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NASA NTRS2008

Rapid Contamination During Storage of Carbonaceous Chondrites Prepared for Micro FTIR Measurements

The carbonaceous chondrites Tagish Lake and Murchison, which contain abundant hydrous minerals, when pressed on aluminum plates and analyzed by micro FTIR, were found to have been contaminated during brief (24 hours) storage. This contamination occurred when the samples were stored within containers which included silicone rubber, silicone grease or adhesive tape. Long-path gas cell FTIR measurements for silicone rubber revealed the presence of contaminant volatile molecules having 2970 cm(sup -1) (CH3) and 1265 cm(sup -1) (Si-CH3) peaks. These organic contaminants are found to be desorbed by in-situ heating infrared measurements from room temperature to 200-300 C. Careful preparation and storage are therefore needed for precious astronomical samples such as meteorites, IDPs and mission returned samples from comets, asteroids and Mars, if useful for FTIR measurements are to be made.

Kebukawa, Yoko↗
NASA NTRS2009

Origin and Evolution of Organic Matter Preserved in Stardust Cometary Aerogel Tracks

The STARDUST spacecraft captured dust samples from Comet 81P/Wild 2 at a relative velocity of 6.1 km/s in a low density silica aerogel and returned them to the Earth. One of the main of the scientific goals established for the mission was to determine whether comets contained complex organic materials and, contingently, the nature and abundance of this material. [1] Although contamination concerns due to carbonaceous impurities intrinsic to the flight aerogel remain, it is generally accepted that at least a fraction of the captured dust particles contain an indigenous organic component. [2] However, understanding the nature and abundance of this material is complicated by nature of the collection process. The rapid dissipation of particle s kinetic energy during its impact and deceleration cause both the particle and surrounding aerogel to experience an intense thermal pulse of upwards of 2000K for a period up to several hundred nanoseconds [3]. During this period thermal alteration and or destruction of organic species present in the impacting particle are likely to occur. We have used the technique of ultrafast two-step laser mass spectrometry (ultra L2MS) [4] to investigate how the nature and distribution of aromatic and conjugated organic species varies between and within aerogel cometary tracks and their associated terminal particles.

McKay, D.S.↗
NASA NTRS2009

Evidence for Changes in 81PIWild 2 Organic Matter Since Collection and Comparison of 82PIWild 2 and IDP Organic Matter to Access the Thermal Effects of Aerogel Capture

NASA s Stardust spacecraft collected cometary material during its passage through the dust coma of comet 81P/Wild 2 on January 2nd, 2004 and delivered this material to Earth on January 15th 2006. The first fragment we analyzed during the preliminary examination was partially vaporized by the X-ray beam. The carbonaceous material that survived was re-analysis approx.2 months later and the carbon spectrum for this material had significantly changed from what we first observed.. We have observed similar changes to the carbonaceous matter in some interplanetary dust particles ( IDPs). Some of the 81P/Wild 2 organic matter volatilized upon impact with the aerogel as observed using IR spectroscopy where IR spectra were collected several mms away from sample tracks [1]. The time-temperature profile experienced by any particular 81P/Wild 2 grain during aerogel capture is not known, although Brownlee, et al. suggest that fine-grained materials, <1 micron in size, fragmented and then partially vaporized during collection, while particles much larger then 1 micron in size were captured intact [2]. Nearly all organic matter is subject to thermal alteration. To assess the heating and alteration experienced by the 81P/Wild 2 organic matter during capture we are comparing 81P/Wild2 organic matter with IDP organic matter where we have evidence of heating in the IDP [3,4].

Wirick, S.↗
NASA NTRS2009

Identification of an Extremely 180-Rich Presolar Silicate Grain in Acfer 094

Presolar silicate grains have been abundantly identified since their first discovery less than a decade ago [1,2,3]. The O isotopic compositions of both silicate and oxide stardust indicate the vast majority (>90%) condensed around Orich asymptotic giant branch (AGB) stars. Though both presolar phases have average sizes of ~300 nm, grains larger than 1 m are extremely uncommon for presolar silicates. Thus, while numerous isotopic systems have been measured in presolar oxide grains [4], very few isotopic analyses for presolar silicates exist outside of O and Si [2,5]. And still, these measurements suffer from isotopic dilution with surrounding matrix material [6]. We conduct a search for presolar silicates in the primitive carbonaceous chondrite Acfer 094 and in some cases obtain high spatial resolution, high precision isotopic ratios.

Nguyen, A. N.↗
NASA NTRS2009

Rare Earth Element Measurements of Melilite and Fassaite in Allende Cai by Nanosims

The rare earth elements (REEs) are concentrated in CAIs by approx. 20 times the chondritic average [e.g., 1]. The REEs in CAIs are important to understand processes of CAI formation including the role of volatilization, condensation, and fractional crystallization [1,2]. REE measurements are a well established application of ion microprobes [e.g., 3]. However the spatial resolution of REE measurements by ion microprobe (approx.20 m) is not adequate to resolve heterogeneous distributions of REEs among/within minerals. We have developed methods for measuring REE with the NanoSIMS 50L at smaller spatial scales. Here we present our initial measurements of REEs in melilite and fassaite in an Allende Type-A CAI with the JSC NanoSIMS 50L. We found that the key parameters for accurate REE abundance measurements differ between the NanoSIMS and conventional SIMS, in particular the oxide-to-element ratios, the relative sensitivity factors, the energy distributions, and requisite energy offset. Our REE abundance measurements of the 100 ppm REE diopside glass standards yielded good reproducibility and accuracy, 0.5-2.5 % and 5-25 %, respectively. We determined abundances and spatial distributions of REEs in core and rim within single crystals of fassaite, and adjacent melilite with 5-10 m spatial resolution. The REE abundances in fassaite core and rim are 20-100 times CI abundance but show a large negative Eu anomaly, exhibiting a well-defined Group III pattern. This is consistent with previous work [4]. On the other hand, adjacent melilite shows modified Group II pattern with no strong depletions of Eu and Yb, and no Tm positive anomaly. REE abundances (2-10 x CI) were lower than that of fassaite. These patterns suggest that fassaite crystallized first followed by a crystallization of melilite from the residual melt. In future work, we will carry out a correlated study of O and Mg isotopes and REEs of the CAI in order to better understand the nature and timescales of its formation process and subsequent metamorphic history.

Ito, M.↗
NASA NTRS2007

SPENVIS Implementation of End-of-Life Solar Cell Calculations Using the Displacement Damage Dose Methodology

This paper presents a method for using the SPENVIS on-line computational suite to implement the displacement damage dose (D(sub d)) methodology for calculating end-of-life (EOL) solar cell performance for a specific space mission. This paper builds on our previous work that has validated the D(sub d) methodology against both measured space data [1,2] and calculations performed using the equivalent fluence methodology developed by NASA JPL [3]. For several years, the space solar community has considered general implementation of the D(sub d) method, but no computer program exists to enable this implementation. In a collaborative effort, NRL, NASA and OAI have produced the Solar Array Verification and Analysis Tool (SAVANT) under NASA funding, but this program has not progressed beyond the beta-stage [4]. The SPENVIS suite with the Multi Layered Shielding Simulation Software (MULASSIS) contains all of the necessary components to implement the Dd methodology in a format complementary to that of SAVANT [5]. NRL is currently working with ESA and BIRA to include the Dd method of solar cell EOL calculations as an integral part of SPENVIS. This paper describes how this can be accomplished.

Walters, Robert↗
NASA NTRS2007

Forward Technology Solar Cell Experiment First On-Orbit Data

This paper presents first on orbit measured data from the Forward Technology Solar Cell Experiment (FTSCE). FTSCE is a space experiment housed within the 5th Materials on the International Space Station Experiment (MISSE-5). MISSE-5 was launched aboard the Shuttle return to flight mission (STS-114) on July 26, 2005 and deployed on the exterior of the International Space Station (ISS). The experiment will remain in orbit for nominally one year, after which it will be returned to Earth for post-flight testing and analysis. While on orbit, the experiment is designed to measure a 36 point current vs. voltage (IV) curve on each of the experimental solar cells, and the data is continuously telemetered to Earth. The experiment also measures the solar cell temperature and the orientation of the solar cells to the sun. A range of solar cell technologies are included in the experiment including state-of-the-art triple junction InGaP/GaAs/Ge solar cells from several vendors, thin film amorphous Si and CuIn(Ga)Se2 cells, and next-generation technologies like single-junction GaAs cells grown on Si wafers and metamorphic InGaP/InGaAs/Ge triple-junction cells. In addition to FTSCE, MISSE-5 also contains a Thin-Film Materials experiment. This is a passive experiment that will provide data on the effect of the space environment on more than 200 different materials. FTSCE was initially conceived in response to various on-orbit and ground test anomalies associated with space power systems. The Department of Defense (DoD) required a method of rapidly obtaining on orbit validation data for new space solar cell technologies, and NRL was tasked to devise an experiment to meet this requirement. Rapid access to space was provided by the MISSE Program which is a NASA Langley Research Center program. MISSE-5 is a completely self-contained experiment system with its own power generation and storage system and communications system. The communications system, referred to as PCSat, transmits and receives in the Amateur Radio band providing a node on the Amateur Radio Satellite Service. This paper presents an overview of the various aspects of MISSE-5 and a sample of the first measured on orbit data.

Walters, R. J.↗
NASA NTRS2007

Quantifying Low Energy Proton Damage in Multijunction Solar Cells

An analysis of the effects of low energy proton irradiation on the electrical performance of triple junction (3J) InGaP2/GaAs/Ge solar cells is presented. The Monte Carlo ion transport code (SRIM) is used to simulate the damage profile induced in a 3J solar cell under the conditions of typical ground testing and that of the space environment. The results are used to present a quantitative analysis of the defect, and hence damage, distribution induced in the cell active region by the different radiation conditions. The modelling results show that, in the space environment, the solar cell will experience a uniform damage distribution through the active region of the cell. Through an application of the displacement damage dose analysis methodology, the implications of this result on mission performance predictions are investigated.

Messenger, Scott R.↗
NASA NTRS2009

Molecular Composition of Carbonaceous Globules in the Bells (CM2) Chondrite

Some meteorites and IDPs contain micron-size carbonaceous globules that are associated with significant H and/or N isotopic anomalies. This has been interpreted as indicating that such globules may contain at least partial preserved organic species formed in the outer reaches of the proto-solar disk or the presolar cold molecular cloud. Owing to their small sizes, relatively little is known about their chemical compositions. Here we present in situ measurements of aromatic molecular species in organic globules from the Bells (CM2) chondrite by microprobe two-step laser mass spectrometry. This meteorite was chosen for study because we have previously found this meteorite to contain high abundances of globules that often occur in clusters. The Bells (CM2) globules are also noteworthy for having particularly high enrichments in H-2. and N-15. In this study, we identified individual globules and clusters of globules using native UV fluorescence.

Clemett, S. J.↗
NASA NTRS2010

Search for Organic Nanoglobules in Carbonaceous Chondrites Using Microtomography

Primitive solar materials have various organic matters. In recent years, novel organic materials called organic nanoglobules of a few hundred micrometers in typical size were discovered in carbonaceous chondrites, IDPs, and comet 81P/Wild 2. The organic globules are spherical shape and in many cases with hollow structures. Composition of the globules are mainly aromatic carbon. The isotopic anomalies of SD and 6N 15 observed in the globules indicate that they were formed from photochemical reaction to ice particles at very low temperature environment, such as molecular clouds or outer protosolar disk. Aqueous alteration of organic matters and the gamma-ray irradiation to PAH are also suggested as alternative possible formation processes. If the globules are made from organic ice particles, the hollow regions of the globules are suggested to be once filled with volatile H20-rich organic ices, while if they were formed by aqueous alteration, the hollow regions should be filled with a fluid which caused the aqueous alteration. However, fluids in the globules have not been detected so far in the previous studies. If fluids were originally preserved in the hollows, they might be lost during destructive processes of sample separation or preparation for TEM observation. X-ray computed tomography (CT) is a nondestructive method which can determine 3-D internal structures of objects. SR (synchrotron radiation)-based imaging microtomography can give submicron spatial resolution [8] and was applied to micro textures in extraterrestrial materials, such as cometary grains captured by the Stardust mission [9]. If organic globules are observed non-destructively in carbonaceous chondrites by tomography, we can check the presence of fluids in the hollows. If fluids are preserved, we may analyze chemical and isotopic compositions of the fluids. The purpose of this study is to observe organic nanoglobules using imaging tomography for future analysis.

Matsumoto, T.↗
NASA NTRS2010

FIB-NanoSIMS-TEM Coordinated Study of a Wark-Lovering Rim in a Vigarano Type A CAI

Wark-Lovering (WL) rims are thin multi layered mineral sequences that surround most Ca, Al-rich inclusions (CAIs). Unaltered WL rims are composed of the same primary high temperature minerals as CAIs, such as melilite, spinel, pyroxene, hibonite, perovskite, anorthite and olivine. It is still unclear whether the rim minerals represent a different generation formed by a separate event from their associated CAIs or are a byproduct of CAI formation. Several models have been proposed for the origins of WL rims including condensation, flashheating, reaction of a CAI with a Mg-Si-rich reservoir (nebular gas or solid); on the basis of mineralogy, abundances of trace elements, O and Mg isotopic studies. Detailed mineralogical characterizations of WL rims at micrometer to nanometer scales have been obtained by TEM observations, but so far no coordinated isotopic - mineralogical studies have been performed. Thus, we have applied an O isotopic imaging technique by NanoSIMS 50L to investigate heterogeneous distributions of O isotopic ratios in minerals within a cross section of a WL rim prepared using a focused ion beam (FIB) instrument. After the isotopic measurements, we determine the detailed mineralogy and microstructure of the same WL FIB section to gain insight into its petrogenesis. Here we present preliminary results from O isotopic and elemental maps by NanoSIMS and mineralogical analysis by FE-SEM of a FIB section of a WL rim in the Vigarano reduced CV3 chondrite.

Cai, A.↗
NASA NTRS2010

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average ~230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

Messenger, Scott R.↗
NASA NTRS2010

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Keller, L. P.↗
NASA NTRS2010

The Search for Interstellar Sulfide Grains

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. 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. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

Keller, Lindsay P.↗
NASA NTRS2011

New Titanium Monosulfide Mineral Phase in Yamato 691 Enstatite Chondrite

Yamato 691, an EH3 enstatite chondrite, was among the first meteorites discovered by chance in Antarctica by the Japanese Antarctic Research Expedition (JARE) team in 1969. This discovery led to follow-up searches for meteorites in Antarctica [1]. These international searches have been very successful recovering over 40,000 total specimens (and still counting), including martian and lunar meteorites. Titanium is partly chalcophile in enstatite-rich meteorites. Previous occurrences of Ti-bearing sulfides include troilite, daubrelite and ferroan alabandite in enstatite chondrites and aubrites [2], and heideite with 28.5 wt% Ti in the Bustee aubrite [3]. Here we report a new mineral from Yamato 691, ideally stoichiometric TiS, titanium monosulfide, a simple two-element mineral phase, yet with a very unique crystal structure that, to our knowledge, has not been observed previously in nature.

Nakamura-Messenger, K↗
NASA NTRS2011

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

Nguyen, A. N.↗
NASA NTRS2011

Stratospheric Collection of Dust from Comet 73P/Schwassmann-Wachmann 3

Interplanetary dust particles (IDPs) collected in the stratosphere are unique materials that are compositionally distinct from meteorites. Astronomical observations and dynamical models indicate that both asteroids and short-period comets are significant sources of IDPs. IDPs having fragile, porous structures, unequilibrated, anhydrous mineralogy, and high atmospheric entry velocities are thought to derive from comets, whereas asteroidal IDPs are identified by their compact structure, hydrated mineralogy and low atmospheric entry velocities. Uncertainty remains in the classification of asteroidal and cometary IDPs owing to our limited sampling of comets and the asteroid belt and the complex dynamical histories of most IDPs in space. Most IDPs spend thousands of years in space prior to being accreted by the Earth. During this time, dust particles undergo orbital evolution, including gradual reduction in their perihelion and eccentricity as a result of Poynting-Robertson drag. Planetary encounters may also significantly change their orbital parameters. Consequently, it is generally not possible to identify the specific parent body of a given IDP. However, it has been proposed that it is possible to identify dust from comets that have formed Earth-crossing dust trails. In this case, the dust particles have been in space for such a short period of time (a few decades or less) that their orbits have not significantly changed. Furthermore, these fresh IDPs could be identified in the laboratory from their short space-exposure histories (low solar noble gas abundance and lack of solar flare tracks). NASA flew several dedicated IDP collection missions attempting to collect dust from comet 26P/Grigg-Skjellerup, the best candidate identified. Remarkably, many particles from those collectors exhibit unusual properties, including low abundances of solar noble gases and high abundances of presolar grains. These observations are consistent with the dust particles originating from comet Grigg-Skjellerup (hereafter G-S). This study considers the prospects for collection of dust from comet 73P/Schwassmann-Wachmann 3 (hereafter SW3). SW3 is a small (2 km diameter) Jupiter family comet whose perihelion is close to and just inside the Earth's orbit. The orbit of SW3 is suitable for producing a low-velocity Earth-crossing dust stream and is the likely parent of the Tau Herculid meteor stream. This study complements a previously published model of the SW3 meteor stream that predicted a very low level of activity for grains 100 micron -- 100 mm in size.

Messenger, Scott R.↗
NASA NTRS2011

Organic Compounds in Stardust

The successful return of the STARDUST spacecraft provides a unique opportunity to investigate the nature and distribution of organic matter in cometary dust particles collected from Comet 81P/Wild-2. Analysis of individual cometary impact tracks in silica aerogel using the technique of two-step laser mass spectrometry (L2MS) demonstrates the presence of complex aromatic organic matter. While concerns remain as to the organic purity of the aerogel collection medium and the thermal effects associated with hypervelocity capture, the majority of the observed organic species appear indigenous to the impacting particles and are hence of cometary origin. While the aromatic fraction of the total organic matter present is believed to be small, it is notable in that it appears to be N-rich. Spectral analysis in combination with instrumental detection sensitivities suggest that N is incorporated predominantly in the form of aromatic nitriles (R-C N). While organic species in the STARDUST samples do share some similarities with those present in the matrices of carbonaceous chondrites, the closest match is found with stratospherically collected interplanetary dust particles. These findings are consistent with the notion that a fraction of interplanetary dust is of cometary origin. The presence of complex organic N-containing species in comets has astrobiological implications since comets are likely to have contributed to the prebiotic chemical inventory of both the Earth and Mars.

McKay, David S.↗