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At least 235 records · Page 13

Rare gases systematics and mantle structure

The following points are emphasized: one of the most important ones is certainly the first set of experimental data on the solubility of noble gases in metal phases at intermediate pressures, since the core was certainly not formed at ultra high pressures, as emphasized by Ahrens and confirmed by trace elements systematics Wanke. The experimental data clearly show that the core can not be a major reservoir for terrestrial rare gases; the second point is a more elaborate reconsideration of the (40)K-(40)Ar budget of the Earth. This shows that (40)Ar contained in continental crust plus upper mantle plus atmosphere is at maximum half of the (40)Ar inventory of the whole earth. This implies the existence of a two layered mantle; the third point is the discovery by the Australian noble gases group of the existence of high (20)Ne/(22)Ne and low (21)Ne/(22)Ne isotopic ratios in Loihi seamount samples. This results which are different to the MORB ratios confirm the idea of a two layered model, but suggest the existence of a primordial solar type Ne reservoir. Several possibilities about the origin of this (20)Ne excess in the mantle will be discussed; The high (40)Ar/(36)Ar, (129)Xe/(130)Xe and (134) Xe/(130)Xe, (136)Xe/(130)Xe are confirmed by new data. The corresponding ratios for the lower mantle will be discussed. (40)Ar/(36)Ar ratios up to 6000 can be accepted and will not modify the general model of the mantle. They confirm the atmosphere chronology, about 85 percent of the atmosphere was formed in the first 50 My and 15 percent later on.

Allegre, C. J.↗

Adsorption and isotopic fractionation of Xe

A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

Bernatowicz, T. J.↗

Noble gas component organization in 14301

A study is conducted of the organization of noble gases in the Apollo 14 breccia 14301, giving particular attention to xenon from the extinct radionuclides I-129 and Pu-244. An essential ingredient of this work is the intercomparison between noble gases released in single-stage melts of grain size fractions and those released in stepwise extractions. This approach resolves 'functional' noble gas components, which are organized by siting, into the specific genetic contributions on the basis of the 'activation energies' for diffusive loss. The procedure makes it possible to resolve various genetic components on the basis of the chemical and structural differences in their specific locations. Consequently, distinctions can be made among components acquired by different processes and among components which have undergone different regolith histories.

Bernatowicz, T. J.↗

Studies on cosmogenic nuclides in meteorites with regard to an application as potential depth indicators

Measurements of stable and radioactive spallation products in meteorites allow to investigate their histories, especially with respect to the exposure to galactic cosmic ray particles and the pre-atmospheric size of the object. While the concentrations of spallation products lead to the determination of exposure and terrestrial ages, production rate ratios are characteristic for the location of the sample in the meteorite. So, one of the aims of this investigation on meteorites is to obtain depth indicators from suitable pairs of cosmogenic nuclides. Because of the different depth profiles for nuclide productions it is necessary to determine the concentrations of a larger number of spallation products in aliquots of a single small sample. Such same sample measurements of Be-10 and light noble gases were performed on 15 ordinary chondrites (7 H- and 8 L-chondrites. Be-10 was determined by accelerator mass spectrometry and the noble gases were measured by static mass spectrometry. The results are summarized and discussed.

Sarafin, R.↗

The regolith history of 14307

Noble gas and trace element analyses of matrix and a clast from breccia 14307 are reported. This sample was exposed to a large neutron fluence, as seen by an elevated Sm-150/Sm-149 ratio and by noble gases, particularly Xe-136 from neutron fission of U-235. Strong constraints on the exposure history result from combined consideration of Sm-150, Xe-136, and spallation noble gases. Both clast and matrix were irradiated for about 1 AE under substantial shielding beginning at least 2 AE ago, probably more than 3 AE ago. The manifestations of soil exposure seen in the matrix - solar wind gases, glass formation, etc. - thus must have been acquired in an ancient epoch. The matrix has had a longer exposure to cosmic rays than the clast, presumably during its prebrecciation history as a soil. Brecciation probably occurred more than 1 AE ago, perhaps more than 3 AE ago, but at least 0.4 AE after the formation of the matrix constituents.

Bernatowicz, T.↗

Production rates of neon xenon isotopes by energetic neutrons

As a first step in an experimental program to study the behavior of noble gases produced in situ in minerals, a suite of minerals and pure chemicals were irradiated with 14.5 MeV neutrons at LLNL's Rotating Target Neutron Source (RTNS-II) and production rates for noble gases were determined. While neutron effects in meteorites and lunar samples are dominated by low-energy neutron capture, more energetic cosmic-ray secondary neutrons can provide significant depth-dependent contributions to production of cosmogenic nuclides through endothermic reactions such as (n,2n), (n,np), (n,d) and (n,alpha). Production rates for nuclides produced by cosmic-ray secondary neutrons are therefore useful in interpreting shielding histories from the relative abundances of cosmogenic nuclides. Absolute production cross sections were calculated from isotope dilution analyses of NaCl, Mg, CsCl, and Ba(NO3)2 samples, assuming purity, stoichiometry, and quantitative noble gas retention and extraction. Relative production cross sections determined from neon isotopic ratios in the mineral samples were also considered in evaluating the neon production cross sections. Results are presented.

Leich, D. A.↗

Effects of natural zeolites on field-scale geologic noble gas transport

Improving predictive models for noble gas transport through natural materials at the field-scale is an essential component of improving US nuclear monitoring capabilities. Several field-scale experiments with a gas transport component have been conducted at the Nevada National Security Site (Non-Proliferation Experiment, Underground Nuclear Explosion Signatures Experiment). However, the models associated with these experiments have not treated zeolite minerals as gas adsorbing phases. This is significant as zeolites are a common alteration mineral with a high abundance at these field sites and are shown here to significantly fractionate noble gases during field-scale transport. This fractionation and associated retardation can complicate gas transport predictions by reducing the signal-to-noise ratio to the detector (e.g. mass spectrometers or radiation detectors) enough to mask the signal or make the data difficult to interpret. Omitting adsorption-related retardation data of noble gases in predictive gas transport models therefore results in systematic errors in model predictions where zeolites are present.Herein is presented noble gas adsorption data collected on zeolitized and non-zeolitized tuff. Experimental results were obtained using a unique piezometric adsorption system designed and built for this study. Data collected were then related to pure-phase mineral analyses conducted on clinoptilolite, mordenite, and quartz. These results quantify the adsorption capacity of materials present in field-scale systems, enabling the modeling of low-permeability rocks as significant sorption reservoirs vital to bulk transport predictions.

58 GEOSCIENCES↗

Noble-gas-rich separates from ordinary chondrites

Acid-resistant residues were prepared by HCl-HF demineralization of three H-type ordinary chondrites: Brownfield 1937 (H3), Dimmitt (H3, 4), and Estacado (H6). These residues were found to contain a large proportion of the planetary-type trapped Ar, Kr, and Xe in the meteorites. The similarity of these acid residues to those from carbonaceous chondrites and LL-type ordinary chondrites suggests that the same phase carries the trapped noble gases in all these diverse meteorite types. Because the H group represents a large fraction of all meteorites, this result indicates that the gas-rich carrier phase is as universal as the trapped noble-gas component itself. When treated with an oxidizing etchant, the acid residues lost almost all their complement of noble gases.

Moniot, R. K.↗

An Experimental Method to Measure Gaseous Diffusivity in Tight and Partially Saturated Porous Media via Continuously Monitored Mass Spectrometry

Detection of radioxenon and radioargon produced by underground nuclear explosions is one of the primary methods by which the Comprehensive Nuclear-Test–Ban Treaty (CTBT) monitors for nuclear activities. However, transport of these noble gases to the surface via barometric pumping is a complex process relying on advective and diffusive processes in a fractured porous medium to bring detectable levels to the surface. To better understand this process, experimental measurements of noble gas and chemical surrogate diffusivity in relevant lithologies are necessary. However, measurement of noble gas diffusivity in tight or partially saturated porous media is challenging due to the transparent nature of noble gases, the lengthy diffusion times, and difficulty maintaining consistent water saturation. Here, the quasi-steady-state Ney–Armistead method is modified to accommodate continuous gas sampling via effusive flow to a mass spectrometer. An analytical solution accounting for the cumulative sampling losses and induced advective flow is then derived. Experimental results appear in good agreement with the proposed theory, suggesting the presence of retained groundwater reduces the effective diffusivity of the gas tracers by 10–1000 times. Finally, by using a mass spectrometer, the method described herein is applicable to a broad range of gas species and porous media.

47 OTHER INSTRUMENTATION↗

Genesis Noble Gas Measurements

The original thrust of our Genesis funding was to extend and refine the noble gas analytical capabilities of this laboratory to improve the precision and accuracy of noble gas measurements in order to optimize the scientific return from the Genesis Mission. This process involved both instrumental improvement (supplemented by a SRLIDAP instrument grant) and refinement of technique. The Genesis landing mishap shifted our emphasis to the irregular aluminum heat shield material from the flat collector wafers. This has required redesign of our laser extraction cells to accommodate the longer focal lengths required for laser extraction from non-flat surfaces. Extraction of noble gases from solid aluminum surfaces, rather than thin coatings on transparent substrates has required refinement of controlled-depth laser ablation techniques. Both of these bring new problems, both with potentially higher blanks form larger laser cells and the larger quantities of evaporated aluminum which can coat the sapphire entrance ports. This is mainly a problem for the heavy noble gases where larger extraction areas are required, necessitating the new aluminum vapor containment techniques described below. With the Genesis Mission came three new multiple multiplier noble gas mass spectrometers to this laboratory, one built solely by us (Supergnome-M), one built in collaboration with Nu-Instruments (Noblesse), and one built in collaboration with GVI (Helix). All of these have multiple multiplier detection sections with the Nu-Instruments using a pair of electrostatic quad lenses for isotope spacing and the other two using mechanically adjustable positions for the electron multipliers. The Supergnome-M and Noblesse are installed and running. The GVI instrument was delivered a year late (in March 2005) and is yet to be installed by GVI. As with all new instruments there were some initial development issues, some of which are still outstanding. The most serious of these are performance issues with the miniature channel electron multipliers. The delayed installation of Helix by the GVI is partly due to failure of the initial batch of Burle channel multipliers to perform as expected. A number of the channel multipliers designed for Noblesse by Burle have also failed upon baking. Burle has now refined the design of these and we have installed two of the new multipliers and are assessing their performance. The remaining multipliers Will be upgraded to the new design from Burle once we confirm that the problem has been fixed.

Hohenberg, Charles M.↗

Leak detector for spacecraft testing with high accuracy

It is convenient to measure the leak rate of spacecraft when the spacecraft is kept in its container and the increment of tracer gas, mostly noble gases, in the container air is measured as function of time. In order to meet the specification of the new voluminous spacecraft, a leak detector with high accuracy is required. This is made difficult, because of the natural abundance of noble gases in air, which mean a considerable background exists. A leak detector is described which allows the measurement of an increment of the concentration of a few % using reference gas.

Saenger, G.↗

Krypton storage capacity of the Earth's lower mantle

Noble gases are important geochemical tracers allowing reconstructing global volatile cycles in Earth's reservoirs. To constrain these fundamental processes, precise data on their partitioning behavior at deep Earth conditions are needed. Such data are only available at moderate pressures up to 25 GPa due to experimental challenges. We have investigated the possibility of noble gas storage in the Earth's lower mantle up to 115 GPa. We studied the incorporation of krypton in the second most abundant lower mantle mineral (Mg 1-x ,Fe x )O (ferropericlase) as well as in liquid metal-alloys by performing experiments up to 115 GPa and 3700 K using the laser-heated diamond anvil cell coupled to post-mortem EMPA analysis and X-ray absorption spectroscopy. The results reveal that, at these extreme conditions, up to 3 wt.% of krypton can be stored in (Mg 1-x ,Fe x )O and 3000 ppm in the Fe-rich liquid metal. For both phases the storage capacities increase with pressure (between 40 GPa and 60 GPa) at a constant high temperature of 2300 K. Fpc has never been considered as a NG host, despite being the second most abundant mineral in the Earth's LM. Using recent accurate compressibility data, we demonstrate that a substitution of krypton into the anion site of (Mg 1-x ,Fe x )O in form of neutral oxygen Schottky defects at diluted lower mantle conditions is possible. This noble gas incorporation mechanism is in agreement with a previous study on bridgmanite. We show that (Mg 1-x ,Fe x )O exhibits higher noble gas storage capacities than bridgmanite through the lower mantle using lattice strain modeling and including experimental solubility and thermoelastic data for neon, argon, krypton and xenon. We also demonstrate that both phases exhibit the highest solubilities for argon and krypton. We used the solubility data from lattice strain modeling to predict noble gas abundances stored in the solid lower mantle after magma ocean crystallization. The modeled abundances show apparent similarities with estimates for the deep noble gas reservoir that are based on either 3He abundances in ocean island basalts or radiogenic 40Ar abundances in the bulk Earth. This strongly indicates that the crystalline lower mantle may play an important role as deep noble gas storage reservoir. We propose, based on considerations on noble gas replenishment from the lower mantle to the atmosphere, that the lower mantle can only contribute to a small fraction of the present-day atmospheric noble gases. This suggests that the lower mantle is an un-degassed reservoir.

58 GEOSCIENCES↗

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.↗

2D Nitrogen‐Doped Graphene Materials for Noble Gas Separation

Abstract Noble gases, notably xenon, play a pivotal role in diverse high‐tech applications. However, manufacturing xenon is an inherently challenging task, due to its unique properties and trace abundance in the Earth's atmosphere. Consequently, there is a pressing need for the development of efficient methods for the separation of noble gases. Using mild fluorographene chemistry, nitrogen‐doped graphene (GNs) materials are synthesized with abundant aromatic regions and extensive nitrogen doping within the vacancies and holes of the aromatic lattice. Due to the organized interlayer “nanochannels”, nitrogen functional groups, and defects within the two‐dimensional (2D) structures, GNs exhibits effective selectivity for Xe over Kr at low pressure. This enhanced selectivity is attributed to the stronger binding affinity of Xe to GN compared to Kr. The adsorption is governed by London dispersion forces, as revealed by theoretical calculations using symmetry‐adapted perturbation theory (SAPT). Investigation of other GNs differing in nitrogen content, surface area, and pore sizes underscores the significance of nitrogen functional groups, defects, and interlayer nanochannels over the surface area in achieving superior selectivity. This work offers a new perspective on the design and fabrication of functionalized graphene derivatives, exhibiting superior noble gas storage and separation activity exploitable in gas production technologies.

Šedajová, Veronika↗

Gas-rich minerals in the Allende meteorite - Attempted chemical characterization

A ten-step etching experiment with HNO3 was performed on a chromite-carbon residue from Allende, in order to characterize the HNO3-soluble minor phase 'Q' that contains most of the primordial Ar, Kr, and Xe. Each etch fraction was analyzed by neutron activation analysis for Cr, Fe, Co, Ir, and Au. The results suggest that Q consists of two minerals, each comprising about 5 per cent of the residue. Phase Q1, of Fe/Cr ratio greater than 20, is soluble in cold dilute HNO3 and seems to contain most of the heavy noble gases. It may be an HCl-insoluble sulfide of nominal composition (Fe84Ni12Cr4)Sx. Phase Q2, of Fe/Cr ratio about 0.5 and somewhat enriched in Co, is slowly soluble in hot concentrated HNO3 and seems to be at least an order of magnitude poorer in heavy noble gases than Q1. It may be daubre-elite or an acid-soluble variety of chromite.

Gros, J.↗

A theoretical investigation of isotopic anomalies of xenon in terrestrial and extra-terrestrial samples

The abundance and isotopic composition of noble gases in meteorites is discussed in relation to the composition of the early solar system. Carbonaceous chondrites contain a unique Xenon-X, which is rich in heavy and light isotopes. Variations in the occurrence of type-X and type-Y (the normal component) noble gases are of such magnitude that neither the injection of material from a nearby supernova nor presence of presolar grains can account for the anomalies in meteorites. Therefore, it is suggested that the entire solar system may have condensed from the debris of a single local supernova.

Sabu, D. D.↗

He-3 and other lunar volatiles

Constraints are considered and estimates are given for the abundances of He-3, other noble gases, and chemically reactive volatiles (e.g., H, C, N, S, F, Cl) on the Moon. For the case of surface inventories, solar wind particles implanted into grains on the surface of the Moon provide an accessible, though not necessarily abundant, source of H, C, N and the noble gases. Solar wind implanted species are concentrated in the infest grain sized, and are only found in the upper few meters of the regolith, where there are grains that have been directly exposed to the Sun. Elemental abundances in surface soils are typically 10s of mg/g, and vary according to the exposure history of the soil. The abundance of the rare, but possibly economically important, isotope He-3 is typically a few mg/g. The largest uncertainty in estimates of the total lunar abundance of solar wind implanted species comes from the lack of knowledge of their distribution with depth below the upper meter or two. For the case of bulk inventories, constraints resulting from lunar sample analyses and from physical chemical models of volatile behavior during the hypothesized giant impact origin of the Moon is used to give estimated abundances.

Fegley, B., Jr.↗

The composition of the atmosphere at the surface of Mars

The current status is summarized of investigations of the composition of the Martian atmosphere, in which use was made of the mass spectrometers that function as the analytical component of the molecular analysis experiments on the two Viking landers. The following points seem well established: N2, Ar-40, Ne, Kr, Xe, and the primordial isotope of Ar are present. The present atmosphere of Mars represents only a small fraction of the total amount of volatiles outgassed by the planet, so that high surface pressure and abundant water may have been present. The noble gases in the Martian atmosphere exhibit a relative abundance pattern similar to that in the earth's atmosphere and (except for Xe) to that in the primordial component of meteorites. The existence of a 'planetary component' is thus proven, supporting the arguments of those who favor a fractionation of noble gases prior to the formation of the planets. In spite of these similarities, the isotopic ratios of nitrogen, argon, and xenon indicate that the histories of the Martian and the earth's atmospheres have been very different.

Owen, T.↗