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At least 199 records · Page 11

Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

Righter, K.↗

Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

"Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston-cylinder experiments at 1 GPa between 950 and 1700 C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to ~1440 C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO2~40-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above approx.1440 C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earth s subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

Martin, A. M.↗

Composition Changes After the "Halloween" Solar Proton Event: The High-Energy Particle Precipitation in the Atmosphere (HEPPA) Model Versus MIPAS Data Intercomparison Study

We have compared composition changes of NO, NO2, H2O2,O3, N2O, HNO3 , N2O5, HNO4, ClO, HOCl, and ClONO2 as observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat in the aftermath of the "Halloween" solar proton event (SPE) in October/November 2003 at 25-0.01 hPa in the Northern hemisphere (40-90 N) and simulations performed by the following atmospheric models: the Bremen 2D model (B2dM) and Bremen 3D Chemical Transport Model (B3dCTM), the Central Aerological Observatory (CAO) model, FinROSE, the Hamburg Model of the Neutral and Ionized Atmosphere (HAMMONIA), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA), the ECHAM5/MESSY Atmospheric Chemistry (EMAC) model, the modeling tool for SO1ar Climate Ozone Links studies (SOCOL and SOCOLi), and the Whole Atmosphere Community Climate Model (WACCM4). The large number of participating models allowed for an evaluation of the overall ability of atmospheric models to reproduce observed atmospheric perturbations generated by SPEs, particularly with respect to NOS, and ozone changes. We have further assessed the meteorological conditions and their implications on the chemical response to the SPE in both the models and observations by comparing temperature and tracer (CH4 and CO) fields. Simulated SPE-induced ozone losses agree on average within 5% with the observations. Simulated NO(y) enhancements around 1 hPa, however, are typically 30% higher than indicated by the observations which can be partly attributed to an overestimation of simulated electron-induced ionization. The analysis of the observed and modeled NO(y) partitioning in the aftermath of the SPE has demonstrated the need to implement additional ion chemistry (HNO3 formation via ion-ion recombination and water cluster ions) into the chemical schemes. An overestimation of observed H2O2 enhancements by all models hints at an underestimation of the OH/HO2 ratio in the upper polar stratosphere during the SPE. The analysis of chlorine species perturbations has shown that the encountered differences between models and observations, particularly the underestimation of observed ClONO2 enhancements, are related to a smaller availability of ClO in the polar night region already before the SPE. In general, the intercomparison has demonstrated that differences in the meteorology and/or initial state of the atmosphere in the simulations causes a relevant variability of the model results, even on a short timescale of only a few days.

Funke, B.↗

Thermal and Evolved Gas Analysis of "Nanophase" Carbonates: Implications for Thermal and Evolved Gas Analysis on Mars Missions

Data collected by the Mars Phoenix Lander's Thermal and Evolved Gas Analyzer (TEGA) suggested the presence of calcium-rich carbonates as indicated by a high temperature CO2 release while a low temperature (approx.400-680 C) CO2 release suggested possible Mg- and/or Fe-carbonates [1,2]. Interpretations of the data collected by Mars remote instruments is done by comparing the mission data to a database on the thermal properties of well-characterized Martian analog materials collected under reduced and Earth ambient pressures [3,4]. We are proposing that "nano-phase" carbonates may also be contributing to the low temperature CO2 release. The objectives of this paper is to (1) characterize the thermal and evolved gas proper-ties of carbonates of varying particle size, (2) evaluate the CO2 releases from CO2 treated CaO samples and (3) examine the secondary CO2 release from reheated calcite of varying particle size.

Lauer, Howard V., Jr.↗

Synthesis of Multiwall Carbon Nanotubes by Inductive Heating CCVD

The CCVD syntheses of MWCNTs from acetylene on Fe:Co:CaCO 3 and Fe:Co:CaO were performed using two different methods of heating: outer furnace and inductive heating. The comparative analysis of the MWCNTs obtained by the two methods show that the tubes grown in inductive heating have smaller diameters (5-25 nm), with fewer walls and aspect ratio of the order of hundreds. The ratio of outer to inner diameter (od/id) is ranging between 2 and 2.5. Inductively assisted CCVD is a very attractive method because of the major advantages that it presents, like low energetic consumption, thinner, well crystallized and more uniform tubes.

Biris, A. R.↗

Analysis of Effluent Gases During the CCVD Growth of Multi Wall Carbon Nanotubes from Acetylene

Catalytic chemical vapor deposition was used to grow multi-walled carbon nanotubes on a Fe:Co:CaCO3 catalyst from acetylene. The influent and effluent gases were analyzed by gas chromatography and mass spectrometry at different time intervals during the nanotubes growth process in order to better understand and optimize the overall reaction. A large number of byproducts were identified and it was found that the number and the level for some of the carbon byproducts significantly increased over time. The CaCO3 catalytic support thermally decomposed into CaO and CO2 resulting in a mixture of two catalysts for growing the nanotubes, which were found to have outer diameters belonging to two main groups 8 to 35 nm and 40 to 60 nm, respectively.

Schmitt, T. C.↗

Complex Formation History of Highly Evolved Basaltic Shergottite, Zagami

Zagami, a basaltic shergottite, contains several kinds of lithologies such as Normal Zagami consisting of Fine-grained (FG) and Coarse-grained (CG), Dark Mottled lithology (DML), and Olivine-rich late-stage melt pocket (DN). Treiman and Sutton concluded that Zagami (Normal Zagami) is a fractional crystallization product from a single magma. It has been suggested that there were two igneous stages (deep magma chamber and shallow magma chamber or surface lava flow) on the basis of chemical zoning features of pyroxenes which have homogeneous Mg-rich cores and FeO, CaO zoning at the rims. Nyquist et al. reported that FG has a different initial Sr isotopic ratio than CG and DML, and suggested the possibility of magma mixing on Mars. Here we report new results of petrology and mineralogy for DML and the Olivine-rich lithology (we do not use DN here), the most evolved lithology in this rock, to understand the relationship among lithologies and reveal Zagami s formation history

Niihara, T.↗

Nanophase Carbonates on Mars: Implications for Carbonate Formation and Habitability

Despite having an atmosphere composed primarily of CO2 and evidence for abundant water in the past, carbonate minerals have only been discovered in small amounts in martian dust [1], in outcrops of very limited extent [2, 3], in soils in the Northern Plains (the landing site of the 2007 Phoenix Mars Scout Mission) [4] and may have recently been detected in aeolian material and drilled and powdered sedimentary rock in Gale Crater (the Mars Science Laboratory [MSL] landing site) [5]. Thermal analysis of martian soils by instruments on Phoenix and MSL has demonstrated a release of CO2 at temperatures as low as 250-300 degC, much lower than the traditional decomposition temperatures of calcium or magnesium carbonates. Thermal decomposition temperature can depend on a number of factors such as instrument pressure and ramp rate, and sample particle size [6]. However, if the CO2 released at low temperatures is from carbonates, small particle size is the only effect that could have such a large impact on decomposition temperature, implying the presence of extremely fine-grained (i.e., "nanophase" or clay-sized) carbonates. We hypothesize that this lower temperature release is the signature of small particle-sized (clay-sized) carbonates formed by the weathering of primary minerals in dust or soils through interactions with atmospheric water and carbon dioxide and that this process may persist under current martian conditions. Preliminary work has shown that clay-sized carbonate grains can decompose at much lower temperatures than previously thought. The first work took carbonate, decomposed it to CaO, then flowed CO2 over these samples held at temperatures >100 degC to reform carbonates. Thermal analysis confirmed that carbonates were indeed formed and transmission electron microsopy was used to determine crystal sized were on the order of 10 nm. The next step used minerals such as diopside and wollastonite that were sealed in a glass tube with a CO2 and H2O source. After reacting these materials for a number of hours, thermal analysis demonstrated the formations of carbonates that decomposed at temperatures as low as 500 degC [7]. Further work is underway to carry out the weathering process under more Mars-like conditions (low pressure and low temperature) to determine if the carbonate decomposition temperature can be shifted to even lower temperatures, consistent with what has been detected by thermal analysis instruments on Mars.

Archer, P. Douglas, Jr.↗

Properties of Desert Sand and CMAS Glass

As-received desert sand from a Middle East country has been characterized for its phase composition and thermal stability. X-ray diffraction analysis showed the presence of quartz (SiO2), calcite (CaCO3), gypsum (CaSO4.2H2O), and NaAlSi3O8 phases in as-received desert sand and showed weight loss of approx. 35 percent due to decomposition of CaCO3 and CaSO4.2H2O when heated to 1400 C. A batch of as-received desert sand was melted into calcium magnesium aluminosilicate (CMAS) glass at approx. 1500 C. From inductively coupled plasma-atomic emission spectrometry, chemical composition of the CMAS glass was analyzed to be 27.8CaO-4MgO-5Al2O3-61.6SiO2-0.6Fe2O3-1K2O (mole percent). Various physical, thermal and mechanical properties of the glass have been evaluated. Bulk density of CMAS glass was 2.69 g/cc, Young's modulus 92 GPa, Shear modulus 36 GPa, Poisson's ratio 0.28, dilatometric glass transition temperature (T (sub g)) 706 C, softening point (T (sub d)) 764 C, Vickers microhardness 6.3 +/- 0.4 GPa, indentation fracture toughness 0.75 +/- 0.15 MPa.m (sup 1/2), and coefficient of thermal expansion (CTE) 9.8 x 10 (exp -6)/degC in the temperature range 25 to 700 C. Temperature dependence of viscosity has also been estimated from various reference points of the CMAS glass using the Vogel-Fulcher-Tamman (VFT) equation. The glass remained amorphous after heat treating at 850 C for 10 hr but crystallized into CaSiO3 and Ca-Mg-Al silicate phases at 900 C or higher temperatures. Crystallization kinetics of the CMAS glass has also been investigated by differential thermal analysis (DTA). Activation energies for the crystallization of two different phases in the glass were calculated to be 403 and 483 kJ/mol, respectively.

Desert sand↗

Impact History on Vesta: Petrographic, Compositional and Future Chronological Studies of Melt Clasts in Howardites

Howardite meteorites are polymict breccias composed mainly of eucritic and diogenitic material that likely originate from the surface of the Asteroid 4 Vesta. They can be separated into two subtypes: Regolithic, which represent the lithified remains of the active vestan regolith; Fragmental, which represent simpler polymict breccias. Amongst the regolithic features observed in the former, melt clasts are particularly striking for their appearance and compositional variability. They range from glassy spherules to finely crystalline (i.e., devitrified) clasts, and clasts containing only relict mineral grains to those containing only phenocrysts. Glasses can be separated into compositional sub-types including those with low FeO/MgO ratios (less than 5) -low alkali glasses, K-rich (K2O greater than 0.2 wt.%), Na-rich (Na2O greater than 0.6 wt.%) and CaO-rich, and those with high FeO/MgO ratios (greater than 10). There is also a distinction to be made between primary volcanic melt clasts and those produced by impacts. While suggested that a lack of chemical homogeneity among their studied melt clasts ruled out a primary volcanic origin, the low siderophile element contents observed in such clasts suggest less compositional influence from impactors than commonly assumed. Studying the chronology of the impact melt clasts in howardites can help us to better determine the timing of impact events on Vesta and the asteroid belt. In this research, we are launching an investigation into the petrology, composition (major/trace element and noble gas) and chronology of melt clasts in howardites. We have selected a set of howardites known to contain large quantities of melt clasts, and have begun the petrological and compositional studies of these materials. Once the melt clasts have been fully classified, we aim to perform chronological studies of individual clasts using both the Ar-40/Ar-39 and Pb-Pb chronometers, as well as determine the noble gas components present. Of particular note, the study will take advantage of the laser ablation techniques associated with the noble gas facilities at ASU, which will allow high-resolution, in-situ analysis of individual clasts. The broader aim of this work is to ascertain whether the impact flux in the region of the asteroid belt was similar to that on the Moon. Our understanding of impact events in the inner Solar System relies heavily on our analyses of lunar meteorites and returned samples, and there is currently some debate regarding whether there was a "Lunar Cataclysm" event around approx. 3.9 Ga, or the end of an epoch of "Late Heavy Bombardment" (LHB) at this time. New and more comprehensive constraints on howardite melt clast ages may help determine whether the asteroid belt experienced such a cataclysm or LHB.

Cartwright, J. A.↗

Gusev-Meridiani-Type Soil Component Dissolved in Some Shock Glasses in Shergottites

Modal analysis, based on APXS, MiniTES and Mossbauer results obtained at Gusev and Meridiani sites on Mars, indicates that Martian soils consist predominantly of igneous minerals such as olivine, pyroxene and feldspar (approximately70 - 80%), with the balance consisting of alteration minerals such as sulfates, silica and chlorides]. These studies also showed that soil alteration did not occur in-situ and igneous and alteration components are derived from different sources. Below, we analyse the chemical abundance data obtained from shock glasses in shergottites using mass balance mixing models. In these models, the two main end members used are (a) host rock chemical composition and (b) the GM soils average composition as the second component. Here, we consider the S-bearing phases as indicators of added alteration phases in the shock glasses and GM soils. Although the S-bearing phase in shock glasses occurs as micron sized sulfide blebs, we showed in earlier abstracts that sulfur was originally present as sulfate in impact glass-precursor materials and was subsequently reduced to sulfide during shock melting. This conclusion is based on results obtained from S-K XANES studies, Fe/S atomic ratios in sulfide blebs and 34S/32S isotopic measurements in these sulfide blebs. Additionally, sulfur in several EET79001 Lith. A glasses is found to correlate positively with Al2O3 and CaO (and negatively with FeO and MgO), suggesting the presence of Al- and Ca- sul-fate-bearing phases. The distribution of the 87Sr/86Sr iso-topic ratios determined in Lith. A glasses (,27 &,188 and,54) indicate that Martian soil gypsum and host rock material were mixed with each other in the glass precursors. In some vugs in Lith A glass,27 detected gypsum laths. Furthermore, the Martian regolith-de-rived component (where sulfur typically occurs as sul-fate) is identified in these glasses by determining neutron produced isotopic excesses/deficits in 80Kr and 149Sm isotopes. Moreover, the suggestion that the large amount of sulfur found in,507 was sourced from pyrrhotite in the host rock, would require that excessive quantities of host rock would need to be stripped of sulfur to make this sulfide-rich glass. These results provide ample evidence that S occurred as sulfate and was added to glass precursor materials prior to impact shock.

Ross, D. K.↗

Nanophase Carbonates on Mars: Does Evolved Gas Analysis of Nanophase Carbonates Reveal a Large Organic Carbon Budget in Near-Surface Martian Materials?

Evolved Gas Analysis (EGA), which involves heating a sample and monitoring the gases released, has been performed on Mars by the Viking gas chromatography/mass spectrometry instruments, the Thermal and Evolved Gas Analyzer (TEGA) on the Phoenix lander, and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory. All of these instruments detected CO2 released during sample analysis at abundances of approx. 0.1 to 5 wt% assuming a carbonate source. The source of the CO2 can be constrained by evaluating the temperature of the gas release, a capability of both the TEGA and SAM instruments. The samples analyzed by SAM show that the majority of the CO2 is released below 400C, much lower than traditional carbonate decomposition temperatures which can be as low as 400C for some siderites, with magnesites and calcites decomposing at even higher temperatures. In addition to mineralogy, decomposition temperature can depend on particle size (among other factors). If carbonates formed on Mars under low temperature and relative humidity conditions, the resulting small particle size (nanophase) carbonates could have low decomposition temperatures. We have found that calcite can be synthesized by exposing CaO to water vapor and CO2 and that the resulting mineral has an EGA peak of approx. 550C for CO2, which is about 200C lower than for other calcites. Work is ongoing to produce Fe and Mg-bearing carbonates using the same process. Current results suggest that nanophase calcium carbonates cannot explain the CO2 released from martian samples. If the decomposition temperatures of Mg and Fe-bearing nanophase carbonates are not significantly lower than 400C, other candidate sources include oxalates and carboxylated organic molecules. If present, the abundance of organic carbon in these samples could be greater than 0.1 wt % (1000s of ppm), a signficant departure from the paradigm of the organic-poor Mars based on Viking results.

Archer, P. Douglas, Jr.↗

Cooling History and Redox State of NWA 8694 Chassignite: Comparison with Chassigny and NWA 2737

NWA 8694 is a new chassignite whose constituent minerals are more Fe-rich than those in the other known chassignites (Chassigny and NWA 2737), and may suggest a petrogenetic relationship to nakhlites. In this abstract we report mineralogy of NWA 8694 to infer its cooling rate and redox state, and discuss its thermal and shock history in comparison with other chassignites. NWA 8694 is a cumulate dunite of approximately 2 mm olivine with interstitial pyroxene and feldspar. Olivine is homogeneous (Fo(sub 55-56)), but Ca decreases at the approximately 50-100 micrometer rim (0.25-0.1 wt% CaO). Because the Ca-depleted rim is narrower than those in other chassignites (approximately 50 micrometer), NWA 8694 may have cooled slightly faster than the others (approximately 30 C/yr), but would be in the same order. Pyroxenes are low- and high-Ca pyroxenes, both exhibiting sub-micron exsolution textures (0.2-0.3 micrometer wide lamellae with the spacing of 0.8-1.8 micrometers). Although the low-Ca pyroxene host has an orthopyroxene composition (Wo approximately 2), the EBSD analysis suggests a pigeonite structure (P2(sub 1)/c), which is also reported from the Chassigny pyroxene. The size of exsolution texture is a bit smaller, but broadly similar to those in other chassignites, implying a similar fast cooling rate (35-43 C/yr). Feldspars are isotropic (plagioclase: clustered around An25Or10, K-feldspar: approximately An19Or78), suggestive of extensive shock metamorphism, consistent with undulatory extinction of olivine. Feldspar compositions are around the equilibrium isotherm of approximately 800 C. The olivine and chromite compositions give an equilibration temperature of 760-810 C and logfO2 of QFM+/-0.3. The inferred fast cooling rate and high fO2 of NWA 8694 are both similar to those of Chassigny and NWA 2737, and suggest a common formation condition (e.g., thick lava flow or shallow intrusion) under oxidizing condition. The Fe-rich mineral compositions of NWA 8694 may be due to crystallization from more fractionated melt than the other chassignites. The shock degree of NWA 8694 would be similar to Chassigny, but distinct from NWA 2737 with darkened olivine showing more extensive shock.

Mikouchi, T.↗

A New Type of Foreign Clast in A Polymict Ureilite: A CAI or AL-Rich Chondrule

Introduction: Polymict ureilites are breccias interpreted to represent regolith formed on a ureilitic asteroid [1-3]. They consist of approximately 90-95% clasts of various ureilite types (olivine-pyroxene rocks with Fo 75-95), a few % indigenous feldspathic clasts, and a few % foreign clasts [4-20]. The foreign clasts are diverse, including fragments of H, L, LL and R chondrites, angrites, other achondrites, and dark clasts similar to CC [6,7,9-19]. We report a new type of foreign clast in polymict ureilite DaG 999. Methods: Clast 8 in Dar al Gani (DaG) 999/1 (Museum fur Naturkunde) was discovered during a survey of feldspathic clasts in polymict ureilites [19,20]. It was studied by BEI, EMPA, and X-ray mapping on the JEOL 8530F electron microprobe at ARES, JSC. Petrography and Mineral Compositions: Clast 8 is sub-rounded to irregular in shape, approximately 85 micrometers in diameter, and consists of approximately 68% pyroxene and 32% mesostasis (by area). Part of the pyroxene (top half of clast in Fig. 1a and 2) shows a coarse dendritic morphology; the rest appears massive. Mesostasis may be glassy and contains fine needles/grains of pyroxene. The pyroxene has very high CaO (23.5 wt.%) and Al2O3 (19.7 wt.%), with the formula: (Ca(0.91)Mg(0.63)Fe(0.01)Al(sup VI) (0.38)Cr(0.01)Ti(0.05)1.99 Si2O6. The bulk mesostasis also has very high Al2O3 (approximately 26 wt.%). A bulk composition for the clast was obtained by combining modal abundances with phase compositions (Table 1, Fig. 3). Discussion: The pyroxene in clast 8 has a Ca-Al-(Ti)- rich (fassaitic) composition that is clearly distinct from compositions of pyroxenes in main group ureilites [22] or indigenous feldspathic clasts in polymict ureilites [4-8]. It also has significantly higher Al than fassaite in angrites (up to approximately 12 wt.% [23]), which occur as xenoliths in polymict ureilites. Ca-Al-Ti rich pyroxenes are most commonly found in CAIs, Al-rich chondrules and other types of refractory inclusions in chondrites [21,24-31]. However, the clast 8 pyroxene matches only the most Al-Ca-rich of these, e.g., pyroxenes in type B CAIs in CV3 chondrites [25,30,31], a pyroxene-hibonite spherule and a pyroxene-anorthitespinel fragment from unique CC Acfer 094 [29], and one Al-rich chondrule from Chainpur (LL3.4) [21]. The mineralogy of clast 8 is not consistent with the mineral assemblages of any of these objects (since it lacks hibonite, spinel and/or anorthite), which suggests that it is unrepresentatively sectioned or is a fragment of a more mineralogically diverse object. Its bulk composition (Table 1; Fig. 3) is similar to bulk compositions of some Al-rich chondrules, as well as those of Type C CAIs (which plot in the sp+An+L field in Fig. 3), although it is enriched in silica relative to type C CAIs [e.g., 31]. This suggests a more likely affinity to Al-rich chondrules, although most Al-rich chondrules have less Al-Ca-rich pyroxene [21,26,27]. These bulk compositional comparisons may not be definitive, however, if the clast is unrepresentatively sampled. One of eleven Al-rich chondrules from UOCs described by [21] has textural and compositional characteristics that make it a possible progenitor type for clast 8. This chondrule (Chainpur 1251-14-2) is anorthiteporphyritic, with an interstitial dendritic intergrowth of pyroxene (similar in composition to that in clast 8) and plagioclase [21]. Clast 8 is conceivably a fragment from the interstitial area of such an object. The occurrence of glassy mesostasis (in clast 8) rather than plagioclase may not be a significant difference; it could result from a difference only in cooling rate. Al-rich chondrules with glassy mesostasis are rare, and known occurrences are Ca-poor [26], unlike clast 8. Polymict ureilites are known to contain xenoliths of various chondrites (including OC, R and CC) as well as individual ferromagnesian and silica-pyroxene chondrules probably derived from OC or RC [6,9,15,16,18]. This is the first report of an individual chondritic refractory inclusion as a xenolith in a polymict ureilite. An RC-like sample from anomalous polymict ureilite Almahata Sitta contains CAIs, but they are spinel-rich and not similar to clast 8 [13,14]. Further studies of this clast (which, unfortunately, may not be possible), or the discovery of additional (more representative?) materials of this type would be needed to determine the exact nature of this xenolith and the type of chondrite from which it is derived.

Goodrich, C. A.↗

Microstructural Constraints on the Formation History of Hibonite in Refractory Inclusions

Hibonite is a primary refractory phase occurring in many Ca-Al-rich inclusions (CAIs), typically with spinel and perovskite [1]. Previous mi-crostructural studies of hibonite in CAIs revealed the presence of numerous stacking defects along the (001) plane and correlated non-stoichiometry in hibonite [2,3]. These features are interpreted as complex inter-growths of stoichiometric and Ca-deficient hibonites, as shown by experimental studies of reaction-sintered CaO-Al2O3 compounds [4]. Here, we extend our transmission electron microscope (TEM) studies to hibonite-bearing CAIs in CM chondrites that have been well characterized isotopically [5-7]. In addition, we have undertaken a series of anneal-ing experiments to explore the effect of minor elements (Mg and Ti) on the microstucure of hibonite [8,9,this study]. The results of these experiments are being applied to hibonite in CAIs in order to better understand its formation conditions.

Han, J.↗

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↗

Impact of Coupled Radiation and Ablation on the Aerothermodynamics of Meteor Entries

A high-fidelity approach for simulating the aerothermodynamic environments of meteor entries is developed. Two primary components of this model are coupled radiation and coupled ablation. Coupled radiation accounts for the impact of radiation on the flow field energy equations, while coupled ablation explicitly models the injection of ablation products within the flow field and radiation simulations. For a meteoroid with a velocity of 20 km/s, coupled radiation reduces the stagnation point radiative heating by over 60%. For altitudes below 40 km, the impact of coupled radiation on the flow field structure is shown to be fundamentally different, as a result of the large optical thicknesses, than that seen for reentry vehicles, which do not reach such altitudes at velocities greater than 10 km/s. The impact of coupled ablation (with coupled radiation) is shown to provide at least a 70% reduction in the radiative heating relative to the coupled-radiation-only cases. This large reduction is partially the result of the low ionization energies, relative to air species, of ablation products. The low ionization energies of ablation products, such as Mg and Ca, provide strong photoionization and atomic line absorption in regions of the spectrum that air species do not. MgO and CaO are also shown to provide significant absorption. Turbulence is shown to impact the distribution of ablation products through the shock- layer, which results in up to a 100% increase in the radiative heating downstream of the stagnation point. To create a database of heat transfer coefficients the developed model was applied to a range of cases. This database considered velocities ranging from 14 to 20 km/s, altitudes ranging from 20 to 50 km, and nose radii ranging from 1 to 100 m. The heat transfer coefficients from these simulations are below 0.045 for the range of cases (with turbulence), which is significantly lower than the canonical value of 0.1.

Johnston, Christopher O.↗

Design and Characteristics of Hydroxyapatites: Effect of Radiation

Hydroxyapatites single crystals have been investigated their applications as the laser host material. Czochralksi and flux growth methods have been utilized to achieve single crystals. Because of their bioactivities with tissues these have attracted interest for bone applications. For low temperature processing we have used several techniques. We utilized some organic melt and oriented the grains by the directional solidification method. This organic treated material has different characteristics than coarsened oxide materials. Our approach involved low temperature processing using nano-engineered powders of the material system MgO-Na2O-K2O-CaO-SrO-SiO2 and also borates were processed by sintering and grain growth. Our results indicate that substitution of calcium and strontium with some other elements such as gallium and magnesium have great potential to improve the mechanical properties of bones.

Bhavsar, Jayati↗