High-temperature and high-pressure equation of state for the hexagonal phase in the system NaAlSiO4 – MgAl2O4

Thermal equation of state of an Al-rich phase with Na_1.13Mg_1.51Al_4.47Si_1.62O₁₂ composition has been derived from in situ X-ray diffraction experiments using synchrotron radiation and a multianvil apparatus at pressures up to 24 GPa and temperatures up to 1,900 K. The Al-rich phase exhibited a hexagonal symmetry throughout the present pressure–temperature conditions and the refined unit-cell parameters at ambient condition were: a=8.729(1) Å, c=2.7695(5) Å, V ₀=182.77(6) Å³ (Z=1; formula weight=420.78 g/mol), yielding the zero-pressure density ρ₀=3.823(1) g/cm³ . A least-square fitting of the pressure-volume-temperature data based on Anderson’s pressure scale of gold (Anderson et al. in J Appl Phys 65:1534–543, 1989) to high-temperature Birch-Murnaghan equation of state yielded the isothermal bulk modulus K ₀=176(2) GPa, its pressure derivative K ₀ ^′ =4.9(3), temperature derivative (?K _T /?T) _P =?0.030(3) GPa K^?1 and thermal expansivity α(T)=3.36(6)×10^?5+7.2(1.9)×10^?9 T, while those values of K ₀=181.7(4) GPa, (?K _T /?T) _P =?0.020(2) GPa K^?1 and α(T)=3.28(7)×10^?5+3.0(9)×10^?9 T were obtained when K ₀ ^′ was assumed to be 4.0. The estimated bulk density of subducting MORB becomes denser with increasing depth as compared with earlier estimates (Ono et al. in Phys Chem Miner 29:527–531 2002; Vanpeteghem et al. in Phys Earth Planet Inter 138:223–230 2003; Guignot and Andrault in Phys Earth Planet Inter 143–44:107–128 2004), although the difference is insignificant (<0.6%) when the proportions of the hexagonal phase in the MORB compositions (～20%) are taken into account.     

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

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

Hydrogen incorporation in enstatite in the system MgO–SiO2–H2O–NaCl

The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na⁺ on the defect chemistry or an exchange between OH^- and Cl⁻in enstatite, appear much less important. A partition coefficient D _Na ^En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

High-pressure phases in the Al2SiO5 system and the problem of aluminous phase in the Earth's lower mantle: ab initio calculations

 One of the main uncertainties in mineralogical models of the Earth's lower mantle is the nature of the aluminous mineral: it is not clear whether Al forms its own minerals or is mainly contained in (Mg,Fe)SiO₃-perovskite. This question is very important, since it is known that if Al were mainly hosted by perovskite, it would radically change Fe/Mg-partitioning and phase equilibria between mantle minerals, and also alter many physical and chemical properties of perovskite, which is currently believed to comprise ca. 70% of the volume of the lower mantle. This, in turn, would require us to reconsider many of our geochemical and geophysical models for the lower mantle. This work considers the possibility of a V₃O₅-type structured modification of Al₂SiO₅ to be the main host of Al in the lower mantle, as proposed by previous workers. We report ab initio calculations, based on density functional theory within the generalised gradient approximation (GGA) with plane wave basis set and nonlocal pseudopotentials. We consider polymorphs of Al₂SiO₅ (kyanite, andalusite, sillimanite, and hypothetical V₃O₅-like and pseudobrookite-like phases), SiO₂ (stishovite, quartz) and Al₂O₃ (corundum). Computational conditions (e.g., plane-wave energy cutoff, Brillouin zone sampling) were carefully chosen in order to reproduce small energy changes associated with phase transitions between the Al₂SiO₅ polymorphs. Good agreement of crystal structures, bulk moduli, atomisation energies and the phase diagram of Al₂SiO₅ with experimental data was found. Strong disagreement between the calculated lattice parameters and density of V₃O₅-like phase of Al₂SiO₅ and experimental values, assigned to it by previous workers, suggests that a V₃O₅-structured phase of Al₂SiO₅ was never observed experimentally. In addition, we found that the most stable high-pressure assembly in Al₂SiO₅ system is corundum+stishovite, and the value of the transition pressure at T = O K (113 kbar) is in excellent agreement with experimental estimates (95–150 kbar). We explain the instability of octahedrally coordinated silicates of Al to decomposition on the basis of Pauling's second rule. Received: 18 May 1999 / Accepted: 5 November 1999     

Mechanisms of the transformations between the α, β and γ polymorphs of Mg2SiO4 at 15 GPa

Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg₂SiO₄ at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg₂GeO₄ and Ni₂SiO₄) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg₂SiO₄ olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.     

Spatial transformations in a “loosening state”: South Africa in a comparative perspective

This study explores the spatial transformation of urban South Africa since the ending of Apartheid rule two decades ago. It places this experience within the context of countries which have also gone through a “loosening” of political control and of related controls over spatial arrangements. The paper provides a discussion of South Africa’s spatial trends between 1996 and 2011, focusing on urbanisation; urban form; and socio-spatial segregation, and exploring the extent to which changes identified are shaped by the state, private sector investment, and the everyday actions of households and individuals. It shows that South Africa’s urban spatial transformation, post-Apartheid, is both idiosyncratic and comparable. The consequences of spatial controls, and of their loosening, have been diverse across countries, but also within countries. Loosening has led to differing relationships between state, citizenry and private enterprise, and to complex new crossing points between these groupings, affecting spatial change. In South Africa, significant trends have been: movement to the major cities where employment growth is stronger; levels of racial desegregation; and densification of parts of cities and towns, along with peripheral growth and employment decentralisation. Many of the changes however are differentiated across space and between settlements. While proactive state policies have had some impact (not necessarily in the direction of desired spatial transformation), and there are complex interrelationships, our empirical studies suggest that the major weight of evidence is towards the roles of private enterprise and people in shaping spatial change, enabled in part by forms of state loosening.     

Phase relations and fractionation sequences in potassic magma series modelled in the system CaMgSi2O6-KAlSiO4-Mg2SiO4-SiO2-F2O−1 at 1 bar to 18 kbar

Liquidus phase relations in the system diopside–kalsilite–forsterite–quartz with 3 wt% F were examined at 1 bar and the locations of important invariant points were determined at 18 kbar. At all pressures within this range a large liquidus field for fluorphlogopite (Phl) exists, and has a large influence on both melting and fractionation processes. One eutectic point was found to the silica-rich side of the plane Lc–Fo–Di at Di₁Ks₃₀Fo₂Qz₆₇, where a melt coexists with San, Qz, Phl and Di at 840 °C and 1 bar. Another eutectic point must exist in the silica-poor part of the system because the phase topology determines that thermal barriers must exist. At this point a feldspathoid, either Lc or Ks, must coexist with Fo, Phl and a Ca-bearing phase such as Di. The exact location and phase assemblage were not determined, but the equilibrium melt must have a composition rich in Di (>29 wt%) and extremely poor in Qz (<8 wt%). The composition of the first eutectic moves towards lower SiO₂ contents with increasing pressure (Di₃Ks₄₀Fo₁Qz₅₆ at 18 kbar), whereas the second does not exist at 18 kbar due to the disappearance of Lc as a stable liquidus phase. Liquids which coexist with mafic minerals such as En, Fo, Phl and Di are important for the genesis of potassium-rich mafic rocks by partial melting in the mantle and for the early stages of fractional crystallisation. The equilibrium melt at the invariant point Fo + En + Phl + Di + L at 1125 °C is very poor in Fo and Di components at atmospheric pressure (Di₅Ks₃₇Fo₅Qz₅₃), whereas at 18 kbar the melt contains large amounts of Fo and Di (Di₁₉Ks₃₁- Fo₂₈Qz₂₁), and has a composition close to that of natural lamproites. Kamafugites do not correspond to melts in this system under any of the studied conditions, and appear to require CO₂ in the source. Fractionation processes from primitive potassic basanite melts are controlled principally by the size (and not the mere presence) of the liquidus phase field for phlogopite: at high pressures where the Phl field is large, olivine is eliminated early from the fractionating assemblage and Cpx + Phl fractionation may lead to relatively silica-rich rock differentiates such as trachytes. At low pressures, extensive olivine and restricted Phl crystallisation prevents silica enrichment in the melt, resulting in phonolitic differentiates. Later crystallisation of alkali feldspar accentuates the trends laid down in the early stages of fractionation. Received: 2 February 1999 / Accepted: 14 October 1999     

Experimental determination of activity-composition relations in Ni2SiO4− Mg2SiO4 and Co2SiO4-Mg2SiO4 olivine solid solutions at 1200 K and 0.1 MPa and 1573 K and 0.5 GPa

Activity-composition relations in the olivine solid solutions Ni₂SiO₄⁻ -Mg₂SiO₄ and Co₂SiO₄-Mg₂SiO₄ have been determined at 1200 K and 0.1 MPa and at 1573 K and 0.5 GPa by equilibration with the corresponding oxide solutions. Both olivine solutions show small positive deviations from ideal (two site) mixing, which, within the limits of accuracy of the method, may be described by the simple regular solution model with parameters W_Ni+Mg^ol= 0.35 ± 1.0 kJ/g-atom and W_Co-Mg^ol = 1.37 ± 0.9 kJ/g-atom. The requirements of internal consistency between the two systems also show that the recent determination by Brousse et al. (1984) of the enthalpy of formation of Mg₂SiO₄is to be preferred over earlier work, and that their value is also probably more accurate than the uncertainty in their own measurements indicates; activities in the NiO-MgO system are close to ideal.     

Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O±Al2O3

The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H₂O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al₂O₃ in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.     

2Alienoptera — A new insect order in the roach–mantodean twilight zone

A new insect species (2Alienopterus brachyelytrus Bai, Beutel, Klass, Wipfler et Zhang gen.etsp. nov.) of a new order and family is described, based on a single male embedded in Cretaceous Burmese amber (ca. 99 Ma). Unusual characters are shortened forewings combined with fully developed, operational hindwings, similar as in Dermaptera, and specialized attachment pads otherwise only found in mantophasmatodeans (heelwalkers). A cladistic analysis suggests a placement as sister to Mantodea, supported by a profemoral brush and other characters. The male genitalia show the same pattern in both groups. Specialized features are the unusual flight apparatus, attachment structures adapted for locomotion on leaves, and a dense profemoral setation suitable for catching small prey. 2Alienopterus was apparently able to fly and likely a predator of small arthropods in bushes or trees. An impressive radiation of Mantodea started in similar habitats at least 35 Ma later in the early Cenozoic. In contrast, 2Alienopterus was an evolutionary dead end in the roach–mantis transition zone.     

Results of tracking a spacecraft in the vicinity of the L2 libration point of the Sun–Earth system

The launch of the Spektrum-Roentgen-Gamma (SRG) international orbiting astrophysical observatory is planned for the near future. It is planned tomaneuver SRGinto the vicinity of the L2 libration point of the Sun–Earth system, where it will be kept in a quasi-stable orbit. The spacecraft orbit must be maintained in order to carry out the scientific program of the project, which requires obtaining information about the current parameters of its motion. With the aim of developing methods for making optical measurements and estimating the required volume of measurement data and their accuracy, observations of the Gaia spacecraft, which is located in the vicinity of L2, were made at the Sayan Observatory in 2014–2015. The results of observations of the Gaia spacecraft on the 1.6-m infrared telescope of the Sayan Observatory are presented. The measured brightness of the spacecraft was 20.7–22^m, which is close to the limiting magnitude of the telescope. The accuracy of these astrometric measurements was about one arcsecond. Possibilities for obtaining accurate astrometric data for the SRG spacecraft in orbit in the vicinity of L2 are discussed, as well as the required observing conditions and the volume of measurement data required for adequate prediction of the spacecraft motion.     

Soil–structure cyclic direct shear tests: a new interpretation of the direct shear experiment and its application to a series of cyclic tests

This paper presents a series of cyclic 2D direct shear tests on sand–rough material interfaces under constant normal load (CNL) and constant normal stiffness (CNS) conditions. The aim of these tests is to describe the behavior of the soil–pile contact subjected to a large number of cycles due to environmental or anthropic loadings. These cycles (typically 10⁴ or less due to an early rupture) are small (10, 20 and 40 kPa in terms of shear stress). A new interpretation of the direct shear tests is proposed. The sample of soil is schematically composed of a sheared interface and of a buffer under oedometric load. The problem of sand leakage between the shear box and the rough plate, classical phenomenon in this type of test, is focused. The effect of initial density, position of “center of cycles” in stress plane (mean cyclic variables) and cyclic amplitude is investigated. The cycles are defined by the initial mean cyclic normal stress, the level of initial mean cyclic stress ratio and the normalized cyclic amplitude. Under CNL condition, either dilation or contraction is exhibited, in agreement with the characteristic state developed by Luong (International symposium on soils under cyclic and transient loading, Swansea, 7–11 January, pp 315–324, 1980). The influence of a prescribed normal stiffness is especially considered. It can be highlighted that CNS cyclic paths are always contractive. This contraction results in a drop of mean cyclic normal stress often called degradation of friction.     

Bellbergite—a new mineral with the zeolite structure type EAB

Summary The new mineral bellbergite, (K, Ba, Sr)₂Sr₂Ca₂(Ca, Na)₄Al₁₈Si₁₈O₇₂ · 30H₂O, has been found in Ca-rich xenoliths at the Bellberg volcano near Mayen, Eifel, Germany. It occurs as well formed bipyramids with a length up to 0.3 mm. Possible space groups are P6₃/mmc, P62c and P6₃mc with a = 13.244(1) Å, c = 15.988(2) Å, V = 2429 ų, Z = 1. The density is: D_m, = 2.20(2) Mg/m³, D_c = 2.19 Mg/m³. The empirical formula based on 72 oxygen atoms is: Ba_0.26Na_0.72K_1.33Sr_2.36Ca_5.32Al_17.55Si_18.36O₇₂ · 30H₂O. The mineral is uniaxial negative with = 1.522(2) and = 1.507(2) ( = 589 nm). The strongest lines in the X-ray powder pattern are (d (Å), I, hkl): 3.80 (100) (300, 212, 104), 6.58 (80) (102), 2.95 (70) (312, 214), 2.21 (70) (330), 2.70 (50) (402), 2.50 (50) (410, 314), 1.83 (50) (416). The crystal structure corresponds to the zeolite structure type EAB.

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Bellbergit—ein neues Mineral mit dem Zeolith-Strukturtyp EAB

Zusammenfassung Das neue Mineral Bellbergit, (K, Ba, Sr)₂Sr₂Ca₂(Ca, Na)₄AlP₁₈OPub₇₂· 30H₂O, wurde in Ca-reichen Xenolithen am Bellberg bei Mayen, Eifel, Deutschland gefunden. Es kommt als gut ausgebildete hexagonale Dipyramiden mit einer Länge von bis zu 0.3 mm vor. Mögliche Raumgruppen sind P6₃/mcc, P62c und P63mc mit a = 13.244(1) Å, c = 15.988(2) Å, V = 2429 ų und Z = 1. Die Dichte beträgt D_m = 2.20(2) Mg/m³, D_c = 2.19 Mg/m³. Die chemische Formel basierend auf 72 Sauerstoffatomen lautet: Ba_0.26Na_0.72K_1.33Sr_2.36Ca_5.32Al_17.55Si_18.36O₇₂ · 30H₂O. Das Mineral ist einachsig negativ mit = 1.522(2) und = 1.507(2) ( = 589nm). Die stärksten Linien des Pulverdiagramms liegen bei (d(Å), I, hkl): 3.80 (100) (300, 212,104), 6.58 (80) (102), 2.95 (70) (312, 214), 2.21 (70) (330), 2.70 (50) (402), 2.50 (50) (410, 314), 1.83 (50) (416). Die Kristallstruktur entspricht dem Zeolith-Strukturtyp EAB.

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Impacts of the carbon emission trading system on China’s carbon emission peak: a new data-driven approach

Natural Hazards - Over the past four decades, China’s extensive economic growth mode has led to substantial greenhouse gas emissions, and China has become the world’s largest emitter...