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Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

Chang, S.↗

The Imprint of Atmospheric Evolution in the D/H of Hesperian Clay Minerals on Mars

The deuterium-to-hydrogen (D/H) ratio in strongly bound water or hydroxyl groups in ancient Martian clays retains the imprint of the water of formation of these minerals. Curiosity's Sample Analysis at Mars (SAM) experiment measured thermally evolved water and hydrogen gas released between 550 degrees Centigrade and 950 degrees Centigrade from samples of Hesperian-era Gale crater smectite to determine this isotope ratio. The D/H value is 3.0 (plus or minus 0.2) times the ratio in standard mean ocean water. The D/H ratio in this approximately 3-billion-year-old mudstone, which is half that of the present Martian atmosphere but substantially higher than that expected in very early Mars, indicates an extended history of hydrogen escape and desiccation of the planet.

Deuterium↗

Sulfur isotope effects associated with protonation of HS- and volatilization of H2S

The isotope effects associated with: (1) formation of H2S from HS- by protonation in aqueous solution; and (2) volatilization of H2S have been experimentally determined. Both isotopic distributions in closed systems at equilibrium and differential rates of volatilization of isotopic species in open systems were measured at 22 +/- 1 degrees C. It was found that, at equilibrium aqueous H2S is enriched in 34S by 2.0 - 2.7% relative to HS- and that H2S volatilized from solution is depleted in 34S by 0.5% relative to dissolved H2S. A small kinetic isotope effect accompanying volatilization of H2S was observed in the open-system experiments.

NASA Discipline Exobiology↗

Composition of solar cosmic rays.

Solar cosmic ray particle composition, charge and energy spectra of nuclear components and isotopic composition of H and He

HELIUM ATOM↗

Laboratory measurements of D/H ratios in interplanetary dust

Measurements of noble gas elemental and isotopic abundance patterns have provided evidence that a subset of the particles collected in the upper atmosphere by NASA aircraft are micrometeorites. It is found that the deuterium in two such particles is enriched relative to hydrogen by 500-1100 per thousand when compared with the terrestrial SMOW standard. This result confirms the extraterrestrial origin of the dust particles and demonstrates that the material preserves a potentially unique isotopic record which may reflect a memory of processes occurring during or before the formation of the solar system. In addition, the deuterium enrichment seen in the particles is analogous to that observed in bulk samples of one carbonaceous meteorite and two unequilibrated ordinary chondrites as well as in chemical separates of a number of other meteorites.

Zinner, E.↗

Evaporation in equilibrium, in vacuum, and in hydrogen gas

Evaporation experiments were conducted for SiO2 in three different conditions: in equilibrium, in vacuum, and in hydrogen gas. Evaporation rate in vacuum is about two orders of magnitude smaller than that in equilibrium, which is consistent with previous works. The rate in hydrogen gas changes depending on hydrogen pressure. The rate at 10 exp -7 bar of hydrogen pressure is as small as that of free evaporation, but at 10 exp -5 bar of hydrogen pressure it is larger than that in equilibrium. In equilibrium and in vacuum, the evaporation rate is limited by decomposition of SiO2 on the crystal surface, but it is limited by a diffusion process for evaporation in hydrogen gas. Therefore, evaporation rate of minerals in the solar nebula can be shown neither by that in equilibrium nor by that in vacuum. The maximum temperature of the solar nebula at the midplane at 2-3 AU where chondrites are believed to have originated is calculated to be as low as 150 K, 1500 K, or in between them. The temperature is, in any case, not high enough for total evaporation of the interstellar materials. Therefore, evaporation of interstellar materials is one of the most important processes for the origin and fractionation of solid materials. The fundamental process of evaporation of minerals has been intensively studied for these several years. Those experiments were carried out either in equilibrium or in vacuum; however, evaporation in the solar nebula is in hydrogen (and much smaller amount of helium) gas. In order to investigate evaporation rate and compositional (including isotopic) fractionation during evaporation, vaporization experiments for various minerals in various conditions are conducted. At first, SiO2 was adopted for a starting material, because thermochemical data and its nature of congruent vaporization are well known. Experiments were carried out in a vacuum furnace system.

Nagahara, Hiroko↗

D/H ratios and H2O contents of mantle-derived amphibole megacrysts from Dish Hill, California

D/H ratios are, in principle, useful in characterizing reservoirs of mantle hydrogen and as tracers of volatile transfer processes in Earth's interior. In practice, however, interpretation of isotopic measurements on mantle derived H is complicated by surface processes such as contamination and degassing which may alter the primary D/H ratio. Although there are indications that water associated with subduction zones and certain chemically enriched basalts is enriched in D relative to 'typical' upper mantle water, the extent of isotopic heterogeneity of mantle H remains uncertain. Kaersutitic amphibole megacrysts in alkaline basalts are one of the most widespread sources of mantle water and are therefore potentially useful for large-scale regional studies of D/H variation. However, D/H ratios of these amphiboles vary widely (from plus 8 to minus 113 percent), even in samples from the same locality, so that this potential has yet to be realized. In order to investigate the origin of this variability, and to explore the possibility that primary mantle D/H ratios may be deduced from these amphiboles, we analyzed the D/H ratios and chemical compositions of a suite of 17 kaersutitic amphiboles from Dish Hill, California. This work contrasts with previous studies in which sampling is widespread, but representatives from any given locality are few. Samples were collected from a restricted area on the southern flank of the volcanic center and are associated with the basal volcanic breccia. Fourteen of the samples were large single crystals or crystal fragments (megacrysts, 0.4 to 30 grams), believed to derive from pegmatitic veins crystallized from melts in the mantle. Two were coarse-grained intergrowths of amphibole with olivine and spinel, and one was a thin (2 mm) selvage on a peridotite xenolith.

Bell, David R.↗

PET - A proton/electron telescope for studies of magnetospheric, solar, and galactic particles

The Proton/Electron Telescope (PET) on SAMPEX is designed to provide measurements of energetic electrons and light nuclei from solar, galactic, and magnetospheric sources. PET is an all solid-state system that will measure the differential energy spectra of electrons from about 1 to about 30 MeV and H and He nuclei from about 20 to about 300 MeV/nuc, with isotope resolution of H and He extending from about 20 to about 80 MeV/nuc. As SAMPEX scans all local times and geomagnetic cutoffs over the course of its near-polar orbit, PET will characterize precipitating relativistic electron events during periods of declining solar activity, and it will examine whether the production rate of odd nitrogen and hydrogen molecules in the middle atmosphere by precipitating electrons is sufficient to affect O3 depletion. In addition, PET will complement studies of the elemental and isotopic composition of energetic heavy (Z greater than 2) nuclei on SAMPEX by providing measurements of H, He, and electrons. Finally, PET has limited capability to identify energetic positrons from potential natural and man-made sources.

Cook, Walter R.↗

Sodium-22, Al-26, and Be-10 in He-3-rich flares

The theory of He-3-rich flares by Colgate et al. (1977) implies that the composition of the solar cosmic ray-event associated with a He-3-rich flare is grossly nonsolar. The relative abundances (relative to hydrogen) of carbon, nitrogen, and oxygen, as well as those of heavier elements are significantly reduced, and the isotopic compositions of virtually all elements are bound to be strongly anomalous. In addition, the abundances of Na-22, Al-26, and Be-10 (of which there are approximately 10 to the 25th power atoms each in a He-3-rich flare) are at least comparable to the abundances of stable isotopes of these elements. Conditions for the detectability of the three radioactive species are discussed.

Heymann, D.↗

Infrared spectroscopy of IRC + 10420

High resolution 1.6, 3.3 and 4.6 micron spectra were obtained on the F8 supergiant star IRC + 10420 on June 9-11, 1984, using the 4 m Mayall telescope and Fourier Transform Spectrometer at Kitt Peak. IRC + 10420 is distinguished by its hydrogen maser, unusual for stars of this type. The measured column densities of CO led to an estimated isotopic carbon ratio of 7-11, supporting a model of the object as a highly evolved star. The redshift is interpreted as due to scattering by outward-moving circumstellar dust grains. The IR spectrum of IRC + 10420 suggests that the object is a post-asymptotic branch star still surrounded by the thick dust shell it produced while it was much cooler.

Fix, John D.↗

Titan's spectrum and atmospheric composition

Spectroscopic evidence shows that hydrogen atoms are major constituents of Titan's atmosphere. Anomalous enhancement of the methane absorption band is attributed to isotopic shifts arising from methane photolysis. Anomalous ultraviolet absorption features suggest high altitude dust and an elevated cloud layer overlaying most of the methane in the atmosphere.

Trafton, L. M.↗

Optical model analyses of galactic cosmic ray fragmentation in hydrogen targets

Quantum-mechanical optical model methods for calculating cross sections for the fragmentation of galactic cosmic ray nuclei by hydrogen targets are presented. The fragmentation cross sections are calculated with an abrasion-ablation collision formalism. Elemental and isotopic cross sections are estimated and compared with measured values for neon, sulfur, and calcium ions at incident energies between 400A MeV and 910A MeV. Good agreement between theory and experiment is obtained.

Townsend, Lawrence W.↗

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

unmanned↗

Mass fractionation in hydrodynamic escape

In mass fractionation during the hydrodynamic escape of gases from an inner planet's atmosphere, the readier escape of light gases generates a linear or concave downward line in a plotting of the log of remaining inventory against atomic mass. Just as such an episode of hydrodynamic escape during Mars' early history could have led to the mass-dependent depletion of the noble gases that has been noted in the Martian atmosphere, in the event that the Martian atmosphere was initially hydrogen-rich, an early earth-history episode may have resulted in a mass-dependent fractionation of the xenon isotopes.

Hunten, Donald M.↗

Structures of aspartic acid-96 in the L and N intermediates of bacteriorhodopsin: analysis by Fourier transform infrared spectroscopy

The light-induced difference Fourier transform infrared spectrum between the L or N intermediate minus light-adapted bacteriorhodopsin (BR) was measured in order to examine the protonated states and the changes in the interactions of carboxylic acids of Asp-96 and Asp-115 in these intermediates. Vibrational bands due to the protonated and unprotonated carboxylic acid were identified by isotope shift and band depletion upon substitution of Asp-96 or -115 by asparagine. While the signal due to the deprotonation of Asp-96 was clearly observed in the N intermediate, this residue remained protonated in L. Asp-115 was partially deprotonated in L. The C = O stretching vibration of protonated Asp-96 of L showed almost no shift upon 2H2O substitution, in contrast to the corresponding band of Asp-96 or Asp-115 of BR, which shifted by 9-12 cm-1 under the same conditions. In the model system of acetic acid in organic solvents, such an absence of the shift of the C = O stretching vibration of the protonated carboxylic acid upon 2H2O substitution was seen only when the O-H of acetic acid is hydrogen-bonded. The non-hydrogen-bonded monomer showed the 2H2O-dependent shift. Thus, the O-H bond of Asp-96 enters into hydrogen bonding upon conversion of BR to L. Its increased hydrogen bonding in L is consistent with the observed downshift of the O-H stretching vibration of the carboxylic acid of Asp-96.

NASA Discipline Exobiology↗

Location, location: deciphering the significance of in-situ hydrogen analyses of Martian meteorite phases

Understanding how inner planets acquired their volatiles such as hydrogen (H) is fundamental to constrain models of solar system formation [e.g. 1]. One avenue of estimating the H content and isotopic characteristics of differentiated planets is to analyze the samples we have from them as meteorites. Ideally, the H content and isotopic characteristic of the mantle sources of these igneous rocks should give insight into the volatile origin of each planetary body. The mantle H signatures can be estimated from that of the parent melt, which in turn may be derived from that of the first crystallized phases. However, we will illustrate the processes that can modify the H content and D/H ratios of pyroxene, olivine and feldspar in selected Martian meteorites relative to those of their mantle sources, with two key protocols for SIMS analysis. The first key is to put each analysis in textural context ("location, location"). In particular, of prime importance is whether an analysis is done at the center or the edge of a mineral grain, close or far from a shock disturbed area, and in a mineral crystallized at the beginning or late in the differentiation sequence. Accompanying the H analyses done by SIMS with major and trace element data at the same analysis locations allows to constrain the history of crystallization, cooling, alteration and shock of the meteorite. For example, volcanic degassing can be evidenced by decreasing water contents and increasing D/H ratios from core to edge of nakhlite pyroxenes [2]. Traverses of H analyses in pyroxene and maskelynite in shergottite LAR 06319 provide examples of H contents and D/H ratios modified during degassing following shock [3]. The second key is to assess if the area analyzed by SIMS has shock generated damage of the mineral structure, as will be shown in pyroxene and olivine from shergottite RBT 04262. Olivine in shergottites have too high water contents to be explained with an igneous origin and their D/H ratios are more consistent with terrestrial alteration, as observed before [4]. A review of all these processes shows how careful one has to be prior to using H measurements in meteorites to infer the origin and amount of water in differentiated planetary interiors.

A.H. Peslier↗

Lipid Biomarkers for a Hypersaline Microbial Mat Community

The use of lipid biomarkers and their carbon isotopic compositions are valuable tools for establishing links to ancient microbial ecosystems. Various lipids associated with specific microbial groups can serve as biomarkers for establishing organism source and function in contemporary microbial ecosystems (membrane lipids), and by analogy, potential relevance to ancient organic-rich sedimentary rocks (geolipids). As witnessed by the stromatolite record, benthic microbial mats grew in shallow water lagoonal environments. Our recent work has focused on lipid biomarker analysis of a potential analogue for such ancient mats growing in a set of hypersaline evaporation ponds at Guerrero Negro, Baja California Sur, Mexico. The aerobic, surface layer of this mat (0 to 1 mm) contained a variety of ester-bound fatty acids (FA) representing a diverse bacterial population including cyanobacteria, sulphate reducers (SRB) and heterotrophs. Biomarkers for microeukaryotes detected in this layer included sterols, C-20 polyunsaturated FA and a highly branched isoprenoid, diagnostic for diatoms. Cyanobacteria were also indicated by the presence of a diagnostic set of mid-chain methylalkanes. C-28, to C-34 wax esters (WXE) present in relatively small amounts in the upper 3 mm of the mat are considered biomarkers for green non-sulphur bacteria. Ether-bound isoprenoids were also identified although in considerably lower abundance than ester-bound FA (approx. 1:l0). These complex ether lipids included archatol, hydroxyarchaeol and a C-40 tetraether, all in small amounts. After ether cleavage with boron tribromide, the major recovered isoprenyl was a C-30:1. This C(sub 30;1) yelded squalane after hydrogenation, a known geobiomarker for hypersaline environments in ancient oils and sediments. In this mat, it represents the dominant Archaeal population. The carbon isotopic composition of biomarker lipids were generally depleted relative to the bulk organic material (delta C-13 TOC -10%). Most depleted were the cyanobacterial methylalkanes at -27% with FA such as the SRB biomarker, 10- methyl C-I6, somewhat heavier at -16%, and WXE at -17%. The C-30:1 isoprenyl was most enriched with delta C-13 in the -7 to -11% range, much too heavy to represent the methanogen population responsible for mat methane values measured at -60%.

Jahnke, Linda↗