Hydrogen sites in the dense hydrous magnesian silicate phase E: a pulsed neutron powder diffraction study

Hydrogen site positions and occupancy in the crystal structure of dense hydrous magnesium silicate (DHMS) phase E were determined for the first time by pulsed neutron powder diffraction. A fully deuterated pure phase E powder sample, which had space group \(R\overline{3} m\) and lattice parameters of a = 2.97065(8) Å and c = 13.9033(4) Å, was synthesized at 15 GPa and 1100 °C. Through quantitative evaluation of refined structure parameters obtained with sufficient spatial resolution and very high signal-to-background ratio, we conclude that the O–D dipoles in the refined phase E structure are tilted by 24° from the direction normal to the layers of edge-shared MgO₆ octahedra (octahedral layers). The tilted dipole structure of phase E is in remarkable contrast to that of brucite, Mg(OH)₂, which has dipoles exactly normal to the octahedral layer. This contrast exists because the O–Si–O bonding unique in the phase E structure connects two adjacent octahedral layers and thereby reduces the interlayer O···O distance. This shrinkage of the interlayer distance induces the tilting of the O–D dipole and also generates unique O–D···O hydrogen bonding connecting all the layers in the phase E structure.     

The effects of possible contamination by sample holders on samples to be returned by Hayabusa2

Chemical compositions of materials used for new sample holders (vertically aligned carbon nanotubes [VACNTs] and polyimide film), which were developed for the analysis of Hayabusa2‐return samples, were determined by instrumental neutron activation analysis and/or instrumental photon activation analysis, to estimate contamination effects from the sample holders. The synthetic quartz plate used for the sample holders was also analyzed. Ten elements (Na, Al, Cr, Mn, Fe, Ni, Eu, W, Au, and Th) and 14 elements (Na, Al, K, Sc, Ti, Cr, Zn, Ga, Br, Sb, La, Eu, Ir, and Au) could be detected in the VACNTs and polyimide film, respectively. The VACNT data show that contamination by this material with respect to the Murchison meteorite is negligible in terms of the elemental ratios (e.g., Fe/Mn, Na/Al, and Mn/Cr) used for the classification of meteorites due to the extremely low density of VACNTs. However, for the Au/Cr ratio, even small degrees (1.7 wt%) of contamination by VACNTs will change the Au/Cr ratio. Elemental ratios used for the classification of meteorites are only influenced by large amounts of contamination (>60 wt%) of polyimide film, which is unlikely to occur. In contrast, detectable effects on Ti isotopic compositions are caused by >0.1 and >0.3 wt% contamination by VACNTs and polyimide film, respectively, and Hf isotopic changes are caused by >0.1 wt% contamination by VACNTs. The new sample holders (VACNTs and polyimide film) are suitable for chemical classification of Hayabusa2‐return samples, because of their ease of use, applicability to multiple analytical instruments, and low contamination levels for most elements.     

Cathodoluminescence of high-pressure feldspar minerals as a shock barometer

Cathodoluminescence (CL) analyses were carried out on maskelynite and lingunite in L6 chondrites of Tenham and Yamato-790729. Under CL microscopy, bright blue emission was observed in Na-lingunite in the shock veins. Dull blue-emitting maskelynite is adjacent to the shock veins, and aqua blue luminescent plagioclase lies farther away. CL spectroscopy of the Na-lingunite showed emission bands centered at ~330, 360–380, and ~590 nm. CL spectra of maskelynite consisted of emission bands at ~330 and ~380 nm. Only an emission band at 420 nm was recognized in crystalline plagioclase. Deconvolution of CL spectra from maskelynite successfully separated the UV–blue emission bands into Gaussian components at 3.88, 3.26, and 2.95 eV. For comparison, we prepared K-lingunite and experimentally shock-recovered feldspars at the known shock pressures of 11.1–41.2 GPa to measure CL spectra. Synthetic K-lingunite has similar UV–blue and characteristic yellow bands at ~550, ~660, ~720, ~750, and ~770 nm. The UV–blue emissions of shock-recovered feldspars and the diaplectic feldspar glasses show a good correlation between intensity and shock pressure after deconvolution. They may be assigned to pressure-induced defects in Si and Al octahedra and tetrahedra. The components at 3.88 and 3.26 eV were detectable in the lingunite, both of which may be caused by the defects in Si and Al octahedra, the same as maskelynite. CL of maskelynite and lingunite may be applicable to estimate shock pressure for feldspar-bearing meteorites, impactites, and samples returned by spacecraft mission, although we need to develop more as a reliable shock barometer.     

Mid-infrared spectra of the shocked Murchison CM chondrite: Comparison with astronomical observations of dust in debris disks

We present laboratory mid-infrared transmission/absorption spectra obtained from matrix of the hydrated Murchison CM meteorite experimentally shocked at peak pressures of 10-49 GPa, and compare them to astronomical observations of circumstellar dust in different stages of the formation of planetary systems. The laboratory spectra of the Murchison samples exhibit characteristic changes in the infrared features. A weakly shocked sample (shocked at 10 GPa) shows almost no changes from the unshocked sample dominated by hydrous silicate (serpentine). Moderately shocked samples (21-34 GPa) have typical serpentine features gradually replaced by bands of amorphous material and olivine with increasing shock pressure. A strongly shocked sample (36 GPa) shows major changes due to decomposition of the serpentine and due to devolatilization. A shock melted sample (49 GPa) shows features of olivine recrystallized from melted material.The infrared spectra of the shocked Murchison samples show similarities to astronomical spectra of dust in various young stellar objects and debris disks. The spectra of highly shocked Murchison samples (36 and 49 GPa) are similar to those of dust in the debris disks of HD113766 and HD69830, and the transitional disk of HD100546. The moderately shocked samples (21-34 GPa) exhibit spectra similar to those of dust in the debris disks of Beta Pictoris and BD+20307, and the transitional disk of GM Aur. An average of the spectra of all Murchison samples (0-49 GPa) has a similarity to the spectrum of the older protoplanetary disk of SU Auriga. In the gas-rich transitional and protoplanetary disks, the abundances of amorphous silicates and gases have widely been considered to be a primary property. However, our study suggests that impact processing may play a significant role in generating secondary amorphous silicates and gases in those disks. Infrared spectra of the shocked Murchison samples also show similarities to the dust from comets (C/2002 V1, C/2001 RX14, 9P/Tempel 1, and Hale Bopp), suggesting that the comets also contain shocked Murchison-like material.     

Growth of ringwoodite reaction rims from MgSiO3 perovskite and periclase at 22.5 GPa and 1,800 °C

The growth rate of ringwoodite reaction rims between MgSiO₃ perovskite and periclase was investigated at 22.5 GPa and 1,800 °C for 1–24 h using the Kawai-type high-pressure apparatus. The reaction was likely to proceed by a diffusion-controlled mechanism in which the dominant diffusion mechanism was grain-boundary diffusion. The reaction constant (the width of the ringwoodite reaction rim squared divided by time) determined from these experiments was between 1.3 × 10^?15 and 5.6 × 10^?15 m²/s. A Pt inert marker experiment indicated that the MgO component migrated faster than the SiO₂ component in ringwoodite. Thus, either Mg or O having the slower diffusion rate controlled the reaction. Because previous diffusion studies have shown that diffusion rates of O are slower than those of Mg, O would be a rate-controlling element for ringwoodite formation from MgSiO₃ perovskite and periclase. The growth rate appeared to be too fast to explain the observed topographic rise (~10 km) inside mantle plumes at the 660-km discontinuity.     

High‐pressure minerals in shocked meteorites

Heavily shocked meteorites contain various types of high‐pressure polymorphs of major minerals (olivine, pyroxene, feldspar, and quartz) and accessory minerals (chromite and Ca phosphate). These high‐pressure minerals are micron to submicron sized and occur within and in the vicinity of shock‐induced melt veins and melt pockets in chondrites and lunar, howardite–eucrite–diogenite (HED), and Martian meteorites. Their occurrence suggests two types of formation mechanisms (1) solid‐state high‐pressure transformation of the host‐rock minerals into monomineralic polycrystalline aggregates, and (2) crystallization of chondritic or monomineralic melts under high pressure. Based on experimentally determined phase relations, their formation pressures are limited to the pressure range up to ~25 GPa. Textural, crystallographic, and chemical characteristics of high‐pressure minerals provide clues about the impact events of meteorite parent bodies, including their size and mutual collision velocities and about the mineralogy of deep planetary interiors. The aim of this article is to review and summarize the findings on natural high‐pressure minerals in shocked meteorites that have been reported over the past 50 years.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

Mechanism of the olivine–ringwoodite transformation in the presence of aqueous fluid

The mechanism of the high pressure transformation of olivine in the presence of aqueous fluid was investigated by high pressure experiments conducted nominally at the wadsleyite + ringwoodite stability field at 14.5 GPa and 700 and 800°C. The microstructures of recovered samples were observed using an analytical transmission electron microscope (ATEM) for which foils were prepared using a focused ion beam technique. Glass films approximately 1 μm in width always occupied the interface between olivine and hydrous ringwoodite. ATEM measurements showed that the chemical compositions of the glass films had approximately the same Mg/Fe ratio as that of olivine, but a higher Si content. Micro-structural and -chemical observations suggest that these glass films formed as quenched glass from the aqueous fluid dissolving olivine and that hydrous ringwoodite was crystallized from the fluid. This indicates that the transformation of olivine to hydrous ringwoodite was prompted by the dissolution–reprecipitation process. The dissolution–reprecipitation process is considered an important mineral replacement mechanism in the Earth’s crust by which one mineral is replaced by a more stable phase or phases. However, this process has not previously been reported for deep mantle conditions.     

Photographic Observations of the 1996 Leonid Fireballs in Japan

Several Leonid fireballs were successfully photographed by the Japanese Fireball Network and by other observers in Japan on 16 November, 1996. A totals of seven of these were simultaneously observed from two or more stations, from which the orbital and physical data were deduced. The radiant of these fireballs were very small, only 0.1°, similar to that of the 1991 Perseids. The 1996 Leonids showed a lower magnitude distribution index similar to those obtained in the 1961 and 1965 Leonids. All of these showers occurred before perihelion passage of the parent comet. We conclude that we have already encountered the elongated front part of the dust trail of the Leonid parent comet, where the trail is probably composed of larger dust particles. This revised version was published online in July 2006 with corrections to the Cover Date.