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NASA NTRS1993

Self diffusion of alkaline-Earth in Ca-Mg-aluminosilicate melts: Experimental improvements on the determination of the self-diffusion coefficients

Experimental studies of self-diffusion isotopes in silicate melts often have quite large uncertainties when comparing one study to another. We designed an experiment in order to improve the precision of the results by simultaneously studying several elements (Mg, Ca, Sr, Ba) during the same experiment thereby greatly reducing the relative experimental uncertainties. Results show that the uncertainties on the diffusion coefficients can be reduced to 10 percent, allowing a more reliable comparison of differences of self-diffusion coefficients of the elements. This type of experiment permits us to study precisely and simultaneously several elements with no restriction on any element. We also designed an experiment to investigate the possible effects of multicomponent diffusion during Mg self-diffusion experiments by comparing cases where the concentrations of the elements and the isotopic compositions are different. The results suggest that there are differences between the effective means of transport. This approach should allow us to investigate the importance of multicomponent diffusion in silicate melts.

Paillat, O.↗
NASA NTRS1993

Euhedral metallic-Fe-Ni grains in extraterrestrial samples

Metallic Fe-Ni is rare in terrestrial rocks, being largely restricted to serpentinized peridotites and volcanic rocks that assimilated carbonaceous material. In contrast, metallic Fe-Ni is nearly ubiquitous among extraterrestrial samples (i.e., meteorites, lunar rocks, and interplanetary dust particles). Anhedral grains are common. For example, in eucrites and lunar basalts, most of the metallic Fe-Ni occurs interstitially between silicate grains and thus tends to have irregular morphologies. In many porphyritic chondrules, metallic Fe-Ni and troilite form rounded blebs in the mesostasis because their precursors were immiscible droplets. In metamorphosed ordinary chondrites, metallic Fe-Ni and troilite form coarse anhedral grains. Some of the metallic Fe-Ni and troilite grains has also been mobilized and injected into fractures in adjacent silicate grains where local shock-reheating temperatures reached the Fe-FeS eutectic (988 C). In interplanetary dust particles metallic Fe-Ni most commonly occurs along with sulfide as spheroids and fragments. Euhedral metallic Fe-Ni grains are extremely rare. Several conditions must be met before such grains can form: (1) grain growth must occur at free surfaces, restricting euhedral metallic Fe-Ni grains to systems that are igneous or undergoing vapor-deposition; (2) the metal (+/-) sulfide assemblage must have an appropriate bulk composition so that taenite is the liquidus phase in igneous systems or the stable condensate phase in vapor-deposition systems; and (3) metallic Fe-Ni grains must remain underformed during subsequent compaction, thermal metamorphism, and shock. Because of these restrictions, the occurrence of euhedral metallic Fe-Ni grains in an object can potentially provide important petrogenetic information. Despite its rarity, euhedral metallic Fe-Ni occurs in a wide variety of extraterrestrial materials. Some of these materials formed in the solar nebula; others formed on parent body surfaces by meteoroid impacts.

Rubin, Alan E.↗
NASA NTRS1994

Absolute calibration and atmospheric versus mineralogic origin of absorption features in 2.0 to 2.5 micron Mars spectra obtained during 1993

We obtained new high resolution reflectance spectra of Mars during the 1993 opposition from Mauna Kea Observatory using the UKIRT CGS4 spectrometer. Fifty spectra of 1600-2000 km surface regions and a number of standard star spectra were obtained in the 2.04 to 2.44 micron wavelength region on 4 February 1993 UT. Near-simultaneous observations of bright standard stars were used to perform terrestrial atmospheric corrections and an absolute flux calibration. Using the known magnitude of the stars and assuming blackbody continuum behavior, the flux from Mars could be derived. A radiative transfer model and the HITRAN spectral line data base were used to compute atmospheric transmission spectra for Mars and the Earth in order to simulate the contributions of these atmospheres to our observed data. Also, we examined the ATMOS solar spectrum in the near-IR to try to identify absorption features in the spectrum of the Sun that could be misinterpreted as Mars features. Eleven absorption features were detected in our Mars spectra. Our data provide no conclusive identification of the mineralogy responsible for the absorption features we detected. However, examination of terrestrial spectral libraries and previous high spectral resolution mineral studies indicates that the most likely origin of these features is either CO3(sup 2-), HCO3(-), or HSO4(-) anions in framework silicates or possibly (Fe, Mg)-OH bonds in sheet silicates.

Bell, James F., III↗
NASA NTRS1994

On the possible role of elemental carbon in the formation of reduced chondrules

Recent experiments have been designed to produce chondrule textures via flash melting while simultaneously studying the nature of chondrule precursors. However, these experiments have only been concerned with silicate starting material. This is a preliminary report concerning what effects elemental carbon, when added to the silicate starting material, has on the origin of chondrules produced by flash melting.

Connolly, Harold C., Jr.↗
NASA NTRS1994

Inhomogeneous distribution of materials in lodranites-acapulcoites and IAB irons and their common formation processes

The two-dimensional chemical mapping analysis (CMA) techniques of EPMA and XRF were applied to a new polished thin section (PTS) of EET84302,28, Acapulco and a 5x3 cm slice of Caddo County to find heterogeneous regional distribution of low temperature fractions in the lodranite-acapulcoite groups and silicate inclusions in the IAB irons. A region richer in metal-plagioclase was found in EET84302,28 and Caddo County. The mineralogy of EET84302,28 is not much different from coarse-grained, metal-rich acapulcoite-like mineral assemblage in EET84302,19, which has chromite-orthopyroxene segregation. Nearly uniform Mg/Fe ratios of silicates modified by reduction at regional oxygen fugacity and large difference in modal abundances of minerals in this meteorite group can be explained by regional concentration of materials when the source materials were partly melted.

Takeda, Hiroshi↗
NASA NTRS1994

Hematite formed from pyroxene on Mars by meteoritic impact

In earlier work, we showed using Mossbauer data that the mineralogy of iron-bearing phases in impact melt rocks from Manicouagan Crater (Quebec, Canada) is to a first approximation hematite and pyroxene. The visible and near-IR reflectivity data for these impact melt rocks show a continuous trend in band position from approximately 850 to approximately 1000 nm, which corresponds to the positions for the hematite and pyroxene endmembers, respectively. The oxidation is thought to occur shortly after the impact when oxidizing vapors and/or solutions reacted with the impact melt which was below its solidus temperature but still relatively hot. The reflectance data have important implications for Mars because band positions which occur between approximately 850 and 1000 nm bands observed for Mars can be attributed to hematite-pyroxene assemblages and not necessarily to different ferric mineralogy. Because oxidation of impact melt rocks at Manicouagan is thought to occur subsolidus, precursors for the hematite include oxides such as magnetite and ilmenite and silicates such as pyroxene and olivine. To determine if the Manicouagan impact-melt rocks are related to each other by simple thermal subsolidus oxidation, we calcined in air a relatively unoxidized Manicouagan impact-melt rock (MAN-74-608A). Previous work has shown that np-Hm (nanophase hematite) particles can be derived by calcination of iron-bearing silicates.

Morris, Richard V.↗
NASA NTRS1994

Measurement of the decay rate of the SiH feature as a function of temperature

We have previously suggested that the SiH fundamental stretch could serve as a diagnostic indicator of the oxidation state of silicate surfaces exposed to the solar wind for prolonged periods. We have now measured the primary decay rate of SiH in vacuo as a function of temperature and find that the primary rate constant for the decay can be characterized by the following equation: k(min(exp -1)) approximately equals 0.186 exp(-9/RT) min(exp -1), where R = 2 x 10(exp -3) kcal deg(exp -1) mole(exp -1). This means that the half-life for the decay of the SiH feature at room temperature is approximately 20 yrs, whereas the half-life at a peak lunar regolith temperature of approximately 500K would be only approximately 20 days. At the somewhat lower temperature of approximately 400K the half-life for the decay is on the order of 200 days. The rate of loss of SiH as a function of temperature provides an upper limit to the quantity of H implanted by the solar wind which can be retained by a silicate grain in a planetary regolith. This will be discussed in more detail here.

Nuth, Joseph A., III↗
NASA NTRS1993

Solubilities of carbon dioxide and water in rhyolitic melt at 850 C and 750 bars

Concentrations of carbon dioxide and water dissolved in glasses quenched from rhyolitic melts equilibrated with H2O-CO2 fluids at 850 C and 750 bar were measured using IR spectroscopy; concentrations of H2O and CO2 in the quenched fluids were measured manometrically. The mole fraction of CO2 in the quenched fluid ranged from 0.06 to 0.91. Concentrations of CO2 in the coexisting rhyolitic melt increased from 23(+/-6) ppm for the sample equilibrated with the most CO2-poor fluid to 515(+/-16) ppm for that equilibrated with the most CO2-rich fluid. The water content of the melt varied from 0.51(+/-0.06) to 3.34(+/-0.08) wt pct. Our results show that concentrations of molecular CO2 and H2O in the glasses obey Henry's Law; the mole fractions of molecular CO2 and molecular H2O in the quenched melts are proportional to their fugacities in the coexisting vapor. CO2 contents of vapor-saturated melts are not enhanced by addition of water to CO2-rich vapor, contrary to previous reports for silicate melts at higher pressures. The Henrian behavior of CO2 and H2O at low pressure considerably simplifies modeling of the degassing of silicic magmas.

Blank, J. G.↗
NASA NTRS1994

What does the fine-scale petrography of IDPs reveal about grain formation and evolution in the early solar system?

The 'pyroxene' interplanetary dust particles (IDP's) may be the best samples for investigation of primordial grain-forming reactions because they appear to have experienced negligible post-accretional alteration. They are likely to continue to yield information about gas-to-solid condensation and other grain-forming reactions that may have occurred either in the solar nebular or presolar interstellar environments. An immediate challenge lies in understanding the nanometer-scale petrography of the ultrafine-grained aggregates in 'pyroxene' IDP's. Whether these aggregates contain components from diverse grain-forming environments may ultimately be answered by systematic petrographic studies using electron microscopes capable of high spatial resolution microanalysis. It may be more difficult to decipher evidence of grain formation and evolution in 'olivine' and 'layer silicate' IDP's because they appear to have experienced post-accretional alteration. Most of the studied 'olivine' IDPs have been subjected to heating and equilibration, perhaps during atmospheric entry, while the 'layer silicate' IDP's have experienced aqueous alteration.

Bradley, John↗
NASA NTRS1994

Chondrule remelting: Evidence from coarse-grained chondrule rims and compound chondrules

The meteorites that best preserve the nebular record are the type 3 ordinary (OC) and carbonaceous chondrites; their major components include chondrules and chondrule fragments, refractory and mafic inclusions, FeO-rich silicate matrix material. Many chondrules are surrounded by nms; these can be divided into two major types: (1) fine-grained rims, which are composed of matrix material; and (2) igneous or coarse-grained rims, which have igneous textures and larger, less-ferroan mafic silicate grains. Fine-grained rims surround most of the chondrules in the least-equilibrated type 3 ordinary and carbonaceous chondrites. They were most likely derived via collapse of clumps of nebular dust that accreted around coarse objects such as chondrules and inclusions. Coarse-grined or igneous rims surround approximately 10% of the chondrules in type 3 OC and approximately 50% of the chondrules in CV3 chondrites as well as some chondrule fragments and isolated mineral grains. They probably formed by partly melting finer-grained dust-rich precursors and admixed chondrule fragments.

Rubin, A. E.↗
NASA NTRS1994

Conference on Deep Earth and Planetary Volatiles

The following topics are covered in the presented papers: (1) rare gases systematics and mantle structure; (2) volatiles in the earth; (3) impact degassing of water and noble gases from silicates; (4) D/H ratios and H2O contents of mantle-derived amphibole megacrysts; (5) thermochemistry of dense hydrous magnesium silicates; (6) modeling of the effect of water on mantle rheology; (7) noble gas isotopes and halogens in volatile-rich inclusions in diamonds; (8) origin and loss of the volatiles of the terrestrial planets; (9) structure and the stability of hydrous minerals at high pressure; (10) recycling of volatiles at subduction zones and various other topics.

Source record↗
NASA NTRS1994

Structure and stability of hydrous minerals at high pressure

The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

Duffy, T. S.↗
NASA NTRS1995

The role of surface chemical analysis in a study to select replacement processes for TCA vapor degreasing

The role of surface-sensitive chemical analysis (ESCA, AES, and SIMS) in a study to select a process to replace 1, 1, 1-trichloroethane (TCA) vapor degreasing as a steel and aluminum bonding surface preparation method is described. The effort was primarily concerned with spray-in-air cleaning processes involving aqueous alkaline and semi-aqueous cleaners and a contamination sensitive epoxy-to-metal bondline. While all five cleaners tested produced bonding strength results equal to or better than those produced by vapor degreasing, the aqueous alkaline cleaners yielded results which were superior to those produced by the semi-aqueous cleaners. The main reason for the enhanced performance appears to be a silicate layer left behind by the aqueous alkaline cleaners. The silicate layer increases the polarity of the surface and enhances epoxy-to-metal bonding. On the other hand, one of the semi-aqueous cleaners left a nonpolar carbonaceous residue which appeared to have a negative effect on epoxy-to-metal bonding. Differences in cleaning efficiency between cleaners/processes were also identified. These differences in surface chemistry, which were sufficient to affect bonding, were not detected by conventional chemical analysis techniques.

Lesley, Michael W.↗
NASA NTRS1994

Self-organization of the earth's biosphere-geochemical or geophysiological?

We explore the implications of indicating the biosphere's self-organization by the trend over time of the net entropic flow from the Earth's surface, the actual physical boundary of virtually all biotic mass. This flow, derived from the radiative surface entropy budget, is approximately inversely related to the surface temperature when the solar incident flux remains constant. In the geophysiological ('gaian') interpretation, biospheric self-organization has increased with the progressive colonization of the continents and evolutionary developments in the land biota, as a result of surface cooling arising from biotic enhancement of weathering. The key site for this self-organization is at the interface between land and atmosphere, the soil, where carbon is sequestered by its reaction (as carbonic and organic acids) with calcium magnesium silicates. Along with disequilibrium (steady-state) levels of carbon dioxide in the atmosphere, the occurrence of differentiated soil is the critical material evidence for biospheric self-organization, whether it be geophysiological or geochemical (ie., purely result of inorganic reactions). The computed equilibrium levels of carbon dioxide and corresponding equilibrium temperatures in the past are dramatically different from the steady-state levels. With future solar luminosity increase, the biospheric capacity for climatic regulation will decrease, leading to the ending of self-organization some two billion years from now. The Earth's surface will then approach chemical equilibrium with respect to the carbonate-silicate cycle.

Schwartzman, David W.↗
NASA NTRS1994

Silica-merrihueite/roedderite-bearing chondrules and clasts in ordinary chondrites: New occurrences and possible origin

Merrihueite (K,Na)2(Fe,Mg)5Si12O30 (na less than 0.5, fe greater than 0.5, where na = Na/(Na + K), fe = Fe/(Fe + Mg) in atomic ratio) is a rare mineral described only in several chondrules and irregularly-shaped fragments in the Mezo-Madaras L3 chondrite (Dodd et al., 1965; Wood and Holmberg, 1994). Roedderite (Na,K)2(Mg,Fe)5Si12O30 (na greater than 0.5, fe less than 0.5) has been found only in enstatite chondrites and in the reduced, subchondritic silicate inclusions in IAB irons (Fuchs, 1966; Rambaldi et al., 1984; Olsen, 1967). We described silica-roedderite-bearing clasts in L/LL3.5 ALHA77011 and LL3.7 ALHA77278, a silica-roedderite-bearing chondrule in L3 Mezo-Madaras, and a silica-merrihueite-bearing chondrule in L/LL3.5 ALHA77115. The findings of merrihueite and roedderite in ALHA77011, ALHA77115, ALHA77278 and Mezo-Madaras fill the compositional gap betweeen previously described roedderite in enstatite chondrites and silicate inclusions in IAB irons and merrihueite in Mezo-Madaras, suggesting that there is a complete solid solution of roedderite and merrihueite in meteorites. We infer that the silica- and merrihueite/roedderite-bearing chondrules and clasts experienced a complex formational history including: (a) fractional condensation in the solar nebular that produced Si-rich and Al-poor precursors, (b) melting of fractionated nebular solids resulting in the formation of silica-pyroxene chondrules, (c) in some cases, fragmentation in the nebula or on a parent body, (d) reaction of silica with alkali-rich gas that formed merrihueite/roedderite on a parent body, (e) formation of fayalitic olivine and feerosilite-rich pyroxene due to reaction of silica with oxidized Fe on a parent body, and (f) minor thermal metamorphism, possibly generated by impacts.

Krot, Alexander N.↗
NASA NTRS1994

Properties of a B0 I stellar wind and interstellar grains derived from Ginga observations of the binary X-ray pulsar 4U 1538-52

From measurements of the X-ray eclipse phenomena of the binary X-ray pulsar 4U 1538-52, we derive properties of the stellar wind of its B0 I companion, QV Nor, and a constraint on models of interstellar grains. Estimates of the wind density as a function of the distance from the center of QV Nor are obtained from an analysis of the variation of X-ray attenuation during an eclipse egress. A Monte Carlo computation of the absorption and scattering of X-rays in the X-ray-ionized wind accounts for approximately two-thirds of the spectrum of X-rays with energies above 4.5 keV observed during the eclipse. Our upper limit on R(sub XV) is 0.06/mag, which implies that the X-ray scattering efficiency of interstellar dust is less than expected for solid grains with a size distribution of the form n(sub g)(a) approximately a(exp -3.5) in the range from 0.005 to 0.25 microns and composed of silicate (R(sub XV) = 0.22/mag) or a silicate-graphite mixture (R(sub XV) = 0.11/mag) as derived from the calculations of Martin & Rouleau (1991). This lends support to the idea (Mathis & Whiffen 1989) that interstellar grains are 'fluffy' aggregates with an average bulk density less than that of their constitutent particles. Such aggregates would have a smaller ratio of X-ray scattering efficiency to optical extinction efficiency compared with solid grains of the same material.

Clark, George W.↗
NASA NTRS1994

Partial melting of apatite-bearing charnockite, granulite, and diorite: Melt compositions, restite mineralogy, and petrologic implications

Melting experiments (P = 6.9 kbar, T = 850-950 deg C, NNO is less than fO2 is less than HM) were done on mafic to felsic charnockites, a dioritic gneiss, and a felsic garnet granulite, all common rock types in the Grenville basement of eastern North America. A graphite-bearing granulite gneiss did not melt. Water (H2O(+) = 0.60 to 2.0 wt %) is bound in low-grade, retrograde metamorphic minerals and is consumed during the earliest stages of melting. Most melts are water-undersaturated. Melt compositions range from metaluminous, silicic granodiorite (diorite starting composition) to peraluminous or weakly metaluminous granites (all others). In general, liquids become more feldspathic, less silicic, and less peraluminous and are enriched in FeO, MgO, and TiO2 with increasing temperature. Residual feldspar mineralogy controls the CaO, K2O, and Na2O contents of the partial melts and the behavior of these elements can be used, particularly if the degree of source melting can be ascertained, to infer some aspects of the feldspar mineralogy of the source. K-feldspar, a common restite phase in the charnockite and granulite (but not the diorite) should control the behavior of Ba and, possibly, Eu in these systems and yield signatures of these elements that can distinguish source regions and, in some cases, bulk versus melt assimilation. Apatite, a common restite phase, is enriched in rare earth elements (REE), especially middle REE. Retention of apatite in the restite will result in steep, light REE-enriched patterns for melts derived from the diorite and charnockites.

Beard, James S.↗
NASA NTRS1994

Nitrogen and xenon isotopic disequilibrium in Bachmut (L6) chondrule J2689 and matrix

Chondrule J2689, a large (8-mm) RP chondrule from Bachmut (L6) was previously found to be in disequilibrium with its host in a variety of features: (1) It has a fine-grained hornfelsic texture; (2) it contains low amounts of metal with a low-Ni taenite composition not found in the matrix; (3) the Ni/Co ratio of that metal is close to the solar ratio, which is equal to the bulk Ni/Co ratio (23) of the chondrule; (4) the bulk alkali content of the chondrule is high and the Na/K ratio is fractionated with respect to the average L chondrite ratio of 8; (5) Cr is depleted in spite of the high pyroxene content; (6) the siderophile elements are strongly depleted but are fractionated with their abundances increasing with volatility; and (7) the O isotopes of the chondrule and the host are out of equilibrium. However, the (Fe,Mg) silicates, feldspar, and chromite have chemical compositions indistinguishable from that of the host chondrite. We have studied a chip of the chondrite and of adjacent matrix by stepwise heating and by combustion in O for N and Xe isotopic abundances. (1) The chondrule preserved distinct bulk, metal, and O isotopic compositional features. It is therefore unlikely that the 'equilibration' of the major silicates Fe/Mg ratios could have taken place after accretion; (2) the chondrule was well equilibrated before break-up and exposure to cosmic rays; (3) two N signatures in the matrix also indicate that the matrix is not equilibrated; and (4) all data collected so far point toward the presence of unequilibrated Bachmut components. Very few reactions took place after accretion.

Kim, Y.↗