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At least 127 records · Page 7

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

Non-NASA Center↗

Submicrometer Organic Grains: Widespread Constituents of the Early Solar System

Primitive meteorites and interplanetary dust particles (IDPs) contain remants of interstellar organic matter, marked by anomalous H and N isotopic ratios. These isotopic anomalies are attributed to mass fractionation during chemical reactions at cryogenic temperatures (10-100K) in a cold molecular cloud. Significant variations in the chemistry and isotopic compositions of organic compounds within and between these samples suggest varying histories of alteration and dilution of the presolar components. Recent studies have reported large H and N isotopic anomalies preserved in sub-m organic inclusions in both meteorites and IDPs. In the Tagish Lake meteorite, the largest H and N isotopic anomalies are associated with sub-m, hollow organic globules. The common physical, chemical, and isotopic characteristics of these globules suggest that they formed before being incorporated into their parent meteorite. These organic globules probably originated as organic ice coatings that formed on preexisting ice or mineral grains in a cold molecular cloud. Radiation driven photochemistry may have processed them into refractory organic grains. This model implies that submicrometer organic grains were widely distributed throughout the solar nebula during the epoch of planet formation. Submicrometer organic particles were detected by the Giotto and Vega encounters with comet Halley, termed CHON particles based on their major element chemistry. The first direct samples of cometary dust (comet Wild-2) were returned by the Stardust spacecraft in January 2006. These samples exhibit widely varying, fine grained mineralogy similar to anhydrous IDPs, including submicrometer carbonaceous grains. The submicrometer organic grains from comet Wild-2 exhibit H and N isotopic anomalies of similar magnitude to those commonly observed in primitive meteorites and IDPs. Isotopically anomalous, submicrometer organic grains have now been observed in meteorites, IDPs, the Oort-cloud comet Halley, and the Kuiper-belt comet Wild-2, suggesting that such grains were prevalent throughout the protoplanetary disk.

Messenger, Scott↗

Impact glasses from the less than 20-micrometer fraction of Apollo 17 soils 72501 and 78221

The chemical compositions of microscopic glasses produced during meteoroid impacts on the lunar surface provide information regarding the various fractionation processes that accompany these events. To learn more about these fractionation processes, we studied the compositions of submicrometer glass spheres from two Apollo 17 sampling sites using electron microscopy. The majority of the analyzed glasses show evidence for varying degrees of impact-induced chemical fractionation. Among these are HASP glasses (high-Al, Si-poor), which are believed to represent the refractory residuum left after the loss of volatile elements (e.g., Si, Fe, Na) from the precursor material. In addition to HASP-type glasses, we also observed a group of volatile-rich, Al-poor (VRAP) glasses that represent condensates of vaporized volatile constituents, and are complementary to the HASP compositions. High-Ti glasses were also found during the course of this study, and are documented here for the first time.

Norris, John A.↗

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.↗

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

Montgomery, Christopher J.↗

A chemical model for generating the sources of mare basalts - Combined equilibrium and fractional crystallization of the lunar magmasphere

A chemical model for simulating the sources of the lunar mare basalts was developed by considering a modified mafic cumulate source formed during the combined equilibrium and fractional crystallization of a lunar magma ocean (LMO). The parameters which influence the initial LMO and its subsequent crystallization are examined, and both trace and major elements are modeled. It is shown that major elements tightly constrain the composition of mare basalt sources and the pathways to their creation. The ability of this LMO model to generate viable mare basalt source regions was tested through a case study involving the high-Ti basalts.

Snyder, Gregory A.↗

Chemistry of Apollo 12 mare basalts - Magma types and fractionation processes

Major and trace element data for a large suite of petrographically diverse Apollo 12 mare basalts are presented, and magma types sampled at the Apollo 12 site are characterized. The data confirm earlier classifications of the basalts into olivine, pigeonite, ilmenite, and feldspathic basalts. The olivine and pigeonite basalts are shown to be comagnetic and related by olivine fractionation. The other types, which differ in trace element and isotopic characteristics, are derived from different sources within the lunar interior. The spatial relations between the main basalt types are discussed in terms of local cratering events, and it is suggested that the younger ilmenite basalts overlie the olivine-pigeonite basalts. The role of olivine-dominated near-surface crystal fractionation in causing chemical variation is examined, and a relation between inferred cooling rate and the position of a sample in the fractionation sequence is determined.

Rhodes, J. M.↗

Oxygen, Magnesium, and Aluminum Isotopes in the Ivuna CAI: Re-Examining High-Temperature Fractionations in CI Chondrites

CI chondrites are thought to approximate the bulk solar system composition since they closely match the composition of the solar photosphere. Thus, chemical differences between a planetary object and the CI composition are interpreted to result from fractionations of a CI starting composition. This interpretation is often made despite the secondary mineralogy of CI chondrites, which resulted from low-T aqueous alteration on the parent asteroid(s). Prevalent alteration and the relatively large uncertainties in the photospheric abundances (approx. +/-5-10%) permit chemical fractionation of CI chondrites from the bulk solar system, if primary chondrules and/or CAIs have been altered beyond recognition. Isolated olivine and pyroxene grains that range from approx. 5 microns to several hundred microns have been reported in CI chondrites, and acid residues of Orgueil were found to contain refractory oxides with oxygen isotopic compositions matching CAIs. However, the only CAI found to be unambiguously preserved in a CI chondrite was identified in Ivuna. The Ivuna CAI's primary mineralogy, small size (approx.170 microns), and fine-grained igneous texture classify it as a compact type A. Aqueous alteration infiltrated large portions of the CAI, but other regions remain pristine. The major primary phases are melilite (Ak 14-36 ), grossmanite (up to 20.8 wt.% TiO 2 ), and spinel. Both melilite and grossmanite have igneous textures and zoning patterns. An accretionary rim consists primarily of olivine (Fa 2-17 ) and low-Ca pyroxene (Fs 2-10 ), which could be either surviving CI2 material or a third lithology.

Frank, D. R.↗

Distribution and geochemistry of aerosols in the tropical North Atlantic troposphere - Relationship to Saharan dust

Estimates of global aerosol production suggest that mobilization of natural eolian material greatly exceeds anthropogenic-related emissions, and it appears that soil material transported from arid regions by wind might be mainly responsible for the distribution of certain clay materials in oceanic sediments. In connection with studies related to an investigation of these possibilities, the present paper provides a discussion of the aerosol spatial distribution and its water-soluble chemical composition in the tropical North Atlantic troposphere during the ABLE-Barbados mission. Particular attention is given to the composition of the water-soluble fraction, since its chemical reactivity is important with respect to various atmospheric and biogeochemical processes. On the basis of the obtained results, it is suggested that Saharan dust has also a significant impact on the aerosol chemistry over the tropical North Atlantic.

Talbot, R. W.↗

Drive tube 60009 - A chemical study of magnetic separates of size fractions from five strata

Each bulk soil and both the magnetic and nonmagnetic components of the 90-150 micron and below 20 micron fractions of five soils from drive tube 60009 were analyzed. Samples were analyzed for FeO, Na2O, Sc, Cr, Co, Ni, Hf, Ta, Th, La, Ce, Sm, Eu, Tb, Yb, and Lu by neutron activation analysis. Several samples were fused and analyzed for major elements by electron microprobe analysis. Compositional variations are not systematically related to depth. The compositions of the five soils studied are well explained by a two-component mixing model whose end members are a submature Apollo 16-type soil and an extremely immature anorthositic material similar to 60025. There is evidence that the anorthositic component had received a small amount of exposure before these soils were mixed. After mixing, the soils received little exposure suggesting mixing and deposition on a rapid time scale.

Blanchard, D. P.↗

Energy Requirements of Hydrogen-Utilizing Microbes: Boundary Condition for Subsurface Life

For planetary bodies with surface conditions that are too harsh to permit continuous occupation by life, the deep subsurface offers a potentially stable and habitable niche. For organisms occupying this niche, the spectrum of possible metabolisms must be limited to those which do not include sunlight as an energy source or oxygen as a chemical reagent - generally, low-energy anaerobic oxidation-reduction processes. The quantity of energy released in such processes is critical, because currently understood mechanisms of biological energy conservation indicate that energy is only 'useful' to an organism when it is available at a certain minimum level - the 'biological energy quantum'. The mere existence of a BEQ implies that a significant fraction of the chemical energy present in the environment cannot be exploited by life; similarly, the absolute magnitude of the BEQ must be a key variable in determining the potential viability and distribution of subsurface microbial communities. Laboratory culture studies suggest that organisms require an energy of about -20 kJ/mol to grow. However, we find that hydrogen-utilizing microorganisms in an energy-limited natural ecosystem are active with energy yields as low as -10 kJ/mol. A lower BEQ would mean a significantly expanded range of energetically viable subsurface habitat for life.

Hoehler, Tori M.↗

Origin of plagioclase-olivine inclusions in carbonaceous chondrites

The origin of plagioclase-olivine inclusions (POIs) from three CV chondrites and one ungrouped chondrite was investigated by examining the chemical, mineralogical, and isotopic characteristics of a group of POIs from these chondrites. Results of these analyses demonstrate that the mixing and the partial melting processes in these inclusions were superimposed on more ancient isotopically heterogeneous material. A comparison of the essential characteristics of POIs and CAIs suggests that the major processes leading to the formation of POIs (such as condensation, dust/gas fractionation, aggregation of chemically and isotopically disparate materials, and partial melting) are common to most CAIs and chondrules. A scenario for the origin of POIs is proposed, showing that the homogeneity of the final assemblage (whether a POI, a CAI, or a chondrite) is primarily a reflection of the thermal history rather than the nature of precursor materials.

Sheng, Y. J.↗

Analysis of turbulent free-jet hydrogen-air diffusion flames with finite chemical reaction rates

A numerical analysis is presented of the nonequilibrium flow field resulting from the turbulent mixing and combustion of an axisymmetric hydrogen jet in a supersonic parallel ambient air stream. The effective turbulent transport properties are determined by means of a two-equation model of turbulence. The finite-rate chemistry model considers eight elementary reactions among six chemical species: H, O, H2O, OH, O2 and H2. The governing set of nonlinear partial differential equations was solved by using an implicit finite-difference procedure. Radial distributions were obtained at two downstream locations for some important variables affecting the flow development, such as the turbulent kinetic energy and its dissipation rate. The results show that these variables attain their peak values on the axis of symmetry. The computed distribution of velocity, temperature, and mass fractions of the chemical species gives a complete description of the flow field. The numerical predictions were compared with two sets of experimental data. Good qualitative agreement was obtained.

Sislian, J. P.↗

Predicting the Influence of Nano-Scale Material Structure on the In-Plane Buckling of Orthotropic Plates

A multi-scale analysis of the structural stability of a carbon nanotube-polymer composite material is developed. The influence of intrinsic molecular structure, such as nanotube length, volume fraction, orientation and chemical functionalization, is investigated by assessing the relative change in critical, in-plane buckling loads. The analysis method relies on elastic properties predicted using the hierarchical, constitutive equations developed from the equivalent-continuum modeling technique applied to the buckling analysis of an orthotropic plate. The results indicate that for the specific composite materials considered in this study, a composite with randomly orientated carbon nanotubes consistently provides the highest values of critical buckling load and that for low volume fraction composites, the non-functionalized nanotube material provides an increase in critical buckling stability with respect to the functionalized system.

Gates, Thomas S.↗

The relationship of the lunar regolith less than 10 micrometer fraction and agglutinates. I - A model for agglutinate formation and some indirect supportive evidence

The first part of a study of the 'less than 10 micrometer' soil fraction and agglutinates is concerned with the chemical systematics of the considered fraction of lunar soils, taking into account a model for agglutinate formation based on the fusion of the finest fraction (FFF). Attention is given to some evidence which supports the FFF model. The evidence is based on some indirect approaches to an estimation of the composition of the fused soil component. It is found that the 'less than 10 micrometer' soil fraction from all Apollo sites except Apollo 16 (which can be explained) is more feldspathic and enriched in incompatible elements (e.g., K and Th) than the bulk soil. It is concluded that these systematics result from simple comminution in which feldspar breaks down to finer sizes than pyroxene and olivine and the fine-grained incompatible-element-enriched mesostasis concentrates in the 'less than 10 micrometer' soil fraction.

Papike, J. J.↗

The origin of the Moon

The fractionation of the chemical compositions of the moon and the earth and the thermal history of the moon for formation of the moon from an earth-orbiting swarm of bodies during the accumulation of the earth are discussed.

Ruskol, Y. L.↗

Isotopic anomalies of noble gases in meteorites and their origins. VI Presolar components in the Murchison C2 chondrite

Rare gases were analyzed by stepped heating in five fractions of a chemically resistant residue from Murchison that had been separated according to grain size and resistance to HClO4. Nine gas components were recognized, of which three appear to be presolar: (1) Ne-E(H) released at 1000-1600 C and located in spinel; (2) Ne-E(L) released at less than 800 C and apparently located in a carbonaceous phase of grain size up to 10 microns; and (3) s-process Xe and Kr released at 1200-1600 C and located in a poorly characterized, possibly carbonaceous phase, distinct from the host phase of Ne-E(L).

Alaerts, L.↗