ДОСЛІДЖЕННЯМ.КОСТОМАРОВА З

На основі наукових праць та досліджень М.І.Костомарова розглянуто історію взаємин українського козацтва та уряду Речі Посполитої в другій половині 1590-х – середині 1620-х років. Підкреслюється особливе значенняпраць історика та йогодослідженнь в галузі вивчення історії козацтва та історіографії даної проблеми.On thebasis ofscientific labours and researches ofM.I.Kostomarovofmutualrelations of Ukrainian the cossacks and government of Polish-Lithuanian Commonwealth is considered in the second half 1590 – the middle 1620 years. The special value of labours of historian is underlined and and his researches in industry of study of history of the cossacks and historiography of this problem

Depth profile analyses by femtosecond laser ablation (multicollector) inductively coupled plasma mass spectrometry for resolving chemical and isotopic gradients in minerals

Femtosecond laser ablation (fs-LA) coupled to a multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) instrument has been proven to be a powerful means to analyze isotope ratios of “non-traditional” stable isotope systems with high spatial resolution, precision, and accuracy. The technique has been successfully applied, e.g., to investigate diffusion-generated isotopic zoning of the elements Li, Mg, and Fe in magmatic crystals. Here, we present a novel sampling technique employing a fs-LA system that is equipped with a computer numerical control (CNC) laser stage, using the open-source software LinuxCNC. Combining this laser set up with ICP-MS or MC-ICP-MS allows us to perform depth profile analyses of major and trace elements, respectively, as well as metal stable isotope variations of Fe and Mg in olivine crystals and in experimental diffusion couples. Samples are ablated in circular patterns with profile diameters of 100–200 µm using a laser spot size of 25–30 µm. Depending on the scan speed and the repetition rate of the laser, each ablated sample layer is between 300 nm and 3.0 µm thick. The integrated signal of one ablated layer represents one data point of the depth profile. We have tested this technique by analyzing 5–50 µm deep depth profiles (consisting of 15–25 individual layers) of homogeneous and chemically zoned olivine crystal cuboids. The minor and trace element analyses of the zoned cuboids, conducted by fs-LA-ICP-MS, were compared with “horizontal” profiles analyzed in polished sections of the cuboids with electron probe microanalysis (EPMA). Furthermore, we analyzed Fe–Mg isotopic depth profiles of the same cuboids with fs-LA-MC-ICP-MS, of which the chemically zoned ones also showed isotopic zoning at identical scales. Isotopic depth profiles were also conducted on an unzoned olivine cuboid that was coated with a 26Mg- and 56Fe-enriched olivine thin film (of ∼ 800 nm) in order to investigate top-to-bottom contamination during depth profiling. Our results indicate that (i) concentration data acquired by fs-LA depth profiling match well with EPMA data, (ii) precise and accurate Fe and Mg isotopic data can be obtained (i.e., precision and accuracy are ≤ 0.12 ‰ and ≤ 0.15 ‰ for both δ26Mg and δ56Fe, respectively), and (iii) potential top-to-bottom contamination during depth profiling of isotope ratios can be avoided. The technique presented herein is particularly suitable for the investigation of minerals or glasses with chemical and/or isotopic gradients (e.g., diffusion zoning) vertical to planar surfaces. It can also be applied in materials sciences in order to analyze thin films, coatings, or surface contaminations on solids

Non-stoichiometric amorphous magnesium-iron silicates in circumstellar dust shells. Dust growth in outflows from supergiants

We investigate the dust growth in oxygen-rich stellar outflows for a set of nine well-observed massive supergiants with optically thin dust shells. Models of the infrared emission from their circumstellar dust shells are compared to their observed infrared spectra so as to derive the essential parameters that govern dust formation in the extended envelope of these stars. The results obtained from the comparative study are also compared with the predictions of a model for silicate dust condensation solely based on laboratory data and basic stellar properties. The infrared emission in the wavelength range between 6 and 25 mu can be reproduced rather well by a mixture of non-stoichiometric iron-bearing silicates, alumina, and metallic iron dust particles for all nine objects. The observed spectra obtained from three objects, mu Cep, RW Cyg, and RS Per, can be reproduced by a stationary and (essentially) spherically symmetric outflow which enables a direct comparison with predictions from a theoretical dust growth model. The temperature at the onset of massive silicate dust growth is of the order of 920 K and the corresponding outflow velocity of the order of the sound velocity for these objects. The condensation temperature suggests that the silicate dust grows on the corundum dust grains that are formed well in the interior of the silicate dust shell at a much higher temperature. Our results propose that regarding the two major problems of dust formation in stellar outflows: (i) formation of seed nuclei; (ii) their growth to macroscopic dust grains, we are gradually coming close to a quantitative understanding of the second item.Comment: 29 pages, 9 figures, accepted by Astronomy & Astrophysic

Li–Na interdiffusion and diffusion-driven lithium isotope fractionation in pegmatitic melts

In this study, we investigate the diffusion of Li and its stable isotopes (6Li and 7Li) in flux-rich (1.8 % Li2O, 2.6 % B2O3, 2.3 % P2O5 and 3 % F) pegmatitic melts in order to contribute to the understanding of Li enrichment in such systems. Two glasses were synthesized with a model pegmatitic composition, one of which is highly enriched in Li (> 1 wt %, PEG2-blue) and the other one essentially Li-free (PEG2-Li-free). Diffusion couple experiments were performed to determine the chemical diffusivity of Li in dry pegmatitic melts. Experiments were conducted using rapid-heat and rapid-quench cold-seal pressure vessels in a temperature range of 650–940 ∘C at 100 MPa with Ar as the pressure medium. We observed rapidly formed diffusion profiles, driven by an interdiffusive exchange of the monovalent alkalis Li and Na, while the other elements are immobile on the timescale of experiments (1–30 min). From these experiments, activation energies for Li–Na interdiffusion were determined as 99 ± 7 kJ mol−1 with a pre-exponential factor of log D0 = −5.05 ± 0.33 (D0 in m2 s−1). Li and Na partitioning between the stronger depolymerized PEG2-blue and the less depolymerized PEG2-Li-free leads to a concentration jump at the interface; i.e. Na is enriched in the more depolymerized PEG2-blue. Li–Na interdiffusion coefficients in the studied melt composition are in a similar range as Li and Na tracer diffusivities in other dry aluminosilicate melts, confirming little to no effect of aluminosilicate melt composition on Li diffusivity. Thus, added fluxes do not enhance the Li diffusivity in the same way as observed for H2O (Holycross et al., 2018; Spallanzani et al., 2022). Using melt viscosity as a proxy for the polymerization of the melt shows that water has a stronger potential to depolymerize a melt compared to other fluxing elements. Faster diffusion of 6Li compared to 7Li leads to a strong Li isotope fractionation along the diffusion profile, resulting in δ7Li as low as −80 ‰ relative to the diffusion-unaffected regions. This diffusive isotope fractionation can be quantified with an empirical isotope fractionation factor (β) of 0.20 ± 0.04, similar to previously observed β values for Li diffusion in melts. This suggests in accordance with previously published data that a β value of ca. 0.2 seems to be universally applicable to diffusive Li isotope fractionation in aluminosilicate melts

ДУБ М.ЗАЛІЗНЯКА: З ІСТОРІЇ ПАМ’ЯТКООХОРОННОЇ РОБОТИ

Стаття присвячена проблемі вивчення, охорони та збереження пам’ятки природи тисячолітнього дуба М.Залізняка. В ній розглядаються етапи дослідження вікового дерева, основні пам’яткоохоронні заходи, проведені для підтримки його життєдіяльностіThis article is about a problem of investigation, saving and protection the monument of nature the millennial oak of M.Zaliznyak. It describes about the stages of research of the tree, the main protection measures in order to obtain it activit

Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates – Relation between textural control on effective element fluxes and resulting carbonate phase

Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9 M MgCl2 and 0.015 M SrCl2 at 200 °C. The replacement of aragonite by a Ca-bearing magnesite and a Mg-Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed reaction rates are highest for the replacement of the initially highly porous coral and lowest for the compact structure of a single aragonite crystal. Therefore, the reaction progress equally depends on effective element fluxes between the fluid at the reaction interface and the bulk solution surrounding the test material as well as the reactive surface area. This study demonstrates that the textural and microstructural properties of the parent material have a significant influence on the chemical composition of the product phase. Moreover, our data highlight the importance of effective fluid-mediated element exchange between the fluid at the reaction interface and the bulk solution controlled by the local microstructure