Cesstibtantite—a geologic introduction to the inverse pyrochlores

Summary The crystal structure of cesstibtantite has been solved from diffractometer data collected on samples from Leshaia, Russia and the Tanco pegmatite, Manitoba. Cesstibtantite from the Leshaia pegmatite (type locality) hasa 10.515(2) Å, space groupFd3m, composition Cs_0.31(Sb_0.57Na_0.31Pb_0.02Bi_0.01)_O.91(Ta_1.88Nb_0.12)₂(O_5.69[OH, F]_0.31)₆(OH, F)_0.69, Z 8; its structure was refined toR 3.8,wR 4.3% using 96 observed (F > 3[F]) reflections (MoK). Cesstibtantite from the Tanco pegmatite hasa 10.496(1) Å, space groupFd3m, composition (Cs_0.22K_0.01)_0.23(Na_0.45Sb_0.39Pb_0.14· Ca_0.06Bi_0.02)_1.06(Ta_1.95Nb_0.05)₂(O_5.78[OH,F]_0.22)₆(OH,F)_0.55,Z 8; its structure was refined toR 3.9w R 3.7% using 104 observed reflections. Cesstibtantite differs from the normal pyrochlores in that it contains significant amounts of very large cations such as Cs. As these cations are too large (^VIII[r] > 1.60 Å) for the conventional [8]-coordinated A site, they occupy the [18]-coordinated site, which normally contains monovalent anions. Natural cesstibtantite samples are non-ideal in that both Cs and monovalent anions occur at the site; thus cesstibtantite is intermediate to thenormal pyrochlores (with only monovalent anions at the site) and theinverse pyrochlores (with only large cations at the site).

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Cesstibtantit—eine geologische Einfiihrung in die inversen Pyrochlore

Zusammenfassung Die Kristallstruktur von Cesstibtantit wurde auf der Basis von Diffraktometerdaten von Proben von Leshaia, Russland and dem Tanco Pegmatit, Manitoba, gelöst. Cesstibtantit aus dem Leshaia Pegmatit (Typlokalität) hat a 10.515(2) Å, RaumgruppeFd3m, die Zusammensetzung CS_0.31(Sb_0.57Na_0.31Pb_0.02Bi_0.01)_0.91(Ta_1.88Nb_0.12)₂· (O_5.69OH, F_0.31)₆(OH, F)_0.69 Z 8; die Struktur wurde aufR 3.8,wR 4.3% verfeinert unter Benützung von 96 beobachteten Reflexen. Cesstibtantit vom Tanco Pegmatit hat a 10.496(1) Å, RaumgruppeFd3m, die Zusammensetzung (Cs_0.22K_0.01)_0.23(Na_0.45· Sb_0.39Pb_0.14Ca_0.06Bi_0.02)_1.06(Ta_1.95Nb_0.05)₂(O_5.78OH,F_0.22)₆(OH,F)_0.55,Z 8; seine Struktur wurde aufR 3.9wR 3.7% auf der Basis von 104 beobachteten Rettexen verfeinert. Cesstibtantit unterscheidet sich von normalen Pyrochloren insofern, als er signifikante Mengen von sehr großen Kationen, wie z.B. Cs enthält. Da these Kationen zu groß sind (^VIII r 1.60 Å) für eine konventionelle [8]-koordinierteA Stelle, nehmen she die [18]-koordinierten Positionen ein, welche normalerweise monovalente Anionen enthalten. Natürliche Cesstibtantitproben sind nicht ideal insofern als sowohl Cs als auch monovalente Anionen in der Position vorkommen. Somit ist Cesstibtantit intermediär zu den normalen Pyrochloren (mit nur monovalenten Anionen auf der Position) and den inversen Pyrochloren (mit ausschließlichen großen Kationen an der Position).

     

Origin of the hydrocarbon component of carbonaceous chondrites: the star-meteorite connection

We report the results of an experiment that produced a residue which closely matches the hydrocarbon component of the Murchison carbonaceous chondrite. This experiment suggests that the parent material of the meteoritic component originated as polycyclic aromatic hydrocarbon species in carbon stars during their later stages of evolution. The experiments also indicate that the pathway from those formation sites to eventual incorporation into the meteorite parent body involved hydrogenation in a plasma in the solar nebula or in H II regions prior to the solar nebula. This model is consistent with what is known about the meteoritic hydrocarbon component including deuterium abundance, the observation of cosmic infrared emission bands best attributed to polycyclic aromatic hydrocarbon molecules, and the inherent stability of these molecules that allows their formation in stars and subsequent survival in the interstellar medium.     

Radiation pressure effects in the oscillations of compressible rotating homogeneous spheroids

Earlier models of compressible, rotating, and homogeneous ellipsoids with gas pressure are generalized to include the presence of radiation pressure. Under the assumptions of a linear velocity field of the fluid and a bounded ellipsoidal surface, the dynamical behaviour of these models can be described by ordinary differential equations. These equations are used to study the finite oscillations of massive radiative models with masses 10M and 30M in which the effects of radiation pressure are expected to be important.Models with two different degrees of equilibrium are chosen: an equilibrium (i.e., dynamically stable) model with an initial asymmetric inward velocity, and a nonequilibrium model with a nonequilibrium central temperature and which falls inwards from rest. For each of these two degrees of equilibrium, two initial configurations are considered: rotating spheroidal and nonrotating spherical models.From the numerical integration of the differential equations for these models, we obtain the time evolution of their principal semi-diametersa ₁ anda ₃, and of their central temperatures, which are graphically displayed by making plots of the trajectories in the (a ₁,a ₃) phase space, and of botha ₁ and the total central pressureP _c against time.It is found that in all the equilibrium radiative models (in which radiation pressure is taken into account), the periods of the oscillations of botha ₁ andP _c are longer than those of the corresponding nonradiative models, while the reverse is true for the nonequilibrium radiative models. The envelopes of thea ₁ oscillations of the equilibrium radiative models also have much longer periods; this result also holds for the nonequilibrium models whenever the envelope is well defined. Further, as compared to the nonradiative models, almost all the radiative models collapse to smaller volumes before rebouncing, with the more massive model undergoing a larger collapse and attaining a correspondingly larger peakP _c.When the mass is increased, the dynamical behavior of the radiative model generally becomes more nonperiodic. The ratio of the central radiation pressure to the central gas pressure, which is small for low mass models, increases with mass, and at the center of the more massive model, the radiation pressure can be comparable in magnitude to the gas pressure. In all the radiative models, the average periods as well as the average amplitudes of both thea ₁ andP _c oscillations also increase with mass.When either rotation or radiation pressure effects or both are included in the equilibrium nonradiative model, the period of the envelope of thea ₁ oscillations is increased. The presence of rotation in the equilibrium radiative model, however, decreases this period.Some astrophysical implications of this work are briefly discussed.     

Compressibility and crystal structure of sillimanite, Al2SiO5, at high pressure

The unit-cell dimensions and crystal structure of sillimanite at various pressures up to 5.29 GPa have been refined from single-crystal X-ray diffraction data. As pressure increases, a and b decrease linearly, whereas c decreases nonlinearly with a slightly positive curvature. The axial compression ratios at room pressure are β_a:β_b:β_c=1.22:1.63:1.00. Sillimanite exhibits the least compressibility along c, but the least thermal expansivity along a (Skinner et al. 1961; Winter and Ghose 1979). The bulk modulus of sillimanite is 171(1) GPa with K′=4 (3), larger than that of andalusite (151 GPa), but smaller than that of kyanite (193 GPa). The bulk moduli of the [Al1O₆], [Al2O₄], and [SiO₄] polyhedra are 162(8), 269(33), and 367(89) GPa, respectively. Comparison of high-pressure data for Al₂SiO₅ polymorphs reveals that the [SiO₄] tetrahedra are the most rigid units in all these polymorphic structures, whereas the [AlO₆] octahedra are most compressible. Furthermore, [AlO₆] octahedral compressibilities decrease from kyanite to sillimanite, to andalusite, the same order as their bulk moduli, suggesting that [AlO₆] octahedra control the compression of the Al₂SiO₅ polymorphs. The compression of the [Al1O₆] octahedron in sillimanite is anisotropic with the longest Al1-OD bond shortening by ～1.9% between room pressure and 5.29 GPa and the shortest Al1-OB bond by only 0.3%. The compression anisotropy of sillimanite is primarily a consequence of its topological anisotropy, coupled with the compression anisotropy of the Al-O bonds within the [Al1O₆] octahedron.     

Crystallization processes in an artificial magma: variations in crystal shape,growth rate and composition with melt cooling history

A large (4.8 m³, 1.3x10⁷ g) artificial mafic melt with a bulk composition similar to that of a basalt (but with a high CaO content of 17 wt%) was generated during a demonstration of in situ vitrification and was allowed to cool naturally. During the melting process, convection was vigorous, resulting in a chemically and thermally homogeneous melt body. Once heating was complete, the cooling rate was rapid with the temperature dropping from 1500°C to 500°C in 6 days within the interior of the 3 m diameter, 1.5 m thick body. A 20 h period of constant temperature (1140°C) observed during colling was the result of latent heat released by widespread crystallization. The final crystalline assemblage consists of diopsidic to hedenbergitic pyroxene and anorthitic feldspar, with a subordinate amount of potassic feldspar, plus a small amount of evolved glass. The compositions and proportions of phases agree well with those predicted by the MELTS thermodynamic model. Thermal and textural evidence suggest that convection within the melt ceased coincident with formation of the first crystals. Textural investigation of core samples reveals large (up to 1 cm in length) acicular diopsidic pyroxenes in a matrix of smaller feldspar and zoned pyroxene crystals (500 m in length). Crystal shape and pyroxene composition vary as a function of position within the solidified body, as a function of cooling rate. Both crystal size and degree of crystallinity are highest in the central, most slowly-cooled parts of the rock. Crystal shape is characterized by tabular, equilibrium-growth forms in the slowly-cooled areas, grading to highly skeletal, dendritic forms at the rapidly-cooled edges of the body. The pyroxene crystals are dominantly homogeneous diopside, but crystals are characterized by thin Fe-rich hedenbergitic rims. These rims were deposited when Mg in the melt was depleted by diopside growth, and melt temperature had cooled sufficiently to allow Fe-rich pyroxene growth. Crystal growth rates can be calculated based on thermal behavior of the melt, reinforced by thermodynamic modelling, and are determined to be between 10^-7 and 10^-8 cm/s in the central part of the melt. These estimates agree well with growth rates in natural systems with similar cooling rates. Pyroxene crystals that formed at a higher cooling rates are characterized by higher Al and lower Mg contents relative to tabular equilibrium crystalline forms, presumably as a result of disequilibrium melt compositions at the crystal-melt interface.New Mexico Bureau of Mines and Mineral Resources, New Mexico Institute of Mining and Technology, Socorro, NM 87801, USA     

Episode 49 of the Pu'u 'O'o-Kupaianaha eruption of Kilauea volcano-breakdown of a steady-state eruptive era

The Pu'u 'O'o-Kupaianaha eruption (1983-present) is the longest lived rift eruption of either Kilauea or neighboring Mauna Loa in recorded history. The initial fissure opening in January 1983 was followed by three years of episodic fire fountaining at the Pu'u 'O'o vent on Kilauea's east rift zone 19km from the summit (episodes 4–47). These spectacular events gave way in July 1986 to five and a half years of nearcontinuous, low-level effusion from the Kupaianaha vent, 3km to the cast (episode 48). A 49th episode began in November 1991 with the opening of a new fissure between Pu'u 'O'o and Kupaianaha. this three week long outburst heralded an era of more erratic eruptive behavior characterized by the shut down of Kupaianaha in February 1992 and subsequent intermittent eruption from vents on the west flank of Pu'u 'O'o (episodes 50 and 51). The events occurring over this period are due to progressive shrinkage of the rift-zone reservoir beneath the eruption site, and had limited impact on eruption temperatures and lava composition.     

A search for ultra-high energy counterparts to gamma-ray bursts

A small air shower array operating over many years has been used to search for ultra-high energy (UHE) gamma radiation ( 50 TeV) associated with gamma-ray bursts (GRBs) detected by the BATSE instrument on the Compton Gamma-Ray Observatory (CGRO). Upper limits for a one minute interval after each burst are presented for seven GRBs located with zenith angles < 20°. A 4.3 excess over background was observed between 10 and 20 minutes following the onset of a GRB on 11 May 1991. The confidence level that this is due to a real effect and not a background fluctuation is 99.8%. If this effect is real then cosmological models are excluded for this burst because of absorption of UHE gamma rays by the intergalactic radiation fields.     

Search for low energyν e,μ,τ andv e,μ,τ in coincidence with BATSE gamma ray bursts

A search for low energy neutrinos of all flavours in correlation with 553 ray bursts detected by BATSE aboard the Compton Observatory has been performed by the LSD (Liquid Scintillator Detector) neutrino telescope. No excess ofe,, orv _e,, candidate has been detected by LSD during the time interval in which BATSE detected the 90% of the photon flux for any of the GRBs analyzed. Upper limits on the neutrino fluxes are given in the paper.     

Magnetically-aided evolution of protoplanetary disks

We investigate the global evolution of a turbulent protoplanetary disk incorporating the effects of Maxwell stress due to a large-scale magnetic field permeating the disk. A magnetic field is produced continuously by an dynamo and the resultant Maxwell stress assists the viscous stress in p roviding the means for disk evolution. The most striking feature of magnetized disk evolution is the presence of the surface density bulge located in the magnetic gap, the region of the disk where the degree of ionization is too low to allow for coupli ng between the magnetic field and the gas. The bulge persists for a time of the order of 10⁵–10⁶ yr. The presence and persistence of the surface density bulge may have important implications for the process of planet formation and the overall characteristics of resultant planetary systems.Operated by USRA under contract No. NASW-4574 with NASA.     

Plasma processing of interstellar PAHs into solar system kerogen

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.