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An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide

As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.

Gregory, Gerald L.↗

CM-like Interplanetary Dust Particles in Lower Stratosphere During 1989 October and 1991 June/July

The stratospheric interplanetary dust particles L2005T12 and L2011O3 are linked to CM chondrite matrix. Particle L2005T12 is dominated by tabular grains of partially dehydrated greenalite-rich serpentine. Its amorphous matrix contains abundant smectite nanocrystals and annular Fe,Ni,S units. A uniquely stratified (partial) maghemite rim occurs only on S-rich parts of the matrix. Formation of this rim and Mg depletions in the matrix occurred during atmospheric entry heating of this particle. Particle L2011O3 has large iron sulfide and magnesiowustite grains in an amorphous low-Al, ferromagnesiosilica matrix. Hydrous crystallisation of this matrix produced ultrafine-grained smectites and disseminated iron sulfides. Atmospheric entry heating of both particles is indicated by the partial iron oxide rim, vesicular sulfides, and the scatter of matrix compositions due to loss of Mg. While many uncertainties remain, the high incidence of chondritic rough particles, which include an unknown amount of CM-like particles, in the lower stratosphere during 1984, 1989, and 1991 suggests annual variations in their abundances. The timing of lower stratospheric dust samplings is critical to collect these particles.

Rietmeijer, Frans J. M.↗

Distinguishing Indigenous from Contaminating Microorganisms in Rock Samples from a Deep Au Mine in South Africa

The concentration and distribution of microbial biomass within deep subsurface rock strata is not well known To date, most analyses are from water samples and a few cores. Hand samples, block samples and cores from an actively mined Carbon Leader ore zone at 3.2 kilometers depth were collected for microbial analyses. The Carbon Leader was comprised of quartz, S-bearing aromatic hydrocarbons, Fe(III) oxyhydroxides, sulfides, uraninite, Au and minor amounts of sulfate. The porosity of the ore was 1% and the maximum pore throat diameter was less than 0.1 microns; whereas, the porosity of the adjacent quartzite was .02 to .9% with a maximum pore throat diameter of 0.9 microns. Rhodamine dye, fluorescent microspheres, microbial enrichments, autoradiography, phospholipid fatty acid (PLEA) and 16S rDNA analyses were performed on these rock samples and the mining water. The date indicate that the levels of solute contamination less than 0.01% for pared rock samples. Despite this low level of contamination, PLEA, microbial enrichment, DNA and tracer analyses and calculations indicate that most of the viable microorganisms in the Carbon Leader represent gram negative aerobic heterotrophs and ammonia oxidizers that are phylogenetically identical or closely related to service water microorganisms. These microbial contaminants probably infiltrated the low permeability rock through mining-induced microfractures. Geochemical data also detected drilling water in a fault zone approx. 1 meter behind the rock face encountered during coring. The mining induced macrofractures that are common at these great depths act as pathways for the drilling water borne microorganisms into the lower temperature zone that extends several meters into rock strata from the rock face. Combined PLEA and T- RFLP analyses of the service water and Carbon Leader samples indicate that the concentration of indigenous microorganisms was less than 10(exp 2) cells/gram. Such a low concentrations result from the submicron pore throat diameters. PLFA. SO4-35 autoradiography and tracer analyses indicate that the bounding quartzite contains thermophilic sulfate reducing bacteria at 10(exp 3) cells/gram that are not attributable to drilling water contamination. The microorganisms may be surviving on sulfate generated by oxidation of sulfide by radiolytic reactions resulting from the high U concentration in the ore zone. The presence of up to 8,000 ppm of Fe(III) oxyhydroxides in the host rock will also act to recycle sulfide generated by the sulfate reducing bacteria into sulfate. The activity of these sulfate-reducing bacteria may be enhanced by mining induced fracturing which can propagate up to 40 meters into virgin rock where the temperatures are ca. 50 C, and decrepitate of sulfate rich fluid inclusions. In ultra deep mines, judicious application of tracers and multiple microbial characterization techniques can distinguish microbial contamination caused by the near field fracturing and drilling water migration from the indigenous microbial communities in rock strata. The importance of far field fracturing on indigenous microbial communities, however, remains unknown.

Onstott, T. C.↗

Clear Evidence for Fe-60 in Silicate from a Semarkona Chondrule

Fe-60 (t(sub 1/2) = 1.5 Ma) is key to understanding the sources of short-lived radionuclides in the early solar system because it is the only one among those known from meteoritic material that is produced only in stars [1]. Within the last year, it has become clear that Fe-60 was present in sulfides from primitive ordinary and enstatite chondrites in amounts sufficient to require a recent stellar input [2-5]. The sulfide data indicate an initial Fe-60/Fe-56 ratio for the early solar system of between approx. 3 10(exp -7) and approx. 1.6 10(exp -6) [2-4]. However, iron (and nickel?) in sulfides is easily mobilized by very mild heating [e.g., 6], so there is considerable uncertainty over the true initial ratio. To resolve this uncertainty, we have begun a search for evidence of Fe-60 in silicates from primitive chondrites. In olivine from type 3.0-3.1 ordinary chondrites, diffusive exchange of iron and magnesium has not occurred to any significant degree, and diffusive exchange in pyroxene is slower [7]. However, the relatively small elemental fractionation of iron from nickel in silicates, coupled with the fact that the daughter nuclide, Ni-60, makes up approx. 26 % of normal nickel, make detection of excesses of radiogenic Ni-60 very difficult. Fortunately, we have found a fine-grained radiating-pyroxene chondrule in Semarkona (LL3.0) with a very high Fe/Ni ratio that gives clear evidence of Fe-60.

Huss, G. R.↗

Global geochemical cycles of carbon, sulfur and oxygen

Time resolved data on the carbon isotopic composition of carbonate minerals and the sulfur isotopic composition or sulfate minerals show a strong negative correlation during the Cretaceous. Carbonate minerals are isotopically heavy during this period while sulfate minerals are isotopically light. The implication is that carbon is being transferred from the oxidized, carbonate reservoir to the reservoir of isotopically light reduced organic carbon in sedimentary rocks while sulfur is being transferred from the reservoir of isotopically light sedimentary sulfide to the oxidized, sulfate reservoir. These apparently oppositely directed changes in the oxidation state of average sedimentary carbon and sulfur are surprising because of a well-established and easy to understand correlation between the concentrations of reduced organic carbon and sulfide minerals in sedimentary rocks. Rocks rich in reduced carbon are also rich in reduced sulfur. The isotopic and concentration data can be reconciled by a model which invokes a significant flux of hydrothermal sulfide to the deep sea, at least during the Cretaceous.

Non-NASA Center↗

Association of a new type of gliding, filamentous, purple phototrophic bacterium inside bundles of Microcoleus chthonoplastes in hypersaline cyanobacterial mats

An unidentified filamentous purple bacterium, probably belonging to a new genus or even a new family, is found in close association with the filamentous, mat-forming cyanobacterium Microcoleus chthonoplastes in a hypersaline pond at Guerrero Negro, Baja California Sur, Mexico, and in Solar Lake, Sinai, Egypt. This organism is a gliding, segmented trichome, 0.8-0.9 micrometer wide. It contains intracytoplasmic stacked lamellae which are perpendicular and obliquely oriented to the cell wall, similar to those described for the purple sulfur bacteria Ectothiorhodospira. These bacteria are found inside the cyanobacterial bundle, enclosed by the cyanobacterial sheath. Detailed transmission electron microscopical analyses carried out in horizontal sections of the upper 1.5 mm of the cyanobacterial mat show this cyanobacterial-purple bacterial association at depths of 300-1200 micrometers, corresponding to the zone below that of maximal oxygenic photosynthesis. Sharp gradients of oxygen and sulfide are established during the day at this microzone in the two cyanobacterial mats studied. The close association, the distribution pattern of this association and preliminary physiological experiments suggest a co-metabolism of sulfur by the two-membered community. This probable new genus of purple bacteria may also grow photoheterotrophically using organic carbon excreted by the cyanobacterium. Since the chemical gradients in the entire photic zone fluctuate widely in a diurnal cycle, both types of metabolism probably take place. During the morning and afternoon, sulfide migrates up to the photic zone allowing photoautotrophic metabolism with sulfide as the electron donor. During the day the photic zone is highly oxygenated and the purple bacteria may either use oxidized species of sulfur such as elemental sulfur and thiosulfate in the photoautotrophic mode or grow photoheterotrophically using organic carbon excreted by M. chthonoplastes. The new type of filamentous purple sulfur bacteria is not available yet in pure culture, and its taxonomical position cannot be fully established. This organism is suggested to be a new type of gliding, filamentous, purple phototroph.

NASA Discipline Exobiology↗

Tracking the Early Thermal History of Asteroids with Trace Siderophiles in Meteorite Metals

A fundamental process in the formation of differentiated bodies is the segregation of metal-sulfide and silicate phases, leading to the formation of a metallic core. The only known direct record of this process is preserved in some primitive achondrites, such as the acapulcoites and lodranites. These meteorites, thought to originate from the same parent asteroid, are the products of thermal metamorphism and igneous processing of a chondritic precursor. Collectively, they have experienced a range of peak metamorphic temperatures relevant to the onset of metal-sulfide partial melting and melt migration. We assessed the siderophile element composition of their metals in an effort to determine the conditions and extent of metal-sulfide melt extraction and thereby gain insight into the earliest stages of core formation.

Herrin, J. S.↗

Postshock Annealing and Postannealing Shock in Equilibrated Ordinary Chondrites: Implications for the Thermal and Shock Histories of Chondritic Asteroids

In addition to shock effects in olivine, plagioclase, orthopyroxene and Ca-pyroxene, petrographic shock indicators in equilibrated ordinary chondrites (OC) include chromite veinlets, chromite-plagioclase assemblages, polycrystalline troilite, metallic Cu, irregularly shaped troilite grains within metallic Fe-Ni, rapidly solidified metal-sulfide intergrowths, martensite and various types of plessite, metal-sulfide veins, large metal and/or sulfide nodules, silicate melt veins, silicate darkening, low-Ca clinopyroxene, silicate melt pockets, and large regions of silicate melt. The presence of some of these indicators in every petrologic type-4 to -6 ordinary chondrite (OC) demonstrates that collisional events caused all equilibrated OC to reach shock stages S3-S6. Those type-4 to -6 OC that are classified as shock-stage S1 (on the basis of sharp optical extinction in olivine) underwent postshock annealing due to burial beneath materials heated by the impact event. Those type-4 to -6 OC that are classified S2 (on the basis of undulose extinction and lack of planar fractures in olivine) were shocked to stage S3-S6, annealed to stage S1 and then shocked again to stage S2. Some OC were probably shocked to stage 253 after annealing. It seems likely that many OC experienced multiple episodes of shock and annealing. Because 40Ar-39Ar chronological data indicate that MIL 99301 (LL6, Sl) was annealed approximately 4.26 Ga ago, presumably as a consequence of a major impact, it seems reasonable to suggest that other equilibrated S1 and S2 OC (which contain relict shock features) were also annealed by impacts. Because some type-6 S1 OC (e.g., Guarena, Kernouve, Portales Valley, all of which contain relict shock features) were annealed 4.44-4.45 Ga ago (during a period when impacts were prevalent and most OC were thermally metamorphosed), it follows that impact-induced annealing could have contributed significantly to OC thermal metamorphism.

Rubin, Alan E.↗

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Flytzani-Stephanopoulos, Maria↗

Comparing Wild 2 Particles to Chondrites and IDPS

We compare the observed composition ranges of olivine, pyroxene and Fe-Ni sulfides in Wild 2 grains, comparing these with chondritic IDPs and chondrite classes to explore whether these data suggest affinities to known hydrous materials in particular. Wild 2 olivine has an extremely wide composition range, from Fo4-100 with a pronounced frequency peak at Fo99. The composition range displayed by the low-calcium pyroxene is also very extensive, from En52 to En100, with a significant frequency peak centered at En95. These ranges are as broad or broader than those reported for any other extraterrestrial material. Wild 2 Fe-Ni sulfides mainly have compositions close to that of FeS, with less than 2 atom % Ni - to date, only two pentlandite grains have been found among the Wild-grains suggesting that this mineral is not abundant. The complete lack of compositions between FeS and pentlandite (with intermediate solid solution compositions) suggests (but does not require) that FeS and pentlandite condensed as crystalline species, i.e. did not form as amorphous phases, which later became annealed. While we have not yet observed any direct evidence of water-bearing minerals, the presence of Ni-bearing sulfides, and magnesium-dominated olivine and low-Ca pyroxene does not rule out their presence at low abundance. We do conclude that modern major and minor element compositions of chondrite matrix and IDPs are needed.

Zolensky, Michael↗

Thermal Constraints from Siderophile Trace Elements in Acapulcoite-Lodranite Metals

A fundamental process in the formation of differentiated bodies is the segregation of metal-sulfide and silicate phases, leading to the formation of a metallic core. The only known direct record of this process is preserved in some primitive achondrites, such as the acapulcoite-lodranites. Meteorites of this clan are the products of thermal metamorphism of a chondritic parent. Most acapulcoites have experienced significant partial melting of the metal-sulfide system but not of silicates, while lodranites have experienced partial melting and melt extraction of both. The clan has experienced a continuum of temperatures relevant to the onset of metal mobility in asteroidal bodies and thus could yield insight into the earliest stages of core formation. Acapulcoite GRA 98028 contains relict chondrules, high modal sulfide/metal, has the lowest 2-pyroxene closure temperature, and represents the least metamorphosed state of the parent body among the samples examined. Comparison of the metal-sulfide component of other clan members to GRA 98028 can give an idea of the effects of metamorphism.

Herrin, Jason S.↗

Sulfur Speciation in the Martian Regolith Component in Shergottite Glasses

We have shown that Gas-Rich Impact-Melt (GRIM) glasses in Shergotty, Zagami, and EET79001 (Lith A and Lith B) contain Martian regolith components that were molten during impact and quenched into glasses in voids of host rock materials based on neutron-capture isotopes, i.e., Sm-150 excesses and Sm-149 deficits in Sm, and Kr-80 excesses produced from Br [1, 2]. These GRIM glasses are rich in S-bearing secondary minerals [3.4]. Evidence for the occurrence of CaSO4 and S-rich aluminosilicates in these glasses is provided by CaO-SO3 and Al2O3-SO3 correlations, which are consistent with the finding of gypsum laths protruding from the molten glass in EET79001 (Lith A) [5]. However, in the case of GRIM glasses from EET79001 (Lith B), Shergotty and Zagami, we find a different set of secondary minerals that show a FeO-SO3 correlation (but no MgOSO3 correlation), instead of CaO-SO3 and Al2O3-SO3 correlations observed in Lith A. These results might indicate different fluidrock interactions near the shergottite source region on Mars. The speciation of sulfur in these salt assemblages was earlier studied by us using XANES techniques [6], where we found that Lith B predominantly contains Fe-sulfide globules (with some sulfate). On the other hand, Lith A showed predominantly Casulfite/ sulfate with some FeS. Furthermore, we found Fe to be present as Fe2+ indicating little oxidation, if any, in these glasses. To examine the sulfide-sulfate association in these glasses, we studied their Fe/Ni ratios with a view to find diagnostic clues for the source fluid. The Fe-sulfide mineral (Fe(0.93)Ni(0.3)S) in EET79001, Lith A is pyrrhotite [7, 8]. It yields an Fe/Ni ratio of 31. In Shergotty, pyrrhotite occurs with a molar ratio of Fe:S of 0.94 and a Ni abundance of 0.12% yielding a Fe/Ni ratio of approx.500 [8]. In this study, we determined a NiO content of approx.0.1% and FeO/NiO ratio of approx.420 in S-rich globules in #507 (EET79001, Lith B) sample using FE-SEM. In the same sample (bulk), using EMPA, we determined a FeO/NiO ratio of approx.700 (raster mode). Using similar techniques, we determined a NiO content of approx.0.015% and a FeO/NiO ratio of approx.800 in #506 (EET79001, Lith A). Moreover, a NiO content of approx.150 ppm and 6.1% FeO were found in Lith A GRIM glasses using neutron activation analysis [9] yielding a FeO/NiO ratio of approx.420. The FeO/NiO ratios in secondary mineral phases in S-rich pockets of EET79001 (Lith A/B) and Shergotty are high (approx.400) compared to the FeO/NiO ratio of 31 in Lith A pyrrhotite. These results suggest similar kind of fluids interacted with different rock materials to yield the observed variations in GRIM glasses in EET79001 Lith A and B.

Rao, M. N.↗

Sulfur Isotopes in Gas-rich Impact-Melt Glasses in Shergottites

Large impact melt glasses in some shergottites contain huge amounts of Martian atmospheric gases and they are known as gas-rich impact-melt (GRIM) glasses. By studying the neutron-induced isotopic deficits and excesses in Sm-149 and Sm-150 isotopes resulting from Sm-149 (n,gamma) 150Sm reaction and 80Kr excesses produced by Br-79 (n,gamma) Kr-80 reaction in the GRIM glasses using mass-spectrometric techniques, it was shown that these glasses in shergottites EET79001 and Shergotty contain regolith materials irradiated by a thermal neutron fluence of approx.10(exp 15) n/sq cm near Martian surface. Also, it was shown that these glasses contain varying amounts of sulfates and sulfides based on the release patterns of SO2 (sulfate) and H2S (sulfide) using stepwise-heating mass-spectrometric techniques. Furthermore, EMPA and FE-SEM studies in basaltic-shergottite GRIM glasses EET79001, LithB (,507& ,69), Shergotty (DBS I &II), Zagami (,992 & ,994) showed positive correlation between FeO and "SO3" (sulfide + sulfate), whereas those belonging to olivine-phyric shergottites EET79001, LithA (,506, & ,77) showed positive correlation between CaO/Al2O3 and "SO3".

Rao, M. N.↗

Coordinated Mineralogical and Isotopic Analysis of a Cosmic Symplectite Identified in a Stardust Terminal Particle

Comet Wild-2 samples returned by the Stardust spacecraft contain a chemically diverse mixture of material, underscoring the complex nature of comets. Studies of entire Stardust aerogel tracks afford the opportunity to examine the fine-grained particle fragments distributed along the length of the track as well as the terminal particles. Previous TEM characterization of a terminal particle (TP) in track #147 revealed a symplectically intergrown iron sulfide and oxide assemblage. Mineralogically similar assemblages, known as cosmic symplectites (COS, formerly termed "new-PCP"), have only been identified in the primitive carbonaceous chondrite Acfer 094. Meteoritic COS have isotopically heavy O compositions (delta (sup 17), O-18 = 180per mille) that point to interactions with early solar system primordial water. In this study we report mineralogical and O isotopic measurements of the Wild-2 COS assemblage. Experimental: Track #147 is a "bulbous"-type track (4600 microns long) containing 7 terminal particles. The TPs were removed from the track, embedded in epoxy, and ultramicrotomed. A JEOL 2500SE 200 keV field-emission scanning-transmission electron microscope was used to obtain quantitative elemental maps and detailed mineralogical characterization. Following TEM analysis, two thin sections of TP4 (12 microns) were analyzed for O isotopes by raster ion imaging with the JSC NanoSIMS 50L. All three O isotopes were measured simultaneously using electron multipliers. San Carlos olivine grains were used as isotopic standards. Results and Discussion: The COS in the Wild-2 track #147 TP4 sample consists of symplectically intergrown pentlandite and nanocrystalline maghemite which coexists with high-Ca pyroxene with Na and Cr (kosmochlor component). This kosmochlor component could have a nebular origin and be precursors to type II chondrules in ordinary chondrites. Yet pentlandite is not a stable phase in the nebula. The COS in Acfer 094 also consists of pentlandite, but contains magnetite [4] rather than the more oxidized maghemite observed in the Wild-2 COS. The Acfer 094 COS display heavy O isotopic compositions that are the result of sulfidization and oxidation of Fe, Ni-metal grains and sulfides by O-17- and O-18-rich water in the solar nebula or possibly on the parent body. The O isotopic composition of the Wild-2 COS, however, is indistinguishable from terrestrial, indicating it was not altered by the same primordial aqueous reservoir as the Acfer 094 COS. The alteration could have occurred on the parent body by isotopically equilibrated ice. The mineralogy and petrography of Wild-2 samples suggests an incomplete or nascent hydration process. In future work we will analyze S isotopes in the track #147 TP4 COS and search for additional COS in Stardust samples.

Nguyen, A. N.↗

Search for Fluid Inclusions in a Carbonaceous Chondrite Using a New X-Ray Micro-Tomography Technique Combined with FIB Sampling

Early solar system aqueous fluids are preserved in some H chondrites as aqueous fluid inclusions in halite (e.g., [1]). Although potential fluid inclusions are also expected in carbonaceous chondrites [2], they have not been surely confirmed. In order to search for these fluid inclusions, we have developped a new X-ray micro-tomography technique combined with FIB sampling and applied this techniqu to a carbanaceous chondrite. Experimental: A polished thin section of Sutter's Mill meteorite (CM) was observed with an optical microscope and FE-SEM (JEOL 7001F) for chosing mineral grains of carbonates (mainly calcite) and sulfides (FeS and ZnS) 20-50 microns in typical size, which may have aqueous fluid inclusions. Then, a "house" similar to a cube with a roof (20-30 microns in size) is sampled from the mineral grain by using FIB (FEI Quanta 200 3DS). Then, the house was atached to a thin W-needle by FIB and imaged by a SR-based imaging microtomography system with a Fresnel zone plate at beamline BL47XU, SPring-8, Japan. One sample was imaged at two X-ray energies, 7 and 8 keV, to identify mineral phases (dual-enegy microtomography: [3]). The size of voxel (pixel in 3D) was 50-80 nm, which gave the effective spatial resolution of approx. 200 nm. A terrestrial quartz sample with an aqueous fluid inclusion with a bubble was also examined as a test sample by the same method. Results and discussion: A fluid inclusion of 5-8 microns in quartz was clearly identified in a CT image. A bubble of approx. 4 microns was also identified as refraction contrast although the X-ray absorption difference between fluid and bubble is small. Volumes of the fluid and bubble were obtained from the 3D CT images. Fourteen grains of calcite, two grains of iron sulfide and one grain of (Zn,Fe)S were examined. Ten calcite, one iron sulfide and one (Zn,Fe)S grains have inclusions >1 micron in size (the maximum: approx. 5 microns). The shapes are spherical or irregular. Tiny inclusions (<1 micron) are also present in all the grains examined. These results show that mineral grains have more inclusions than expected from 2D observations. The X-ray absorption of the inclusions shows that they are not solid inclusions. No bubbles were observed inside, indicating that we cannot determine whether they are really aqueous fluids or merely voids. One calcite grain has an inclusion approx. 2 microns in size, which seems to have a bubble and a tiny solid daughter crystal inside (three-phase inclusion). As we know the exact 3D position of the inclusion, we will anlyze the inclusion by SIMS after freezing the sample as has been done for a halite sample [3]. The present technique is useful for finding small inclusions not only in carbonaceous chondrites but also for terrestrial materials.

Tsuchiyama, A.↗

Aubrite and Enstatite Chondrite Impact Melt Meteorites: Analogs to Mercury?

New data obtained during the MESSENGER mission has allowed us to better contrain the composition and mineralogy of the mercurian surface. One unique feature of Mercury is its extremely low oxygen fugacity (ƒO2) (Iron Wustite (IW) -7.3 to IW-2.6). At such extreme conditions, elements that exhibit lithophile behavior on Earth can exhibit chalcophile or siderophile behavior, leading to the formation of exotic sulfides and metals. As no samples have been returned from Mercury, it is critical to study meteorite analogs to better under-stand the formation conditions of the minerals present at the mercurian surface, as well as mercurian magmatic processes. Given the low fO2 on Mercury, we have selected to investigate potential meteoritic analogs for Mercury among the most reduced meteorite types, including the aubrites and enstatite chondrite impact melts. The aubrites are differentiated meteorites that show varying degrees of brecciation, have a similar ƒO2 to the mercurian surface and interior, and contain exotic sulfides that have been inferred to be present on the mercurian surface. The enstatite chondrite impact melts are from undifferentiated parent bodies, have a similar ƒO2 to the mercurian surface and interior, and contain exotic sulfides that have been inferred to be present on the mercurian surface. In this study, we present a comprehensive analysis of a representative suite of aubrites and enstatite chondrite impact melts and assess their relevance to under-standing magmatic processes on Mercury.

Wilbur, Z. E.↗

Potential Mercurian Analogues: Aubrite and Enstatite Chondrite Impact Melt Meteorites

The MESSENGER (MErcury Surface Space ENvironment GEochemistry and Ranging Spacecraft) mission provided new data that have helped us better constrain the surficial mineralogy and composition of Mercury. Mercury has an extremely low oxygen fugacity (f O2) (Iron Wustite (IW) -7.3 to IW -2.6), and at these unique conditions, elements, which usually exhibit lithophile behavior on Earth, can exhibit chalcophile or siderophile behavior on Mercury. No samples have been returned from Mercury; therefore, we must study candidate meteorite analogs to better understand the formation conditions of minerals inferred to be present at the Mercurian surface and Mercurian magmatic processes. In this study, we present a comprehensive analysis of a representative suite of eight aubrites and four enstatite chondrite impact melts (ECIM), which both have a similar f O2 to Mercury, and contain exotic sulfides that have been inferred to be present at the Mercurian surface. These characteristics allow us to assess their relevance for understanding the mineralogy and magmatic processes of Mercury. The ECIM were previously classified as aubrites, but we show that they are actually ECIM with a potential EH (high enstatite) parent body origin due to the presence of niningerite, Si-enriched kamacite, and uniform Ni in schreibersite. We propose that, with respect to the aubrites, the ECIM represent an ideal candidate for Mercurian studies due to their mineralogy and modal mineralogy. Compared to the aubrites, the ECIM samples do not contain forsterite or diopside, show a poorer sulfide diversity, contain graphite, and have a higher volume percentage of metal phases. Although the Mercurian surface contains forsterite and diopside, graphite and a similar amount of metal and sulfides as seen in the ECIM are inferred to be present on Mercury. According to the calculated normative Mercurian mineralogy, both candidate meteorites are most analogous to the Caloris Basin and Northern Plains Lower Mg regions.

Wilbur, Zoe E.↗

The Geochemistry of Aubrites: Investigating Reduced Parent Bodies

The aubrites (~30 known meteorites) are a unique group of differentiated meteorites that formed on asteroids with oxygen fugacities (ƒO2) from ~2 to ~6 log units below the iron-wüstite buffer [1–2]. At these highly reduced conditions, elements deviate from the geochemical behavior exhibited at terrestrial ƒO2, forming FeO-poor silicates, Si-bearing metals, and exotic sulfides [3]. Here we examine the 3D mineralogy and the geochemistry of fourteen aubrites, including mineral major element compositions, bulk-rock compositions, and oxygen isotopic compositions to understand their formation and evolution at extreme ƒO2 conditions. While previous studies have described the petrology and 2D modal abundances of aubrites, this work investigates the 3D modal mineralogies of silicate, metal, and sulfide phases in aubrite samples, which are then com-pared to the available 2D data. We utilize X-ray computed tomography (XCT) to non-destructively analyze the distribution and abundances of mineral phases in aubrites and locate composite clasts of sulfide grains for future analysis.

Wilbur, Z. E.↗