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NASA NTRS1975

Mare basalts - Melting experiments and petrogenetic interpretations

Equilibrium crystallization sequences are determined in melting experiments in vacuum at Fe saturation on synthetic mare basalt compositions 70215 and 15318 Red Glass (both high-Ti) as well as 15555-15016 (low-Ti). The experiments confirm that much of the chemical variation within both the high- and low-Ti suites is controlled by near-surface fractionation processes, although the two suites cannot be related by such mechanisms. The components and crystallization products of the liquidus at various temperatures and pressures are reported. Mare basalt petrogenesis is interpreted in terms of high-pressure equilibria at Fe saturation; it is suggested that low-Ti basalts represent partial melts of a differentiated olivine-pyroxenite lunar mantle at 240 km or deeper, while cumulus clinopyroxene in the source is responsible for their REE characteristics. The formation of high-Ti basalts is considered.

Kesson, S. E.↗
NASA NTRS1975

Differentiation of a very thick magma body and implications for the source regions of mare basalts

Mass-balance calculations indicate that the molten layer originally covering the moon may have been several hundred kilometers deep. The solidification of this magma ocean involved some unusual effects resulting from the large-pressure differential in the thick magma layer. The sunken cumulates from this differentiation would be more iron-rich, less refractory, and would contain more incompatible elements than would be expected in simple isobaric fractional crystallization and crystal sinking models of magma differentiation. These lower cumulates can have the mineralogical and chemical properties of the source regions of the low-Ti mare basalts.

Walker, D.↗
NASA NTRS1991

Abundance and chemistry of interstellar HOCO(+)

Column densities of 10 to the 15th/sq cm toward the Galactic center and not more than 10 to the 12th/sq cm for cold dark clouds are derived from observations using an LVG model, and the chemical implications are discussed. The HOCO(+) 4(04)-3(03) line toward Sgr A is mapped. The fractional abundance of HOCO(+) in the Galactic center region was found to be three orders of magnitude larger than predicted by quiescent ion-molecule chemistry and an order of magnitude larger than predicted by an MHD shock model. It is suggested that the possibly high CO2 abundance, and consequently the observed HOCO(+) abundance in the Galactic center, may result from UV photolysis of grain mantles.

Minh, Y. C.↗
NASA NTRS2003

Model of Fluidized Bed Containing Reacting Solids and Gases

A mathematical model has been developed for describing the thermofluid dynamics of a dense, chemically reacting mixture of solid particles and gases. As used here, "dense" signifies having a large volume fraction of particles, as for example in a bubbling fluidized bed. The model is intended especially for application to fluidized beds that contain mixtures of carrier gases, biomass undergoing pyrolysis, and sand. So far, the design of fluidized beds and other gas/solid industrial processing equipment has been based on empirical correlations derived from laboratory- and pilot-scale units. The present mathematical model is a product of continuing efforts to develop a computational capability for optimizing the designs of fluidized beds and related equipment on the basis of first principles. Such a capability could eliminate the need for expensive, time-consuming predesign testing.

Bellan, Josette↗
NASA NTRS1994

Numerical Simulations of High-Speed Chemically Reacting Flow

The Essentially NonOscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Ton, V. T.↗
NASA NTRS1994

Numerical Simulations of High-Speed Chemically Reacting Flow

The essentially nonoscillatory (ENO) shock-capturing scheme for the solution of hyperbolic equations is extended to solve a system of coupled conservation equations governing two-dimensional, time-dependent, compressible chemically reacting flow with full chemistry. The thermodynamic properties of the mixture are modeled accurately, and stiff kinetic terms are separated from the fluid motion by a fractional step algorithm. The methodology is used to study the concept of shock-induced mixing and combustion, a process by which the interaction of a shock wave with a jet of low-density hydrogen fuel enhances mixing through streamwise vorticity generation. Test cases with and without chemical reaction are explored here. Our results indicate that, in the temperature range examined, vorticity generation as well as the distribution of atomic species do not change significantly with the introduction of a chemical reaction and subsequent heat release. The actual diffusion of hydrogen is also relatively unaffected by the reaction process. This suggests that the fluid mechanics of this problem may be successfully decoupled from the combustion processes, and that computation of the mixing problem (without combustion chemistry) can elucidate much of the important physical features of the flow.

Ton, V. T.↗
NASA NTRS2005

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

Until recently, the stable isotopic composition of chemically and datively important stratospheric species, such as ozone (O3), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4), was largely unexplored, despite indications from the few measurements available and theoretical studies that global-scale isotopic variations will provide a unique tool for quantifying rates of global-scale mass transport into, within, and out of the stratosphere and for understanding the mechanisms of chemical reactions involved in ozone production. The number and geographical extent of observations are beginning to increase rapidly, however, as access to the stratosphere, both directly and by remote-sensing, has increased over the last 10 years and as new analytical techniques have been developed that make global-scale isotope measurements by whole-air sampling more feasible. The objective of this study, begun in April 1999, is to incorporate into the Livermore 2D model the likely photochemical fractionation processes that determine the isotopic compositions of stratospheric CO2, N2O, CH4, and O3, and to use the model results and new observations from NASA field campaigns in 1996 and 1997 to investigate stratospheric chemistry and mass transport. Additionally, since isotopic signatures from the stratosphere are transferred to the troposphere by downward transport at middle and high latitudes, the isotopic compositions may also serve as sensitive tracers of stratosphere-totroposphere transport. Comparisons of model results with stratospheric and upper tropospheric observations from these campaigns, as well as with ground-based observations from new NOAA and NSF-sponsored studies, will help determine whether the magnitudes of the stratospheric fractionation processes are large enough to use as global-scale tracers of transport into the troposphere and, if so, will be used to help constrain the degree of coupling between the troposphere and the stratosphere.

Boering, Kristie A.↗
NASA NTRS1996

Lipid biomarkers for bacterial ecosystems: studies of cultured organisms, hydrothermal environments and ancient sediments

This paper forms part of our long-term goal of using molecular structure and carbon isotopic signals preserved as hydrocarbons in ancient sediments to improve understanding of the early evolution of Earth's surface environment. We are particularly concerned with biomarkers which are informative about aerobiosis. Here, we combine bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems to construct models for the nature, behaviour and preservation potential of primitive microbial communities. We use a combined molecular and isotopic approach to characterize lipids produced by cultured bacteria and test a variety of culture conditions which affect their biosynthesis. This information is then compared with lipid mixtures isolated from contemporary hot springs and evaluated for the kinds of chemical change that would accompany burial and incorporation into the sedimentary record. In this study we have shown that growth temperature does not appear to alter isotopic fractionation within the lipid classes produced by a methanotropic bacterium. We also found that cultured cyanobacteria biosynthesize diagnostic methylalkanes and dimethylalkanes with the latter only made when growing under low pCO2. In an examination of a microbial mat sample from Octopus Spring, Yellowstone National Park (USA), we could readily identify chemical structures with 13C contents which were diagnostic for the phototrophic organisms such as cyanobacteria and Chloroflexus. We could not, however, find molecular evidence for operation of a methane cycle in the particular mat samples we studied.

NASA Discipline Exobiology↗
NASA NTRS2010

Experimental Investigation of Space Radiation Processing in Lunar Soil Ilmenite: Combining Perspectives from Surface Science and Transmission Electron Microscopy

Energetic ions mostly from the solar wind play a major role in lunar space weathering because they contribute structural and chemical changes to the space-exposed surfaces of lunar regolith grains. In mature mare soils, ilmenite (FeTiO3) grains in the finest size fraction have been shown in transmission electron microscope (TEM) studies to exhibit key differences in their response to space radiation processing relative to silicates [1,2,3]. In ilmenite, solar ion radiation alters host grain outer margins to produce 10-100 nm thick layers that are microstructurally complex, but dominantly crystalline compared to the amorphous radiation-processed rims on silicates [1,2,3]. Spatially well-resolved analytical TEM measurements also show nm-scale compositional and chemical state changes in these layers [1,3]. These include shifts in Fe/Ti ratio from strong surface Fe-enrichment (Fe/Ti >> 1), to Fe depletion (Fe/Ti < 1) at 40-50 nm below the grain surface [1,3]. These compositional changes are not observed in the radiation-processed rims on silicates [4]. Several mechanism(s) to explain the overall relations in the ilmenite grain rims by radiation processing and/or additional space weathering processes were proposed by [1], and remain under current consideration [3]. A key issue has concerned the ability of ion radiation processing alone to produce some of the deeper- penetrating compositional changes. In order to provide some experimental constraints on these questions, we have performed a combined X-ray photoelectron spectroscopy (XPS) and field-emission scanning transmission electron (FE-STEM) study of experimentally ion-irradiated ilmenite. A key feature of this work is the combination of analytical techniques sensitive to changes in the irradiated samples at depth scales going from the immediate surface (approx.5 nm; XPS), to deeper in the grain interior (5-100 nm; FE-STEM).

Christoffersen, R.↗
NASA NTRS1988

Small scale structure and mixing at the edge of the Antarctic vortex

Small scale correlations and patterns in the chemical tracers measured from the NASA ER-2 aircraft in the 1987 AAOE campaign can be used to investigate the structure of the edge of the polar vortex and the chemically perturbed region within it. Examples of several types of transport processes can be found in the data. Since ClO and O3 have similar vertical gradients and opposite horizontal gradients near the chemically perturbed region, the correlation between ClO and O3 can be used to study the extent of horizontal transport at the edge of the chemically perturbed region. Horizontal transport dominates the correlation for a latitude band up to 4 degrees on each side of the boundary. This implies a transition zone containing a substantial fraction of the mass of the total polar vortex. Similar horizontal transport can be seen in other tracers as well. It has not been possible to distinguish reversible transport from irreversible mixing. One manifestation of the horizontal transport is that the edge of the chemically perturbed region is often layered rather than a vertical curtain. This can be seen from the frequent reversed vertical gradients of NO2, caused by air with high NO2 overlapping layers with lower mixing ratios. Water and NO2 are positively correlated within the chemically perturbed region. This is the opposite sign to the correlation in the unperturbed stratosphere. The extent of the positive correlation is too great to be attributed solely to horizontal mixing. Instead, it is hypothesized that dehydration and descent are closely connected on a small scale, possibly due to radiative cooling of the clouds that also cause ice to fall to lower altitudes.

Murphy, D. M.↗
NASA NTRS1979

Comets: Cosmic connections with carbonaceous meteorites, interstellar molecules and the origin of life

The ions, radicals, and molecules observed in comets may be derived intact or by partial decomposition from parent compounds of the sort found either in the interstellar medium or in carbonaceous meteorites. The early loss of highly reducing primitive atmosphere and its replacement by a secondary atmosphere dominated by H2O, CO2, and N2, as depicted in current models of the earth's evolution, pose a dilemma for the origin of life: the synthesis of organic compounds necessary for life from components of the secondary atmosphere appears to be difficult, and plausible mechanisms have not been evaluated. Both comets and carbonaceous meteorites are implicated as sources for the earth's atmophilic and organogenic elements. A mass balance argument involving the estimated ratios of hydrogen to carbon in carbonaceous meteorites, comets, and the crust and upper mantle suggests that comets supplied the earth with a large fraction of its volatiles. The probability that comets contributed significantly to the earth's volatile inventory suggests a chemical evolutionary link between comets, prebiotic organic synthesis, and the origin of life.

Chang, S.↗
NASA NTRS1988

Chemical dispersion among Apollo 15 olivine-normative mare basalts

Analysis of Apollo 15 olivine-normative mare basalts for major and minor elements suggests that the hypothesis that the coarser-grained varieties (olivine microgabbros) consist of two chemical groups is incorrect. Instead, it is found that there is a single group including vesicular, coarse-grained, and fine-grained basalts. For the entire suite, the dispersion of compositions along the olivine trend is too great to be explained by short-range unmixing of an unfractionated flow. It is suggested that the general trend for the suite is olivine separation, probably through crystal settling. The textures, mineralogical characteristics, and chemical variation of the olivine-normative basalts are shown to be consistent with a sequence of thin fractionating flows, all from a common parent.

Ryder, Graham↗
NASA NTRS1997

Calibration of the QCM/SAW Cascade Impactor for Measurement of Ozone in the Stratosphere

The Quartz Crystal Microbalance Surface Acoustic Wave (QCM/SAW) cascade impactor collects size-fractionated distributions of aerosols on a series of 10 MHz quartz crystals and employs SAW devices coated with chemical sensors for gas detection. Presently, we are calibrating the ER-2 certified QCM/SAW cascade impactor in the laboratory for the detection of ozone. Experiments have been performed to characterize the QCM and SAW mass loading, saturation limits, mass frequency relationships, and sensitivity. We are also characterizing sampling efficiency by measuring the loss of ozone on different materials. There are parallel experiments underway to measure the variations in the sensitivity and response of the QCM/SAW crystals as a function of temperature and pressure. Results of the work to date will be shown.

Wright, Cassandra K.↗
NASA NTRS2008

The LHT (Lunar Highlands Type) Regolith Simulant Series

Three NU-LHT (NASA/USGS-Lunar Highlands Type) regolith simulants have been produced to date: NU-LHT-1M, -ID, and -2M. A fourth simulant is currently in production: NU-LHT-3C. The "M" (medium) designation indicates a simulant with a grain size of <1 mm, "D" (dust) a simulant with a grain size of <36 microns, and "C" (coarse) a simulant with a 10 cm maximum particle size. The composition of these simulants is based on a NASA average Apollo 16 regolith chemical composition, However, the mixing model used to create our simulants is based on cationic nonnative mineral proportions derived from the target chemical composition to approximate lunar modal mineralogy rather than chemical composition per se. Accordingly, the amount of plagioclase, pyroxenes, olivine, and trace minerals in the simulant crystalline fraction approximates that of the lunar regolith. We also added synthetic agglutinate in amounts approximate for low-medium regolith maturity. A pure glass fraction was also added to simulate other types of lunar glasses present in the regolith. In addition, the 3C simulant will include synthetic impact melt breccia clasts for the >1 cm particles. The bulk raw materials used to create these simulants include clinopyroxene-norite, anorthosite, hartzburgite and noritic mill waste from the Stillwater Mine, Nye, MT, and olivine from the Twin Sisters dunite, WA. Added trace minerals include beach sand ilmenite, chromite, synthetic p-tricaicium phosphate (whitiockite), gem grade fluor-apatite, and pyrite. The agglutinate, glasses, and synthetic breccia were designed and prepared at an industrial plasma melting facility in Boulder, CO, using Stillwater mill waste feedstock for the melt. These simulants do not include nanophase-feO. The M and C simulant grain size distribution (down to 0.4 microns) approximates that of Apollo 16 regolith and the regolith in general.

Stoeser, Douglas↗
NASA NTRS2012

Isotopic Ratios in Titan's Methane: Measurements and Modeling

The existence of methane in Titan's atmosphere (approx. 6% level at the surface) presents a unique enigma, as photochemical models predict that the current inventory will be entirely depleted by photochemistry in a timescale of approx 20 Myr. In this paper, we examine the clues available from isotopic ratios (C-12/C-13 and D/H) in Titan's methane as to the past atmosphere history of this species. We first analyze recent infrared spectra of CH4 collected by the Cassini Composite Infrared Spectrometer, measuring simultaneously for the first time the abundances of all three detected minor isotopologues: (13)CH4, (12)CH3D, and (13)CH3D. From these we compute estimates of C-12/C-13 = 86.5 +/- 8.2 and D/H = (1.59 +/- 0.33) x 10(exp -4) , in agreement with recent results from the Huygens GCMS and Cassini INMS instruments. We also use the transition state theory to estimate the fractionation that occurs in carbon and hydrogen during a critical reaction that plays a key role in the chemical depletion of Titan's methane: CH4 + C2H yields CH3 + C2H2. Using these new measurements and predictions we proceed to model the time evolution of C-12/C-13 and D/H in Titan's methane under several prototypical replenishment scenarios. In our Model 1 (no resupply of CH4), we find that the present-day C-12/C-13 implies that the CH4 entered the atmosphere 60-1600 Myr ago if methane is depleted by chemistry and photolysis alone, but much more recently-most likely less than 10 Myr ago-if hydrodynamic escape is also occurring. On the other hand, if methane has been continuously supplied at the replenishment rate then the isotopic ratios provide no constraints, and likewise for the case where atmospheric methane is increasing, We conclude by discussing how these findings may be combined with other evidence to constrain the overall history of the atmospheric methane.

Nixon, C. A.↗
NASA NTRS2014

Tracking the Martian Mantle Signature in Olivine-Hosted Melt Inclusions of Basaltic Shergottites Yamato 980459 and Tissint

The Martian shergottite meteorites are basaltic to lherzolitic igneous rocks that represent a period of relatively young mantle melting and volcanism, approximately 600-150 Ma (e.g. [1,2]). Their isotopic and elemental composition has provided important constraints on the accretion, evolution, structure and bulk composition of Mars. Measurements of the radiogenic isotope and trace element concentrations of the shergottite meteorite suite have identified two end-members; (1) incompatible trace element enriched, with radiogenic Sr and negative epsilon Nd-143, and (2) incompatible traceelement depleted, with non-radiogenic Sr and positive epsilon 143-Nd(e.g. [3-5]). The depleted component represents the shergottite martian mantle. The identity of the enriched component is subject to debate, and has been proposed to be either assimilated ancient martian crust [3] or from enriched domains in the martian mantle that may represent a late-stage magma ocean crystallization residue [4,5]. Olivine-phyric shergottites typically have the highest Mg# of the shergottite group and represent near-primitive melts having experienced minimal fractional crystallization or crystal accumulation [6]. Olivine-hosted melt inclusions (MI) in these shergottites represent the most chemically primitive components available to understand the nature of their source(s), melting processes in the martian mantle, and origin of enriched components. We present trace element compositions of olivine hosted melt inclusions in two depleted olivinephyric shergottites, Yamato 980459 (Y98) and Tissint (Fig. 1), and the mesostasis glass of Y98, using Secondary Ionization Mass Spectrometry (SIMS). We discuss our data in the context of understanding the nature and origin of the depleted martian mantle and the emergence of the enriched component.

Peters, T. J.↗
NASA NTRS2010

Mineralogical and Chemical Characterization of Lunar Highland Soils: Insights into the Space Weathering of Soils on Airless Bodies

With reflectance spectroscopy, one is measuring only properties of the fine-grained regolith, most affected by space weathering. The Lunar Soil Characterization Consortium has undertaken the task of coordinated characterization of lunar soils, with respect to their mineralogical and chemical makeup. It is these lunar soils that are being used as "ground-truth" for all air30 less bodies. Modal abundances and chemistries of minerals and glasses in the finest size fractions (20-45, 10-20, and <10 microns) of four Apollo 14 and six Apollo 16 highland soils have been determined, as well as their bulk chemistry and IS/FeO values. Bi-directional reflectance measurements (0.3-2.6 microns) of all samples were performed in the RELAB. A significant fraction of nanophase Fe(sup 0) (np-Fe(sup 0)) appears to reside in agglutinitic glasses. However, as grain size of a soil decreases, the percentage of total iron present as np-Fe0 increases significantly, whereas the agglutinitic glass content rises only slightly; this is evidence for a large contribution to the IS/FeO values from the surface-correlated nanophase Fe(sup 0), particularly in the <10 micron size fraction. The compositions of the agglutinitic glasses in these fine fractions of the highland soils are different from the bulk-chemistry of that size; however, compositional trends of the glasses are not the same as those observed for mare soils. It is apparent that the glasses in the highland soils contain chemical components from outside their terrains. It is proposed that the Apollo 16 soils have been adulterated by the addition of impact-transported soil components from surrounding maria.

Taylor, Lawrence A.↗
NASA NTRS1976

Chemical aspects of agglutinate formation - Relationships between agglutinate composition and the composition of the bulk soil

Attention is centered on the nature and intensity of geochemical fractionation accompanying agglutination of several size fractions of the immature Apollo-16 soil sample 67460, from North Ray Crater. The soil features coarse mean grain size about 150 microns, low (20 wt.%) magnetic agglutinate content, and a bimodal grain size distribution. The magnetic fraction included both agglutinates and magnetic non-agglutinates (glass-free microbreccias with 30-60 micron native FeNi grains hosted in a matrix of pyroxene, ilmenite, and olivine). The separation process residue contained nonmagnetic agglutinates with compositions near pure plagioclase. The magnetic agglutinate fraction appears selectively enriched in ferromagnesian elements to the partial exclusion of plagioclase elements. Agglutinate glass chemistry based solely on magnetic separation is deprecated on the basis of the results.

Via, W. N.↗