Origin of K-rich diamond-forming immiscible melts and CO2 fluid via partial melting of carbonated pelites at a depth of 180–200 km

Melt inclusions in kimberlitic and metamorphic diamonds worldwide range in composition from potassic aluminosilicate to alkali-rich carbonatitic and their low-temperature derivative, a saline high-density fluid (HDF). The discovery of CO₂ inclusions in diamonds containing eclogitic minerals are also essential. These melts and HDFs may be responsible for diamond formation and metasomatic alteration of mantle rocks since the late Archean to Phanerozoic. Although a genetic link between these melts and fluids was suggested, their origin is still highly uncertain. Here we present experimental results on melting phase relations in a carbonated pelite at 6 GPa and 900–1500 °C. We found that just below solidus K₂O enters potassium feldspar or K₂TiSi₃O₉ wadeite coexisting with clinopyroxene, garnet, kyanite, coesite, and dolomite. The potassium phases react with dolomite to produce garnet, kyanite, coesite, and potassic dolomitic melt, 40(K_0.90Na_0.10)₂CO₃·60Ca_0.55Mg_0.24Fe_0.21CO₃ + 1.9 mol% SiO₂ + 0.7 mol% TiO₂ + 1.4 mol% Al₂O₃ at the solidus established near 1000 °C. Molecular CO₂ liberates at 1100 °C. Potassic aluminosilicate melt appears in addition to carbonatite melt at 1200 °C. This melt contains (mol/wt%): SiO₂ = 57.0/52.4, TiO₂ = 1.8/2.3, Al₂O₃ = 8.5/13.0, FeO = 1.4/1.6, MgO = 1.9/1.2, CaO = 3.8/3.2, Na₂O = 3.2/3.0, K₂O = 10.5/15.2, CO₂ = 12.0/8.0, while carbonatite melt can be approximated as 24(K_0.81Na_0.19)₂CO₃·76Ca_0.59Mg_0.21Fe_0.20CO₃ + 3.0 mol% SiO₂ + 1.6 mol% TiO₂ + 1.4 mol% Al₂O₃. Both melts remain stable to at least 1500 °C coexisting with CO₂ fluid and residual eclogite assemblage consisting of K-rich omphacite (0.4–1.5 wt% K₂O), almandine-pyrope-grossular garnet, kyanite, and coesite. The obtained immiscible alkali‑carbonatitic and potassic aluminosilicate melts resemble compositions of melt inclusions in diamonds worldwide. Thus, these melts entrapped by diamonds could be derived by partial melting of the carbonated material of the continental crust subducted down to 180–200 km depths. Given the high solubility of chlorides and water in both carbonate and aluminosilicate melts inferred in previous experiments, the saline end-member, brine, could evolve from potassic carbonatitic and/or silicic melts by fractionation of Ca-Mg carbonates/eclogitic minerals and accumulation of alkalis, chlorine and water in the residual low-temperature supercritical fluid. Direct extraction from the hydrated marine sediments under conditions of cold subduction would be another possibility for the brine formation.     

Experiments on silicate melt immiscibility in the system Fe2SiO4–KAlSi3O8–SiO2–CaO–MgO–TiO2–P2O5 and implications for natural magmas

The effect of CaO and MgO, with or without TiO₂ and P₂O₅, on the two-melt field in the simplified system Fe₂SiO₄–KAlSi₃O₈–SiO₂ has been experimentally determined at 1,050°–1,240°C, 400 MPa. Despite the suppressing effect of MgO, CaO, and pressure on silicate melt immiscibility, our experiments show that this process is still viable at mid-crustal pressures when small amounts (0.6–2.0 wt%) of P₂O₅ and TiO₂ are present. Our data stress that the major element partition coefficients between the two melts are highly correlated with the degree of polymerisation (nbo/t) of the SiO₂-rich melt, whatever temperature, pressure, or exact composition. Experimental immiscible melt compositions in natural systems at 0.1 MPa from the literature (lunar and tholeiitic basalts) plot on similar but distinct curves compared to the simplified system. These relations between melt polymerisation and partition coefficients, which hold for a large range of compositions and fO₂, are extended to various volcanic and plutonic rocks. This analysis strengthens the proposal that silicate melt immiscibility can be important in volcanic rocks of various compositions (from tholeiitic basalts to lamprophyres). However, the majority of proposed immiscible compositions in plutonic rocks are at least not coexisting melts, but may have suffered accumulation of early crystallized minerals.     

Solubility and solution mechanism of H2O in alkali silicate melts and glasses at high pressure and temperature

The solubility behavior of H₂O in melts in the system Na₂O-SiO₂-H₂O was determined by locating the univariant phase boundary, melt = melt + vapor in the 0.8-2 GPa and 1000°-1300°C pressure and temperature range, respectively. The NBO/Si-range of the melts (0.25-1) was chosen to cover that of most natural magmatic liquids. The H₂O solubility in melts in the system Na₂O-SiO₂-H₂O (X_H2O) ranges between 18 and 45 mol% (O = 1) with (∂X_H2O/∂P)_T∼14-18 mol% H₂O/GPa. The (∂X_H2O/∂P)_T is negatively correlated with NBO/Si (= Na/Si) of the melt. The (∂X_H2O/∂T)_P is in the −0.03 to +0.05 mol% H₂O/°C range, and is negatively correlated with NBO/Si. The [∂X_H2O/∂(NBO/Si)]_P,T is in the −3 to −8 mol% H₂O/(NBO/Si) range. Melts with NBO/Si similar to basaltic liquids (∼0.6-∼1.0) show (∂X_H2O/∂T)_P<0, whereas more polymerized melts exhibit (∂X_H2O/∂T)_P>0. Complete miscibility between hydrous melt and aqueous fluid occurs in the 0.8-2 GPa pressure range for melts with NBO/Si ≤0.5 at T >1100°C. Miscibility occurs at lower pressure the more polymerized the melt.     

High temperature structural investigation of Na2O·0.5Fe2O3·3SiO2 and Na2O·FeO·3SiO2 melts and glasses

The structure of glasses and melts of Na₂O· 0.5Fe₂O₃·3SiO₂ and Na₂O·FeO·3SiO₂ compositions have been measured using high temperature Raman spectroscopy. For the oxidized sample it has been demonstrated that there is a close structural relationship between melt and glass. No coordination changes of Fe³⁺ with temperature and no new anionic species have been observed in the oxidized melt. The Raman spectra of the reduced sample clearly show a decrease in the degree of polymerization, as determined by the observation of the polarization character of the spectra and the details of the change of the Raman intensities during heating in hydrogen. Mössbauer spectra suggest that Fe³⁺ is tetrahedrally coordinated in the oxidized glass and part of the Fe²⁺ is tetrahedrally coordinated in the reduced glass.     

Viscosity-temperature relationships in the system Na2Si2O5-Na4Al2O5

The viscosity-temperature relationships of five melts on the join Na₂Si₂O₂-Na₄Al₂O₅ (5, 10, 20, 30 and 40 mole percent Na₄Al₂O₅) have been measured in air, at 1 atm and 1000–1350°C with a concentric cylinder viscometer. All the melts on this join of constant bulk polymerization behave as Newtonian fluids, in the range of shear rates investigated, and the melts exhibit Arrhenian viscosity-temperature relationships.Isothermal viscosities on this join initially decrease and then increase with increasing mole percent Na₄Al₂O₅. The minimum viscosity occurs near 20 mole percent Na₄Al₂O₅ at 1000°C and moves to higher Na₄Al₂O₅ content with increasing temperature.The observation of a viscosity minimum along the join Na₂Si₂-O₅-Na₄Al₂O₅ is not predicted based on earlier viscosity data for the system Na₂O-Al₂O₃-SiO₂ (RlEBLlNG, 1966) or based on calculation methods derived from this and other data (Bottinga and Weill, 1972). This unexpected behavior in melt viscosity-temperature relations emphasizes the need for a more complete data set in simple silicate systems.Previous spectroscopic investigation of melts on the join Na₂2Si₂O₅-Na₄Al₂O₅ offer a structural explanation for the observed viscosity data in terms of a disproportionation reaction involving polyanionic units. Macroscopically, the viscosity data may be qualitatively reconciled with the configurational entropy model for viscous flow (Richet, 1984).     

Na2O solubility in CaO-MgO-SiO2 melts

The sodium solubility in silicate melts in the CaO-MgO-SiO₂ (CMS) system at 1400 °C has been measured by using a closed thermochemical reactor designed to control alkali metal activity. In this reactor, Na_(g) evaporation from a Na₂O-xSiO₂ melt imposes an alkali metal vapor pressure in equilibrium with the molten silicate samples. Because of equilibrium conditions in the reactor, the activity of sodium-metal oxide in the molten samples is the same as that of the source, i.e., aNa₂O_(sample) = aNa₂O_(source). This design also allows to determine the sodium oxide activity coefficient in the samples. Thirty-three different CMS compositions were studied. The results show that the amount of sodium entering from the gas phase (i.e., Na₂O solubility) is strongly sensitive to silica content of the melt and, to a lesser extent, the relative amounts of CaO and MgO. Despite the large range of tested melt compositions (0 < CaO and MgO < 40; 40 < SiO₂ < 100; in wt%), we found that Na₂O solubility is conveniently modeled as a linear function of the optical basicity (Λ) calculated on a Na-free basis melt composition. In our experiments, γNa₂O_(sample) ranges from 7 × 10⁻⁷ to 5 × 10⁻⁶, indicating a strongly non-ideal behavior of Na₂O solubility in the studied CMS melts (γNa₂O_(sample) ? 1). In addition to showing the effect of sodium on phase relationships in the CMS system, this Na₂O solubility study brings valuable new constraints on how melt structure controls the solubility of Na in the CMS silicate melts. Our results suggest that Na₂O addition causes depolymerization of the melt by preferential breaking of Si-O-Si bonds of the most polymerized tetrahedral sites, mainly Q⁴.     

The role of phosphorus in rhyolitic liquids as determined from the homogeneous iron redox equilibrium

The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO–Al₂O₃–K₂O–FeO–Fe₂O₃–P₂O₅). Glasses containing 80–85 mol% SiO₂ with 1 mol% Fe₂O₃ and compositions covering a range of K₂O/Al₂O₃ were synthesized at 1400°C in air (fixed fO₂). Variations in the ratio FeO/FeO_1.5 resulting from the addition of P₂O₅ are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO₂ peralkaline melts the redox ratio, expressed as FeO/FeO_1.5, is unchanged relative to the reference curve with the addition of 3 mol% P₂O₅. Yet, the iron redox ratio in the 85 mol% SiO₂ potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P₂O₅ (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P₂O₅ concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe⁺³–O–P⁺⁵ and Al⁺³–O–P⁺⁵ occur. The activity coefficient of Fe⁺³ is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P⁺⁵ is removing K⁺ from either Al⁺³ or Fe⁺³ species. In chargebalanced melts with 3 mol% Fe₂O₃ and very high P₂O₅ concentrations, phosphorus removes K⁺ from K–O–Fe⁺³ complexes resulting in a redox increase. P₂O₅ should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

The compressibility of silicate liquids containing Fe2O3 and the effect of composition,temperature, oxygen fugacity and pressure on their redox states

Ultrasonic longitudinal acoustic velocities in oxidized silicate liquids indicate that the pressure derivative of the partial-molar volume of Fe₂O₃ is the same in iron-rich alkali-, alkaline earth- and natural silicate melt compositions at 1 bar. The dV/dP for multicomponent silicate liquids can be expressed as a linear combination of partial-molar constants plus a positive excess term for Na₂O−Al₂O₃ mixing. Partial-molar properties for FeO and Fe₂O₃ components allow extension of the empirical expression of Sack et al. (1980) to permit the calculation of Fe-redox equilibrium in a natural silicate liquid as a function of composition, temperature, fo₂ and pressure; a more formal thermodynamic expression is presented in the Appendix. The predicted equilibrium fo₂ of natural silicate melts, of fixed oxygen content, closely parallels that defined by the metastable assemblage fayalite+magnetite+β-quartz (FMQ), in pressure-temperature space. A silicate melt initially equilibrated at 3 GPa and FMQ, will remain within approximately 0.5 log₁₀ units of FMQ during its closed-system ascent. Thus, for magmas closed to oxygen, iron-redox equilibrium in crystal-poor pristine glassy lavas represents an excellent probe of the relative oxidation state of their source regions.     

Phosphorus solubility mechanisms in haplogranitic aluminosilicate glass and melt: effect of temperature and aluminum content

The solubility behavior of phosphorus in glasses and melts in the system Na₂O-Al₂O₃-SiO₂-P₂O₅ has been examined as a function of temperature and Al₂O₃ content with microRaman spectroscopy. The Al₂O₃ was added (2, 4, 5, 6, and 8 mol% Al₂O₃) to melts with 80 mol% SiO₂ and ∼2 mol% P₂O₅. The compositions range from peralkaline, via meta-aluminous to peraluminous. Raman spectra were obtained of both the phosphorus-free and phosphorous-bearing glasses and melts between 25 and 1218 °C. The Raman spectrum of Al-free, P-bearing glass exhibits a characteristic strong band near 940 cm⁻¹ assigned to P=O stretching in orthophosphate complexes together with a weaker band near 1000 cm⁻¹ assigned P₂O₇ complexes. With increasing Al content, the proportion of P₂O₇ initially increases relative to PO₄ and is joined by AlPO₄ complexes which exhibit a characteristic P-O stretch mode slightly above 1100 cm⁻¹. The latter complex appears to dominate in meta-aluminosilicate glass and is the only phosphate complex in peraluminous glasses. When P-bearing peralkaline silicate and aluminosilicate glasses are transformed to supercooled melts, there is a rapid decrease in PO₄/P₂O₇ so that in the molten state, PO₄ units are barely discernible. The P₂O₇/AlPO₄ abundance ratio in peralkaline compositions increases with increasing temperature. This decrease in PO₄/P₂O₇ with increasing temperature results in depolymerization of the silicate melts. Dissolved P₂O₅ in peraluminous glass and melts forms AlPO₄ complexes only. This solution mechanism has no discernible influence on the aluminosilicate melt structure. There is no effect of temperature on this solution mechanism. Received: 7 October 1997 / Accepted: 11 May 1998     

Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.     

Effects of F,B2O3 and P2O5 on the solubility of water in haplogranite melts compared to natural silicate melts

The effects of F, B₂O₃ and P₂O₅ on the H₂O solubility in a haplogranite liquid (36 wt. % SiO₂, 39 wt. % NaAlSi₃O₈, 25 wt. % KAlSi₃O₈) have been determined at 0.5, 1, 2, and 3 kb and 800, 850, and 900°C. The H₂O solubility increases with increasing F and B content of the melt. The H₂O solubility increase in more important at high pressure (2 and 3 kb) than at low pressure (0.5 kb). At 2 kb and 800°C, the H₂O solubility increases from 5.94 to 8.22 wt. % H₂O with increasing F content in the melt from 0 to 4.55 wt. %, corresponding to a linear H₂O solubility increase of 0.53 mol H₂O/mol F. With addition of 4.35 wt. % B₂O₃, the H₂O solubility increases up to 6.86 wt. % H₂O at 2 kb and 800°C, corresponding to a linear increase of 1.05 mol H₂O/mol B₂O₃. The results allow to define the individual effects of fluorine and boron on H₂O solubility in haplogranitic melts with compositions close to that of H₂O-saturated thermal minima (at 0.5–3 kb). Although P has a dramatic effect on the phase relations in the haplogranite system, its effect on the H₂O solubility was found to be negligible in natural melt compositions. The concominant increase in H₂O solubility and F can not be interpreted on the basis of the available spectroscopic data (existence of hydrated aluminofluoride complexes or not). In contrast, hydrated borates or more probably boroxol complexes have been demonstrated in B-bearing hydrous melts.     

The temperature dependence of the speciation of water in NaAlSi3O8-KAlSi3O8 melts: an application of fictive temperatures derived from synthetic fluid-inclusions

 The speciation of water dissolved in glasses along the join NaAlSi₃O₈-KAlSi₃O₈ has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040^° C and 2 kbar. These melts have been isobarically and rapidly (200^° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5^° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H₂O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113^° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H₂O] [O _m ]/[OH]² is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995     

Experimental determination of the spinel peridotite to garnet peridotite inversion at 900° C and 1,000° C in the system CaO-MgO-Al2O3-SiO2, and at 900° C with natural garnet and olivine

Hydrothermal experiments were carried out at 2 kbar water pressure, 700 °–800 ° C, with the objective of determining the level of dissolved Zr required for precipitation of zircon from melts in the system SiO₂-Al₂O₃-Na₂O-K₂O. The saturation level depends strongly upon molar (Na₂O + K₂O)/Al₂O₃ of the melts, with remarkably little sensitivity to temperature, SiO₂ concentration, or melt Na₂O/ K₂O. For peraluminous melts and melts lying in the quartz-orthoclase-albite composition plane, less than 100 ppm Zr is required for zircon saturation. In peralkaline melts, however, zircon solubility shows pronounced, apparently linear, dependence upon (Na₂O + K₂O)/Al₂O₃, with the amount of dissolvable Zr ranging up to 3.9 wt.% at (Na₂O + K₂O)/Al₂O₃ = 2.0. Small amounts (1 wt.% each) of dissolved CaO and Fe₂O₃ cause a 25% relative reduction of zircon solubility in peralkaline melts.The main conclusion regarding zirconium/zircon behavior in nature is that any felsic, non-peralkaline magma is likely to contain zircon crystals, because the saturation level is so low for these compositions. Zircon fractionation, and its consequences to REE, Th, and Ta abundances must, therefore, be considered in modelling the evolution of these magmas. Partial melting in any region of the Earth's crust that contains more than 100 ppm Zr will produce granitic magmas whose Zr contents are buffered at constant low (< 100 ppm) values; unmelted zircon in the residual rock of such a melting event will impart to the residue a characteristic U- or V-shaped REE abundance pattern. In peralkaline, felsic magmas such as those that form pantellerites and comendites, extreme Zr (and REE, Ta) enrichment is possible because the feldspar fractionation that produces these magmas from non-peralkaline predecessors does not drive the melt toward saturation in zircon.Zircon solubility in felsic melts appears to be controlled by the formation of alkali-zirconosilicate complexes of simple (2:1) alkali oxide: ZrO₂ stoichiometry.     

The combined effects of chlorine and fluorine on the viscosity of aluminosilicate melts

The effect of fluorine and fluorine + chlorine on melt viscosities in the system Na₂O-Fe₂O₃-Al₂O₃-SiO₂ has been investigated. Shear viscosities of melts ranging in composition from peraluminous [(Na₂O + FeO) < (Al₂O₃ + Fe₂O₃)] to peralkaline [(Na₂O + FeO) > (Al₂O₃ + Fe₂O₃)] were determined over a temperature range 560-890 °C at room pressure in a nitrogen atmosphere. Viscosities were determined using the micropenetration technique in the range of 10^8.8 to 10^12.0 Pa s. The compositions are based on addition of FeF₃ and FeCl₃ to aluminosilicate melts with a fixed amount of SiO₂ (67 mol%). Although there was a significant loss of F and Cl during glass syntheses, none occurred during the viscometry experiments. The presence of fluorine causes a decrease in the viscosity of all melts investigated. This is in agreement with the structural model that two fluorines replace one oxygen; resulting in a depolymerisation of the melt and thus a decrease in viscosity. The presence of both chlorine and fluorine results in a slight increase in the viscosity of peraluminous melts and a decrease in viscosity of peralkaline melts. The variation in viscosity produced by the addition of both fluorine and chlorine is the opposite to that observed in the same composition melts, with the addition of chlorine alone (Zimova M. and Webb S.L. (2006) The effect of chlorine on the viscosity of Na₂O-Fe₂O₃-Al₂O₃-SiO₂ melts. Am. Mineral.91, 344-352). This suggests that the structural interaction of chlorine and fluorine is not linear and the rheology of magmas containing both volatiles is more complex than previously assumed.     

Synthesis of kosmochlor and phase equilibria in the join CaMgSi2O6-NaCrSi2O6

Kosmochlor (NaCrSi₂O₆) was synthesized by the flux method from melts along the join Na₂O·2 SiO₂-Na₂O·Cr₂O₃·4 SiO₂ at 1000° C in air, and isolated by dissolving the glassy matrix with hydrofluoric and perchloric acids. The join CaMgSi₂O₆-NaCrSi₂O₆ was studied at 1 atmosphere in air by the quenching technique at temperatures between 900° and 1450° C, using mixtures of kosmochlor and diopside crystals or diopside glass as starting materials. The phases are diopside solid solution, kosmochlor, spinel (Mg-chromite), eskolaite (Cr₂O₃) and glass. The maximum solubility of kosmochlor in diopside is 24 wt percent at 1140° C, while diopside is not soluble at all in kosmochlor, resulting in the existence of a wide range of immiscibility. Petrologic significance of the results is discussed.     

Chemical composition,volatile components,and trace elements in the melts of the Gorely volcanic center,southern Kamchatka: Evidence from inclusions in minerals

Melt inclusions in olivine and plagioclase phenocrysts from rocks (magnesian basalt, basaltic andesite, andesite, ignimbrite, and dacite) of various age from the Gorely volcanic center, southern Kamchatka, were studying by means of their homogenization and by analyzing the glasses in 100 melt inclusions on an electron microprobe and 24 inclusions on an ion probe. The SiO₂ concentrations of the melts vary within a broad range of 45–74 wt %, as also are the concentrations of other major components. According to their SiO₂, Na₂O, K₂O, TiO₂, and P₂O₅ concentrations, the melts are classified into seven groups. The mafic melts (45–53 wt % SiO₂) comprise the following varieties: potassic (on average 4.2 wt % K₂O, 1.7 wt % Na₂O, 1.0 wt % TiO₂, and 0.20 wt % P₂O₅), sodic (3.2% Na₂O, 1.1% K₂O, 1.1% TiO₂, and 0.40% P₂O₅), and titaniferous with high P₂O₅ concentrations (2.2% TiO₂, 1.1% P₂O₅, 3.8% Na₂O, and 3.0% K₂O). The melts of intermediate composition (53–64% SiO₂) also include potassic (5.6% K₂O, 3.4% Na₂O, 1.0% TiO₂, and 0.4% P₂O₅) and sodic (4.3% Na₂O, 2.8% K₂O, 1.3% TiO₂, and 0.4% P₂O₅) varieties. The acid melts (64–74% SiO₂) are either potassic (4.5% K₂O, 3.6% Na₂O, 0.7% TiO₂, and 0.15% P₂O₅) or sodic (4.5% Na₂O, 3.1% K₂O, 0.7% TiO₂, and 0.13% P₂O₅). A distinctive feature of the Gorely volcanic center is the pervasive occurrence of K-rich compositions throughout the whole compositional range (silicity) of the melts. Melt inclusions of various types were sometimes found not only in a single sample but also in the same phenocrysts. The sodic and potassic types of the melts contain different Cl and F concentrations: the sodic melts are richer in Cl, whereas the potassic melts are enriched in F. We are the first to discover potassic melts with very high F concentrations (up to 2.7 wt %, 1.19 wt % on average, 17 analyses) in the Kuriles and Kamchatka. The average F concentration in the sodic melts is 0.16 wt % (37 analyses). The melts are distinguished for their richness in various groups of trace elements: LILE, REE (particularly HREE), and HFSE (except Nb). All of the melts share certain geochemical features. The concentrations of elements systematically increase from the mafic to acid melts (except only for the Sr and Eu concentrations, because of active plagioclase fractionation, and Ti, an element contained in ore minerals). The paper presents a review of literature data on volcanic rocks in the Kurile-Kamchatka area in which melt inclusions with high K₂O concentrations (K₂O/Na₂O > 1) were found. K-rich melts are proved to be extremely widespread in the area and were found on such volcanoes as Avachinskii, Bezymyannyi, Bol’shoi Semyachek, Dikii Greben’, Karymskii, Kekuknaiskii, Kudryavyi, and Shiveluch and in the Valaginskii and Tumrok Ranges.     

Compressibility of titanosilicate melts

The effect of composition on the relaxed adiabatic bulk modulus (K₀) of a range of alkali- and alkaline earth-titanosilicate [X ₂ ^n/n+ TiSiO₅ (X=Li, Na, K, Rb, Cs, Ca, Sr, Ba)] melts has been investigated. The relaxed bulk moduli of these melts have been measured using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz in the temperature range of 950 to 1600°C (0.02 Pa s < _s < 5 Pa s). The bulk moduli of these melts decrease with increasing cation size from Li to Cs and Ca to Ba, and with increasing temperature. The bulk moduli of the Li-, Na-, Ca- and Ba-bearing metasilicate melts decrease with the addition of both TiO₂ and SiO₂ whereas those of the K-, Rb- and Cs-bearing melts increase. Linear fits to the bulk modulus versus volume fraction of TiO₂ do not converge to a common compressibility of the TiO₂ component, indicating that the structural role of TiO₂ in these melts is dependent on the identity of the cation. This proposition is supported by a number of other property data for these and related melt compositions including heat capacity and density, as well as structural inferences from X-ray absorption spectroscopy (XANES). The compositional dependence of the compressibility of the TiO₂ component in these melts explains the difficulty incurred in previous attempts to incorporate TiO₂ in calculation schemes for melt compressibility. The empirical relationship KV^-4/3 for isostructural materials has been used to evaluate the compressibility-related structural changes occurring in these melts. The alkali metasilicate and disilicate melts are isostructural, independent of the cation. The addition of Ti to the metasilicate composition (i.e. X₂TiSiO₅), however, results in a series of melts which are not isostructural. The alkaline-earth metasilicate and disilicate compositions are not isostructural, but the addition of Ti to the metasilicate compositions (i.e. XTiSiO₅) would appear, on the basis of modulus-volume systematics, to result in the melts becoming isostructural with respect to compressibility.     

The effect of phosphorus on the iron redox ratio,viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO₂. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P₂O₅ is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P₂O₅ on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P₂O₅ results in a relatively small change in viscosity, while further addition of P₂O₅ results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm³/mol for P₂O₅ in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm³/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P₂O₅ on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully.     

The role of P2O5 in silicate melts

Phase equilibria data in the systems SiO₂-P₂O₅, P₂O₅-M_xO_y, and P₂O₅-M_xO_y-SiO₂ are employed in conjunction with Chromatographic and spectral data to investigate the role of P₂O₅ in silicate melts. Such data indicate that the behavior of P₂O₅ is complex. P₂O₅ depolymerizes pure SiO₂ melts by entering the network as a four-fold coordinated cation, but polymerizes melts in which an additional metal cation other than silicon is present. The effect of this polymerization is apparent in the widening of the granite-ferrobasalt two-liquid solvus. In this complex system P₂O₅ acts to increase phase separation by further enrichment of the high charge density cations Ti, Fe, Mg, Mn, Ca, in the ferrobasaltic liquid. P₂O₅ also produces an increase in the ferrobasalt-granite REE liquid distribution coefficients. These distribution coefficients are close to 4 in P₂O₅-free melts, but close to 15 in P₂O₅-bearing melts.The dual behavior of P₂O₅ is explained in a model which requires complexing of phosphate anions (analogous to silicate anions) and metal cations in the melt. This interaction destroys Si-O-M-O-Si bonds polymerizing the melt. The higher concentration of Si-O-M-O-Si bond complexes in immiscible ferrobasaltic liquids relative to their conjugate immiscible granite liquids explains the partitioning of P₂O₅ into the ferrobasaltic liquid.