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At least 181 records · Page 10

The Significance of Slope 1 Variation in Early Solar System Solids

As originally demonstrated by Clayton and co-workers, primitive meteorites and their components commonly display mass-independent oxygen isotopic variation. As a tool to understand this behaviour, a number of reference lines have been defined, with slopes of approximately 1. The Carbonaceous Chondrite Anhydrous Mineral (CCAM) line, derived predominantly from analyses of components in the Allende (CV3) meteorite, is the most widely used reference and has a slope of 0.94 plus or minus 0.01 (2 sigma). However, the fundamental significance of the CCAM line has been questioned. Based on the results of a UV laser ablation study of an Allende CAI (calcium-aluminum–rich inclusion), it was suggested that a line of exactly slope 1 (Y&R line - Young and Russell line) was of more fundamental significance. SIMS (Secondary Ion Mass Spectrometry) analysis of chondrules from primitive CRs and related chondrites define a third, distinct slope 1 line, known as the Primitive Chondrule Minerals (PCM) line. Here we discuss the results of bulk oxygen isotope analysis of CO, CV and CR chondrites and various separated components, with the aim of better understanding the origin of slope 1 behaviour in early Solar System materials.

Greenwood, R. C.↗

Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

Merritt, Dawn A.↗

A Primordial Atmospheric Origin of Hydrospheric Deuterium Enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (~6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA’s Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ~3×SMOW, demonstrating that most of the enrichment occurs early in Mars’s history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars’s D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensed (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH2=1-102 bars) yields surface temperatures high enough (Ts=290-560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Mars↗

In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large isotopic fractionation would argue for a low temperature (CM-like, T approximately 0 deg) formation. Magnetite probably formed during a separate event. Tagish Lake magnetite data is surprisingly compatible with that of R-chondrites and unequilibrated ordinary (LL3) chondrites. Our oxygen isotope data strongly supports the hypothesis of a single precursor for both lithologies. Drastic mineralogical changes between the two lithologies not being accompanied with isotopic fractionation seem compatible with the alteration model presented by Young et aI. Tagish Lake probably represents the first well preserved large sample of the C2 matter that dominates interplanetary matter since the formation of the solar system.

Zolensky, Michael E.↗

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

We investigated the isotopic fractionation of CH4 and hydrogen (H2) in the stratosphere by incorporating isotope-specific rate coefficients into the Lawrence Livermore National Laboratory (LLNL) 2D model and comparing the model results with new observations from the NASA ER-2 aircraft (funded through a separate task under the Upper Atmosphere Research Program). The model results reveal that fractionation which occurs in the stratosphere has a significant influence on isotope compositions in the free troposphere, an important point which had previously been ignored, unrecognized or unquantified for many long-lived trace gases, including CH4 and H2 which we have focused our efforts on to date. Our analyses of the model results and new isotope observations have also been used to test how well the kinetic isotope effects are known, at least to within the uncertainties in model chemistry and transport. Overall, these results represent an important step forward in our understanding of isotope fractionation in the atmosphere and demonstrate that stratospheric isotope fractionation cannot be ignored in modeling studies which use isotope observations in the troposphere to infer the global budgets of CH4 (an important greenhouse gas) and of H2 (a gas whose atmospheric budget must be better quantified, particularly before a large human perturbation from fuel cell use is realized). Our analyses of model results and observations from the NASA ER-2 aircraft are briefly summarized separately below for CH4, H2, and H2O and for the contribution of these modeling studies to date to our understanding of isotope fractionation for N2O, CO2, and O3 as well.

Boering, Kristie A.↗

Thermal and nonthermal escape mechanisms for terrestrial bodies

A survey is given of the classical thermal escape (Jeans or blowoff) and some eight nonthermal processes involving ions. Diffusional, energetic, and other limitations on the escape flux are discussed. Isotopic fractionation, due to differences in thermal escape rates or diffusive separation, is considered. The dominant processes acting at the five terrestrial planets and six major satellites are summarized. In general, nonthermal processes dominate over the classic thermal ones.

Hunten, D. M.↗

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Socki, Richard A.↗

Stable carbon isotope measurements using laser spectroscopy

The 2300 cm(exp -1) spectral region is especially interesting because (12)CO2 and (13)CO2 bands overlap in such a way that their rotational lines have approximately equal absorbance at the anticipated isotopic ratio (approximately 90) of carbon on Earth and Mars. Pairs of rotational lines we have studied are separated by as little as 0.050 cm(exp -1), but are well resolved with a tunable diode laser. Using sophisticated sweep integration and signal averaging techniques, we have measured the stable isotope ratio in carbon dioxide to a precision of better than 1 percent.

Sauke, T. B.↗

Solar noble gases revealed by closed system stepped etching of a metal separate from Fayetteville

Solar He, Ne, and Ar in a Fe-Ni separate from the chondrite Fayetteville are analyzed by closed system stepped oxidation. We report here data of the first 15 steps comprising 55 percent of the total solar gases. He-4/Ar-36 and Ne-20/Ar-36 are quite constant at values about 20 percent below those of present day solar wind (SWC). In this, Fe-Ni differs from lunar ilmenites where He-4/Ar-36 and Ne-20/Ar-36 in the first steps are several times below SWC. Thus, metal retains SW-noble gases even better than ilmenite, almost without element fractionation. Nevertheless, the isotopic composition of SW-He, -Ne, and -Ar in the first steps of the metal sample are identical to those found in a recently irradiated lunar ilmenite, indicating that ilmenites and chondritic metal both contain isotopically unfractionated SW noble gases. A preliminary analysis of a smaller Fayetteville metal separate shows Ne from solar energetic particles (SEP-Ne) with Ne-20/Ne-22 less than or equal to 11.5.

Murer, CH.↗

Isotopic Composition of Trapped and Cosmogenic Noble Gases in Several Martian Meteorites

Isotopic abundances of the noble gases were measured in the following Martian meteorites: two shock glass inclusions from EET79001, shock vein glass from Shergotty and Y793605, and whole rock samples of ALH84001 and QUE94201. These glass samples, when combined with literature data on a separate single glass inclusion from EET79001 and a glass vein from Zagami, permit examination of the isotopic composition of Ne, Ar, Kr, and Xe trapped from the Martian atmosphere in greater detail. The isotopic composition of Martian Ne, if actually present in these glasses, remains poorly defined. The Ar-40/Ar-36 ratio of Martian atmospheric Ar may be much less than the ratio measured by Viking and possibly as low as approx. 1900. The atmospheric Ar-36/Ar-38 ratio is less than or equal to 4.0. Martian atmospheric Kr appears to be enriched in lighter isotopes by approx. 0.4%/amu compared to both solar wind Kr and to the Martian composition previously reported. The Martian atmospheric Ar-36/Xe-132 and Kr-84/Xe-132 Xe elemental ratios are higher than those reported by Viking by factors of approx. 3.3 and approx. 2.5, respectively. Cosmogenic gases indicate space exposure ages of 13.9 +/- 1 Myr for ALH84001 and 2.7 +/- 0.6 Myr for QUE94201. Small amounts of Ne-21 produced by energetic solar protons may be present in QUE94201, but are not present in ALH84001 or Y793605. The space exposure age for Y793605 is 4.9 +/- 0.6 Myr and appears to be distinctly older than the ages for basaltic shergottites.

Garrison, Daniel H.↗

Mars atmosphere loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

The effects of loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the last 3.8 b.y. were examined. Sputtering is capable of efficiently removing all species from the upper atmosphere, including the light noble gases; N also is removed by photochemical processes. Due to the diffusive separation by mass above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For C and O, this allows us to determine the size of nonatmospheric reservoirs that mix with the atmosphere; these reserviors can be accounted for by exchange with CO2 adsorbed in the regolith and with H2O in the polar ice deposits. Both simple analytical models and time-dependent models of the loss of volatiles from and supply to the Martian atmosphere were constructed. Both Ar and Ne require continued replenishment from outgassing over geologic time.

Jakosky, B. M.↗

Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

We examine the effects of loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the last 3.8 b.y. Sputtering is capable of efficiently removing all species from the upper atmosphere including the light noble gases; N is removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species with the lighter mass being preferentially lost. For C and O, this allows us to determine the size of nonatmospheric reservoirs that mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith or H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss from and supply of volatiles to the Martian atmosphere.

Jakosky, B. M.↗

Lead in Martian Meteorites-- Observations and Inconsistencies: I. Chassigny

The history of Pb isotope analyses of the martian meteorites (SNC) and their interpretations is laden with difficulties. Two different analytical groups have interpreted their ancient (≥ 4 Ga) shergottite Pb ages as primary [1-5]. A Nakhla age of approximately 4.3 Ga has been interpreted to be primary as well [2]. This is in stark contrast to the young (≤ 1.4 Ga) crystallization ages defined by the Rb-Sr, Sm-Nd, Lu-Hf, and KAr systems [6]. Possibly, a better interpretation for the ancient Pb ages is that they reflect the formation times of the various SNC source regions [7]. A difficulty in dealing with Pb is that terrestrial contamination is ubiquitous, unlike the other chronometer systems noted above. This issue is complicated by the fact that radioactive decay causes localized mineral damage. So washing and leaching to remove Pb contamination tends to remove in situ radiogenic Pb. This issue is further compounded because U and Th are often concentrated in phosphates and other minor phases, so the leaching process tends to remove these, especially phosphates. Another difficulty is that it is not clear whether the observed Pb isotopic variation in leachates, residues, and ion-microprobe analyses is due to terrestrial or to indigenous martian Pb contamination [e.g., 8]. A third difficulty is that the shergottites on the one hand, and the nakhlites and chassignites on the other, appear to have come from separate source regions with different chemical compositions [e.g., 7]. Thus, it is expected that their Pb isotopic characteristics would be different. And even if all these meteorite types came from the same source region, their igneous ages differ considerably. The nakhlites and chassignites are ~1.4 Ga and the shergottites are ≤ 600 Ma [e.g., 6]. This age difference alone should assure that the two distinct SNC groups have differing Pb isotopic signatures.

Jones, J. H.↗

Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

We examine the effects of the loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the past 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere, including the light noble gases; nitrogen and oxygen are removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For carbon and oxygen, this allows us to determine the size of nonatmospheric reservoirs which mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith and H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss of volatiles from and supply to the martian atmosphere. Both argon and neon require continued replenishment from outgassing over geologic time. For argon, sputtering loss explains the fractionation of (Ar-36)/(Ar-38) without requiring a distinct epoch of hydrodynamic escape (although fractionation of Xe isotopes still requires very early hydrodynamic loss). For neon, the current (Ne-22)/(Ne-20) ratio represents a balance between loss to space and continued resupply from the interior; the similarity of the ratio to the terrestrial value is coincidental. For nitrogen, the loss by both sputtering and photochemical escape would produce a fractionation of (N-15)/(N-14) larger than observed; an early, thicker carbon dioxide atmosphere could mitigate the nitrogen loss and produce the observed fractionation, as could continued outgassing of juvenile nitorgen. Based on the isotopic constraints, the total amount of carbon dioxide lost over geologic time is probably on the order of tens of millibars rather than a substantial fraction of a bar. The total loss from solar-wind-induced sputtering and photochemical escape, therefore, does not seem able to explain the loss of a putative thick, early atmosphere withput requiring formation of extensive surface carbonate deposits or other nonatmospheric reservoirs for CO2.

Jakosky, Bruce M.↗

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.↗

Noble gases in Luna 24 core soils

Isotopic abundances of the noble gases have been determined in grain size separates of six soils from different depths in the Luna 24 core. Concentrations of cosmogenic Ne-21 in these soils show a complex pattern as a function of soil depth, and are inconsistent with a single stage, in situ production in a static regolith or with a simple model of slow accumulation of previously unirradiated soils followed by a static period. All soils have apparently had a complex pre-irradiation history. Some soils show significant differences in the concentration of cosmogenic Ne-21 between different grain sizes, which is consistent with suggestions that they formed as a mixture of soils with different maturities. The exact subsurface depth relationships of the soils are not known, and several possibilities are discussed. Because of this factor and the complex nature of the soils, the cosmogenic Ne data do not define the depositional-irradiational history of the core. Luna 24 core soils may have been deposited any time during the past 300 million years.

Bogard, D. D.↗

Cosmic Ray Helium Intensities over the Solar Cycle from ACE

Observations of cosmic-ray helium energy spectra provide important constraints on cosmic ray origin and propagation. However, helium intensities measured at Earth are affected by solar modulation, especially below several GeV/nucleon. Observations of helium intensities over a solar cycle are important for understanding how solar modulation affects galactic cosmic ray intensities and for separating the contributions of anomalous and galactic cosmic rays. The Cosmic Ray Isotope Spectrometer (CRIS) on ACE has been measuring cosmic ray isotopes, including helium, since 1997 with high statistical precision. We present helium elemental intensities between approx. 10 to approx. 100 MeV/nucleon from the Solar Isotope Spectrometer (SIS) and CRIS observations over a solar cycle and compare these results with the observations from other satellite and balloon-borne instruments, and with GCR transport and solar modulation models.

DeNolfo, G. A.↗

Do Mesosiderites Reside on 4 VESTA? an Assessment Based on Dawn Grand Data

Almost a century ago, simple petrographic observations were used to suggest a close genetic link between eucrites and the silicates in mesosiderites [1]. Mesosiderites are composed of roughly equal proportions of silicates that are very similar in mineralogy and texture to howardites, and Fe, Ni metal (Fig. 1) [2]. This similarity has led some to conclude that mesosiderites come from the howardite, eucrite and diogenite (HED) parent asteroid [3, 4]. Subsequent petrologic study demonstrated a number of differences between mesosiderite silicates and HEDs that are more plausibly explained as requiring separate parent asteroids [5]. However, HEDs and mesosiderites are identical in oxygen isotopic composition, and this has been used to argue for a common parent 4 Vesta [6].

Mittlefehldt, D. W.↗