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Carbon and Si isotopic ratios of SiC grains of type Y point to an origin in AGB stars of lower-than-solar metallicity. Comparison with model calculations indicate that stars with metallicity Z = 0.01 and 3-5 solar masses best account for the experimental data.
The combination of density functional theory (DFT) frequencies and infrared (IR) intensities and experimental spectra is a very powerful tool in the identification of molecules and ions. The computed and measured isotopic ratios make the identification much more secure than frequencies and intensities alone. This will be illustrated using several examples, such as Mn(CO)n and Mn(CO)n-. The accuracy of DFT metal-ligand bond energies will also be discussed.
Establishing chemical links between meteorites and small solar system bodies, such as comets and asteroids, provides a tool for investigating the processes that occurred during the formation of the solar system. Carbonaceous meteorites are of particular interest, since they may have seeded the early Earth with a variety of prebiotic organic compounds including amino acids, purines and pyrimidines, which are thought to be necessary for the origin of life. Here we report the results of high-performance liquid chromatography (HPLC) based amino acid analyses of the acid-hydrolyzed hot water extracts from pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna and the CM meteorites Murchison and Murray. We found that the CI meteorites Orgueil and Ivuna contained high abundances of beta-alanine and glycine, while only traces of other amino acids like alanine, alpha-amino-n-butryic acid (ABA) and alpha-aminoisobutyric acid (AIB) were detected in these meteorites. Carbon isotopic measurements of beta-alanine and glycine in Orgueil by gas chromatography combustion-isotope ratio mass spectrometry clearly indicate an extraterrestrial origin of these amino acids. The amino acid composition of Orgueil and Ivuna was strikingly different from the CM chondrites Murchison and Murray. The most notable difference was the high relative abundance of B-alanine in Orgueil and Ivuna compared to Murchison and Murray. Furthermore, AIB, which is one of the most abundant amino acids found in Murchison and Murray, was present in only trace amounts in Orgueil and Ivuna. Our amino acid data strongly suggest that the CI meteorites Orgueil and Ivuna came from a different type of parent body than the CM meteorites Murchison and Murray, possibly from an extinct comet. It is generally thought that carbonaceous meteorites are fragments of larger asteroidal bodies delivered via near Earth objects (NEO). Orbital and dynamic studies suggest that both fragments of main belt asteroids and comets replenish the NEO population, therefore extinct comets may contribute up to half of all NEO's. A comparison of an amino acid analysis of a returned NEO sample to CI and CM carbonaceous chondrites would help establish a link between small solar system bodies and meteorites. Based on our amino acid measurements of CI and CM chondrites, amino acid chemistry can be included as an additional set of criteria to constrain the nature of meteorite parent bodies.
This grant aimed to establish how the global carbon cycle has responded and will respond to global change. We proposed to use models to predict measurements of atmospheric CO2 concentration and C-13/C-12 isotopic ratio, and thereby to establish how sources and sinks of atmospheric CO2 have been influenced by climatic change and human activities. As the work progressed we developed strategies involving finding regional sources and sinks of atmospheric CO2 by an inverse approach, and studying their seasonal and interannual variability.
Extraterrestrial material is the source of metal ions in the Earth's atmosphere, Each year approx. 10(exp 8) kg of material is intercepted by the Earth. The origin of this material is predominantly solar orbiting interplanetary debris from comets or asteroids that crosses the Earth's orbit. It contains a very small amount of interstellar material. On occasion the Earth passes through enhanced amounts of debris associated with the orbit of a decaying comet. This leads to enhanced meteor shower displays for up to several days. The number flux of shower material is typically several times the average sporadic background influx of material. Meteoric material is some of the earliest material formed in the solar system. By studying the relative elemental abundances of atmospheric metal ions, information can be gained on the chemical composition of cometary debris and the chemical makeup of the early solar system. Using in situ sampling with rocket-borne ion mass spectrometers; there have been approximately 50 flights that made measurements of the metal ion abundances at attitudes between 80 and 130 km. It is this altitude range where incoming meteoric particles am ablated, the larger ones giving rise to visible meteor. displays. In several rocket measurements isotopic ratios of different atomic ion mass components and metal molecular ion concentrations have been determined and used to identify unambiguously the measured species and to investigate the processes controlling the metal ion distributions The composition of the Earth's ionosphere was first sampled by an ion mass spectrometer flown an a rocket in 1956. In 1958 a rocket-borne ion spectrometer identified, fbr the first time, a layer of metal ions near 95 km. These data were interpreted as evidence of an extraterrestrial rather than a terrestrial source. Istomin predicted: "It seems probable that with some improvement in the method that analysis of the ion composition in the E-region may be used for determining the chemical composition of those meteors which do not reach the ground. Particularly, we hope to get information about the composition difference between particles of different meteor showers and also sporadic and shower meteoroids". These visions categorized the aims of many subsequent rocket-borne ion mass spectrometer experiments in the lower ionosphere, Although the use such measurements to deduce the composition of different classes of meteoroids has not been successful, the past four decades of rocket observations have provided po%erful sets of data for advancing our understanding of meteor ablation, meteoric composition, metal neutral and ion chemistry as well as ionospheric dynamics.
The research supported by this grant has focused on isotopic ratios in comets and in the atmosphere of Titan, and the determinations of surface compositions of outer solar system bodies.
Miniature mass filters (e.g., quadrupoles, ion traps) have been the subject of several miniaturization efforts. A project is currently in progress at JPL to develop a miniaturized Gas Chromatograph/Mass Spectrometer (GC/MS) system, incorporating and/or developing miniature system components including turbomolecular pumps, scroll type roughing pump, quadrupole mass filter, gas chromatograph, precision power supply and other electronic components. The preponderance of the system elements will be fabricated using microelectromechanical systems (MEMS) techniques. The quadrupole mass filter will be fabricated using an X-ray lithography technique producing high precision, 5x5 arrays of quadrupoles with pole lengths of about 3 mm and a total volume of 27 cubic mm. The miniature scroll pump will also be fabricated using X-ray lithography producing arrays of scroll stages about 3 mm in diameter. The target detection range for the mass spectrometer is 1 to 300 atomic mass units (AMU) with are solution of 0.5 AMU. This resolution will allow isotopic characterization for geochronology, atmospheric studies and other science efforts dependant on the understanding of isotope ratios of chemical species. This paper will discuss the design approach, the current state-of-the art regarding the system components and the progress toward development of key elements. The full system is anticipated to be small enough in mass, volume and power consumption to allow in situ chemical analysis on highly miniaturized science craft for geochronology, atmospheric characterization and detection of life experiments applicable to outer planet roadmap missions.
Two models for generation of heterogeneous He, Ne and Ar isotopic ratios in Icelandic basalts are evaluated using a mixing model and the observed noble gas elemental ratios in Icelandic basalts,Ocean island Basalt (OIBs) and Mid-Ocean Ridge Basalt (MORBs). Additional information is contained in the original extended abstract.
Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of perdeuterated naphthalene, phenanthrene, pyrene, and chrysene. We also report matrix- isolation spectra for these four species. The theoretical and experimental frequencies and relative intensities for the perdeuterated species are in generally good agreement. The effect of perdeuteration is to reduce the sum of the integrated intensities by a factor of about 1.75. This reduction occurs for all vibrational motions, except for the weak low frequency ring deformation modes. There is also a significant redistribution of the relative intensities between the out-of-plane C-D bands relative to those found for the out-of-plane C-H bands. The theoretical isotopic ratios provide an excellent diagnostic of the degree of C-H(C-D) involvement in the vibrational bands, allowing in most cases a clear distinction of the type of motion.
Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described by Rao et al. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.
Infrared spectroscopy of the dust in comets reveals a complex mix of silicate materials, including both crystalline and non-crystalline components of both olivine (forsterite) and pyroxene composition. These various components do not necessarily share a common origin. Since comets formed in cold regions of the solar nebula, pre-solar grains in the nebula could have been accreted into comets with little alteration. Some of the cometary silicates may be of circumstellar (formed in circumstellar outflows of evolved stars) or interstellar (formed in dense region of the interstellar medium) origin. Spectral similarities to both circumstellar and interstellar silicates are seen in comet spectra. the short-period Kuiper Belt comets) show weak or no spectral features. The lack of features is generally explained as a particle size effect: the small silicate grains are embedded in larger, optically thick particles. However, compositional differences cannot be ruled out. For example, no unambiguous signature of forsterite has yet been seen in the spectrum of a short-period comet. Thus, the Stardust sample from short-period comet P/Wild 2 will be extremely valuable. Not only grain by grain composition and isotopic ratios but also grain morphology, irradiation history, and evidence of organic refractory mantles are important for understanding their origin. The relative abundance and distinguishing characteristics of the various crystalline and non-crystalline silicate components needs to be established. While some comets, such as Hale-Bopp, display a rich infrared spectrum, others (particularly
Martian meteorite (shergottite) impact melt glasses that contain high concentrations of martian atmospheric noble gases and show significant variations in Sr-87/Sr-86 isotopic ratios are likely to contain Martian surface fines mixed with coarser regolith materials. The mixed soil constituents were molten due to shock at the time of meteoroid impact near the Martian surface and the molten glass got incorporated into the voids and cracks in some shergottite meteorites. Earlier, Rao et al. found large enrichments of sulfur (sulfate) during an electron-microprobe study of several impact melt glass veins and pods in EET79001,LithC thin sections. As sulfur is very abundant in Martian soil, these S excesses were attributed to the mixing of a soil component containing aqueously altered secondary minerals with the LithC precursor materials prior to impact melt generation. Recently, we studied additional impact melt glasses in two basaltic shergottites, Zagami and Shergotty using procedures similar to those described. Significant S enrichments in Zagami and Shergotty impact melt glass veins similar to the EET79001, LithC glasses were found. In addition, we noticed the depletion of the mafic component accompanied by the enrichment of felsic component in these impact melt glass veins relative to the bulk host rock in the shergottites. To explain these observations, we present a model based on comminution of basaltic rocks due to meteoroid bombardment on martian regolith and mechanical fractionation leading to enrichment of felsics and depletion of mafics in the fine grained dust which is locally mobilized as a result of saltation and deflation due to the pervasive aeolian activity on Mars.
The Milton pallasite was found in Missouri, U.S.A. in October, 2000. It consists of a single stone that originally weighed approximately 2040 g. The chemistry of the olivine and metal phases, plus the oxygen isotope ratios of the olivines, differ significantly from other pallasites, making Milton unique. Unfortunately, the meteorite is heavily fractured and weathered.
Grain size separate CG from the Murray CM2 carbonaceous chondrite contains mostly spinel grains of average diameter 0.5 m. Zinner et al. found that approximately 1% of these spinel grains are of presolar origin as determined by their large O isotopic anomalies. These O isotopic measurements were made with the NanoSIMS on individual grains that were well separated from one another on a gold foil. The grains were selected for analysis from secondary electron and secondary O-16(-) images. The primary beam was then successively deflected onto these single grains for O isotopic analysis. While single grain analysis on dispersed samples is effective for finding relatively abundant anomalous grains, ion imaging in a raster mode on tightly packed grains might be more efficient for locating few anomalous grains among predominantly isotopically normal grains. In fact, this was the analysis mode used by Messenger et al. to discover presolar silicates in interplanetary dust particles. In an exploratory effort that is also geared toward establishing the optimum isotopic imaging technique in the search for presolar silicate grains in primitive meteorites, we measured O isotopic ratios in spinel grains from the Murray CG separate by raster imaging of areas with more or less tightly packed grains.
The Isotope Magnet Experiment (ISOMAX) a balloon-borne superconducting magnet spectrometer was designed to measure the isotopic composition of the light isotopes (3 less than or equal to Z less than or equal to 8) of the cosmic radiation up to 4 GeV nucleon (exp -1) with a mass resolution of better than 0.25 amu by using the velocity vs. rigidity technique. To achieve this stringent mass resolution ISOMAX was comprised of three major detector systems, a magnetic rigidity spectrometer with a precision drift chamber tracker in conjunction with a three-layer time-of-flight system and two silica-aerogel Cherenkov counters for the velocity determination. A special emphasis of the ISOMAX program was the accurate measurement of radioactive Be-10 with respect to its stable neighbor isotope Be-9, which provides important constraints on the age of cosmic rays in the Galaxy. ISOMAX had its first balloon flight on August 4-5, 1998, from Lynn Lake, Manitoba, Canada. Thirteen hours of data were recorded during this flight at a residual atmosphere of less than 5 g per square centimeter. The isotopic ratio at the top of the atmosphere for Be-10/Be-9 was measured to be 0.195 plus or minus 0.036 (statistical) plus or minus 0.039 (systematic) between 0.26 - 1.03GeV nucleon (exp -1) and 0.317 plus or minus 0.109 (statistical) plus or minus 0.042 (systematic) between 1.13 - 2.03GeV nucleon(exp -1). This is the first measurement of its kind above 1 GeV nucleon (exp -1). ISOMAX results tend to be higher than predictions from current propagation models.
The NASA Genesis spacecraft was launched August 8, 2001 on a mission to collect samples of solar wind for 2 years and return them to earth September 8, 2004. Detailed analyses of the solar wind ions implanted into high-purity collection substrates will be carried out using various mass spectrometry techniques. These analyses are expected to determine key isotopic ratios and elemental abundances in the solar wind, and by extension, in the solar photosphere. Further, the photospheric composition is thought to be representative of the solar nebula with a few exceptions, so that the Genesis mission will provide a baseline for the average solar nebula composition with which to compare present-day compositions of planets, meteorites, and asteroids. The collection of solar wind samples is almost complete. Collection began for most substrates in early December, 2001, and is scheduled to be complete on April 2 of this year. It is critical to understand the solar-wind conditions during the collection phase of the mission. For this reason, plasma ion and electron spectrometers are continuously monitoring the solar wind proton density, velocity, temperature, the alpha/proton ratio, and angular distribution of suprathermal electrons. Here we report on the solar-wind conditions as observed by these in-situ instruments during the first half of the collection phase of the mission, from December, 2001 to present.
Topics discussed include: Presolar Silicate Grains; Presolar Silicates from Primitivr Chondrites; Oxygen and Magnesium Isotopic Ratios of Presolar Spinel Grains; Study of Two New Presolar Grains from Bishunpur Ordinary Chondrite; Extinct Technetium in Presolar Grains; etc.
Titan is unique in the solar system, the only moon that has a dense atmosphere. The major constituents of the atmosphere, nitrogen and methane, are continuously broken apart by a combination of solar UV, impinging electrons from Saturn s magnetosphere, and a steady flux of cosmic rays. The resulting molecular fragments recombine and form a variety of new species, many of which were detected for the first time by Voyager1 . The ubiquitous, surface- hiding aerosol blanket manifests the existence of still more complex compounds. In addition to hydrocarbons and nitriles, the atmosphere is known to contain CO, CO2 and externally delivered H2O. The Gas Chromatograph Mass Spectrometer (GCMS) on the Huygens Probe will measure the chemical composition of the atmosphere of Titan from 170 Km altitude (approximately 1hPa) to the surface (approximately 1500hPa) and determine the isotope ratios of the major constituents. The GCMS will also analyze gas samples from the Aerosol Collector Pyrolyser (ACP) and may be able to obtain compositional information of several surface materials. The GCMS consists of a quadrupole mass spectrometer (QP) with a secondary electron multiplier ion detector, a three-column gas chromatograph (GC) and an elaborate gas sampling system. The gas sampling system will provide atmospheric samples to the QP for nearly continuous analysis during the Probe descent and batch samples at several altitudes for GC analysis. It also contains a chemical scrubber for noble gas analysis and an enrichment cell for trace constituent enhancement. In addition to the sampling of the atmosphere periodic gas samples, derived from the pyrolysis of aerosols, will be transferred from the ACP to the GCMS for direct QP and full GCMS analysis. The QP can analyze molecular masses from 2 to 141Dalton. The nominal detection threshold is at a mixing ratio of 10E-8. Data rate is 885 bits/sec. The mass of the instrument is 17.3 kg and the energy required for operation during the descent is 110 Watt-hours.