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All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Acquisition and Early Losses of Rare Gases from the Deep Earth

Direct observations show that the deep Earth contains rare gases of solar composition distinct from those in the atmosphere. We examine the implications of mantle rare gas characteristics on acquisition of rare gases from the solar nebula and subsequent losses due to a large impact. Deep mantle rare gas concentrations and isotopic compositions can be obtained from a model of transport and distribution of mantle rare gases. This model assumes the lower mantle closed early, while the upper mantle is open to subduction from the atmosphere and mass transfer from the lower mantle. Constraints are derived that can be incorporated into models for terrestrial volatile acquisition: (1) Calculated lower-mantle Xe-isotopic ratios indicate that the fraction of radiogenic Xe produced by I-129 and Pu-244 during the first about 10(exp 8) yr was lost, a conclusion also drawn for atmospheric Xe. Thus, either the Earth was made from materials that had lost >99% of rare gases about (0.7-2) x 10(exp 8) yr after the solar system formed, or gases were then lost from the fully formed Earth. (2) Concentrations of 3He and 20Ne in the lower mantle were established after these losses. (3) Neon-isotopic data indicates that mantle Ne has solar composition. The model allows for solar Ar/Ne and Xe/Ne in the lower mantle if a dominant fraction of upper mantle Ar and Xe are subduction-derived. If Earth formed in the presence of the solar nebula, it could have been melted by accretional energy and the blanketing effect of a massive, nebula-derived atmosphere. Gases from this atmosphere would have been sequestered within the molten Earth by dissolution at the surface and downward mixing. It was found that too much Ne would be dissolved in the Earth unless the atmosphere began to escape when the Earth was only partially assembled. Here we consider conditions required to initially dissolve sufficient rare gases to account for the present lower mantle concentrations after subsequent losses at 10(exp 8) yr. It is assumed that equilibration of the atmosphere with a thoroughly molten mantle was rapid, so that initial abundances of gases retained in any mantle layer reflected surface conditions when the layer solidified. For subsequent gas loss of 99.5% and typical solubility coefficients, a total pressure of 100 atm was required for an atmosphere of solar composition. Calculations of the pressure at the base of a primordial atmosphere indicate that this value might be exceeded by an order of magnitude or more for an atmosphere supported by accretional energy. Surface temperatures of about 4000 K would have been produced, probably high enough to melt the deep mantle. Initial distributions of retained rare gases would then be determined by the history of surface pressure and temperature during mantle cooling and solidification, i.e., the coupled cooling of Earth and atmosphere. The Earth's thermal state was determined by its surface temperature and the efficiency of convection in the molten mantle, estimated to be sufficient to maintain an adiabatic gradient. Because the melting curve is steeper than the adiabat, solidification of the mantle proceeded outward from the interior. Incorporation of atmospheric gases in the mantle therefore occurred over a range in surface temperature of a few thousand degrees Kelvin. The thermal state of the atmosphere was controlled by total luminosity of the Earth (energy) released by accreting planetesimals and the cooling Earth), nebular temperature and pressure, and atmospheric opacity. The energy released by accretion declined with time as did nebular pressure. Analytical solutions for an idealized (constant opacity radiative atmosphere show that declining energy sources under constant nebular conditions result in slowly diminishing surface temperature but dramatically increasing surface pressure. For such an atmosphere with declining nebular pressure but constant total luminosity, surface pressure decreases gradually with decreasing temperaure. A decline in accretion luminosity might be compensated by energy released as the mantle cools for about 10(exp 5) year, after which luminosity must decline. The total complement of dissolved rare gases will depend on the particular evolutionary path determined by the declining accretional luminosity, the Earth thermal history, removal of the nebula, and opacity variations of the atmosphere. Models for these coupled evolutionary histories for Earth's acquisition of nebular-derived noble gases are in progress. The later losses required at about 10(exp 8) yr (depleting the interior concentrations of the sequestered solar gases by a factor of > 100) were presumably related to the major impact in which the Moon formed.

Porcelli, D.↗
NASA NTRS1998

The Origin and Time Dependence of the Amount and Composition of Non-Constituent Gases Present in Crystal Growth Systems

Presence of different, non-constituent gases may be a critical factor in crystal growth systems. In Physical Vapor Transport processes the cras(es) can be used intentionally (to prevent excessively high, unstable growth conditions), or can evolve unintentionally during the course of the process (which may lead to undesired reduction in the -rowth rate). In melt growth, particularly under low gravity conditions (reduced hydrostatic pressure) the gas present in the system may contribute to formation of voids in the growing crystals and even to a separation of the crystal and the liquid phase [1]. On the other hand, some amount of gas may facilitate 'contactless' crystal growth particularly under reduced gravity conditions [2 - 6]. Different non-constituent gases may be present in growth ampoules, and their amount and composition may change during the crystallization process. Some gases can appear even in empty ampoules sealed originally under high vacuum: they may diffuse in from the outside, and/or desorb from the ampoule walls. Residual gases can also be generated by the source materials: even very high purity commercial elements and compounds may contain trace amounts of impurities, particularly oxides. The oxides may have low volatilities themselves but their reaction with other species, particularly carbon and hydrogen, may produce volatile compounds like water or carbon oxides. The non-constituent gases, either added initially to the system or evolved during the material processing, may diffuse out of the ampoule during the course of the experiment. Gases present outside (e.g. as a protective atmosphere or thermal conductor) may diffuse into the ampoule. In either case the growth conditions and the quality of the crystals may be affected. The problem is of a particular importance in sealed systems where the amount of the gases cannot be directly controlled. Therefore a reasonable knowledge and understanding of the origin, composition, magnitude, and change with time of gases present in sealed ampoules may be important for a meaningful control and interpretation of crystal growth processes. This problem is of a particular importance for processing of electronic materials in space because (i) safety considerations require using sealed systems only, and (ii) high cost of crystal growth experiments in microgravity calls for a throughout, accurate description of the processing conditions necessary for a meaningful, efficient, and conclusive interpretation of the space results. In this paper we present the results of our extensive studies on gases in closed crystal growth systems which include: (a) Degassing properties of fused silica; (b) Generation of inert gases by source materials (CdTe, ZnTe, CdZnTe, ZnSe, PbTe, PbSe, PbSeTe); (c) Diffusive cas losses from silica glass ampoules.

Palosz, Witold↗
NASA NTRS1985

Noble gases in meteorites and terrestrial planets

Terrestrial planets and chondrites have noble gas platforms that are sufficiently alike, especially Ne/Ar, that they may have acquired their noble gases by similar processes. Meteorites presumably obtained their noble gases during formation in the solar nebula. Adsorption onto C - the major gas carrier in chondrites - is the likely mechanism for trapping noble gases; recent laboratory simulations support this hypothesis. The story is more complex for planets. An attractive possibility is that the planets acquired their noble gases in a late accreting veneer of chondritic material. In chondrites, noble gases correlate with C, N, H, and volatile metals; by Occam's Razor, we would expect a similar coupling in planets. Indeed, the Earth's crust and mantle contain chondritic like trace volatiles and PL group metals, respectively and the Earth's oceans resemble C chondrites in their enrichment of D (8X vs 8-10X of the galactic D/H ratio). Models have been proposed to explain some of the specific noble gas patterns in planets. These include: (1) noble gases may have been directly trapped by preplanetary material instead of arriving in a veneer; (2) for Venus, irradiation of preplanetary material, followed by diffusive loss of Ne, could explain the high concentration of AR-36; (3) the Earth and Venus may have initially had similar abundances of noble gases, but the Earth lost its share during the Moon forming event; (4) noble gases could have been captured by planetestimals, possibly leading to gravitational fractionation, particularly of Xe isotopes and (5) noble gases may have been dissolved in the hot outer portion of the Earth during contact with a primordial atmosphere.

Wacker, J. F.↗
NASA NTRS1988

On the siting of gases shock-emplaced from internal cavities in basalt

Laboratory experiments were carried out on shock-emplaced gases from Servilleta basalt samples that contained gas-filled cavities to answer the following questions: (1) what is the role of shock melting in trapping gases; (2) how are the glassy pockets that contain trapped gases formed; and (3) are the gases trapped in laboratory shocked basalts sited similarly to, and emplaced with the same efficiency as, the gases in the EETA 79001 shergottite? Noble gases were extracted by stepped combustion and crushing followed by shock at 40 GPa, and were analyzed for abundances. Results obtained indicate that noble gases trapped from internal cavities of shock-exposed basalt are associated with glass and are sited predominantly in microvesicles, with a significant fraction of the gases released by crushing. The presence of gas-filled cavities prior to shock results in substantially greater shock effects locally. Thus, glassy pockets similar to those seen in EETA 79001 can be produced in situ within a matrix shocked to only moderate pressures. However, the siting of the gases points to a more complex scenario.

Wiens, R. C.↗
NASA NTRS2006

Relative Contribution of Greenhouse Gases and Ozone Change to Temperature Trends in the Stratosphere: A Chemistry/Climate Model Study

Long-term changes in greenhouse gases, primarily carbon dioxide, are expected to lead to a warming of the troposphere and a cooling of the stratosphere. We examine the cooling of the stratosphere and compare the contributions greenhouse gases and ozone change for the decades between 1980 and 2000. We use 150 years of simulation done with our coupled chemistry/climate model (GEOS 4 GCM with GSFC CTM chemistry) to calculate temperatures and constituents fiom,1950 through 2100. The contributions of greenhouse gases and ozone to temperature change are separated by a time-series analysis using a linear trend term throughout the period to represent the effects of greenhouse gases and an equivalent effective stratospheric chlorine (EESC) term to represent the effects of ozone change. The temperature changes over the 150 years of the simulation are dominated by the changes in greenhouse gases. Over the relatively short period (approx. 20 years) of ozone decline between 1980 and 2000 changes in ozone are competitive with changes in greenhouse gases. The changes in temperature induced by the ozone change are comparable to, but smaller than, those of greenhouse gases in the upper stratosphere (1-3 hPa) at mid latitudes. The ozone term dominates the temperature change near both poles with a negative temperature change below about 3-5 hPa and a positive change above. At mid latitudes in the upper stratosphere and mesosphere (above about 1 hPa) and in the middle stratosphere (3 to 70 ma), the greenhouse has term dominates. From about 70 hPa down to the tropopause at mid latitudes, cooling due to ozone changes is the largest influence on temperature. Over the 150 years of the simulation, the change in greenhouse gases is the most important contributor to temperature change. Ozone caused a perturbation that is expected to reverse over the coming decades. We show a model simulation of the expected temperature change over the next two decades (2006-2026). The simulation shows a crossover between lower atmospheric heating and upper atmospheric cooling that is located at about 90 hPa in the tropics and 30-40 hPa in the polar regions. This results from the combination of continuing increases in greehouse gases and recovery from ozone depletion.

Stolarski, Richard S.↗
DOE OSTI2022

Kinetic and equilibrium reactions on natural and laboratory generation of thermogenic gases from Type II marine shale

The phenomenon that laboratory pyrolysis experiments produce much wetter gases than those in natural reservoirs is a long-recognized and debated problem in the investigation of natural gases in sedimentary basins. In this study, we explore the discrepancy by pyrolyzing a type II kerogen from the Woodford Shale in Oklahoma, compared with the previous results on the produced natural gases from the Arkoma Basin generated from the same source rock (Liu et al., 2019) with the discussion of gas and isotopic compositions at bulk and position-specific (PS) levels. An improved GC-pyrolysis-GC IRMS method is applied for the determination of PS δ 13 C of propane produced in the pyrolysis of the Woodford Shale at Easy %R o from 0.76 to 3.27. Kinetic and thermodynamic considerations of the chemical and isotopic compositions of the natural and laboratory pyrolysis gases suggest that the generation of light hydrocarbons involves uni-directional cracking reactions, exchange reactions with water, and likely reversible reactions among light hydrocarbons and other H-containing volatiles. After the gas generation in the unconventional Woodford Shale reservoirs, the C 1 -C 4 gases might have approached close to chemical equilibrium of C 1 -C 3 and isotope equilibrium of C 2 -C 1 and C 3 -C 1 pairs at their peak temperatures. The capping H for the generation of C 1 -C 4 in the Woodford Shale gases appears to have experienced at least partial exchange with the water, while that in the pyrolysis gases is only originated from organic-bound compounds with large kinetic isotope effects (KIE). Our findings indicate that elevated compound-specific and PS δ 13 C values of propane in the wet-gas cracking stage are significantly influenced by the breakdown of the thermally stable compounds (e.g., remaining kerogen, residues). A first synthesis of PS δ 13 C and δ 2 H isotopic compositions of propane from this study and the literature data suggests relatively similar isotopic structures of propane precursors in kerogens. Finally, this study demonstrates that PS isotope analysis of propane can contribute to identifying various geological (e.g., maturation, wet-gas cracking, H exchange, diffusion) and biodegradation processes.

58 GEOSCIENCES↗
NASA NTRS1974

Inert gases in Sea of Fertility regolith

The content and isotopic composition were studied of inert gases -- He, Ne, Ar, Kr, and Xe -- in samples of lunar regolith returned by the Luna 16 automatic station. The samples were taken from depths of about 12 and 30 cm. The high concentrations of inert gases exceed by several orders their concentrations observed in ordinary stony meteorites. The gases in lunar regolith were a complex mixture of gases of different origins: Solar, cosmogenic, radiogenic, and so on. Solar wind gases predominated, distributed in the thin surficial layer of the regolith grains. The concentrations of these gases in the surficial layer is several cubic centimeters per gram. The isotopic composition of the inert gases of solar origin approaches their composition measured in gas-rich meteorites.

Vinogradov, A. P.↗
NASA NTRS1998

Incorporation of Solar Noble Gases from a Nebula-Derived Atmosphere During Magma Ocean Cooling

The presence of solar noble gases in the deep interior of the Earth is inferred from the Ne isotopic compositions of MORB (Mid-ocean Ridge Basalts) and OIB (Oceanic Island Basalt); Ar data may also consistent with a solar component in the deep mantle. Models of the transport and distribution of noble gases in the earth's mantle allow for the presence of solar Ar/Ne and Xe/Ne ratios and permit the calculation of lower mantle noble gas concentrations. These mantle data and models also indicate that the Earth suffered early (0.7 to 2 x 10(exp 8) yr) and large (greater than 99 percent) losses of noble gases from the interior, a result previously concluded for atmospheric Xe. We have pursued the suggestion that solar noble gases were incorporated in the forming Earth from a massive, nebula-derived atmosphere which promoted large-scale melting, so that gases from this atmosphere dissolved in the magma ocean and were mixed downward. Models of a primitive atmosphere captured from the solar nebula and supported by accretion luminosity indicate that pressures at the Earth's surface were adequate (and largely more than the required 100 Atm) to dissolve sufficient gases. We have calculated the coupled evolution of the magma ocean and the overlying atmosphere under conditions corresponding to the cessation (or severe attenuation) of the sustaining accretion luminosity, prior to the complete removal of the solar nebula. Such a condition was likely to obtain, for instance, when most of the unaccumulated mass resided in large bodies which were only sporadically accreted. The luminosity supporting the atmosphere is then that provided by the cooling Earth, consideration of which sets a lower limit to the time required to solidify the mantle and terminate the incorporation of atmospheric gases within it. In our initial calculations, we have fixed the nebula temperature at To = 300K, a value likely to be appropriate for nebular temperatures at lAU in the early planet-building epoch. We treated the background (nebula) pressure as an adjustable, time-dependent parameter. Additional information is contained within the original extended abstract.

Woolum, D. S.↗
DOE OSTI2020

Mixed gases in compressed cylinders: some popular misconceptions and explanations

Many industrial applications and scientific investigations require gaseous premixes. These are generally available in compressed gas cylinders from commercial vendors. Despite many decades of working knowledge with compressed premixed gases, various individuals from the production plants have expressed concerns regarding the ability of the gases to remain mixed in storage and delivery. In this brief tutorial, we show the mathematics and physics that underwrite our confidence in the use of premixed gases as we explain the following: The conditions in which separation of gases due to gravity is of practical concern; The conditions for preferential extraction of lighter gases from premixed gas tank; The time length necessary for homogeneous mixing of gases by molecular kinetics.

36 MATERIALS SCIENCE↗
NASA NTRS1974

Composition of the gases associated with the magmas that produced rocks 15016 and 15065

Gases may be trapped in crystallizing minerals in many different ways but gas analyses can provide geologically meaningful information only if the gases can be related to their specific locations in the host mineral. The gases trapped in glass inclusions can be representative samples of the gases associated with the magma adjacent to the mineral at the time it crystallized. Analyses of the gases in glass inclusions in gabbro 15065,44 and basalt 15016,48 show that in both cases the gases in the parent magma started with a composition close to 46% oxygen, 42% carbon and 12% hydrogen and became more water-rich as crystallization progressed. This enrichment is probably due to a selective removal of the less soluble carbon compounds into the vapor phase. Some of the volatile components may react with the rock as temperature falls to give siderite and possibly hydrous phases.

Barker, C.↗
NASA NTRS1978

Classification and generation of terrestrial rare gases

A Kr-84/Xe-130 versus Ne-20/Ar-36 diagram is a very useful format with which to study the elemental ratios of rare gases from terrestrial materials. It can separate not only the three types of rare gases which Ozima and Alexander (1976) classified but also the 'planetary' type rare gases from the other three types of rare gases. When all the available terrestrial rare gas data are plotted in a Kr-84/Xe-130 versus Ne-20/Ar-36 diagram, several observations can be made. First, most of the analyses of rare gases from shales yield Kr-84/Xe-130 ratios between the 'planetary' and atmospheric values. If, however, the atmosphere's high Kr-84/Xe-130 ratio was produced by the selective adsorption of xenon onto shales from an initially 'planetary' atmosphere, as is widely accepted, then the Kr-84/Xe-130 ratio in shales should be even lower than the 'planetary' value. Second, the rare gas pattern in the quenched rims of submarine basalts may be explained as fractionated samples of the rare gases in sea water.

Saito, K.↗
NASA NTRS1991

Noble gases in 'phase Q' - Closed-system etching of an Allende residue

Results are presented from an analysis, in nearly pure form, of noble gases from the 'phase-Q' in an HF/HCl residue of the Allende C3V meteorite, using the closed-system stepped etching technique developed by Wieler et al. (1986) and Benkert et al. (1988) to extract noble gases from the residue. The results yield precise values of element and isotope abundances of all five noble gases in phase-Q, which is the major carrier of the planetary gases in carbonaceous chondrites. It was found that Ne-Q and Xe-Q in Allende are very similar to trapped gases in ureilites and in oxidizable carriers in several classes of ordinary chandrites, indicating that Q-gases are present in the formation locations of all these meteorites.

Wieler, Rainer↗
NASA NTRS1991

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗
NASA NTRS1991

Source gases: Concentrations, emissions, and trends

Source gases are defined as those gases that influence levels of stratospheric ozone (O3) by transporting species containing halogen, hydrogen, and nitrogen to the stratosphere. Examples are the CFC's, methane (CH4), and nitrous oxide (N2O). Other source gases that also come under consideration in an atmospheric O3 context are those that are involved in the O3 or hydroxyl (OH) radical chemistry of the troposphere. Examples are CH4, carbon monoxide (CO), and nonmethane hydrocarbons (NMHC's). Most of the source gases, along with carbon dioxide (CO2) and water vapor (H2O), are climatically significant and thus affect stratospheric O3 levels by their influence on stratospheric temperatures. Carbonyl sulphide (COS) could affect stratospheric O3 through maintenance of the stratospheric sulphate aerosol layer, which may be involved in heterogeneous chlorine-catalyzed O3 destruction. The previous reviews of trends and emissions of source gases, either from the context of their influence on atmospheric O3 or global climate change, are updated. The current global abundances and concentration trends of the trace gases are given in tabular format.

Fraser, Paul J.↗
NASA NTRS1994

Solar wind noble gases and nitrogen in metal from lunar soil 68501

Noble gases and N were analyzed in handpicked metal separates from lunar soil 68501 by a combination of step-wise combustions and pyrolyses. Helium and Ne were found to be unfractionated with respect to one another when normalized to solar abundances, for both the bulk sample and for all but the highest temperature steps. However, they are depleted relative to Ar, Kr and Xe by at least a factor of 5. The heavier gases exhibit mass-dependent fractionation relative to solar system abundance ratios but appear unfractionated, both in the bulk metal and in early temperature steps, when compared to relative abundances derived from lunar ilmenite 71501 by chemical etching, recently put forward as representing the abundance ratios in solar wind. Estimates of the contribution of solar energetic particles (SEP) to the originally implanted solar gases, derived from a basic interpretation of He and Ne isotopes, yield values of about 10%. Analysis of the Ar isotopes requires a minimum of 20% SEP, and Kr isotopes, using our preferred composition for solar wind Kr, yield a result that overlaps both these values. It is possible to reconcile the data from these gases if significant loss of solar wind Ar, Kr and presumably Xe has occurred relative to the SEP component, most likely by erosive processes that are mass independent, although mass-dependent losses (Ar greater than Kr greater than Xe) cannot be excluded. If such losses did occur, the SEP contribution to the solar implanted gases must have been no more than a few percent. Nitrogen is a mixture of indigenous meteoritic N, whose isotopic composition is inferred to be relatively light, and implanted solar N, which has probably undergone diffusive redistribution and fractionation. If the heavy noble gases have not undergone diffusive loss, then N/Ar in the solar wind can be inferred to be at least several times the accepted solar ratio. The solar wind N appears, even after correction for fractionation effects, to have a minimum delta N-15 value equal to or greater than +150% and a more probable value equal to or greater than +200%.

Becker, Richard H.↗
NASA NTRS1959

Halogen-Containing Gases as Boundary Lubricants for Corrosion-Resistant Alloys at 1200 F

The extreme temperatures anticipated for lubricated parts in advanced flight powerplants dictate the consideration of unconventional methods of lubrication such as solid lubricants and the reactive gases described in the present research. These halogen-containing "reactive" gases such as dichlorodifluoromethane, CF2Cl2, are among the most stable of organic molecules. The high "flash" temperatures generated at the contacting asperities as a result of frictional heat are sufficient to cause local decomposition of the halogen-containing gases. The active atoms thus released (e.g., chlorine) then react with the metal to be lubricated to form halides capable of effective lubrication. The presence of small amounts of a sulfur-containing gas (e.g., 1 percent sulfur hexafluoride, SF6) was found to catalyze the formation of metal halides. Friction and wear studies were made with a hemisphere (3/16-in. rad.) rider sliding in a circumferential path on the flat surface of a rotating disk (2 1/2-in. diam.). The specimens of corrosion-resistant 2 alloys were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 120 feet per minute, and temperature from 75 to 1200 F. An effective lubricant for ferritic materials (M-1 tool steel) was CF2Cl2, but significant corrosion occurred above 600 F. Corrosion evaluation in CF2Cl2 suggested a number of nickel- and cobalt-base alloys for additional lubrication study. Several combinations of gases and these metals were found to lubricate to 1200 F without excessive corrosion. The gases were CF2Cl2 Plus 1 percent SF6, monobromotrifluoromethane CF3Br plus 1 percent SF6, dibromodifluoromethane CF2Br2, iodotrifluoromethane, CF3I, and I2. Careful selection of metals and gas are necessary for successful lubrication over specific temperature ranges. Optimum combinations give friction coefficients as low as 0.05 without

Buckley, Donald H.↗
NASA NTRS1997

On the Relation between Stratospheric Chlorine/Bromine Loading and Short-Lived Tropospheric Source Gases

Current methods for estimating the concentrations of inorganic chlorine/bromine species Cl(y)/Br(y) in the stratosphere due to decomposition of tropospheric source gases assume that the Cl(y)/Br(y) concentration in the stratosphere is determined mainly by the balance between production from in situ oxidation of the source gases in the stratosphere and removal by transport of Cl(y)/Br(y) out of the stratosphere. The rationale being that for source gases whose lifetimes are of the order of several months or longer the concentration of Cl(y)/Br(y) in the troposphere is small because they are produced at a relatively slow rate and also removed efficiently by washout processes. As a result of the small concentration, the rate at which Cl(y)/Br(y) is transported to the stratosphere is expected to be small compared to the in situ stratospheric production. Thus the transport of Cl(y)/Br(y) from the troposphere contributes little to the stratospheric concentration. In contrast, the origin of stratospheric Cl(y)/Br(y) from reactive source gases with tropospheric lifetimes comparable to the washout lifetime of Cl(y)/Br(y) (of the order of 10-30 days) in the troposphere is distinctly different. The in situ source in the stratosphere is expected to be significantly smaller because only a small portion of the source gas is expected to survive the troposphere to be transported into this region. At the same time these short-lived source gases produce appreciable amounts of Cl(y)/Br(y) in the troposphere such that transport to the stratosphere offers a larger source for stratospheric Cl(y)/Br(y) than in situ production. Thus, for reactive source species, simple methods of estimating the concentration of stratospheric Cl(y)/Br(y) that ignore the tropospheric contribution will seriously underestimate the loading. Therefore estimation of the stratospheric Cl(y)/Br(y) loading requires not only measurements of tropospheric source gases but also measurements of Cl(y)/Br(y) at the tropopause. This paper illustrates the mechanism by using results from a two-dimensional chemistry-transport model. However, in view of the importance of tropospheric transport on stratospheric loading the detailed values should be further evaluated using a three-dimensional model with appropriate treatment of convective transport.

Ko, Malcolm K. W.↗
NASA NTRS2000

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact-generated gases

Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.

Non-NASA Center↗