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At least 91 records · Page 5

Thermal effects in rapid directional solidification - Linear theory

We study the morphological instability of the planar solid/liquid interface for a unidirectionally-solidified dilute binary mixture. We use a model developed by Boettinger et al. (1985, 1986), Aziz (1982), and Jackson et al. (1980), which allows for nonequilibrium effects on the interface through velocity-dependent segregation and attachment kinetics. Two types of instabilities are found in the linear stability analysis: (1) a cellular instability, and (2) an oscillatory instability driven by disequilibrium effects. Merchant and Davis (1990) characterized these instabilities subject to the frozen-temperature approximation (FTA). The present work relaxes the FTA by including the effects of latent heat and the full temperature distribution. Thermal effects slightly postpone the onset of the cellular instability but dramatically postpone the onset of the oscillatory instability; however, the absolute-stability conditions, at which at high speed the cellular and oscillatory instabilities are suppressed, remain unchanged from the FTA.

Huntley, D. A.↗

Thorium-uranium fractionation by garnet - Evidence for a deep source and rapid rise of oceanic basalts

Mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs) are derived by partial melting of the upper mantle and are marked by systematic excesses of thorium-230 activity relative to the activity of its parent, uranium-238. Experimental measurements of the distribution of thorium and uranium between the melt and solid residue show that, of the major phases in the upper mantle, only garnet will retain uranium over thorium. This sense of fractionation, which is opposite to that caused by clinopyroxene-melt partitioning, is consistent with the thorium-230 excesses observed in young oceanic basalts. Thus, both MORBs and OIBs must begin partial melting in the garnet stability field or below about 70 kilometers. A calculation shows that the thorium-230-uranium-238 disequilibrium in MORBs can be attributed to dynamic partial melting beginning at 80 kilometers with a melt porosity of 0.2 percent or more. This result requires that melting beneath ridges occurs in a wide region and that the magma rises to the surface at a velocity of at least 0.9 meter per year.

Latourrette, T. Z.↗

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Martens, Christopher S.↗

Micro-zoning in minerals of a Landes silicate inclusion

There is an increasing number of meteorites with chondritic bulk composition but completely different textures than the conventional chondrite groups. Winonaites, Acapulcoites and silicate inclusions in IAB-iron meteorites have in common coarse grain size, highly equilibrated mineralogy with frequent 120 deg triple junctions and they record a significantly lower degree of oxidation than ordinary chondrites. They all have equilibration temperatures, based on Ca-exchange among pyroxenes, of around 900 to 1100 deg C. However, on cooling disequilibrium features may develop: (1) Olivine in IAB-inclusions has lower Fa-content than equilibrium Fs-content of pyroxenes requires; (2) CaO-zoning in olivine was established at temperatures of around 500 deg C, several hundred degrees below pyroxene equilibration temperatures. Obviously, olivine responded faster to changes in fO2 (Fa in olivine) and temperature (Ca-zoning) than pyroxenes. Differences in diffusion coefficients can readily explain the observed trends. Here we report on much more subtle zoning features in pyroxenes. TEM-observations reveal large compositional gradients in Ca, Na, Cr, Ti and Fe within the first micrometer of cpx and opx crystals. In summary, the data reflect the complicated subsolidus history of a chondritic mineral assemblage that was in thermodynamic equilibrium at about 900 deg C and cooled slowly from this temperature whereby oxidation reactions and different closure temperatures for various minerals and elements played an important role. The oxidation of P dissolved in metal and formation of phosphate, which is thermodynamically stable at low temperatures, is suggested to be responsible for most of the observed zoning.

Eisenhour, D. D.↗

Olivines in the Kaba carbonaceous chondrite and constraints on their formation

Kaba is unique in containing almost pure fayalitic olivine (Fo(sub 0.1)). Its coexistence with pure forsterite up to Fo(sub 99.6) and normal (Fo(sub 92) to Fo(sub 59)) and reversely (Fo(sub 0.4) to Fo(sub 4.7)) zoned olivines suggest that the Kaba olivines are in thermodynamic disequilibrium and experienced a complicated history. The fayalite is sufficiently pure that it is unlikely that it could have been produced by fractional crystallization. A gas-solid reaction under oxidizing conditions (H2O/H2 ratio approximately 10) is probably responsible for its formation.

Hua, X.↗

Self-organization of the earth's biosphere-geochemical or geophysiological?

We explore the implications of indicating the biosphere's self-organization by the trend over time of the net entropic flow from the Earth's surface, the actual physical boundary of virtually all biotic mass. This flow, derived from the radiative surface entropy budget, is approximately inversely related to the surface temperature when the solar incident flux remains constant. In the geophysiological ('gaian') interpretation, biospheric self-organization has increased with the progressive colonization of the continents and evolutionary developments in the land biota, as a result of surface cooling arising from biotic enhancement of weathering. The key site for this self-organization is at the interface between land and atmosphere, the soil, where carbon is sequestered by its reaction (as carbonic and organic acids) with calcium magnesium silicates. Along with disequilibrium (steady-state) levels of carbon dioxide in the atmosphere, the occurrence of differentiated soil is the critical material evidence for biospheric self-organization, whether it be geophysiological or geochemical (ie., purely result of inorganic reactions). The computed equilibrium levels of carbon dioxide and corresponding equilibrium temperatures in the past are dramatically different from the steady-state levels. With future solar luminosity increase, the biospheric capacity for climatic regulation will decrease, leading to the ending of self-organization some two billion years from now. The Earth's surface will then approach chemical equilibrium with respect to the carbonate-silicate cycle.

Schwartzman, David W.↗

Martian carbonates in ALH 84001: Textural, elemental, and stable isotopic compositional evidence on their formation

Martian orthopyroxenite ALH 84001 is unusual compared to other martian meteorites in its abundance of Mg-Fe-Ca carbonites. Becasue textural evidence indicates that these carbonates are undoubtedly of martian origin, we have undertaken stable isotopic studies to elucidate their origin by evaluating whether they represent primordial martian C that was outgassing from the mantle of Mars, or volatile additions to the ALH 84001 protolith that equilibrated with the martian atmosphere. If precipitation occurred in a closed system then the isotopic results are compatible with the observed chemical zonation. A unique temperature of formation can be calculated using the difference in C-13 and O-18 between the Fe and Mg carbonates, assuming that precipitation occurred at a constant temperature. Precipitation of approximately one-half of the CO2 reservoir at 320 C can account for the observed values, with the original CO2 reservoir having a delta C-13 of approximately 45% and delta O-18 of approximately 22%. If carbonate precipitated in equilibrium with a large isotopically homogeneous CO2 reservoir (open system), isotopic differences must be attributed to a change in temperature of at least several hundreds of degrees. This temperature change is compatible with a calculated range of temperatures based on carbonate geothermometry. Clearly, carbonate in ALH 84001 is in delta O-18 disequilibrium with orthopyroxene groundmass. Most likely, the carbonate precipitated from a fluid that equilibrated with the martian atmosphere. The deposits or fluids in equilibrium with these deposits were remobilized in the crust producing the carbonate in ALH 84001. This observation establishes a link for the first time between the atmospheric and lithospheric C and O pools that reside on Mars.

Romanek, C. S.↗

Geochemical constraints on chemolithoautotrophic reactions in hydrothermal systems

Thermodynamic calculations provide the means to quantify the chemical disequilibrium inherent in the mixing of reduced hydrothermal fluids with seawater. The chemical energy available for metabolic processes in these environments can be evaluated by taking into account the pressure and temperature dependence of the apparent standard Gibbs free energies of reactions in the S-H2-H2O system together with geochemical constraints on pH, activities of aqueous sulfur species and fugacities of H2 and/or O2. Using present-day mixing of hydrothermal fluids and seawater as a starting point, it is shown that each mole of H2S entering seawater from hydrothermal fluids represents about 200,000 calories of chemical energy for metabolic systems able to catalyze H2S oxidation. Extrapolating to the early Earth, which was likely to have had an atmosphere more reduced than at present, shows that this chemical energy may have been a factor of two or so less. Nevertheless, mixing of hydrothermal fluids with seawater would have been an abundant source of chemical energy, and an inevitable consequence of the presence of an ocean on an initially hot Earth. The amount of energy available was more than enough for organic synthesis from CO2 or CO, and/or polymer formation, indicating that the vicinity of hydrothermal systems at the sea floor was an ideal location for the emergence of the first chemolithoautotrophic metabolic systems.

Shock, Everett L.↗

Sulfur Chemistry in the Wake of Comet Shoemaker-Levy 9

A curious and unexpected result of the impact of P/Shoemaker Levy 9 with Jupiter was the production of enormous amounts of molecular sulfur (S2). Here we show that S2 is the natural product of disequilibrium chemistry at low pressures in shocked Jovian air, its formation a byproduct of hydrogen recombination. The species observed by the Hubble Space Telescope (HST) - S2, CS2, and H2S - imply that the G fragment penetrated the NH4SH cloud but did not reach the water table. A typical impact within or below the NH4SH clouds produces about 0.03 - 0.1 impactor masses of S2. Because comets are relatively hydrogen-poor, SO2, not S2, is the major product of shocking a water-rich comet, while S2, CS2 and OCS are major products of a dessicated comet. In all cases we find that as the gas cools, S2 converts to the stable low temperature allotrope S8, although other chemical fates not modeled here might intervene first.

Zahnle, Kevin↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

The results of the investigation were presented at a Astrobiology Institute General Meeting. Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions.

Shock, Everett L.↗

An Integrated Use of Experimental, Modeling and Remote Sensing Techniques to Investigate Carbon and Phosphorus Dynamics in the Humid Tropics

Moist tropical forests comprise one of the world's largest and most diverse biomes, and exchange more carbon, water, and energy with the atmosphere than any other ecosystem. In recent decades, tropical forests have also become one of the globe's most threatened biomes, subjected to exceptionally high rates of deforestation and land degradation. Thus, the importance of and threats to tropical forests are undeniable, yet our understanding of basic ecosystem processes in both intact and disturbed portions of the moist tropics remains poorer than for almost any other major biome. Our approach in this project was to take a multi-scale, multi-tool approach to address two different problems. First, we wanted to test if land-use driven changes in the cycles of probable limiting nutrients in forest systems were a key driver in the frequently observed pattern of declining pasture productivity and carbon stocks. Given the enormous complexity of land use change in the tropics, in which one finds a myriad of different land use types and intensities overlain on varying climates and soil types, we also wanted to see if new remote sensing techniques would allow some novel links between parameters which could be sensed remotely, and key biogeochemical variables which cannot. Second, we addressed to general questions about the role of tropical forests in the global carbon cycle. First, we used a new approach for quantifying and minimizing non-biological artifacts in the NOAA/NASA AVHRR Pathfinder time series of surface reflectance data so that we could address potential links between Amazonian forest dynamics and ENSO cycles. Second, we showed that the disequilibrium in C-13 exchanged between land and atmosphere following tropical deforestation probably has a significant impact on the use of 13-CO2 data to predict regional fluxes in the global carbon cycle.

Townsend, Alan R.↗

Land Use Effects on Atmospheric C-13 Imply a Sizable Terrestrial CO2 Sink in Tropical Latitudes

Records of atmospheric CO2 and 13-CO2, can be used to distinguish terrestrial vs. oceanic exchanges of CO2 with the atmosphere. However, this approach has proven difficult in the tropics, partly due to extensive land conversion from C-3 to C-4 vegetation. We estimated the effects of such conversion on biosphere-atmosphere C-13 exchange for 1991 through 1999, and then explored how this 'land-use disequilibrium' altered the partitioning of net atmospheric CO2 exchanges between ocean and land using NOAA-CMDL data and a 2D, zonally averaged atmospheric transport model. Our results show sizable CO2 uptake in C-3-dominated tropical regions in seven of the nine years; 1997 and 1998, which included a strong ENSO event, are near neutral. Since these fluxes include any deforestation source, our findings imply either that such sources are smaller than previously estimated, and/or the existence of a large terrestrial CO2 sink in equatorial latitudes.

Townsend, Alan R.↗

Brown Dwarfs: Discovery and Detailed Studies

We obtained the optical and IR spectra of Gliese 229B and identified Cs, I, and CO features - as expected in theoretical models. Our optical IR spectrum showed that most of the refractory metals have condensed out of the atmosphere and the presence of Cs, I and CO shows evidence for disequilibrium chemistry. We reported orbital evidence for Gliese 229B. The HST measured optical magnitudes provide additional evidence for the absence of dust in the atmosphere of this cool object. The luminosity of brown dwarfs depend on their masses and ages and in order to interpret the results of the survey we have carried out an extensive Monte Carlo analysis. Our conclusion is that warm brown dwarfs are rare, as companions in the orbital period range beyond approximately 30 - 50 AU. The Palomer survey poses no constraint for brown dwarfs in planetary orbits similar to those of the outer planets. We have just started a program of imaging nearby stars with the newly commissioned AO system at Palomar and Keck and have already found a brown dwarf candidate.

Kulkarni, Shrinivas R.↗

Sampling of Trace Atmospheric Constituents Above the Surface of Mars from a Montgolfiere Balloon

We suggest that use of an aerially deployed, solar-heated balloon, or Montgolfiere, during a Martian polar summer could provide an optimal platform for atmospheric measurements near the surface. Solar Montgolfieres are empty balloons with a hole in the bottom that fill with ambient atmosphere while failing and are rapidly heated in by the sun, thus providing buoyancy. Such a balloon would be driven by the Martian winds in the constant sunlight of a high latitude entry and could provide a traverse of thousands of kilometers. It would encircle the Martian north polar region over a period,likely lasting over one earth month, and its altitude could be controlled as low as 100 meters to as high as 4000 meters above the surface. The significant payload of tens of kilograms allowed by this technology could readily accommodate the mass of instrumentation and the power source needed for a sensitive search for disequilibrium species that might provide the atmospheric signature of localized subsurface biological or geological activity. A mass spectrometer used in combination with gas enrichment techniques can provide sensitivities to sub parts per billion for several species of interest. Additional highly specific and sensitive detectors can search for other species or measurements of their mixing ratio variation along the path of the balloon. It would be useful to combine these atmospheric measurements with electromagnetic sounding to search for variations in subsurface conductivity that might indicate the presence of subsurface water. After a month of operation, the balloon could also soft land the DBMS to provide additional data on soil samples from a 1-2 meter subsurface drill. In order to float a 30-kg payload at altitudes between 100 m and 4000 m above the Martian north polar surface, an aluminized polyethylene Montgolfiere would be approximately 29 meters in diameter and have a mass of 27 kg. Altitude variations could be accomplished by means of an upper vent to release hot gas, as has been tested at JPL, or be means of a simple, internal winch mechanism to decrease the volume of the balloon. JPL has successfully deployed three polyethylene Montgolfieres at 4-6 mbar pressure in the Earth's stratosphere and will be deploying a 20-m diameter polyethylene Montgolfiere later in 2001.

Jones, Jack A.↗

Remote Sensing and Geochemistry of Planetary Surfaces

We have been examining the resources required to support potential life on Mars, as a way of understanding the possible abundance and distribution of life. Based on our understanding of the Earth, the necessary requirements for the environment to allow it to support life are (i) presence of liquid water, (ii) access to the biogenic elements (C, H, O, N, S, P, Ca, Fe, etc.), and (iii) a source of energy to drive chemical disequilibrium, such that the reactions back toward equilibrium can release energy to support metabolism. While even demonstrating that all of these requirements have been met would not mean that life would necessarily exist on Mars, they provide the context in which a search for life or analysis of geochemical characteristics that might be indicative of life might be carried out. Our previous work has focused on the first and third of these characteristics determine where and when liquid water might have been present, and understanding the availability of chemical energy from weathering reactions that might ID support life. In the analysis supported by this grant (covering the time period 2/15/01-2/14/02), we have been examining the second requirement--the abundance of the necessary biogenic elements, their geographical distribution on Mars and the information on the possible vertical distribution within the crust, and their geochemical accessibility and mobility within the crust and at the surface. In particular, our work during the performance period has emphasized phosphorous.

Jakosky, Bruce M.↗

Numerical Simulations of the Evolution of the CO2 Atmosphere of Mars: 4.53 Ga to the Present

In this paper we approach four key questions that are central to our understanding of the nature of climate change on Mars: 1. By what mechanism has the evolution of the CO2 atmosphere, dominated at early times by violent process, been guided to the moderate quantities present today? 2.How do obliquity cycles affect the migration of CO2 between the various reservoirs of CO2, and what effect does this have on the bulk atmosphere of the planet in time? 3. Is the geophysical evidence that the last few Myr experienced periods that are substantially wetter than the present attributable to a substantially more massive greenhouse atmosphere? 4. Is the current atmospheric pressure determined primarily by the partial pressure of CO2 in cold (approx. 148 K) ice caps, or is it because disequilibrium water, and hence weathering, ceases at pressures below the triple point of water?

C V Manning↗

The Nakhla Martian Meteorite is a Cumulate Igenous Rock. Comment on "Glass-Bearing Inclusions in Nakhla (SNC Meteorite) Augite: Heterogeneously Trapped Phases"

All the properties of the Nakhla Martian meteorite suggest that it is a cumulate igneous rock, formed from a basaltic parental magma. Anomalous magmatic inclusions in Nakhla s augite grains can be explained by disequilibrium processes during crystal growth, and have little significance in the geological history of the meteorite.

Treiman, A. H.↗