Nataliakulikite, Ca4Ti2(Fe3+,fe2+)(Si,fe3+,al)o11, a new perovskite-supergroup mineral from hatrurim basin, negev desert, Israel

Nataliakulikite, Ca4Ti2(Fe3+,Fe2+)(Si,Fe3+,Al)O11, is a mineral intermediate between perovskite CaTiO3 and brownmillerite Ca2(Fe,Al)2O5. It was discovered as a minor mineral in a high-temperature pyrometamorphic larnite-gehlenite rock at the Nahal Morag Canyon of the Hatrurim Basin, Israel. Nataliakulikite is associated with larnite, flamite, gehlenite, magnesioferrite, Fe3+-rich perovskite, fluorapatite, barite, Hashemite, and retrograde phases (afwillite, hillebrandite, portlandite, calcite, ettringite, hydrogarnet, and other hydrated Ca-silicates). The mineral forms brown subhedral or prismatic grains (up to 20 µm) and their intergrowths (up to 50 µm). Its empirical formula (n = 47) is (Ca3.992Sr0.014U0.004)(Ti1.933Zr0.030Nb0.002) (Fe3+0.610Fe2+0.405Cr0.005Mn0.005)(Si0.447Fe3+0.337Al0.216)O11 and shows Si predominance in tetrahedral site. The unit-cell parameters (HRTEM data) and space group are: a = 5.254, b = 30.302, c = 5.488 Å, V = 873.7 Å3, Pnma, Z = 4. These dimensions and Electron backscatter diffraction (EBSD) data strongly support the structural identity between nataliakulikite and synthetic Ca4Ti2Fe3+2O11 (2CaTiO3·Ca2Fe3+2O5), an intermediate compound in the system CaTiO3-Ca2Fe3+2O5. In general, this mineral is a Si-Fe2+-rich natural analog of synthetic Ca4Ti2Fe3+2O11. The X-ray powder diffraction data (CuKα-radiation), calculated from unit-cell dimensions, show the strongest lines {d [Å], (Icalc)} at: 2.681(100), 1.898(30), 2.627(26), 2.744(23), 1.894(22), 15.151(19), 1.572(14), 3.795(8). The calculated density is 4.006 g/cm3. The crystal structure of nataliakulikite has not been refined because of small sizes of grains. The Raman spectrum shows strong bands at 128, 223, 274, 562, and 790 cm−1. Nataliakulikite from the Hatrurim Basin crystallized under the conditions of combustion metamorphism at high temperatures (1160–1200◦C) and low pressures (HT-region of the spurrite-merwinite facies). © 2019 by the authors. Licensee MDPI, Basel, Switzerland.Russian Science Foundation, RSF: 0330-2016-0004, 17-17-01056, IGM SD 0330-2016-0005Ben-Gurion University of the Negev, BGUThis research was funded by the Russian Science Foundation, grant number 17-17-01056. The field work and sample collection was partly supported the State assignment projects (IGM SD 0330-2016-0005, 0330-2016-0004). Acknowledgments: The authors would like to thank M.V. Khlestov (IGM SD RAS) for technical assistance at SEM studies. Yevgeny Vapnik (Ben-Gurion University, Beer-Sheva, Israel) is thanked for providing of fruitful field trips in the Hatrurim Basin in 2004 and 2019. The last version of the manuscript was improved through comments and suggestions by T. Perepelova (IGM, Novosibirsk). We are highly appreciative of the valuable comments and suggestions of two anonymous reviewers

Ion association in concentrated NaCI brines from ambient to supercritical conditions: results from classical molecular dynamics simulations

Highly concentrated NaCl brines are important geothermal fluids; chloride complexation of metals in such brines increases the solubility of minerals and plays a fundamental role in the genesis of hydrothermal ore deposits. There is experimental evidence that the molecular nature of the NaCl–water system changes over the pressure–temperature range of the Earth's crust. A transition of concentrated NaCl–H(2)O brines to a "hydrous molten salt" at high P and T has been argued to stabilize an aqueous fluid phase in the deep crust. In this work, we have done molecular dynamic simulations using classical potentials to determine the nature of concentrated (0.5–16 m) NaCl–water mixtures under ambient (25°C, 1 bar), hydrothermal (325°C, 1 kbar) and deep crustal (625°C, 15 kbar) conditions. We used the well-established SPCE model for water together with the Smith and Dang Lennard-Jones potentials for the ions (J. Chem. Phys., 1994, 100, 3757). With increasing temperature at 1 kbar, the dielectric constant of water decreases to give extensive ion-association and the formation of polyatomic (Na(n)Cl(m))(n-m )clusters in addition to simple NaCl ion pairs. Large polyatomic (Na(n)Cl(m))(n-m )clusters resemble what would be expected in a hydrous NaCl melt in which water and NaCl were completely miscible. Although ion association decreases with pressure, temperatures of 625°C are not enough to overcome pressures of 15 kbar; consequently, there is still enhanced Na–Cl association in brines under deep crustal conditions

Generalized ambiguity matrix of a vector time-spatial radar signal

There is introduced the concept of an ambiguity function of a time-spatial vector signal. Unlike the well known radar signal ambiguity function, the introduced matrix allows the estimation of the potential resolution ability not only by range and Doppler velocity, but also by angle co-ordinate parameters in the case of joint estimation of all these parameters with the help of radars with full polarization analysis

Magma chamber-scale liquid immiscibility in the Siberian Traps represented by melt pools in native iron

Magma unmixing (i.e., separation of a homogeneous silicate melt into two or more liquids) is responsible for sudden changes in the evolution of common melts, element fractionation, and potential formation of orthomagmatic ore deposits. Although immiscible phases are a common phenomenon in the mesostasis of many tholeiitic basalts, evidence of unmixing in intrusive rocks is more difficult to record because of the transient nature of immiscibility during decompression, cooling, and crystallization. In this paper, we document a clear case of liquid immiscibility in an intrusive body of tholeiitic gabbro in the Siberian large igneous province, using textures and compositions of millimeter-sized silicate melt pools in native iron. The native iron crystallized from a metallic iron liquid, which originated as disseminated globules during reduction of the basaltic magma upon interaction with coal-bearing sedimentary rocks in the Siberian craton. The silicate melts entrapped and armored by the native iron are composed of two types of globules that represent the aluminosilicate (60–77 wt% SiO2) and silica-poor, Fe-Ti-Ca-P–rich (in wt%: SiO2, 15–46; FeO, 15–22; TiO2, 2–7; CaO, 11–27; P2O5, 5–30) conjugate liquids. Different proportions and the correlated compositions of these globules in individual melt pools suggest a continuously evolving environment of magmatic immiscibility during magma cooling. These natural immiscible melts correspond extremely well to the conjugate liquids experimentally produced in common basaltic compositions at <1025 °C. Our results show that immiscibility can occur at large scale in magma chambers and can be instrumental in generating felsic magmas and Fe-Ti-Ca-P–rich melts in the continental igneous provinces