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.     

Helium and argon isotopes in lower crustal xenoliths from the belomorian mobile belt

The isotopic systematics of noble gases (He and Ar) were studied in Neoarchean and Paleoproterozoic lower crustal xenoliths from the Belomorian mobile belt. The xenolith suite is dominated by garnet granulites (Grt + Cpx + Pl ± Opx ± Qtz ± Kfs ± Phl ± Hbl) and two-pyroxene or garnet pyroxenites (Cpx + Pl ± Grt ± Opx ± Hbl ± Qtz). The xenoliths and the host Devonian ultramafic lamprophyres forming diatremes and explosion dikes contain fluid with similar He and Ar isotopic compositions. It was found that the fluid was trapped by the rocks and xenolith minerals approximately simultaneously with the formation of the lamprophyres. This conclusion is based on the identical K-Ar ages of the majority of xenoliths and ultramafic lamprophyres. When the xenoliths were transported toward the surface by high-temperature ultrabasic melts, the noble gases occurring in them were partly (Ar) or completely (He) lost. The melts were contaminated by meteoric waters during their emplacement in the upper crust, which resulted in that the Ar isotopic composition of lamprophyres approached the composition of atmospheric Ar. The fluid phase that was liberated during melt crystallization severely affected the xenoliths, diminishing the difference between the isotope compositions of He and Ar in the xenoliths and ultramafic lamprophyres. The He isotope composition includes an admixture of mantle ³He, which is suggested by the high measured ³He concentrations, exceeding the calculated values, and high ³He/³⁶Ar ratios in the xenoliths and their host lamprophyres. The fraction of the mantle component in the fluid trapped by the xenoliths was estimated as ～20%.     

Specifics of the Neoarchean Plume–Lithospheric Processes in the Kola–Norwegian Province of the Fennoscandian Shield: II. Petrology and Geodynamic Nature of Komatiite–Tholeiite Association

Numerical modeling of the generation and evolution of parental melts of the komatiite–tholeiite association of the Uraguba structure was carried out using previously obtained geochemical and isotope data. It was established that komatiite, komatiite and tholeiite basalts depleted in LREE and having ε_Nd(Т = 2.79) = +2.9…+3.2 were generated by equilibrium partial melting (F > 15%) of a depleted source (garnet-bearing Ol_0.63 + Opx_0.22 + Cpx_0.06 + Grt_0.09 mantle peridotite) at 4–8 GPa, while the genesis of primary melts of LREE-enriched komatiites (La_N/Sm_N ~ 1.2–1.6) with ε_Nd(Т = 2.79) = +2.5…+2.2 was related to the equilibrium partial melting (F > 20%) of an “enriched mantle peridotite” (EM–Ol_0.60 + Opx_0.20 + Cpx_0.08 + Grt_0.12) at pressure of 2.5–4 GPa. Coexistence in space and time of two types of melting products of mantle peridotites formed at different depths is explained by melting of different parts of adiabatically ascending mantle plume.     

Compressional behavior of omphacite to 47 GPa

Omphacite is an important mineral component of eclogite. Single-crystal synchrotron X-ray diffraction data on natural (Ca, Na) (Mg, Fe, Al)Si₂O₆ omphacite have been collected at the Advanced Photon Source beamlines 13-BM-C and 13-ID-D up to 47 GPa at ambient temperature. Unit cell parameter and crystal structure refinements were carried out to constrain the isothermal equation of state and compression mechanism. The third-order Birch–Murnaghan equation of state (BM3) fit of all data gives V ₀ = 423.9(3) Å³, K _T0 = 116(2) GPa and K _T0′ = 4.3(2). These elastic parameters are consistent with the general trend of the diopside–jadeite join. The eight-coordinated polyhedra (M2 and M21) are the most compressible and contribute to majority of the unit cell compression, while the SiO₄ tetrahedra (Si1 and Si2) behave as rigid structural units and are the most incompressible. Axial compressibilities are determined by fitting linearized BM3 equation of state to pressure dependences of unit cell parameters. Throughout the investigated pressure range, the b-axis is more compressible than the c-axis. The axial compressibility of the a-axis is the largest among the three axes at 0 GPa, yet it quickly drops to the smallest at pressures above 5 GPa, which is explained by the rotation of the stiffest major compression axis toward the a-axis with the increase in pressure.     

Structural systematics of Ge substitution in primitive pyroxenes

Pyroxenes of general stoichiometry Mg(Ge _x Si_1?x )O₃ were encountered in attempts to synthesise Ge-substituted talcs at 0.2 GPa, 650–700 °C. Orthopyroxenes (Pbca) of compositions x = 0.21, 0.30, and 0.34 were identified, and also a P2₁/c clinopyroxene of composition x = 0.63, and C2/c clinopyroxenes of compositions x = 0.91 and 1. End-member clinoenstatite MgSiO₃-P2₁/c synthesised at 16 GPa, 1300 °C and transformed from C2/c was also included in the study. Crystal structure refinements using single-crystal XRD data showed that unit-cell parameters vary linearly with Si–Ge for the Pbca and P2₁/c pyroxenes, both of which have two symmetrically non-equivalent tetrahedral chains. Refinement of Si–Ge occupancies at tetrahedral sites showed that the two chains of all primitive pyroxenes have very different compositions, with X_Ge(TB) ? X_Ge(TA). This difference arises from the greater flexibility of the B-chain to rotate in response to tetrahedral expansion due to increasing Ge content. The TA-M2 shared polyhedral edge imposes significant constraints on the flexibility of the A-chain, which can accommodate much less Ge than the B-chain. Linear trends of cell parameters, site occupancies, and structural parameters for the primitive pyroxenes, when extrapolated to published data for MgGeO₃–Pbca, extend across the entire Si–Ge join.     

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P2₁/c natural Mg-rich pigeonite sample with composition ca. Wo₆En₇₆Fs₁₈ using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P2₁/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P2₁/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P2₁/c fitting. The equation of state coefficients are V ₀ = 424.66(6) ų, K _T0 = 104(2) GPa and K′ = 8(1) for the P2₁/c phase, and V ₀ = 423.6(1) ų, K _T0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P2₁/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P2₁/c phase. In general the C2/c phase exhibits axial compressibilities (β _c > β _a >> β _b) lower than those of the P2₁/c phase (β _b > β _c ≈ β _a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P2₁/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P _c and M2 average cation radius (i.r.) has been updated using all the literature data on P2₁/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P _c (GPa) = 26(4) ? 28(5) ×  i.r (Å), R ² = 0.97. This improved equation can be used to predict the critical pressure of natural P2₁/c clinopyroxene samples just knowing the composition at M2 site.     

Order/disorder phase transition in cordierite and its possible relationship to the development of symplectite reaction textures in granulites

Based on a consistent set of empirical interatomic potentials, static structure energy calculations of various Al/Si configurations in the supercell of Mg-cordierite and Monte Carlo simulations the phase transition between the orthorhombic and hexagonal modifications of cordierite (Crd) is predicted at 1623 K. The temperature dependences of the enthalpy, entropy, and free energy of the Al/Si disorder were calculated using the method of thermodynamic integration. The simulations suggest that the commonly observed crystallization of cordierite in the disordered hexagonal form could be related to a tendency of Al to occupy T₁ site, which is driven by local charge balance. The increase in the Al fraction in the T₁ site over the ratio of 2/3(T1): 1/3(T2), that characterizes the ordered state, precludes formation of the domains of the orthorhombic phase. This intrinsic tendency to the crystallization of the metastable hexagonal phase could have significantly postponed the formation of the association of orthorhombic cordierite and orthopyroxene over the association of quartz and garnet in metapelites subjected to granulite facies metamorphism. The textures of local metasomatic replacement (the formation of Crd + Opx Or Spr + Crd symplectites between the grains of garnet and quartz) indicate the thermodynamic instability of the association of Qtz + Grt at the moment of the metasomatic reaction. This instability could have been caused by the difficulty of equilibrium nucleation of orthorhombic cordierite.     

Mineral thermometry and the composition of fluids of the sodalite syenites of the Lovozero alkaline massif

In order to determine the conditions of mineral formation, a suite of sodalite syenite samples was investigated from the differentiated complex and in part from the eudialyte lujavrite complex of the Lovozero alkaline massif. The compositions of major and accessory minerals were analyzed using an electron microprobe. Various mineral geothermometers (Bt-Cpx, Amph-Cpx, and Amph-Bt) were applied to estimate the temperature of formation of clinopyroxene-bearing assemblages from the sodalite syenites. The temperature varied from ～990 to 595–630°C, which reflects various stages of crystallization. The temperatures of formation of sodalite assemblages were estimated from the compositions of coexisting sodalite phases as 625–530°C and appeared to be in good agreement with estimates obtained by other mineral geothermometers. Based on the data on the composition and crystallization temperature of sodalites, the minimum concentration of salts (NaCl and Na₂SO₄) in the mineral-forming fluid was estimated as 10–20 wt % NaCl eq. for the two-sodalite assemblages and 1.5–3.0 wt % NaCl eq. for the nosean-bearing assemblages. The molar fraction of sulfur in the fluid was also estimated: 0.02 for the two-sodalite assemblages and 0.04–0.27 for the nosean-bearing assemblages.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Radial pulsations of helium stars and a model for BX CIR

The results of hydrodynamical calculations of radially pulsating helium stars with masses 0.5M_⊙≤M≤0.9M_⊙, bolometric luminosities 600L_⊙≤5×10³L_⊙, and effective temperatures 1.5×10⁴ K≤T_eff≤3.5×10⁴ K are presented. The pulsation instability of these stars is due to the effects of ionization of iron-group elements in layers with temperatures T～2×10⁵ K. The calculations were carried out using opacities for the relative mass abundances of hydrogen and heavy elements X=0 and Z=0.01, 0.015, and 0.02. Approximate formulas for the pulsation constant Q over the entire range of pulsation instability of the hot helium stars in terms of the mass M, radius R, effective temperature T_eff, and heavy-element abundance Z are derived. The instability of BX Cir to radial pulsations with the observed period Π=0.1066 d occurs only for a mass M≥0.55M_⊙, effective temperature T_eff≥23000 K, and heavy-element abundance Z≥0.015. The allowed mass of BX Cir is in the range 0.55M_⊙≤M≤0.8M_⊙, which corresponds to luminosities 800L_⊙≤M≤1400L_⊙ and mean radii 1.7R_⊙?R?2.1R_⊙.     

Separation of chemical elements in the atmospheres of CP stars under the action of light induced drift

A mechanism for the separation of chemical elements and isotopes in the atmospheres of chemically peculiar (CP) stars due to light-induced drift (LID) of ions is discussed. The efficiency of separation due to LID is proportional to the relative difference of the transport frequencies for collisions of ions of heavy elements located in the excited state (collision frequency ν _e ) and ground state (collision frequency ν _g ) with neutral buffer particles (hydrogen and helium), (ν _e ? ν _g )/ν _g . The known interaction potentials are used to numerically compute the relative difference (ν _e ^H ? ν _g ^H )/νg H for collisions between the ions Be⁺, Mg⁺, Ca⁺, Sr⁺, Cd⁺, Ba⁺, Al⁺, and C⁺ and hydrogen atoms. These computations show that, at the temperatures characteristic of the atmospheres of CP stars, T = 7000?20 000 K, values of |ν _e ^H ?ν _g ^H |/ν _g ^H ≈ 0.1?0.4 are obtained. With such relative differences in the transport collision frequencies, the LID rate of ions in the atmospheres of coolCP stars (T < 10000 K) can reach ~0.1 cm/s,which exceeds the drift rate due to light pressure by an order of magnitude. This means that, under these conditions, the separation of chemical elements under the action of LID of ions could be an order of magnitude more efficient than separation due to light pressure. Roughly the same manifestations of LID and light pressure are also expected in the atmospheres of hotter stars (20 000 > T > 10 000 K). LID of heavy ions is manifest only weakly in very hot stars (T > 20 000 K).     

Thermoelastic properties of chromium oxide Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> (eskolaite) at high pressures and temperatures

A new synchrotron X-ray diffraction study of chromium oxide Cr₂O₃ (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch–Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus (K _0,T0), 206 ± 4 GPa; its pressure derivative K′_0,T , 4.4 ± 0.8; (?K _0,T /?T) = ?0.037 ± 0.006 GPa K^?1; a = 2.98 ± 0.14 × 10^?5 K^?1 and b = 0.47 ± 0.28 × 10^?8 K^?2, where α _0,T  = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr₂O₃ was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α _0,T0 was determined to be 2.95 × 10^?5 K^?1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α ₀ value suggested by Rigby et al. (Brit Ceram Trans J 45:137–148, 1946) widely used in many physical and geological databases. Fitting the Mie–Grüneisen–Debye EoS with the present ambient and high-pressure data yielded the following parameters: K _0,T0 = 205 ± 3 GPa, K′_0,T  = 4.0, Grüneisen parameter (γ ₀) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr₂O₃ undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr₂O₃ is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with \({\text{d}}P/{\text{d}}T = - 0.014\) GPa/K) was found to be consistent with experimental data.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

<Emphasis Type="Italic">P</Emphasis>–<Emphasis Type="Italic">V</Emphasis>–<Emphasis Type="Italic">T</Emphasis> equation of state of CaAl<Subscript>4</Subscript>Si<Subscript>2</Subscript>O<Subscript>11</Subscript> CAS phase

The thermoelastic parameters of the CAS phase (CaAl₄Si₂O₁₁) were examined by in situ high-pressure (up to 23.7 GPa) and high-temperature (up to 2,100 K) synchrotron X-ray diffraction, using a Kawai-type multi-anvil press. P–V data at room temperature fitted to a third-order Birch–Murnaghan equation of state (BM EOS) yielded: V _0,300 = 324.2 ± 0.2 Å³ and K _0,300 = 164 ± 6 GPa for K′ _0,300 = 6.2 ± 0.8. With K′ _0,300 fixed to 4.0, we obtained: V _0,300 = 324.0 ± 0.1 Å³ and K _0,300 = 180 ± 1 GPa. Fitting our P–V–T data with a modified high-temperature BM EOS, we obtained: V _0,300 = 324.2 ± 0.1 Å³, K _0,300 = 171 ± 5 GPa, K′ _0,300 = 5.1 ± 0.6 (?K _0,T /?T) _P  = ?0.023 ± 0.006 GPa K^?1, and α_0,T  = 3.09 ± 0.25 × 10^?5 K^?1. Using the equation of state parameters of the CAS phase determined in the present study, we calculated a density profile of a hypothetical continental crust that would contain ~10 vol% of CaAl₄Si₂O₁₁. Because of the higher density compared with the coexisting minerals, the CAS phase is expected to be a plunging agent for continental crust subducted in the transition zone. On the other hand, because of the lower density compared with lower mantle minerals, the CAS phase is expected to remain buoyant in the lowermost part of the transition zone.     

Equation of state of synthetic qandilite Mg<Subscript>2</Subscript>TiO<Subscript>4</Subscript> at ambient temperature

Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg_2.00(1)Ti_1.00(1)O₄ has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K _T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K _T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K _S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K _T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K _T0 values of the ulvöspinel (Fe₂TiO₄; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg₂SiO₄–Fe₂SiO₄ join, our finding suggests that the substitution of Mg²⁺ for Fe²⁺ on the T sites of the 4–2 spinels can have more significant effect on the K _T0 than that on the M sites.     

Pressure induced phase transition in Pb<Subscript>6</Subscript>Bi<Subscript>2</Subscript>S<Subscript>9</Subscript>

The crystal structure of Pb₆Bi₂S₉ is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb₆Bi₂S₉ at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb²⁺ and Bi³⁺ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb₆Bi₂S₉, is solved in Pna2 ₁ (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb₃Bi₂S₆ (lillianite).     

Experimental study of amphibole interaction with H<Subscript>2</Subscript>O–NaCl Fluid at 900°C, 500 MPa: toward granulite facies melting and mass transfer

Interaction between natural pargasite [Prg, SiO₂ = 43.89 wt %, FeO/(FeO + MgO) = 0.35, (Na + K)_A = 0.51] and H₂O–NaCl fluid, whose composition (NaCl mole fraction) varied within the range X _NaCl = NaCl/(NaCl + H₂O) = 0–0.45, was experimentally studied in an internally heated apparatus at 900°C and 500 MPa. Natural pargasite begins to melt at a temperature 120–150°C lower than its synthetic analogue. In the presence of pure H₂O, the subliquidus mineral assemblage involves amphibole Hbl ₁, whose composition is closely similar to the starting Prg, clinopyroxene Cpx, calcic plagioclase Pl, and minor amounts of hercynite-magnetite spinel. With increasing X _NaCl, the subliquidus assemblage systematically changed: calcic plagioclase disappeared and more Fe- rich amphibole Hbl ₂ appeared at X _NaCl = 0.07; Cpx disappeared at X _NaCl = 0.14; and appearance of Na-Phl compositionally close to wonesite and almost complete disappearance of Hbl ₁ was observed at X _NaCl = 0.31. The composition of the melt also changed: its Na₂O gradually increased (from 1.5 to 9–10 wt %), and CaO and SiO₂ decreased(from 8.6 to 2 wt % and from 64 to 60 wt %, respectively, in recalculation to the anhydrous basis); at X _NaCl ≥ 0.35, the melt was transformed from quartz- to nepheline-normative. The maximum Cl concentration of 1.2 wt % was measured in the melt poorest in SiO₂. The experimental products contained spherical objects less than 10 μm in diameter that consisted of material that precipitated from the quenched fluid. These particles are richer than the melt in SiO₂ (62–80 wt %) and poorer in Al₂O₃ (11–19 wt %) in experiments with X _NaCl ≤ 0.24, but the differences between the compositions of the melt and particles decreased with increasing XNaCl. The relatively high concentrations of aluminosilicate material in the fluid is most likely explained by the high solubility of the melt in the fluid phase, with the formation in the fluid aqueous Si, Al–Si, Na–Al–Si, and other polymeric species. It is suggested that interaction of host rocks with such fluids, rich in granitic components, might be responsible for granitization (charnockitization) of mafic, and, particularly, ultramafic rocks described in the literature.     

Atmospheric chemical abundances and the evolutionary status of the spectroscopic and speckle-interferometric binary 9 Cyg

We have performed speckle interferometry with the 6-m telescope of the Special Astrophysical Observatory and spectroscopy (at 3700–9200 Å) with the 2-m telescope at Peak Terskol of the spectroscopic and interferometric binary 9 Cyg, which is a composite-spectrum star with an orbital period of 4.3 yrs. The atmosphere of the system’s primary component is analyzed in detail. The luminosities of both components estimated to be L ₁ = 103.8 L _⊙, L ₂ = 55.2 L _⊙, where L _⊙ is the solar luminosity, and their effective temperatures to be T _e (1) = 5300 K and T _e (2) = 9400 K. The abundances of C, N, O, Fe, and other elements in the primary’s atmosphere have been derived. The chemical composition shows signatures of mixing of material from its atmosphere and the region of nuclear reactions. The evolutionary status of 9 Cyg has been determined. The binary’s age is about 400 million years; the brighter star is already in the transition to becoming a red giant, while the secondary is still in the hydrogen-burning stage near the zero-age main sequence. We suggest an evolutionary model for the binary’s orbit that explains the high eccentricity, e = 0.79.