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At least 37 records · Page 2

Organic Aggregates with (delta)D and delta(sup 15)N Anomalies in the Zag Clast Revealed by STXM and NanoSIMS

Xenolithic clasts are often found in a wide variety of meteorite groups. Some ordinary chondrite clasts are interesting since these clasts might have originated from Ceres which shares crossing orbits with a possible ordinary chondrite parent body, Hebe. The Zag meteorite contains a dark clast dominated by saponite, serpentine, carbonates, sulfides, magnetite, minor olivine and pyroxene, which is consistent with formation on a large, carbonaceous, aqueously active body, e.g., Ceres. Abundant large C-rich grains up to 20 microns were found in the Zag clast as well. Such large C-rich grains are unique among any other meteorites in our knowledge, and will provide important clues to decipher the origin of the clast and accretion history. C-rich grains were selected in the Zag dark clast using SEM and approximately 100 nm-thick sections were prepared using a focused ion beam (FIB) at NASA-JSC. The sections were analyzed using the scanning transmission X-ray microscope (STXM) on beamline 5.3.2.2 at Advanced Light Source, LBNL, and BL-13A at the Photon Factory, KEK. Subsequently, the FIB section was analyzed for H, C and N isotopic compositions using a CAMECA NanoSIMS 50L ion microprobe at Kochi Institute for Core Sample Research, JAMSTEC

Kebukawa, Y.↗

Elucidating Drought-Tolerance Mechanisms in Plant Roots through 1H NMR Metabolomics in Parallel with MALDI-MS, and NanoSIMS Imaging Techniques

As direct mediators between plants and soil, roots play an important role in metabolic responses to environmental stresses such as drought, yet these responses are vastly uncharacterized on a plant-specific level, especially for co-occurring species. Here, we aim to examine the effects of drought on root metabolic profiles and carbon allocation pathways of three tropical rainforest species by combining cutting-edge metabolomic and imaging technologies in an in situ position-specific 13C-pyruvate root-labeling experiment. Further, washed (rhizosphere-depleted) and unwashed roots were examined to test the impact of microbial presence on root metabolic pathways. Drought had a species-specific impact on the metabolic profiles and spatial distribution in Piper sp. and Hibiscus rosa sinensis roots, signifying different defense mechanisms; Piper sp. enhanced root structural defense via recalcitrant compounds including lignin, while H. rosa sinensis enhanced biochemical defense via secretion of antioxidants and fatty acids. In contrast, Clitoria fairchildiana, a legume tree, was not influenced as much by drought but rather by rhizosphere presence where carbohydrate storage was enhanced, indicating a close association with symbiotic microbes. This study demonstrates how multiple techniques can be combined to identify how plants cope with drought through different drought-tolerance strategies and the consequences of such changes on below-ground organic matter composition.

Drought, Carbon cycle, MALDI-MSI, Metabolomics, Na↗

Nitrogen and Carbon Isotopic Composition of Silicon Carbide in the CO3.0 Meteorite ALHA 77307, a NanoSIMS Study

Presolar grains have been identified in primitive members of all chondrite classes [1, 2]. The study of the isotopic compositions of presolar grains provides information on galactic evolution and nucleosynthesis in stars [3, 4], while the abundances and characteristics of presolar grains contain a record of thermal processing in the solar system [2, 5]. Much of the detailed work on presolar silicon carbide grains has focused on Murchison [e.g., 2] and Orgueil [4], but several other carbonaceous [6, 7], ordinary, and enstatite chondrites [8-11] have also been studied. This study investigates the isotopic composition of silicon carbide from the CO3.0 carbonaceous chondrites ALHA77307 and Colony. SiC is present in ALHA77307 at a matrix normalized abundance of ~8.8 ppm [5], which is approximately twice the abundance of Colony [5], but less than in CI chondrites and the matrices of CM and primitive ordinary and enstatite chondrites [3]. The abundances of SiC and other presolar grains in ALHA77307 seem to correlate with the degree of chemical processing that produced CO3 chondrites [2, 5]. This implies that the same nebular processing that produced the bulk composition of the CO3 chondrite class also modified the assemblage of known presolar grains [5]. To test whether all chondrite classes originated from the same reservoir of presolar dust it is necessary to look for primary differences, not related to thermal processing, between SiC in CO3 chondrites and other chondritic meteorites.

Smith, J. B.↗

NanoSIMS Determination of Carbon and Oxygen Isotopic Compositions of Presolar Graphites from the Murchison Meteorite

Graphite from the Murchison density separate KFC1 (2.15 - 2.20 g/cu cm) has previously been studied by combined SEM/EDX and ion microprobe analysis. These studies found several distinct morphological types of graphites and C isotopic compositions that vary over more than 3 orders of magnitude, clearly establishing their presolar origin. Subsequent TEM measurements of a subset of these particles found abundant embedded crystals of metal (Zr, Mo, Ti, Ru) carbides which were incorporated during the growth of the graphites. A new TEM study of a large set of KFC1 graphites led to the discovery of another type of presolar material, Ru-Fe metal. Here we report results of the C and O isotopic measurements in the same graphite sections, which makes it possible for the first time to directly correlate isotopic and TEM data of KFC1 grains.

Stadermann, F. J.↗

TEM and NanoSIMS Study of Hydrated/Anhydrous Phase Mixed IDPs: Cometary or Asteroidal Origin?

Chondritic interplanetary dust particles (IDPs) are subdivided into (1) particles that form highly porous aggregates (chondritic porous "CP" IDPs), and (2) smooth particles ("CS" IDPs). Infrared (IR) spectroscopy has been a valuable tool for non-destructively determining the bulk mineralogy of IDPs. Most IDPs fall within three distinct IR groups: (1) olivine-rich particles, (2) pyroxene-rich particles, and (3) phyllosilicate-rich particles. From the IR studies, IDPs dominated by anhydrous minerals tend to be fine grained (CP), while phyllosilicate-rich IDPs are mostly CS. CP IDPs have been linked to cometary sources based on their compositions, spectral properties, and atmospheric entry velocities. Since no spectral signatures of hydrated minerals have been detected in comets, CS IDPs are thought to derive from primitive asteroids. Transmission electron microscopy (TEM) studies have revealed that the mineralogical distinctions between CP and CS IDPs are not always clear. Previous investigators have reported trace amounts of hydrous minerals in dominantly anhydrous particles. A better understanding of these particles will help to elucidate whether there is a genetic relationship between anhydrous and hydrated IDPs, provide insight into the earliest stages of aqueous alteration of primitive materials, and may help to determine whether comets have experienced any aqueous processing. Here we report a combined TEM and isotopic imaging study of an unusual anhydrous IDP with hydrated phases. Additional information is included in the original extended abstract.

Nakamura, K.↗

Coordinated Stem and NanoSIMS Analysis of Enstatite Whiskers in Interplanetary Dust Particles

Enstatite whiskers (less than 10 micrometer length, less than 200 nanometer width) occur in chondritic-porous interplanetary dust particles (CP IDPs), an Antarctic micrometeorite and a comet 81P/Wild-2 sample. The whiskers are typically elongated along the [100] axis and contain axial screw dislocations, while those in terrestrial rocks and meteorites are elongated along [001]. The unique crystal morphologies and microstructures are consistent with the enstatite whiskers condensing above approximately 1300 K in a low-pressure nebular or circumstellar gas. To constrain the site of enstatite whisker formation, we carried out coordinated mineralogical, chemical and oxygen isotope measurements on enstatite whiskers in a CP IDP.

Nakamura-Messenger, K.↗

Coordinated In Situ Nanosims Analyses of H-C-O Isotopes in ALH 84001 Carbonates

The surface geology and geomorphology of Mars indicate that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. This study reports the hydrogen, carbon, and oxygen isotope compositions of the ancient atmosphere/hydrosphere of Mars based on in situ ion microprobe analyses of approximately 4 Ga-old carbonates in Allan Hills (ALH) 84001. The ALH 84001 carbonates are the most promising targets because they are thought to have formed from fluid that was closely associated with the Noachian atmosphere. While there are a number of carbon and oxygen isotope studies of the ALH 84001 carbonates, in situ hydrogen isotope analyses of these carbonates are limited and were reported more than a decade ago. Well-documented coordinated in situ analyses of carbon, oxygen and hydrogen isotopes provide an internally consistent dataset that can be used to constrain the nature of the Noachian atmosphere/hydrosphere and may eventually shed light on the hypothesis of ancient watery Mars.

Usui, T.↗

Coordinated NanoSIMS and TEM Analysis of a Large 26Mg-Rich AGB Silicate from the Meteorite Hills 00426 CR2 Chondrite

Silicates are one of the most abundant presolar phases around evolved stars, in the inter-stellar medium (ISM), and in our Solar System. These grains afford the opportunity for O, Si, Mg, Fe, and Ca isotopic analyses to constrain stellar nucleosynthetic and mixing processes, and Galactic chemical evolution (GCE). While Mg and Fe isotopic studies have been successfully conducted on presolar silicates, isotopic analyses beyond O and Si are often hampered by the small grain sizes (average ~250 nm). This also makes coordinated mineral and chemical characterization challenging. These studies provide insight into the dust condensation conditions as well as subsequent alteration in the ISM and/or the Solar System. TEM studies of presolar silicates have shown that they are much more mineralogically and chemically diverse than other presolar phases [1 and references therein]. Large (>500nm) presolar silicate grains are rare, but they allow for detailed isotopic, mineral, and chemical characterization. We identified a large presolar silicate grain in the MET 00426 CR2 chondrite and report the O, Si, Mg, and Fe isotopic compositions and TEM study of this grain.

Nguyen, A. N.↗

Correlating Nanoscale Secondary Ion Mass Spectrometry and Atom Probe Tomography Analysis of Uranium Enrichment in Metallic Nuclear Fuel

Distribution and enrichment of 235U within nuclear fuels are essential to material performance and reactor safety. With the development of metallic U fuels, understanding 235U homogeneity has become increasingly important, however, it is difficult to map with high spatial, and mass resolution to analyze both matrix and secondary phase precipitates. Here, we analyze 235U enrichment in matrix and carbide phases in LEU-Mo via two chemical imaging modalities: nanoscale secondary ion mass spectrometry (nanoSIMS) and atom probe tomography (APT). NanoSIMS and APT provided consistent results, with no statistically significant difference between measured and nominal enrichment (19.75 % 235U).

U-10Mo, atom probe tomography, nanoscale secondary↗

'Nano' Morphology and Element Signatures of Early Life on Earth: A New Tool for Assessing Biogenicity

The relatively young technology of NanoSIMS is unlocking an exciting new level of information from organic matter in ancient sediments. We are using this technique to characterize Proterozoic organic material that is clearly biogenic as a guide for interpreting controversial organic structures in either terrestrial or extraterrestrial samples. NanoSIMS is secondary ion mass spectrometry for trace element and isotope analysis at sub-micron resolution. In 2005, Robert et al. [1] combined NanoSIMS element maps with optical microscopic imagery in an effort to develop a new method for assessing biogenicity of Precambrian structures. The ability of NanoSIMS to map simultaneously the distribution of organic elements with a 50 nm spatial resolution provides new biologic markers that could help define the timing of life s development on Earth. The current study corroborates the work of Robert et al. and builds on their study by using NanoSIMS to map C, N (as CN), S, Si and O of both excellently preserved microfossils and less well preserved, non-descript organics in Proterozoic chert from the ca. 0.8 Ga Bitter Springs Formation of Australia.

Oehler, D. Z.↗

The History of Presolar Grains

Below we summarize the results of our investigations into the history of presolar grains that were conducted in the last year. During this time we have expended much of our effort in the development of experimental techniques and sample preparation methods that are needed to laboratory in December, 2000. Specific information on this instrument is contained in the Full Proposal of PI Ernst Zinner and will not be repeated here. Our general strategy in the past year has been in large measure to explore novel sample handling methods for the very small (sub-micron), but more representative, presolar grains that can now be characterized isotopically in the NanoSIMS. We have developed experimental techniques that will permit NanoSIMS analyses of the very same ultramicrotome sections studied in the TEM, and we have developed grain dispersion, handling and mounting techniques that permit NanoSIMS isotopic analysis as well as field emission SEM, high energy TEM, and atomic force microscopy of pristine presolar grains. Although much of this has been slow and very difficult work that has no immediate payoff in terms of publishable results, we considered it absolutely necessary groundwork for future discoveries, especially in the realm of individual presolar grains that have been inaccessible to past studies due to size constraints. As discussed below, we have been largely successful in these endeavors, and expect to reap the benefits of this work in the next year. We also report on our continued morphologic studies of pristine presolar grains, on our investigations of presolar graphite grains from supernovae as well as on rarer types of presotar SIC, on the search for presolar silicates, and on our efforts to obtain direct size-distribution information on presolar SiC through X-ray mapping techniques.

Bernatowicz, Thomas J.↗

SIMS Studies of Allende Projectiles Fired into Stardust-type Aluminum Foils at 6 km/s

We have explored the feasibility of C-, N-, and O-isotopic measurements by NanoSIMS and of elemental abundance determinations by TOF-SIMS on residues of Allende projectiles that impacted Stardust-type aluminum foils in the laboratory at 6 km/s. These investigations are part of a consortium study aimed at providing the foundation for the characterization of matter associated with micro-craters that were produced during the encounter of the Stardust space probe with comet 81P/Wild 2. Eleven experimental impact craters were studied by NanoSIMS and eighteen by TOF-SIMS. Crater sizes were between 3 and 190 microns. The NanoSIMS measurements have shown that the crater morphology has only a minor effect on spatial resolution and on instrumental mass fractionation. The achievable spatial resolution is always better than 200 nm, and C- and O-isotopic ratios can be measured with a precision of several percent at a scale of several 100 nm, the typical size of presolar grains. This clearly demonstrates that presolar matter, provided it survives the impact into the aluminum foil partly intact, is recognizable even if embedded in material of Solar System origin. TOF-SIMS studies are restricted to materials from the crater rim. The element ratios of the major rockforming elements in the Allende projectiles are well characterized by the TOF-SIMS measurements, indicating that fractionation of those elements during impact can be expected to be negligible. This permits information on the type of impactor material to be obtained. For any more detailed assignments to specific chondrite groups, however, information on the abundances of the light elements, especially C, is crucial.

Hoppe, Peter↗

Comparing Analysis of Hydrogen Concentration in Astromaterials Nominally Anhydrous Minerals by Multiple SIMS

Secondary Ion Mass Spectrometry (SIMS) is utilized to determine hydrogen (H) concentration in astromaterials nominally anhydrous minerals (NAMs) and their inclusions [e.g., 1]. This data is interpreted to refine the volatile history of planetary bodies. Four instruments are being used to compare H concentration analysis: a large geometry SIMS (The University of Hawaiʻi Cameca IMS 1280), a compact SIMS (Arizona State University (ASU) Cameca IMS 6f), and two Cameca NanoSIMS 50L at ASU and NASA-Johnson Space Center (JSC). Results on the first three instruments are available. Although fundamentally similar, SIMS instruments and their modifications [2] may produce different values or pose advantages for H analysis, especially for shocked samples that are susceptible to contamination filling their fractures. New data from the IMS 1280 is reported, using its microchannel plate (MCP) to image high H signals in grain fractures during pre-sputtering to avoid them as much as possible. Between fractures, 16 OH/ 30 Si was measured with a Cs + 4 nA primary beam, 30 micron spot size, and central ~5x5 micron collection area. First order comparison of H concentration (reported in ppm H 2 O) is achieved on a terrestrial gem quality clinopyroxene (SLP114, 162±12 ppm H 2 O [3]), with 157±7 and 215±40 ppm H 2 O by the IMS 1280 and 6f respectively. SIMS comparison is then extended to analysis of two Martian shergottites: RBT 04262 and NWA 5789. Due to a dense fracture network (< 20 micron) in RBT 04262, only one clinopyroxene hosted glassy inclusion was analyzed (n=6, ≤1 ppm H 2 O), while six olivine grains in NWA 5789 (n=12, ≤ 2 ppm H 2 O) (1s ±0.21) were analyzed. Higher concentrations were obtained for RBT 04262 olivine by the ASU NanoSIMS 50L (up to 350 ppm H 2 O [4]), and IMS 6f (300+ ppm H 2 O, [5]), for which contamination in fractures could not be avoided. Work on the JSC NanoSIMS 50L will further develop the SIMS comparison.

J.-M. Dudley↗

Recombination between 13 C and 2 H to Form Acetylide ( 13 C 2 2 H – ) Probes Nanoscale Interactions in Lipid Bilayers via Dynamic Secondary Ion Mass Spectrometry: Cholesterol and GM 1 Clustering

Although it is thought that there is lateral heterogeneity of lipid and protein components within biological membranes, probing this heterogeneity has proven challenging. The difficulty in such experiments is due to both the small length scale over which such heterogeneity can occur, and the significant perturbation resulting from fluorescent or spin labeling on the delicate interactions within bilayers. Atomic recombination during dynamic nanoscale secondary ion imaging mass spectrometry (NanoSIMS) is a non-perturbative method for examining nanoscale bilayer interactions. Atomic recombination is a variation on conventional NanoSIMS imaging, whereby an isotope on one molecule combines with a different isotope on another molecule during the ionization process, forming an isotopically enriched polyatomic ion in a distance-dependent manner. In this work, we show that the recombinant ion, 13 C 2 2 H – , is formed in high yield from 13 C- and 2 H-labeled lipids. The low natural abundance of triply labeled acetylide also makes it an ideal ion to probe GM 1 clusters in model membranes and the effects of cholesterol on lipid–lipid interactions. We find evidence supporting the cholesterol condensation effect as well as the presence of nanoscale GM 1 clusters in model membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗