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Carbon and nitrogen biogeochemistry in the ocean: A study using stable isotope natural abundance

Determining the biogeochemical pathways traveled by carbon and nitrogen in the ocean is fundamental to the understanding of how the ocean participates in the cycling of these elements within the biosphere. Because biological production, metabolism, and respiration can significantly alter the natural abundance of C-13 and N-15, these abundances can provide important information about the nature of these biological processes and their variability in the marine environment. The research initially seeks to characterize the spatial and temporal patterns of stable isotope abundances in organic matter, and to relate these abundances to C and N biogeochemical processes within selected areas of the northeastern Pacific Ocean.

Rau, G. H.↗

Mercury Abundances and Isotopic Compositions in the Murchison (CM) and Allende (CV)Carbonaceous Chondrites

The abundance and isotopic composition of Hg was determined in bulk samples of both the Murchison (CM) and Allende (CV) carbonaceous chondrites using single- and multi-collector inductively coupled plasma mass spectrometry (ICP-MS). The bulk abundances of Hg are 294 6 15 ng/g in Murchison and 30.0 6 1.5 ng/g in Allende. These values are within the range of previous measurements of bulk Hg abundances by neutron activation analysis (NAA). Prior studies suggested that both meteorites contain isotopically anomalous Hg, with d l 96/202Hg values for the anomalous, thermal-release components from bulk samples ranging from 2260 %o to 1440 9/00 in Murchison and from 2620 9/00 to 1540 9/00 in Allende (Jovanovic and Reed, 1976a; 1976b; Kumar and Goel, 1992). Our multi-collector ICP-MS measurements suggest that the relative abundances of all seven stable Hg isotopes in both meteorites are identical to terrestrial values within 0.2 to 0.5 9/00m. On-line thermal-release experiments were performed by coupling a programmable oven with the singlecollector ICP-MS. Powdered aliquots of each meteorite were linearly heated from room temperature to 900 C over twenty-five minutes under an Ar atmosphere to measure the isotopic composition of Hg released fiom the meteorites as a h c t i o n of temperature. In separate experiments, the release profiles of S and Se were determined simultaneously with Hg to constrain the Hg distribution within the meteorites and to evaluate the possibility of Se interferences in previous NAA studies. The Hg-release patterns differ between Allende and Murchison. The Hg-release profile for Allende contains two distinct peaks, at 225" and 343"C, whereas the profile for Murchison has only one peak, at 344 C. No isotopically anomalous Hg was detected in the thermal-release experiments at a precision level of 5 to 30 9/00, depending on the isotope ratio. In both meteorites the Hg peak at ;340"C correlates with a peak in the S-release profile. This correlation suggests that Hg is associated with S-bearing phases and, thus, that HgS is a major Hg-bearing phase in both meteorites. The Hg peak at 225 C for Allende is similar to release patterns of physically adsorbed Hg on silicate and metal grains.

Lauretta, D. S.↗

Origin of heavy xenon in meteoritic diamonds

The neutrino burst from the collapsed core in Type II supernovae liberates free neutrons by nu, nu-prime(n) reactions which drive isotopic abundances several mass steps heavier. The neutron fluence in the He shell, abetted by another burst 10 s later from alpha, n reactions, is about right for rendering Xe-136, the most abundant Xe isotope. The Xe isotopic composition is a good match to Xe-H, the unshielded neutron-rich Xe component abundant in carbonaceous meteorites. The He shell is implicated because it is the only C-rich shell in massive stars that can be expected to condense solid carbon thermally, a requirement for locating the Xe-H in meteoritic diamonds, which are so common as to require an abundant Galactic source of unoxidized carbon.

Clayton, Donald D.↗

In-Lab Rapid Analytical Detection of Lunar Volatiles By Universal Gas Analyzer With Comparison to GC-MS System

Introduction: The curation of permanently shadowed regions (PSRs) [1] on the lunar surface is centered around studies based upon the observed volatiles from the LCROSS mission [2]. The rapid detection of important volatile gases and vapors present in planetary bodies and Astromaterials by a standalone analytical device is an area of intense research interest in our group and Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility and this work is relevant to the future preparation of viable lunar simulants for testing curation efforts down the road. The groundbreaking results obtained from the LCROSS Mission [2] open the requirements for the direct detection of volatiles present in regolith materials collected from the lunar surface. The mass spectrometry of volatile chemicals is a general technique that utilizes a set of instruments that creates charged ions from a gaseous chemical species and measures the intensities vs. mass-to-charge ratio (m/z) [3]. In this context, we discuss in-lab experimental results and procedures for rapid qualitative analysis of main LCROSS volatiles (water, H2S, NH3, CO2, and CH3OH) by a Universal Gas Analyzer (UGA) instrument. Additionally, the instrument performance was evaluated by measuring the isotopic abundance ratio of atmospheric Ar-40 to Ar-36 present in room air since, argon is a relevant gas in planetary studies as it can provide an insight and reference point to isotope studies [4]. Additional, cross comparisons were attempted and made between the two instruments to develop a robust analytical technique by comparing mass spectral data for H2S headspace samples with a Trace-1310/ ISQ 7000 (ThermoFisher Scientific.) GC-MS system. Background: The benchtop UGA System is equipped with an SRS UGA 300 quadrupole mass spectrometer designed and built by Stanford Research Systems [5]. This system can be configured for several types of gaseous chemical analysis. The inlet line continuously samples gases at low flow rates (several milliliters per minute) through a capillary limiting the intake pressure making the instrument ideal for online analysis of select gases and/or room atmosphere. Moreover, in our current UGA system, a change in composition at the inlet can be detected in about 200 milliseconds and a complete spectrum is acquired (for a range of 1-100 amu) in under 45 sec with masses measured at rates up to 25 msec per point [5]. This system provides a quick upstream analytical data that we can then compare to results obtained by our GC-MS system. Sample Preparation: Small volume (2-4 mL) of analyte sample was taken in a 10 mL glass vial and sealed with a crimped cap and purged with pure Ar or N2 gas to displace air from the top. The headspace sample was scanned by the UGA instrument at analog, histogram, and pressure vs. time modes. The isotopic abundance ratio for 40Ar-to-36Ar was estimated by measuring partial pressure vs. time scans and setting the mass at 40 and 36 respectively. Results and Discussions: In this work, we have investigated the applicability of the UGA system by qualitative analysis of a series of LCROSS volatiles measured individually. Fig. 1 demonstrates a set of vertically offset spectra for the partial pressures measured as a function of mass-to-charge (m/z) ratios. The average acquisition time for each spectrum was less than a minute suggesting that the UGA system is ideal for quick analysis of geochemical volatiles. For the cross-comparison, we analyzed an H2S headspace sample by a Trace-1310/ISQ-7000 system and compared mass spectral data with previously measured UGA histogram scan data (Fig. 2). In both cases, major peak positions are the same, however, the intensities of fragment ions ([1H132S]+ and [32S]+) are higher for UGA suggesting that the fragment ionization process is stronger in UGA compared to that of GC-MS. To investigate how the integrated area under each chromatogram varies with the headspace sample volume, a set of five H2S headspace samples with increasing volumes was analyzed by the GC-MS system (Fig. 3, inset). A small volume (e.g., 200 to 1000 µL) of H2S/H2O vapor was withdrawn from a 20 mL stock sample vial containing ~5 mL of 0.4% H2S in water by a gas-tight syringe and added to another 20 mL vial filled with argon and analyzed by the GC-MS system. Finally, the UGA detector sensitivity was evaluated by calculating the atmospheric 40Ar-to-36Ar isotopic abundance ratio in room air by running a partial pressure vs. time scan with setting the atomic mass at 40, and 36. Fig. 4(a) shows a ~25 min duration “P vs. time” scan for 40Ar (plot for 36Ar is not shown). The partial pressure values (~100 points) were corrected by subtracting the corresponding background pressure value for 37Ar and utilized to calculate 40Ar-to-36Ar isotopic abundance ratios as shown by Fig. 4b. The average isotopic abundance ratio is ~306 with a 2*STDEV ~13. This abundance ratio is significantly close to the previously reported value of 298.56 [6] and the ratio obtained by our GC-MS system (303 for a UHP grade Ar sample). Conclusions: Our study strongly evidenced that the benchtop UGA system is a valuable analytical tool for the detection of major LCROSS volatiles. The rapid scanning capability, the inexpensiveness of the whole system, and impressive detection sensitivity prove its worthiness as an essential device for advanced geochemical applications. Moreover, cross comparisons with the GC-MS provide important bridges into advanced curatorial efforts into the future. References: [1] Bickel, V.T., et al. (2021) Nat Commun 12, 5607. [2] Colaprete, A., et al. (2010) Science, 330, 463-468. [3] Glavin, D. P. et al. (2012) 2012 IEEE Aerospace Conference, 1-11. [4] Willett, C. D., et al. (2022) Geochimica et Cosmochimica Acta 329, 119-134. [5] Operation Manual and Programming Reference. (2018) Universal gas Analyzers, Stanford Research Systems. [6] Lee, J. Y., et al. (2006) Geochimica et Cosmochimica Acta 70, 4507–4512. Notes: (4 figures are attached with text as shown by the attached file)

Curation↗

The effect of pressure and excitation energy on the isotopic fractionation in the formation of ozone by discharge of O2

Isotopic fractionation processes in the formation of O3 by discharge (at 20 kV and 3 MHz) of O2 in a fused silica container at 77 K are investigated experimentally, with a focus on the effects of changes in the isotopic abundances in the predischarge O2, the O2 pressure, and the excitation energy on the isotope abundances in the postdischarge O2 and O3. The results are presented in extensive tables and graphs and characterized in detail, and good general agreement is found with data obtained using 60-kHz excitation (Yang and Epstein, 1987). It is shown that O-17 and O-18 enrichment of the residual O2 (when the predischarge gas is enriched) or of the O3 (when atmospheric isotope abundances are used) can occur independently of one another. It is inferred that the rate of anharmonic predissociation of vibrationally hot O3 depends on the symmetry and mass of the O3 molecules. The significance of the present findings for studies of anomalous oxygen isotope abundances in meteorites is indicated.

Yang, Jongmann↗

Carbonaceous chondritic xenoliths and planetary-type noble gases in gas-rich meteorites

The source of the planetary-type noble gases in gas-rich meteorites is identified as finely divided (submillimeter to millimeter-sized), widely dispersed carbonaceous chondritic fragments. Trace-element abundances, noble-gas elemental abundances and isotopic abundances of xenon are compatible with the hypothesis that the carbonaceous chondritic carrier is present in amounts of a few percent in the gas-bearing portions of gas-rich chondrites and achondrites.

Wilkening, L. L.↗

The isotopic composition of solar flare noble gases

The relative elemental and isotopic abundances of noble gases provide insights into a number of topics related to the solar system. Neon is in many ways the most diagnostic of the noble gases. The diagnostic character is mainly related to the variation in the relative abundance of the two most abundant neon isotopes, Ne-20 and Ne-22. The available evidence suggests that trapped neon found in meteorites and in lunar samples consists of as many as five isotopically distinct components, including neon A, B, C, D, and E. Neon B has been shown to be due to solar wind neon which has been directly implanted into the material found in a meteorite. It appears that neon E is extrasolar in origin. There exist ambiguities regarding the origins of the remaining three components. The present investigation is concerned with a reexamination of the existing data in an effort to eliminate or at least clarify these ambiguities. It is found that neon C is apparently due to directly implanted, low-energy solar flare neon nuclei.

Black, D. C.↗

The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

During the three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. At the time the grant started, our collaborating PI, Dante Lauretts, was a postdoctoral research associate working with Peter Buseck at Arizona State University. The work on chondritic Hg was done in collaboration with Dante Lauretta and Peter Buseck and this study was published in Lauretta et a1 (2001a). In July, 2001 Dante Lauretta accepted a position as an Assistant Professor in the Lunar and Planetary Laboratory at the University of Arizona. His funding was transferred and this grant has supported much of his research activities during his first two years at the U of A. Several other papers are in preparation and will be published soon. We presented papers on this topic at Goldschmidt Conferences, the Lunar and Planetary Science Conferences, and the Annual Meetings of the Meteoritical Society. The work done under this grant has spurred several new directions of inquiry, which we are still pursuing. Included in this paper are the studies of bulk abundances and isotopic compositions of metreoritic Mercury, and the development of a thermal analysis ICP-MS technique applied to thermally liable elements.

Blum, J. D.↗

The isotropic condition of energetic particles emitted from a large solar flare

Isotope abundance ratios for 5 to 50 MeV/nuc nuclei from a large solar flare were measured. The measurements were made by the heavy isotope spectrometer telescope (HIST) on the ISEE-3 satellite orbiting the Sun near an Earth-Sun liberation point approximately one million miles sunward of the Earth. Finite values for the isotope abundance ratios C-13/C-12, N-15/N-14, O-18/O-16, Ne-22/Ne-20, Mg-25/Mg-24, and Mg-26/Mg-24, and upper limits for the isotope abundance ratios He-3/He-4, C-14/C-12, O-17/O-16 and Ne-21/Ne-20 were reported. Element abundances and spectra were measured to compare the flare with other reported flares. The flare is a typical large flare with low Fe/O abundance or = to 0.1). For C-13/C-12, N-15/N-14, O-18/O-16, Mg-25/Mg-24 and Mg-26/Mg-24 isotope abundance ratios agree with the solar system abundance ratios. Measurement for Ne-22/Ne-20 agree with the isotopic composition of the meteoritic component neon-A.

Spalding, J.↗

Isotopes of titanium in cool stars

A program of stellar Ti isotopic-abundance determinations is described and related to changes that may have occurred in the Ti isotopic abundance ratios during the chemical evolution of the Galaxy, and to whether the abundance ratios are perturbed in the S and MS stars having atmospheres with enhanced abundances of s-process nuclei resulting from convective mixing after internal exposure to neutrons. High-resolution (0.07 A) Reticon spectra of portions of the TiO gamma (0,0), gamma (0,1), and delta (0,0) bands were the source material, and particular emphasis was placed on the definition of the continuum level. The isotopic abundance ratios are terrestrial in all of the sample, and errors in the (Ti-i)/(Ti-48) ratio are typically plus or minus 25% for the dwarfs and plus or minus 50% for the giants. The observations show that the magic nucleus Ti-50 is not enhanced in S and MS stars.

Clegg, R. E. S.↗

The abundances of isotopes in the cosmic radiation

Studies of the isotopic composition of nuclei in the cosmic radiation are reviewed, including abundances of the isotopes of elements from H to Ni, together with their implications for cosmic ray origin, acceleration, and transport in the Galaxy. The review focuses on determinations of the composition of cosmic ray source material, and the extent to which the isotopic composition of this material is different from, or similar to, typical solar system material and other samples of Galactic matter. Theoretical models that have been advanced to explain the observed overabundance of neutron-rich isotopes in cosmic rays are described. Also discussed are studies of various radioactive clocks that record the time-scales associated with the nucleosynthesis, acceleration, and transport of cosmic ray nuclei, and studies of the so-called anomalous cosmic ray component, thought to represent a sample of the neutral interstellar medium.

Mewaldt, R. A.↗

Carbon, hydrogen and nitrogen in carbonaceous chondrites Abundances and isotopic compositions in bulk samples

Whole-rock samples of 25 carbonaceous chondrites were analyzed for contents of C, H and N and delta C-13, delta D and delta N-15. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100 percent reliability; Al Rais and Renazzo clearly constitute a discrete 'grouplet', and there are hints that both CI and CM groups may each be divisible into two subgroups.

Kerridge, J. F.↗

The effect of the isotopic composition of oxygen on the non-mass-dependent isotopic fractionation in the formation of ozone by discharge of O2

Isotopic fractionation processes in the formation of O3 by 20-kV 60-kHz discharge of O2 in a fused silica container at 77 K are investigated experimentally, with a focus on the effects of changes in the isotopic composition of O2, the O2 pressure, the degree of O3 formation, and the discharge geometry on the isotope abundances in the postdischarge O2 and O3. The results are presented in tables and graphs and compared with the predictions of theoretical models involving vibrational anharmonicity and symmetry effects on O3 predissociation. In experiments using O2 enriched with O-17 and O-18, the heavy isotope is enriched in the residual O2 and not in the O3, whereas the opposite is true when atmospheric isotope abundances are used. It is inferred that the predissociation rate depends on the symmetry and mass of the O3 molecules and not on self-shielding or symmetry effects in the reactant O2. The potential value of the present findings for studies of anomalous isotope abundances in meteorites is indicated.

Yang, Jongmann↗

Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism

The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

NASA Program Exobiology↗

The isotopic and elemental abundances of neon nuclei accelerated in solar flares

The relative isotopic abundances of Ne-20 and Ne-22 in seven solar flares were determined from measurements of the satellite IMP 8, yielding the ratio Ne-20/Ne-22 = 7.7 (+2.3, -1.5) for solar chromospheric matter. This value is in agreement with the ratio for the component neon-A (the 'primordial' component) found in carbonaceous chondrites. An elemental abundance ratio Ne/O = 0.14 + or - 0.01 also has been obtained which agrees closely with earlier reported measurements. It is shown that the effects of preferential acceleration relative to solar-system abundances with increasing charge number observed for some solar flares - though biasing the elemental ratio - does not appear to influence the neon isotopic abundances.

Dietrich, W. F.↗

Abundances of isotopes in planetary atmospheres

Carbon and oxygen isotopes show no large anomalies on Venus (no more than 10-15%) or Mars (less than 5%); the high value of N-15/N-14 found on Mars is explained by nonthermal escape of nitrogen. The isotopes of nonradiogenic noble gases in the atmosphere of Mars exhibit abundance patterns similar to those in the primordial component of meteoritic gases and in the earth's atmosphere. This implies that gas fractionation took place in the inner solar nebula prior to planet formation. The relatively high value of Xe-129 on Mars emphasizes its deficiency on earth, implying a difference in accretion histories of volatiles for the two planets. In the outer solar system, normal isotope ratios for nitrogen and carbon on Jupiter, and for carbon on Saturn are found, but precision is low (+ or - 15% at best). Controversy exists about the correct value of D/H, with current estimates ranging from 2.3 plus or minus 1.1 to 5.1 plus or - 0.7 times 10 to the minus 5th. Planetary missions planned for the next few years should add considerably to the quantity and quality of these data.

Owen, T.↗

Isotopic variations in the rock-forming elements in meteorites

Variations in isotopic abundances of the major rock-forming elements can be used as tracers for chemical processes in the solar nebula, and may also provide links to the presolar cloud from which the solar nebula was derived. The paper reviews recent developments involving meteoritic abundances of the isotopes of O, Mg, Si, Ca, Ti, Cr, Fe, and Ni). Some of the effects observed are due to mass-dependent fractionation, and some are due to interaction of isotopically distinct reservoirs, reflecting incomplete homogenization of materials with different nucleosynthetic histories.

Clayton, R. N.↗

Long-term changes in solar wind elemental and isotopic ratios - A comparison of two lunar ilmenites of different antiquities

The solar wind components in two lunar ilmenites are examined. The noble gas and nitrogen elemental and isotopic abundances of lunar regolith breccia sample 79035, assumed to have been exposed to solar winds more than 2 Ga ago, are analyzed using stepwise oxidation and pyrolysis. This sample is compared with the data of Frick et al. (1988) for soil sample 71501, recently exposed to solar winds. It is observed that the two elements differ in terms of xenon abundance, helium and neon isotopic rates, and He/Ar elemental ratios. It is concluded that there have been isotopic and elemental abundance changes in solar wind composition over time.

Becker, Richard H.↗