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Microscopic studies of ultra-high pressure glasses from impactites of the Kara astrobleme

Authors:
Yevgeny Golubev at Institute of Geology of Komi Sc of RAS
Yevgeny Golubev
  • Institute of Geology of Komi Sc of RAS
Tatyana Shumilova at Komi Scientific Center
Tatyana Shumilova
Sergey Isaenko at Komi Scientific Center
Sergey Isaenko
Viktor A. Radaev
Viktor A. Radaev
Viktor A. Radaev
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Abstract

UHPHT natural glasses are interesting not only to geologists and mineralogists, but also to physicists, chemists, and materials scientists from the point of view of the fundamental problem of the existence of matter under extreme PT-conditions. The specificity of the structure of such materials requires complex study. In this work we used optical, electron and atomic force microscopy, as well as Raman spectroscopy to assess the phase separation in UHPHT glasses of the Kara astrobleme. Their microscopic images show the separation of disordered aluminosilicate and silicate phases, their heterogeneous and partially heterogeneous structure with domain sizes of several tens of nanometers. The revealed highest structural homogeneity at the nanoscale level of UHPHT vein silica impact glasses, compared to high-pressure and low-pressure silica-rich glasses, confirms the specificity of the formation of UHPHT glasses and indicates promising further physical studies of this natural material to analyze the matter at ultra-high pressure conditions.
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... Investigations of impact structures allow the search for new concepts of crater formation on Earth and give useful information about the structure and evolution of the lithosphere, as well as the solution of important issues of the formation of planets in the solar system. Impactites are the result of impact melting of the silicate rocks under high pressure and temperature (see, e.g., Dence, 1971;Golubev et al., 2020;Osinski et al., 2013) and contain glasses and remelted minerals embedded into the matrix. ...
... Therefore, the study of the impact melt rocks and shock metamorphic materials from the impact craters using various spectroscopic and structural techniques is of interest to extract important information about variations of chemical composition, and structural and physical parameters resulting from impact melt rocks formation. For these reasons, various features of different impact melt rocks (impactites and tektites) were studied by chemical analysis, scanning and transmission electron microscopy, Raman spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction (XRD), 57 Fe M€ ossbauer spectroscopy, and some other techniques (see, e.g., Bustamante et al., 2005;Ding & Veblen, 2004;Dunlap et al., 1998;Dunlap & McGraw, 2007;Dunlap & Sibley, 2004;Golubev et al., 2019Golubev et al., , 2020Loayza & Cabrejos, 2014;Ostroumov et al., 2002;Shumilova et al., 2018;Verma et al., 2008). ...
... A hump at the diffraction pattern in the 2Θ range of 20-40°indicates the presence of an amorphous component in the sample. A similar amorphous halo was observed in the XRD patterns of impact melts from Kara astrobleme and Ries crater (Golubev et al., 2020;Shumilova et al., 2018). Reflections of crystalline phases are visible against the background of the amorphous halo. ...
Impact melt rock from Jänisjärvi astrobleme: Study of the iron‐bearing phases using Raman spectroscopy, X‐ray diffraction, and Mössbauer spectroscopy
Article
  • Mar 2022
Iron‐bearing phases in the impact melt rock (impactite) from Jänisjärvi astrobleme (Karelia, Russian Federation) were studied by optical microscopy, electron probe microanalysis, Raman spectroscopy, X‐ray diffraction, and 57Fe Mössbauer spectroscopy. The phase composition and the contents of elements were determined in the studied impactite. The Raman spectra of cordierite, chamosite, and ilmenite in the impact melt rock were measured and analyzed. The 57Fe Mössbauer spectrum of Jänisjärvi impactite demonstrated the presence of different iron microenvironments in the iron‐bearing phases in the impact melt rock, which were assigned to cordierite; the M1, M2, M3, and M4 sites in chamosite; ilmenite; and ferrihydrite.
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... In the Raman spectra of the Kara UHPHT glasses [16], in addition to vibrational bands of the SiO4-framework in the region of 400-800 cm -1 , the stretching band of Si-OH groups (960-970 cm −1 ) and the bands related to the vibrations of SiO4 groups with 1, 2 and 4 non-bridging oxygen atoms (so-called Q 3 , Q 2 and Q 0 units) were identified in the range of 800-1200 cm -1 . Interestingly, in the Raman spectra of aluminosilicate and pure silicate fragments of the Kara glass, the band shapes in the range of 800-1200 cm -1 were almost identical, with a small predominance of Q 2 and Q 3 units over Q 0 in the former and their uniform distribution in the latter. ...
... The discovery of a high concentration of non-bridging oxygen atoms was highly unexpected based on the results [17] used for the interpretation of Raman spectra. In addition, electron microscopic images presented in [13,16] showed the presence of widespread pyroxene (Q 2 ) microcrystallites in the glass matrix. These observations call for further investigation of the polymerization of the UHPHT impact Kara glasses. ...
... UHPHT melt impact glasses were sampled in 2015 and 2017 from impactites of the southern sector of the Kara crater from vein bodies cutting suevite massif ( Figure 1) at the Kara River (Pay-Khoy, Russia) and these are samples KP15-12-115 and KP15-12-118. A preliminary analysis of the structural state of these glasses was carried out using a set of standard mineralogical research methods [13,14,16]. The main feature distinguishing UHPHT melts from clast type glasses and massive melt impactites was found to be the multilevel differentiation of impact melt, including liquation of silicate and aluminosilicate melts and partial silica melt crystallization to UHP SiO2 variety-monocrystalline coesite [13,14]. ...
NMR Spectral Characteristics of Ultrahigh Pressure High Temperature Impact Glasses of the Giant Kara Crater (Pay-Khoy, Russia)
Article
Full-text available
  • Dec 2021
In this study, we carried out the analysis of the impact melt vein glasses from the Kara impact crater (Russia) in comparison to low-pressure impact melt glasses (tektites) of the Zham-anshin crater (Kazakhstan). 27 Al, 23 Na, and 29 Si MAS NMR spectra of the samples of these glasses were analyzed. The samples of the natural glass contained inclusions of crystalline phases, para-magnetic elements that greatly complicate and distort the NMR signals from the glass phase itself. Taking into account the Mossbauer distribution of Fe in these glasses, the analysis of the spectra of MAS NMR of glass network-former (Si, Al) and potential network-modifiers (Na) of nuclei leads to the conclusion that the Kara impact melt vein glasses are characterized by complete polymerization of (Si,Al)O4 tetrahedral structural units. The NMR features of the glasses are consistent with the vein hypothesis of their formation under conditions of high pressures and temperatures resulting in their fluidity, relatively slow solidification with partial melt differentiation, polymerization, and precipitation of mineral phases as the impact melt cools. The 70 Ma stability of the Kara impact vein glass can be explained by the stabilization of the glass network with primary fine-dispersed pyroxene and coesite precipitates and by the high polymerization level of the impact glass.
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... Vein UHPHT glass has a fluid microstructure with an aluminosilicate matrix and silicate inclusions of hundreds of micrometres in size [15] (Fig. 1). In addition, numerous rounded inclusions of mixed-layer aluminosilicates are presented. ...
... The aluminosilicate glass has a variable composition with a significant presence of iron, calcium, and magnesium (Table 1). Silicate inclusions are chemically homogeneous shapeless areas without contrasting boundaries with the surrounding feldspar glass [15]. The carbon inclusions are presented primarily in the silicate regions. ...
... The ratio of D and G bands maxima values is about 0.7 and the ratio of the integrals ranges from 1.8 to 1.9. A wide band of water in 3200-3500 cm -1 , which is present in silicate and aluminosilicate glasses [15], is absent in the carbon matter. ...
Microscopic studies of disordered carbon-rich inclusions in ultra-high pressure glasses from impactites of the Kara astrobleme
Article
Full-text available
  • Dec 2019
The paper presents the results of study of the carbon-containing phase discovered in the impact glass of the Kara astrobleme. We used the following research methods: optical, scanning electron, and atomic force microscopies, as well as Raman spectroscopy. This phase represents carbon-containing inclusions up to several tens of micrometres in size with an amorphous diamond-like structure. At the nanoscale, the studied phase is characterized mainly by a homogeneous structure.
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... Силикатные стёкла Карской астроблемы ранее изучались В. П. Лютоевым и А. Ю. Лысюком, ими были исследованы кремнеземистые образцы ряда импактного преобразования кварца, в том числе диаплектовые кварцевые стекла с коэситом, обнаруженным в зювите (Лютоев и др., 2015). Позднее были изучены силикатные расплавные стекла с коэситом и смектитом в виде капель в алюмосиликатных стеклах жильного типа (Shumilova et al., 2018;Golubev et al., 2020). Присутствующие в жильных расплавных телах одновременно и диаплектовые, и расплавные силикатные стёкла позволяют in situ выполнить сопоставление структурных особенностей принципиально различных по механизму формирования стёкол. ...
... Спектры также содержат ряд малоинтенсивных узких линий (кристаллических фаз) 640, 740, 1005 и 1113 см -1 , относящихся к пироксену. Непосредственно в расплавном стекле SiO 2 включения пироксенов, по данным СЭМ, не регистрируются, однако в окружающей алюмосиликатной матрице выделения пироксена многочисленны (Shumilova et al., 2018;Golubev et al., 2020). В связи с этим полосы пироксена в анализируемых спектрах силикатного стекла могут возникнуть за счет сигнала от окружающей матрицы алюмосиликатного стекла с микрокристаллами пироксена. ...
Comparative characteristics of diaplectic and melt silicate glasses of the Kara astrobleme
Article
Full-text available
  • Dec 2023
The objects of study are diaplectic and melt silicate glasses from vein melt impactites of the Kara astrobleme. Microscopic and spectroscopic characteristics of two glasses with fundamentally different formation mechanisms were obtained, which allowed comparing their structural features. We found that silicate diaplectic and melt impact glasses from high-pressure/high-temperature vein bodies of the Kara astrobleme were characterized by similar structural features — a high degree of polymerization, the presence of four-membered and polymembered SiO4 rings, which was characteristic of all glasses were the SiO2 composition. Diaplectic glasses are characterized by the constant presence of three-membered SiO4 rings; melt glasses were characterized by the absence of this feature, which was determined by more extreme conditions for the glass from melt.
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Mechanical properties of natural ultra-high-pressure high-temperature impact glasses at the nanoscale by PeakForce QNM
Article
  • Nov 2021
  • J NON-CRYST SOLIDS
Ultra-high-pressure high-temperature (UHPHT) glass from astroblems is a very promising natural material from the point of view of the fundamental problem of the structure and properties of a substance formed under extreme PT-conditions. Such glasses consist of disordered aluminosilicate and silicate micro-sized phases with a heterogeneous structure with domain from units to tens of nanometers in size. We used AFM to evaluation the mechanical properties distribution at nanoscale in UHPHT glasses from the Kara astrobleme. The results of AFM were supplemented with optical and electron microscopy data. It is shown in the work that the nanomechanical properties of glasses measured using by PeakForce QNM generally correspond to the macroscopic properties of a bulk sample. We measured the Young's modulus for the first time for aluminosilicate and silicate phases of UHPHT glasses. AFM can be an effective tool for studying at the micro- and nanoscale mechanical properties of such rigid materials.
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Physico-chemical study of an exogenic fulgurite from a thunderstorm on 10th August 2013 in Dallas, TX
Article
Full-text available
  • Mar 2021
  • PHYS CHEM MINER
Droplet-like exogenic fulgurites comprise a minor grouplet of natural glasses resulting from powerful lightning strikes. Reports on such type-V fulgurites are scarce in the literature. In this work, a fulgurite specimen from the thunderstorm that took place on 10th August 2013, in Dallas, TX, USA, has been analyzed using X-ray powder diffraction, X-ray fluorescence, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and infrared and Raman spectroscopy techniques. X-ray diffraction revealed the amorphous nature of the exofulgurite, and X-ray fluorescence showed a high Si, Al and Ca content. Infrared and Raman spectroscopy were key in revealing clear Si-O modes related signatures and a very significant presence of water (OH/H 2 O). A parallel with glassy silicate materials, but also with opal-A, was essential in the understanding of the fulgurite's characteristics. In particular, Raman data evidenced the exofulgurite to have a high degree of depolymerization.
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Mysterious long-living ultrahigh-pressure or secondary impact crisis
Article
Full-text available
  • Feb 2020
High-pressure glass has attracted interest in terms of both its fundamental state under extreme conditions and its possible applications as an advanced material. In this context, natural impact glasses are of considerable interest because they are formed under ultrahigh-pressure and high-temperature (UHPHT) conditions in larger volumes than laboratory fabrication can produce. Studying the UHPHT glasses of the unique giant Kara astrobleme (Russia), we found that the specific geological position of the UHPHT melt glass veins points to an origin from a secondary ultrahigh-pressure (UHP) melt according to the characteristics of the host suevites, which suggest later bottom flow. Here, we propose a fundamentally novel model involving an upward-injected UHP melt complex with complicated multi-level and multi-process differentiation based on observations of the UHP silica glass, single-crystal coesite and related UHP smectite that crystallized from an impact-generated hydrous melt. This model proposes a secondary UHP crisis during the modification stage of the Kara crater formation. The results are very important for addressing fundamental problems in fields as diverse as condensed matter states under extreme pressure and temperature (PT) conditions, material and geological reconstructions of impact structures, water conditions in mineral substances under UHP conditions in the deep Earth, and the duration and magnitude of the catastrophic effects of large asteroid impacts.
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Ultrahigh-Pressure Liquation of an Impact Melt
Article
Full-text available
  • May 2018
Liquation structures were described in ultrahigh-pressure impact glasses of the Kara astrobleme (Pay-Khoy) with differentiation into the bisilica, aluminosilicate, and ore components for the first time. The sequence of differentiation of mineral phases upon solidification of an ultrahigh-pressure impact melt was established: coesite, silicate glass, augite, aluminosilicate glass of albite composition, and pyrite. The discovered impact glasses are highly resistant to postimpact alterations.
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Spectroscopic features of ultrahighpressure impact glasses of the Kara astrobleme
Article
Full-text available
  • May 2018
The state of substances under ultrahigh pressures and temperatures (UHPHT) now raises a special interest as a matter existing under extreme conditions and as potential new material. Under laboratory conditions only small amounts of micrometer-sized matter are produced at a pressure up to 100 GPa and at room temperature. Simultaneous combination of ultrahigh pressures and temperatures in a lab still requires serious technological effort. Here we describe the composition and structure of the UHPHT vein-like impact glass discovered by us in 2015 on the territory of the Kara astrobleme (Russia) and compare its properties with impact glass from the Ries crater (Germany). A complex of structural and spectroscopic methods presents unusual high pressure marks of structural elements in 8-fold co-ordination that had been described earlier neither in synthetic nor natural glasses. The Kara natural UHPHT glasses being about 70 Ma old have well preserved initial structure, presenting some heterogeneity as a result of partial liquation and crystallization differentiation where an amorphous component is proposed to originate from low level polymerization. Homogeneous parts of the UHPHT glasses can be used to deepened fundamental investigation of a substance under extreme PT conditions and to technological studies for novel material creations. The full paper text is available by the link https://rdcu.be/Nbgr
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Scanning probe microscopy in mineralogical studies: about origin of the observed roughness of natural silica-rich glasses
Article
Full-text available
  • Oct 2017
We have studied different mineralogical objects: natural glasses of impact (tektites, impactites) and volcanic (obsidians) origin, using atomic force microscopy, X-ray microanalysis, infrared and Raman spectroscopy. The spectroscopy showed the difference in the structure and chemical composition of the glasses of different origin. The analysis of the dependence of nanoscale heterogeneity of the glasses, revealed by the atomic force microscopy, on their structural and chemical features was carried out.
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Nanoscale Heterogeneous Structures in GeO2-GeS2 Glasses
Article
Full-text available
  • Oct 2008
Atomic bonding structures in xGeO2-(100-x)GeS2 glasses have been studied through structural and chemical experiments. Atomic force microscope images in alkali-etched samples with x = 80 mol % show nano-scale dips, which are ascribable to isolated GeS2 clusters. Transmission electron microscope images and small angle X-ray scattering patterns suggest that the glass with x ≈ 50 has pronounced heterogeneous structures in nanoscales. Composition dependence of an etching rate exhibits a characteristic change at x = 60, which can be interpreted as a percolation threshold of tetrahedral GeS4 units. These results support a nanostructure model for the oxy-chalcogenide glass.
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Nano-heterogeneity of natural impact silica-rich glasses according to atomic force microscopy and spectroscopy data
Article
  • Aug 2018
  • J NON-CRYST SOLIDS
In nature extreme PT-conditions result in numerous glass-like solids, the study of which allows specifying various structural and chemical features of extreme materials, which have a great application potential in various fields of technology. We studied features of nanostructure of natural impact glasses, including recently discovered ultrahigh-pressure high-temperature impact glasses, compared to low-pressure natural and synthetic standard silica glasses. In this paper we presented complex data of atomic force microscopy, X-ray diffraction, X-ray energy-dispersive spectrometry, infrared and Raman spectroscopy. We described nanostructural characteristics of impact glasses and showed influence of chemical composition on the features of their structure. We discovered that the elemental composition was the most important factor determining the glasses nano-heterogeneity. We noted an essential role of influence of Na impurity on glass nanostructure. The impact glasses with pure SiO2 composition have the smallest sizes of nanostructural elements.
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Atomic scale imaging of amorphous silicate glass surfaces by scanning force microscopy
Article
  • May 2005
  • J NON-CRYST SOLIDS
The determination of the atomic structure of amorphous materials with conventional diffraction techniques is hindered by the missing periodicity of the samples. Consequently, a deeper insight into the structural properties of glasses can only be obtained in real space. In this work AFM investigations of silicate glass surfaces, namely fresh barium silicate and silica glass fracture surfaces, are described. The observed atomic-scale features and arrangements are compared with each other as well as with results from other methods and discussed in the context of classical glass structure theories. The results clearly demonstrate that AFM is able to provide atomically resolved surface structures of amorphous glass surfaces.
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Spectroscopy of natural silica-rich glasses
Article
  • Nov 2005
Natural-silica-rich glasses (impaetites, tektites and obsidians) have been investigated with infrared (IR), Raman and optical spectroscopy. Comparison with artificial glasses with silica-rich and alkali-rich compositions is made. The vibrational data of these compounds are discussed in relationship with their structures, particularly with respect to (i) Si-O-Si bonding differences, (ii) SiO4-ring arrangements, (iii) lattice disorder. IR spectra are strongly dependent on silica content: frequencies of the v3 and vD bands increase with the silica content. A general finding in the Raman spectra of tektites, is the relationship between silica, alumina, sodium contents and the presence of vibrational bands peaked at very specific energies. Raman spectra of Lybian desert glass (LOG), Darwin glass (DG) and vitreous silica are almost identical with the typical doublet at 440-490 cm-1 whereas in tektites the band at 440 cm-1 has relatively less pronounced doublet structure. A common character of Raman spectra of tektites and obsidians is the appearance of broad bands centered around 1000 and 1600 cm-1 due to substitutions of silicon by metals. Tektites have a strong absorption band at 1100 nm which originates from Fe2+ ions. In the other glasses, this absorption is slightly shifted towards 1110-1130 nm. Additional sharp features of impaetites and obsidians at 1380, 2210-2250 nm are completely absent in the absorption spectra of tektites. These bands are the signature of molecular water trapped inside the structure.
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Evaluation of Phase Separation in Glasses With the Use of Atomic Force Microscopy
Article
  • Dec 2007
  • J NON-CRYST SOLIDS
Glass forming melts frequently exhibit liquid–liquid immiscibility resulting in phase separation. The chemical and spatial variation of phase separated morphologies in glasses can range from a few angstroms to microns, often requiring very high magnification for detection. Historically, phase separated glasses have been characterized by transmission electron microscopy (TEM). This technique is very time consuming and costly, requiring specialized equipment and training. Atomic force microscopy (AFM) provides an inexpensive alternative to TEM and has proven to be a powerful tool in the characterization of phase separation in glasses. AFM provides rapid and accurate evaluation of the type, degree and scale of phase separation in glasses down to the nanometer level. Using a combination of topographical and phase imaging AFM we were able to quantitatively determine the microstructures of phase separated glasses with a resolution down to 50nm. Additionally we were able to quantitatively confirm the time dependence of the chemical segregation and growth processes for phase separation in glass by spinodal decomposition. This paper will present sample preparation techniques and results for evaluation of phase separation in alkali borosilicate and sodium silicate glass systems.
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