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At least 199 records · Page 11

Stimulated Mid-Infrared Luminescence Experiment: Contribution to the Study of Pre-Earthquake Phenomena and UV Absorption by Interstellar Dust

The work performed under this proposal is based on the experimentally supported observation - or inference - that a small fraction of the oxygen anions in silicate minerals in igneous and high-grade metamorphic rocks on Earth may not be in the usual 2- oxidation state, O(sup 2-), but in a higher oxidation state, as O(sup -). If this is true, the same would likely apply to the fine dust that fills the diffuse interstellar medium. An (sup -) in a matrix of O(sup 2-) represents a defect electron in the valence band, also known as positive hole or p-hole for short. When two O(sup -) combine, they undergo spin-pairing and form a positive hole pair, PHP. Chemically speaking a PHP is a peroxy bond. In an oxide matrix a peroxy bond takes the form of a peroxy anion, O2(sup 2-). In a silicate matrix it probably exists in the form of peroxy links between adjacent [SiO4] tetrahedral, O3Si00\SiO3. From a physics perspective a PHP is an electrically inactive point defect, which contains dormant electronic charge carriers. When the peroxy bond breaks, p-hole charge carriers are released. These p-holes are diffusively mobile and spread through the O 2p-dominated valence band of the otherwise insulating mineral matrix.

Freund, Friedemann↗

Cometary origin of carbon, nitrogen, and water on the earth

In this paper, two assumptions on the origin of the earth are substantiated: (1) that the earth accreted from fine hot degassed dust particles containing no volatiles; and (2) that, after the accretion was finished, all the volatiles of the biosphere, including the atmosphere and the oceans, were brought to the earth by cometary bombardment. A temperature of more than 1000 K is deduced at the time when the dust that was going to form the earth was separated from the gas phase. This implies grains of anhydrous silicates and of reduced iron, without either water, carbon, or any labile elements, which remained in gas phase; thus, the minor bodies could not produce atmosphere or oceans. The second assumption is based on the evidence that cometary nuclei are formed in the outer space, by accumulation of frosty particles containing large amounts of ice and volatile molecules. It is shown that the icy bodies which hit the earth are more than enough to explain the whole biosphere.

Delsemme, A. H.↗

The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

Danielson, Lisa R.↗

Partitioning of rare earth elements between hibonite and melt and implications for nebular condensation of the rare earth elements

The effect of oxygen fugacity on the partitioning of REEs between hibonite and silicate melt is investigated in hibonite-growth experiments at 1470 C. The experimental procedures and apparatus are described, and the results are presented in extensive tables and graphs and characterized in detail. The absolute activity coefficients in hibonite are estimated as 330 for La, 1200 for Eu(3+), and 24,000 for Yb. It is inferred that ideal solution behavior cannot be assumed when calculating REE condensation temperatures for (Ca, Al)-rich inclusions in carbonaceous chondrites.

Drake, Michael J.↗

Distribution of Alkalis (Na, Cs, Rb) Between Silicate and Sulfide: Implications for Planetary Volatile Depletion

The abundances of volatile elements in the Earth's mantle are correlated with their temperatures of condensation. This depletion can be due to either incomplete condensation of the elements during the nebula condensation or evaporation processes during planetary growth. Elements that have affinities with metals (siderophile) and sulfides (chalcophile) are additionally depleted due to their segregation into the core. Therefore, study of lithophile elements could be useful to isolate processes of volatilization and their effect on the abundance of the elements in the Earth's mantle. However, the correlation of these lithophile elements including alkali elements, with their temperatures of condensation shows a significant scatter, which is difficult to reconcile with a depletion by vaporization or incomplete condensation alone.

Boujibar, A.↗

Pressure regimes and core formation in the accreting earth

Recent work suggests that a large degree of melting is required to segregate metal from silicates, suggesting a connection with the formation of magma oceans. At low pressures metallic liquids do not wet silicate minerals, preventing the metal from aggregating into large masses that can sink. At high pressures, above 25 GPa, the dihedral angles of grains in contact with oxygen-rich metallic liquids may be reduced enough to allow percolation of metal, but this has not been confirmed. Physical models of core formation and accretion may therefore involve the formation of magma oceans and the segregation of metal at both high and low pressures. Models of core formation involving different pressure regimes are discussed as well as chemical evidence bearing on the models. Available geophysical data is ambiguous. The nature of the 670 km boundary (chemical difference or strictly phase change) between the upper and lower mantle is in doubt. There is some evidence that plumes are derived from the lower mantle, and seismic tomography strongly indicates that penetration of subducting oceanic crust into the lower mantle, but the tomography data also indicates that the 670 km discontinuity is a significant barrier to general mantle convection. The presence of the D' layer at the base of the lower mantle could be a reaction zone between the mantle and core indicating core-mantle disequilibrium, or D' layer could be subducted material. The abundance of the siderophile elements in the mantle could provide clues to the importance of high pressure processes in Earth, but partition coefficients at high pressures are only beginning to be measured.

Newsom, H. E.↗

Inferences from other bodies for the earth's composition and evolution

Properties of the earth are considered in the light of the earth's presumed status as an end member of the class of predominantly silicate solar system bodies. Bulk composition data for the inner planets are presented and processes which may account for compositional variations are discussed. Problems posed by Viking findings on Mars and Pioneer findings on Venus are mentioned. Prominent evolutionary patterns of the inner planets are discussed, including the inverse correlation of lithospheric and crustal thickness with planetary size, and the thermotectonics of Venus, Mars, and earth are compared.

Kaula, W. M.↗

Greenhouse warming by minor gases on early Mars

The early atmospheres of Earth and Mars were non-oxidizing mixtures likely derived from volcanic outgassing of a silicate mantle, with some fraction of the volatiles also contributed by impacting comets and meteorites. Here the authors investigate the potential of minor atmospheric constituents produced by ultraviolet and auroral chemistry to contribute to the thermal opacity of early Earth and Mars atmospheres. Using a very simple two-stream thermal opacity model, the authors show that HCN at 10 parts per million (ppm) and N2O at 100 ppm can each block radiation in thermal infrared windows sufficiently to increase the surface temperature by 7 K separately, or 14 K together. Small quantities of other species are also produced in such experiments. Some of these have especially complex infrared spectra and should be further investigated for their potential to help close windows in the CO2 + H2O infrared transmission. Enhancement of greenhouse warming by minor atmospheric species different from those present in today's atmosphere may have played important roles in the climate of early Earth and Mars.

Heinrich, M. N.↗

Bulk compositions of the moon and earth, estimated from meteorites

The present work calculates the bulk compositions of the earth and moon, based on the assumption that these planets formed by the same processes as chondrites. In terms of the model presented, the earth contains 9.2% early condensate and 1.5% carbonaceous, volatile-rich silicate. For the moon these percentages are 30.1 and 0.04, respectively. When lunar and terrestrial basalt data are normalized to these model compositions, element abundance patterns based on the percentages (assuming that each component carried its cosmic complement of trace elements) demonstrate the essential identity of igneous processes on both celestial bodies.

Ganapathy, R.↗

Calderas - A planetary perspective

It is pointed out that volcanoes are morphological expressions of magma composition, eruption processes, and regional tectonics. Thus, the lack of unambiguous silicic volcanoes and pyroclastic flows on Mars implies that compared to earth, its crust is deficient in volatiles and/or the planet lacks a thick granitic crust. Such deductions are examples of comparative planetology, in which knowledge of landforms and processes on one planet are utilized to interpret features and histories on others. In the present study calderas are considered in a comparative planetology context to provide perspective for students who investigate only terrestrial calderas and to search for broadscale relationships between calderas and planetary characteristics. Attention is given to terrestrial calderas, lunar calderas, Martian calderas, calderas on Jupiter's satellite Io, and calderas on Venus. A planetary definition of calderas is proposed.

Wood, C. A.↗

Lunar Dust and Lunar Simulant Activation and Monitoring

Prior to returning to the moon, understanding the effects of lunar dust on both human physiology and mechanical equipment is a pressing concern, as problems related to lunar dust during the Apollo missions have been well documented (J.R. Gaier, The Effects of Lunar Dust on EVA Systems During the Apollo Missions. 2005, NASA-Glenn Research Center. p. 65). While efforts were made to remove the dust before reentering the lunar module, via brushing of the suits or vacuuming, a significant amount of dust was returned to the spacecraft, causing various problems. For instance, astronaut Harrison Schmitt complained of hay fever effects caused by the dust, and the abrasive nature of the material was found to cause problems with various joints and seals of the spacecraft and suits. It is clear that, in order to avoid potential health and performance problems while on the lunar surface, the reactive properties of lunar dust must be quenched. It is likely that soil on the lunar surface is in an activated form, i.e. capable of producing oxygen-based radicals in a humidified air environment, due to constant exposure to meteorite impacts, UV radiation, and elements of the solar wind. An activated silica surface serves as a good example. An oxygen-based radical species arises from the breaking of Si-OSi bonds. This system is comparable to that expected for the lunar dust system due to the large amounts of agglutinic glass and silicate vapor deposits present in lunar soil. Unfortunately, exposure to the Earth s atmosphere has passivated the active species on lunar dust, leading to efforts to reactivate the dust in order to understand the true effects that will be experienced by astronauts and equipment on the moon. Electron spin resonance (ESR) spectroscopy is commonly used for the study of radical species, and has been used previously to study silicon- and oxygen-based radicals, as well as the hydroxyl radicals produced by these species in solution (V. Vallyathan, et al., Am. Rev. Respir. Dis. 138 (1988) 1213-1219). The size and cost of these instruments makes them unattractive for the monitoring of lunar dust activity. A more suitable technique is based on the change in fluorescence of a molecule upon reaction with a hydroxyl radical (or other radical species). Fluorescence instruments are much less costly and bulky than ESR spectrometers, and small fluorescence sensors for space missions have already been developed (F. Gao, et al., J. Biomed. Opt. 10 (2005) 054005). For the current fluorescence studies, the terephthalate molecule has been chosen for monitoring the production of hydroxyl radicals in solution. As shown in Scheme 1, the reaction between the non-fluorescent terephthalate molecule and a hydroxyl radical produces the highly-fluorescent 2-hydroxyterephthalate molecule.

Wallace, W. T.↗

Sulfur in Earth's Mantle and Its Behavior During Core Formation

The density of Earth's outer core requires that about 5-10% of the outer core be composed of elements lighter than Fe-Ni; proposed choices for the "light element" component of Earth's core include H, C, O, Si, S, and combinations of these elements [e.g. 1]. Though samples of Earth's core are not available, mantle samples contain elemental signatures left behind from the formation of Earth's core. The abundances of siderophile (metal-loving) elements in Earth's mantle have been used to gain insight into the early accretion and differentiation history of Earth, the process by which the core and mantle formed, and the composition of the core [e.g. 2-4]. Similarly, the abundance of potential light elements in Earth's mantle could also provide constraints on Earth's evolution and core composition. The S abundance in Earth's mantle is 250 ( 50) ppm [5]. It has been suggested that 250 ppm S is too high to be due to equilibrium core formation in a high pressure, high temperature magma ocean on early Earth and that the addition of S to the mantle from the subsequent accretion of a late veneer is consequently required [6]. However, this earlier work of Li and Agee [6] did not parameterize the metalsilicate partitioning behavior of S as a function of thermodynamic variables, limiting the different pressure and temperature conditions during core formation that could be explored. Here, the question of explaining the mantle abundance of S is revisited, through parameterizing existing metal-silicate partitioning data for S and applying the parameterization to core formation in Earth.

Chabot, Nancy L.↗

Thermochemistry of Calcium-Magnesium-Aluminum-Silicate (CMAS) and Components of Advanced Thermal and Environmental Barrier Coating Systems

There is increasing interest in the degradation mechanism studies of thermal and environmental barrier coatings (TEBCs) of gas turbines by molten CaO-MgO-Al(exp. 2)O(exp. 3)-SiO(exp. 2) CMAS). CMAS minerals are usually referred as silicon-containing sand dust and volcano ash materials that are carried by the intake air into gas turbines, e.g. in aircraft engines, and their deposits often react at high temperatures (greater than 1200 degrees C) with the engine turbine coating systems and components. The high temperature reactions causes degradation and accelerated failure of the static and rotating components of the turbine engines. We discuss some results of the reactions between the CMAS and Rare-Earth (RE = Y, Yb, Dy, Gd, Nd and Sm) - oxide stabilized ZrO(exp. 2) or HfO(exp. 2) systems, and the stability of the resulting oxides and silicates. Plasma sprayed hollow tube samples (outside diameter = 4.7 mm, wall thickness = 0.76 mm and = 26 mm height) were half filled with CMAS powder, wrapped and sealed with platinum foil, and heat treated at 1310 degrees C for 5h. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, and cross-section electron microscopy analysis and energy dispersive X-ray spectroscopy. It was found that CMAS penetrated the samples at the grain boundaries and dissolved the TEBC materials to form silicate phases containing the rare-earth elements. Furthermore, it was found that apatite crystalline phases were formed in the samples with total rare-earth content higher than 12 mol% in the reaction zone for the ZrO(exp. 2) system. In general, samples with the nominal compositions (30YSZ), HfO(exp. 2)-7Dy(exp. 2)O(exp. 2) and ZrO(exp. 2)-9.5Y(exp. 2)O(exp. 3)-2.25Gd(exp. 2)O(exp. 3)-2.25Yb(exp. 2)O(exp. 3) exhibited lower reactivity or more resistance to CMAS than the other coating compositions of this work.

degradation↗

Multi-Anvil Experimentation Applied to Planetary Differentiation

Planets undergo differentiation that includes segregation of metal from silicate at high temperatures and pressures ranging from deep planetary core pressures (>300 GPa for Earth)to very shallow conditions of asteroids (<100 MPa).The multi-anvil solid media apparatus accesses the middle part of this range from 3 to 30 GPa –pressure relevant to the interior of Mercury, Venus, Earth, Earth’s Moon, and Mars. Early planets are thought to have experienced high temperatures from a combination of heat sources including radioactive decay, gravitational and accretional heating, and impact processes. These heating events led to melting of mantles and cores, thus requiring an understanding of solid-liquid equilibria in metal-silicate systems. In 2006 we established a multi-anvil facility at NASA-JSC combining an 880 ton press and a Kawai/Walker type module from Rockland Research. Our high PT work has been greatly facilitated by use of the COMPRES multi-anvil assemblies (1). Our recent work has included studies of element partitioning between liquid metal and liquid silicate(e.g., 2), as well as between minerals and melts(e.g., 3), both of which have led to better constraints on the timing and conditions of planetary differentiation(e.g. 4). Several examples involving sustained efforts will be summarized below and for the presentation. The distribution of siderophile (iron-loving) elements between core and mantle is controlled by metal-silicate equilibrium across a wide range of pressures. Therefore, experimentation across this pressure range helps to calibrate elemental partitioning models that can be applied to planets, and used to predict mantle chemistry and composition during planetary differentiation. Our studies have focused on a wide range of siderophile elements (refractory Ni, Co, W, Mo; volatile P, Ga, Cu, Sn, Sb; highly siderophile Au, Pd) that have constrained partitioning, valence, and isotopic fractionation, and applied to Earth, Moon, and Mars. When molten mantles (magma oceans) cool enough to initiate crystallization, the solids precipitate at depth and in large planets this involves high pressure phases like garnet, majorite, akimotoite, and ringwoodite. As these solids precipitate they can segregate from liquid by density contrasts, thus causing elemental fractionation which can be used to decipher timing of differentiation. Mineral/melt and metal/silicate equilibria in our lab have helped to better understand high pressure fractionation of isotopic parent/daughter pairs Hf/W, Mn/Cr, Pd/Ag, Pt/Os, Re/Os, and U/Pb, and their application to Earth, Moon and Mars. There remains great potential for multi-anvil experimentation to shed light on many pressure–dependent aspects of planetary evolution such as core formation, high pressure phase equilibria, redox equilibria, and volatile evolution and storage. References1. Leinenweber, K., et al.(2012) American Mineralogist,97, 353–368. 2.Righter, K., et al.(2020) Geochem. Persp. Lett.15, 1-6.3. Righter, K., et al.(2020) Met. Planet. Sci 55, 2741-2757.4. Righter, K., et al.(2020)Earth and Planetary Science Letters,552, 116590.

pressure↗

Viscosity of lunar lavas

Synthetic silicate liquid viscosity with lunar rock composition compared with volcanic rock on earth

Mcbirney, A. R.↗

Origin of the moon from a circumterrestrial disk

The paper reveals the possibility that the moon could have formed from the long-term evolution of a circumterrestrial disk emplaced during the earth's final stages of formation. A model is presented which emphasizes silicate enrichment (or iron depletion) of lunar material within the disk. This model depends on the late-stage planetesimal population being dominated by small bodies.

Weidenschilling, S. J.↗

Thermal Expansion Coefficients of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 Apatite-type Silicates

High temperature X-ray diffraction (XRD) scans of Y2Si2O7 and Yb2Si2O7 reactions with calcium-magnesium-aluminosilicates (CMAS) were utilized to determine thermal expansion coefficients (CTEs) of Ca2Y8(SiO4)6O2 and Ca2Yb8(SiO4)6O2 apatite materials. In order to validate these measurements, the CTEs of Y2Si2O7, Yb2Si2O7 and SiO2 were also determined from the same scans. The directional CTEs for γ-Y2Si2O7 were determined to be αa=5.84×10-6/K, αb=6.81×10-6/K and αc=0.81×10-6/K, and β-Yb2Si2O7 was determined to have values of αa=6.89×10-6/K, αb=4.81×10-6/K and αc=2.78×10-6/K. The average CTEs of γ-Y2Si2O7 and β-Yb2Si2O7 were determined to be 4.5×10-6/K and 4.7×10-6/K, respectively, which agreed with previous analyses. Ca2Y8(SiO4)6O2 exhibited directional CTEs of αa=9.36×10-6/K and αc=7.95×10-6/K (averaged between two sets of data), whereas Ca2Yb8(SiO4)6O2 had values that were very similar (αa=9.63×10-6/K, αc=7.45×10-6/K). Both results for the Ca2RE8(SiO4)6O2 apatites correlated well with the limited data on apatite-type silicates available in literature.

rare earth↗