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At least 613 records · Page 34

Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

Schidlowski, M.↗

Determination of solid mass fraction in partially frozen hydrocarbon fuels

Filtration procedures alone are insufficient to determine the amounts of crystalline solid in a partially frozen hydrocarbon distillate fraction. This is due to the nature of the solidification process by which a large amount of liquid becomes entrapped within an interconnected crystalline structure. A technique has been developed to supplement filtration methods with an independent determination of the amount of liquid in the precipitate thereby revealing the actual value of mass percent crystalline solid, %S. A non-crystallizing dye is injected into the fuel and used as a tracer during the filtration. The relative concentrations of the dye in the filtrate and precipitate fractions is subsequently detected by a spectrophotometric comparison. The filtration apparatus was assembled so that the temperature of the sample is recorded immediately above the filter. Also, a second method of calculation has been established which allows significant reduction in test time while retaining acceptable accuracy of results. Data have been obtained for eight different kerosene range hydrocarbon fuels.

Cotterell, E. M.↗

Carbon isotopic fractionation in heterotrophic microbial metabolism

Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

Blair, N.↗

Experimental investigations of trace element fractionation in iron meteorites. III - Elemental partitioning in the system Fe-Ni-S-P

Measurements of solid metal/liquid metal trace element partition coefficients, which are used to interpret the crystallization history of magmatic iron meteorite groups differ greatly between different research groups, using different experimental techniques. Specifically, partition coefficients measured utilizing 'static' experiments which approach equilibrium cannot be reconciled with the results of 'dynamic' experiments which mimic fractional crystallization. We report new tests of our 'static' experimental technique and demonstrate that our methodology yields reliable equilibrium values for Ni, P and Ge partition coefficients. Partition coefficients in the Fe-Ni-S-P system are well matched by interpolation between the Fe-Ni-S and Fe-Ni-P subsystems. In contrast, the predictions of 'dynamic' experiments do not agree with our measurements and, consequently, the ability of 'dynamic' experiments to reproduce iron meteorite Ge vs. Ni fractionation trends successfully must be regarded as fortuitous.

Malvin, D. J.↗

Adsorption and isotopic fractionation of Xe

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

Bernatowicz, T. J.↗

Mass fractionation in hydrodynamic escape

In mass fractionation during the hydrodynamic escape of gases from an inner planet's atmosphere, the readier escape of light gases generates a linear or concave downward line in a plotting of the log of remaining inventory against atomic mass. Just as such an episode of hydrodynamic escape during Mars' early history could have led to the mass-dependent depletion of the noble gases that has been noted in the Martian atmosphere, in the event that the Martian atmosphere was initially hydrogen-rich, an early earth-history episode may have resulted in a mass-dependent fractionation of the xenon isotopes.

Hunten, Donald M.↗

Deuterium fractionation in the presolar nebula - Kinetic limitations on surface catalysis

A quantitative test is presented for the possibility that grain-based catalysis could shorten the equilibration times of low temperature equilibrium fractionation sufficiently to account for the D/H ratio values of the solar system even at nebular temperatures. It is found that under the highly idealized conditions in which the full cosmic abundance of Ni is available for catalysis in pure, 5-micron grains, the equilibration time constant becomes greater than the nebular lifetime at temperatures below 560 K. This lower limit is not, however, sufficiently low to permit strong fractionation.

Grinspoon, David H.↗

Mechanisms and observations for isotope fractionation of molecular species in planetary atmospheres

Chemcial and physical processes which may give rise to isotope fractionation of molecular species in the atmospheres of both earth and other planets are reviewed, along with observations of isotopically substituted molecules in planetary atmospheres. Mechanisms for production of isotope fractionation considered include atmospheric escape and the effect of isotope substitution on equilibrium constants (including those of phase changes), photolysis rates, and chemical reaction rates. The isotopes considered for compounds in the terrestrial atmosphere include D, T, C-13, C-14, N-15, O-18, and S-34. Compounds for which data about isotopic composition in the terrestrial atmosphere are summarized include CO, CO2, O3, N2O, NH3, SO2, H2S, H2O, H, H2, and CH4. Planetary atmospheres discussed include those of Venus, Mars, Jupiter, Saturn, Uranus, and Titan; isotopes reviewed are D, C-13, N-15, and O-18. Suggestions for additional research in the area of isotopically substituted molecules in atmospheres are offered.

Kaye, Jack A.↗

On the origin of Venus' atmosphere - Possible contributions from simple component mixtures and fractionated solar wind

It is suggested that while an origin of the volatiles of the Venus atmosphere as a single, fractionated component derivable from the solar wind can account for Ar, Kr, and Xe relative abundances, it does so only with an excess of C, and perhaps of N. A similarity is noted in relative abundances between Venus volatiles and fractionated solar wind gases in the lunar regolith which implies that such a lunar-type component is a major contributor to Venus' volatiles. A variety of Venus atmosphere models is considered; these fail to explain the low Ne/Ar ratio on Venus.

Bogard, Donald D.↗

Kinetic isotopic fractionation and the origin of HDO and CH3D in the solar system

It is suggested that photochemical enrichment processes driven by stellar UV emissions could result in a large deuterium fractionation of water and methane relative to H2 in the primitive solar nebula. These enrichment processes could have profoundly influenced the isotopic content of water in the terrestrial planets, if a large fraction of their volatiles had been added by impacts of meteorites and comets formed in the outer parts of the solar nebula. Efficient mixing could have exposed the material in the interior of the solar nebula to starlight.

Yung, Yuk L.↗

Noble metals in mid-ocean ridge volcanism: A significant fractionation of gold with respect to platinum group metals

Hydrothermal precipitates, black smoker particulate, and massive sulphide dredge samples from the Explorer Ridge on the Juan de Fuca Plate and the TAG hydrothermal area on the Mid-Atlantic Ridge were analyzed for selected noble metals including Au, Ir and Pd by radiochemical neutron activation analysis. The preliminary results indicate that gold contents may reach the ppm range although values in the neighborhood of 100 to 200 ppb are more typical. The platinum group elements (PGE) represented by Ir and Pd are typically less than 0.02 ppb and less than 2 ppb respectively. These abundances represent a significant enrichment of gold relative to the PGE in comparison with average noble metal abundances in mid-ocean ridge basalts (MORB). A partial explanation of this distinctive fractionation can be found in the concepts of sulfur-saturation of basic magma in mid-ocean ridge (MOR) settings, and the origin of MOR hydrothermal fluids. Experimental and petrological data suggest that MORBs are sulfur-saturated at the time of magma generation and that an immiscible sulfide component remains in the mantle residue. Hence, MORBs are noble metal-poor, particularly with respect to PGE. Consequently, black smoker fluids can be expected to reflect the low Ir and Pd contents of the rock column. The average Au content of MORB is 1.3 ppb, and so the rock column is not significantly enriched in Au. The generation of fluids which precipitate solids with 200 ppb Au is apparently dependent on highly efficient fluid chemistry to mobilize Au from the rock column, high Au solubility in seawater hydrothermal fluids and efficient precipitation mechanisms to coprecipitate Au on Fe, Zn and Cu sulfides. Significant differences in these parameters appear to be the ultimate cause of the strong Au-PGE fractionation in the MOR setting. It does not appear from the current data base that MOR hydrothermal fluids are significant contributors to the Ir enrichment seen in Cretaceous-Tertiary boundary sediments.

Crocket, James H.↗

Apollo 14 mare basalt petrogenesis - Assimilation of KREEP-like components by a fractionating magma

Based on analysis of whole rock and mineral data from 22 samples, it is shown that the trace element characteristics of 14321 high-AL mare basalts exhibit variations that cannot be related to short-range mixing alone. It is suggested that the five groups defined for Apollo 14 high-Al basalts are due to sampling. It is found that the addition of new data results in a continuum of compositions. Detailed trace element modeling demonstrates that a primitive parental magma evolves by assimilation and fractional crystallization (AFC) with KREEP. The ratio of mass assimilated to mass crystallized is found to be 0.22. It is suggested that this AFC process occurs within the lunar crust and that the fractionating phases are effectively removed from the system.

Neal, Clive R.↗

Windward fraction of the total mass or heat transport for flow past a circular cylinder

The windward fraction of the total mass or heat transport for flow past a cylindrical aerodynamic object was estimated using the available experimental data for the angular distribution of the Nusselt transfer coefficient, Nu(theta, Re). The Re dependence of the windward surface fraction was calculated for the values of Re between 2 and 400,000. The results obtained from polar integrations of data from eight sources indicate that, for Reynolds numbers up to about 2000, more than 70 percent of the total transfer occurs on the windward surface. For the Re values above 100,000, the windward percentage is less than 50 percent.

Gokoglu, S.↗

Siderophile element fractionation

The cosmic volatility of the siderophile elements appears to have played an important role in the determination of their chondritic-material abundances, and has led to minor but significant fractionations: (1) the formation and fractionation of a component bearing elements more refractory than Fe, Ni, or Co; (2) the formation of a common FeNiCo component that separated from the common silicates; and (3) the depletion of moderately volatile elements by factors of as much as 5, where abundance decreased with increasing volatility. A refractory siderophile component is noted to be required in order to account for bulk siderophile trends among closely related chondrite groups.

Larimer, John W.↗

Quantum disorder, duality, and fractional statistics in 2 + 1 dimensions

A low-energy equivalence between two apparently unrelated Lagrangians with fractional statistics is reported. Exploiting this equivalence, it is possible to study the quantum disordered phase of the nonlinear sigma model with Hopf term. It is found that the quasi-particles in the disordered phase also have fractional statistics. There appears to be a dual relationship between the ordered and disordered phases.

Wen, X. G.↗

Review and statistical analysis of the ultrasonic velocity method for estimating the porosity fraction in polycrystalline materials

A review and statistical analysis of the ultrasonic velocity method for estimating the porosity fraction in polycrystalline materials is presented. Initially, a semi-empirical model is developed showing the origin of the linear relationship between ultrasonic velocity and porosity fraction. Then, from a compilation of data produced by many researchers, scatter plots of velocity versus percent porosity data are shown for Al2O3, MgO, porcelain-based ceramics, PZT, SiC, Si3N4, steel, tungsten, UO2,(U0.30Pu0.70)C, and YBa2Cu3O(7-x). Linear regression analysis produced predicted slope, intercept, correlation coefficient, level of significance, and confidence interval statistics for the data. Velocity values predicted from regression analysis for fully-dense materials are in good agreement with those calculated from elastic properties.

Roth, D. J.↗

An eight-month climatology of marine stratocumulus cloud fraction, albedo, and integrated liquid water

As part of the FIRE/Extended Time Observations (ETO) program, extended time observations were made at San Nicolas Island (SNI) from March to October, 1987. Hourly averages of air temperature, relative humidity, wind speed and direction, solar irradiance, and downward longwave irradiance were recorded. The radiation sensors were standard Eppley pyranometers (shortwave) and pyrgeometers (longwave). The SNI data were processed in several ways to deduce properties of the stratocumulus covered marine boundary layer (MBL). For example, from the temperature and humidity the lifting condensation level, which is an estimate of the height of the cloud bottom, can be computed. A combination of longwave irradiance statistics can be used to estimate fractional cloud cover. An analysis technique used to estimate the integrated cloud liquid water content (W) and the cloud albedo from the measured solar irradiance is also described. In this approach, the cloud transmittance is computed by dividing the irradiance measured at some time by a clear sky value obtained at the same hour on a cloudless day. From the transmittance and the zenith angle, values of cloud albedo and W are computed using the radiative transfer parameterizations of Stephens (1978). These analysis algorithms were evaluated with 17 days of simultaneous and colocated mm-wave (20.6 and 31.65 GHz) radiometer measurements of W and lidar ceilometer measurements of cloud fraction and cloudbase height made during the FIRE IFO. The algorithms are then applied to the entire data set to produce a climatology of these cloud properties for the eight month period.

Fairall, C. W.↗

Injectant mole fraction measurements of transverse injection in constant area supersonic ducts

Planar measurements of the injectant mole fraction distribution in a nonreacting model SCRAMJET combustor have been made using a nonintrusive optical technique, laser-induced iodine fluorescence. The combustor geometry investigated in this work was staged, transverse sonic injection of air into Mach 2 and Mach 2.9 freestreams. Accurate three-dimensional surveys of the injectant mole fraction distribution for both freestream Mach numbers have been generated. These experimental measurements provide valuable insight into the fluid mechanics of the mixing process. The existence of streamwise vortices is shown to dominate the mixing in the injector nearfield while shock wave interactions with the injectant plume are seen to significantly enhance mixing downstream of the injectors. The effect of combustor Mach number on injectant mixing is found to be small for this geometry. These measurements provide an accurate data set for the validation of computational fluid dynamics codes being developed for the calculation of highly three-dimensional nonreacting supersonic combustor flow fields.

Hollo, Steven D.↗