Elasticity of CaTiO3–CaSiO3 perovskites

Polycrystalline specimens in the CaTiO₃–CaSiO₃ perovskite system have been hot-pressed in a 2000-ton uniaxial split-sphere apparatus (USSA-2000) at pressures up to 15 GPa and temperature of 1550°C, for the compositions CaTiO₃, Ca(Ti_0.75Si_0.25)O₃, Ca(Ti_0.5Si_0.5)O₃. For the specimens with the bulk densities within 1% of the X-ray density, compressional and shear wave velocity measurements have been conducted using ultrasonic interferometry. The measured adiabatic bulk moduli (K _s ) for the CaTiO₃ and Ca(Ti_0.5Si_0.5)O₃ perovskites are 175(1) and 188(1) GPa and shear moduli (G) of 106(1) and 109(1) GPa. In situ X-ray diffraction studies at high pressure and temperature resulted in isothermal values for K ₀ of 170(5) and 185(5) GPa, respectively. For the unquenchable CaSiO₃ perovskite, elasticity theory and systematics were used to predict K ₀=212(7) GPa and G ₀=112(5) GPa; this shear modulus is 37% less than that for (Mg,Fe)SiO₃ perovskite, suggesting that CaSiO₃ perovskite cannot be ignored in modeling the composition of the Earth’s lower mantle. Received: 27 June 1997 / Revised, accepted: 25 November 1997     

Monitoring of the temperature–moisture regime in St. Martin’s Cathedral tower in Bratislava

Buildings are often composed of materials with a porous structure. Moisture in the masonry has a destructive impact caused by cycles of drying–wetting and freezing–thawing. A new sensor principle for monitoring moisture in the masonry is presented herein. This sensor utilizes changes in the thermal conductivity of porous structures when they are filled with moist air, water, or ice depending on the existing thermodynamic conditions. Herein, the “hot-ball” method is used to measure the thermal conductivity. The moisture sensor is prepared for porous material corresponding to the parent material, whether it is rock, brick, or concrete. This parent sample is taken from a borehole drilled into the wall. Methodology for moisture sensor calibration is also presented. Sensors were placed in the masonry walls of St. Martin’s Cathedral tower in the North, South, and West orientations. The sensors were placed in the plaster and bricks at depths up to 60 mm in the wall surface, just below the window sill. The temperature–moisture regime was monitored from August 19th, 2011 to March 30th, 2012. Changes in temperature and moisture were then correlated with meteorological data.     

The P–V–T equation of state of CaPtO3 post-perovskite

Orthorhombic post-perovskite CaPtO₃ is isostructural with post-perovskite MgSiO₃, a deep-Earth phase stable only above 100 GPa. Energy-dispersive X-ray diffraction data (to 9.4 GPa and 1,024 K) for CaPtO₃ have been combined with published isothermal and isobaric measurements to determine its P–V–T equation of state (EoS). A third-order Birch–Murnaghan EoS was used, with the volumetric thermal expansion coefficient (at atmospheric pressure) represented by α(T) = α₀ + α₁(T). The fitted parameters had values: isothermal incompressibility, $ K_{{T_{0} }} $  = 168.4(3) GPa; $ K_{{T_{0} }}^{\prime } $  = 4.48(3) (both at 298 K); $ \partial K_{{T_{0} }} /\partial T $  = ?0.032(3) GPa K^?1; α₀ = 2.32(2) × 10^?5 K^?1; α₁ = 5.7(4) × 10^?9 K^?2. The volumetric isothermal Anderson–Grüneisen parameter, δ _T , is 7.6(7) at 298 K. $ \partial K_{{T_{0} }} /\partial T $ for CaPtO₃ is similar to that recently reported for CaIrO₃, differing significantly from values found at high pressure for MgSiO₃ post-perovskite (?0.0085(11) to ?0.024 GPa K^?1). We also report axial P–V–T EoS of similar form, the first for any post-perovskite. Fitted to the cubes of the axes, these gave $ \partial K_{{aT_{0} }} /\partial T $  = ?0.038(4) GPa K^?1; $ \partial K_{{bT_{0} }} /\partial T $  = ?0.021(2) GPa K^?1; $ \partial K_{{cT_{0} }} /\partial T $  = ?0.026(5) GPa K^?1, with δ _T  = 8.9(9), 7.4(7) and 4.6(9) for a, b and c, respectively. Although $ K_{{T_{0} }} $ is lowest for the b-axis, its incompressibility is the least temperature dependent.     

Genesis of volatile components at Saturn’s regular satellites. Origin of Titan’s atmosphere

Jupiter’s and Saturn’s regular satellites, which posses much ice, are currently thought to have been formed during the early evolution of the Solar System in circumplanetary protosatellite disks. Two of Saturn’s regular satellites—Titan and Enceladus—were experimentally proved to contain, along with water, other volatile components: molecular nitrogen, and methane (which are the major components of Titan’s atmosphere) and various nitrogen and carbon compounds in water plumes of Enceladus. The protomaterial of these rocky–icy satellites was formed in the outer regions of the gas–dust circumsolar nebula, and its closest analogue currently accessible to study is cometary material. The paper presents a review of experimental data on the chemical and isotopic composition of cometary material as possible sources of volatile components on Titan and Enceladus and model evaluations of temperatures in the circumsolar gas–dust protoplanetary disk and Jupiter’s and Saturn’s protosatellite disks during various evolutionary episodes of the solar system. The P–T parameters of the origin of the protomaterial of Jupiter’s and Saturn’s regular satellites were proved to have been remarkably different, and hence, the material of Europa, a Jupiter’s regular satellite, cannot contain any volatile components other than water, in contrast to Titan and Enceladus. This conclusion is supported by experimental data. Cometary material is likely genetically related to the material of Saturn’s regular satellites Titan and Enceladus. The paper presents results of thermodynamic simulation of the evolution of the chemical and phase composition of Saturn’s satellites and suggests a model for the origin of Titan’s nitrogen–methane atmosphere.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Estimation of Accumulation of Chromium Ion Impurities in the CaSiO3 and MgSiO3 Phases of the Earth’s Lower Mantle at Pressures of 18–25 GPa

Doklady Earth Sciences - Based on the data of atomic modeling, the different schemes of isomorphic incorporation of Cr3+ ions into the crystal structures of CaSiO3 and MgSiO3 were tested in the...     

The molar volume of FeO–MgO–Fe2O3–Cr2O3–Al2O3–TiO2 spinels

We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe²⁺)(Al, Cr, Fe³⁺)₂O₄ ? (Mg, Fe²⁺)₂TiO₄. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg²⁺, Al³⁺, and Fe³⁺ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.     

A.P. Vinogradov’s concept of biogeochemical provinces and its development

This paper addresses the concept of biogeochemical provinces introduced by A.P. Vinogradov and developed by V.V. Kovalsky and other researchers. The importance of this scientific direction was emphasized in the context of the anthropogenic impact on the biosphere. The most general characteristics, genesis, and evolution of biogeochemical provinces were discussed. Special attention was given to modern natural–anthropogenic biogeochemical provinces and anomalies. It was pointed out that this modern and vitally important scientific direction should be further pursued.     

Physicochemical studies of magma and of related phenomena conducted in U.S.S.R. in 1957–1959

A review of 174 Soviet publications on physicochemical studies in magmatism, post-magmatic phenomena, origins of rocks, minerals ores, and related subjects, with particular attention to the impact of the derivations of Korzhinskiy of the Phase Rule upon modern physical chemistry in petrology. — V.P. Sokoloff     

P–V–T equation of state of Mn3Al2Si3O12 spessartine garnet

The thermoelastic parameters of synthetic Mn₃Al₂Si₃O₁₂ spessartine garnet were examined in situ at high pressure up to 13 GPa and high temperature up to 1,100 K, by synchrotron radiation energy dispersive X-ray diffraction within a DIA-type multi-anvil press apparatus. The analysis of room temperature data yielded K ₀ = 172 ± 4 GPa and K ₀ ^′  = 5.0 ± 0.9 when V _0,300 is fixed to 1,564.96 Å³. Fitting of P–V–T data by means of the high-temperature third-order Birch–Murnaghan EoS gives the thermoelastic parameters: K ₀ = 171 ± 4 GPa, K ₀ ^′  = 5.3 ± 0.8, (?K _0,T /?T) _P  = ?0.049 ± 0.007 GPa K^?1, a ₀ = 1.59 ± 0.33 × 10^?5 K^?1 and b ₀ = 2.91 ± 0.69 × 10^?8 K^?2 (e.g., α _0,300 = 2.46 ± 0.54 × 10^?5 K^?1). Comparison with thermoelastic properties of other garnet end-members indicated that the compression mechanism of spessartine might be the same as almandine and pyrope but differs from that of grossular. On the other hand, at high temperature, spessartine softens substantially faster than pyrope and grossular. Such softening, which is also reported for almandine, emphasize the importance of the cation in the dodecahedral site on the thermoelastic properties of aluminosilicate garnet.     

Trace metal–humate interactions. I. Experimental determination of conditional stability constants

The enhancement of mobility of radionuclides in the geosphere through complexation by humic substances is a source of uncertainty in performance assessment of radioactive waste repositories. Only very few data sets are available which are relevant for performance assessment of an underground repository for radioactive waste. Using the equilibrium dialysis-ligand exchange method developed at the Paul Scherrer Institut, conditional stability constants for the formation of complexes of Aldrich humic acid with Ca²⁺, NpO₂⁺, Co²⁺, Ni²⁺, UO₂²⁺ and Eu³⁺ and complexes of Laurentian soil- and Suwannee River fulvic acid with Co²⁺, UO₂²⁺ and Eu³⁺ were measured. pH was varied between 5 and 10 and ionic strength between 0.02 and 0.2 M. The data are presented as equilibrium coefficients that are free from any model assumptions. The equilibrium coefficients increased in the order Ca²⁺≅NpO₂⁺<Co²⁺< Ni²⁺<UO₂²⁺< Eu³⁺. The quality of the data is assessed in an extended discussion of statistical and systematical errors, and by a critical ‘rereview’ of the auxiliary stability constants used for the calculation of the equilibrium coefficients. An approximate overall uncertainty of 0.5 log-units is estimated for the stability data reported. The conditional stability constants were found to increase markedly with increasing pH in the case of Co²⁺, UO₂²⁺ and Eu³⁺. For Ni²⁺, Ca²⁺ and NpO₂⁺ this effect was less pronounced. For all metal ions tested, the influence of ionic strength was of less importance, and the conditional stability constants did not show a significant dependence on the type of humic substances investigated.     

Signs of power: Fascist urban iconographies in Ethiopia (1930s–1940s)

The aim of the present paper is to compare two different patterns of urban iconographies in Ethiopia during 1930s: the one of the Amhara – the traditionally Ethiopian dominant ethnic group – and the one of the Italian fascism. The paper gives an historical account of the structure of the Amhara settlements, focusing on the ways the power of their politico-military chiefs, being they the Negus or the Ras, shaped the spatial order of these settlements. When the Italians conquered military Ethiopia in 1936, they started re-shaping this spatial order, erasing the signs of the previous power and imposing their new iconographic apparatus. This was mainly done through urban planning which was devised to `write' the Fascist concepts of progress, order, hierarchy, and racial segregation on the territory. Owing to the short duration of the occupation, the poor material conditions of the colony and the lack of financial resources, such town-planning projects turned out to be just a political rhetoric exercise.     

Optical absorption investigation of Cr3+ ion-bearing minerals in the temperature range 77–797 K

The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr³⁺ was studied for various point symmetries of the Cr³⁺-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr³⁺-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm^-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr³⁺-transitions derived from ⁴ A _2g ⁴ T _2g (F) and ⁴ T _1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr³⁺, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr³⁺-centered octahedra, _loc, were derived on the basis of the R _M-0 ^-5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging r_m-o for all the respective octahedral positions.     

The influence of Fe<Superscript>3+</Superscript> on garnet–orthopyroxene and garnet–olivine geothermometers

Applying Fe²⁺–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe³⁺ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO₂ buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe³⁺/Fe²⁺ ratios were generated. The Fe³⁺ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fe_total = Fe²⁺, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe²⁺–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe³⁺ in garnet (i.e. using only measured Fe²⁺) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe³⁺ whilst direct accounting of Fe³⁺ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers.     

Origin of the Early Sial Crust and U–Pb Isotope–Geochemical Heterogeneity of the Earth’s Mantle

It is shown that presence of the Early Precambrian sial crust in the Indo–Atlantic segment of the Earth and its absence in the Pacific has been caused by geochemical differences in the mantle underlying these segments. These differences were examined on the basis of Nd–Hf and U–Pb isotopes in modern basalts. The U–Pb isotope system is of particular interest, since uranium is a member of a group of heat-generating radioactive elements providing heat for plumes. It is shown that in the Indo–Atlantic segment, a distribution of areas of the modern HIMU type mantle is typical, while it is almost completely absent in the Pacific segment. In the Archean, in the upper HIMU type paleo-mantle areas, plume generation and formation of the primordial basic crust occurred; this was followed by its remelting resulting in the appearance of an early sial crust forming cratons of the Indo–Atlantic segment.     

Areas of the U.S. wildland–urban interface threatened by wildfire during the 2001–2010 decade

The wildland–urban interface (WUI) is defined in terms of housing density and proximity to wildlands, yet its relevance seems to be only in conjunction with wildland fire threats. The objective of this paper is to (1) identify the WUI areas threatened from wildfire during the 2000’s and (2) quantify the values that were threatened. We use 1 km fire detection data generated using MODIS satellite imagery over a 10-year period combined with population densities to identify threatened areas of the WUI. We then use data on structures, structure content, and population to identify the people and property threatened from identified fires within the WUI. We find that 6.3 % of the U.S. population (17.5 million) resided within these areas and that 2.1 % of the population lived in WUI areas where more than one fire has occurred. However, we find that only a third of the affected population was threatened during daytime hours, as most leave the threatened portion of the WUI during peak ignition hours. The threatened area comprised 4.1 % of the coterminous USA and 44.9 % of the WUI. Within these areas were 7.8 million residential, commercial, industrial, governmental, religious, and educational structures, with a building and building content value estimated at $1.9 trillion. Overall, 7.3 % of residential structures in the USA were found within the WUI with wildfire activity; however, for some states, this number was as high as 25.4 %.     

Variability of the Blazar 1156+295 in 2005–2020

Astronomy Reports - We present and analyze the monitoring results of the blazar 1156+295 in radio, optical, and gamma ranges in 2005–2020. After a long period of relative quietness at the end...