at simulated lower crustal conditions of temperature, pressure and saturation, on electrolyte saturated rocks thought to have been derived from the lower crust, have not been possible up until now due to their experimental difficulty. It is necessary to subject electrolyte-saturated rock samples to independently controlled confining and pore-fluid pressure, which implies that the rock be sleeved in some impermeable but deformable material, that can withstand the very high temperatures required. Metals are the only materials capable of being used, but these cause great difficulties for cell sealing and conductivity measurement. In this paper we describe recent breakthroughs in experimental work, specifically the development of two new types of sophisticated metal/ceramic seal, and a conductivity measurement technique that enables the measurement of saturated rock conductivity in the presence of a highly conducting metallic sleeve. The advances in experimental technique have enabled us to obtain data on the electrical conductivity of brine saturated basic, acidic and graphite-bearing rocks at lower crustal temperatures and raised pressures. These data have facilitated the comparison of MT derived crustal electrical conductivity profiles with profiles obtained from laboratory experiments for the first time. Initial modelling shows a good agreement between laboratory derived and MT derived profiles only if the mid-crust is composed of amphibolite pervaded by aqueous fluids, and the lower crust is composed of granulite that is saturated with aqueous fluids and/or contains interconnected grain surface films of graphite. The experimental data are consistent with a three layer crust consisting of an aqueous fluid saturated acidic uppermost layer, above an aqueous fluid saturated amphibolite mid-crust, and a granulite lowermost crust, which may or may not be saturated with aqueous fluids, but if not, requires the presence of an additional conduction mechanism such as conduction through thin graphite films.     

The influence of silicate melt composition on distribution of siderophile elements among metal and silicate liquids

Liquid metal-liquid silicate partitioning of Fe, Ni, Co, P, Ge, W and Mo among a carbon-saturated metal and a variety of silicate melts (magnesian-tholeiitic-siliceous-aluminous-aluminosiliceous basalts) depends modestly to strongly upon silicate melt structure and composition. Low valency siderophile elements, Fe, Ni and Co, show a modest influence of silicate melt composition on partitioning. Germanium shows a moderate but consistent preference for the depolymerized magnesian melt. High valency siderophile elements, P, Mo, and W, show more than an order of magnitude decrease in metal-silicate partition coefficients as the silicate melt becomes more depolymerized. Detailed inspection of our and other published W data shows that polymerization state, temperature and pressure are more important controls on W partitioning than oxidation state. For this to be true for a high and variable valence element implies a secondary role in general for oxidation state, even though some role must be present. Equilibrium core segregation through a magma ocean of ‘ultrabasic’ composition can provide a resolution to the ‘excess’ abundances of Ge, P, W and Mo in the mantle, but the mantle composition alone cannot explain the excess abundances of nickel and cobalt in chondritic proportions.     

Laboratory Electrical Conductivity Measurement of Mantle Minerals

Electrical conductivity structures of the Earth’s mantle estimated from the magnetotelluric and geomagnetic deep sounding methods generally show increase of conductivity from 10⁻⁴–10⁻² to 10⁰ S/m with increasing depth to the top of the lower mantle. Although conductivity does not vary significantly in the lower mantle, the possible existence of a highly conductive layer has been proposed at the base of the lower mantle from geophysical modeling. The electrical properties of mantle rocks are controlled by thermodynamic parameters such as pressure, temperature and chemistry of the main constituent minerals. Laboratory electrical conductivity measurements of mantle minerals have been conducted under high pressure and high temperature conditions using solid medium high-pressure apparatus. To distinguish several charge transport mechanisms in mantle minerals, it is necessary to measure the electrical conductivity in a wider temperature range. Although the correspondence of data has not been yet established between each laboratory, an outline tendency of electrical conductivity of the mantle minerals is almost the same. Most of mineral phases forming the Earth’s mantle exhibit semiconductive behavior. Dominant conduction mechanism is small polaron conduction (electron hole hopping between ferrous and ferric iron), if these minerals contain iron. The phase transition olivine to high-pressure phases enhances the conductivity due to structural changes. As a result, electrical conductivity increases in order of olivine, wadsleyite and ringwoodite along the adiabat geotherm. The phase transition to post-spinel at the 660 km discontinuity further can enhance the conductivity. In the lower mantle, the conductivity once might decrease in the middle of the lower mantle due to the iron spin transition and then abruptly increase at the condition of the D″ layer. The impurities in the mantle minerals strongly control the formation, number and mobility of charge carriers. Hydrogen in nominally anhydrous minerals such as olivine and high-pressure polymorphs can enhance the conductivity by the proton conduction. However, proton conduction has lower activation enthalpy compared with small polaron conduction, a contribution of proton conduction becomes smaller at high temperatures, corresponding to the mantle condition. Rather high iron content in mantle minerals largely enhances the conductivity of the mantle. This review focuses on a compilation of fairly new advances in experimental laboratory work together with their explanation.     

Analyzing electromagnetic induction data: Suggestions from laboratory measurements

Recent inversions of electrical profiles of the upper mantle beneath the oceans permit a variety of conductivity-depth profiles ranging from models with monotonically increasing conductivity to layered models having decreases of conductivity with depth. Laboratory data on possible mantle materials can physically explain high mantle conductivities in terms of a fluid phase (partial melt, hydrous fluid) or a good solid conductor (amorphous or graphitic carbon) and favor a profile having a high conductivity layer (HCL) underlain by a more resistive layer.     

Pressure dependence of nickel partitioning between forsterite and aluminous silicate melts

Nickel partitioning between forsterite and aluminosilicate melt of fixed bulk composition has been determined at 1300°C to 20 kbar pressure. The value of the forsterite-liquid nickel partition coefficient is lowered from >20 at pressures equal to or less than 15 kbar to <10 at pressures above 15 kbar.Published data indicate that melts on the join Na₂O-Al₂O₃-SiO₂ become depolymerized in the pressure range 10–20 kbar as a result of Al shifting from four-coordination at low pressure to higher coordination as the pressure is increased. This coordination shift results in a decreasing number of bridging oxygens in the melt. It is suggested that the activity coefficient of nickel decreases with this decrease in the number of bridging oxygens. As a result, the nickel partition coefficient for olivine and liquid is lowered.Magma genesis in the upper mantle occurs in the pressure range where the suggested change in aluminum coordination occurs in silicate melts. It is suggested, therefore, that data on nickel partitioning obtained at low pressure are not applicable to calculation of the nickel distribution between crystals and melts during partial melting in the upper mantle. Application of high-pressure experimental data determined here for Al-rich melts to the partial melting process indicates that the melts would contain about twice as much nickel as indicated by the data for the low-pressure experiments. If, as suggested here, the polymerization with pressure is related to the Al content of the melt, the difference in the crystal-liquid partition coefficient for nickel at low and high pressure is reduced with decreasing Al content of the melt. Consequently, the change ofD_Ni^{ol-andesite melt} is greater than that ofD_Ni^{ol-basalt melt}, for example.     

Viscosity and structural changes of albite (NaAlSi3O8) melt at high pressures

Viscosity of anhydrous albite melt, determined by the falling-sphere method in the solid-media, piston-cylinder apparatus, decreases with increasing pressure from 1.13 × 10⁵ P at 1 atm to 1.8 × 10⁴ P at 20 kbar at 1400°C. The rate of decrease in viscosity is larger between 12 and 15 kbar than in other pressure ranges examined. The density of the quenched albite melt increases with increasing pressure of quenching from 2.38 g/cm³ at 1 atm to 2.53 g/cm³ at 20 kbar. The rate of increase in density is largest at pressures between 15 and 20 kbar. The melting curve of albite shows an inflexion at about 16 kbar. These observations strongly suggest that structural changes of albite melt would take place effectively at pressures near 15 kbar. Melt of jadeite (NaAlSi₂O₆) composition shows very similar changes in viscosity and density and a melting curve inflexion at pressures near 10 kbar. Difference in pressure for the suggested effective structural changes of albite and jadeite melts is 5–6 kbar, which is nearly the same as that between the subsolidus reaction curves nepheline + albite= 2jadeite and albite=jadeite + quartz. The structural changes of the melts are, however, continuous and begin to take place at pressures lower than those of the crystalline phases.     

The enhanced element enrichment in the supercritical states of granite–pegmatite systems

In this paper, we show that supercritical fluids have a greater significance in the generation of pegmatites,and for ore-forming processes related to granites than is usually assumed. We show that the supercritical melt or fluid is a silicate phase in which volatiles; principally H_2O are completely miscible in all proportions at magmatic temperatures and pressures. This phase evolves from felsic melts and changes into hydrothermal fluids, and its unique properties are particularly important in sequestering and concentrating low abundance elements, such as metals. In our past research, we have focused on processes observed at upper crustal levels, however extensive work by us and other researchers have demonstrated that supercritical melt/fluids should be abundant in melting zones at deep-crustal levels too. We propose that these fluids may provide a connecting link between lower and upper crustal magmas,and a highly efficient transport mechanism for usually melt incompatible elements. In this paper, we explore the unique features of this fluid which allow the partitioning of variouselements and compounds, potentially up to extreme levels,and may explain various features both of mineralization and the magmas that produced them.     

Connectivity of molten Fe alloy in peridotite based on in situ electrical conductivity measurements: implications for core formation in terrestrial planets

The connectivity of molten Fe-S in peridotite has been experimentally investigated by means of in situ electrical conductivity measurements at high temperatures and 1 GPa. Starting materials were powdered mixtures of peridotite KLB-1 with various amounts (0, 3, 6, 13, 19, 24 vol.%) of the 1 GPa eutectic composition in the Fe-FeS binary system. At temperatures above the eutectic point in the Fe-FeS system (∼980 °C) and below the solidus of KLB1 (∼1200 °C), molten Fe-S in a solid silicate matrix interconnects when the volume fraction is over ∼5%. Conductivity-temperature paths indicate that in the presence of partial silicate melting the connectivity of molten Fe-S in a peridotite matrix is inhibited. Based on observations of retrieved samples, the percolation threshold of Fe-S melts in the presence of low to moderate degrees of silicate melt is estimated at 13±2 vol.%. These results indicate that if the volume fraction of Fe-alloy in a planetesimal was initially greater than 5%, and if early heating by decay of radionuclides raised the temperature of the interior above the Fe-alloy melting point, initial metal segregation was controlled by permeable flow of molten iron alloy in a solid silicate matrix. These conditions were likely met by many terrestrial objects in the early solar nebula. Efficient removal of residual Fe-alloy (5 vol.%) from silicate requires high-degree melting of silicate so that metal can segregate as droplets. Giant impacts during the final stage of accretion of large planetary objects could supply the energy required for high-degrees of melting. Alternatively, if initial metal segregation were delayed until a planetary object grew to large size (∼1000 km in diameter), release of gravitational potential energy due to metal segregation could contribute enough heat to form a magma ocean.     

Conductivity of NaCl solution at 0.4–5.0 GPa and 25–500 °C

NaCI-H₂O is the most fundamental ternary system in geology. Until now, the measurements of electrical conductivity of NaCl solutions are still little at high pressures (> O.5 GPa) We measured the conductivity of 0.01 m NaCl solution at 0.4–5.0 GPa and 25-500°C. The results are consistent with that of Quist and Marshall (1968) at 0.4 GPa. The conductivity of NaCl solution increases with increasing temperature. The results also show that the conductivity of NaCl solution changes little with increasing pressure below 1.5 GPa and changes rapidly with increasing pressure above 1.5 GPa. The rapid increase of the conductivity of NaCl solution may play an important role in many geological processes (such as the genesis of ore deposits under hydrothermal condition) and other fields. Project supported by the National Natural Science Foundation of China.     

Silicate and carbonate melt inclusions associated with diamonds in deeply subducted carbonate rocks

Deeply subducted carbonate rocks from the Kokchetav massif (Northern Kazakhstan) recrystallised within the diamond stability field (P = 4.5–6.0 GPa; T ≈ 1000 °C) and preserve evidence for ultra high-pressure carbonate and silicate melts. The carbonate rocks consist of garnet and K-bearing clinopyroxene embedded in a dolomite or magnesian calcite matrix. Polycrystalline magnesian calcite and polyphase carbonate–silicate inclusions occurring in garnet and clinopyroxene show textural features of former melt inclusions. The trace element composition of such carbonate inclusions is enriched in Ba and light rare earth elements and depleted in heavy rare earth elements with respect to the matrix carbonates providing further evidence that the inclusions represent trapped carbonate melt. Polyphase inclusions in garnet and clinopyroxene within a magnesian calcite marble, consisting mainly of a tight intergrowth of biotite + K-feldspar and biotite + zoisite + titanite, are interpreted to represent two different types of K-rich silicate melts. Both melt types show high contents of large ion lithophile elements but contrasting contents of rare earth elements. The Ca-rich inclusions display high REE contents similar to the carbonate inclusions and show a general trace element characteristic compatible with a hydrous granitic origin. Low SiO₂ content in the silicate melts indicates that they represent residual melts after extensive interaction with carbonates. These observations suggest that hydrous granitic melts derived from the adjacent metapelites reacted with dolomite at ultra high-pressure conditions to form garnet, clinopyroxene – a hydrous carbonate melt – and residual silicate melts. Silicate and carbonate melt inclusions contain diamond, providing evidence that such an interaction promotes diamond growth. The finding of carbonate melts in deeply subducted crust might have important consequences for recycling of trace elements and especially C from the slab to the mantle wedge.     

Structure of sodium alumino-silicate melts quenched at high pressure; infrared and aluminum K-radiation data

Infrared and X-ray radiation data indicate that the effect of pressure on Na-Al-Si-O quenched melt is to change the coordination number of trivalent aluminum ions from four to six. This conclusion is based upon an observed decrease in the intensity of the infrared vibration involving a “bridging” oxygen in the polymer structure and a shift in both Al K_α (7 × 10^?4Å) and Al K_β (20 × 10^?4Å) radiation. The amount of Al^IV or Al^VI seems to be a continuous function of the pressure at which the melt was formed and is thus independent of the coordination change effected at high pressure in solids crystallized from the NaAlSi₂O₆ composition used in this study. The importance of the continuous shift of coordination number of aluminum ions in silicate melts at high pressure is discussed. The change in coordination of Al would also be expected in natural silicate melts (magmas) at high pressures.     

Melting relations in the chloride–carbonate–silicate systems at high-pressure and the model for formation of alkalic diamond–forming liquids in the upper mantle

The experiments in the model system CaMgSi₂O₆–(Na₂CO₃, CaCO₃)–KCl are performed at 5 GPa and 1400–1600 °C in order to study the phase relations, including liquid immiscibility, in the chloride–carbonate–silicate systems with application to alkali and chlorine-rich liquids preserved in kimberlitic diamonds. Experiments in the boundary joins of the system demonstrated that both the carbonate–silicate and chloride–carbonate melts are homogeneous; while high-temperature (above 1800 °C) liquid immiscibility is assumed for the chloride–silicate join of the above system. Addition of silicate component into the chloride–carbonate melts and chloride component into the carbonate–silicate melts results in splitting of the homogeneous liquids into the immiscible chloride–carbonate brine and carbonate–silicate melt. Carbonate–silicate and chloride–carbonate branches of the miscibility gap converge within the carbonate-rich region of the system. Regular temperature evolution of the shape and size of the miscibility gap is deduced. With decreasing temperature, the convergence point moves toward more Si-rich compositions, expanding fields of homogeneous chloride–carbonate silica-saturated melts. This effect is governed by the precipitation of the silicate phases even from silica-bearing chloride–carbonate melts. In addition, experiments revealed regular evolution of both Cl-bearing carbonate–silicate melt and Si-bearing chloride–carbonate brine toward the low-temperature chlorine–bearing carbonatitic liquid with decreasing temperature. These trends are similar to the evolution of the melt and brine inclusions in some diamonds from Botswana, Brazil, Canada, and Yakutia, indicating their growth during cooling. The model for interaction of the chloride–carbonate brine with the mantle rocks is developed on the basis of the present experimental data. This model is applied to the chlorine-enriched kimberlites of the Udachnaya–East pipe.