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At least 541 records · Page 30

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom–molecular ion and ion–molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral–neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

astrochemistry – molecular processes – comets: gen↗

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of (15)N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense loud chemistry show that the revised (15)N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirstrom et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included (15)N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing (15)N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching (14)N/(15)N ratios of > 2000. Taking the updated nitrogen chemistry into account, no sigificant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the (14)N/(15)N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk (15)N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

Astrochemistry↗

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modfications on the chemical model of Wirstrom et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of > 2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

astrochemistry – molecular processes – comets: gen↗

An Evolutionary System of Mineralogy. Part I: Stellar Mineralogy (>13 to 4.6 Ga)

Minerals preserve records of the physical, chemical, and biological histories of their origins and subsequent alteration, and thus provide a vivid narrative of the evolution of Earth and other worlds through billions of years of cosmic history. Mineral properties, including trace and minor elements, ratios of isotopes, solid and fluid inclusions, external morphologies, and other idiosyncratic attributes, represent information that points to specific modes of formation and subsequent environmental histories—information essential to understanding the co-evolving geosphere and biosphere. This perspective suggests an opportunity to amplify the existing system of mineral classification, by which minerals are defined solely on idealized end-member chemical compositions and crystal structures. Here we present the first in a series of contributions to explore a complementary evolutionary system of mineralogy—a classification scheme that links mineral species to their paragenetic modes. The earliest stage of mineral evolution commenced with the appearance of the first crystals in the universe at >13 Ga and continues today in the expanding, cooling atmospheres of countless evolved stars, which host the high-temperature (T > 1000 K), low-pressure (P < 10-2 atm) condensation of refractory minerals and amorphous phases. Most stardust is thought to originate in three distinct processes in carbon- and/or oxygen-rich mineral-forming stars: (1) condensation in the cooling, expanding atmospheres of asymptotic giant branch stars; (2) during the catastrophic explosions of supernovae, most commonly core collapse (Type II) supernovae; and (3) classical novae explosions, the consequence of runaway fusion reactions at the surface of a binary white dwarf star. Each stellar environment imparts distinctive isotopic and trace element signatures to the micro- and nanoscale stardust grains that are recovered from meteorites and micrometeorites collected on Earth’s surface, by atmospheric sampling, and from asteroids and comets. Although our understanding of the diverse mineral-forming environments of stars is as yet incomplete, we present a preliminary catalog of 41 distinct natural kinds of stellar minerals, representing 22 official International Mineralogical Association (IMA) mineral species, as well as 2 as yet unapproved crystalline phases and 3 kinds of non-crystalline condensed phases not codified by the IMA.

Robert M. Hazen↗

Stratospheric profiles of heavy water vapor isotopes and CH3D from analysis of the ATMOS Spacelab 3 infrared solar spectra

The isotopic composition of stratospheric water vapor and methane was investigated. Stratospheric profiles of HDO, (H-18)2O, (H-17)2O, and CH3D were derived from solar occultation spectra recorded on April 30 - May 1, 1985 by the Atmospheric Trace Molecule Spectroscopy Fourier transform spectrometer aboard Spacelab 3. The profiles of the three water-vapor isotopes showed an increase in the volume mixing ratio with altitude. The measured profiles of D/H in water vapor showed a large depletion in the lower stratosphere (about 63 percent relative to standard mean ocean water, SMOW, at 20 km) and a small increase in D/H with altitude at higher altitudes, up to 34 km. The D/H ratio in stratospheric methane was close to the corresponding isotopic ratio in SMOW.

Rinsland, C. P.↗

Mass spectrometer-pyrolysis experiment for atmospheric and soil sample analysis on the surface of Mars

Results from the Viking mission will form the foundation for future in-depth investigations of atmosphere-surface interactions on Mars. The two Viking landers carried impressive instrumentation to obtain and analyze soil samples: the sites were observed by cameras, and the collector head was located on a long boom and allowed the collection of large samples at various depths. A selection of grain sizes was possible and a distribution system supplied a number of experiments with soil material. Despite stationary vehicles, a wide sampling field was reachable. The GCMS system, responsible for atmospheric as well as surface soil analysis, worked well on both landers. Atmospheric measurements resulted in the determination of the abundance of noble gases as well as of other molecular species. Isotopic composition measurements included the important ratios of C-13/C-12, N-15/N-14, and Ar-36/Ar-40. To verify these past results and to advance detailed studies of noble gas isotope ratios and minor constituents, better instrument sensitivities, higher precision, and lower background contributions are required in future Mars missions. Soil analysis during the Viking mission concentrated on organic material. Heating cycles were performed to 500 C and only water and carbon dioxide were identified. Higher pyrolysis temperatures are of primary importance to advance our understanding of the mineralogy and gas loading of surface material and atmospheric exchange.

Mauersberger, Konrad↗

The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

Chen, J. H.↗

CNO isotopes in red giant stars

The production and distribution of the CNO nuclides is discussed in light of observed abundance ratios in red giants and in the interstellar medium. Isotope abundances have been measured in the atmospheres and in the recent ejecta of cool giants, including carbon stars, S-type stars and red supergiants as well as in oxygen-rich giants making their first ascent of the giant branch. Several of the observations suggest revision of currently accepted nuclear cross-sections and of the mixing processes operating in giant envelopes. By comparing red giant abundances with high-quality observations of the interstellar medium, conclusions are reached about the contribution of intermediate-mass stars to galactic nuclear evolution. The three oxygen isotopes, O-16, -17 and -18, are particularly valuable for such comparison because they reflect three different stages of stellar nucleosynthesis. One remarkable result comes from observations of O-17/O-18 in several classes of red giant stars. The observed range of values for red giants excludes the entire range of values seen in interstellar molecular clouds. Furthermore, both the observations of stars and interstellar clouds exclude the isotopic ratio found in the solar system.

Wannier, P. G.↗

An experimental study of the isotopic enrichment in Ar, Kr, and Xe when trapped in water ice

The isotopic enrichment of argon, krypton, and xenon, when trapped in water ice, was studied experimentally. The isotopes were found to be enriched according to their (m1/m2)1/2 ratio. These enrichment factors could be useful for comparison among the uncertain cosmic or solar isotopic ratios, the hopeful in situ cometary ratio, and those in Earth's atmosphere, in the context of cometary delivery of volatiles to Earth.

NASA Discipline Exobiology↗

Krypton and xenon in the atmosphere of Venus

The paper reports a determination by the Pioneer Venus large probe neutral mass spectrometer of upper limits to the concentration of krypton and xenon along with most of their isotopes in the atmosphere of Venus. The upper limit to the krypton mixing ratio is estimated at 47 ppb, with a very conservative estimate at 69 ppb. The probable upper limit to the sum of the mixing ratios of the isotopes Xe-128, Xe-129, Xe-130, Xe-131, and Xe-132 is 40 ppb by volume, with a very conservative upper limit three times this large.

Donahue, T. M.↗

Stable carbon and sulfur isotopes as records of the early biosphere

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

Desmarais, David J.↗

Li Isotope Studies of Olivine in Mantle Xenoliths by SIMS

Variations in the ratio of the stable isotopes of Li are a potentially powerful tracer of processes in planetary and nebular environments [1]. Large differences in the 7Li/6Li ratio between the terrestrial upper mantle and various crustal materials make Li isotope composition a potentially powerful tracer of crustal recycling processes on Earth [2]. Recent SIMS studies of terrestrial mantle and Martian meteorite samples report intra-mineral Li isotope zoning [3-5]. Substantial Li isotope heterogeneity also exists within and between the components of chondritic meteorites [6,7]. Experimental studies of Li diffusion suggest the potential for rapid isotope exchange at elevated temperatures [8]. Large variations in 7Li, exceeding the range of unaltered basalts, occur in terrestrial mantle-derived xenoliths from individual localities [9]. The origins of these variations are not fully understood.

Bell, D. R.↗

The isotopic composition of neon and magnesium in the low energy cosmic rays

The ratios Ne-22/Ne-20 and Mg-26/Mg-24 were measured in galactic cosmic rays by the IMP-7 satellite in the 60 to 230 MeV/nucleon range. The neon cosmic ray source ratio Ne-22/Ne-20 is about 0.38, which is much larger than the current solar system relationship; the Mg data agrees with the solar system isotopic ratio of 0.14 at the cosmic ray source. The Ne and Mg source ratios are explained by supernova models, and become a new constraint which should be satisfied by any model of cosmic ray origin.

Garcia-Munoz, M.↗

Nd isotopic variations and petrogenetic models

The isotopic composition of Nd in selected terrestrial rocks is investigated to gain information about its implications for petrogenesis and the history of the earth's crust and mantle. Chemical and mass-spectrometric measurements of the Nd-143/Nd-144 ratio in terrestrial rocks of different ages show that the Sm/Nd ratio and the rare-earth-element (REE) abundance pattern are equal within a few per cent to those of chondritic meteorites. Variations in the Nd isotopic ratio in young basalts are found to permit the identification of distinctive mantle sources and to indicate the preservation of significant heterogeneities in the mantle for times of 1 to 4 billion years ago. The isotopic data also show that mantle source regions with a Sm/Nd ratio which differs from the chondritic value by a factor of two are not preserved for more than a few hundred million years. The average continental crust material is found to have a much lower isotopic ratio than the mantle, reflecting the crust's low Sm/Nd ratio resulting from REE fractionation during crust formation from the mantle.

Depaolo, D. J.↗

Consensus on Aquatic Primary Productivity Field Protocols for Satellite Validation and Model Synthesis

The NASA PACE project, in conjunction with the IOCCG, EUMETSAT, and JAXA, have initiated an Aquatic Primary Productivity working group, with the aim to develop community consensus on multiple methods for measuring aquatic primary productivity used for satellite validation and model synthesis. A workshop to commence the working group efforts was held December 05-07, 2018 at the University Space Research Association headquarters in Columbia, MD U.S.A., bringing together 26 active researchers from 16 institutions. The group discussed the primary differences, nuances, scales, uncertainties, definitions, and best practices for measurements of primary productivity derived from in situ/on-deck/laboratory radio/stable isotope incubations, dissolved oxygen concentrations (from incubations or autonomous platforms such as floats or gliders), oxygen-argon ratios, triple oxygen isotope, natural fluorescence, and FRRF/ETR/kinetic analysis. These discussions highlighted the necessity to move the community forward towards the establishment of climate-quality primary productivity measurements that follow uniform protocols, which is imperative to ensure that existing and future measurements can be compared, assimilated, and their uncertainties determined for model development and validation. The specific deliverable resulting from of this activity will be a protocol document, published in coordination with the IOCCG. This presentation will discuss the findings of the meeting, and address future activities of the working group.

Vandermeulen, Ryan A.↗

Sulphur isotopic compositions of deep-sea hydrothermal vent animals

The S-34/S-32 ratios of tissues from vestimentiferan worms, brachyuran crabs, and giant clams living around deep hydrothermal vents are reported. Clean tissues were dried, ground, suspended in 0.1 M LiCl, shaken twice at 37 C to remove seawater sulfates, dried at 60 C, combusted in O2 in a Parr bomb. Sulfur was recovered as BaSO4, and the isotopic abundances in SO2 generated by thermal decomposition of 5-30-mg samples were determined using an isotope-ratio mass spectrometer. The results are expressed as delta S-34 and compared with values measured in seawater sulfates and in normal marine fauna. The values ranged from -4.7 to 4.7 per thousand, comparable to vent sulfide minerals (1.3-4.1 per thousand) and distinct from seawater sulfates (20.1 per thousand) and normal marine fauna (about 13-20 per thousand). These results indicate that vent sulfur rather than seawater sulfur is utilized by these animals, a process probably mediated by chemoautotrophic bacteria which can use inorganic sulfur compounds as energy sources.

Fry, B.↗

The energy dependence of the neon-22 excess in the cosmic radiation

It has been recognized now for some time that the heavy neon isotope, neon-22, is overabundant by a factor of 3 to 4 with respect to neon-22 in the cosmic ray source compared to the ratio of these isotopes in the Solar System. In view of the otherwise remarkable similarity of the chemical composition of the cosmic ray source and the composition of the Solar Energetic Particles, the anomaly regarding the neon isotopes is so much more striking. The observed excess of neon-22 is too large to be explained as a result of the chemical evolution of the Galaxy since the formation of the Solar System. Further information on the origin of the neon-22 excess may come from a comparison of the energy spectra of the two neon isotopes. If the cosmic radiation in the solar neighborhood is a mixture of material from several sources, one of which has an excess of neon-22, then the source energy spectra of neon-20 and neon-22 may differ significantly.

Herrstroem, N. Y.↗

High D/H ratios of water in magmatic amphiboles in Chassigny: Possible constraints on the isotopic composition of magmatic water on Mars

The D/H ratios of kaersutitic amphiboles contained in magmatic inclusions in the Shergottites Nakhlites Chassignites (SNC) meteorite Chassigny using the ion microprobe were measured. A lower limit on the delta(D(sub SMOW)) of the amphiboles is +1420 +/- 47 percent. Assuming Chassigny comes from Mars and the amphiboles have not been subject to alteration after their crystallization, this result implies either that recycling of D-enriched Martian atmosphere-derived waters into the planetary interior has taken place, or that the primordial hydrogen isotopic composition of the interior of Mars differs significantly from that of the Earth (delta(D(sub SMOW)) approximately 0 percent). In addition, the measurements indicate that the amphiboles contain less than 0.3 wt. percent water. This is much lower than published estimates, and indicates a less-hydrous Chassigny parent magma than previously suggested.

Watson, L. L.↗