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At least 145 records · Page 8

Heterogeneities in the solar nebula

Oxygen isotopic compositions of the high-temperature phases in carbonaceous chondrites define a mixing line with an 0-16-rich component and show little superimposed chemical isotope fractionation. Within a single inclusion in Allende, variations of delta 0-18 and delta 0-17 of 39 thousands are found. The ordinary chondrites are slightly displaced from the terrestrial fractionation trend, implying that at least 0.2 percent of the oxygen in terrestrial rocks was derived from the 0-16-rich component.

Clayton, R. N.↗

The Apollo 17 drill core - Chemical systematics of grain size fractions

Data for 35 major, minor, and trace elements in 40 bulk and size fractions of core 70005-70003 (140-250 cm) are presented. The core is heterogeneous with depth. Moreover, the 1000 to 90 micron coarse fractions are nearly identical but quite different from the less than 20 micron fine fraction. The bulk soil chemistry is governed by the coarse fractions, because of their greater weight proportion in the sample. The 1000-90 micron fraction contains more ilmenite basalt and less orange glass components than the 90-20 micron fraction. The less than 20 micron fraction is consistently enriched in highland material at all depths in the drill core.

Laul, J. C.↗

Nitrogen isotopic compositions of iron meteorites

Iron meteorites analyzed in this study have nitrogen concentrations 70 microg/g or less and delta N-15 from -90 to +150 percent. Although the iron meteorites have a large range of delta N-15, most have values more negative than -50 percent. The nitrogen isotopic compositions were established by cosmochemical processes and were little modified by fractional crystallization or other chemical processes within the parent bodies. The data do not suggest the existence of a well-mixed solar nebular reservoir for nitrogen, as was already inferred from data from stony meteorites. The range of greater than 1100 percent observed for delta N-15 in bulk meteorites is probably too large to be accounted for by physical and chemical mass-dependent fractionation processes in the solar nebula, and thus reflects nebular inhomogeneities of nucleosynthetic origin.

Prombo, Carol A.↗

Scaling up the Single Transducer Thickness-Independent Ultrasonic Imaging Method for Accurate Characterization of Microstructural Gradients in Monolithic and Composite Tubular Structures

Ultrasonic velocity/time-of-flight imaging that uses back surface reflections to gauge volumetric material quality is highly suited for quantitative characterization of microstructural gradients including those due to pore fraction, density, fiber fraction, and chemical composition variations. However, a weakness of conventional pulse-echo ultrasonic velocity/time-of-flight imaging is that the image shows the effects of thickness as well as microstructural variations unless the part is uniformly thick. This limits this imaging method's usefulness in practical applications. Prior studies have described a pulse-echo time-of-flight-based ultrasonic imaging method that requires using a single transducer in combination with a reflector plate placed behind samples that eliminates the effect of thickness variation in the image. In those studies, this method was successful at isolating ultrasonic variations due to material microstructure in plate-like samples of silicon nitride, metal matrix composite, and polymer matrix composite. In this study, the method is engineered for inspection of more complex-shaped structures-those having (hollow) tubular/curved geometry. The experimental inspection technique and results are described as applied to (1) monolithic mullite ceramic and polymer matrix composite 'proof-of-concept' tubular structures that contain machined patches of various depths and (2) as-manufactured monolithic silicon nitride ceramic and silicon carbide/silicon carbide composite tubular structures that might be used in 'real world' applications.

Roth, Don J.↗

A Novel Ultrasonic Method for Characterizing Microstructural Gradients in Tubular Structures

Ultrasonic velocity and time-of-flight (TOF) imaging that uses back surface reflections to gage volumetric material quality is highly suited for quantitative characterization of microstructural gradients including those due to pore fraction, density, fiber fraction, and chemical composition variations. However, a weakness of conventional pulse echo ultrasonic velocity and TOF imaging is that the image shows the effects of thickness as well as microstructural variations, unless the part is uniformly thick. This limits this imaging method's usefulness in practical applications. Prior studies have described a pulse echo TOF based ultrasonic imaging method that requires using a single transducer in combination with a reflector plate placed behind samples which, eliminates the effect of thickness variation in the image. In those studies, this method was successful at isolating ultrasonic variations due to material in plate like samples of silicon nitride, metal matrix composite, and polymer matrix composite. In this study, the method is engineered for inspection of more complex shaped structures- those having (hollow) tubular or curved geometry. The experimental inspection technique and results are described as applied to a polymer matrix composite "proof of concept" tube that contains machined patches of various depths and an as manufactured monolithic silicon nitride ceramic tube that might be used in "real world" applications.

Roth, Don J.↗

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.↗

An acidic polysaccharide (AGC3) isolated from North American ginseng ( Panax quinquefolius ) suspension culture as a potential immunomodulatory nutraceutical

Polysaccharides isolated from Panax quinquefolius roots are widely used as nutraceuticals due to their immunomodulatory properties. Despite their popularity, several challenges exist in isolating ginseng root polysaccharides such as batch-to-batch structural inconsistencies and bacterial endotoxin contamination. A plant tissue culture-based platform offers a potential solution to isolate natural polysaccharide fractions with consistent chemical characteristics and reduced endotoxin content. In this study, an acidic polysaccharide fraction (AGC3) with immunomodulatory properties was isolated from Panax quinquefolius suspension cultures. The heterogeneous fraction (molecular weight: 4.81 and 32.14 kDa), purified by anion exchange chromatography, was predominantly composed of galactose (>60%) along with the presence of rhamnose, arabinose, glucose, glucuronic acid and galacturonic acid. The major glycosidic linkages were found to be t-Galp (47.7%), 4-Galp (15.6%), 2,4-Rhap (8.1%), 6-Galp (8.1%) and 4-GalAp (6.8%). Structural analyses indicated the presence of a pectic rhamnogalacturonan I polysaccharide in AGC3. AGC3 significantly (p < 0.05) stimulated RAW 264.7 murine macrophage cells and primary murine splenocytes by enhancing the production of several immunomodulatory mediators such as IL-6, TNF-α, GM-CSF and MCP-1. The results also indicated the putative roles of NF-κB (p65/RelA) and MAPK (p38) signaling pathways in the immunostimulatory response. Additionally, AGC3 induced murine splenocyte proliferation, another major indicator of immunostimulation. Overall, AGC3 has the potential to be used as an immunostimulatory nutraceutical.

59 BASIC BIOLOGICAL SCIENCES↗

Impacts of Biopolymer Structural and Chemical Attributes on the Products Distributions of Pyrolyzed Loblolly Pine

This presentation evaluates the impact that biopolymer structural and chemical attributes of pyrolyzed loblolly pine has on product distributions, with a focus on how how the anatomical fractions lead to chemical variability, and then how this variability impacts conversion. As an example, bark and needles represent extreme compositional fractions, and these result in differences in pyrolysis yield.

biomass↗

Cycloalkane-rich sustainable aviation fuel production via hydrotreating lignocellulosic biomass-derived catalytic fast pyrolysis oils

Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.

09 BIOMASS FUELS↗

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.↗