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A unique high Mn/Fe microgabbro in the Parnallee (LL3) ordinary chondrite - Nebular mixture or planetary differentiate from a previously unrecognized planetary body?

We studied a unique microgabbro fragment from the Parnallee (LL3) unequilibrated ordinary chondrite. The fragment, which was originally identified by its ophitic to sub-ophitic texture, exhibits features characteristic of lunar and terrestrial tholeiitic basalts (i.e., extreme compositional zoning in clinopyroxene (Wo10En65Fs25 to Wo15En2FS83), a multiply saturated major element composition similar to mid-ocean ridge basalt with 3.1 wt pct Na2O and 0.15 wt pct K2O, and uniformly enriched rare earth elements (c. 10 x C1). A high bulk MnO/FeO ratio (0.064) distinguishes the microgabbro from other basaltic rocks and suggests the precursor material formed or reached equilibrium in a reducing environment. However, the absence of Fe metal and the extreme enrichment of FeO (up to 40 wt pct), in late crystallizing pyroxferroite, requires the last crystallization event to have occurred in a relatively oxidizing environment. We suggest the microgabbro formed by partial melting in a planetary body after removal of metallic Fe.

Kennedy, A. K.↗

The effect of oxygen fugacity on the partitioning of nickel and cobalt between olivine, silicate melt, and metal

The effect of oxygen fugacity, f(O2), on the partitioning behavior of Ni and Co between olivine, silicate melt, and metal was investigated in the CaO-MgO-Al2O3-SiO2-FeO-Na2O system, an analogue of a chondrule composition from an ordinary chondrite. The conditions were 1350 C and 1 atm, with values of f(O2) varying between 10 exp -5.5 and 10 exp -12.6 atm (i.e., the f(O2) range relevant for crystal/liquid processes in terrestrial planets and meteorite parent bodies). Results of chemical analysis showed that the values of the Ni and Co partitioning coefficients begin to decrease at values of f(O2) that are about 3.9 log units below the nickel-nickel oxide and cobalt-cobalt oxide buffers, respectively, near the metal saturation for the chondrule analogue composition.

Ehlers, Karin↗

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.↗

Geochemical evidence for mixing of three components in martian orthopyroxenite ALH 84001

ALH 84001, a ferroan martian orthopyroxenite, originally consisted of three petrographically defined components: a cumulus assemblage of orthopyroxene + chromite, a trapped melt assemblage of orthopyroxene(?) + chromite + maskelynite + apatite + augite +/- pyrite, and a metasomatic assemblage of carbonate +/- pyrite. We present the results of Instrumental Neutron Activation Analysis (INAA) study of five bulk samples of ALH 84001, combined with Scanning Ion Mass Spectrometer (SIMS) data on the orthopyroxene, in order to attempt to set limits on the geochemical characteristics of the latter two components, and therefore on the petrogenesis of ALH 84001. The INAA data support the petrographic observations, suggesting that there are at least three components in ALH 84001. We will assume that each of the three geochemically required components can be equated with one of the petrographically observed components. Both trapped melt and metasomatic components in ALH 84001 have higher Na than orthopyroxene based on compositions of maskelynite, apatite, and carbonate. For the metasomatic component, we will assume its Na content is that of carbonate, while for a trapped melt component, we will use a typical Na content inferred for martian meteorite parent melts, approximately 1 wt% Na2O. Under these assumptions, we can set limits on the Light Rare Earth Elements/Heavy Rare Earth Elements (LREE/HREE) ratios of the components, and use this information to compare the petrogenesis of ALH 84001 with other martian meteorites. The above calculations assume that the bulk samples are representative of different portions of ALH 84001. We will also evaluate the possible heterogeneous distribution of mineral phases in the bulk samples as the cause of compositional heterogeneity in our samples.

Mittlefehldt, D. W.↗

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Gaetani, Glenn A.↗

Apollo 17 Soil Characterization for Reflectance Spectroscopy

It is the fine fractions that dominate the observed spectral signatures of bulk lunar soil, and the next to the smallest size fractions are the most similar to the overall properties of the bulk soil. Thus, our Lunar Soil Characterization Consortium has concentrated on understanding the inter-relations of compositional, mineralogical, and optical properties of the <45-micron size fraction and its component sizes (20-44 micron, 10-20 micron, and <10 micron size fractions). To be able to generalize our results beyond the particular sample set studied, it is necessary to quantitatively identify the observed effects of space weathering and evaluate the processes involved. For this, it is necessary to know the chemistry of each size fraction, modal abundances of each phase, average compositions of the minerals and glasses, I(sub s)/FeO values, reflectance spectra, and the physical makeup of the individual particles and their patinas. This characterization includes the important dissection of the pyroxene minerals into four separate populations, with data on both modes and average chemical compositions. Armed with such data, it should be possible to effectively isolate spectral effects of space weathering from spectral properties related to mineral and glass chemistry. Four mare soils from the Apollo 17 site were selected for characterization based upon similarities in bulk composition and their contrasting maturities, ranging from immature to submature to mature. The methodology of our characterization has been discussed previously. Results of the Apollo 17 mare soils, outlined herein, are being prepared for publication in MAPS. As shown, with decreasing grain size, the agglutinitic (impact) glass content profoundly increases. This is the most impressive change for the mare soils. In several soils we have examined, there is an over two-fold increase in the agglutinitic glass contents between the 90-150- micron and the 10-20-micron size fractions. Accompanying this increase in agglutinitic glass is a definite decrease in pyroxenes and to lesser extents, the oxides (ilmenite), volcanic glass, and olivine. Unexpectedly, however, the absolute plagioclase abundances stay relatively constant throughout the different grain sizes, although the abundance of plagioclase relative to the mafic minerals increases with decreasing particle size. These soils were chosen for study based upon their similarities in FeO and Ti02 content, allowing for direct comparisons between evolutions of chemistry between size fractions and among different maturities of soils. The bulk chemistry of these fractions was determined by EMP analyses of fused glass beads. In contrast to the systematic variations in bulk chemistry discussed below, the relatively uniform composition of agglutinitic glass with grain size and soil maturity is illustrated. The composition of the bulk fraction of each size fraction becomes more feldspathic with increasing maturity, with the effect being most pronounced for the finest fractions. The composition of the agglutinitic glass, however, is relatively invariant and more feldspathic (i.e., rich in Al2O3) than even the <10-micron fraction. This relation not only strengthens the "fusion of the finest fraction" (F(sup 3)) hypothesis, but also highlights the important role of plagioclase in the formation of agglutinitic glass. With decreasing grain size, FeO, MgO, and TiO2 contents decrease, whereas CaO, Na2O, and Al2O3 (plag components) increase for all soils. These chemical variations would appear to be coupled with the significant increase in agglutinitic glass and decrease in oxide (ilmenite),pyroxene, and volcanic glass. These changes in chemistry do not appear to be due to distinct changes in the compositions of individual phases but to their abundances. Values of I(sub s)/FeO increase with decreasing grain size, even though the bulk FeO contents decrease. That is, the percentage of the total Fe that is present as nanophase Fe(sup O) has increased substantially in the smaller size fraction. Note that the increase in nanophase FeO in smaller size fractions is significantly greater than the increase in agglutinitic glass content, with its single-domain FeO component. This would seem to indicate that at least some of the FeO is surface correlated. To illustrate this effect, if it is assumed that the nanophase FeO is entirely surface correlated, then equal masses of 15-micron and 6-micron spheres should have about 3x as much FeO in the finer fraction. The recent findings of Kelleret al. of the major role of vapor-deposited, nanophase FeO-containing patinas on most soil particles is a major breakthrough in our understanding of the distribution of FeO within agglutinitic glass and upon grain surfaces. Bidirectional reflectance spectra for a representative Apollo 17 soil (70181) are shown. The size separates all have similar albedo in the blue and follow a regular sequence in which the continuum slope increases, ferrous bands weaken, and albedo, increases with decreasing particle size. The bulk <45-micron soil is typically close to the 10-20 micron spectrum. It is important to note that although the finest fraction (<10 micron) is close in composition to the abundant agglutinitic glass in each size fraction, this size fraction is relatively featureless and does not dominate the spectrum of the bulk <45-micron soil. It has long been suspected that agglutinitic glass, to a large extent, is the product of melting of the finest fraction of the soils, with a dominance of plagioclase. Given the low abundance of pyroxene in the finest fractions of each soil the source of the FeO in these Apollo 17 agglutinitic glasses is not fully identified. We suspect the abundant volcanic glass in these samples may be a significant contributor and this hypothesis will be tested with the suite under study from other Apollo sites.

Taylor, L. A.↗

Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

Yakshinskiy, B. V.↗

Studies Conducted of Sodium Carbonate Contaminant Found on the Wing Leading Edge and the Nose Cap of the Space Shuttle Orbiter

In early 2001, three of the space shuttle orbiters were found to have a sodium carbonate contaminant on the wing leading edge and nose cap. These parts are made of a reinforced carbon/carbon material protected by silicon carbide (SiC) and a glass coating. The glass coating is known as Type A and is primarily sodium silicate with particles of SiC. NASA Glenn Research Center's Environmental Durability Branch was asked to determine the chemistry of this deposit formation and assess any possible detrimental effects. At low temperatures, the reverse reaction is favorable. Previous studies of the corrosion of glass show that carbon dioxide in the presence of water does form sodium carbonate on sodium silicate glass (ref. 1). It is quite likely that a similar scenario exists for the orbiter wing leading edge. All three orbiters that formed sodium carbonate were exposed to rain. This formation of sodium carbonate was duplicated in the laboratory. The Type A glass, which coats the wing leading edge and nose cap, was made in a freestanding form and exposed to water in two separate experiments. In one set of experiments, the coating was placed in a petri dish filled with water. As the water evaporated, sodium carbonate formed. In another case, water was slowly dripped on the coating and sodium carbonate formed. The sodium carbonate was detected by chemical analysis and, in some cases, xray diffraction showed a hydrated sodium carbonate. The next step was to examine possible detrimental effects of this sodium carbonate. There are three likely scenarios for the sodium carbonate deposit: (1) it may be removed with a simple rinse, (2) it may remain and flow back into the Type A glass after heating during reentry, or (3) it may remain and flow onto unprotected SiC and/or other parts after heating during reentry. The effect of case 1 is to remove the Na2O constituent from the Type A glass, thus decreasing its effectiveness as a sealant. Even so, overall, it is probably the best approach and was used by the NASA Kennedy Space Center when the deposits were first observed. The effect of case 2 is minimal and would actually restore the the Type A glass to its composition before carbonate formation. However, the problem with allowing the carbonate to remain leads to the third scenario, the deposit flowing onto other parts. A series of tests were conducted on unprotected SiC, and minimal effects were found in the short-term, but other ceramic and metal parts could be damaged by the molten sodium carbonate and would require close monitoring.

Jacobson, Nathan S.↗

Experimental and Petrological Constraints on Lunar Differentiation from the Apollo 15 Green Picritic Glasses

Phase equilibrium experiments on the most magnesian Apollo 15C green picritic glass composition indicate a multiple saturation point with olivine and orthopyroxene at 1520 C and 1.3 GPa (about 260 km depth in the moon). This composition has the highest Mg# of any lunar picritic glass and the shallowest multiple saturation point. Experiments on an Apollo 15A composition indicate a multiple saturation point with olivine and orthopyroxene at 1520 C and 2.2 GPa (about 440 km depth in the moon). The importance of the distinctive compositional trends of the Apollo 15 groups A, B, and C picritic glasses merits the reanalysis of NASA slide 15426,72 with modern electron microprobe techniques. We confirm the compositional trends reported by Delano (1979, 1986) in the major element oxides SiO2, TiO2, Al2O3, Cr2O3, FeO, MnO, MgO, and CaO, and we also obtained data for the trace elements P2O5, K2O, Na2O, NiO, S, Cu, Cl, Zn, and F. Petrogenetic modeling demonstrates that the Apollo 15 A-B-C glass trends could not have been formed by fractional crystallization or any continuous assimilation/fractional crystallization (AFC) process. The B and C glass compositional trends could not have been formed by batch or incremental melting of an olivine + orthopyroxene source or any other homogeneous source, though the A glasses may have been formed by congruent melting over a small pressure range at depth. The B compositional trend is well modeled by starting with an intermediate A composition and assimilating a shallower, melted cumulate, and the C compositional trend is well modeled by a second assimilation event. The assimilation process envisioned is one in which heat and mass transfer were separated in space and time. In an initial intrusive event, a picritic magma crystallized and provided heat to melt magma ocean cumulates. In a later replenishment event, the picritic magma incrementally mixed with the melted cumulate (creating the compositional trends in the green glass data set), ascended to the lunar surface, and erupted as a fire fountain. A barometer created from multiple saturation points provides a depth estimate of other glasses in the A-B-C trend and of the depths of assimilation. This barometer demonstrates that the Apollo 15 A-B-C trend originated over a depth range of approx.460 km to approx.260 km within the moon.

Elkins-Tanton, Linda T.↗

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.↗

Phosphorus Equilibria Among Mafic Silicate Phases

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗

Experimental Constraints on a Vesta Magma Ocean

A magma ocean model was devised to relate eucrites (basalts) and diogenites (orthopyroxenites), which are found mixed together as clasts in a suite of polymict breccias known as howardites. The intimate association of eucritic and diogenitic clasts in howardites argues strongly that these three classes of achondritic meteorites all originated from the same planetoid. Reflectance spectral evidence (including that from the DAWN mission) has long suggested that Vesta is indeed the Eucrite Parent Body. Specifically, the magma ocean model was generated as follows: (i) the bulk Vesta composition was taken to be 0.3 CV chondrite + 0.7 L chondrite but using only 10% of the Na2O from this mixture; (ii) this composition is allowed to crystallize at 500 bar until approx. 80% of the system is solid olivine + low-Ca pyroxene; (iii) the remaining 20% liquid crystallizes at one bar from 1250C to 1110C, a temperature slightly above the eucrite solidus. All crystallization calculations were performed using MELTS. In this model, diogenites are produced by cocrystallization of olivine and pyroxene in the >1250C temperature regime, with Main Group eucrite liquids being generated in the 1300-1250C temperature interval. Low-Ca pyroxene reappears at 1210C in the one-bar calculations and fractionates the residual liquid to produce evolved eucrite compositions (Stannern Trend). We have attempted to experimentally reproduce the <1250C portion of the MELTS Vesta magma ocean. In the MELTS calculation, the change from 500 bar to one bar results in a shift of the olivine:low-Ca pyroxene boundary so that the 1250C liquid is now in the olivine field and, consequently, olivine should be the first-crystallizing phase, followed by low-Ca pyroxene at 1210C, and plagioclase at 1170C. Because at one bar the olivine:low-Ca pyroxene boundary is a peritectic, fractional crystallization of the 1210C liquid proceeds with only pyroxene crystallization until plagioclase appears. Thus, the predictions of the MELTS calculation are clear and straightforward.

Hoff, C.↗

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.↗

Distinct Igneous APXS Rock Compositions on Mars from Pathfinder, MER and MSL

The alpha particle x-ray spectrometer (APXS) on all four Mars Rovers returned geochemical data from about 1000 rocks and soils along the combined traverses of over 50 kilometers. Here we discuss rocks likely of igneous origin, which might represent source materials for the soils and sediments identified along the traverses. Adirondack-type basalts, abundant in the plains of Gusev Crater, are primitive, olivine bearing basalts. They resemble in composition the basaltic soils encountered at all landing sites, except the ubiquitous elevated S, Cl and Zn in soils. They have been postulated to represent closely the average Martian crust composition. The recently identified new Martian meteorite Black Beauty has similar overall geochemical composition, very distinct from the earlier established SNC meteorites. The rim of the Noachian crater Endeavour, predating the sulfate-bearing Burns formation at Meridiani Planum, also resembles closely the composition of Adirondack basalts. At Gale Crater, the MSL Curiosity rover identified a felsic rock type exemplified by the mugearitic float rock JakeM, which is widespread along the traverse at Gale. While a surprise at that time, possibly related more evolved, alkaline rocks had been previously identified on Mars. Spirit encountered the Wishstone rocks in the Columbia Hills with approx. 6% Na2O+K2O, 15 % Al2O3 and low 12% FeO. Pathfinder rocks with elevated K and Na and >50% SiO2 were postulated to be andesitic. Recently Opportunity encountered the rock JeanBaptisteCharbonneau with >15% Al2O3, >50% SiO2 and approx. 10% FeO. A common characteristic all these rocks is the very low abundance of Cr, Ni and Zn, and an Fe/Mn ratio of about 50, indicating an unaltered Fe mineralogy. Beside these likely igneous rock types, which occurred always in several rocks, a few unique rocks were encountered, e.g. Bounce Rock, a pyroxene-bearing ejecta rock fragment resembling the Shergottite EETA 79001B meteorite. The APXS data can be used to relate the findings of all 4 landing sites, constrain the water to rock ratio of sediments or imply source rock provenance. Beyond that the capability to quantify important volatile elements like P, S, Cl, and Br have provided new insights into the chemistry and the environment present during the formation of the sediments.

Gellert, Ralf↗

Mineralogy, Provenance, and Diagenesis of a Potassic Basaltic Sandstone on Mars: CheMin X-Ray Diffraction of the Windjana Sample (Kimberley Area, Gale Crater)

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, approximately Or(sub 95)); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (approximately 25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, approximately 1.8 times that of Windjana, implying a sediment component with greater than 40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g.,mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

Treiman, Allan H.↗

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↗

Design and Characteristics of Hydroxyapatites: Effect of Radiation

We have prepared silicate based hard materials and have processed it with organic flux. Because of the bioactivities of hydroxyapatites with tissues, this class of materials have attracted interest for bone applications. We have utilized low temperature processing techniques. Organic melt was used and the directional solidification method to cast the shaped sample. This organic treated material has different characteristics than coarsened oxide materials. Our approach involved low temperature processing using nano and micron sized powders of the material system Na2O-K2O-CaO- MgO-Ga2O3-SiO2, and titanates were processed by sintering and grain growth. Our results indicate that substitution of gallium and magnesium or titanium with some variation in processing methods have great potential to improve the glassy characteristics without decreasing the mechanical properties of bones. Effect of radiation on bone was studied by exposing with commercially available Cs137 gamma ray source. It was observed that electrical resistivity increased due to radiation exposure for this system.

Bhavsar, Jayati↗