Adsorption of hydrogen, carbon monoxide, and oxygen on vacuum degassed stainless steel 304 at 20 C.
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Recent noble gas studies suggests the Earth's atmosphere outgassed from the Earth's upper mantle synchronous with sea floor spreading, ocean ridge hydrothermal activity and the formation of continents by partial melting in subduction zones. The evidence for formation of the atmosphere by outgassing of the mantle is the presence of radionuclides H3.-4, Ar-040 and 136 Xe-136 in the atmosphere that were produced from K-40, U and Th in the mantle. How these radionuclides were formed is reviewed.
The Na, K, Rb, Cs, and P abundances in eucrites, diogenites, basaltic clasts from polymict eucrite, howardites, and mesosiderites are examined, and compared with an average of highly incompatible refractory (AHIR) elements normalized to cosmic abundances. It is observed that basaltic eucrites and basaltic clasts show a positive correlation between K, Rb, and Cs, and alkali element/AHIR ratios; the volatile loss of the alkali elements from the basalt affects the parent body inventory of volatile elements. The data reveal that for diogenites, the alkali /AHIR ratios are 1.4-2 times greater than in basaltic eucrites and are more variable; and the negative relation between K, Rb, Cs, and the alkali/AHIR ratio correlate with progressive alkali loss through volatile outgassing during crystallization of one or more magmas resulting in a greater than 90 percent loss of the volatile element inventory from the parent body. It is also detected that P displays volatile loss from the basaltic eucrites and elevated P/AHIR ratios in diogenites.
Measurements of the concentration of rare gases and trace elements in oceanic basalts provided a new information concerning the structure if the Earth mantle and its evolution. The results set important constraints that need to be incorporated into any comprehensive understanding of the early history of the planets. Some of the highlights of these results are described and an indication is given how they are derived.
The volatile contents of a number of enstatite chondrite falls of different chemical groups (EH; EL) and petrologic types (EH3-5; EL6) were investigated in order to find evidence of explosive pyroclastic volcanism, supporting the mechanism proposed by Wilson and Keil (1991) to explain the lack of aubritic basalts in aubrites. It is shown that abundant volatiles are likely to have been released upon partial melting of enstatite chondritelike precursor materials of aubrites, enough to drive pyroclastic volcanic eruptions which would explain the lack of aubritic basalts.
Geophysical and geochemical observations strongly suggest a 'hot origin of Mars,' i.e., the early formation of both the core and the crust-mantle system either during or just after planetary accretion. To consider the behavior of H2O in the planetary interior it is specifically important to determine by what mechanism the planet is heated enough to cause melting. For Mars, the main heat source is probably accretional heating. Because Mars is small, the accretion energy needs to be effectively retained in its interior. Therefore, the three candidates of heat retention mechanism are discussed first: (1) the blanketing effect of the primordial H2-He atmosphere; (2) the blanketing effect of the impact-induced H2O-CO2 atmosphere; and (3) the higher deposition efficiency of impact energy due to larger impacts. It was concluded that (3) the is the most plausible mechanism for Mars. Then, its possible consequence on how wet the early martian mantle was is discussed.
Diamonds are unique samples for inferring ancient mantle conditions, because of their enormous stability, antiquity and also of mantle origin. However, as temperatures in the mantle where diamonds have existed are very high (greater than 1000 C) and residence time of some diamonds could be more than a few billion years, it is imperative to examine whether or not diamonds have retained their pristine characteristics, especially those of noble gases, under such extreme conditions. As discussed in a review article by Ozima, there are rather large variations in the diffusivity of helium in diamonds obtained in the early determinations. The data are also limited to temperatures higher than 1200 C. In the present study, we conducted more refined diffusion experiments for He using carbonado diamonds, which have large amounts of radiogenic (4)He approximately 10(exp -2) cu cm STP/g. On the basis of the experimentally estimated diffusion coefficients, we will discuss retentivity of He in diamonds in the mantle condition.
Thermal desorption spectroscopy (TDS), along with Auger electron spectroscopy, was used to study the desorption of H2 and CO from baked 304 and 347 stainless-steel samples exposed only to residual gases. Both 347 and 304 samples gave identical TDS spectra. The spectra for CO contained a sharp leading peak centered in the temperature range 410-440C and an exponentially increasing part for temperatures higher than 500C, with a small peak around 600C appearing as a shoulder. The leading peak followed a second-order desorption behavior with an activation energy of 28+/-2 kcal/mol, suggesting that the rate-limiting step for this peak is most likely a surface reaction that produces the CO molecules in the surface layer. The amount of desorbed CO corresponding to this peak was approximately 0.5X10(exp 14) molecules/cm(exp 2) . The exponentially rising part of the CO spectrum appeared to originate from a bulk diffusion process. The TDS spectrum for H2 consisted of a main peak centered also in the temperature range 410-440C, with two small peaks appearing as shoulders at approximately 500 and 650C. The main peak in this case also displayed a second-order behavior with an activation energy of 14+/-2 kcal/mol. The amount of desorbed H2, approximately 1.9X 10(exp 15) molecules/cm(exp 2) , appeared to be independent of the concentration of hydrogen in the bulk, indicating that the majority of the desorbed H2 originated from the surface layer.
Thermodynamic calculations show that hydrogen, recently detected in Io's ionosphere by the Galileo spacecraft, can degas from high-temperature silicate magmas on Io in the form of H2O, H2S, HS, NaOH, H2, KOH, and HCl in order of decreasing abundance.
Carbon stability in planetary mantles has been studied by numerous authors because it is thought to be the source of C-bearing atmospheres and of C-rich lavas observed at the planetary surface. In the Earth, carbonaceous peridotites and eclogites compositions have been experimentally studied at mantle conditions [1] [2] [3]. [4] showed that the fO2 variations observed in martian meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Based on thermodynamic calculations [4] and [5] inferred that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond), and equilibrium with melts would be a source of CO2 for the martian atmosphere. Considering the high content of iron in the Martian mantle (approx.18.0 wt% FeO; [6]), compared to Earth s mantle (8.0 wt% FeO; [7]) Fe/C redox interactions should be studied in more detail.
Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form collision induced absorptions (CIA) involving H2 and/or CH4 provide enough extra greenhouse power in a predominately CO2 atmosphere to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. Surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level for CIA to be effective. Atmospheres with 1-2 bars of CO2 and 2- 10% H2 can sustain surface environments favorable for liquid water. Smaller concentrations of H2 are sufficient if CH4 is also present. If thick CO2 atmospheres with percent level concentrations of reduced gases are the solution to the faint young Sun paradox for Mars, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks. In this paper we focus on impact delivered reduced gases.
Hydrogen in nominally anhydrous minerals (NAMs) in meteorites provides insight to mantle sources of indigenous water on differentiated bodies: e.g. Peslier et al. 2017 [1], including Mars [2-4]. However, all meteorite samples, including Martian shergottites, record impact events as fractures, deformation, silicate darkening, shock melt veins and pockets, etc. The effect of shock on hydrogen in NAMs is poorly constrained, and must be understood prior to using these data to infer planetary indigenous water. Here we present water contents and D/H ratios (calculated as dD, i.e. the variation of the D/H ratio relative to a standard, in this case sea water "SMOW") in pyroxene, olivine and maskelynite in the olivine-phyric shergottite Larkman Nunatak 06319 (LAR 06319) as a function of proximity to impact melt. While the results suggest impact may have a role in fractionating H isotopes, the magmatic signature of H2O in Mars can be preserved in some pyroxene.
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High quality gas compositional data are an important factor in interpreting the genetic source of natural gas hosted in hydrate-bearing sediments and other subsurface systems. In order to accurately characterize the composition of gas samples degassed from hydrate-bearing pressure cores, one must use a reproducible sampling technique that minimizes artifacts of the sampling process. Herein, we review sediment core degassing techniques and compare data obtained from a commonly used degassing approach, which we term the standard quantitative degassing (SQD) technique, to our newly developed modified quantitative degassing (MQD) method designed to minimize atmospheric contamination and gas-water interactions. The SQD method allows sample gas to interact with water in a bubbling chamber, which we hypothesize could alter the gas composition following mixing with water or dissolved gases in the bubbling chamber. Whereas, the MQD method allows for the collection of sample gas prior to the bubbling chamber. To compare the SQD and MQD methods, we performed a side-by-side comparison of noble (He, Ne, Ar, Kr, and Xe), major (H 2 , N 2 , O 2 , and CO 2 ), and hydrocarbon (CH 4 , C 2 H 6 , C 3 H 8 , i-C 4 H 10 , C 4 H 10 , i-C 5 H 12 , C 5 H 12 ) gas concentrations and select isotopic compositions obtained using both sample collection techniques. Gas samples were collected from hydrate-bearing pressure cores recovered and maintained under hydrate stable conditions from the northern Gulf of Mexico during the UT-GOM 2 -1 Expedition. The MQD method displayed significantly lower concentrations of atmospheric gases, higher proportions of hydrocarbon gases, lower ratios of C 1 /C 2 + , and heavier stable carbon and hydrogen isotopes of methane than the SQD method. These results demonstrate that the MQD method reduced air contamination and minimized alteration of the hydrocarbon gases. Finally, we conclude this method may be important for future work that seeks to determine the composition of natural gas from pressure cores using quantitative degassing experiments, especially those seeking to measure major (e.g., N 2 ) and noble gases.
The effects of varying the vacuum degassing parameters on the microstructure and properties of Al-4Cu-1Mg-X-X (X-X = 1.5Li-0.2Zr or 1.5Fe-0.75Ce) alloys processed from either prealloyed (PA) or mechanically alloyed (M) powder, and consolidated by either using sealed aluminum containers or containerless vacuum hot pressing were studied. The consolidated billets were hot extruded to evaluate microstructure and properties. The MA Li-containing alloy did not include Zr, and the MA Fe- and Ce-containing alloy was made from both elemental and partially prealloyed powder. The alloys were vacuum degassed both above and below the solution heat treatment temperature. While vacuum degassing lowered the hydrogen content of these alloys, the range over which the vacuum degassing parameters were varied was not large enough to cause significant changes in degassing efficiency, and the observed variations in the mechanical properties of the heat treated alloys were attributed to varying contributions to strengthening by the sub-structure and the dispersoids. Mechanical alloying increased the strength over that of alloys of similar composition made from PA powder. The inferior properties in the transverse orientation, especially in the Li-containing alloys, suggested deficiencies in degassing. Among all of the alloys processed for this study, the Fe- and Ce-containing alloys made from MA powder possessed better combinations of strength and toughness.