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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS2023

Temperature Effect on Silicate Melt-Sulfide-Metal Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.

B A Anzures↗
NASA NTRSDate not supplied

Calcium and Magnesium Distribution Between Sulfide and Silicate Melts: Thermodynamic Modeling and Insights into Mercury's Mantle-Crust Differentiation

Mercury stands out as the terrestrial planet with the lowest degree of oxidation among all planets of our solar system. It is characterized by a high abundance of sulfur, which is expected to replace oxygen in silicate melts. This sulfur enrichment could lead to sulfide saturation in its mantle, potentially resulting in the formation of sulfides rich in calcium and magnesium. Utilizing experimental data from the literature, we constructed a thermodynamic model to explore the partitioning of calcium and magnesium between sulfide and silicate melts. This model aims to improve our comprehension of the chemical equilibria driving the process of mantle-crust differentiation on Mercury. Our models indicate that increased temperature, decreased pressure, and low concentrations of iron, oxygen, and carbon within the sulfide phase, along with low sulfur concentrations in the silicate phase, favor calcium’s partitioning into the sulfide. Additionally, magnesium partitioning into the sulfide melt is favored with decreased pressure, decreased temperature, low concentrations of iron and calcium within the sulfide, and low concentrations of sulfur within the silicate. Our results suggest that up 9.4% and 5.6% Ca and Mg, respectively, can be present in sulfides equilibrated with sulfide-saturated silicate melts during mantle-crust differentiation. Further investigation will focus on the distribution of sulfide phases within the mantle and crust to better constrain Mercury’s internal structure.

Taylor McCombs↗
DOE OSTI2021

Initial hydration process of calcium silicates in Portland cement: A comprehensive comparison from molecular dynamics simulations

As the main components of Portland cement, calcium silicates show substantial differences in their hydration reactivity which have not been fully explained. A comprehensive comparison of the initial hydration process of calcium silicates, namely dicalcium silicate (C{sub 2}S) and tricalcium silicate (C{sub 3}S), was conducted using molecular dynamics simulations. The initial hydration process was divided into three stages using cut-off times of 0.001 ns and 3 ns. The hydration of M{sub 3}-C{sub 3}S (010) was more evident than that of β-C{sub 2}S (100), supported by the hydroxylation degree, radial distribution function, atomic density profile, etc. The coordination number of the surface Ca atoms might be the underlying reason for such a difference. Interactions between cement surfaces and water molecules were mainly characterised by solid OH bonding and Ca-water O bonding. Dissolution of Ca atoms was observed, although quite scarce, while no dissolution of Si atoms was observed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

Infrared (IR) and Raman spectroscopic features of silicate glasses are usually interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na 2 O] x [Al 2 O 3 ] 2 [SiO 2 ] 98- x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order-based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Hence, the bond length and angle distributions as well as Si– Q n species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF-MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050-1120 cm -1 ) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Q n speciation; and (c) assignment of the Raman bands in the 420-600 cm -1 region to the bending modes of (SiO) n rings with different sizes (typically, n = 3-6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF-MD simulations. This result invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Theoretical studies of the infrared emission from circumstellar dust shells: the infrared characteristics of circumstellar silicates and the mass-loss rate of oxygen-rich late-type giants

We have modeled the infrared emission of spherically symmetric, circumstellar dust shells with the aim of deriving the infrared absorption properties of circumstellar silicate grains and the mass-loss rates of the central stars. As a basis for our numerical studies, a simple semianalytical formula has been derived that illustrates the essential characteristics of the infrared emission of such dust shells. A numerical radiative transfer program has been developed and applied to dust shells around oxygen-rich late-type giants. Free parameters in such models include the absorption properties and density distribution of the dust. An approximate, analytical expression is derived for the density distribution of circumstellar dust driven outward by radiation pressure from a central source. A large grid of models has been calculated to study the influence of the free parameters on the emergent spectrum. These results form the basis for a comparison with near-infrared observations. Observational studies have revealed a correlation between the near-infrared color temperature, Tc, and the strength of the 10 micrometers emission or absorption feature, A10. This relationship, which essentially measures the near-infrared optical depth in terms of the 10 micrometers optical depth, is discussed. Theoretical A10-Tc relations have been calculated and compared to the observations. The results show that this relation is a sensitive way to determine the ratio of the near-infrared to 10 micrometers absorption efficiency of circumstellar silicates. These results as well as previous studies show that the near-infrared absorption efficiency of circumstellar silicate grains is much higher than expected from terrestrial minerals. We suggest that this enhanced absorption is due to the presence of ferrous iron (Fe2+) color centers dissolved in the circumstellar silicates. By using the derived value for the ratio of the near-infrared to 10 micrometers absorption efficiency, the observed A10-Tc relation can be calibrated in terms of the total dust column density of the circumstellar shell and thus the mass-loss rate of late-type giants can easily be derived. Detailed models have been made of the infrared emission of three well-studied Miras: R Cas, IRC 10011, and OH 26.5+0.6, with the emphasis on the shape of the 10 micrometers emission or absorption feature. The results show that the intrinsic shape of the 10 micrometers resonance varies from a very broad feature in R Cas to a relatively narrower feature in OH 26.5+0.6, with IRC 10011 somewhere in between. Possible origins of this variation are discussed. The mass-loss rates from these objects are calculated to be 3 x 10(-7), 2 x 10(-5), and 2 x 10(-4) M Sun yr-1 for R Cas, IRC 10011, and OH 26.5+0.6, respectively. These results are compared to other determinations in the literature.

NASA Discipline Exobiology↗
DOE OSTI2021

Deciphering the non-linear impact of Al on chemical durability of silicate glass

The role of Al in aluminosilicate glasses remains somewhat a mystery: at low concentrations, it increases the resistance to hydrolysis of the glass, whereas at high concentrations an opposite effect is observed. To understand the origin of the phenomenon on a fundamental atomistic scale, we performed 577 MD simulations and applied potential mean force (PMF) calculations to estimate the activation barriers for hydrolysis and to statistically correlate them with local structural features of the glass. Models of pure silicate and aluminosilicate glasses are constructed and investigated. PMF simulation results are further validated by the experimental measurements and revealed that Al is very easy to dissociate, but it also increases the glass chemical durability through significantly increasing both the strength of Si and network connectivity of the glass. In contrast, at high Al concentration, preferential dissolution of Al weakens the silicate network, which it supposes to strengthen, and so the glass resistance becomes poor. Through PMF calculations, we evaluated the activation barriers for dissociating bonds around Al as 0.49 eV, which is less than a half of the energy to dissociate bonds around Si in pure silicate (1.22 eV) and around Si in aluminosilicate glass (1.34 eV), all these energy differences being statistically significant. Molecular structural level investigation revealed that Si with Al as a second neighbor in the glass network has a significantly higher activation energy for dissociation than Si in pure silicate glass. Furthermore, the proposed approach opens the way to the development of quantitative predictive models of glass durability.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural evolution of two-dimensional silicates using a “bond-switching” algorithm

Silicates are the most abundant materials in the earth's crust. In recent years, two-dimensional (2D) versions of them grown on metal supports (known as bilayer silicates) have allowed their study in detail down to the atomic scale. These structures are self-containing. Furthermore, they are not covalently bound to the metal support but interact with it through van der Waals forces. Like their three-dimensional counterparts, the 2D-silicates can form both crystalline and vitreous structures. Furthermore, the interconversion between vitreous to crystalline structures has been experimentally observed at the nanoscale. While theoretical work has been carried out to try to understand these transformations, a limitation for ab initio methods, and even molecular dynamics methods, is the computational cost of studying large systems and long timescales. In this work, we present a simple and computationally inexpensive approach, that can be used to represent the evolution of bilayer silicates using a bond-switching algorithm. This approach allows reaching equilibrium ring size distributions as a function of a parameter that can be related to the ratio between temperature and the energy required for the bond-switching event. The ring size distributions are compared to experimental data available in the literature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Silicate minerals as a direct source of limiting nutrients: Siderophore synthesis and uptake promote ferric iron bioavailability from olivine and microbial growth

Iron is a micronutrient critical to fundamental biological processes including respiration and photosynthesis, and it can therefore impact primary and heterotrophic productivity. Yet in oxic environments, iron is highly insoluble, rendering it, in principle, unavailable as a nutrient for biological growth. Life has “solved” this problem via the invention of iron chelates, known as siderophores, that keep iron available for microbial productivity. In this work, we examined the impact of siderophore synthesis on the speciation, mobility, and bioavailability of iron from rock-forming silicate minerals—shedding new light on the mechanisms by which microbes use mineral substrates to support primary productivity, as well as the consequent effects on silicate dissolution. Growth experiments were performed with Shewanella oneidensis MR-1 in an oxic, iron-depleted minimal medium, amended with olivine minerals as the sole source of iron. Experiments included the wild-type strain MR-1, and a siderophore synthesis gene deletion mutant strain (ΔMR-1). Relative to MR-1, ΔMR-1 exhibited a very pronounced growth penalty and an extended lag phase. However, substantial growth of ΔMR-1, comparable to MR-1 growth, was observed when the mutant strain was provided with siderophores in the form of either filtrate from a well-grown MR-1 culture, or commercially available deferoxamine. These observations suggest that siderophores are critical for S. oneidensis to acquire iron from olivine. Growth-limiting concentrations of deferoxamine amendments were observed to be ≤5–10 µM, concentrations significantly lower than previously recorded as necessary to impact mineral dissolution rates. X-ray photoelectric spectroscopy analyses of the incubated olivine surfaces suggest that siderophores deplete mineral surface layers of ferric iron. Combined, these results demonstrate that low micromolar concentrations of siderophores can effectively mobilize iron bound within silicate minerals, supporting very significant biological growth in limiting environments. The specific mechanism would involve siderophores removing a protective layer of nanometer-thick iron oxides, enhancing silicate dissolution and nutrient bioavailability.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

29Si solid state NMR and Ti K-edge XAFS pre-edge spectroscopy reveal complex behavior of Ti in silicate melts

Abstract An understanding of the mechanisms of Ti is incorporation into silicate glasses and melts is critical for the field of petrology. Trace-element thermobarometry, high-field-strength element partitioning, and the physical properties of magmas are all be influenced by Ti incorporation into glasses and changes therein in response to changes in composition and temperature. In this study, we combine 29 Si solid state NMR and Ti K -edge XAFS spectroscopy to investigate how Ti is incorporated into quenched Na-silicate glasses, and the influence of Ti on the structure of silicate species in these glasses. 29 Si NMR shows that in both Ti-bearing Na 2 O•4SiO 2 (NS4) and Na 2 O•8SiO 2 (NS8) glasses, increasing the amount of Ti in the melt results in a shift of Si Q 4 peak in the 29 Si NMR spectra reflecting Ti nearest neighbors for Si in Q 4 speciation. The Ti XAFS results from NS8 glass indicate that Ti is primarily incorporated in [5]-fold coordination. At higher Ti content, there is a shift of the XAFS pre-edge feature suggesting mixing of [4]-fold Ti into the spectra. Combined, the 29 Si NMR and XAFS pre-edge data are consistent with Ti incorporation as isolated [5] Ti atoms and the formation of [5] Ti clusters at relatively low Ti concentrations, with no evidence for Ti–Na interactions as suggested by previous studies. As the Ti content increases, the Ti atoms begin to occupy 4-fold coordinated sites interacting primarily with Si in Q 4 speciation (no significant Na– [4] Ti bonding). The internal consistency of these two techniques provides a uniquely complete snapshot of the complexity of Ti incorporation in silicate melts and underlies the importance of understanding Ti incorporation mechanisms in natural magmatic systems.

Ackerson, Michael R.↗
NASA NTRS1978

An experimental investigation of the condensation of silicate grains

Results are presented for a series of laboratory experiments designed to investigate the nucleation of small silicate grains from a vapor of astrophysically significant elements and compounds. In the experiments, magnesium silicate grains were condensed by simultaneously evaporating Mg and SiO solids into an atmosphere of argon or hydrogen at a pressure of a few torr. The results show that at low temperatures (up to a few hundred degrees C) the condensates are amorphous grains and have widely varying stoichiometries. The thermodynamically most stable compounds (Mg2SiO4, MgSiO3, SiO2) do not form readily, but all initial condensates can be converted to crystalline forsterite (Mg2SiO4) by heating to 1000 C in vacuum. At higher temperatures (above 700 K) it becomes more difficult to nucleate any silicates, and those that do form are amorphous, indicating that surface energies and kinetic effects are very important in determining under what conditions condensation will occur. The IR spectra of the experimentally produced magnesium silicates are found to have a strong resemblance to those observed in many astronomical clouds.

Day, K. L.↗
NASA NTRS1979

Effect of silicate ions on electrode overvoltage

The influence of the addition of a silicate to a caustic solution (KOH) is studied in order to determine the degree to which silicates inhibit the corrosion of chrysotile under conditions of electrolysis at working temperatures of 100 C and above. In an alkaline solution containing various silicate concentrations, current density was increased and electrode overvoltage was measured. Results show that silicate ion concentrations in the electrolyte increase with temperature without effecting electrochemical performance up to 115 C at 700 MA/sqcm. At this point the concentration is about 0.5 g Si/100 g KOH. Beyond this limit, electrolytic performance rapidly degenerates due to severe oxidation of the electrodes.

Gras, J. M.↗
NASA NTRS1980

Visible and ultraviolet /800-130 nm/ extinction of vapor-condensed silicate, carbon, and silicon carbide smokes and the interstellar extinction curve

The extinction curves from 800 to 130 nm (1.25-7.7/micron) of amorphous silicate smokes nominally of olivine and pyroxene composition, carbon smokes, and crystalline SiC smokes are presented. The SiC smoke occurred in the low-temperature (beta) cubic structural form. The SiC smoke showed an absorption edge which occurred at significantly longer wavelengths than the calculated extinction profile of the hexagonal SiC form previously used to calculate the interstellar extinction profile. Neither SiC nor amorphous silicates show an extinction band similar to the observed 6.6/micron astronomical extinction band. The infrared absorption peaks for the silicate and SiC samples near 10 microns and 11-13 microns, respectively, were also measured. The ultraviolet to infrared extinction ratio for the amorphous silicate samples is similar to the observed astronomical extinction ratio. The measured extinction ratios for SiC smokes are significantly below the interstellar extinction ratio. The extinction peak of the carbon smokes occurred at 4.0 and 4.25/micron, for samples of mean radii 13 and 6 nm, respectively. The extinction profile is distinctly different from that predicted for graphite grains of the same size, and is similar to that predicted for glassy carbon grains.

Stephens, J. R.↗
NASA NTRS1986

Laboratory studies of the infrared small-particle extinction of amorphous silicates

The broad interstellar IR extinction features located at 9.7 and 18 microns wavelength are believed to originate from silicate dust grains. Cosmic abundances suggest that the silicate should have a chemical composition similar to that of olivine, (Mg,Fe)2 SiO4. Olivine is a very common terrestrial silicate mineral of crystalline structure. However, crystalline olivine grains do not fit the interstellar features well. Based on spectroscopic data obtained in laboratory studies and astronomical observations it was concluded that the interstellar silicate grains consist of a material with amorphous rather than crystalline structure. The astronomical arguments and the results obtained in our laboratory experiments which support this view are reviewed.

Kraetschmer, W.↗
NASA NTRS1986

Silicate volcanism on Io

This paper is mainly concerned with the nature of volcanic eruptions on Io, taking into account questions regarding the presence of silicates or sulfur as principal component. Attention is given to the generation of silicate magma, the viscous dissipation in the melt zone, thermal anomalies at eruption sites, and Ionian volcanism. According to the information available about Io, it appears that its volcanism and hence its surface materials are dominantly silicic. Several percent of volatile materials such as sulfur, but also including sodium- and potassium-rich materials, may also be present. The volatile materials at the surface are continually vaporized and melted as a result of the high rates of silicate volcanism.

Carr, M. H.↗
NASA NTRS1986

Nature of very small grains - PAH molecules or silicates?

The predictions of the model of Puget et al. (1985) for the emission from Very Small Grains (VSGs) including both graphitic and silicate components are compared with published 8-13-micron observations of astronomical sources. The VSGs are found to be mainly graphitic and an upper limit is placed on the relative mass of silicates based on lack of the 9.7-micron silicate emission feature on M 82 and NGC 2023. This dissymetry in the composition of VSGs supports the suggestion that they are formed in grain-grain collisions where the behaviors of graphite and silicate grains are expected to be quite different.

Desert, F. X.↗
NASA NTRS1987

Ubiquitous high-FeO silicates in enstatite chondrites

SEM and EMPA were used to determine the mineral contents of four EH3 chondrites. All four showed the dominant enstatite peak, Fs 0-5, with 4-8 percent of FeO-rich pyroxene with Fs 5-20. Among the 542 objects found to contain high-FeO silicates, 18 were chondrules, 381 were rimmed or unrimmed grains, and 143 were aggregates. The high-FeO silicates in these objects are very largely pyroxene with Fs 5-23. Large grains of both FeO-rich and FeO-poor silicates were found to be present in the FeO-rich chondrules. This fact, together with the absence of clasts of FeO-rich chondritic material in the EH3 chondrites, suggests that FeO-rich grains were introduced before or during chondrule formation. It is concluded that FeO-rich and FeO-poor silicates were both present in the nebular region where E chondrites originated.

Lusby, David↗
NASA NTRS1990

Constraints on astronomical silicate dust

Numerical radiative-transfer models are used to discuss the properties of circumstellar dust grains around the premain-sequence star AB Aur (HD 31293). It is assumed that the dust consists of a silicate-graphite mixture with Draine and Lee (1984) optical properties. The modeling technique is to match the observed FUV through FIR energy distribution with the spectral energy distribution predicted for a spherical dust shell around a luminous hot star. Special attention is given to matching the observed 10-micron silicate emission feature and the observed circumstellar absorption curve at UV wavelengths, making it possible to strengthen constraints on dust-grain opacity and chemical composition. It is concluded that, although silicate grains can explain the observed 10-micron emission feature, the Draine and Lee silicate-graphite mixture cannot explain the observed FUV circumstellar absorption at the same time. The dust shell around AB Aur contains an additional population of small particles, the most likely candidate being amorphous carbon grains in a nonhydrogenated form.

Sorrell, Wilfred H.↗
NASA NTRS1990

The circumstellar dust envelopes of red giant stars. I - M giant stars with the 10-micron silicate emission band

Spherical dust envelope models of red giant stars are constructed by solving the radiative transfer equations of the generalized two-stream Eddington approximation. The IRAS observations of M giant stars which show the 10-micron silicate emission band in IRAS LRS spectra are explained by the models with the dirty silicate grains with K proportional to lambda exp -1.5 for lambda greather than 28 microns. Under the assumption of steady mass flow in the envelope, this model analysis gives the following conclusions: (1) the strength of the silicate emission peak at 10 microns is a good indicator of the mass loss rate of the star, (2) no stars with the 10-microns silicate emission feature are observed in the range of mass loss rate smaller than 7 x 10 to the -8th solar mass/yr, and (3) the characteristic time of the mass loss process of M stars does not exceed a few 10,000 years.

Hashimoto, O.↗