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At least 127 records · Page 7

Petrogenesis of the nakhlite meteorites - Evidence from cumulate mineral zoning

Attention is given to a simple igneous petrogenesis for the meteorite Nakhla, which was previously called into question because Mg/Fe ratios in olivine indicate substantial disequilibrium between the predominant cumulus minerals (olivine and augite). Comparative analyses of simulated diffusive zoning and the observed cumulus mineral zoning for all three nakhlites (Nakhla, Governador Valadares, and Lafayette) show that their current compositions do not necessarily reflect parental magma compositions. Diffusion has altered primary cumulus compositions to varying degrees, Nakhla being the least affected, and Lafayette being almost completely reequilibrated. Since mineral zoning in each meteorite is strongly concentric around mesostasis areas, it is inferred that reaction with intercumulus liquid has controlled the observed zoning. It is argued that the nakhlites appear to be a series of relatively simple cumulate rocks which have undergone various amounts of late-magmatic and subsolidus diffusion, possibly reflecting their relative positions in a cooling cumulate pile.

Harvey, Ralph P.↗

Relationship between wind speed and gas exchange over the ocean

A quadratic dependence of gas exchange on wind speed is employed to analyze the relationship between gas transfer and wind speed with particular emphasizing variable and/or low wind speeds. The quadratic dependence is fit through gas-transfer velocities over the ocean determined by methods based on the natural C-14 disequilibrium and the bomb C-14 inventory. The variation in the CO2 levels is related to these mechanisms, but the results show that other causes play significant roles. A weaker dependence of gas transfer on wind is suggested for steady winds, and long-term averaged winds demonstrate a stronger dependence in the present model. The chemical enhancement of CO2 exchange is also shown to play a role by increasing CO2 fluxes at low wind speeds.

Wanninkhof, Rik↗

Phase transformations in 40-60-GPa shocked gneisses from the Haughton Crater (Canada): An Analytical Transmission Electron Microscopy (ATEM) study

In order to better understand phase transformations, chemical migration, and isotopic disequilibrium in highly shocked rocks, we have performed a microprobe and an ATEM study on gneisses shocked up to 60 GPa from the Haughton Crater. This study reveals the following chemical and structural characteristics: (1) SiO2 dominant areas are formed by a mixture of pure SiO2 polycrystalline quartz identified by electron diffraction pattern and chemical analysis and a silica-rich amorphous phase containing minor amounts of aluminium, potassium, and iron; (2) Areas with biotitelike composition are formed by less than 200-nm grains of iron-rich spinels embedded in a silica-rich amorphous phase that is very similar to the one described above; (3) Layers with feldsparlike composition are constituted by 100-200-nm-sized alumina-rich grains (the indexation of the crystalline structure is under progress) and the silica-rich amorphous phase; (4) Zones characterized by the unusual Al/Si ratio close to 1 are formed by spinel grains (200-nm-sized) embedded in the same silica-rich amorphous phase; and (5) The fracturated sillimanites contain domains with a lamellar structure, defined by the intercalation of 100-nm-wide lamellae of mullite crystals and of a silica-rich amorphous phase. These mullite crystals preserved the crystallographical orientation of the preshock sillimanite. All compositional domains, identified at the microprobe scale, can thus be explained by a mixture in different proportion between the following phases: (1) a silica-rich amorphous phase, with minor Al and K; (2) quartz crystals; (3) spinel crystals and alumina-rich crystals; (4) sillimanite; and (5) mullite. Such mixtures of amorphous phases and crystals in different proportions explain disturbed isotope systems in these rocks and chemical heterogeneities observed on the microprobe.

Martinez, I.↗

Electronystagmography and audio potentials in space flight

Beginning with the fourth flight of the Space Transport System (STS-4), objective measurements of inner ear function were conducted in near-zero G conditions in earth orbit. The problem of space motion sickness (SMS) was approached much like any disequilibrium problem encountered clinically. However, objective testing techniques had built-in limitations superimposed by the strict parameters inherent in each mission. An attempt was made to objectively characterize SMS, and to first ascertain whether the objective measurements indicated that this disorder was of peripheral or central origin. Electronystagmography and auditory brain stem response recordings were the primary investigative tools. One of the authors (W.E.T.) was a mission specialist on board the orbiter Challenger on the eighth shuttle mission (STS-8) and had the opportunity to make direct and personal observations regarding SMS, an opportunity which has added immeasurably to our understanding of this disorder. Except for two abnormal ENG records, which remain to be explained, the remaining ENG records and all the ABR records made in the weightless environment of space were normal.

Thornton, William E.↗

The concentration and isotopic composition of carbon in basaltic glasses from the Juan de Fuca Ridge, Pacific Ocean

The abundance and C-13/C-12 ratios of carbon were analyzed in basaltic glass from twenty locations along the Juan de Fuca Ridge using a 3-step combustion/extraction technique. Carbon released during the first two combustion steps at 400-500 C and 600-650 C is interpreted to be secondary, and only the carbon recovered during a final combustion step at about 1200 C is thought to be indigenous to the samples. For carbon released at about 1200 C, glasses analyzed as 1-2 mm chips contained 23-146 ppm C with delta C-13 values of -4.8 to -9.3 per mil, whereas samples crushed to 38-63 microns or 63-90 microns yielded 56-103 ppm C with delta C-13 values of -6.1 to -9.2 per mil. The concentrations and isotopic compositions of the primary carbon dissolved in the glasses and present in the vesicles are similar to those previously reported for other ocean-ridge basalts. The Juan de Fuca basaltic magmas were not in equilibrium with respect to carbon when they erupted and quenched on the sea floor. Evidence of disequilibrium includes (1) a large range of carbon contents among glasses collected at similar depths, (2) a highly variable calculated carbon isotopic fractionation between melt and vapor determined by comparing crushed and uncrushed splits of the same sample, and (3) a lack of correlation between vesicle abundance, carbon concentration, and depth of eruption. Variations in carbon concentration and delta C-13 ratios along the ridge do not correlate with major element chemistry. The observed relationship between carbon concentrations and delta C-13 values may be explained by late-stage, variable degrees of open-system (Rayleigh-like) degassing.

Blank, Jennifer G.↗

Matrix and fine-grained rims in the unequilibrated CO3 chondrite, ALHA77307 - Origins and evidence for diverse, primitive nebular dust components

SEM, TEM, and electron microprobe analysis were used to investigate in detail the mineralogical and chemical characteristics of dark matrix and fine-grained rims in the unequilibrated CO3 chondrite ALHA77307. Data obtained revealed that there was a remarkable diversity of distinct mineralogical components, which can be identified using their chemical and textural characteristics. The matrix and rim components in ALHA77307 formed by disequilibrium condensation process as fine-grained amorphous dust that is represented by the abundant amorphous component in the matrix. Subsequent thermal processing of this condensate material, in a variety of environments in the nebula, caused partial or complete recrystallization of the fine-grained dust.

Brearley, Adrian J.↗

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.↗