Raman spectroscopy of olivine in dunite experimentally shocked to pressures between 5 and 59 GPa

Abstract— Previous Raman investigations on experimentally shocked ingle‐crystal olivine indicated that the olivine Raman bands seemingly shift to a higher wave number with increasing shock pressure. If this effect could be confirmed, Raman analysis of natural shock‐metamorphosed minerals could potentially provide an important shock barometric tool. We carried out a Raman spectroscopic study on olivine in a series of natural dunite samples experimentally shocked to pressures between 5 and 59 GPa. In addition, we analyzed olivine grains in a sample of the Cold Bokkeveld C1 meteorite. We studied samples of several dunites with olivine of 90.64–92.00 mole% Fo to determine Raman effects in the region from 200 to 900 cm^?1. Several olivine grains per sample/shock pressure stage were analyzed. Raman analysis, however, showed little or no shift with increasing shock pressure. The shifts to higher or lower frequencies observed were not specific for a given pressure stage, with some grains within a sample showing more shift than others. This finding is unrelated to the crystallographic orientation of analyzed grains and cannot be related systematically to the different degrees of optically determined shock metamorphism of the analyzed grains. We identified an increase in full width at half maximum (FWHM) for the 824 cm^?1 band with increased shock pressure in the shocked Åheim samples above 45 GPa and, to a lesser extent, for the 856 cm^?1 band. Evaluation of band broadening of olivine in the Cold Bokkeveld meteorite showed FWHM values that were much greater (9–20 cm^?1) than those of olivine in the shocked dunite samples (7–12 cm^?1). We concluded that these differences in FWHM are due to differences in chemical composition between the meteoritic and the experimentally shocked olivine. Therefore, using Raman spectroscopy to detect small shifts in wave numbers to higher frequencies with increased shock pressure does not yield consistent effects for polycrystalline dunite. An extra band at 650 cm^?1 was identified in the Raman spectra of the unshocked Mooihoek dunite and the Åheim dunite samples shocked to 5, 29.3, and 59 GPa, as well as another at 696 cm^?1 in all the spectra of the 59 GPa Åheim sample. The cause of these extra bands is not known. Comparison of these results with Raman spectra of olivine from the Cold Bokkeveld C1 meteorite did not allow us to determine shock pressures for the meteoritic olivine.     

H,not O or pressure,causes eutectic T depression in the Fe‐FeS System to 8 GPa

The Fe‐FeS system maintains a eutectic temperature of 990 ± 10 °C to at least 8 GPa if starting materials and pressure media are rigorously dehydrated. Literature reports of pressure‐induced freezing point depression of the eutectic for the Fe‐FeS system are not confirmed. Modest addition of oxygen alone is confirmed to cause negligible freezing point depression at 6 GPa. Addition of H alone causes a progressive decrease in the eutectic temperature with P in the Fe‐FeS‐H system to below 965 °C at 6 GPa to below 950 °C at 8 GPa. It is our hypothesis that moisture contamination in unrigorously dried experiments may be an H source for freezing point depression. O released from H₂O disproportionation reacts with Fe and is sequestered as ferropericlase along the sample capsules walls, leaving the H to escape the system and/or enter the Fe‐FeS mixture. The observed occurrence of ferropericlase on undried MgO capsule margins is otherwise difficult to explain, because an alternate source for the oxygen in the ferropericlase layer is difficult to identify. This study questions the use of pressure‐depressed Fe‐S eutectic temperatures and suggests that the lower eutectic temperatures sometimes reported are achieved by moving into the ternary Fe‐S‐H system. These results adjust slightly the constraints on eutectic temperatures allowed for partly solidified cores on small planets. H substantially diminishes the temperature extent of the melting interval in Fe‐S by reducing the melting points of the crystalline phases more than it depresses the eutectic.     

Optical constants from 370 nm to 900 nm of Titan tholins produced in a low pressure RF plasma discharge

Determining the optical constants of Titan aerosol analogues, or tholins, has been a major concern for the last three decades because they are essential to constrain the numerical models used to analyze Titan’s observational data (albedo, radiative transfer, haze vertical profile, surface contribution, etc.). Here we present the optical constant characterization of tholins produced with an RF plasma discharge in a (95%N₂–5%CH₄) gas mixture simulating Titan’s main atmospheric composition, and deposited as a thin film on an Al–SiO₂ substrate. The real and imaginary parts, n and k, of the tholin complex refractive index have been determined from 370 nm to 900 nm wavelength using spectroscopic ellipsometry. The values of n decrease from n = 1.64 (at 370 nm) to n = 1.57 (at 900 nm) as well as the values of k which feature two behaviors: an exponential decay from 370 nm to 500 nm, with k = 12.4 × e^?0.018λ (where λ is expressed in nm), followed by a plateau, with k = (1.8 ± 0.2) × 10^?3. The trends observed for the PAMPRE tholins optical constants are compared to those determined for other Titan tholins, as well as to the optical constants of Titan’s aerosols retrieved from observational data.     

Cathodoluminescence as a tool to discriminate impact melt,shocked and unshocked volcanics: A case study of samples from the El'gygytgyn impact structure

El'gygytgyn (Chukotka, Arctic Russia) is a well‐preserved impact structure, mostly excavated in siliceous volcanic rocks. For this reason, the El'gygytgyn structure has been investigated in recent years and drilled in 2009 in the framework of an ICDP (International Continental Scientific Drilling Program) project. The target rocks mostly consist of rhyodacitic ignimbrites and tuffs, which make it difficult to distinguish impact melt clasts from fragments of unshocked target rock within the impact breccia. Several chemical and petrologic attempts, other than dating individual clasts, have been considered to distinguish impact melt from unshocked volcanic rock of the targets, but none has proven reliable. Here, we propose to use cathodoluminescence (imaging and spectrometry), whose intensity is inversely correlated with the degree of shock metamorphism experienced by the investigated lithology, to aid in such a distinction. Specifically, impact melt rocks display low cathodoluminescence intensity, whereas unshocked volcanic rocks from the area typically show high luminescence. This high luminescence decreases with the degree of shock experienced by the individual clasts in the impact breccia, down to almost undetectable when the groundmass is completely molten. This might apply only to El'gygytgyn, because the luminescence in volcanic rocks might be due to devitrification and recrystallization processes of the relatively old (Cretaceous) target rock with respect to the young impactites (3.58 Ma). The alteration that affects most samples from the drill core does not have a significant effect on the cathodoluminescence response. In conclusion, cathodoluminescence imaging and spectra, supported by Raman spectroscopy, potentially provide a useful tool for in situ characterization of siliceous impactites formed in volcanic target.     

Shock experiments in range of 10–45 GPa with small multidomain magnetite in porous targets

Abstract– Physical properties of multidomain magnetite‐bearing porous pellets shocked up to 45 GPa were measured. The results show general magnetic softening as a result of shock. However, a relative magnetic hardening trend and slight magnetic susceptibility decrease is observed with increasing pressure among shocked samples. Initially, the shock also seems to cause a slight decrease in porosity, but at higher shock pressures macroscopic porosity increases progressively in our pellets. The microscopic porosity remains almost unchanged. Since our samples have distinctly higher initial porosity compared with samples used in previous studies, our results may be representative for impacts into highly porous magnetite‐bearing sedimentary or volcanic rocks and are relevant to impacts into such target rocks on Earth and Mars.     

The 0.1–100 keV spectrum and variability of Mrk 421 in a high state

The results of a BeppoSAX target of opportunity (TOO) observation of the BL Lac object Mrk 421 during a high-intensity state are reported and compared with monitoring X-ray data collected with the BeppoSAX Wide Field Cameras (WFC) and the RXTE All Sky Monitor (ASM). The 0.1–100 keV spectrum of Mrk 421 shows continuous convex curvature that can be interpreted as the high-energy end of the synchrotron emission. The source shows significant short-term temporal and spectral variability, which can be interpreted in terms of synchrotron cooling. The comparison of our results with those of previous observations when the source was a factor 3–5 fainter shows evidence for strong spectral variability, with the maximum of the synchrotron power shifting to higher energy during high states. This behaviour suggests an increase in the number of energetic electrons during high states.     

Fine‐structures of planar deformation features in shocked olivine: A comparison between Martian meteorites and experimentally shocked basalts as an indicator for shock pressure

We performed shock recovery experiments on an olivine‐phyric basalt at shock pressures of 22.2–48.5 GPa to compare with shock features in Martian meteorites (RBT 04261 and NWA 1950). Highly shocked olivine in the recovered basalt at 39.5 and 48.5 GPa shows shock‐induced planar deformation features (PDFs) composed of abundant streaks of defects. Similar PDFs were observed in olivine in RBT 04261 and NWA 1950 while those in NWA 1950 were composed of amorphous lamellae. Based on the present results and previous studies, the width and the abundance of lamellar fine‐structures increased with raising shock pressure. Therefore, these features could be used as shock pressure indicators while the estimated pressures may be lower limits due to no information of temperature dependence. For Martian meteorites that experienced heavy shocks, the minimum peak shock pressures of RBT 04261 and NWA 1950 are estimated to be 39.5–48.5 GPa and 48.5–56 GPa, respectively, which are found consistent with those estimated by postshock temperatures expected by the presence of brown olivine. We also investigated shock‐recovered basalts preheated at 750 and 800 °C in order to check the temperature effects on shock features. The results indicate a reduction in vitrifying pressure of plagioclase and a pressure increase for PDFs formation in olivine. Further temperature‐controlled shock recovery experiments will provide us better constraints to understand and to characterize various features found in natural shock events.     

Revision and recalibration of existing shock classifications for quartzose rocks using low‐shock pressure (2.5–20 GPa) recovery experiments and mesoscale numerical modeling

A combination of shock recovery experiments and numerical modeling of shock deformation in the low‐shock pressure range from 2.5 to 20 GPa for two dry sandstone types of different porosity, a completely water‐saturated sandstone, and a well‐indurated quartzite provides new insights into strongly heterogeneous distribution of different shock features. (1) For nonporous quartzo‐feldspathic rocks, the traditional classification scheme (Stöffler 1984 ) is suitable with slight changes in pressure calibration. (2) For water‐saturated quartzose rocks, a cataclastic texture (microbreccia) seems to be typical for the shock pressure range up to 20 GPa. This microbreccia does not show formation of PDFs but diaplectic quartz glass/SiO₂ melt is formed at 20 GPa (~1 vol%). (3) For porous quartzose rocks, the following sequence of shock features is observed with progressive increase in shock pressure (1) crushing of pores, (2) intense fracturing of quartz grains, and (3) increasing formation of diaplectic quartz glass/SiO₂ melt replacing fracturing. The formation of diaplectic quartz glass/SiO₂ melt, together with SiO₂ high‐pressure phases, is a continuous process that strongly depends on porosity. This experimental observation is confirmed by our concomitant numerical modeling. Recalibration of the shock classification scheme results in a porosity versus shock pressure diagram illustrating distinct boundaries for the different shock stages.     

High‐pressure phases in shock‐induced melt of the unique highly shocked LL6 chondrite Northwest Africa 757

Northwest Africa 757 is unique in the LL chondrite group because of its abundant shock‐induced melt and high‐pressure minerals. Olivine fragments entrained in the melt transform partially and completely into ringwoodite. Plagioclase and Ca‐phosphate transform to maskelynite, lingunite, and tuite. Two distinct shock‐melt crystallization assemblages were studied by FIB‐TEM analysis. The first melt assemblage, which includes majoritic garnet, ringwoodite plus magnetite‐magnesiowüstite, crystallized at pressures of 20–25 GPa. The other melt assemblage, which consists of clinopyroxene and wadsleyite, solidified at ~15 GPa, suggesting a second veining event under lower pressure conditions. These shock features are similar to those in S6 L chondrites and indicate that NWA 757 experienced an intense impact event, comparable to the impact event that disrupted the L chondrite parent body at 470 Ma.     

Fracture‐related intracrystalline transformation of olivine to ringwoodite in the shocked Sixiangkou meteorite

Abstract— Magnesium‐iron olivine in the Sixiangkou L6 chondrite contains abundant fractures induced by plastic deformation during shock metamorphism. This study reports the discovery of lamellar ringwoodite that incoherently nucleated and grew along planar and irregular fractures in olivine. Magnesium‐iron interdiffusion took place between olivine matrix and crystallizing ringwoodite at high pressures and high temperatures, which resulted in higher FeO content in ringwoodite lamellae than in olivine. This suggests that a quasi‐hydrostatic high pressure lasting for several minutes should have been produced in the shock veins of the meteorite. The intracrystalline transformation of olivine to ringwoodite also has implications for phase transitions in subducting lithospheric slabs because planar and irregular fractures are commonly produced in olivine that suffered plastic deformation.     

Energy dissipation at the silica glass/compressed aerogel interface: The fate of Wild 2 mineral grains and fragments smaller than ~100 nm

Allocation FC6,0,10,0,26 from Stardust track 10 shows a slightly wavy silica glass/compressed silica aerogel interface exposing a patchwork of compressed silica aerogel domains and domains of silica glass with embedded Wild 2 materials in ultra‐thin TEM sections. This interface is where molten silica encountered compressed silica aerogel at temperatures <100 °C, and probably near room temperature, causing steep thermal gradients. An Mg, Fe‐olivine grain, and a plagioclase‐leucite intergrowth survived without melting in silica glass. A Mg‐, Al‐, Ca‐, K‐bearing silica globule moved independently as a single object. Two clusters of pure iron, low‐Ni iron, and low‐Ni, low‐sulfur Fe‐Ni‐S grains also survived intact and came to rest right at the interface between silica glass/compressed silica aerogel. There are numerous Fe‐Ni‐S nanograins scattered throughout MgO‐rich magnesiosilica glass, but compositionally similar Fe‐Ni‐S are also found in the compressed silica aerogel, where they are not supposed to be. This work could not establish how deep they had penetrated the aerogel. Iron nanograins in this allocation form core‐ring grains with a gap between the iron core and a surrounding ring of thermally modified aerogel. This structure was caused when rapid, thermal expansion of the core heated the surrounding compressed aerogel that upon rapid cooling remained fixed in place while the iron core shrank back to its original size. The well‐known volume expansion of pure iron allowed reconstruction of the quench temperature for individual core‐ring grains. These temperatures showed the small scale of thermal energy loss at the silica glass/compressed silica aerogel interface. The data support fragmentation of olivine, plagioclase, and iron and Fe ± low‐Ni grains from comet 81P/Wild 2 during hypervelocity capture.     

Analysis of the thin layer of Galactic warm ionized gas in the range

We present an analysis of the thin layer of Galactic warm ionized gas at an angular resolution ∼10 arcmin. This is carried out using radio continuum data at 1.4, 2.7 and 5 GHz in the coordinate region     . For this purpose, we evaluate the zero level of the 2.7- and 5-GHz surveys using auxiliary data at 2.3 GHz and 408 MHz. The derived zero-level corrections are   T _zero(2.7 GHz) = 0.15 ± 0.06 K  and   T _zero(5 GHz) = 0.1 ± 0.05 K  . We separate the thermal (free–free) and non-thermal (synchrotron) component by means of a spectral analysis performed adopting an antenna temperature spectral index −2.1 for the free–free emission, a realistic spatial distribution of indices for the synchrotron radiation and by fitting, pixel-by-pixel, the Galactic spectral index. We find that at 5 GHz, for  | b | = 0°  , the fraction of thermal emission reaches a maximum value of 82 per cent, while at 1.4 GHz, the corresponding value is 68 per cent. In addition, for the thermal emission, the analysis indicates a dominant contribution of the diffuse component relative to the source component associated with discrete H  ii regions.     

Maohokite,a post‐spinel polymorph of MgFe2O4 in shocked gneiss from the Xiuyan crater in China

Maohokite, a post‐spinel polymorph of MgFe₂O₄, was found in shocked gneiss from the Xiuyan crater in China. Maohokite in shocked gneiss coexists with diamond, reidite, TiO₂‐II, as well as diaplectic glasses of quartz and feldspar. Maohokite occurs as nano‐sized crystallites. The empirical formula is (Mg_0.62Fe_0.35Mn_0.03)²⁺Fe³⁺₂O₄. In situ synchrotron X‐ray microdiffraction established maohokite to be orthorhombic with the CaFe₂O₄‐type structure. The cell parameters are a = 8.907 (1) Å, b = 9.937(8) Å, c = 2.981(1) Å; V = 263.8 (3) ų; space group Pnma. The calculated density of maohokite is 5.33 g cm^?3. Maohokite was formed from subsolidus decomposition of ankerite Ca(Fe²⁺,Mg)(CO₃)₂ via a self‐oxidation‐reduction reaction at impact pressure and temperature of 25–45 GPa and 800–900 °C. The formation of maohokite provides a unique example for decomposition of Fe‐Mg carbonate under shock‐induced high pressure and high temperature. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2017‐047). The mineral was named maohokite after Hokwang Mao, a staff scientist at the Geophysical Laboratory, Carnegie Institution of Washington, for his great contribution to high pressure research.     

Fluid inclusions in microstructures of shocked quartz from the Keurusselkä impact site,Central Finland

Granitoid rock samples from the assumed center of the Keurusselkä impact site were subjected to a systematic study of fluid‐inclusion compositions and densities in various microstructures of the shocked quartz. The results are consistent with the following impact‐induced model of formation. After cessation of all major regional tectonic activity and advanced erosional uplift of the Fennoscandian shield, a meteorite impact (approximately 1.1 Ga) caused the formation of planar fractures (PFs) and planar deformation features (PDFs) and the migration of shock‐liberated metamorphic fluid (CO₂ ± H₂O) to the glass in the PDFs. Postimpact annealing of the PDFs led to the formation of CO₂ (±H₂O) fluid‐inclusion decorated PDFs. The scarce fluid‐inclusion implosion textures (IPs) suggest a shock pressure of 7.6–10 GPa. The postimpact pressure release and associated heating initiated hydrothermal activity that caused re‐opening of some PFs and their partial filling by moderate‐salinity/high temperature (>200 °C) H₂O (+ chlorite + quartz) and moderate‐density CO₂. The youngest postimpact endogenic sub‐ and nonplanar microfractures (MFs) are characterized by low‐density CO₂ and low‐salinity/low‐temperature (<200 °C) H₂O.     

The Hα echoes of ε Carinae from 1985 to 1997

Spatially resolved, broad Hα line profiles from both the luminous blue variable star ε Carinae (ε Car) and the surrounding filamentary Car II ('Keyhole') nebula, where they have been scattered and reflected by dust, have been observed periodically from 1985 to 1997. The Hα line profiles from ε Car in this 12-yr period show some, albeit not dramatic, changes. The sharp and deep P Cygni-type absorption feature that was observed first in 1985 in the broad, scattered/reflected profiles from the surrounding Keyhole nebula is not present in any of the direct ε Car profiles. This distinctive feature is now shown to be spatially variable over the Keyhole nebula and most prominent along the direction of the axis of the bipolar Homunculus nebula at PA 132°. No evidence of any temporal variability of this sharp feature has been found in 12 yr of monitoring, even from the most well-defined scattering/reflecting cloud along PA 132°.
It is concluded that a 46°-wide cone of light from ε Car is relatively unobscured along the axis of the Homunculus nebula and that this must be the consequence of a dense torus close to the star.     

Discovery of a single faint AGN in a large sample of z > 5 Lyman break galaxies

As part of a large spectroscopic survey of   z > 5  Lyman break galaxies (LBGs), we have identified a single source which is clearly hosting an active galactic nucleus (AGN). Out of a sample of more than 50 spectroscopically confirmed R -band dropout galaxies at   z ∼ 5  and above, only J104048.6−115550.2 at   z = 5.44  shows evidence for a high ionization potential emission line indicating the presence of a hard ionizing continuum from an AGN. Like most objects in our sample the rest-frame-UV spectrum shows the UV continuum breaking across a Lyα line. Uniquely within this sample of LBGs, emission from N  v is also detected, a clear signature of AGN photoionization. The object is spatially resolved in Hubble Space Telescope ( HST ) imaging. This, and the comparatively high Lyα/N  v flux ratio indicates that the majority of the Lyα (and the UV continuum longward of it) originates from stellar photoionization, a product of the ongoing starburst in the LBG. Even without the AGN emission, this object would have been photometrically selected and spectroscopically confirmed as a Lyman break in our survey. The measured optical flux  ( I _AB= 26.1)  is therefore an upper limit to that from the AGN and is of order 100 times fainter than the majority of known quasars at these redshifts. The detection of a single object in our survey volume is consistent with the best current models of high redshift AGN luminosity function, providing a substantial fraction of such AGN is found within luminous starbursting galaxies. We discuss the cosmological implications of this discovery.     

Spectrum of hot water in the 4750–13 000 cm−1 wavenumber range (0.769–2.1 μm)

The high resolution laboratory spectrum of hot water vapour has been recorded in the 500–13 000 cm⁻¹ wavenumber range and we report on the analysis of the 4750–13 000 cm⁻¹ (0.769–2.1 μm) portion. The emission spectrum was recorded using an oxy-acetylene welding torch and a Fourier transform spectrometer. Line assignments in the laboratory spectrum as well as in an absorption spectrum of a sunspot umbra were made with the help of the BT2 line-list. Our torch spectrum is the first laboratory observation of the 9300 Å'steam bands' seen in M-stars and brown dwarfs.