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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

In-Situ and Experimental Evidence for Acidic Weathering of Rocks and Soils on Mars

Experimental data for alteration of synthetic Martian basalts at pH=0-1 indicate that chemical fractionations at low pH are vastly different from those observed during terrestrial weathering. Rock analyses from Gusev crater are well described by the relationships apparent from low pH experimental alteration data. A model for rock surface alteration is developed which indicates that a leached alteration zone is present on rock surfaces at Gusev. This zone is not chemically fractionated to a large degree from the underlying rock interior, indicating that the rock surface alteration process has occurred at low fluid-to-rock ratio. The geochemistry of natural rock surfaces analyzed by APXS is consistent with a mixture between adhering soil/dust and the leached alteration zone. The chemistry of rock surfaces analyzed after brushing with the RAT is largely representative of the leached alteration zone. The chemistry of rock surfaces analyzed after grinding with the RAT is largely representative of the interior of the rock, relatively unaffected by the alteration process occurring at the rock surface. Elemental measurements from the Spirit, Opportunity, Pathfinder and Viking 1 landing sites indicate that soil chemistry from widely separated locations is consistent with the low-pH, low fluid to rock ratio alteration relationships developed for Gusev rocks. Soils are affected principally by mobility of FeO and MgO, consistent with alteration of olivine-bearing basalt and subsequent precipitation of FeO and MgO bearing secondary minerals as the primary control on soil geochemistry.

Hurowitz, J. A.↗
NASA NTRS2012

Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex~ ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes it feasible to observe its less common isotopologues. As a step in our investigation of C-13 fractionation patterns in the ISM, we here present comparisons between observations of the C-13 fraction in formaldehyde, and chemical fractionation models.

Wirstrom, E. S.↗
NASA NTRS2000

Nonbiological fractionation of iron isotopes

Laboratory experiments demonstrate that iron isotopes can be chemically fractionated in the absence of biology. Isotopic variations comparable to those seen during microbially mediated reduction of ferrihydrite are observed. Fractionation may occur in aqueous solution during equilibration between inorganic iron complexes. These findings provide insight into the mechanisms of iron isotope fractionation and suggest that nonbiological processes may contribute to iron isotope variations observed in sediments.

NASA Discipline Exobiology↗
NASA NTRS1999

The SNC Meteorites Are From Mars

The thirteen SNC meteorites are all igneous rocks, either basalts or basaltic cumulates. They are inferred to be from Mars, based on direct comparison with martian materials and on consistency with inferences about Mars. Most telling is that the SNC meteorites contain traces of gas which is very similar in elemental and isotopic compositions to the modem Martian atmosphere as measured by Viking. The martian atmosphere appears to be unique in the solar system, so its presence in the SNCs is accepted as virtually unequivocal proof that they formed on Mars. Independent of this link, the SNC meteorites must be from a planet with a significant atmosphere because they contain several abundant gas components, some of which carry large isotopic fractionations characteristic of atmospheric processing. The chemical compositions of the SNC meteorites are also consistent with data from in situ analyses of martian soils and rocks, and are quite different from compositions of other meteorites, rocks from the Earth, and rocks from the Moon. The range of formation ages for the SNC meteorites, 4.5 Ga to 0. 18 Ga, is consistent with the varied ages of the Martian surface (based on its cratering record) and inconsistent with surface ages on any other solar system body. The extreme chemical fractionations in the SNC meteorites suggest complex internal processes on a large planet, which is inconsistent with an asteroidal origin. Some SNCs were altered by aqueous solutions at greater than 0.7 Ga, consistent with the recent presence of liquid groundwater in Mars inferred independently from the geology of its surface. There seems little likelihood that the SNCs are not from Mars. If they were from another planetary body, it would have to be substantially identical to Mars as it now is understood.

Treiman, Allan H.↗
NASA NTRS1993

Mineral equilibrium in fractionated nebular systems

We investigated the equilibrium mineral assemblages in chemically fractionated nebular systems, using a computer routine that finds the set of minerals and gases which minimizes the Gibbs free energy of a system with stipulated elemental abundances. Diagrams are presented showing the equilibrium mineralogy, as a function of temperature (400-2300 K), for unfractionated solar material and five fractionated systems. The fractionated systems were defined by mixing, in various proportions, the following four volatility components that solar material can be divided into: refractory dust, carbonaceous matter, ices, and H2 gas. Dust enrichment is seen to increase temperatures of condensation/evaporation and the Fe(2+) content of mafic minerals and to permit existence of stable melt phases. Enrichment of dust and organic matter produces mineral assemblages that are similar in many ways to those of enstatite chondrites, but with mafic minerals that are far more reduced than those in primitive enstatite chondrites. Enrichment of dust, organics, and ices leads to highly ferrous mineralogies even at the highest temperatures but does not predict the stability of hydrous phases above about 450 K.

Wood, John A.↗
DOE OSTI2026

Thermal Gradient Effects on Redox Evolution and Volatility-Driven Fractionation in Ternary U/Ce/Cs Condensates

Understanding how thermal history influences redox evolution and chemical fractionation is essential for characterizing high-temperature condensation in complex materials, including nuclear debris. Here, we tested the hypothesis that distinct thermal regimes in a plasma flow reactor influence redox pathways and elemental partitioning in ternary U/Ce/Cs systems. A configurable plasma flow reactor was modified with an external tube furnace to impose two distinct thermal gradients: continuous ambient cooling and a furnace-assisted thermal hold-up near 1400 K followed by rapid cooling. Transmission electron microscopy characterized phase identity, morphology, and nanoscale element distributions, while inductively coupled plasma-mass spectrometry quantified bulk elemental ratios. Across both thermal regimes, uranium and cerium condensed as UO 2 and CeO 2 as dominant refractory oxide products. Uranium partially oxidized to α-UO 3 during extended ambient cooling, while furnace-assisted hold-up preserved UO 2 and produced partial reduction of cerium to Ce 2 O 3 . Cesium remained volatile upstream and condensed later in the reactor, forming Cs 2 O and Cs-uranate phases with the highest incorporation after thermal hold-up. Bulk ICP-MS measurements supported these observations. U/Ce ratios remained comparatively stable and Cs displayed delayed and apparent transient enrichment that matched the nanoscale measurements. This integrated approach provides a quantitative method for linking thermal gradients to redox evolution and volatility-driven fractionation. These results show how the plasma flow reactor can identify where equilibrium descriptions remain adequate and where kinetic effects from residence time and temperature history must be considered when interpreting condensation behavior in multicomponent systems.

and nuclear chemistry↗
DOE OSTI2021

Reactive oxygen species alter chemical composition and adsorptive fractionation of soil organic matter

Reactive oxygen species (ROS), formed during redox fluctuations in iron-rich soils, have been known to stimulate lignin degradation, although not much is known about how they alter soil organic matter (SOM) composition and interaction with mineral surfaces. We conducted a laboratory experiment to see how ROS altered SOM composition and adsorptive fractionation onto Fe-mineral surfaces. We reacted water extracts of SOM with ·OH, produced by the Fenton reaction, and then conducted a sorption experiment of the extracts with goethite to analyze the amount and quality of SOM adsorbed. The Fenton reaction preferentially consumed low-O, mostly aromatic molecules, and new high-O molecules were detected post-Fenton, nearly half of which were carbohydrate-like. Although the amount of C adsorbed did not change after oxidation, the post-Fenton adsorbed molecules were more oxidized. Pre-Fenton adsorption was dominated by aromatic molecules (90%), but post-Fenton, the adsorbed molecules were 75% aromatic and 25% carbohydrate-like. We show that the ·OH radical oxidized SOM and shifted patterns of adsorption to a more oxidized pool. Because adsorption to minerals is thought to stabilize SOM, our results suggest that ROS may alter the availability and stabilization patterns of SOM.

Patel, Kaizad F.↗
NASA NTRS1977

Chemical variation and fractionation of KREEP basalt magmas

The fact that 53 Apollo 15 igneous KREEP basalts show a range of 100 Mg/(Mg + Fe) from 73 to 35, and that there are systematic variations in K2O and trace element abundances with the Mg/(Mg + Fe) ratio, suggests that the KREEP basalts are a magma series generated by fractional crystallization processes. Experimental and chemical evidence indicate that this magma series results from low-pressure, possibly subvolcanic, fractional crystallization of a magnesian parental liquid (100 Mg/(Mg + Fe) equal to approximately 72) by removal of low-Ca pyroxene and plagioclase, with eventual production of liquids similar in composition to 15405 quartz-monozodiorites. One soil sample, SAO 465-11, corresponds to the postulated parental liquid, which might have been a direct partial melt of troctolitic materials in the deep lunar crust.

Irving, A. J.↗
DOE OSTI2022

High throughput exploration of the oxidation landscape in high entropy alloys

We report high entropy alloys (HEAs) have gained interest for structural applications in extreme environments. With a potentially vast chemical and phase space, there are significant opportunities to discover superior performing alloys. Crucial for most high-temperature applications is understanding and mitigating the oxidation behavior of these chemically complex alloys. Most experimental and computational HEA studies have focused on a limited set of compositions and only a fraction these compositions have been characterized for oxidation. We present a high-throughput framework that utilizes density-functional theory (DFT) in concert with a combined machine-learning model and grand-canonical linear programming for assessing phase stability, phase-fraction, chemical activity and high-temperature survivability of arbitrary HEAs. This framework considers temperature dependent contributions to the Gibbs energy of the competing phases arising from short-range order and vibrational entropy. We demonstrate the effectiveness of the framework by assessing the thermodynamic stability, oxidation behavior, chemical activity, and phase decomposition of body-centered cubic Mo-W-Ta-Ti-Zr refractory HEAs. A total of 51 compositions were analyzed and ranked in order of their survivability based on the Pareto-front analysis. Oxidation was performed at 1373 K on fours samples in air showing the difference in oxidation behavior determined experimentally through scale thickness and their mass changes. The insights on oxidation behavior presented in this work will enable the fast assessment of technologically useful HEAs needed for future structural application in extreme conditions

36 MATERIALS SCIENCE↗
NASA NTRS1983

Reduction, partial evaporation, and spattering - Possible chemical and physical processes in fluid drop chondrule formation

The major chemical differences between fluid drop chondrules and their probable parent materials may have resulted from the loss of volatiles such as S, H2O, Fe, and volatile siderophile elements by partial evaporation during the chondrule-forming process. Vertical access solar furnace experiments in vacuum and hydrogen have demonstrated such chemical fractionation trends using standard rock samples. The formation of immiscible iron droplets and spherules by in situ reduction of iron from silicate melt and the subsequent evaporation of the iron have been observed directly. During the time that the main sample bead is molten, many small spatter spherules are thrown off the main bead, thereby producing many additional chondrule-like melt spherules that cool rapidly and generate a population of spherules with size frequency distribution characteristics that closely approximate some populations of fluid drop chondrules in chondrites. It is possible that spatter-produced fluid drop chondrules dominate the meteoritic fluid drop chondrule populations. Such meteoritic chondrule populations should be chemically related by various relative amounts of iron and other volatile loss by vapor fractionation.

King, E. A.↗
NASA NTRS1980

Trace elements in ocean ridge basalt glasses - Implications for fractionations during mantle evolution and petrogenesis

Seven documented and fresh glassy selvages from ocean floor basalt pillows were analyzed for trace elements including Ag, Au, Bi, Br, Ni, Pd, and Zn using radiochemical activation analysis. Glasses from DSDP leg 24, site 238 in the Indian Ocean have a trace element pattern which reflects secondary processes at a shallow depth. Chemical fractionations in petrogenesis of tholeiitic basalts indicate that (Ir, Os), Au, Pd, Ni, and Re are strongly fractionated in igneous processes; the unfractionated chondritic mantle pattern thus imposes constraints on mantle evolution models. Finally, the limited Rb/Cs fractionation in oceanic tholeiites reflects the low abundance of volatiles and hydrous silicates in normal ocean ridge basalts.

Hertogen, J.↗
NASA NTRS2009

A Simple Mechanism for Fractionating Oxygen Isotopes in the Solar Nebula

Lightning in the Solar Nebula is caused by the tribo-electric charging of dust grains carried by massive turbulent flows and driven by the accretion energy in the disk: it has long been one agent assumed responsible for the formation of chondrules. The degree to which charge separation can occur is dependent upon a number of factors, including the concentration of radioactive sources and the total level of ionization in the nebula, and these factors determine the maximum energy likely to be released by a single bolt. While chondrule formation requires a massive discharge, even a small lightning bolt can vaporize grains in the ionized discharge channel. Experimental studies have shown that silica, iron silicate and iron oxide grains formed from a high voltage discharge in hydrogen rich gas containing some oxygen produces solids that are enriched in O-17 and O-18 relative to the composition of the starting gas. Vaporization of silicates produces SiO, metal and free oxygen atoms in each discharge and these species will immediately begin to recondense from the hot plasma. Freshly condensed grains are incrementally enriched in heavy oxygen while the gas is enriched in O-16. Repeated evaporation and condensation of silicates in continuously occurring lightning discharges will monotonically increase the fractionation of oxygen isotopes between the O-17 and O-18 rich dust and the O-16 rich gas. The first mass independently fractionated refractory oxide particles were produced in the lab following the condensation of a flowing gas mixture containing variable amounts of hydrogen, silane, pentacarbonyl iron and oxygen that passed through a high voltage discharge powered by a Tesla coil. While the exact chemical pathway is still uncertain, the most probable reaction mechanisms involve oxidation of the growing refractory clusters by O3, OH or O atoms. This model has some interesting consequences for chemical processes in the early solar nebula. Chemical fractionation of recondensed dust evaporated via lightning discharges should be strongly time dependent. At earlier times, the accretion rate is maximal, thus driving strong turbulence, energetic grain-grain collisions, tribo-electric charging and charge separation, leading to frequent, powerful lightning discharges. As the accretion rate diminishes, turbulence decreases and lightning discharges will become both less powerful and less frequent, thus decreasing the rate of dust-gas fractionation. The most rapid increase in the formation of O-16 poor dust will occur early in nebular history. Generation of fractionated dust should be distributed throughout the inner disk. Once condensed, grain dispersal would average out any significant isotopic anomalies within the inner disk.

Nuth, Joseph A., III↗
DOE OSTI2021

Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ 41 K and δ 87 Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Oxygen isotopic constraints on the composition of the moon

The mean oxygen isotopic composition of 5 Apollo 17 soils, one Apollo 17 breccia and one Apollo 12 soil is delta O-18 = 5.63 + or - .05 and delta O-17 = 3.8 + or - .2%. These values are within several tenths of a part permil of the composition of a large fraction of the lunar interior. High-temperature condensate aggregates from Allende and other C2 and C3 chondrites are vastly enriched in O-16 compared to this composition. The moon cannot be a mixture of ordinary chondrites and Allende inclusions, nor can it be derived from such a mixture by chemical fractionation processes. The moon's isotopic composition is consistent with a mixture of high- and low-temperature condensates but the refractory fraction would have to be free of the O-16-rich component so prevalent in the meteoritic aggregates, a fact which makes such models less attractive than they once seemed.

Grossman, L.↗
NASA NTRS2012

Observations of Nitrogen Fractionation in Prestellar Cores: Nitriles Tracing Interstellar Chemistry

Primitive materials provide important clues on the processes that occurred during the formation and early evolution of the Solar System. Space-based and ground-based observations of cometary comae show that comets appear to contain a mixture of the products of both interstellar and nebular chemistries. Significant 15-nitrogen enrichments have been measured in CN and HCN towards a number of comets and may suggest an origin of interstellar chemical fractionation. Additionally, large N-15 enhancements are found in meteorites and has also led to to the view that the N-15 traces material formed in the interstellar medium (ISM), although multiple sources cannot be excluded. Here, we show the results of observations of the nitrogen and carbon fractionation in prestellar cores for various N-bearing species to decipher the origin of primitive material isotopic enrichments.

Milam, S. N.↗
NASA NTRS2010

Chemical Evolution of Presolar Organics in Astromaterials

Sub-micron, hollow organic globules reported from several carbonaceous chondrites, interplanetary dust particles, and comet Wild-2 samples returned by NASA?s Stardust mission are enriched in N-15/N-14 and D/H compared with terrestrial materials and the parent materials [1-4]. These anomalies are ascribed to the preservation of presolar cold molecular cloud material from where H, C, and N isotopic constraints point to chemical fractionation near 10 K [5]. An origin well beyond the planet forming region and their survival in meteorites suggests submicrometer organic globules were once prevalent throughout the solar nebula. The survival of the membrane structures indicates primitive meteorites and cometary dust particles would have delivered these organic precursors to the early Earth as well as other planets and satellites. The physical, chemical, and isotopic properties of the organic globules varies to its meteorite types and its lithologies. For example, organic globules in the Tagish Lake meteorite are always embedded in fined grained (poorly crystallized) saponite, and hardly encapsulated in coarse grained serpentine, even though saponite and serpentine are both main components of phyllosilicate matrix of the Tagish Lake meteorite. The organic globules are commonly observed in the carbonate-poor lithology but not in the carbonate-rich one. In Tagish Lake, isolated single globules are common, but in the Bells (CM2) meteorite, globules are mostly aggregated. We will review the evolutions of the organic globules from its birth to alteration in the parent bodies in terms of its own physical and chemical properties as well as its associated minerals.

Nakamura-Messenger, K.↗
NASA NTRS1973

Vitrification darkening of rock powders - Implications for optical properties of the lunar surface

Laboratory experiments show that albedoes as low as those on the moon can be produced by vacuum vitrification and associated chemical fractionation of ordinary terrestrial basaltic material. Vitrification is established as an unequivocal process that can account for the low albedo and apparent local darkening with age of the lunar surface. The spectral reflectance curves of glass powders are significantly different than those of the parent rock mineralogy; thus, the presence of ubiquitous glass in lunar surface material complicates compositional determinations by interpretation of spectral reflectance curves. Vitrification of rocks on the moon may highly modify the chemical composition of the resulting glass; thus, glass fragments found in lunar fines cannot be assumed to represent bulk parent rock material. Progressive impact vitrification of lunar surface material throughout the moon's history may have led to a fine-grain, opaque, refractory-rich material we call 'ultimate glass.' This unidentified and, at this point, hypothetical component may exist in dark regolith material; if found, it may be a useful indicator of regolith maturity.

Nash, D. B.↗
NASA NTRS1997

Chondritic Meteorites: Nebular and Parent-Body Formation Process

Chondritic meteorites are the products of condensation, agglomeration and accretion of material in the solar nebula; these objects are the best sources of information regarding processes occurring during the early history of the solar system. We obtain large amounts of high-quality chemical and petrographic data and use them to infer chemical fractionation processes that occurred in the solar nebula and on meteorite parent bodies during thermal metamorphism, shock metamorphism and aqueous alteration. We compare diverse groups of chondrites and model their different properties in terms of processes that differed at different nebular locations or on different parent-bodies. In order to expand our set of geochemically important elements (particularly Si, C, P and S) and to distinguish the different oxidation states of Fe, Greg Kallemeyn spent three months (1 Sept. - 30 Nov. 1995) at the Smithsonian Institution to learn Eugene Jarosewich's wet chemical techniques. Key specimens from the recently established CK, CR and R chondrite groups were analyzed.

Rubin, Alan E.↗