Composition,Structure, and Conditions of Formation of Fluorine-Bearing Sodalite: Experimental Evidence

Fluoro-sodalite was synthesized for the first time at temperatures of 400–800°C and H₂O pressures of 1–2 kbar in the Si–Al–Na–H–O–F system. X-ray diffraction and infrared spectroscopic investigations showed that fluorine is incorporated in the sodalite structure as anionic octahedral groups, [AlF₆]^3–, the number of which can vary from 0 to 1. Correspondingly, the end-members of the F-sodalite series are Na₇(H₂O)₈[Si₅Al₇O₂₄] and Na₈(AlF₆)(H₂O)₄[Si₇Al₅O₂₄]. Depending on the composition of the system, F-sodalite associates at 500–650°C with nepheline, albite, cryolite, and villiaumite, which are joined by analcime below 500°C and aluminosilicate melt above 650°C. Fluorine-bearing sulfate–chlorine-sodalite was found for the first time in a pegmatite sample from the Lovozero massif. The highest fraction of the fluorine end-member in natural sodalite is 0.2. The incorporation of F into the sodalite structure requires much more energy compared with Cl^– and SO ₄ ^2- , because it is accompanied by a structural rearrangement and a transition from tetrahedral Al to octahedral Al.     

A New 190Pt-4He method of native platinum age determination

A new method of determining the age of native platinum based on alpha-radioactivity of one of its natural isotopes ¹⁹⁰Pt is proposed. Due to a special form of occurrence of radiogenic helium in the crystal lattice of native metals as a helium cluster-bubbles, the stability of ¹⁹⁰Pt-⁴He of the isotope system is extremely high in the natural environment. To check the efficiency of the proposed ¹⁹⁰Pt-⁴He method of isotope geochronology, six independent mineral aggregates of native platinum from chromite-bearing dunites of the southern part of platinum-bearing zonal Galmoenan dunite-cllinopyroxenite-gabbro plutonic complex (Koryak-Kamchatka belt, Russia) were analyzed. The age calculated by the tangent of the ¹⁹⁰Pt-⁴He isochrone slope angle equals 69.5 ± 4.9 mln years. The obtained age value coincides with the results of isotope datings, which were made previously by different methods of isotope geochronology.     

U-Th-He dating of native gold: First results,problems, and outlooks

In this paper, we consider the application of the U-Th-He method of isotope geochronology for native gold dating. It was shown that inclusions of uranium- and thorium-bearing minerals, including rare earth element phosphates, are one of the main form of uranium and thorium occurrence and, consequently, the main source of radiogenic helium in native gold. Since these inclusions are submicrometer-sized, the radiogenic helium formed in them is not accumulated but implanted in the structure of native gold, which suggests its good preservation over billions of years. This suggestion was experimentally supported by the investigation of the kinetics of radiogenic helium release from native gold. The first results of the U-Th-He dating of native gold from the Pedrolampi (central Karelia) and Witwatersrand (South Africa) deposits are in adequate agreement with available independent geochronological data. This allows us to consider native gold as a U-Th-He mineral geochronometer for the direct dating of ore-forming processes.     

Magnesioneptunite, KNa2Li(Mg,Fe)2Ti2Si8O24, a new mineral species of the neptunite group

A new mineral of the neptunite group, magnesioneptunite KNa₂Li(Mg,Fe)₂Ti2Si₈O₂₄, a Mg-dominant analogue of neptunite and manganoneptunite, has been found in the Upper Chegem caldera near Mount Lakargi, Kabardino-Balkaria, the North Caucasus, Russia in a xenolith of altered sandstone located between skarnified carbonate xenoliths and ignimbrite. Magnesioneptunite occurs as nearly isometric grains and aggregates up to 0.1 mm in size in the cores of some grains of a Mg-rich variety of neptunite with Mg/(Fe + Mn) = 0.7?1.0. The chemical composition of magnesioneptunite with a maximum Mg content is as follows, wt %: 3.63 K₂O, 8.21 Na₂O, 1.73 Li₂O, 6.47 MgO, 0.04 MnO, 5.87 FeO, 0.07 Al₂O₃, 18.73 TiO₂, 56.88 SiO₂, 99.62 in total. The empirical formula is (K_0.67Na_0.32Ca_0.01)_Σ1.00Na_2.06Li_1.00 · (Mg_1.39Fe _0.71 ²⁺ )_Σ2.10(Si_7.90Al_0.01)_Σ7.91O₂₄. Grains of magnesioneptunite are dark brown to red-brown, translucent, with vitreous luster. D _calc = 3.15 g/cm³, and the Mohs hardness is 5–6. Cleavage parallel to the (110) is perfect. The new mineral is optically biaxial, positive, α = 1.697(2), β = 1.708 (3), γ = 1.725(3), 2V _meas = 45(15)°. The mineral is associated with quartz, alkali feldspar, rutile, aegirine, and neptunite. Magnesioneptunite and the Mg-rich variety of neptunite were formed as products of ilmenite alteration. Magnesioneptunite is monoclinic, C2/c; unit-cell parameters: a = 16.327(7), b = 12.4788(4), c = 9.9666(4) Å, β = 115.6519(5)°, V = 1830.5(1) ų, Z = 4. The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Production of 3He in rocks by reactions induced by particles of the nuclear-active and muon components of cosmic rays: Geological and petrological implications

The paper presents data on the production of the ³He nuclide in rocks under the effect of cosmicray particles. The origin of the nuclide in the ground in neutronand proton-induced spallation reactions, reactions induced by high-energy muons, and negative muon capture reactions is analyzed. The cross sections of reactions producing ³He and ³H are calculated by means of numerical simulations with the GEANT4 simulation toolkit. The production rate of the ³He nuclide in the ground is evaluated for the average level of solar activity at high geomagnetic latitudes and at sea level. It is proved that the production of ³He in nearsurface ground layers by spallation reactions induced by cosmic-ray protons may be approximately 20% of the total production rate of cosmogenic ³He. At depths of 10–50 m.w.e., the accumulation of ³He is significantly contributed by reactions induced by cosmic-ray muons. Data presented in the paper make it possible to calculate the accumulation rate of ³He in a rock depending on depth that is necessary for the evaluation of the exposure time of the magmatic or metamorphic complex on the Earth’s surface (³He dating).     

New geochronometer for the direct isotopic dating of native platinum minerals (190Pt-4He method)

A new method of isotope geochronology was proposed for dating native platinum minerals on the basis of the ??-decay of the natural isotope ¹⁹⁰Pt. The analysis of the thermal desorption of helium in the crystal lattice of native metals, including platinum, allowed us to predict a very high thermal stability (retentivity) of radiogenic ⁴He in native platinum minerals up to their melting temperatures. In order to validate the proposed ¹⁹⁰Pt-⁴He method, direct isotopic dating was performed for isoferroplatinum from the Galmoenan dunite-clinopyroxenite and Kondyor alkaline ultramafic massifs. The results of dating obtained by this method for primary ore platinum from the Galmoenan Massif (70 ± 5 Ma) are consistent with geological observations and mean Sm-Nd and Rb-Sr isotopic age estimates. The ¹⁹⁰Pt-⁴He age obtained for placer isoferroplatinum from the Kondyor Massif (112 ± 7 Ma) also agrees with geological observations and is close to the K-Ar and Rb-Sr ages of koswites (phlogopite-magnetite pyroxenites, gabbros, nepheline syenites, and metasomatic rocks after dunites). Our experimental data demonstrated that the ¹⁹⁰Pt-⁴He method is a promising tool for dating native platinum minerals.     

Geothermochronology based on noble gases: III. Migration of radiogenic He in the crystal structure of native metals with applications to their isotopic dating

It was shown that the behavior of ⁴He in native and technical metals is very similar owing to the symmetric and stable electron shells of its atoms, which cannot gain electrons from other atoms or donate their own electrons to metal atoms in a crystal lattice. Therefore, they rapidly migrate toward grain boundaries and dislocations, where they are released as vesicles or He clusters. It was found that the thermal desorption of radiogenic He occurring in the crystal lattice of native metals as gas clusters requires activation energies of 100 and even 180 kcal/mol up to the attainment of the melting temperature of the metal. The frequency factor is several orders of magnitude higher than the limiting value k ₀ ∼ 10¹³ s⁻¹ for the migration of single atoms in the crystal lattice. Near the melting temperature and tens-hundreds degrees above it, the character of the thermal desorption of radiogenic ⁴He changes fundamentally. The migration is strongly accelerated, and sharp narrow peaks appear on the kinetic curves of thermal desorption. A similar phenomenon was observed during the annealing of technical metals and is known as the burst-effect. The destruction of the crystal structure results in the disappearance of helium clusters (vesicles). At the very high temperature, He migrates as individual atoms relatively rapidly from the melt. The activation energy for He thermal desorption and the pre-exponential frequency factor acquire values characteristic of ordinary migration. Such peculiarities of radiogenic He provide unique opportunities for its preservation in the structure of gold and other native metals below their melting temperatures. The rapid advances of (U-Th)/He geochronology is still hampered by the experimentally established extremely heterogeneous distribution of U, He, and, probably, Th in the structure of gold and other natural metals. This difficulty can be circumvented by the development of a method for the determination of the contents of all the mentioned chemical elements in a single aliquot from each sample.     

Geothermochronology based on noble gases: II. Stability of the (U-Th)/He isotope system in zircon

The kinetics of He migration from zircon of variable degree of metamictization was investigated. The migration parameters of He were experimentally determined, the influence of radiation damage and the degree of metamictization on the stability of the (U-Th)/He isotope system was evaluated, the mechanisms of noble gas escape from zircon were investigated, new data on the kinetics of He migration were obtained and compared with previous results for the kinetics of Xe migration from zircon of the same geologic objects. It was shown that He occurs in two energy positions in the zircon lattice: the main position (more than 80% He) with an activation energy of ∼39 kcal/mol and k ₀ = 10¹¹ yr⁻¹ and the second position with an activation energy for migration of 5–10 kcal/mol and k ₀ ∼ 10⁶ yr⁻¹. It was concluded that He migration from the main energy position is better described by a single-jump mechanism. The migration of He from the second energy position is consistent with the diffusion mechanism. It was shown that deviations from the linear dependence in the lnln(He₀/He_t)-1/T coordinates are probably related to the destruction of volume defects containing He atoms at high temperatures (more than 1000°C on the experimental time scale) resulting in a change from the single-jump to diffusion mechanism and the presence of atoms migrating via the diffusion mechanism. It was shown that the peak width in the spectrum of radiogenic He release and the appearance of a second peak also depend on the fraction of atoms migrating in accordance with the diffusion mechanism. It was found that the low activation energy for He release from the second energy position indicates the existence of continuous He loss from the zircon lattice.     

Kyanoxalite,a new cancrinite-group mineral species with extraframework oxalate anion from the Lovozero alkaline pluton,Kola Peninsula

Kyanoxalite, a new member of the cancrinite group, has been identified in hydrothermally altered hyperalkaline rocks and pegmatites of the Lovozero alkaline pluton, Kola Peninsula, Russia. It was found at Mount Karnasurt (holotype) in association with nepheline, aegirine, sodalite, nosean, albite, lomonosovite, murmanite, fluorapatite, loparite, and natrolite and at Mt. Alluaiv. Kyanoxalite is transparent, ranging in color from bright light blue, greenish light blue and grayish light blue to colorless. The new mineral is brittle, with a perfect cleavage parallel to (100). Mohs hardness is 5–5.5. The measured and calculated densitiesare 2.30(1) and 2.327 g/cm³, respectively. Kyanoxalite is uniaxial, negative, ω = 1.794(1), ɛ = 1.491(1). It is pleochroic from colorless along E to light blue along O. The IR spectrum indicates the presence of oxalate anions C₂O₄²⁻ and water molecules in the absence of CO₃²⁻ Oxalate ions are confirmed by anion chromatography. The chemical composition (electron microprobe; water was determined by a modified Penfield method and carbon was determined by selective sorption from annealing products) is as follows, wt %: 19.70 Na₂O, 1.92 K₂O, 0.17 CaO, 27.41 Al₂O₃, 38.68 SiO₂, 0.64 P₂O₅, 1.05 SO₃, 3.23 C₂O₃, 8.42 H₂O; the total is 101.18. The empirical formula (Z = 1) is (Na_6.45K_0.41Ca_0.03)_Σ6.89(Si_6.53Al_5.46O₂₄)[(C₂O₄)_0.455(SO₄)_0.13(PO₄)_0.09(OH)_0.01]_Σ0.68 · 4.74H₂O. The idealized formula is Na₇(Al₅₋₆Si₆₋₇O₂₄)(C₂O₄)_0.5−1 · 5H₂O. Kyanoxalite is hexagonal, the space group is P6₃, a = 12.744(8), c = 5.213(6) -ray powder diffraction pattern are as follows, [d, [A] (I, %)(hkl)]: 6.39(44) (110), 4.73 (92) (101), 3.679 (72) (300), 3.264 (100) (211, 121), 2.760 (29) (400), 2.618 (36) (002), 2.216, (29) (302, 330). According to the X-ray single crystal study (R = 0.033), two independent C₂O₄ groups statistically occupy the sites on the axis 6₃. The new mineral is the first natural silicate with an additional organic anion and is the most hydrated member of the cancrinite group. Its name reflects the color (κɛανgoΣς is light blue in Greek) and the species-forming role of oxalate anions. The holotype is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration no. 3735/1.     

Extraterrestrial dust flux monitoring at Antarctic Vostok station: New collection of extraterrestrial spherules fallen from May to September 2017

Dust particles obtained by filtering fresh snow collected from May to September 2017 in the vicinity of Vostok station in Antarctica were examined using a scanning electron microscope. The collection of dust particles contains 197 spherules ranging from 0.5 to 117 μm in diameter, the most abundant ones (n = 188) by far being iron oxide spherules. Analyses of meteorological and human activity data suggest an extraterrestrial origin of most of the spherical particles. The particle size distribution histogram showed a smooth increase in their number with decreasing size and a dramatic drop at sizes smaller than 3 μm. The number of spherical particles has an uneven distribution over time, with an intense peak in July 27–28, 2017 which correlates by dates with the peak of the Southern Delta Aquariids meteor shower. The size distribution of the particles collected during the same period indicates the presence of a mechanism that accelerates their fall to the Earth. We propose that they are effective centers of condensation of ice crystals in stratospheric clouds. Our data indicate that collection of micrometeorites with sizes of several microns from the fresh snow is possible, opening a new way for sampling micrometeorites, including separate meteor showers.