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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

Experimentation to Understand Planet and Proto-Planet Formation

Experimental petrology has placed constraints on a wide variety of nebular and planet formation processes such as chondrule formation, CAI (Calcium-Aluminum-rich Inclusions) crystallization, asteroid magmatism, mantle melting, core formation, element partitioning related to radiogenic isotopes and heat production. Although great progress has been made, there remain several key problems where more data are required to constrain modelling, both empirical and thermodynamics-based. Here I will focus on several areas with implications for meteoritics and planetary science, including systems of low fO2 (Oxygen fugacity), constructing models that include both metal and silicate for mantle melting and differentiation, high pressure phase equilibria relevant to full range of silicate mantles, and core-mantle equilibria where H and O are specified, and their effects are measured.

Righter, K.↗
NASA NTRS2021

Machine Learning the COSMO Model for Predicting Thermodynamics of Electrolyte Mixtures

Bottom-up design of electrolyte mixtures for battery systems requires predicting macro thermodynamic properties from molecular constituents. For instance, molten salt electrolyte batteries require conditions far above room temperature to operate. Therefore, discovering mixtures with increasingly lower eutectic melting points is desirable. A model that can approximate chemical activity is a valuable tool to search through the vast compositional design space. Machine learning can predict properties of materials such as vibrational free energies, electronic energy gaps, and thermal conductivities. Moreover, they can learn physical models such as interatomic potentials. The COSMO-SAC model uses theory and empirical parameterization to predict liquid-vapor and liquid-solid properties using first-principles calculations. However, obtaining activity coefficients required for parameterizing the COSMO-SAC model is costly and limited to a select chemical space. In this work, we explored if machine learning methods could improve the COSMO-SAC model and bridge density functional theory calculations to liquid phase thermodynamic properties. Our data-driven approach uses existing databases for sigma-profiles of organic solvents and reconciles their methodological differences via ensemble averaging. First, an optimal machine learning model is constructed for each dataset. Our machine learning algorithms use the sigma-profile as an input feature to predict binary mixtures' activity coefficients using multi-output regression. Each dataset uses different choices of functionals, methods, and basis sets. Therefore, our ensemble model attempts to predict corrected activity coefficients given the combination of all the model outputs. The activity coefficients used for training are generated using the COSMO-SAC model. This approach enables the extraction of meaningful information from the existing datasets to improve the COSMO-SAC model for obtaining thermodynamic properties of electrolyte mixtures. With the liquid phase activities, we can identify electrolyte mixtures that meet desired phase equilibria conditions.

Thermodynamics↗
NASA NTRSDate not supplied

Compostional Variation of Venusian Melts as A Function of Thermal Gradient and Protolith

Average surface pressure and temperature conditions of 92 bars and 460 °C and thermal gradients in the range of 5-25 °C/km and up to 50 °C/km for specific cases on Venus suggest that the lower crust and upper mantle are exposed to conditions suitable for partial melting. Further, constraints from terrestrial crystallization experiments are indicative of magmatic diversity on Venus due to variations in melting depths and volatile content. Here, we use phase equilibria modeling to determine the melt compositions resulting from partial melting of a mantle protolith and two mafic crustal compositions for sever-al Venusian thermal gradients. The modeled melt compositions are then compared to experimental eclogite and peridotite melt compositions and analyses from the Venusian surface to further constrain melting processes.

J Semprich↗
NASA NTRS2024

Understanding Mercury’s Magmatic History: Geochemical Affinity, Compatibility, & Volatility Changes Due to Reduction

Mercury’s depletion in O and abundance of S substituting in as S2- has fundamental effects on the physicochemical properties of minerals and melts because O2- is the dominant rock-forming anion. These changes exert a first order effect on planetary body evolution, including the initial distribution of elements, crystallization paths, stability of phases, and mineral chemistry. Experimental and empirical data have revealed that most nominally lithophile elements become more chalcophile and/or siderophile at reducing conditions, which can be visualized through a re-interpreted Goldschmidt classification table prepared for McCubbin & Anzures’s Treatises of Geochemistry 3rd edition chapter under review. Additionally, the S bonding environment influences Mercurian phase equilibria by decreasing the stability of forsterite and anorthite while increasing the stability of enstatite, silica, and albite through re-projection of silicate ternaries.

Brendan Anthony Anzures↗
NASA NTRS2024

Effects of Water on the Density and Elevation of Tesserae on Venus

While the current conditions on Venus are inhospitable, with surface temperatures of ~ 470 °C, pressures of 92 bars, and a CO 2 dominated atmosphere, early Venus may have had a more temperate climate with water on the surface. Water is not only crucial to understanding the habitability potential of Venus, but also has major implications for the tectonic regime and thermal evolution of a planet. Tesserae are believed to be the oldest exposed features on the surface of Venus and may have formed during a period with higher water content. Some of this water might have been preserved as hydrous minerals in the Venusian subsurface. The presence of these minerals has an effect on the density profiles and isostatic behaviour of the tesserae and therefore requires a more detailed investigation. Here we will present results of phase equilibria and isostasy modelling on a range of Tesserae-analogue rock compositions with varying water content and along a range of potential thermal gradients. We compare our results to anhydrous models performed previously under similar thermal regime to constrain the conditions (rock composition, thermal gradient, and water content) needed for tesserae stability.

A R Baker↗
NASA NTRSDate not supplied

A New Era of H-O-C-S Magma Solubility Modeling: Better, Faster, Stronger

H 2 O, CO 2 , and S are the most abundant volatiles in magmatic systems and are critical to understanding magma storage, phase equilibria, and volcanic eruptions. Models that consider all three of these components, however, may not allow for critical examination and adjustment of assumptions underlying the model, or provide benchmark testing or extensible interfaces. Thus, understanding why models produce different results can be challenging. We have gathered authors of established (D-Compress) and recent (VolFe, EVo, Sulfur_X, MAGEC) H-O-C-S volatile solubility models to work together to understand how and why our models diverge. We present a series of benchmark basalt degassing scenarios revealing that often understated model assumptions such as fO 2 buffer equations, fO 2 -Fe 3+ /ΣFe relationships, and even major element normalization routines have outsized effects on model results. All models consider S 2- and S 6+ melt species but with different approaches to sulfate/sulfide capacities, partition coefficients, and species fugacities, leading to divergence in the evolution of modeled gas compositions, melt S and Fe speciation, and fO 2 , with the extent of divergence depending on melt composition. Such scenarios enable meaningful intercomparison of existing models and lay the groundwork for a user-friendly yet powerful solubility modeling framework. Given our wealth of existing solubility literature, we suggest that the field of magmatic volatiles should focus now on the creation of modern tools and the modular implementation of existing model equations or methods, and that the evaluation of code usability, transparency, and benchmarking should be codified pillars of the peer-review process. As an example of such an endeavor, we present early work coupling these sulfur solubility models with VESIcal, an extensible and rigorously tested python library containing seven existing H 2 O-CO 2 solubility models. VESIcal includes the ability to extract, edit, and even interchange assumptions underlying any model. For example, users may combine or swap separately published H 2 O, CO 2 , and S models, as well as underlying model choices, such as Equations of State and redox models.

volatiles in magmas↗
NASA NTRS2002

Phosphorus Equilibria Among Mafic Silicate Phases

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Berlin, Jana↗
NASA NTRS1984

Design and performance analysis of gas sorption compressors

Compressor kinetics based on gas adsorption and desorption processes by charcoal and for gas absorption and desorption processes by LaNi5 were analyzed using a two-phase model and a three-component model, respectively. The assumption of the modeling involved thermal and mechanical equilibria between phases or among the components. The analyses predicted performance well for compressors which have heaters located outside the adsorbent or the absorbent bed. For the rapidly-cycled compressor, where the heater was centrally located, only the transient pressure compared well with the experimental data.

Chan, C. K.↗
NASA NTRS1980

The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/

Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.

Lee, N.↗
NASA NTRS1974

Equilibria bearing on the behavior of titanate phases during crystallization of iron silicate melts under strongly reducing conditions

Titanate phase relations at liquidus temperatures are determined for the CaAl2Si2O8-Fe2TiO4-FeTi2O5 system in contact with metallic iron by reflected- and transmitted-light microscopy, electron microprobe, and X-ray diffraction analyses. Results of critical equilibration runs are presented, various primary phase areas and liquidus isotherms are illustrated, and the geometry of the system is described. Three piercing points are determined, and it is noted that the compositional interrelations among coexisting crystalline and liquid phases as well as the sequence of the various titanate phases are indicative of the significant effects of the various cations on the relative stability of these phases. It is found that Al2O3 exerts a strong stabilizing effect on the phase assemblage of ulvospinel plus ferropseudobrookite relative to ilemite.

Lipin, B. R.↗
NASA NTRS1985

Was core formation violent enough to homogenize the early mantle?

The dynamics of iron, its thermal state and its phase in the accreting Earth probably played a major role in the Earth's early thermal evolution. Plausible impact thermal histories make it possible that pure iron was molten in the accreting Earth after it was about 10% grown. Hence, iron eutectic alloys (FeS, FeO) certainly were. Additionally, the initial temperature of the core is an important constraint on the secular cooling of the early Earth and on the strength of the early geodynamo. Whether iron is solid or molten would influence geochemical equilibria in the upper and lower mantle; the mode of core formation, by spherical or near-spherical blobs, stalk-like instabilities, or something more catastrophic would influence the partitioning of siderophiles between silicate and iron phases. Early descent of iron (during accretion) favors partitioning according to low-pressure phase equilibria, whereas late descent favors higher pressure. The later core formation occurs, the greater the heat pulse, due to the strong dependence of gravitational potential energy on planetary radius. The heat may homogenize the mantle if core formation is global; otherwise, heterogeneity of iron differentiation may leave some of the pre-archean mantle unaffected. The larger the chunks of proto-core (and hence smaller surface/volume ratios) the greater the heterogeneity.

Cooperman, S. A.↗
NASA NTRSDate not supplied

Multi-Anvil Experimentation Applied to Planetary Differentiation

Planets undergo differentiation that includes segregation of metal from silicate at high temperatures and pressures ranging from deep planetary core pressures (>300 GPa for Earth)to very shallow conditions of asteroids (<100 MPa).The multi-anvil solid media apparatus accesses the middle part of this range from 3 to 30 GPa –pressure relevant to the interior of Mercury, Venus, Earth, Earth’s Moon, and Mars. Early planets are thought to have experienced high temperatures from a combination of heat sources including radioactive decay, gravitational and accretional heating, and impact processes. These heating events led to melting of mantles and cores, thus requiring an understanding of solid-liquid equilibria in metal-silicate systems. In 2006 we established a multi-anvil facility at NASA-JSC combining an 880 ton press and a Kawai/Walker type module from Rockland Research. Our high PT work has been greatly facilitated by use of the COMPRES multi-anvil assemblies (1). Our recent work has included studies of element partitioning between liquid metal and liquid silicate(e.g., 2), as well as between minerals and melts(e.g., 3), both of which have led to better constraints on the timing and conditions of planetary differentiation(e.g. 4). Several examples involving sustained efforts will be summarized below and for the presentation. The distribution of siderophile (iron-loving) elements between core and mantle is controlled by metal-silicate equilibrium across a wide range of pressures. Therefore, experimentation across this pressure range helps to calibrate elemental partitioning models that can be applied to planets, and used to predict mantle chemistry and composition during planetary differentiation. Our studies have focused on a wide range of siderophile elements (refractory Ni, Co, W, Mo; volatile P, Ga, Cu, Sn, Sb; highly siderophile Au, Pd) that have constrained partitioning, valence, and isotopic fractionation, and applied to Earth, Moon, and Mars. When molten mantles (magma oceans) cool enough to initiate crystallization, the solids precipitate at depth and in large planets this involves high pressure phases like garnet, majorite, akimotoite, and ringwoodite. As these solids precipitate they can segregate from liquid by density contrasts, thus causing elemental fractionation which can be used to decipher timing of differentiation. Mineral/melt and metal/silicate equilibria in our lab have helped to better understand high pressure fractionation of isotopic parent/daughter pairs Hf/W, Mn/Cr, Pd/Ag, Pt/Os, Re/Os, and U/Pb, and their application to Earth, Moon and Mars. There remains great potential for multi-anvil experimentation to shed light on many pressure–dependent aspects of planetary evolution such as core formation, high pressure phase equilibria, redox equilibria, and volatile evolution and storage. References1. Leinenweber, K., et al.(2012) American Mineralogist,97, 353–368. 2.Righter, K., et al.(2020) Geochem. Persp. Lett.15, 1-6.3. Righter, K., et al.(2020) Met. Planet. Sci 55, 2741-2757.4. Righter, K., et al.(2020)Earth and Planetary Science Letters,552, 116590.

pressure↗
NASA NTRS1972

Review of critical flow rate, propagation of pressure pulse, and sonic velocity in two-phase media

For single-phase media, the critical discharge velocity, the sonic velocity, and the pressure pulse propagation velocity can be expressed in the same form by assuming isentropic, equilibria processes. In two-phase mixtures, the same concept is not valid due to the existence of interfacial transports of momentum, heat, and mass. Thus, the three velocities should be treated differently and separately for each particular condition, taking into account the various transport processes involved under that condition. Various attempts are reviewed to predict the critical discharge rate or the propagation velocities by considering slip ratio (momentum change), evaporation (mass and heat transport), flow pattern, etc. Experimental data were compared with predictions based on various theorems. The importance is stressed of the time required to achieve equilibrium as compared with the time available during the process, for example, of passing a pressure pulse.

Hsu, Y.↗
NASA NTRS1994

Establishment of redox conditions during planetary collisions as an origin of chondrites

Collisions between a 'cometlike' body (mixtures of chondritic materials and ice) and a slightly differentiated body were proposed for shock origin of ordinary chondrites. In this model, chondrules were formed with shock melting, and matrices were formed both by fracturing of materials and by recondensation of evaporated materials. This model can explain different redox conditions of chondrite formations by ice evaporation. Although this model was originally proposed for ordinary chondrites, we assume here that the model can be extended to chondrite formation in general. In this paper, redox conditions during chondrite formation by collisions will be discussed in the light of phase diagrams for solid-vapor equilibria.

Tsuchiyama, A.↗
NASA NTRS1986

Influence of transient baroclinic eddies on planetary-scale waves

Low-order models with a mean zonal flow forced by zonally symmetric heating and one planetary-scale wave forced by topography have multiple flow equilibria. Two stable equilibria are characterized by strong zonal flow with low wave amplitude (high index circulation) and weak zonal flow with a high wave amplitude (low index circulation) fixed in phase with the topography. These two states presumably represent normal zonal circulation and a blocking configuration, respectively. When a shorter, baroclinically unstable wave is dded to this low-order model, the planetary-scale wave no longer stays in stable equilibrium states. Instead, the long wave remains in weather regimes or preferred regions in phase space. These regimes are, in general, different from the equilibria of the model with the planetary-scale wave only. Thus, the short unstable wave adds some randomness to planetary-scale circulation and changes its position with respect to the planetary-scale topography. The Reinhold and Pierrehumbert model is further explored here by adding a long-wave in the thermal forcing and exploring wider parameter space. When the symmetric thermal forcing is weak so that the short wave is stable, the planetary scale wave is fixed in amplitude and phase by the asymmetric forcing. However, when the symmetric forcing is increased to an unstable level, the planetary-scale wave becomes less organized. With asymmetric thermal forcing only (i.e., no topography) the long-wave is randomly distributed through phase space. Thermal forcing seems to be less effective in organizing weather regimes than topographic forcing.

Branscome, L. E.↗
NASA NTRS1994

The sensitivity of tropospheric chemistry to cloud interactions

Clouds, although only occupying a relatively small fraction of the troposphere volume, can have a substantial impact on the chemistry of the troposphere. In newly formed clouds, or in clouds with air rapidly flowing through, the chemistry is expected to be far more active than in aged clouds with stagnant air. Thus, frequent cycling of air through shortlived clouds, i.e. cumulus clouds, is likely to be a much more efficient media for altering the composition of the atmosphere than an extensive cloud cover i.e. frontal cloud systems. The impact of clouds is tested out in a 2-D channel model encircling the globe in a latitudinal belt from 30 to 60 deg N. The model contains a detailed gas phase chemistry. In addition physiochemical interactions between the gas and aqueous phases are included. For species as H2O2, CH2O, O3, and SO2, Henry's law equilibria are assumed, whereas HNO3 and H2SO4 are regarded as completed dissolved in the aqueous phase. Absorption of HO2 and OH is assumed to be mass-transport limited. The chemistry of the aqueous phase is characterized by rapid cycling of odd hydrogen, (H2O2, HO2, and OH). O2(-) (produced through dissociation of HO2) reacting with dissolved O3 is a major source of OH in the aqueous phase. This reaction can be a significant sink for O3 in the troposphere. In the interstitial cloud air, odd hydrogen is depleted, whereas NO(x) remains in the gas phase, thus reducing ozone production due to the reaction between NO and HO2. Our calculations give markedly lower ozone levels when cloud interactions are included. This may in part explain the overpredictions of ozone levels often experienced in models neglecting cloud chemical interactions. In the present study, the existence of clouds, cloud types, and their lifetimes are modeled as pseudo random variables. Such pseudo random sequences are in reality deterministic and may, given the same starting values, be reproduced. The effects of cloud interactions on the overall chemistry of the troposphere are discussed. In particular, tests are performed to determine the sensitivity of cloud frequencies and cloud types.

Jonson, Jan E.↗
NASA NTRS1995

Formation of a very thin current sheet in the near-earth magnetotail and the explosive growth phase of substorms

A magnetofricional method is used to construct two-dimensional MHD equilibria of the Earth's magnetosphere for a given distribution of entropy functions(S = pV(exp gamma), where p is the plasma pressure and V is the tube volume per unit magnetic flux. It is found that a very thin current sheet with B (sub zeta) is less than 0.5 nu T and thickness less than 1000 km can be formed in the near-earth magnetotail (x is approximately -8 to -20R(sub e) during the growth phase of substorm. The tail current sheets are found to become thinner as the entropy or the entropy gradient increases. It is suggested that the new entropy anti-diffusion instability associated with plasma transport across field lines leads to magnetic field dipolarization and accelerates the formation of thin current sheet, which may explain the observed explosive growth phase of substorms.

Lee, L. C.↗