X-ray spectroscopy of stellar coronae

Summary From the early discovery in 1948 of X-rays from the Solar corona, X-ray spectroscopy has proven to be an invaluable tool in studying hot astrophysical and laboratory plasmas. Because the emission line spectra and continua from optically thin plasmas are fairly well known, high-resolution X-ray spectroscopy has its most obvious application in the measurement of optically thin sources such as the coronae of stars. In particular X-ray observations with theEINSTEIN observatory have demonstrated that soft X-ray emitting coronae are a common feature among stars on the cool side of the Hertzsprung-Russell diagram, with the probable exception of single very cool giant and supergiant stars and A-type dwarfs. Observations with the spectrometers aboardEINSTEIN andEXOSAT have shown that data of even modest spectral resolution (/ = 10–100) permit the identification of coronal material at different temperatures whose existence may relate to a range of possible magnetic loop structures in the hot outer atmospheres of these stars. The higher spectral resolution of the next generation of spectrometers aboard NASA'sAXAF and ESA'sXMM will allow to fully resolve the coronal temperature structure and to enable velocity diagnostics and the determination of coronal densities, from which the loop geometry (i.e. surface filling factors and loop lengths) can be derived. In this paper various diagnostic techniques are reviewed and the spectral results fromEINSTEIN andEXOSAT are discussed. A number of spectral simulations forAXAF andXMM, especially high-resolution iron K-shell, L-shell, and2s-2p spectra in the wavelength regions around 1.9 Å, 10 Å, and 100 Å, respectively, are shown to demonstrate the capabilities for temperature, density, and velocity diagnostics. Finally, iron K-shell spectra are simulated for various types of detectors such as microcalorimeter, Nb-junction, and CCD.     

Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3)

 Premelting effects in gehlenite (Ca₂Al₂SiO₇) have been studied by Raman spectroscopy and calorimetry, and in gehlenite and pseudowollastonite (CaSiO₃) by electrical conductivity. The enthalpy of premelting of gehlenite is 17.3 kJ mol⁻¹ and represents 9% of the reported enthalpy of fusion, which is in the range of the reported fraction of other minerals. The Raman and electrical conductivity experiments at high temperatures, for gehlenite and pseudowollastonite, show that the premelting effects of both compositions are associated with enhanced dynamics of calcium atoms near the melting point. This conclusion agrees with the results obtained for other minerals like diopside, but contrasts with those found for sodium metasilicate in which the weaker bonding of sodium allows the silicate framework to distort near the melting temperature and deform in such a way to prefigure the silicate entities present in the melt. Received: 30 April 2002 / Accepted: 7 August 2002 Acknowledgements We thank Y. Linard for help with DSC measurements and two anonymous reviewers for their constructive comments. This work has been partly supported by the EU Marie-Curie fellowship contract no. HPMF-CT-1999-00329, the CNRS-Carnegie Institution of Washington program PICS no.192, and the NSF grants EAR-9614432 and EAR-9901886 to B.O.M.     

Column Amounts of ClONO2, HCl, HNO3, and HF from Ground-Based FTIR Measurements Made Near Kiruna, Sweden, in Late Winter 1994

During SESAME phase I ground-based FTIR measurements were performed atEsrange near Kiruna, Sweden, from 28 January to 26 March 1994. Zenith columnamounts of ClONO₂, HCl, HF, HNO₃,O₃, N₂O, CH₄, and CFC-12 werederived from solar absorption spectra. Time series of ClONO₂and HCl indicate a chlorine activation at the end of January and around 1March. On 1 March a very low amount of HCl of 2.09times; 10¹⁵molec. cm^-2 was detected, probably caused by a second chlorineactivation phase starting from an already decreased amount of HCl. The ratioof column amounts of HCl to ClONO₂ decreased inside the vortexfrom about 1 in January to 0.4 in late March compared to values of about 2outside the vortex. Although the Arctic stratosphere was rather warm in winter1993/94 and PSCs occurred seldom, chlorine partitioning into its reservoirspecies HCl and ClONO₂ changed during that winter andClONO₂ is the major chlorine reservoir at the end of thewinter as in cold winters like 1991/92 and 1994/95.     

Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

An infrared spectroscopic study of lawsonite to 20 GPa

The infrared spectrum of CaAl₂Si₂O₇ · H₂O-lawsonite, has been characterized to pressures of 20 GPa at 300 K. Our results constrain the response to compression of the silicate tetrahedra, hydroxyl units, and water molecules in this material. The asymmetric and symmetric stretching and bending vibrations of the Si₂O₇ groups (at zero pressure frequencies between 600 and 1000 cm⁻¹) increase in frequency with pressure at rates between 3.6 and 5.9 cm⁻¹/GPa. All silicate modes appear to shift continuously with pressure to 20 GPa, although the lowest frequency stretching vibration becomes unresolvable above 18 GPa, and a splitting of the main bending vibration is observed near this pressure. The O-H stretches of the hydroxyl units exhibit a discontinuity in their mode shifts at ∼8–9 GPa, which we interpret to be produced by a pressure-induced change in hydrogen bonding. The stretching and bending vibrations of the water molecule are relatively unaffected by compression to 20 GPa, thus demonstrating that the structural cavities in which water molecules reside are relatively rigid. Significant changes in the amplitude of the O-H stretches of the hydroxyl and water units are observed at this pressure as well; nevertheless, our results demonstrate that the dominant structural units in lawsonite persist metastably at 300 K with only modest structural modifications well beyond the known stability field of this phase. Received: 10 July 1998 / Revised, accepted: 23 October 1998     

Structural properties of (Mn1-x Fe x )Nb2O6 columbites from X-ray diffraction and IR spectroscopy

A suite of (Mn_1-x Fe _x )Nb₂O₆ (x=0, 0.05, 0.25, 0.50, 0.75, 1) columbite samples has been prepared by solid-state reaction from oxides. X-ray diffraction and spectroscopic investigations have been carried out in order to gain different perspectives on how the solid solution adapts at different length scales to cation mixing. X-ray powder diffraction and powder absorption IR spectroscopy data are presented. The powder diffraction data show that there is no significant excess volume of mixing on the Fe–Mn columbite join. All the unit-cell parameters decrease linearly as a function of increasing Fe content. Substitution of Fe²⁺ for the larger Mn²⁺ cation causes a decrease in the volume of the A polyhedron, which also becomes more regular with respect to both bond-length and edge-length distortion parameters. No significant variation of the B site has been observed. Wavenumber shifts of the IR peaks nearly all vary linearly with composition, consistent with linear variations of the lattice parameters. Line broadening has been quantified by autocorrelation analysis of the IR spectra. This is interpreted as suggesting that there is some element of local strain or positional disorder at the length scale of second or third nearest neighbours around sites occupied by Fe.     

Isothermal annealing of partially metamict zircon: evidence for a three-stage recovery process

 Raman spectroscopy and the powder diffraction technique have been used to monitor the recovery process of two partially metamict zircons (2.6 and 4.8 × 10¹⁸ α-decays g⁻¹) from Sri Lanka during a series of isothermal annealing experiments in the temperature range from 870 to 1622 K. These experiments show for the first time that structural recovery in partially metamict zircon proceeds via three distinct recovery stages, each of which occurs within a distinct time-temperature regime. Whereas the first two stages have previously been recognized (recovery of damaged crystalline remnants and epitaxial recrystallization), the third stage has not yet been identified as a single activated process. It is suggested that anisotropic defect annealing during the first stage at low temperatures, where the structure recovers preferentially along the a(b) plane, produces a geometrical situation where large structural rearrangements are necessary to remove the remaining defects inside the crystalline material. This situation is approximately reached when the amorphous domains start to recrystallize. The reason for anisotropic annealing can be found in a different connectivity between polyhedral linkages in both directions of the zircon lattice. High apparent activation energies, in the range of 6.4 to 7.9 eV, were determined for the third recovery stage from the Raman data, which are interpreted to reflect large structural rearrangements (i.e. polyhedral tilting) associated with the final recovery of the c axis. This explains the occurrence of a distinct recrystallization stage without defect annealing. Finally, it should be mentioned that the first recovery stage is not necessarily expected to occur in less damaged zircon crystals (<∼2 × 10¹⁸ α-decays g⁻¹), since less stable defects along the basal plane might have already been self-annealed during radiation damage accumulation under ambient temperatures. Received: 6 September 2001 / Accepted: 25 February 2002     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

且干布拉克蛭石的矿物学研究

本文对产于新疆且干布拉克的我国最大蛭石矿的组成、结构和谱学特征做了系统的阐述。研究表明:且干布拉克蛭石是由金云母风化而成。由于风化的不完全,该蛭石保留了许多金云母的特征。该蛭石不是个严格矿物学意义上的蛭石,它是由金云母、严格矿物学意义上的蛭石、以及两者组成的多种混层矿物的混合物。金云母风化过程中可能有杂质铁相生成。蛭石的颜色和多色性,可能起因于其中的O~(2-)→Fe~(2+23+)和Fe~(2+)→Fe~(3+)