Temperature independent thermal expansivities of calcium aluminosilicate melts between 1150 and 1973 K in the system anorthite-wollastonite-gehlenite (An-Wo-Geh): A density model

The thermal expansivities of 10 compositions from within the anorthite-wollastonite-gehlenite (An-Wo-Geh) compatibility triangle have been investigated using a combination of calorimetry and dilatometry on the glassy and liquid samples. The volumes at room temperature were derived from densities measured using the Archimedean buoyancy method. For each sample, density was measured at 298 K using glass that had a cooling-heating history of 10-10 K min⁻¹. The thermal expansion coefficient of the glass from 298 K to the glass transition interval was measured by a dilatometer and the heat capacity was measured using a differential scanning calorimeter from 298 to 1135 K. The thermal expansion coefficient and the heat flow were determined at a heating rate of 10 K min⁻¹ on glasses which were previously cooled at 10 K min⁻¹. Supercooled liquid density, molar volume and molar thermal expansivities were indirectly determined by combining differential scanning calorimetric and dilatometric measurements assuming that the kinetics of enthalpy and shear relaxation are equivalent. The data obtained on supercooled liquids were compared to high-temperature predictions from the models of (Lange, R.A., Carmichael, I.S.E., 1987. Densities of Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ liquids: New measurements and derived partial molar properties. Geochim. Cosmochim. Acta51, 2931-2946; Courtial, P., Dingwell, D.B., 1995. Nonlinear composition dependence of molar volume of melts in the CaO-Al₂O₃-SiO₂ system. Geochim. Cosmochim. Acta59 (18), 3685-3695; Lange, R.A., 1997. A revised model for the density and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids from 700 to 1900 K: extension to crustal magmatic temperatures. Contrib. Mineral. Petrol.130, 1-11). The best linear fit combines the supercooled liquid data presented in this study and the high temperature data calculated using the Courtial and Dingwell (1995) model. This dilatometric/calorimetric method of determining supercooled liquid molar thermal expansivity greatly increases the temperature range accessible for thermal expansion. It represents a substantial increase in precision and understanding of the thermodynamics of calcium aluminosilicate melts. This enhanced precision demonstrates clearly the temperature independence of the melt expansions in the An-Wo-Geh system. This contrasts strongly with observations for neighboring system such as anorthite-diopside and raises the question of the compositional/structural origins of temperature dependence of thermal expansivity in multicomponent silicate melts.     

Equilibrium density and expansivity of silicate melts in the glass transition range

Equilibrium volumes and expansivities of three liquids in the system anorthite (CaAl₂Si₂O₈)–diopside (CaMgSi₂O₆) have been derived from dilatometric measurements of the equilibrium length of samples in the glass transition range. The typical temperature range of 40 K for the measurements is limited at low temperature by the very long times necessary to reach structural equilibrium and at high temperature by the penetration of the rod used to measure sample dilatation. Despite such narrow intervals, the expansivities are determined to better than 3% thanks to the high precision with which length changes are measured. The coefficient of volume thermal expansion (1/V dV/dT) of the fully relaxed liquid just above the glass transition is found to decrease linearly from diopside composition (139 ± 4 × 10⁻⁶ K⁻¹) to anorthite composition (59 ± 2 × 10⁻⁶ K⁻¹). These values are greater than those determined for the same liquids at superliquidus temperatures, demonstrating that expansivities of silicate melts may decrease markedly with increasing temperature. A predictive model based upon partial molar volumes which vary as a linear function of the logarithm of temperature is proposed. Received: 25 February 2000 / Accepted: 29 May 2000     

Thermal expansion of plagioclase feldspars

The volume thermal expansion coefficient and the anisotropy of thermal expansion were determined for nine natural feldspars with compositions, in terms of albite (NaAlSi₃O₈, Ab) and anorthite (CaAl₂Si₂O₈, An), of Ab₁₀₀, An₂₇Ab₇₃, An₃₅Ab₆₅, An₄₆Ab₅₄, An₆₀Ab₄₀, An₇₈Ab₂₂, An₈₉Ab₁₁, An₉₆Ab₄ and An₁₀₀ by high resolution powder diffraction with a synchrotron radiation source. Unit-cell parameters were determined from 124 powder patterns of each sample, collected over the temperature range 298–935 K. The volume thermal expansion coefficient of the samples determined by a linear fit of V/V ₀ = α(T − T ₀) varies with composition (X _An in mol %) as:

Oxygen diffusion in three silicate melts along the join diopside-anorthite

The self-diffusion of oxygen has been measured for three silicate melts along the join diopsideanorthite. The experiments were done by isotope exchange between an “infinite” reservoir of oxygen gas and spheres of melt. The oxygen self-diffusion coefficients for the three melts are given as: C-1(diopside): D = 1.64 × 10¹ exp(?(63.2 ± 20)(kcal/mole)/RT) cm²/sec C-2(Di₅₈An₄₂): D = 1.35 × 10^?1 exp(?(46.8 ± 9)(kcal/mole)/RT) cm²/sec C-3(Di₄₀An₆₀): D = 1.29 × 10^?2 exp(?(44.2 ± 6)(kcal/mole)/RT) cm²/secThe self-diffusion coefficients do not agree with the Eyring equation unless mean ionic jump distances (λ) considerably larger than the diameter of oxygen anion are assumed. However, the sense of variation of the actual diffusivities is as the Eyring equation predicts.Consideration of the results of this study and the bulk of previous work shows that oxygen appears to conform to the compensation law for cationic diffusion in silicate melts and glasses. The range of oxygen diffusivities was also found to encompass the field of divalent cation diffusivities in silicate melts.Those results imply that the diffusion of oxygen in silicate melts may involve a contribution from a cation-like diffusion mechanism (discrete O^2? anions) as well as contributions from the diffusion of larger structural units.     

Refractive index and compressibility of Di64An36 glass over a pressure range of 0–5.0 GPa

Data on the refractive index, density, and bulk modulus variations of Di₆₄An₃₆ glass, which is used as a model basalt melt, were obtained with a polarization interference microscope and a high-pressure diamond anvil cell at ambient temperature and pressure up to 5.0 GPa. An anomalous decrease in the bulk modulus, K _t , was observed in the pressure range 0?C1.0 GPa. The values of the zero-pressure isothermal bulk modulus, K _t,0 = 22.2, and variation of the bulk modulus with pressure, ??K _t /??P = 11.35, were derived using a linear equation relating K _t and P over the pressure range with the normal behavior of the compressibility. A comparison of our results with previous data on other glasses and melts showed that the bulk moduli of silicate glasses are similar to those of corresponding melts. The values of the pressure coefficient of the bulk moduli, ??K _t /??P, for glasses derived from linear equations are 2.5 times higher than the pressure derivative of the bulk modulus, K?? _T , derived using the Birch-Murnaghan equation for corresponding melts. The difference in ??K _t /??P and K?? _T has an effect on the compressibility of glasses and melts. The compressibility of glasses up to 5.0 GPa calculated as (d ? d ₀)/d is almost two times lower than that of corresponding melts.     

Non-linear temperature dependence of liquid volumes in the system albite-anorthite-diopside

The temperature-dependent thermal expansivities of glasses and liquids in the ternary albite-anorthite-diopside have been determined using a combination of calorimetry, dilatometry and Pt and Ir double bob Archimedean densitometry. Supercooled liquid volumes and molar thermal expansivities were determined across the glass transition using a combination of scanning calorimetry and dilatometry, based upon the equivalence of relaxation of volume and enthalpy in the vicinity of the glass transition. Superliquidus volumes were determined using double Pt bob Archimedean densitometry at temperatures up to 1,650°C and double Ir bob densitometry at 1,800°C. Experimental access to liquid volumes near the glass transition temperatures (680–920°C) and at superliquidus temperatures (1,400–1,800°C) for these compositions results in the observation of a nonlinear temperature dependence of molar volume, i.e., temperature-dependent thermal expansivities. The diopside composition wxhibits the largest temperature dependence of thermal expansivity, decreasing by 50% between 800 and 1,500°C. Linear extrapolation of the high-temperature volume data of diopside to 810°C would result in a 3% overestimation of the molar voltime. The temperature dependence of the molar volume of anorthite is approximately linear. The thermal expansivities of the liquids in the albite-anorthite-diopside system appear to converge at high temperature. This study uses a combination of methods that allows interpolation rather than extrapolation of the extant melt-volume data into the petrologically meaningful (subliquidus) temperature range.     

New density measurements on carbonate liquids and the partial molar volume of the CaCO<Subscript>3</Subscript> component

Density measurements on nine liquids in the CaCO₃–Li₂CO₃–Na₂CO₃–K₂CO₃ quaternary system were performed at 1 bar between 555 and 969 °C using the double-bob Archimedean method. Our density data on the end-member alkali carbonate liquids are in excellent agreement with the NIST standards compiled by Janz (1992). The results were fitted to a volume equation that is linear in composition and temperature; this model recovers the measured volumes within experimental error (±0.18% on average, with a maximum residual of ±0.50%). Our results indicate that the density of the CaCO₃ component in natrocarbonate liquids is 2.502 (±0.014) g/cm³ at 800 °C and 1 bar, which is within the range of silicate melts; its coefficient of thermal expansion is 1.8 (±0.5)×10^–4 K^–1 at 800 °C. Although the volumes of carbonate liquids mix linearly with respect to carbonate components, they do not mix linearly with silicate liquids. Our data are used with those in the literature to estimate the value of in alkaline silicate magmas (20 cm³/mol at 1400 °C and 20 kbar), where CO₂ is dissolved as carbonate in close association with Ca. Our volume measurements are combined with sound speed data in the literature to derive the compressibility of the end-member liquids Li₂CO₃, Na₂CO₃, and K₂CO₃. These results are combined with calorimetric data to calculate the fusion curves for Li₂CO₃, Na₂CO₃, and K₂CO₃ to 5 kbar; the calculations are in excellent agreement with experimental determinations of the respective melting reactions.Editorial responsibility: I Carmichael     

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.     

Liquidas phase relationships in the system CaAl2Si2O8-NaAlSi3O8-KAlSi3O8-NaAlSiO4-KAlSiO4 atP(H2O)=5 kb

Liquidus phase equilibria have been determined in the system CaAl₂Si₂O₈-NaAlSi₃O₈-KAlSi₃O₈-NaAlSiO₄-KAlSiO₄ (An-Ab-Or-Ne-Ks) at a pressure of water of 5 kb, for low anorthite contents. The main effects of increasing anorthite content on phase relationships in the system Ab-Or-Ne-Ks include the expansion of the plagioclase stability field towards the potassium-rich part of the system, and an accompanying contraction of the alkali feldspar, leucite, nepheline and kalsilite stability fields; and an increase in liquidus temperatures throughout most of the compositional range. Two quaternary invariant points have been identified in the system, one a reaction point between the fields of alkali feldspar, plagioclase, nepheline and kalsilite at approximately An₄, and the other probably a quaternary eutectic between the fields of alkali feldspar, plagioclase, leucite and kalsilite at approximately An₆. A shallow minimum trough in liquidus temperatures occurs on the two-feldspar surface, and this would be expected to control the paths of liquids cooling under equilibrium conditions. Phase relationships in this quaternary system have been applied to the interpretation of the histories of the potassium-rich rocks of the Roman Volcanic Region, Italy. Differentiation of the phonolitic series in this region may have occurred by two-feldspar fractionation.     

Thermal expansion and glass transition temperatures of synthetic glasses of plagioclase-like compositions

The glass transition temperatures and the thermal expansions both below and above the glass transition temperature region of synthetic glasses of compositions close to those of plagioclases have been determined. The linear thermal expansion coefficient of the rigid glasses decreases on average from 7.4×10^–6/dgC for albite glass to 4.9×10^–6/dgC for glass close to anorthite composition. The glass transition temperature of the glasses initially decreases from 763° C for albite glass to 752°C for An_9.7 glass and then increases nearly linearly with further increasing anorthite content to 813° C for glass close to anorthite composition.—Measurements made for comparison on a glass prepared from Madagascar orthoclase yielded a linear thermal expansion coefficient of 6.1×10^–6/dgC and a glass transition temperature of 905° C.The variations in thermal expansion and glass transition temperature of the feldspar glasses with composition are discussed in terms of structural changes which are assumed to be associated with cation replacement.     

A revised model for the density and thermal expansivity of K2O-Na2O-CaO-MgO-Al2O3-SiO2 liquids from 700 to 1900 K: extension to crustal magmatic temperatures

A revised model for the volume and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids, which can be applied at crustal magmatic temperatures, has been derived from new low temperature (701–1092 K) density measurements on sixteen supercooled liquids, for which high temperature (1421–1896 K) liquid density data are available. These data were combined with similar measurements previously performed by the present author on eight sodium aluminosilicate samples, for which high temperature density measurements are also available. Compositions (in mol%) range from 37 to 75% SiO₂, 0 to 27% Al₂O₃, 0 to 38% MgO, 0 to 43% CaO, 0 to 33% Na₂O and 0 to 29% K₂O. The strategy employed for the low temperature density measurements is based on the assumption that the volume of a glass is equal to that of the liquid at the limiting fictive temperature, T _f ^′. The volume of the glass and liquid at T _f ^′ was obtained from the glass density at 298 K and the glass thermal expansion coefficient from 298 K to T _f ^′. The low temperature volume data were combined with the existing high temperature measurements to derive a constant thermal expansivity of each liquid over a wide temperature interval (767–1127 degrees) with a fitted 1 error of 0.5 to 5.7%. Calibration of a linear model equation leads to fitted values of Vˉ _i ±1 (cc/mol) at 1373 K for SiO₂ (26.86 ± 0.03), Al₂O₃ (37.42±0.09), MgO (10.71±0.08), CaO (15.41±0.06), Na₂O (26.57±0.06), K₂O (42.45 ± 0.09), and fitted values of dVˉ _i /dT (10⁻³ cc/mol-K) for MgO (3.27±0.17), CaO (3.74±0.12), Na₂O (7.68±0.10) and K₂O (12.08±0.20). The results indicate that neither SiO₂ nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT ^liq is independent of temperature between 701 and 1896 K over a wide range of composition. Between 59 and 78% of the thermal expansivity of the experimental liquids is derived from configurational (vs vibrational) contributions. Measured volumes and thermal expansivities can be recovered with this model with a standard deviation of 0.25% and 5.7%, respectively. Received: 2 August 1996 / Accepted: 12 June 1997     

Calorimetric measurements of fusion enthalpies for Ni2SiO4 and Co2SiO4 olivines and application to olivine-liquid partitioning

Calorimetric measurements of fusion enthalpies for Ni₂SiO₄ and Co₂SiO₄ olivines were carried out using a high-temperature calorimeter, and Ni and Co partitioning between olivine and silicate liquid was analyzed using the measured heats of fusion. The fusion enthalpy of Co₂SiO₄ olivine measured by transposed-temperature drop calorimetry was 103 ± 15 kJ/mol at melting point (1688 K). The fusion enthalpy of Ni₂SiO₄ olivine was calculated based on the enthalpies of liquids in the system An₅₀Di₅₀-Ni₂SiO₄ measured by transposed-temperature drop calorimetry at 1773 K, and was 221 ± 26 kJ/mol at its metastable melting point (1923 K). The fusion enthalpy of Ni₂SiO₄ is the largest among those of olivine group, this is caused by the large crystal field stabilization energy of six-coordinated Ni²⁺ in olivine. The larger fusion enthalpy of Ni₂SiO₄ can account for the large and variable partition coefficient of Ni between olivine and silicate liquid. Based on the comparison between partition coefficients calculated from thermodynamic data and those observed in partition experiments, it is considered that the magnitude of partition coefficients is primarily dependent on the heats of fusion of the components. Furthermore, the activity coefficients for Ni-, Co- and Mn-bearing components in magmatic liquid are nearly of the same magnitude.     

Supercooled diopside melt: confirmation of temperature-dependent expansivity using container-based dilatometry

The expansivity of supercooled diopside liquid has been determined using techniques of container-based dilatometry. Two thermal strategies have been employed, one in which the sample is brought to volumetric equilibrium by long-duration dwells at low temperatures (817 °C) and one in which scanning dilatometry of the sample has been performed at somewhat higher temperatures (890–913 °C). The results of both experiments yield a supercooled liquid expansivity for diopside liquid in the temperature range of 817–913 °C of 84.4 ± 2.8 × 10⁻⁴ cm³/mol K. The expansivity is 65% higher than that obtained for diopside melt obtained at superliquidus temperatures using the double bob Archimedean method. Combined fitting of the new low temperature, volume–temperature data from the present study and the superliquidus data from the literature has been performed. The combined fit yields the following equations for the volume–temperature relationship of diopside liquid (T=temperature in °C):

Plagioclase buoyancy in basaltic liquids as determined with a centrifuge furnace

Plagioclase buoyancy experiments have been carried out in a high-temperature centrifuge furnace using seventeen basaltic liquids and plagioclase crystals of three compositions: An₈₉, An⁷⁶ and An₅₅. The results show that the floating tendency of plagioclase in basaltic liquids is at least 0.03 g/cm³ greater than indicated by the calculations. If this correction factor is applied to calculations of plagioclase buoyancy in the Skaergaard Intrusion, it is found that the plagioclase crystals in the lower and middle zones were less dense than the coexisting liquids.Other phenomena relevant to crystal transport in basaltic liquids were observed in the centrifuge experiments. These included crystal flotation by rising bubbles, plagioclase sinking because of the formation of plagioclase-magnetite composite grains, graded bedding of olivine and magnetite, and more than 60% intercumulus basaltic liquid between settled olivine crystals.     

The origin of plagioclase phenocrysts in basalts from continental monogenetic volcanoes of the Kaikohe-Bay of Islands field,New Zealand: implications for magmatic assembly and ascent

Late Quaternary, porphyritic basalts erupted in the Kaikohe-Bay of Islands area, New Zealand, provide an opportunity to explore the crystallization and ascent history of small volume magmas in an intra-continental monogenetic volcano field. The plagioclase phenocrysts represent a diverse crystal cargo. Most of the crystals have a rim growth that is compositionally similar to groundmass plagioclase (~?An₆₅) and is in equilibrium with the host basalt rock. The rims surround a resorbed core that is either less calcic (~?An_20–45) or more calcic (>?An₇₀), having crystallized in more differentiated or more primitive melts, respectively. The relic cores, particularly those that are less calcic (<?~?An₄₅), have ⁸⁷Sr/⁸⁶Sr ratios that are either mantle-like (~?0.7030) or crustal-like (~?0.7040 to 0.7060), indicating some are antecrysts formed in melts fractionated from plutonic basaltic forerunners, while others are true xenocrysts from greywacke basement and/or Miocene arc volcanics. It is envisaged that intrusive basaltic forerunners produced a zone where various degrees of crustal assimilation and fractional crystallization occurred. The erupted basalts represent mafic recharge of this system, as indicated by the final crystal rim growths around the entrained antecrystic and xenocrystic cargo. The recharge also entrained cognate gabbros that occur as inclusions, and produced mingled groundmasses. Multi-stage magmatic ascent and interaction is indicated, and is consistent with the presence of a partial melt body in the lower crust detected by geophysical methods. This crystallization history contrasts with traditional concepts of low-flux basaltic systems where rapid ascent from the mantle is inferred. From a hazards perspective, the magmatic system inferred here increases the likelihood of detecting eruption precursor phenomena such as seismicity, degassing and surface deformation.     

Water solubility in a calcium aluminosilicate melt

We have measured the water solubility between 1 atmosphere and 5 kilobars for a calcium aluminosilicate melt of molar composition CaO 0.28, Al₂O₃ 0.06, SiO₂ 0.66 (An₉Wo₃₈Qz₅₃). The water contents were measured via thermogravimetric analysis of isobarically quenched glasses, and range from 0.121 wt% H₂O near 1 aim to 9.25 wt% H₂O at 5 kilobars. The molar water solubility lies between those of SiO₂ and albite melts below around three kilobars, and crosses the albite solubility curve above this pressure. The present results are compared with data in the literature on related calcium aluminosilicate melts. There seems to be little variation of water solubility with composition for calcium aluminosilicate melts, unlike analogous alkali aluminosilicate compositions. Examination of the data suggests that there may be a maximum in molar water solubility along the albite-anorthite join.     

Magma fractionation systems beneath the mid-Atlantic ridge at 36–37 ° N

Variation of major and trace elements in drilled basalts from the Mid-Atlantic Ridge (DSDP Leg 37) reflects distinct cycles of low pressure fractionation operating independently within a complex network of magma storage reservoirs beneath the crustal spreading axis. Low pressure phase relations are determined by parental magma composition, which varies from An-rich (An/Di > ca. 1.4) to Di-rich (An/Di < ca. 1.4). High An/Di magmas probably formed under slightly hydrous conditions in the mantle. They have low LIL element contents, low P/Y and high Mg/(Mg + Fe) ratios. Zr, P and Y abundance and inter-element ratios are highly diagnostic of primary magma type, and are used to quantify fractional crystallization models.Low pressure fractionation hypotheses were tested by least-squares modelling of whole-rock and phenocryst chemistry, which indicated removal or addition of phenocryst assemblages: ol; pl; ol + pl; ol + pl + cpx; pl + cpx, (± sp). Accumulation of plagioclase or olivine is an important mechanism for generating highly porphyritic rocks. A rare 3-phase (ol + pl + cpx) cumulate resulted from cotectic fractionation of a low An/Di magma type. Olivine and plagioclase cumulates appear to be related to high An/Di magmas. Olivine accumulation has been monitored by comparison of olivine/bulk rock partitioning of Fe and Mg to experimental measurements of the equilibrium K_D value. A single extensive sub-axial magma chamber could not account for the observed chemical variation and would probably be dynamically unstable.     

New thermoelastic parameters of natural <Emphasis Type="Italic">C</Emphasis>2/<Emphasis Type="Italic">c</Emphasis> omphacite

The compressibility at room temperature and the thermal expansion at room pressure of two disordered crystals (space group C2/c) obtained by annealing a natural omphacite sample (space group P2/n) of composition close to Jd₅₆Di₄₄ and Jd₅₅Di₄₅, respectively, have been studied by single-crystal X-ray diffraction. Using a Birch–Murnaghan equation of state truncated at the third order [BM3-EoS], we have obtained the following coefficients: V ₀ = 421.04(7) Å³, K _T0 = 119(2) GPa, K′ = 5.7(6). A parameterized form of the BM3 EoS was used to determine the axial moduli of a, b and c. The anisotropy scheme is β _c  ≤ β _a  ≤ β _b , with an anisotropy ratio 1.05:1.00:1.07. A fitting of the lattice variation as a function of temperature, allowing for linear dependency of the thermal expansion coefficient on the temperature, yielded α_V(1bar,303K) = 2.64(2) × 10⁻⁵ K⁻¹ and an axial thermal expansion anisotropy of α _b  ≫ α _a  > α _c . Comparison of our results with available data on compressibility and thermal expansion shows that while a reasonable ideal behaviour can be proposed for the compressibility of clinopyroxenes in the jadeite–diopside binary join [K _T0 as a function of Jd molar %: K _T0 = 106(1) GPa + 0.28(2) × Jd_(mol%)], the available data have not sufficient quality to extract the behaviour of thermal expansion for the same binary join in terms of composition.     

Iron and titanium solution properties in peraluminous and peralkaline rhyolitic liquids

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

Physicochemical model for the crystallization of rocks of the calc-alkaline series

The Al-rich region of the CaO-MgO-Al₂O₃-SiO₂ system was experimentally studied at pressures of 1.0–2.8 GPa and temperatures of 1300–1535°C. The slopes of the lines of the monovariant reactions An + Sp = Cpx + Cor + (Ga) and L = Cpx + Ga + Cor + Sp and the compositions of the phases involved in these reactions are determined. The results are utilized in the topological analysis of the aluminous region of the CaO-MgO-Al₂O₃-SiO₂ system. On this basis, the principal structure of the phase diagram is analyzed, and a phase diagram is constructed for the junction region of the quaternary system and the CaO-Al₂O₃-SiO₂ ternary system. A continuous series of the monovariant eutectic: L = Cpx + Opx + Fo + An, L = Cpx + Opx + An + Sp, L = Cpx + (Ga) + An + Sp, L = Cpx + Cor + (Ga) + An, L = An + Ga + Cpx + Ky and L = Ga + Cpx + Ky + Qz is examined within the pressure range from atmospheric to 3.0 GPa and higher. Analogous “telescoped” eutectic series are of fundamental character for interpreting the evolution of magmatic melts. A physicochemical model is suggested for the evolution of magmatic melts that produce rocks of the calc-alkaline series, with this model underlain by the fact that a change in the composition of magmatic melt at a pressure decrease should correspond to the minimum melting temperatures, i.e., to melts in the fundamental series of eutectic reactions. The comparison of our physicochemical model and rocks of the calc-alkaline series shows that the compositions of rocks of the calc-alkaline series are close to the compositions determined for the eutectic equilibria, and the mineralogical composition of xenoliths and megacrysts in volcanic and dike varieties of the rocks are similar to the subsolidus phases of the established fundamental eutectic system.