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At least 19 records

Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

Non-NASA Center↗

Planetary noble gas components in Orgueil

In the reported investigation, the approach employed by Jeffery and Anders (1970) and Eberhardt (1974), who used colloidal suspensions in separating minerals of the Orgueil carbonaceous chondrite (C1), was extended to an application involving the enrichment of a planetary noble gas carrier in several C1 and C2 meteorites. The thermal release pattern of Orgueil 'carbon' is considered, taking into account elemental effects, a comparison of noble gas release from 'carbon' separates and bulk meteorite samples, isotopic effects, and a comparison with Murray 'carbon'. An evaluation is conducted of the noble gas components in carbonaceous chondrites. The origin of primordial noble gases in carbonaceous chondrites is also discussed, giving attention to the origin of solar gases, the role of 'carbon' as the novel vehicle for planetary gases, and plausible astrophysical sites for the production of anomalous krypton and xenon.

Frick, U.↗

An Update on the Non-Mass-Dependent Isotope Fractionation under Thermal Gradient

Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.

Sun, Tao↗

The isotopic composition of helium at high rigidities

The isotopic abundance distribution of the cosmic radiation at energies beyond 1 GeV/AMU can at the present time be determined only with the geomagnetic method. A balloon-borne instrument was flown for 12 hours near the geomagnetic equator to measure the relative abundance of the helium isotopes He-3 and He-4 around 12 GV rigidity. The sharp rigidity cut-off at equatorial latitudes permitted separation of the two isotopes using a high-resolution-gas Cerenkov counter. The experiment thus confirms the predicted sharp cut-off at those latitudes and demonstrates the potential for isotopic separation of other elements, once flights of longer duration can be made.

Jordan, S. P.↗

s-process Ba, Nd, and Sm in presolar SiC from the Murchison meteorite

Ion microprobe isotopic measurements of Ba, Nd, and Sm in the K-series SiC size separates on which noble gas measurements were made by Lewis et al. (1990) are reported. All elements show isotopic abundance patterns characteristic for the s-process. The Ba-134/Ba-136 ratios are distinct from solar, indicating that s-Ba in SiC is different from that in the solar system. Ba-138/Ba-136 ratios decrease with grain size; if interpreted as being due to different neutron exposures, this trend is opposite of that shown by the Kr-86/Kr-82 ratios. Although other isotropic ratios for Ba and those for Nd and Sm differ in detail from theoretical predictions, the disagreements probably being due to uncertainties in the n-capture cross sections and simplifications in the models, the general agreement of the data with models of s-process nucleosynthesis support an AGB star origin for the relatively fine-grain SiC under consideration. Ba-136 in SiC is up to 85 percent pure s-process.

Zinner, Ernst↗

Isotopic composition and concentration of sulfur in carbonaceous chondrites

New sulfur isotopic ratio measurements are reported for seven carbonaceous chondrites. Newly developed procedures permit measurement of delta S-33, delta S-34, and delta S-36 at precisions significantly greater than previously reported. A search for S-36 nucleosynthetic anomalies coproduced with anomalies in, for example, Ti-50 and Ca-48 was negative. The high endemic sulfur concentration probably dilutes any S-36 anomaly, and separation of individual sulfur phases may be needed to identify S-36 carrier phases. Large internal isotopic variations are observed, deriving from parent body and possibly nebular processes. Chondrule separates from Allende demonstrate isotopic compositions which vary as a function of diameter. High-temperature gas-solid exchange and a two-component mixing model may account for the observations. High-resolution isotopic data and structural information are reported for organic sulfur compounds separated by chemical extractions. The insoluble organics appear to be of either aliphatic or alicyclic structure and are dominant phases.

Gao, Xia↗

Olivine separates from Murchison and Cold Bokkeveld - Particle tracks and noble gases

Olivine separates from Murchison and Cold Bokkeveld were analyzed for particle tracks and noble gases. The matrix remaining after olivine separation was also analyzed for noble gases. The olivines from both meteorites have comparable fractions of solar-flare-irradiated grains, but the highest track densities in Murchison are an order of magnitude greater than those in Cold Bokkeveld. Solar Ne content in Murchison olivines follows this trend, being at least an order of magnitude higher than that in Cold Bokkeveld. Track gradients in Cold Bokkeveld olivines are flatter than those in Murchison or recently exposed lunar crystals. Relative to the matrix, olivine separates in both meteorites have small enrichments at the heavy and light Xe isotopes and smaller Ar-36/Ar-38 ratios. These noble-gas effects may be related to a chromite impurity in the olivine separates.

Macdougall, J. D.↗

Composition of solar wind noble gases released by surface oxidation of a metal separate from the Weston meteorite

The paper reports on a set of experiments intended to test the feasibility of determining elemental and isotopic ratios of the noble gases and nitrogen in the solar wind in metal separates from gas-rich ordinary chondrites. Helium, neon, and argon show clear evidence of a solar wind signature, while no solar component could be identified for xenon and nitrogen. Helium, neon, and argon elemental isotopic ratios appear to depend on depth within the metal grains. The ratios derived indicate that the Weston meteorite did not acquire its solar wind gases from a recent exposure to solar wind, but more probably at a time in the past similar to or even earlier than the exposure time of Apollo 17 breccias. The Ar-36/Ar-38 ratio, in tandem with other recent determinations of this value, indicates that the solar and terrestrial values can no longer be assumed to be equivalent.

Becker, R. H.↗

Noble gases in presolar diamonds I: Three distinct components and their implications for diamond origins

High-purity separates of presolar diamond were prepared from 14 primitive chondrites from 7 compositional groups. Their noble gases were measured using stepped pyrolysis. Three distinct noble gas components are present in diamonds, HL, P3, and P6, each of which is found to consist of five noble gases. P3, released between 200 C and 900 C, has a 'planetary' elemental abundance pattern and roughly 'normal' isotopic ratios. HL, consisting of isotopically anomalous Xe-HL and Kr-H, Ar with high Ar-38/Ar-36, and most of the gas making up Ne-A2 and He-A, is released between 1100 C and 1600 C. HL has 'planetary' elemental ratios, except that it has much more He and Ne than other known 'planetary' components. HL gases are carried in the bulk diamonds, not in some trace phase. P6 has a slightly higher median release temperature than HL and is not cleanly separated from HL by stepped pyrolysis. Our data suggest that P6 has roughly 'normal' isotopic compositions and 'planetary' elemental ratios. Both P3 and P6 seem to be isotopically distinct from P1, the dominant 'planetary' noble-gas component in primitive chondrites. Release characteristics suggest that HL and P6 are sited in different carriers within the diamond fractions, while P3 may be sited near the surfaces of the diamonds. We find no evidence of separability of Xe-H and Xe-L or other isotopic variations in the HL component. However, because approximately 10(exp 10) diamonds are required to measure a Xe composition, a lack of isotopic variability does not constrain diamonds to come from a single source. In fact, the high abundance of diamonds in primitive chondrites and the presence of at least three distinct noble-gas components strongly suggest that diamonds originated in many sources. Relative abundances of noble-gas components in diamonds correlate with degree of thermal processing, indicating that all meteorites sampled essentially the same mixture of diamonds. That mixture was probably inherited from the Sun's parent molecular cloud.

Huss, Gary R.↗

Cosmogenic Records in 18 Ordinary Chondrites from the Dar Al Gani Region, Libya: Noble Gases - 1

In the last decade thousands of meteorites have been recovered from hot deserts in the Sahara and Oman. One of the main meteorite concentration surfaces in the Sahara is the Dar al Gani plateau in Libya, which covers a total area of ~8000 km2. More than 1000 meteorites have been reported from this area. The geological setting, meteorite pairings and the meteorite density of the Dar al Gani (DaG) field are described in more detail in [1]. In this work we report concentrations of the noble gas isotopes of He, Ne, Ar as well as 84Kr and 132Xe in 18 DaG meteorites. In a separate paper we will report the cosmogenic radionuclides [2]. We discuss the thermal history and cosmic-ray exposure (CRE) history of these meteorites, and evaluate the effects of the hot desert environment on the noble gas record.

Schultz, L.↗

Chemical composition of HAL, an isotopically-unusual Allende inclusion

Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

Davis, A. M.↗

Variable-temperature cryogenic trap for the separation of gas mixtures

The paper describes a continuous variable-temperature U-shaped cold trap which can both purify vacuum-line combustion products for subsequent stable isotopic analysis and isolate the methane and ethane constituents of natural gases. The canister containing the trap is submerged in liquid nitrogen, and, as the gas cools, the gas mixture components condense sequentially according to their relative vapor pressures. After the about 12 min required for the bottom of the trap to reach the liquid-nitrogen temperature, passage of electric current through the resistance wire wrapped around the tubing covering the U-trap permits distillation of successive gas components at optimal temperatures. Data on the separation achieved for two mixtures, the first being typical vacuum-line combustion products of geochemical samples such as rocks and the second being natural gas, are presented, and the thermal behavior and power consumption are reported.

Des Marais, D. J.↗

Evidence of an Extended Period of Aqueous Alteration on the Bennu Parent Body Revealed By I-Xe Analyses

NASA’s OSIRIS-REx mission delivered to Earth 121.6 g of regolith material from asteroid Bennu on 24th September 2023. We report multi-step laser pyrolysis xenon isotopic analysis to investigate the I-Xe system in individual particles separated from aggregate material (a mixture of small particles of undefined lithology). The high sensitivity of the RELAX mass spectrometer allows us to observe small excesses of individual isotopes and separate out different components, which may not be possible using a conventional noble gas mass spectrometer. The temperature resolution of RELAX is sufficient to seek an I-Xe isochron from step heating analysis of a sample mass <100 μg, which can contribute to our understanding of the nature and timing of aqueous alteration on Bennu’s parent body. We also aim to better estimate and understand the iodine concentration of CI chondrite-like material.

S A Crowther↗

Mars Solar Balloon Landed Gas Chromatograph Mass Spectrometer

A Mars surface lander Gas Chromatograph Mass Spectrometer (GCMS) is described to measure the chemical composition of abundant and trace volatile species and isotope ratios for noble gases and other elements. These measurements are relevant to the study of atmospheric evolution and past climatic conditions. A Micromission plan is under study where a surface package including a miniaturized GCMS would be delivered to the surface by a solar heated hot air balloon based system. The balloon system would be deployed about 8 km above the surface of Mars, wherein it would rapidly fill with Martian atmosphere and be heated quickly by the sun. The combined buoyancy and parachuting effects of the solar balloon result in a surface package impact of about 5 m/sec. After delivery of the package to the surface, the balloon would ascend to about 4 km altitude, with imaging and magnetometry data being taken for the remainder of the daylight hours as the balloon is blown with the Martian winds. Total atmospheric entry mass of this mission is estimated to be approximately 50 kg, and it can fit as an Ariane 5 piggyback payload. The GCMS would obtain samples directly from the atmosphere at the surface and also from gases evolved from solid phase material collected from well below the surface with a Sample Acquisition and Transport Mechanism (SATM). The experiment envisioned in the Mars Micromission described would obtain samples from a much greater depth of up to one meter below the surface, and would search for organic molecules trapped in ancient stratified layers well below the oxidized surface. Insitu instruments on upcoming NASA missions working in concert with remote sensing measurement techniques have the potential to provide a more detailed investigation of mineralogy and the extent of simple volatiles such as CO2 and H2O in surface and subsurface solid phase materials. Within the context of subsequent mission opportunities such as those provided by the Ariane 5 piggyback payload based Micromissions, it is essential to implement an even broader chemical analysis and to enable a significant extension of previous isotope measurements. Such a development would enhance the presently very active study of questions of atmospheric evolution and loss and past climatic conditions. The method selected to implement this program can be based on well-established mass spectrometry techniques. Sampled gas is chemically and physically processed to separate the gas mixture into components using gas chromatograph and related enrichment techniques. This allows trace species to be identified and reveals isotopic distributions in many cases with improved precision. Samples of interest, such as organic molecules, may lie deep below the highly oxidized surface layer and the suggested program includes enhanced sampling techniques to measure volatiles preserved in solid phase material deep below the surface as well as gas from the well mixed atmosphere.

Mahaffy, P.↗

Anomalous krypton in the Allende meteorite

The reported investigation provides important new data for the heavy noble gases, especially Kr, in the Allende meteorite. The data are used to criticize the original model of Lewis et al. (1975) based on the noble gas data of these researchers. The conclusions reached in the investigation support alternative models which have been mainly based on Xe data by Lewis et al. (1975, 1977). Because of the relatively high noble gas abundances in the separates studied, disturbance from nuclear effects occurring in situ such as spallation and neutron capture is insignificant, offering an opportunity to study primordial Ar, Kr, and Xe. The isotopic and abundance data obtained from the samples largely confirm the noble gas results of Lewis et al. (1975, 1977) where isotopic correlations agree with the correlations of the considered samples. It is found that both Kr and Xe data are consistent with a two component mixture of 'ordinary' as well as 'anomalous' planetary gases.

Frick, U.↗

Noble gas evidence for the depositional and irradiational history of 60010-60009 core soils

Isotopic abundances of the noble gases have been determined in grain size separates of eleven soils from different depths in the 60010-60009 double drive tube and in magnetic and plagioclase separates from a few of these soils. Data for the 60010 core are presented here. The entire core was deposited a maximum of approximately 125 m.y. ago as deduced from the Ar-38 cosmic ray exposure age of soil 60009,457. Soils in the topmost 12 cm of the core show loss of cosmogenic He-3 and Ne-21 and gain of trapped solar gases in proportion to the degree of surface reworking by micrometeorites as deduced from FMR data. A variety of compositional and irradiational evidence suggests that soils in the core were formed by mixing of three or more components during or immediately prior to core deposition less than about 125 m.y. ago. Based on cosmogenic noble gases and a variety of other data soils 60009,457 and 60010,3107 are similar (and possibly identical) to two of the end member soils which formed the mixture. More mature soils in the core, however, could not have matured in situ from these two soils because of significant differences in noble gas abundances and chemical composition.

Bogard, D. D.↗

Troctolite 76535 - A study in the preservation of early isotopic records

The lunar rock considered in the present investigation is a coarse-grained troctolite granulite containing about 58(vol)% plagioclase, 37% olivine, 4% pyroxene, and less than 1% accessory phases with a texture which indicates formation as a cumulate at depths between 10 and 30 km followed by an extended period of slow cooling. A description is presented of noble gas studies of separated minerals from 76535. The quantity of fission xenon from the in situ decay of Pu-244 provides further evidence for different, mineral-specific, isotopic closure times. The presented data shows that 76535 loses its surface-correlated xenon component upon disaggregation. No other xenon component is lost. The presence of solar gases in 76535 would seem to argue in favor of the external acquisition of the parentless extinct isotope effects and consequently favor 'thermal diffusion' and 'adsorption' over local redistribution models.

Caffee, M.↗

Permeation Rate Equations for Hydrogen and Deuterium in a Palladium-Silver Alloy

Mass transfer of a gas through a selective, solid membrane is an effective method for separation of desired species. This selective permeability is evident in the flow of hydrogen and the isotope deuterium through palladium-silver metal alloy media. In this study, based upon Sieverts’s law and the Arrhenius diffusion equation, an empirical correlation was developed to determine the steady-state permeation rate R, dependence on media temperature T, gas supply pressure p(sub S), and gas backpressure p(sub B) on the lower pressure side. Because of an extensive range of experimental conditions and complete reporting of raw data, the research by Ackerman and Koskinas was used as a source for data allowing empirical equation fitting. Unfortunately, those authors reported best-fit equations that poorly represented their own results. To improve the modeling of the original data and demonstrate the quality of the measurements, the current study develops improved hydrogen and deuterium permeation rate equations: P = 4.22×10(exp −6) A[exp(−704/T)](sq. root p(sub S) − sq. root p(sub B))/t for hydrogen P = 2.12×10(exp −6) A[exp(−468/T )](sq. root p(sub S) − sq. root p(sub B))/t for deuterium for values of cross-sectional area A (sq.cm), medium thickness t (cm), pressure p (psia), and temperature T (Kelvin), giving a permeation rate in mole/minute. These equations model permeation rate data more closely than do several other existing literature sources.

Smith, Phillip J.↗