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Irradiation of FeS: Implications for the Lifecycle of Sulfur in the Interstellar Medium and Presolar FeS Grains

Fe(Ni) sulfides are ubiquitous in chondritic meteorites and cometary samples where they are the dominant host of sulfur. Despite their abundance in these early solar system materials, their presence in interstellar and circumstellar environments is poorly understood. Fe-sulfides have been reported from astronomical observations of pre- and post-main sequence stars [1, 2] and occur as inclusions in bonafide circumstellar silicate grains [3, 4]. In cold, dense molecular cloud (MC) environments, sulfur is highly depleted from the gas phase [e.g. 5], yet observations of sulfur-bearing molecules in dense cores find a total abundance that is only a small fraction of the sulfur seen in diffuse regions [6], therefore the bulk of the depletion must reside in an abundant unobserved phase. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium (ISM) [7-9], indicating that little sulfur is incorporated into solid grains in this environment. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. The main destruction mechanism is sputtering due to supernova shocks in the warm, diffuse ISM [10]. This process involves the reduction of Fe-sulfide with the production of Fe metal as a by-product and returning S to the gas phase. In order to test this hypothesis, we irradiated FeS and analyzed the resulting material using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).

Keller, Lindsay P.↗

Sulfide Stability of Planetary Basalts

The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

Caiazza, C. M.↗

Ultraviolet observations of NGC 4395, the least luminous and nearest known Seyfert 1 nucleus

The purpose of the grant was to obtain and analyze International Ultraviolet Explorer (IUE) spectra of the spiral galaxy NGC 4395, which contains the nearest and least luminous known Seyfert nucleus. The ultraviolet (UV) spectra was to be used to test the intriguing hypothesis that the 'activity' could be explained by purely stellar phenomena, and to further explore the unprecedented properties of this nucleus. To test the feasibility of the project (the nucleus of NGC 4395 is very faint), one IUE shift was allocated, with the possibility of three additional shifts later on. Ultraviolet observations were attempted with IUE on 4 June 1989. Unfortunately, it was found that the only available guide star could no longer be detected sufficiently well with the FES, whose present sensitivity is lower than it was at the beginning of the IUE mission. Thus, it is no longer possible to observe NGC 4395 with IUE. Given these circumstances, as well as the faintness of the nucleus of NGC 4395, a Cycle 2 HST proposal for observations of this object was submitted.

Filippenko, Alexei V.↗

Extreme incompatibility of Pb during the crystallization of magmatic iron meteorites

The partitioning behavior of Pb in the three-phase system metal-troilite-sulfide liquid was investigated. Microscopic examination and electron microprobe analysis of a polished section showed three phases--Fe metal, troilite and an Fe-S-Pb-O metallic liquid. The Pb concentration of the metallic liquid was 1.4 wt.%; the Pb contents of both the troilite and the Fe metal were below the detection limit of the electron probe. To better define the Pb concentrations of the solid phases, the same sample was analyzed for Pb and Fe using the M.I.T., Harvard and Brown ion microprobe. Even at this level of precision, some conclusions and speculations are possible: (1) The D(Pb) (troilite/metallic liquid) is low (.01 to .001) and, contrary to expectation, troilite, like metal, excludes Pb very effectively during the crystallization of metallic liquids; (2) Pb in iron meteorites is conceivably concentrated in trace phases which are less susceptible to contamination than metal and troilite; and (3) taken at face value D(Pb)(metal/troilite) is 0.1, but given the Pb and Fe ion yields from simple endmember phases (Fe, FeS, Pb, PbS), this D is more likely to be 0.05 to 0.03.

Jones, J. H.↗

Removal and Replacement of Primary Metal in Ferroan Lodranite MAC 88177

Collectively, acapulcoites and lodranites form a clan of primitive achondrites generally thought to have originated from the same parent body on the basis of similarities in petrology, mineral compositions, bulk compositions, cosmic ray exposure ages and oxygen isotope compositions, although considerable variation in some of these parameters has shown that the parent body was not entirely uniform. The presence of relict chondrules in several acapulcoites indicates that all were likely derived from chondrite-like precursor materials. The transition from acapulcoite to lodranite is gradual and corresponds to increasing metamorphic grade. Lodranites are generally coarser grained, but petrographic distinction between the two groups can also be made by modal abundances of troilite and plagioclase. Depletion of both these phases and incompatible lithophile trace elements in lodranites is consistent with their restitic origin formed by greater than 10% extraction of basaltic melt. Magnesian lodranites (e.g. Gibson, GRA 95209, Y-75274, Y-8002), some of which might also be considered transitional acapulcoites, have mineral and chemical compositions consistent with derivation by thermal metamorphism and partial melt extraction from acapulcoites, as would seem logical if samples represented different grades of metamorphism along a linear evolution trend. Ferromagnesian silicates in these lodranites tend to be displaced toward lower fe# (opx fe# 4-6) than the distribution observed in acapulcoites (opx fe# 6-11). A subset of lodranites, termed ferroan lodranites (e.g. FRO 90011, LEW 88280, Lodran, MAC 88177, Y-74357, Y- 791491/Y-791493), have ferromagnesian silicate minerals that are too Fe-rich (fe#>10) to have formed as simple restites from any known acapulcoite. Like silicates, metal-sulfide systematics of the ferroan lodranites are also inconsistent with a simple restitic origin. Logically, restitic lodranites should have been depleted in FeS during extraction of partial melts, since melting of the metal-sulfide system initiates at lower temperatures than melting of silicates. Yet, puzzingly, ferroan lodranites contain significant quantities (1.9-5.3 modal%) of troilite, indicating either (1) metal sulfide partial melts were retained during basaltic melt extraction or (2) later infusion of metal sulfide melts has occurred. In this study, we use trace siderophile elements in metals to assess the relative importance of each in creating the observed troilite enrichment.

Herrin, J. S.↗

Origin, Bulk Chemical Composition and Physical Structure of the Galilean Satellites of Jupiter: A Post-Galileo Analysis

The origin of Jupiter and the Galilean satellite system is examined in the light of the new data that has been obtained by the NASA Galileo Project. In particular, special attention is given to a theory of satellite origin which was put forward at the start of the Galileo Mission and on the basis of which several predictions have now been proven successful. These predictions concern the chemical composition of Jupiter's atmosphere and the physical structure of the satellites. According to the proposed theory of satellite origin, each of the Galilean satellites formed by chemical condensation and gravitational accumulation of solid grains within a concentric family of orbiting gas rings. These rings were cast off equatorially by the rotating proto-Jovian cloud (PJC which contracted gravitationally to form Jupiter some 4 1/2 billion years ago. The PJC formed from the gas and grains left over from the gas ring that had been shed at Jupiter's orbit by the contracting proto-solar cloud (PSC Supersonic turbulent convection provides the means for shedding discrete gas rings. The temperatures T (sub n) of the system of gas rings shed by the PSC and PJC vary with their respective mean orbital radii R (sub n) (n = 0, 1,2,...) according as T (sub n) proportional to R (sub n) (exp -0.9). If the planet Mercury condenses at 1640 K, so accounting for the high density of that planet via a process of chemical fractionation between iron and silicates, then T (sub n) at Jupiter's orbit is 158 K. Only 35% of the water vapour condenses out. Thus fractionation between rock and ice, together with an enhancement in the abundance of solids relative to gas which takes place through gravitational sedimentation of solids onto the mean orbit of the gas ring, ensures nearly equal proportions of rock and ice in each of Ganymede and Callisto. Io and Europa condense above the H20 ice point and consist solely of hydrated rock (h-rock). The Ganymedan condensate consists of h-rock and H20 ice. For Callisto, NH3 ice makes up -5% of the condensate mass next to h-rock (approximately 50%) and H2O ice (approximately 45%). Detailed thermal and structural models for each of Europa, Ganymede and Callisto are constructed on the basis of the above initial bulk chemical compositions. For Europa (E), a predicted 2-zone model consisting of a dehydrated rock core of mass 0.912 M (sub E) and a 150 km thick frozen mantle of salty H2O yields a moment-of-inertia coefficient which matches the Galileo Orbiter gravity measurement. For Ganymede (G), a 3-zone model possessing an inner core of solid FeS and mass approximately 0.116 M (sub G), and an outer H2O ice mantle of mass approximately 0.502 M (sub G) is needed to explain the gravity data. Ganymede's native magnetic field was formed by thermoremanent magnetization of Fe3O4. A new Callisto (C) model is proposed consisting of a core of mass 0.826 M (sub C) containing a uniform mixture of h-rock (60% by mass) and H2O and NH3 ices, and capped by a mantle of pure ice. This model may have the capacity to yield a thin layer of liquid NH3 (raised dot) 2H2O at the core boundary, in line with Galileo's discovery of an induced magnetic field.

Prentice, A. J. R.↗

Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

Oxygen fugacity (fO2) plays an important role in thephysicochemical properties of that system because fO2 has asubstantial impact on the partitioning behavior between andsolubility of elements in various phases. The reduced nature ofMercury and the aubrite parent bodies (APB) have raised manyquestions regarding the geochemical behavior of typicallylithophile, heat-producing, and rare-earth elements (REE) inmagmas at low fO2. In fact, interpretations of magmaticprocesses on reduced rocky bodies are difficult at presentbecause of the small number of experimental studies relevant tothe extremely low fO2 and high sulfur content of Mercury andthe APB, and our only natural analogs are the highly reducedenstatite chondrites and aubrites [e.g., 1]. Preliminaryobservations suggest that major and minor elements exhibitdifferent geochemical affinities in highly reduced, S-richsystems compared to terrestrial rocks. The partitioning behavior of major, minor, and traceelements between silicate melt, sulfide melt, and metal underhighly reduced conditions will be determined in a suite of super-liquidus experiments at a range of pressures (1 bar to 4 GPa) atNASA Johnson Space Center (JSC). Based on previous studies,heat-producing elements U and Th become more chalcophile,while K becomes less chalcophile, with more reducingconditions [2]. The nominally lithophile elements Mg and Cabecoming more chalcophile and appear as minor elements in(Fe,Mg,Ca)-S with more reducing conditions [3]. Additionally, itappears that nominally siderophile elements become moresiderophile and chalcophile with more reducing conditions,although the partitioning behavior into Mg- and Ca-bearingsulfide melts, rather than FeS, is less understood. Current workis focused on investigating elements for which we currently haveMESSENGER data as well as a host of geochemically relevanttrace elements such as REE.

Brendan A Anzures↗

The thermal state and internal structure of Mars

The evolution and state of the interior of Mars are studied through the use of theoretically calculated thermal history and density models. Invoking melting of an Fe-FeS mixture permits initial core formation within the first billion years. At the present time the core radius ranges from about 1300 to 1800 km, depending on composition, and the core is liquid even if the composition is varied from the eutectic. Large-scale differentiation of the silicates occurs in the last 2 b.y. When the mean density is 3.96 g/cu cm, the radius is 3389 km, and the moment of inertia factor is 0.377, the density models indicate high mantle densities near 3.74 g/cu cm. Thus an FeO content of about 29% is implied, consistent with the production of a low-viscosity magma. Chemical models of the Martian mantle indicate a composition primarily of olivine with about 56% forsterite.

Johnston, D. H.↗

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.↗

Thermomagnetic analysis of meteorites, 2.C2 chondrites

Samples of all eighteen known C2 chondrites have been analyzed thermomagnetically. For eleven of these, initial Fe3O4 content is low (generally less than 1%) and the saturation magnetization-vs.-temperature curves are irreversible. The heating curves show variable and erratic behavior, whereas the cooling curves are similar to that of Fe3O4. The saturation moment after cooling is greater (up to 10 times) than it is initially. This behavior is attributed to the production of magnetite from a thermally unstable phase - apparently FeS. Four of the remaining seven C2 chondrites contain Fe3O4 as the only significant magnetic phase; initial magnetite contents range from 4 to 13%. The remaining three C2 chondrites contain iron or nickel-iron in addition to Fe3O4. These seven C2 chondrites show little evidence of the breakdown of a thermally unstable phase.

Watson, D. E.↗

Thermomagnetic analysis of meteorites, 2: C2 chondrites

Samples of all eighteen of the known C2 chondrites were analyzed thermomagnetically. For eleven of these, initial Fe3O4 content is low(generally 1%) and the J sub s-T curves are irreversible. The heating curves show variable and erratic behavior, whereas the cooling curves appear to be that of Fe3O4. The saturation moment after cooling is greater (up to 10 times larger) than it is initially. This behavior is interpreted to be the result of the production of magnetite from a thermally unstable phase--apparently FeS. Four of the remaining 7 C2 chondrites contain Fe3O4 as the only significant magnetic phase: initial magnetite contents range from 4 to 13 percent. The remaining three C2 chondrites contain iron or nickel-iron in addition to Fe3O4. These seven C2 chondrites show little evidence of the breakdown of a thermally unstable phase.

Watson, D. E.↗

Advanced Optical Measurement Techniques

This research analyzes four areas: (1) Improved Techniques for Optical Measurement; (2) KC-135 Low Gravity Simulation Flight Preparation; (3) In-Line Holographic Microscopy; and (4) Holographic Optical Schlieren System (HOSS). The first task provides for laboratory breadboarding of advanced optical measurement techniques which appear promising for use in Material Processing System (MPS) flight experiments. A laboratory schlieren system has been constructed which simulates a similar optical system on the Fluids Experiment System (FES) which is to be flown on Spacelab 3. The second task allows improved optical systems and breadboards to be built for experiments and hardware tests on the KC-135 aircraft. A new, more stable Mach-Zehnder interferometer has been developed and components have been ordered. The third task is concerned with improvements on the optical system being used to study immiscible fluids. Experiments studying the dynamics of nucleation and the separation of immiscible fluids have been conducted. The four task involves building breadboard reconstruction systems for holograms taken in the HOSS. The HOSS is an early prototype of the Fluids Experiments System (FES) which is scheduled to fly on Spacelab 3.

Owen, R. B.↗

Euhedral metallic-Fe-Ni grains in extraterrestrial samples

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

Rubin, Alan E.↗

Acid-Sulfate-Weathering Activity in Shergottite Sites on Mars Recorded in Grim Glasses

Based on mass spectrometric studies of sulfur species in Shergotty and EET79001, [1] and [2] showed that sulfates and sulfides occur in different proportions in shergottites. Sulfur speciation studies in gas-rich impact-melt (GRIM) glasses in EET79001 by the XANES method [3] showed that S K-XANES spectra in GRIM glasses from Lith A indicate that S is associated with Ca and Al presumably as sulfides/sulfates whereas the XANES spectra of amorphous sulfide globules in GRIM glasses from Lith B indicate that S is associated with Fe as FeS. In these amorphous iron sulfide globules, [4] found no Ni using FE-SEM and suggested that the globules resulting from immiscible sulfide melt may not be related to the igneous iron sulfides having approximately 1-3% Ni. Furthermore, in the amorphous iron sulfides from 507 GRIM glass, [5] determined delta(sup 34)S values ranging from +3.5%o to -3.1%o using Nano-SIMS. These values plot between the delta(sup 34)S value of +5.25%o determined in the sulfate fraction in Shergotty [6] at one extreme and the value of -1.7%o obtained for igneous sulfides in EET79001 and Shergotty [7] at the other. These results suggest that the amorphous Fe-S globules likely originated by shock reduction of secondary iron sulfate phases occurring in the regolith precursor materials during impact [7]. Sulfates in the regolith materials near the basaltic shergottite sites on Mars owe their origin to surficial acid-sulfate interactions. We examine the nature of these reactions by studying the composition of the end products in altered regolith materials. For the parent material composition, we use that of the host shergottite material in which the impact glasses are situated.

Rao, M. N.↗

Possible roles of manganese redox chemistry in the sulfur cycle

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Nealson, K. H.↗

Nanoscale Analysis of Space-Weathering Features in Soils from Itokawa

Space weathering alters the spectral properties of airless body surface materials by redden-ing and darkening their spectra and attenuating characteristic absorption bands, making it challenging to characterize them remotely [1,2]. It also causes a discrepency between laboratory analysis of meteorites and remotely sensed spectra from asteroids, making it difficult to associate meteorites with their parent bodies. The mechanisms driving space weathering include mi-crometeorite impacts and the interaction of surface materials with solar energetic ions, particularly the solar wind. These processes continuously alter the microchemical and structural characteristics of exposed grains on airless bodies. The change of these properties is caused predominantly by the vapor deposition of reduced Fe and FeS nanoparticles (npFe(sup 0) and npFeS respectively) onto the rims of surface grains [3]. Sample-based analysis of space weathering has tra-ditionally been limited to lunar soils and select asteroidal and lunar regolith breccias [3-5]. With the return of samples from the Hayabusa mission to asteroid Itoka-wa [6], for the first time we are able to compare space-weathering features on returned surface soils from a known asteroidal body. Analysis of these samples will contribute to a more comprehensive model for how space weathering varies across the inner solar system. Here we report detailed microchemical and microstructal analysis of surface grains from Itokawa.

Thompson, M. S.↗

Material Concerns: Evaluating Sulfur Concrete for use in the Lunar Environment

On Earth sulfur "concrete" is an established construction material that has good mechanical properties, generally better than Portland cement, and can be used in corrosive environments. Troilite (FeS) has been found on the moon and raises the question of using extracted sulfur as a lunar construction material, an attractive alternative to conventional concrete as it does not require water. Troilite reduction to elemental sulfur and using it to make concrete in a lunar setting has been previously discussed. However, little has been experimentally done to evaluate its performance in the extreme lunar environment. This study subjected sets of sulfur concrete samples, prepared using JSC-1 lunar simulant, to I ) extended periods of high vacuum and 2) extreme temperature cycles. Here an overview of sulfur concrete and experimentally assessed properties, put in context of the lunar environment, is presented and discussed.

Grugel, Richard N.↗

Metallic phases in the Luna 24 soil samples

The metal and sulfide phases in the Luna 24 soil samples were studied with the optical microscope and the electron microprobe. The compositions of the metal particles fall into three groups based on their Ni and Co contents: (1) Samples of meteoritic composition which have undergone metamorphism on the lunar surface. (2) Samples of submeteoritic, low Ni and low Co contents, including most of the metal particles observed. These particles are contained in glass and agglutinate particles and were probably formed by the mixing of meteoritic metal with lunar metal produced by the reduction of silicates during shock-impact. (3) Samples of high-CO content probably formed by mixing of meteoritic material with high-Co metal from the mare basalt or by fractional crystallization from a metal silicate melt. The sulfide minerals were also studied. These are almost pure FeS, and crystallized from a late stage liquid in the mare basalt. Three high-Ni sulfides were also found in the glass phase of agglutinates.

Friel, J. J.↗