Experimental segregation of iron-nickel metal, iron-sulfide, and olivine in a thermal gradient: Preliminary results

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, J. H.

1993-01-01

Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.

Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

2012-09-01

Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

Metal-silicate interaction in quenched shock-induced melt of the Tenham L6-chondrite

NASA Astrophysics Data System (ADS)

Leroux, Hugues; Doukhan, Jean-Claude; Guyot, François

2000-07-01

The metal-silicate microstructures in the shock-induced melt pockets of the Tenham (L6) chondrite have been investigated by analytical transmission electron microscopy. The melt areas, formed under high-pressure, high-temperature dynamic shock conditions, consist of spherical Fe-Ni metal/iron sulfide globules embedded in a silicate glass matrix, showing that the melt was quenched at high cooling rate. The Fe-Ni fraction in the globules is two-phase, composed of a bcc phase (˜5 wt% Ni) and an fcc phase (˜49 wt% Ni), indicating that fractional crystallisation of the metal occurred during the fast cooling. The metal fraction also contains appreciable amounts of non-siderophile elements (mostly Si, Mg and O) suggesting that these elements were trapped in the metal, either as alloying components or as tiny silicate or oxide inclusions. In the iron sulfide fraction, the Na content is high (>3 wt%), suggesting chalcophile behaviour for Na during the shock event. The composition of the silicate glass reflects non-equilibrium melting of several silicate phases (olivine, pyroxene and plagioclase). Moreover, the FeO content is high compared to the FeO contents of the unmelted silicates. Some Fe redistribution took place between metal and silicate liquids during the shock event. The silicate glass also contains tiny iron sulfide precipitates which most probably originated by exsolution during quench, suggesting that the molten silicate retained significant amounts of S, dissolved at high temperature and high pressure. Based on these observations, we suggest that non-equilibrium phenomena may be important in determining the compositions of metal and silicate reservoirs during their differentiation.

Influence of dispersing agents and solution conditions on the solubility of crude kaolin.

PubMed

Zaman, Abbas A; Mathur, Sharad

2004-03-01

Experiments measuring the solubility of kaolin particles in terms of the concentration of aluminum and silicon ions in supernatant were carried out as a function of the pH of the slurry over a wide range of dosages of different dispersing agents varying from 0.5 to 12 mg/(g solids). The concentrations of the metal ions in supernatant were found to be strongly affected by the type and the dosage of the dispersants and pH of the solution. In this study, the mechanism of the reaction between the dispersing agents and kaolin particles was studied and the dissolution capacities of metal ions (aluminum and silicon) were identified from kaolin particles in the absence and presence of dispersing agents. The three anionic dispersing agents used were sodium polyacrylate (Na-PAA), sodium hexametaphosphate (Na-HMP), and sodium silicate (Na-silicate), based on the industrial application of these agents and their ability to produce a stable dispersion for this purpose.

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

The influence of oxalate-promoted growth of saponite and talc crystals

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2013-01-01

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge −0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC = 18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.

Corrosion resistant thermal barrier coating. [protecting gas turbines and other engine parts

NASA Technical Reports Server (NTRS)

Levine, S. R.; Miller, R. A.; Hodge, P. E. (Inventor)

1981-01-01

A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.

An empirical model to estimate density of sodium hydroxide solution: An activator of geopolymer concretes

NASA Astrophysics Data System (ADS)

Rajamane, N. P.; Nataraja, M. C.; Jeyalakshmi, R.; Nithiyanantham, S.

2016-02-01

Geopolymer concrete is zero-Portland cement concrete containing alumino-silicate based inorganic polymer as binder. The polymer is obtained by chemical activation of alumina and silica bearing materials, blast furnace slag by highly alkaline solutions such as hydroxide and silicates of alkali metals. Sodium hydroxide solutions of different concentrations are commonly used in making GPC mixes. Often, it is seen that sodium hydroxide solution of very high concentration is diluted with water to obtain SHS of desired concentration. While doing so it was observed that the solute particles of NaOH in SHS tend to occupy lower volumes as the degree of dilution increases. This aspect is discussed in this paper. The observed phenomenon needs to be understood while formulating the GPC mixes since this influences considerably the relationship between concentration and density of SHS. This paper suggests an empirical formula to relate density of SHS directly to concentration expressed by w/w.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applicationsa

PubMed Central

Li, M.; Kim, D.-P.; Jeong, G.-Y.; Seo, D.-K.; Park, C.-P.

2012-01-01

Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH2]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl4) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip. PMID:24324531

Spectroscopy `outside the box': Towards wider application of NMR to minerals and glasses with abundant paramagnetic cations - Fe, Ni, Co, and Cu silicates

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2017-12-01

Since the early applications of solid-state NMR (Nuclear Magnetic Resonance) to silicates in the early 1980's, this powerful method has been widely applied to problems of short- to medium-range structure, particularly for materials in which order/disorder is critical, such as crystalline solid solutions, glasses, and even melts. However, almost all such work has been on materials with low (< a few %) contents of ions with unpaired electron spins. Such spins interact strongly with NMR-observed nuclear spins, and can cause severe line broadening and loss of information, in some cases making spectra nearly unobservable. Many groups of minerals with abundant, paramagnetic transition metals (notably Fe2+) and rare earth cations, as well as wide, petrologically important ranges of glass composition have thus been excluded. Inspired by in-depth NMR studies of 31P, 7Li, and other nuclides in lithium-transition metal oxide and phosphate battery materials (C. Grey and others), and with some serendipitous discovery plus persistence to look far outside of "normal" parameter space, we have recently shown that high resolution, structurally informative spectra can actually be obtained for silicate, oxide, and phosphate solid solutions with moderate (0.1 up to 10%) contents of paramagnetic cations such as Fe2+, Ni2+, Co2+ and REE3+. Very recently we have extended this to observe some of the first quantitative NMR spectra of silicate minerals in which a paramagnetic transition metal is the major cation, obtaining useful data for a series of Cu2+ silicates, fayalite (Fe2SiO4) and Ni- and Co- equivalents of diopside (CaMSi2O6). New data for glasses of the latter compositions may be the first such accurate results for any transition metal-rich glass. Although we are still far from a detailed theoretical understanding of these data, the spectra for the glasses are quite different from those of the crystals, suggesting the possibility of medium-range ordering and clustering of NiO and CoO-rich regions. If this conclusion holds up, it may have major implications for thermodynamic models of activities of such components in melts, which in turn are important for a number of geothermometers and barometers based on mineral-melt partitioning.

Removal of copper (II) from aqueous solutions by flotation using polyaluminum chloride silicate (PAX-XL60 S) as coagulant and carbonate ion as activator.

PubMed

Ghazy, S E; Mahmoud, I A; Ragab, A H

2006-01-01

Flotation is a separation technology for removing toxic heavy metal ions from aqueous solutions. Here a simple and rapid flotation procedure is presented for the removal of copper(II) from aqueous solutions. It is based on the use of polyaluminum chloride silicate (PAX-XL60 S) as coagulant and flocculent, carbonate ion as activator and oleic acid (HOL) as surfactant. Both ion and precipitate flotation are included depending on the solution pH. Ion and precipitate flotation in the aqueous HOL-PAX-XL60 S-Cu2+-CO3(2-) system gave powerful preferential removal of Cu2+ (F -100%) over the HOL-PAX-XL60 S-Cu2+ system containing no CO3(2+) ion (F approximately 86%). The role of CO3(2-) ion is also evident from decreasing the dose of PAX-XL60 S from 700 mg l(-1) to 200 mg l(-1). The other parameters, influencing the flotation process, namely: metal ion, surfactant and PAX-XL60 S concentrations, ionic strength, temperature and foreign ions were examined. Moreover, the procedure was successfully applied to recover Cu2+ ions from different volumes up to 11 and from natural water samples.

Influence of Silicate Melt Composition on Metal/Silicate Partitioning of W, Ge, Ga and Ni

NASA Technical Reports Server (NTRS)

Singletary, S. J.; Domanik, K.; Drake, M. J.

2005-01-01

The depletion of the siderophile elements in the Earth's upper mantle relative to the chondritic meteorites is a geochemical imprint of core segregation. Therefore, metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle. The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. Several recent studies have shown the importance of silicate melt composition on the partitioning of siderophile elements between silicate and metallic liquids. It has been demonstrated that many elements display increased solubility in less polymerized (mafic) melts. However, the importance of silicate melt composition was believed to be minor compared to the influence of oxygen fugacity until studies showed that melt composition is an important factor at high pressures and temperatures. It was found that melt composition is also important for partitioning of high valency siderophile elements. Atmospheric experiments were conducted, varying only silicate melt composition, to assess the importance of silicate melt composition for the partitioning of W, Co and Ga and found that the valence of the dissolving species plays an important role in determining the effect of composition on solubility. In this study, we extend the data set to higher pressures and investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid.

Chemical-garden formation, morphology, and composition. II. Chemical gardens in microgravity.

PubMed

Cartwright, Julyan H E; Escribano, Bruno; Sainz-Díaz, C Ignacio; Stodieck, Louis S

2011-04-05

We studied the growth of metal-ion silicate chemical gardens under Earth gravity (1 g) and microgravity (μg) conditions. Identical sets of reaction chambers from an automated system (the Silicate Garden Habitat or SGHab) were used in both cases. The μg experiment was performed on board the International Space Station (ISS) within a temperature-controlled setup that provided still and video images of the experiment downlinked to the ground. Calcium chloride, manganese chloride, cobalt chloride, and nickel sulfate were used as seed salts in sodium silicate solutions of several concentrations. The formation and growth of osmotic envelopes and microtubes was much slower under μg conditions. In 1 g, buoyancy forces caused tubes to grow upward, whereas a random orientation for tube growth was found under μg conditions.

An Iron-Rain Model for Core Formation on Asteroid 4 Vesta

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Mittlefehldt, David W.

2016-01-01

Asteroid 4 Vesta is differentiated into a crust, mantle, and core, as demonstrated by studies of the eucrite and diogenite meteorites and by data from NASA's Dawn spacecraft. Most models for the differentiation and thermal evolution of Vesta assume that the metal phase completely melts within 20 degrees of the eutectic temperature, well before the onset of silicate melting. In such a model, core formation initially happens by Darcy flow, but this is an inefficient process for liquid metal and solid silicate. However, the likely chemical composition of Vesta, similar to H chondrites with perhaps some CM or CV chondrite, has 13-16 weight percent S. For such compositions, metal-sulfide melting will not be complete until a temperature of at least 1350 degrees Centigrade. The silicate solidus for Vesta's composition is between 1100 and 1150 degrees Centigrade, and thus metal and silicate melting must have substantially overlapped in time on Vesta. In this chemically and physically more likely view of Vesta's evolution, metal sulfide drops will sink by Stokes flow through the partially molten silicate magma ocean in a process that can be envisioned as "iron rain". Measurements of eucrites show that moderately siderophile elements such as Ni, Mo, and W reached chemical equilibrium between the metal and silicate phases, which is an important test for any Vesta differentiation model. The equilibration time is a function of the initial metal grain size, which we take to be 25-45 microns based on recent measurements of H6 chondrites. For these sizes and reasonable silicate magma viscosities, equilibration occurs after a fall distance of just a few meters through the magma ocean. Although metal drops may grow in size by merger with other drops, which increases their settling velocities and decreases the total core formation time, the short equilibration distance ensures that the moderately siderophile elements will reach chemical equilibrium between metal and silicate before metal drop merger becomes important. In this model, there must be at least 30 percent melting of the silicate phase when metal melting is complete, corresponding to a crust thickness of at least 30 kilometers on Vesta, consistent with Dawn gravity observations. Greater degrees of silicate melting and a correspondingly thicker crust are possible if Vesta accreted sufficiently rapidly.

Deep-Earth Equilibration between Molten Iron and Solid Silicates

NASA Astrophysics Data System (ADS)

Brennan, M.; Zurkowski, C. C.; Chidester, B.; Campbell, A.

2017-12-01

Elemental partitioning between iron-rich metals and silicate minerals influences the properties of Earth's deep interior, and is ultimately responsible for the nature of the core-mantle boundary. These interactions between molten iron and solid silicates were influential during planetary accretion, and persist today between the mantle and liquid outer core. Here we report the results of diamond anvil cell experiments at lower mantle conditions (40 GPa, >2500 K) aimed at examining systems containing a mixture of metals (iron or Fe-16Si alloy) and silicates (peridotite). The experiments were conducted at pressure-temperature conditions above the metallic liquidus but below the silicate solidus, and the recovered samples were analyzed by FIB/SEM with EDS to record the compositions of the coexisting phases. Each sample formed a three-phase equilibrium between bridgmanite, Fe-rich metallic melt, and an oxide. In one experiment, using pure Fe, the quenched metal contained 6 weight percent O, and the coexisting oxide was ferropericlase. The second experiment, using Fe-Si alloy, was highly reducing; its metal contained 10 wt% Si, and the coexisting mineral was stishovite. The distinct mineralogies of the two experiments derived from their different starting metals. These results imply that metallic composition is an important factor in determining the products of mixed phase iron-silicate reactions. The properties of deep-Earth interfaces such as the core-mantle boundary could be strongly affected by their metallic components.

The effect of melt composition on metal-silicate partitioning of siderophile elements and constraints on core formation in the angrite parent body

NASA Astrophysics Data System (ADS)

Steenstra, E. S.; Sitabi, A. B.; Lin, Y. H.; Rai, N.; Knibbe, J. S.; Berndt, J.; Matveev, S.; van Westrenen, W.

2017-09-01

We present 275 new metal-silicate partition coefficients for P, S, V, Cr, Mn, Co, Ni, Ge, Mo, and W obtained at moderate P (1.5 GPa) and high T (1683-1883 K). We investigate the effect of silicate melt composition using four end member silicate melt compositions. We identify possible silicate melt dependencies of the metal-silicate partitioning of lower valence elements Ni, Ge and V, elements that are usually assumed to remain unaffected by changes in silicate melt composition. Results for the other elements are consistent with the dependence of their metal-silicate partition coefficients on the individual major oxide components of the silicate melt composition suggested by recently reported parameterizations and theoretical considerations. Using multiple linear regression, we parameterize compiled metal-silicate partitioning results including our new data and report revised expressions that predict their metal-silicate partitioning behavior as a function of P-T-X-fO2. We apply these results to constrain the conditions that prevailed during core formation in the angrite parent body (APB). Our results suggest the siderophile element depletions in angrite meteorites are consistent with a CV bulk composition and constrain APB core formation to have occurred at mildly reducing conditions of 1.4 ± 0.5 log units below the iron-wüstite buffer (ΔIW), corresponding to a APB core mass of 18 ± 11%. The core mass range is constrained to 21 ± 8 mass% if light elements (S and/or C) are assumed to reside in the APB core. Incorporation of light elements in the APB core does not yield significantly different redox states for APB core-mantle differentiation. The inferred redox state is in excellent agreement with independent fO2 estimates recorded by pyroxene and olivine in angrites.

Core formation in the shergottite parent body and comparison with the earth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Treiman, A.H.; Jones, J.H.; Drake, M.J.

1987-03-30

The mantle of the shergottite parent body (SPB) is depleted relative to the bulk SPB in siderophile and chalcophile elements; these elements are inferred to reside in the SPB's core. Our chemical model of these depletions rests on a physically plausible process of segregation of partially molten metal form partially molten silicates as the SPB grows and is heated above silicate and metallic solidi during accretion. Metallic and silicate phases equilibrate at low pressures as new material is accreted to the SPB surface. Later movement of the metallic phases to the planet's center is so rapid that high-pressure equilibration ismore » insignificant. Partitioning of siderophile and chalcophile elements among solid and liquid metal and silicate determines their abundances in the SPB mantle. Using partition coefficients and the SPB mantle composition determined in earlier studies, we model the abundances of Ag, Au, Co, Ga, Mo, Ni, P, Re, S, and W with free parameters being oxygen fugacity, proportion of solid metal formed, proportion of metallic liquid formed, and proportion of silicate that is molten.« less

Rice husks as a sustainable silica source for hierarchical flower-like metal silicate architectures assembled into ultrathin nanosheets for adsorption and catalysis.

PubMed

Zhang, Shouwei; Gao, Huihui; Li, Jiaxing; Huang, Yongshun; Alsaedi, Ahmed; Hayat, Tasawar; Xu, Xijin; Wang, Xiangke

2017-01-05

Metal silicates have attracted extensive interests due to their unique structure and promising properties in adsorption and catalysis. However, their applications were hampered by the complex and expensive synthesis. In this paper, three-dimensional (3D) hierarchical flower-like metal silicate, including magnesium silicate, zinc silicate, nickel silicate and cobalt silicate, were for the first time prepared by using rice husks as a sustainable silicon source. The flower-like morphology, interconnected ultrathin nanosheets structure and high specific surface area endowed them with versatile applications. Magnesium silicate was used as an adsorbent with the maximum adsorption capacities of 557.9, 381.3, and 482.8mg/g for Pb 2+ , tetracycline (TC), and UO 2 2+ , respectively. Ni nanoparticles/silica (Ni NPs/SiO 2 ) exhibited high catalytic activity and good stability for 4-nitrophenol (4-NP) reduction within only ∼160s, which can be attributed to the ultra-small particle size (∼6.8nm), good dispersion and high loading capacity of Ni NPs. Considering the abundance and renewability of rice husks, metal silicate with complex architecture can be easily produced at a large scale and become a sustainable and reliable resource for multifunctional applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Impact-melt origin for the Simondium, Pinnaroo, and Hainholz mesosiderites: implicatiions for impact processes beyond the Earth--Moon system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Floran, R J; Caulfield, J B.D.; Harlow, G E

The Simondium, Pinnaroo, and Hainholz mesosiderites are interpreted to be clast-laden impact melts that crystallized from immiscible silicate, metallic (Fe-FeS) liquids. The existence of silicate melts is shown by intergranular basaltic textures. Metallic melts are inferred on the basis of smooth boundaries between metal and troilite and the occurrence of troilite as anastomosing areas that radiate outward into the silicate fractions. These relations suggest that troilite crystallized after silicates, concentrating as a late-stage residuum. Evidence for impact melting includes: diversity and abundance of clast types (mineral, metal, lithic) in various stages of recrystallization and assimilation; differences in mineral chemistries betweenmore » clasts and igneous-textured matrix silicates; unusual metal plus silicate bulk composition. Silicate clasts consist primarily of orthopyroxene and minor olivine with a range of Fe/Fe + Mg ratios, anorthitic plagioclase, and rare orthopyroxenite (diogenite) fragments. Substantial amounts of Fe-Ni metal were melted during the impact events and minor amounts were incorporated into the melts as clasts. The clast populations suggest that at least four rock types were melted and mixed: (a) diogenite, (b) a plagioclase-rich source, possibly cumulate eucrite, (c) dunite, and (d) metal. Most orthopyroxene appears to have been derived from fragmentation of diogenites. Orthopyroxene (En/sub 82-61/) and olivine (Fo/sub 86-67/) clasts include much material unsampled as individual meteorites and probably represent a variety of source rocks.« less

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

Metal/Silicate Partitioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition

NASA Technical Reports Server (NTRS)

Bailey, Edward; Drake, Michael J.

2004-01-01

The distinctive pattern of element concentrations in the upper mantle provides essential evidence in our attempts to understand the accretion and differentiation of the Earth (e.g., Drake and Righter, 2002; Jones and Drake, 1986; Righter et al., 1997; Wanke 1981). Core formation is best investigated through use of metal/silicate partition coefficients for siderophile elements. The variables influencing partition coefficients are temperature, pressure, the major element compositions of the silicate and metal phases, and oxygen fugacity. Examples of studies investigating the effects of these variables on partitioning behavior are: composition of the metal phase by Capobianco et al. (1999) and Righter et al. (1997); silicate melt composition by Watson (1976), Walter and Thibault (1995), Hillgren et al. (1996), Jana and Walker (1997), and Jaeger and Drake (2000); and oxygen fugacity by Capobianco et al. (1999), and Walter and Thibault (1995). Here we address the relative influences of silicate melt composition, pressure and temperature.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

Metamorphic reactions in mesosiderites - Origin of abundant phosphate and silica

NASA Technical Reports Server (NTRS)

Harlow, G. E.; Delaney, J. S.; Prinz, M.; Nehru, C. E.

1982-01-01

In light of a study of the Emery mesosiderite, it is determined that the high modal abundances of merrillite and tridymite in most mesosiderites are attributable to redox reactions between silicates and P-bearing Fe-Ni metal within a limited T-fO2 range at low pressure. The recalculated amounts of dissolved P and S in the metallic portion of Emery reduce the metal liquidus temperature to less than 1350 C, and the solidus to less than 800 C, so that the mixing of liquid metal with cold silicates would have resulted in silicate metamorphism rather than melting. This redox reaction and redistribution of components between metal and silicates illuminates the complexities of mesosiderite processing, with a view to the recalculation of their original components.

Si and O partitioning between core metal and lower mantle minerals during core formation

NASA Astrophysics Data System (ADS)

Nakajima, Y.; Frost, D. J.; Rubie, D. C.

2010-12-01

In addition to Fe and Ni, the Earth’s core contains light alloying elements (e.g., H, C, O, Si, and/or S) in order to explain the 10% core density deficit (e.g., Birch, 1964, JGR). Experimental data on the partitioning behavior of siderophile elements such as Ni and Co between liquid Fe and mantle minerals indicate that equilibration between core-forming metal and a silicate magma ocean likely occurred at lower-mantle pressures (e.g., Li and Agee, 1996 Nature). If core-mantle differentiation has occurred under such conditions, significant quantities of O or Si could have entered the core. At these conditions the nature of the dominant light element in the core will depend strongly on the oxygen fugacity at which equilibration occurred. High pressure experiments were carried out at 25 GPa and 2400-2950 K using a Kawai-type multi-anvil apparatus in order to investigate the partitioning of Si and O between liquid Fe and (Mg,Fe)SiO3 perovskite (Pv), silicate melt, and (Mg,Fe)O ferropericlace (Fp). Starting materials consisting of metallic Fe (+-Si) and olivine (Fo70-95) were contained in single-crystal MgO capsules. Over the oxygen fugacity range IW-0.5 to -3, the Si molar partition coefficient D* (= [Si]metal /[Si]silicate) between metal and Pv increases linearly with decreasing oxygen fugacity at a fixed given temperature. The partition coefficient between metal and silicate melt is of a similar magnitude but is less dependent on the oxygen fugacity. The obtained oxygen distribution coefficient Kd (= [Fe]metal[O]metal /[FeO]Fp) is in agreement with that determined in the Fe-Fp binary system (Asahara et al., 2007 EPSL) below the silicate liquidus temperature. In contrast, a correlation between the O partitioning and Si concentration in Fe is observed above 2700 K where liquid metal coexists with silicate melt + Fp. With an increasing concentration of Si in the liquid metal, O partitioning into Fp is strongly enhanced. Five atomic% Si in the metal reduces the metal-silicate O partition coefficient by about 1 order magnitude. Near the base of a deep magma ocean where pressures exceed 20 GPa, liquid metal could have coexisted with silicate melt, Pv, and Fp. Our results show that Si would readily partitioned into core-forming metal from both perovskite and silicate liquid at a relevant oxygen fugacity (e.g., IW-2). Simultaneously, the Si solubility would hinder the dissolution of O in the liquid metal. This implies that the presence of Si in liquid metal must be included in models of O partitioning.

Partial Melting of the Indarch (EH4) Meteorite : A Textural, Chemical and Phase Relations View of Melting and Melt Migration

NASA Technical Reports Server (NTRS)

McCoy, Timothy J.; Dickinson, Tamara L.; Lofgren, Gary E.

2000-01-01

To Test whether Aubrites can be formed by melting of enstatite Chondrites and to understand igneous processes at very low oxygen fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000-1500 C. Silicate melting begins at 1000 C. Substantial melt migration occurs at 1300-1400 C and metal migrates out of the silicate change at 1450 C and approx. 50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts 9Si-, and C-rich), two immiscible sulfide melts(Fe-and FeMgMnCa-rich) and Silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite Chondrite suggest that igneous processes at low fO2 exhibit serveral unique features. The complete melting of sulfides at 1000 C suggest that aubritic sulfides are not relicts. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO2. This exchange may help explain the formation of aubrites from known enstatite chondrites.

Genesis of IIICD Iron Meteorites: Evidence From Silicate Inclusions

NASA Astrophysics Data System (ADS)

McCoy, T. J.; Keil, K.; Scott, E. R. D.; Haack, H.

1992-07-01

The IAB and IIICD iron meteorite groups exhibit much larger ranges in siderophile concentrations than other groups and commonly contain silicate inclusions. Extensive studies of metal in both groups and silicates in IAB irons have led to a variety of ideas to explain the genesis of these groups. Wasson et al. (1980) envision each meteorite forming in a separate impact melt pool. Kracher (1982, 1985) suggested that the siderophile trends might result from fractional crystallization of both metal and troilite in a S-saturated magma. A role for oxidation-reduction in these groups has been proposed by Scott and Bild (1974). Similarities in siderophile elemental trends indicate that IIICD metal has a similar origin, although data on silicate inclusions in IIICD irons are scarce (Ramdohr, 1973; Scott and Bild, 1974; Kracher and Kurat, 1977; Prinz et al., 1982; Clayton et al., 1983). We report the first detailed study of silicate inclusions in IIICD iron meteorites in an attempt to elucidate their history. We have studied the only silicate-bearing IIICD irons - Carlton, Dayton, and the recently reported Maltahohe. Silicate-graphite-phosphate inclusions comprise at most a few percent of the bulk meteorite, and silicates comprise <25 vol% of the inclusion. Silicate mineralogy and chemistry vary systematically with increasing M content of the metal. Maltahohe (10.7 wt% Ni) and Carlton (13.0%) contain olivine, pyroxene, and plagioclase, whereas Dayton (17.0%) contains pyroxene, plagioclase, and SiO2. Pyroxene becomes more FeO-rich from Maltahohe (FS(sub)7.8) to Carlton (Fs(sub)9.7) to Dayton (Fs(sub)11.6). Inverse FeO zoning in silicates and lower Fa than Fs indicate reduction in all three meteorites. Plagioclase compositions in IIICD (An(sub)1.1-4.9) are lower than IAB (An(sub)9.2-2l.5) and uncorrelated with Ni content. The abundances of associated phases also vary. Graphite comprises ~25 vol% of Maltahohe silicate inclusions, but only a few percent in Carlton, and is absent in Dayton silicate inclusions. Phosphate mineralogy and modal abundance also vary, with phosphates absent in Maltahohe, chlorapatite comprising 0-70 vol% of inclusions in Carlton, and the unusual phosphates brianite and panethite, along with whitlockite, comprising up to 55 vol% of Dayton's inclusions. The small number of silicate-bearing IIICD irons require that any conclusions must be considered tentative. The precursor silicate assemblage was similar for IAB and IIICD, as suggested by the general similarity between Maltahohe and IAB silicate inclusions. With increasing Ni contents, however, IIICD and IAB silicate inclusions become dramatically different, as indicated by the mineralogical and chemical trends present in IIICD and absent in IAB silicate inclusions. Silicate inclusions in the Ni-rich IAB irons (e.g., San Cristobal, 25 wt% Ni) do not resemble the phosphate-rich, evolved-silicate assemblages observed in Dayton. It is clear that one or more processes were capable of producing changes in metal compositions and silicate inclusion mineralogy, which correlated with one another. None of the observed trends in silicate mineralogy are predicted by the impact-melt model, although impact might have played a role in mixing silicates into the metallic magma. Some trends are consistent with oxidation-reduction, but variations in some siderophiles (e.g., Ir, Cu) cannot be explained easily by this mechanism. We believe that solid silicates must have been mixed with an evolving metallic melt, with the metallic magma dramatically influencing the mineralogy and chemistry of the inclusion, similar to the fractional crystallization model of Kracher (1982,1985). However, many details of this process remain obscure, including the mechanism that concentrated a S-rich melt, the mixing of metal and silicates, and the fractionation of S. References: Clayton et al. (1983) EPSL 65, 229-232. Kracher (1982) GRL 9, 412-415. Kracher (1985) PLPSC 15, C689-C698. Kracher and Kurat (1977) Meteoritics 12, 282-283. Scott and Bild (1974) GCA 38, 1379-1391. Prinz et al. (1982) LPSC XIlI, 632-633. Ramdohr (1973) Elsevier Pub. Co. Wasson et al. (1980) Z. Naturforsch. 35a, 781-795.

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

NASA Technical Reports Server (NTRS)

King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2010-01-01

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate?

NASA Technical Reports Server (NTRS)

Righter, Kevin

2006-01-01

Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated.

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

NASA Technical Reports Server (NTRS)

Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.

2010-01-01

The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

Tharsis Formation by Chemical Plume Due to Giant Impact Event

NASA Astrophysics Data System (ADS)

Fleck, J.; Weeraratne, D. S.; Olson, P.

2014-12-01

Tharsis formed early in the history of Mars, likely during the Noachian but later than the hemispheric crustal dichotomy that it partially overprints (Johnson and Phillips, 2005; Solomon et al., 2005; Wenzel et al., 2004). It has been suggested that the crustal dichotomy may have been formed by a giant impact (Andrews-Hanna et al., 2008; Marinova et al., 2008; Nimmo et al., 2008). Several models have been proposed to explain a localized orogeny, but predict multiple, evenly-spaced plumes or have instability growth and rise times which are longer than Tharsis formation. We use fluid dynamic experiments to model the differentiation process during Mars accretion using low viscosity glucose syrup solutions and an emulsion of liquid gallium for the metal-rich magma ocean and a high viscosity glucose syrup for the mantle. Our experiments demonstrate the formation of metal-silicate diapirs from metal emulsion drops that form a pond at the base of the magma ocean. The diapirs descend through the underlying mantle with trailing conduit of low viscosity silicate material. The silicate material is buoyant and eventually ascends back through the conduit. Remaining emulsion drops that do not adhere with the diapir fall through the conduit, forcing the buoyant molten silicate material to exit the conduit laterally and ascend along a new trajectory. The time elapsed between diapir formation and ascent of the chemical plume in experiments scales with the time between the formation of the crustal dichotomy on Mars and the formation of Tharsis. Our model offers an explanation for the rapid formation of Tharsis on the edge of the crustal dichotomy via a single large upwelling event followed by smaller upwellings producing and the late stages of effusive volcanism observed in the Tharsis region.

Metal silicate mixtures - Spectral properties and applications to asteroid taxonomy

NASA Technical Reports Server (NTRS)

Cloutis, Edward A.; Smith, Dorian G. W.; Lambert, Richard St. J.; Gaffey, Michael J.

1990-01-01

The reflectance spectra of combinations of olivine, orthopyroxene, and iron meteorite metal are experimentally studied, and the obtained variations in spectral properties are used to constrain the physical and chemical properties of the assemblages. The presence of metal most noticeably affects band area ratios, peak-to-peak and peak-to-minimum reflectance ratios, and band widths. Band width and band areas are useful for determining metal abundance in olivine and metal and orthopyroxene and metal assemblages, respectively. Mafic silicate grain size variations are best determined using band depth criteria. Band centers are most useful for determining mafic silicate composition. An application of these parameters to the S-class asteroid Flora is presented.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions.

PubMed

Bennett, Neil R; Brenan, James M; Fei, Yingwei

2015-06-13

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

PubMed Central

Bennett, Neil R.; Brenan, James M.; Fei, Yingwei

2015-01-01

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied. PMID:26132380

The role of interfacial metal silicates on the magnetism in FeCo/SiO 2 and Fe 49% Co 49% V 2% /SiO 2 core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desautels, R. D.; Freeland, J. W.; Rowe, M. P.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less

Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Mittlefehldt, David W.

2017-01-01

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft, suggest that Vesta resembles H chondrites in bulk chemical composition, possibly with about 25% of a CM-chondrite like composition added in. For this model, the core is 15% by mass (or 8 volume %) of the asteroid. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. Melting in the Fe-Ni-S system begins at a cotectic temperature of 940 deg. C. Only about 40% of the total metal phase, or 3-4 volume % of Vesta, melts prior to the onset of silicate melting. Liquid iron in solid silicate initially forms isolated pockets of melt; connected melt channels, which are necessary if the metal is to segregate from the silicate, are only possible when the metal phase exceeds about 5 volume %. Thus, metal segregation to form a core does not occur prior to the onset of silicate melting.

Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

NASA Technical Reports Server (NTRS)

Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.

2012-01-01

The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au, Ru and Pd in minerals (olivine and diopside) and in silicate melts, but also to characterize the sizes, density and chemistry of HSE nuggets when present in the samples.

Copper solubility in a basaltic melt and sulfide liquid/silicate melt partition coefficients of Cu and Fe

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.; Li, Chusi

2002-09-01

The solubility of copper in a sulfur-saturated basaltic melt has been determined at 1245°C as a function of fO 2 and fS 2. Copper solubilities at log fO 2 values between -8 and -11 fall into two distinct populations as a function of fS 2. At log fS 2 values < -1.65, sulfide liquid that coexists with the basaltic glass quenches to sulfur-poor bornite solid solution. At log fS 2 values in excess of -1.65, the sulfide liquid quenches to a complex intergrowth of sulfur-rich bornite and intermediate solid solution. Copper solubilities in the low-fS 2 population range from 594 to 1550 ppm, whereas those in the high-fS 2 population range from 80 to 768 ppm. Sulfide liquid/silicate liquid partition coefficients (D) for Cu and Fe range from 480 to 1303 and 0.7 to 13.6, respectively. Metal-sulfur complexing in the silicate liquid is shown to be insignificant relative to metal-oxide complexing for Fe but permissible for Cu at high fS 2 values. On log D Fe (sulfide-silicate) and log D Cu (sulfide-silicate) vs. 1/2 (log fS 2 - log fO 2) diagrams, both fS 2 populations show distinct but parallel trends. The observation of two D values for any fS 2/fO 2 ratio indicates nonideal mixing of species involved in the exchange reaction. The two distinct trends observed for both Cu and Fe are thought to be due to variations in activity coefficient ratios (e.g., γ FeO/γ FeS and γ CuO 0.5/γ CuS 0.5). Results of the experiments suggest that accurate assessments of fS 2/fO 2 ratios are required for the successful numerical modeling of processes such as the partial melting of sulfide-bearing mantle and the crystallization of sulfide-bearing magmas, as well as the interpretation of sulfide mineralogical zoning. In addition, the experiments provide evidence for oxide or oxy-sulfide complexing for Cu in silicate magmas and suggest that the introduction of externally derived sulfur to mafic magma may be an important process for the formation of Cu-rich disseminated magmatic sulfide ore deposits.

REM-containing silicate concentrates

NASA Astrophysics Data System (ADS)

Pavlov, V. F.; Shabanova, O. V.; Pavlov, I. V.; Pavlov, M. V.; Shabanov, A. V.

2016-01-01

A new method of advanced complex processing of ores containing rare-earth elements (REE) is proposed to obtain porous X-ray amorphous aluminosilicate material with a stable chemical composition which concentrates oxides of rare-earth metals (REM). The ferromanganese oxide ores of Chuktukon deposit (Krasnoyarsk Region, RF) were used for the experiment. The obtained aluminosilicate material is appropriate for treatment with 5 - 15% solutions of mineral acids to leach REM.

Regenerable sorbents for CO.sub.2 capture from moderate and high temperature gas streams

DOEpatents

Siriwardane, Ranjani V [Morgantown, WV

2008-01-01

A process for making a granular sorbent to capture carbon dioxide from gas streams comprising homogeneously mixing an alkali metal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxide, alkali titanate, alkali zirconate, alkali silicate and combinations thereof with a binder selected from the group consisting of sodium ortho silicate, calcium sulfate dihydrate (CaSO.sub.4.2H.sub.2O), alkali silicates, calcium aluminate, bentonite, inorganic clays and organic clays and combinations thereof and water; drying the mixture and placing the sorbent in a container permeable to a gas stream.

Final report on the safety assessment of potassium silicate, sodium metasilicate, and sodium silicate.

PubMed

Elmore, Amy R

2005-01-01

Potassium Silicate, Sodium Metasilicate, and Sodium Silicate combine metal cations with silica to form inorganic salts used as corrosion inhibitors in cosmetics. Sodium Metasilicate also functions as a chelating agent and Sodium Silicate as a buffering and pH adjuster. Sodium Metasilicate is currently used in 168 formulations at concentrations ranging from 13% to 18%. Sodium Silicate is currently used in 24 formulations at concentrations ranging from 0.3% to 55%. Potassium Silicate and Sodium Silicate have been reported as being used in industrial cleaners and detergents. Sodium Metasilicate is a GRAS (generally regarded as safe) food ingredient. Aqueous solutions of Sodium Silicate species are a part of a chemical continuum of silicates based on an equilibrium of alkali, water, and silica. pH determines the solubility of silica and, together with concentration, determines the degree of polymerization. Sodium Silicate administered orally is readily absorbed from the alimentary canal and excreted in the urine. The toxicity of these silicates has been related to the molar ratio of SiO2/Na2O and the concentration being used. The Sodium Metasilicate acute oral LD50 ranged from 847 mg/kg in male rats to 1349.3 mg/kg in female rats and from 770 mg/kg in female mice to 820 mg/kg in male mice. Gross lesions of variable severity were found in the oral cavity, pharynx, esophagus, stomach, larynx, lungs, and kidneys of dogs receiving 0.25 g/kg or more of a commercial detergent containing Sodium Metasilicate; similar lesions were also seen in pigs administered the same detergent and dose. Male rats orally administered 464 mg/kg of a 20% solution containing either 2.0 or 2.4 to 1.0 ratio of sodium oxide showed no signs of toxicity, whereas doses of 1000 and 2150 mg/kg produced gasping, dypsnea, and acute depression. Dogs fed 2.4 g/kg/day of Sodium Silicate for 4 weeks had gross renal lesions but no impairment of renal function. Dermal irritation of Potassium Silicate, Sodium Metasilicate, and Sodium Silicate ranged from negligible to severe, depending on the species tested and the molar ratio and concentration tested. Sodium Metasilicate was negative in the local lymph node assay (LLNA), but a delayed-type hypersensitivity response was observed in mice. Potassium Silicate was nonirritating in two acute eye irritation studies in rabbits. Sodium Metasilicate (42.4% H2O) was corrosive to the rabbit eye. Sodium Silicate was a severe eye irritant in some eye irritation studies, but was irritating or nonirritating in others. A skin freshener containing Sodium Silicate was nonirritating. Sodium Metasilicate was nonmutagenic in bacterial cells. Rats given Sodium Silicate (600 and 1200 ppm of added silica) in the drinking water in reproductive studies produced a reduced number of offspring: to 67% of controls at 600 ppm and to 80% of controls at 1200 ppm. Three adult rats injected intratesticularly and subcutaneously with 0.8 mM/kg of Sodium Silicate showed no morphological changes in the testes and no effect on the residual spermatozoa in the ductus deferens. Sodium Metasilicate (37% in a detergent) mixed with water was a severe skin irritant when tested on intact and abraded human skin, but 6%, 7%, and 13% Sodium Silicate were negligible skin irritants to intact and abraded human skin. Sodium Silicate (10% of a 40% aqueous solution) was negative in a repeat-insult predictive patch test in humans. The same aqueous solution of Sodium Silicate was considered a mild irritant under normal use conditions in a study of cumulative irritant properties. The Cosmetic Ingredient Review (CIR) Expert Panel recognized the irritation potential of these ingredients, especially in leave-on products. However, because these ingredients have limited dermal absorption and Sodium Metasilicate is a GRAS direct food substance, the Panel deemed the ingredients safe for use in cosmetic products in the practices of use and concentration described in this safety assessment, when formulated to avoid irritation.

Protecting health.

PubMed

Armour, Margaret-Ann; Linetsky, Asya; Ashick, Donna

2008-10-01

Water-soluble heavy metal salts injure health when they leach into water supplies. It is important that students who may later be employed in industries generating aqueous solutions of such salts are aware of the methods that can be used to recover the metal salt or transform it to non-health threatening products. The research was in the management of small quantities of hazardous wastes, such as are generated in school, college, and university teaching laboratories; in research laboratories; in industrial quality control and testing laboratories; and in small industries. Methods for the recovery of silver, nickel, and cobalt salts from relatively small volumes of aqueous solutions of their soluble salts were developed and tested. Where it was not practical to recover the metal salt, the practice has been to convert it to a water-insoluble salt, often the sulfide. This requires the use of highly toxic reagents. It was found that a number of heavy metal salts can be precipitated as the silicates, returning them to the form in which they are found in the natural ore. These salts show similar solubility properties to the sulfides in neutral, acidic, and basic aqueous solutions. The work has determined the conditions, quantities, and solution acidity that result in the most effective precipitation of the heavy metal salt. The concentration of the metal ions remaining in solution was measured by AA and ICP spectrometry. Specific methods have been developed for the conversion of salts of mercury and chromium to nonsoluble products.

Partitioning of Mo, P and other siderophile elements (Cu, Ga, Sn, Ni, Co, Cr, Mn, V, and W) between metal and silicate melt as a function of temperature and silicate melt composition

NASA Astrophysics Data System (ADS)

Righter, K.; Pando, K. M.; Danielson, L.; Lee, Cin-Ty

2010-03-01

Metal-silicate partition coefficients can provide information about the earliest differentiation histories of terrestrial planets and asteroids. Systematic studies of the effects of key parameters such as temperature and melt composition are lacking for many elements. In particular, data for Mo is scarce, but given its refractory nature, is of great value in interpreting metal-silicate equilibrium. Two series of experiments have been carried out to study Mo and P partitioning between Fe metallic liquid and basaltic to peridotitic silicate melt, at 1 GPa and temperatures between 1500 and 1900 °C. Because the silicate melt utilized was natural basalt, there are also measurable quantities of 9 other siderophile elements (Ni, Co, W, Sn, Cu, Mn, V, Cr, Ga and Zn). The Ni and Co data can be used to assess consistency with previous studies. In addition, the new data also allow a first systematic look at the temperature dependence of Cu, Ga, Sn, Cr, Mn V and W for basaltic to peridotitic melts. Many elements exhibit an increase in siderophile behavior at higher temperature, contrary to popular belief, but consistent with predictions from thermodynamics. Using these new data we examine DMomet/sil and DPmet/sil in detail and show that increasing temperature causes a decrease in the former and an increase in the latter, whereas both increase with MgO content of the silicate melt. The depletions of Mo and P in the mantle of the Earth can be explained by metal-silicate equilibrium at magma ocean conditions — both elements are satisfied at PT conditions of an intermediate depth magma ocean for the Earth 22.5 GPa and 2400 °C.

Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Drake, M. J.

1983-01-01

An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth's mantle

NASA Astrophysics Data System (ADS)

Mann, Ute; Frost, Daniel J.; Rubie, David C.; Becker, Harry; Audétat, Andreas

2012-05-01

The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal-silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5-18 GPa and 2423-2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2-98.9 wt% (XFe = 0.03-0.67) such that oxygen fugacities of IW - 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1-119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized. The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ˜6 GPa and much weaker in the range 6-18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P-T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60-80 GPa) we conclude that the P-T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal-silicate equilibration at a common set of P-T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35-50 GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60 GPa in the late stage of accretion. With most of the HSE partition coefficients at 60 GPa still differing by 0.5-3 orders of magnitude, metal-silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal-silicate partitioning as well as an overprint by late accretion.

Hydration of dicalcium silicate and diffusion through neo-formed calcium-silicate-hydrates at weathered surfaces control the long-term leaching behaviour of basic oxygen furnace (BOF) steelmaking slag.

PubMed

Stewart, Douglas I; Bray, Andrew W; Udoma, Gideon; Hobson, Andrew J; Mayes, William M; Rogerson, Mike; Burke, Ian T

2018-04-01

Alkalinity generation and toxic trace metal (such as vanadium) leaching from basic oxygen furnace (BOF) steel slag particles must be properly understood and managed by pre-conditioning if beneficial reuse of slag is to be maximised. Water leaching under aerated conditions was investigated using fresh BOF slag at three different particle sizes (0.5-1.0, 2-5 and 10 × 10 × 20 mm blocks) and a 6-month pre-weathered block. There were several distinct leaching stages observed over time associated with different phases controlling the solution chemistry: (1) free-lime (CaO) dissolution (days 0-2); (2) dicalcium silicate (Ca 2 SiO 4 ) dissolution (days 2-14) and (3) Ca-Si-H and CaCO 3 formation and subsequent dissolution (days 14-73). Experiments with the smallest size fraction resulted in the highest Ca, Si and V concentrations, highlighting the role of surface area in controlling initial leaching. After ~2 weeks, the solution Ca/Si ratio (0.7-0.9) evolved to equal those found within a Ca-Si-H phase that replaced dicalcium silicate and free-lime phases in a 30- to 150-μm altered surface region. V release was a two-stage process; initially, V was released by dicalcium silicate dissolution, but V also isomorphically substituted for Si into the neo-formed Ca-Si-H in the alteration zone. Therefore, on longer timescales, the release of V to solution was primarily controlled by considerably slower Ca-Si-H dissolution rates, which decreased the rate of V release by an order of magnitude. Overall, the results indicate that the BOF slag leaching mechanism evolves from a situation initially dominated by rapid hydration and dissolution of primary dicalcium silicate/free-lime phases, to a slow diffusion limited process controlled by the solubility of secondary Ca-Si-H and CaCO 3 phases that replace and cover more reactive primary slag phases at particle surfaces.

The role of interfacial metal silicates on the magnetism in FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desautels, R. D., E-mail: rddesautels@physics.umanitoba.ca; Toyota Research Institute of North America, Ann Arbor, Michigan 48169; Freeland, J. W.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, andmore » vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.« less

Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

NASA Technical Reports Server (NTRS)

Righter, K.; Ghiorso, M.

2009-01-01

Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

2016-02-01

The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations between the silicate mantle and metallic core of terrestrial planetary bodies would depend on the average pressure at which their core-mantle differentiation occurred.

Oxidation of the Ru(0001) surface covered by weakly bound, ultrathin silicate films

DOE PAGES

Emmez, Emre; Anibal Boscoboinik, J.; Tenney, Samuel; ...

2015-06-30

Bilayer silicate films grown on metal substrates are weakly bound to the metal surfaces, which allows ambient gas molecules to intercalate the oxide/metal interface. In this work, we studied the interaction of oxygen with Ru(0001) supported ultrathin silicate and aluminosilicate films at elevated O 2 pressures (10 -5–10 mbar) and temperatures (450–923 K). The results show that the silicate films stay essentially intact under these conditions, and oxygen in the film does not exchange with oxygen in the ambient. O 2 molecules readily penetrate the film and dissociate on the underlying Ru surface underneath. Also, the silicate layer does howevermore » strongly passivate the Ru surface towards RuO 2(110) oxide formation that readily occurs on bare Ru(0001) under the same conditions. Lastly, the results indicate considerable spatial effects for oxidation reactions on metal surfaces in the confined space at the interface. Moreover, the aluminosilicate films completely suppress the Ru oxidation, providing some rationale for using crystalline aluminosilicates in anti-corrosion coatings.« less

Protective Coating For Laser Drilling Of Silicon

NASA Technical Reports Server (NTRS)

Shlichta, Paul J.

1988-01-01

Sodium silicate prevents spattered silicon from fusing with surrounding material. Sodium silicate solution applied to wafer by dipping and draining or by spinning; application by spraying also works. When dried in oven, solution leaves thin coating of sodium silicate glass.

Metal/Silicate Partitioning at High Pressures and Temperatures

NASA Technical Reports Server (NTRS)

Shofner, G.; Campbell, A.; Danielson, L.; Righter, K.; Rahman, Z.

2010-01-01

The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.

On the metallicity dependence of crystalline silicates in oxygen-rich asymptotic giant branch stars and red supergiants

NASA Astrophysics Data System (ADS)

Jones, O. C.; Kemper, F.; Sargent, B. A.; McDonald, I.; Gielen, C.; Woods, Paul M.; Sloan, G. C.; Boyer, M. L.; Zijlstra, A. A.; Clayton, G. C.; Kraemer, K. E.; Srinivasan, S.; Ruffle, P. M. E.

2012-12-01

We investigate the occurrence of crystalline silicates in oxygen-rich evolved stars across a range of metallicities and mass-loss rates. It has been suggested that the crystalline silicate feature strength increases with increasing mass-loss rate, implying a correlation between lattice structure and wind density. To test this, we analyse Spitzer Infrared Spectrograph and Infrared Space Observatory Short Wavelength Spectrometer spectra of 217 oxygen-rich asymptotic giant branch and 98 red supergiants in the Milky Way, the Large and Small Magellanic Clouds, and Galactic globular clusters. These encompass a range of spectral morphologies from the spectrally rich which exhibit a wealth of crystalline and amorphous silicate features to 'naked' (dust-free) stars. We combine spectroscopic and photometric observations with the GRAMS grid of radiative transfer models to derive (dust) mass-loss rates and temperature. We then measure the strength of the crystalline silicate bands at 23, 28 and 33 μm. We detect crystalline silicates in stars with dust mass-loss rates which span over 3 dex, down to rates of ˜10-9 M⊙ yr-1. Detections of crystalline silicates are more prevalent in higher mass-loss rate objects, though the highest mass-loss rate objects do not show the 23-μm feature, possibly due to the low temperature of the forsterite grains or it may indicate that the 23-μm band is going into absorption due to high column density. Furthermore, we detect a change in the crystalline silicate mineralogy with metallicity, with enstatite seen increasingly at low metallicity.

Measuring DAC metal-silicate partitioning experiments by electron microprobe: Thickness, fluorescence, and oxide spheres

NASA Astrophysics Data System (ADS)

Jennings, E. S.; Wade, J.; Laurenz, V.; Kearns, S.; Buse, B.; Rubie, D. C.

2017-12-01

The process by which the Earth's core segregated, and its resulting composition, can be inferred from the composition of the bulk silicate Earth if the partitioning of various elements into metal at relevant conditions is known. As such, partitioning experiments between liquid metal and liquid silicate over a wide range of pressures and temperatures are frequently performed to constrain the partitioning behaviour of many elements. The use of diamond anvil cell experiments to access more extreme conditions than those achievable by larger volume presses is becoming increasingly common. With a volume several orders of magnitude smaller than conventional samples, these experiments present unique analytical challenges. Typically, sample preparation is performed by FIB as a 2 mm thick slice, containing a small iron ball surrounded by a layer of silicate melt. This implies that analyses made by EPMA will be made near boundaries where fluoresced X-rays from the neighbouring phase may be significant. By measuring and simulating synthetic samples, we investigate thickness and fluorescence limitations. We find that for typical sample geometries, a thickness of 2 μm contains the entire analytical volume for standard 15kV analyses of metals. Fluoresced X-rays from light elements into the metal are below detection limits if there is no direct electron interaction with the silicate. Continuum fluorescence from higher atomic number elements from the metal into silicate poses significant difficulties [1]. This can cause metal-silicate partition coefficients of siderophile elements to be underestimated. Finally, we examine the origin and analytical consequences of oxide-rich exsolutions that are frequently found in the metal phase of such experiments. These are spherical with diameters of 100 nm and can be sparsely to densely packed. They appear to be carbon-rich and result in low analytical totals by violating the assumption of homogeneity in matrix corrections (e.g. φρz), which results in incorrect relative abundances. Using low kV analysis, we explore their origin i.e. whether they originate from quench exsolution or dynamic processes. Identifying their composition is key to understanding their origin and the interpretation of DAC experimental results.[1] Wade J & Wood B. J. (2012) PEPI 192-193, 54-58.

EFFECT OF SILICATE ON GRAM STAINING AND VIABILITY OF PNEUMOCOCCI AND OTHER BACTERIA

PubMed Central

MacLeod, Colin M.; Roe, Amy S.

1956-01-01

Application of silicate solutions to living or heat-killed pneumococci and to certain "viridans" streptococci causes their conversion from a Gram-positive to a Gram-negative state. The original staining properties can be restored by suspending the silicate-treated bacteria in alkaline solutions of various salts but not by simple washing in water. Living pneumococci and the strains of streptococci whose staining properties are similarly affected are killed when suspended in silicate solutions. In other Gram-positive species silicate causes conversion to Gram negativity but restoration to positivity occurs upon washing in water. In a third group of Gram-positive organisms silicate has no effect on the Gram reaction. The viability of organisms in these two groups is unaffected by silicate under the conditions employed. No effect on staining or viability of Gram-negative bacteria has been observed. The effects of silicate on staining and viability are inhibited by nutrient broth or whole serum but not by purified serum albumin. Lecithin, choline, and other substituted ammonium compounds also inhibit the effects of silicate on pneumococci. PMID:13306854

New Approach for Fractioning Metal Compounds Studies in Soils

NASA Astrophysics Data System (ADS)

Minkina, Tatiana; Motuzova, Galina; Mandzhieva, Saglara; Bauer, Tatiana; Burachevskaya, Marina; Sushkova, Svetlana; Nevidomskaya, Dina; Kalinitchenko, Valeriy

2016-04-01

A combined approach for fractioning metal compounds in soils on the basis of sequential (Tessier, 1979) and parallel extractions (1 N NH4Ac, pH 8; 1% EDTA in NH4Ac; and 1N HCl) is proposed. Metal compounds in sequential and parallel extracts are grouped according to the strength of their bonds with soil components. A given group includes metal compounds with similar strengths of bonds and, hence, with similar migration capacities. The groups of firmly and loosely bound metal compounds can be distinguished. This approach has been used to assess the group composition of Zn, Cu, and Pb compounds in an ordinary chernozem and its changes upon the soil contamination with metals. Contamination of an ordinary chernozem from Rostov oblast with heavy metals caused a disturbance of the natural ratios between the metal compounds. In the natural soil, firmly bound metals predominate (88-95%of the total content), which is mainly caused by the fixation of metals in lattices of silicate minerals (56-83%of the total content). The mobility of the metals in the natural soil is low (5-12%) and is mainly related to metal compounds loosely bound with the soil carbonates. Upon the soil contamination with metals (application rates of 100-300 mg/kg), the content of all the metal compounds increases, but the ratio between them shifts towards a higher portion of the potentially mobile metal compounds (up to 30-40% of the bulk contents of the metals). Organic substances and non-silicate Fe, Al, and Mn minerals become the main carriers of the firmly and loosely bound metals. The strengths of their bonds with Cu, Pb, and Zn differ. Lead in the studied chernozems is mainly fixed in a loosely bound form with organic matter, whereas copper and zinc are fixed both by the organic matter and by the non-silicate Fe, Al, and Mn compounds. Firm fixation of the applied Cu and Pb is mainly ensured by the soil organic matter and non-silicate minerals, whereas firm fixation of Zn is mainly due to non-silicate minerals. The amount of the applied metals fixed in the lattices of the silicate minerals is insignificant. Hence, all the soil components participate in the loose and firm fixation of the metals. The leading role in mobilization-immobilization of natural metal compounds in the ordinary chernozem belongs to carbonates and silicate minerals. For exogenic metal compounds, this role belongs to the soil organic matter and Fe-Mn oxides and hydroxides. The obtained data are important for ecology because they enable us to predict the transformation of soil components responsible for metal fixation and the possibility of their secondary mobilization. The danger of metal mobilization is more probable for metal compounds with organic substances that are particularly active in the loose binding of the introduced metals. This work was supported by the Ministry of Science of the Russian Federation, project no. 5.885.2014/K, the Russian Foundation for Basic Research, projects no. № 14-05-00586_a.

Silicate Inclusions in the Kodaikanal IIE Iron Meteorite

NASA Technical Reports Server (NTRS)

Kurat, G.; Varela, M. E.; Zinner, E.

2005-01-01

Silicate inclusions in iron meteorites display an astonishing chemical and mineralogical variety, ranging from chondritic to highly fractionated, silica- and alkali-rich assemblages. In spite of this, their origin is commonly considered to be a simple one: mixing of silicates, fractionated or unfractionated, with metal. The latter had to be liquid in order to accommodate the former in a pore-free way which all models accomplish by assuming shock melting. II-E iron meteorites are particularly interesting because they contain an exotic zoo of silicate inclusions, including some chemically strongly fractionated ones. They also pose a formidable conundrum: young silicates are enclosed by very old metal. This and many other incompatibilities between models and reality forced the formulation of an alternative genetic model for irons. Here we present preliminary findings in our study of Kodaikanal silicate inclusions.

Solubility of oxygen in liquid Fe at high pressure and consequences for the early differentiation of Earth and Mars

NASA Astrophysics Data System (ADS)

Rubie, D. C.; Gessmann, C. K.; Frost, D. J.

2003-04-01

Knowledge of the solubility of oxygen in liquid iron enables the partitioning of oxygen between metal and silicates and the oxidation state of residual silicates to be constrained during core formation in planetary bodies. We have determined oxygen solubility experimentally at 5--23 GPa, 2100--2700 K and oxygen fugacities 1--4 log units below the iron-wüstite buffer in samples of liquid Ni-Fe alloy contained in magnesiowüstite capsules using a multianvil apparatus. Results show that oxygen solubility increases with increasing temperature but decreases slightly with increasing pressure over the range of experimental conditions, at constant oxygen fugacity. Using an extrapolation of the results to higher pressures and temperatures, we have modeled the geochemical consequences of metal-silicate separation in magma oceans in order to explain the contrasting FeO contents of the mantles of Earth and Mars. We assume that both Earth and Mars accreted originally from material with a chondritic composition; because the initial oxidation state is uncertain, we vary this parameter by defining the initial oxygen content. Two metal-silicate fractionation models are considered: (1) Metal and silicate are allowed to equilibrate at fictive conditions that approximate the pressure and temperature at the base of a magma ocean. (2) The effect of settling Fe droplets in a magma ocean is determined using a simple polybaric metal-silicate fractionation model. We assume that the temperature at the base of a magma ocean is close to the peridotite liquidus. In the case of Earth, high temperatures in a magma ocean with a depth >1200 km would have resulted in significant quantities of oxygen dissolving in the liquid metal with the consequent extraction of FeO from the residual silicate. In contrast, on Mars, even if the magma ocean extended to the depth of the current core-mantle boundary, temperatures would not have been sufficiently high for oxygen solubility in liquid metal to be significant. The results show that Earth and Mars could have accreted from similar material, with an initial FeO content around 18 wt%. On Earth, oxygen was extracted from silicates by the segregating metal during core formation, leaving the mantle with its present FeO content of ˜8 wt%. On Mars, in contrast, the segregating metal extracted little or no oxygen and left the FeO content unaltered at ˜18 wt%. A consequence of this model is that oxygen should be an important light element in the Earth's core but not in the Martian core.

High temperature low friction surface coating

DOEpatents

Bhushan, Bharat

1980-01-01

A high temperature, low friction, flexible coating for metal surfaces which are subject to rubbing contact includes a mixture of three parts graphite and one part cadmium oxide, ball milled in water for four hours, then mixed with thirty percent by weight of sodium silicate in water solution and a few drops of wetting agent. The mixture is sprayed 12-15 microns thick onto an electro-etched metal surface and air dried for thirty minutes, then baked for two hours at 65.degree. C. to remove the water and wetting agent, and baked for an additional eight hours at about 150.degree. C. to produce the optimum bond with the metal surface. The coating is afterwards burnished to a thickness of about 7-10 microns.

Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

DOE PAGES

Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; ...

2017-07-28

While olivine LiFePO 4 shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li + migration pathways in the framework, replacing the [PO 4] 3- polyanion with a silicate [SO 4] 4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO 4 and LiScSiO 4 as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc sitemore » were investigated by computational modelling via atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo 2-x-ySiO 4. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.« less

Platinum Partitioning at Low Oxygen Fugacity: Implications for Core Formation Processes

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Lanziroti, A.; Newville, M.

2016-01-01

Highly siderophile elements (HSE = Au, Re, and the Pt-group elements) are tracers of silicate / metal interactions during planetary processes. Since most core-formation models involve some state of equilibrium between liquid silicate and liquid metal, understanding the partioning of highly siderophile elements (HSE) between silicate and metallic melts is a key issue for models of core / mantle equilibria and for core formation scenarios. However, partitioning models for HSE are still inaccurate due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variable like temperature, pressure, and oxygen fugacity. In this abstract, we describe a self-consistent set of experiments aimed at determining the valence of platinum, one of the HSE, in silicate melts. This is a key information required to parameterize the evolution of platinum partitioning with oxygen fugacity.

Core formation conditons in planetesimals: constraints from isotope fractionation experiments.

NASA Astrophysics Data System (ADS)

Guignard, J.; Quitté, G.; Toplis, M. J.; Poitrasson, F.

2016-12-01

Planetesimals are small objects (10 to 1000 km) early accreted in the history of the solar system which show a wide variety of thermal history due to the initial amount of radiogenic elements [1] (26Al and 60Fe), from a simple metamorphism to a complete metal-silicate differentiation. Moreover, isotope compositions of siderophile element, e.g. Fe, Ni, and W in meteorites spread on a range that can be attributed to the process of core-mantle segregation. We therefore performed isotope fractionation experiments of nickel and tungsten between metal and silicate in a gas-mixing (CO-CO2) vertical furnace, at different temperatures (from 1270°C to 1600°C), oxygen fugacity (from IW+2 to IW-6) and annealing times (from 20 minutes to 48 hours). The starting silicate is an anorthite-diopside eutectic composition glass, synthesize from the respective oxides. The starting metal is either a nickel or tungsten wire according to the element to study. After each experiment, metal and silicate are mechanically separated and digested in acids. Nickel and Tungsten separation have been made according to the methods developed by [2] and [3] and isotopes measurements have been made using a high resolution MC-ICP-MS (Neptune; Thermofisher©). Results show evidence for a strong kinetic isotope fractionation during the first annealing times with a faster diffusion of lightest isotopes than heaviest. Similar mechanism has been already highlighted for iron isotope fractionation between silicate and metal [4]. Chemical and isotopic equilibrium is also reached in our experiments but the time required dependent on the conditions of temperature and oxygen fugacity. Therefore, at equilibrium, metal-silicate isotope fractionation has also been quantified as well its temperature dependence. These experimental data can be used in order to bring new constraints on the metal silicate segregation in the planetesimals early accreted. [1] Lee T., et al., GRL, 3, 41-44 (1976) [2] Quitté G., and Oberli F., JAAS, 21, 1249-1255 (2006) [3] Breton T., and Quitté G., JAAS, 29, 2284-2293 (2014) [4] Roskosz M., et al., EPSL, 248, 851-867 (2006)

Electrochemistry and the Earth's Core-Mantle Boundary

NASA Astrophysics Data System (ADS)

Kavner, A.; Walker, D.

2001-12-01

The Earth's core-mantle boundary consists of a highly heterogeneous metal-oxide interface subjected to high temperatures, pressures, and additionally, to the presence of a temporally- and spatially-varying electrical field generated by the outer core dynamo. An understanding of the core-mantle boundary should include the nature of its electrical behavior, its electrically induced chemical partitioning, and any resultant core-mantle dynamic coupling. To this end, we have developed a method to measure the electrical behavior of metal-silicate interfaces at high pressures (15-25 kbar) and temperatures (1300-1400° C) in a piston-cylinder apparatus. Platinum electrical leads are placed at each end of the sample, which consists of a layer of iron and/or iron alloy below a layer of silicate. The sample is enclosed in a sintered MgO chamber which is then surrounded by a metal Faraday cage, allowing the sample to be electrically insulated from the AC field of the graphite heater. The platinum electric leads are threaded through the thermocouple tube and connected with an HP4284A LCR meter to measure AC impedance, or to a DC power supply to apply a field such that either the silicate or the metal end is the anode (+). AC impedance measurements performed in-situ on samples consisting of Fe, Fe-Ni-S, and a basalt-olivine mixture in series show that conductivity is strongly dependent on the electrical polarization of the silicate relative to the sulfide. When the silicate is positively charged (silicate is the anode) and when there is no applied charge, the probe-to-probe resistance displays semiconductor behavior, with conductivity ( ~10-2 S/cm) strongly thermally activated. However, when the electrical polarity is reversed, and the sulfide is the anode, the electrical conductivity between the two probes increases dramatically (to ~1 S/cm) over timescales of minutes. If the polarity is removed or reversed, the conductivity returns to its original values over similar timescales. A second set of experiments examined the behavior of iron-silicate interfaces subjected to electric fields of 1-10 V, applied for times ranging from several minutes to several days. The samples were quenched from high temperatures, mounted, and examined using both light and electron microscopy. When the iron/iron-sulfide end is charged positively (+1-2 V) with respect to the silicate, oxides form around the platinum electrode embedded within the iron metal, suggesting the reaction Fe->Fe+2+2e- occurs in the metal. When the electric field is reversed, the silicate and MgO surrounding the + electrode turns red, implying the reaction Fe+2\\rightarrowFe^{+3}+e^{-}$ occurs at the silicate (anode end) of the sample. The richness of electrical and electrically activated chemical behavior observed at metal-silicate interfaces may be relevant to the Earth's core mantle boundary.

Silica metal-oxide vesicles catalyze comprehensive prebiotic chemistry.

PubMed

Bizzarri, Bruno Mattia; Botta, Lorenzo; Pérez-Valverde, Maritza Iveth; Saladino, Raffaele; Di Mauro, Ernesto; Garcia Ruiz, Juan Manuel

2018-03-30

It has recently been demonstrated that mineral self-assembled structures catalyzing prebiotic chemical reactions may form in natural waters derived from serpentinization, a geological process widespread in the early stages of Earth-like planets. We have synthesized self-assembled membranes by mixing microdrops of metal solutions with alkaline silicate solutions in the presence of formamide (NH2CHO), a single carbon molecule, at 80ºC. We found that these bilayer membranes, made of amorphous silica and metal oxide-hydroxide nanocrystals, catalyze the condensation of formamide, yielding the four nucleobases of RNA, three aminoacids and several carboxylic acids in a single pot experiment. Besides manganese, iron and magnesium, two abundant elements in the earliest Earth crust that are key in serpentinization reactions, are enough to produce all these biochemical compounds. These results suggest that the transition from inorganic geochemistry to prebiotic organic chemistry is common on a universal scale and, most probably, earlier than ever thought for our planet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfur Saturation Limits in Silicate Melts and their Implications for Core Formation Scenarios for Terrestrial Planets

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2002-01-01

This study explores the controls of temperature, pressure, and silicate melt composition on S solubility in silicate liquids. The solubility of S in FeO-containing silicate melts in equilibrium with metal sulfide increases significantly with increasing temperature but decreases with increasing pressure. The silicate melt structure also exercises a control on S solubility. Increasing the degree of polymerization of the silicate melt structure lowers the S solubility in the silicate liquid. The new set of experimental data is used to expand the model of Mavrogenes and O'Neill(1999) for S solubility in silicate liquids by incorporating the influence of the silicate melt structure. The expected S solubility in the ascending magma is calculated using the expanded model. Because the negative pressure dependence of S solubility is more influential than the positive temperature dependence, decompression and adiabatic ascent of a formerly S-saturated silicate magma will lead to S undersaturation. A primitive magma that is S-saturated in its source region will, therefore, become S-undersaturated as it ascends to shallower depth. In order to precipitate magmatic sulfides, the magma must first cool and undergo fractional crystallization to reach S saturation. The S content in a metallic liquid that is in equilibrium with a magma ocean that contains approx. 200 ppm S (i.e., Earth's bulk mantle S content) ranges from 5.5 to 12 wt% S. This range of S values encompasses the amount of S (9 to 12 wt%) that would be present in the outer core if S is the light element. Thus, the Earth's proto-mantle could be in equilibrium (in terms of the preserved S abundance) with a core-forming metallic phase.

Experimental Liquidus Studies of the Pb-Fe-Si-O System in Equilibrium with Metallic Pb

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Jak, E.

2018-02-01

Phase equilibria of the Pb-Fe-Si-O system have been investigated at 943 K to 1773 K (670 °C to 1500 °C) for oxide liquid in equilibrium with liquid Pb metal and solid oxide phases: (a) quartz, tridymite, or cristobalite; (b) (fayalite + tridymite) or (fayalite + spinel); (c) spinel (Fe3O4); (d) complex lead-iron silicates (melanotekite PbO·FeO1.5·SiO2, barysilite 8PbO·FeO·6SiO2, 5PbO·FeO1.5·SiO2, and 6PbO·FeO1.5·SiO2); (e) lead silicates (Pb2SiO4, Pb11Si3O17); (f) lead ferrites (magnetoplumbite Pb1+ x Fe12- x O19- x solid solution range); and (g) lead oxide (PbO, massicot). High-temperature equilibration on primary phase or iridium substrates, followed by quenching and direct measurement of Pb, Fe, and Si concentrations in the phases with the electron probe X-ray microanalysis, has been used to accurately characterize the system in equilibrium with Pb metal. All results are projected onto the PbO-"FeO"-SiO2 plane for presentation purposes. The present study is the first systematic characterization of liquidus over a wide range of compositions in this system in equilibrium with metallic Pb.

Howardites and Mesosiderites: Contrasting Polymict Breccias from Two Similar Differentiated Asteroids

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.

2014-01-01

Silicates in mesosiderites commonly show anomalous characteristics compared to howardites. These characteristics indicate that many of the mesosiderite lithologies were formed during and/or after metal silicate mixing. Petrologic evidence indicates that impact gardening occurred on the mesosiderite asteroid after metal-silicate mixing. Thus the anomalous materials ought to be widely distributed on that asteroid. The compositions of howardites suggest a well-mixed regolith on Vesta. The lack of distinctive mesosiderite-like materials in howardites favors separate parents for the two meteorite groups.

Ferrous Silicate Spherules with Euhedral Fe,Ni-Metal Grains in CH Carbonaceous Chondrites: Evidence for Condensation Under Highly Oxidizing Conditions

NASA Technical Reports Server (NTRS)

Krot, A. N.; Meibom, A.; Petaev, M. I.; Keil, K.; Zolensky, M. E.; Saito, A.; Mukai, M.; Ohsumi, K.

2000-01-01

A population of ferrous silicate spherules composed of cryptocrystalline ol-px-normative material, +/-SiO2-rich glass and rounded-to-euhedral Fe,Ni-metal grains preserved a condensation signature of the precursors formed under oxidizing conditions.

The Effect of Core-Mantle Differentiation on V, Cr, and Mn: Experimental Metal/Silicate Partitioning Results

NASA Technical Reports Server (NTRS)

Chabot, N. L.; Agee, C. B.

2001-01-01

The abundances of V, Cr, and Mn are similarly depleted in the Earth and Moon. We present metal/silicate partitioning results which examine if the depletions can be explained by a core formation event. Additional information is contained in the original extended abstract.

Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

NASA Astrophysics Data System (ADS)

Zhang, S.; Zhang, H.; Huang, F.

2017-12-01

Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation during core formation. More experiments will be performed to explore the effect of Si and S in the metal on V isotope fractionation between metal and silicate melt.References: [1] Prytulak et al. (2013) EPSL 365, 177-189 [2] Nielsen et al. (2014) EPSL 389, 167-175 [3] Cottrell et al. (2009) CG 268, 167-179 [4] Wu et al. (2016) CG 421, 17-25

Plasma carburizing with surface micro-melting

NASA Astrophysics Data System (ADS)

Balanovsky, A. E.; Grechneva, M. V.; Van Huy, Vu; Ponomarev, B. B.

2018-03-01

This paper presents carburizing the surface of 20 low carbon steel using electric arc and graphite prior. A carbon black solution was prepared with graphite powder and sodium silicate in water. A detailed analysis of the phase structure and the distribution profile of the sample hardness after plasma treatment were given. The hardened layer consists of three different zones: 1 – the cemented layer (thin white zone) on the surface, 2 – heat-affected zone (darkly etching structure), 3 – the base metal. The experimental result shows that the various microstructures and micro-hardness profiles were produced depending on the type of graphite coating (percentage of liquid glass) and processing parameters. The experiment proved that the optimum content of liquid glass in graphite coating is 50–87.5%. If the amount of liquid glass is less than 50%, adhesion to metal is insufficient. If liquid glass content is more than 87.5%, carburization of a metal surface does not occur. A mixture of the eutectic lamellar structure, martensite and austenite was obtained by using graphite prior with 67% sodium silicate and the levels of the hardness layer increased to around 1000 HV. The thickness of the cemented layer formed on the surface was around 200 μm. It is hoped that this plasma surface carburizing treatment could improve the tribological resistance properties.

Release of Si from Silicon, a Ferrosilicon (FeSi) Alloy and a Synthetic Silicate Mineral in Simulated Biological Media

PubMed Central

Herting, Gunilla; Jiang, Tao; Sjöstedt, Carin; Odnevall Wallinder, Inger

2014-01-01

Unique quantitative bioaccessibility data has been generated, and the influence of surface/material and test media characteristics on the elemental release process were assessed for silicon containing materials in specific synthetic body fluids at certain time periods at a fixed loading. The metal release test protocol, elaborated by the KTH team, has previously been used for classification, ranking, and screening of different alloys and metals. Time resolved elemental release of Si, Fe and Al from particles, sized less than 50 µm, of two grades of metallurgical silicon (high purity silicon, SiHG, low purity silicon, SiLG), an alloy (ferrosilicon, FeSi) and a mineral (aluminium silicate, AlSi) has been investigated in synthetic body fluids of varying pH, composition and complexation capacity, simple models of for example dermal contact and digestion scenarios. Individual methods for analysis of released Si (as silicic acid, Si(OH)4) in synthetic body fluids using GF-AAS were developed for each fluid including optimisation of solution pH and graphite furnace parameters. The release of Si from the two metallurgical silicon grades was strongly dependent on both pH and media composition with the highest release in pH neutral media. No similar effect was observed for the FeSi alloy or the aluminium silicate mineral. Surface adsorption of phosphate and lactic acid were believed to hinder the release of Si whereas the presence of citric acid enhanced the release as a result of surface complexation. An increased presence of Al and Fe in the material (low purity metalloid, alloy or mineral) resulted in a reduced release of Si in pH neutral media. The release of Si was enhanced for all materials with Al at their outermost surface in acetic media. PMID:25225879

Solid phase immobilization of optically responsive liposomes insol-gel materials for chemical and biological sensing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamanaka, Stacey A.; Charych, Deborah H.; Loy, Douglas A.

1997-04-01

Liposomes enhanced with surface recognition groups have previously been found to have high affinity for heavy metal ions and virus particles with unique fluorescent and colorimetric responses, respectively. These lipid aggregate systems have now been successfully immobilized in a silica matrix via the sol-gel method, affording sensor materials that are robust, are easily handled, and offer optical clarity. The mild processing conditions allow quantitative entrapment of preformed liposomes without modification of the aggregate structure. Lipid extraction studies of immobilized nonpolymerized liposomes showed no lipid leakage in aqueous solution over a period of 3 months. Heavy metal fluorescent sensor materials preparedmore » with 5 percent N-[8-[1-octadecyl-2-(9-(1-pyrenyl)nonyl)-rac-glyceroyl]-3,6-dioxaoctyl]imino acid/distearylphosphatidylcholineliposomes exhibited a 4-50-fold enhancement in sensitivity to various metal ions compared to that of the liposomes in free solution. Through ionic attraction the anionic silicate surface, at the experimental pH of 7.4, may act as a preconcentrator of divalent metal ions, boosting the gel's internal metal concentration. Entrapped sialic acid-coated polydiacetylene liposomes responded with colorimetric signaling to influenza virus X31, although slower than the free liposomes in solution. The successful transport of the virus (50-100 nm diameter) reveals a large pore diameter of the gel connecting the liposome to the bulk solution. The porous and durable silica matrix additionally provides a protective barrier to biological attack (bacterial, fungal) and allows facile recycling of the liposome heavy metal sensor.« less

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2002-01-01

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

Metal-Silicate Partitioning of Various Siderophile Elements at High Pressure and High Temperatures: a Diamond Anvil Cell Study

NASA Astrophysics Data System (ADS)

Badro, J.; Blanchard, I.; Siebert, J.

2015-12-01

Core formation is the major chemical fractionation that occurred on Earth. This event is widely believed to have happened at pressures of at least 40 GPa and temperatures exceeding 3000 K. It has left a significant imprint on the chemistry of the mantle by removing most of the siderophile (iron-loving) elements from it. Abundances of most siderophile elements in the bulk silicate Earth are significantly different than those predicted from experiments at low P-T. Among them, vanadium, chromium, cobalt and gallium are four siderophile elements which abundances in the mantle have been marked by core formation processes. Thus, understand their respective abundance in the mantle can help bringing constraints on the conditions of Earth's differentiation. We performed high-pressure high-temperature experiments using laser heating diamond anvil cell to investigate the metal-silicate partitioning of those four elements. Homogeneous glasses doped in vanadium, chromium, cobalt and gallium were synthesized using a levitation furnace and load inside the diamond anvil cell along with metallic powder. Samples were recovered using a Focused Ion Beam and chemically analyzed using an electron microprobe. We investigate the effect of pressure, temperature and metal composition on the metal-silicate partitioning of V, Cr, Co and Ga. Three previous studies focused on V, Cr and Co partitioning at those conditions of pressure and temperature, but none explore gallium partitioning at the relevant extreme conditions of core formation. We will present the first measurements of gallium metal-silicate partitioning performed at the appropriate conditions of pressure and temperature of Earth's differentiation.

Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

NASA Astrophysics Data System (ADS)

Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

2009-10-01

Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth's core-forming metal and silicate mantle, there should be an isotopic signature of Si in the core. Our experiments, combined with previous measurements of Si isotope ratios in meteorites and rocks representing the bulk silicate Earth, suggest that the formation of the Earth's core imparted a high 30Si/ 28Si signature to the bulk silicate Earth due to dissolution of ~ 6 wt% Si into the early core.

Experimental determination of the partitioning of gallium between solid iron metal and synthetic basaltic melt Electron and ion microprobe study

NASA Technical Reports Server (NTRS)

Drake, M. J.; Newsom, H. E.; Reed, S. J. B.; Enright, M. C.

1984-01-01

The distribution of Ga between solid Fe metal and synthetic basaltic melt is investigated experimentally at temperatures of 1190 and 1330 C, and over a narrow range of oxygen fugacities. Metal-silicate reversal experiments were conducted, indicating a close approach to equilibrium. The analysis of the partitioned products was performed using electron and ion microprobes. At one bar total pressure, the solid metal/silicate melt partition coefficient D(Ga) is used to evaluate metal-silicate fractionation processes in the earth, moon, and Eucrite Parent Body (EPB). It is found that the depletion of Ga abundances in the EPB is due to the extraction of Ga into a metallic core. Likewise, the depletion of Ga in the lunar mantle is consistent with the extraction of Ga into a smaller lunar core if Ga was originally present in a subchondritic concentration. The relatively high Ga abundances in the earth's mantle are discussed, with reference to several theoretical models.

Nanotubes within transition metal silicate hollow spheres: Facile preparation and superior lithium storage performances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; An, Yongling; Zhai, Wei

2015-10-15

Highlights: • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were successfully prepared by a facile hydrothermal method using SiO{sub 2} nanosphere. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were tested as anode materials for lithium batteries. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} delivered superior electrochemical performance. • The lithium storage mechanism is probe via cyclic voltammetry and XPS. - Abstract: A series of transition metal silicate hollow spheres, including cobalt silicate (Co{sub 2}SiO{sub 4}), manganese silicate (MnSiO{sub 3}) and copper silicate (CuSiO{sub 3}.2H{sub 2}O, CuSiO{sub 3} as abbreviationmore » in the text) were prepared via a simple and economic hydrothermal method by using silica spheres as chemical template. Time-dependent experiments confirmed that the resultants formed a novel type of hierarchical structure, hollow spheres assembled by numerous one-dimensional (1D) nanotubes building blocks. For the first time, the transition metal silicate hollow spheres were characterized as novel anode materials of Li-ion battery, which presented superior lithium storage capacities, cycle performance and rate performance. The 1D nanotubes assembly and hollow interior endow this kind of material facilitate fast lithium ion and electron transport and accommodate the big volume change during the conversion reactions. Our study shows that low-cost transition metal silicate with rationally designed nanostructures can be promising anode materials for high capacity lithium-ion battery.« less

The Chaunskij Meteorite: Mineralogical, Chemical and Isotope Data, Classification and Proposed Origin

NASA Astrophysics Data System (ADS)

Petaev, M. I.; Zaslavskaya, N. I.; Clarke, R. S., Jr.; Olsen, E. J.; Jarosewich, E.; Kononkova, N. N.; Holmberg, B. B.; Davis, A. M.; Ustinov, V. I.; Wood, J. A.

1992-07-01

The 1990 g Chaunskij meteorite was found in 1985 and classified as an anomalous ungrouped iron (Meteoritical Bulletin, 1988). The meteorite contains about 10 vol% mono- and polymineralic troilite-phosphate-silicate inclusions, microns to centimeters in size. STRUCTURE AND MINERALOGY. Chaunskij metal displays a mesosiderite structure with unusually high levels of shock damage in the kamacite. Tetrataenite borders 5-10 mm wide enclose large regions of cloudy taenite, which, in turn, sometimes enclose martensitic regions. Much of the tetrataenite has apparently been disordered by shock. Schreibersite occurs as occasional very small precipitates at tetrataenite borders, and infrequently as larger masses at grain boundaries. Shock-affected troilite in moderately large globules (up to several mm) and rounded phosphate inclusions are erratically distributed. Silicate areas of the polymineralic inclusions are, as a rule, irregular in shape. In larger inclusions, these areas are usually surrounded by phosphate rims. The groundmass of the polymineralic inclusions is a fine- grained intergrowth of low-Ca pyroxene (mg' = 28-31), whitlockite, and cordierite (mg' = 83-87), with rare large (50-100 mm) porphyritic grains of the first two minerals. Porphyritic pyroxene grain edges are generally rough. Minor minerals in the silicate inclusions are SiO2, kamacite, taenite, troilite, chromite, ilmenite, rutile, and small relict grains of plagioclase (An 83-95). The chromite and ilmenite vary in MgO, MnO, and Al2O3 contents. Rare grains of pyrophanite, alabandite, native copper, stanfieldite, and of a graftonite-farringtonite mineral are also observed in the meteorite. BULK CHEMISTRY. Bulk chemical data for the silicate-rich portion of one polymineralic inclusion (obtained by defocused beam analyses; Zaslavskaya et al.,1991) suggest a differentiated nature for the inclusions. High Al/Si (0.34) and Mn/Fe (0.029) ratios indicate a basalt-like precursor similar to HED and mesosiderite silicates. CLASSIFICATION. The proportion of metal suggests that Chaunskij should be classified as an iron with silicate inclusions. However, characteristics such as the mesosiderite-like structure of the metal, compositions of the pyroxene and plagioclase, and bulk Fe/Mn ratio all point to a relationship between Chaunskij and the mesosiderites, though the bulk Ni content in the metal (14.4 wt%; Zaslavskaya et al., 1991) is higher than previously observed in mesosiderites. In light of these data, Chaunskij may be tentatively classified as a highly-metamorphosed mesosiderite. Oxygen isotope data (R.N. Clayton, personal communication) for two Chaunskij inclusions plot outside the HED and mesosiderite clusters and lie between the terrestrial fractionation line and the silicates of the IAB irons. PROPOSED ORIGIN. The structural relationships of silicates and metal argue against simultaneous melting of these phases and suggest the incorporation of silicate fragments into plastic (molten?) metal. In such a scenario, the phosphate- silicate assemblage may be the result of a metamorphic reaction between silicates and phosphorus dissolved in the metal: Px + An + P [ss in metal] + O --> Cord + Q + Whit, which would take place under moderate temperatures (750-820 degrees C) and relatively high (for meteorites!) pressures (3.5-5.0 kbar) (Hess, 1969) in the interior of the Chaunskij parent body. REFERENCES Hess P.C.(1969) Contrib. Miner. Petrol., 24, 191- 207. The Meteoritical Bulletin (1988) Meteoritics, 23, 171- 173. Zaslavskaya N.I., Petaev M.I., Kononkova N.N., Barsukova L.D. (1991) Lunar Planet. Sci. (abstract), 22, 1545-1546.

Solubility of K in Fe-S liquid, silicate-K/Fe-S/liq equilibria, and their planetary implications

NASA Technical Reports Server (NTRS)

Gangully, J.; Kennedy, G. C.

1977-01-01

Potassium has been found to have extremely limited absolute solubility in Fe-S liquid in the pressure-temperature range of 18 to 40 kbars, 1050 to 1150 C, and fO2 within the field of metallic iron. It also partitioned into a certain silicate phase highly in preference to Fe-S liquid at 30 kbar and 1100 C. The dependence of the partitioning of K between solid silicate and Fe-S liquid on fO2 and compositions of mineral solid solutions have been analyzed. These experimental data, along with those of others, limit the amount of K that could fractionate in Fe-S liquid layers or a core in the early history of the moon and, thus, act as localized heat sources in its thermal history models; the data also seem to argue against a chondritic abundance of potassium for earth. The question of fractionation of enough K-40 in an Fe-S liquid outer core of earth to provide the necesary thermal energy for the geomagnetic dynamo remains unresolved.

Biomimetic mineral self-organization from silica-rich spring waters.

PubMed

García-Ruiz, Juan Manuel; Nakouzi, Elias; Kotopoulou, Electra; Tamborrino, Leonardo; Steinbock, Oliver

2017-03-01

Purely inorganic reactions of silica, metal carbonates, and metal hydroxides can produce self-organized complex structures that mimic the texture of biominerals, the morphology of primitive organisms, and that catalyze prebiotic reactions. To date, these fascinating structures have only been synthesized using model solutions. We report that mineral self-assembly can be also obtained from natural alkaline silica-rich water deriving from serpentinization. Specifically, we demonstrate three main types of mineral self-assembly: (i) nanocrystalline biomorphs of barium carbonate and silica, (ii) mesocrystals and crystal aggregates of calcium carbonate with complex biomimetic textures, and (iii) osmosis-driven metal silicate hydrate membranes that form compartmentalized, hollow structures. Our results suggest that silica-induced mineral self-assembly could have been a common phenomenon in alkaline environments of early Earth and Earth-like planets.

Quantitative and Qualitative Aspects of Gas-Metal-Oxide Mass Transfer in High-Temperature Confocal Scanning Laser Microscopy

NASA Astrophysics Data System (ADS)

Piva, Stephano P. T.; Pistorius, P. Chris; Webler, Bryan A.

2018-05-01

During high-temperature confocal scanning laser microscopy (HT-CSLM) of liquid steel samples, thermal Marangoni flow and rapid mass transfer between the sample and its surroundings occur due to the relatively small sample size (diameter around 5 mm) and large temperature gradients. The resulting evaporation and steel-slag reactions tend to change the chemical composition in the metal. Such mass transfer effects can change observed nonmetallic inclusions. This work quantifies oxide-metal-gas mass transfer of solutes during HT-CSLM experiments using computational simulations and experimental data for (1) dissolution of MgO inclusions in the presence and absence of slag and (2) Ca, Mg-silicate inclusion changes upon exposure of a Si-Mn-killed steel to an oxidizing gas atmosphere.

Metal/Silicate Partitioning, Melt Speciation, Accretion, and Core Formation in the Earth

NASA Astrophysics Data System (ADS)

Drake, M. J.; Hillgren, V. J.; Dearo, J. A.; Capobianco, C. J.

1993-07-01

Core formation in terrestrial planets was concomitant with accretion. Siderophile and chalcophile element signatures in the mantles of planets are the result of these processes. For Earth, abundances of most siderophile and chalcophile elements are elevated relative to predictions from simple metal/silicate equilibria at low pressures [1]. This observation has led to three hypotheses for how these abundances were established: heterogeneous accretion [2], inefficient core formation [3], and metal/silicate equilibria at magma ocean pressures and temperatures [4]. Knowledge of speciation of siderophile elements in silicate melts in equilibrium with metal may help distinguish between these hypotheses. But there is some uncertainty regarding speciation. For example, Ni and Co have been reported to be present as 1+ or zero valence species in silicate melts at redox states appropriate to planetary accretion, rather than the expected 2+ state [5-7]. Independent metal/silicate partitioning experiments by three members of this group using two different experimental designs on both synthetic and natural compositions do not show evidence for Ni and Co in valence states other than 2+ over a wide range of redox states. For example, solid metal/silicate melt partition coefficients for Ni at 1260 degrees C obtained by VJH from experiments investigating the partitioning of Ni, Co, Mo, W, and P are indistinguishable from those obtained by JAD in similar experiments investigating the partitioning of Ni, Ge, and Sn. Both datasets define a line with the equation: log D(Ni) = - 0.54log fO2 - 3.14 with r^2 > 0.995. (Note that fO2 was calculated in both studies from thermodynamic data and phase compositions. A small, systematic offset from the true fO2 as measured by a solid electrolyte cell affects both equations similarly, but does not diminish their close agreement.) The valence of Ni in the silicate melt is obtained by multiplying the slope of the line by -4, indicating divalent Ni in both studies. Experiments by [8] between 1300 degrees C and 1550 degrees C and fO2 from air to just below iron-wustite in which Ni and Co are partitioned between Pt metal and CaO-Al2O3-SiO2 silicate melt also show evidence only for 2+ valence. Capobianco et al. [1] have noted that reliable extrapolation from current laboratory temperatures (1190 degrees C-1600 degrees C) to magma ocean temperatures is not possible. The hypothesis that siderophile and chalcophile element abundances in the mantle of Earth were established by metal/silicate equilibria at magma ocean pressures and temperatures needs to be tested using direct experimental measurements at magma ocean temperatures and pressures. Such experiments are currently being conducted. References: [1] Capobianco et al. (1993) J. Geophys. Res., 98, 5433. [2] Wanke (1981) Phil. Trans. R. Soc. London, A303, 287. [3] Jones and Drake (1986) Nature, 322, 221. [4] Murthy (1991) Science, 253, 303. [5] Schmitt et al. (1989) GCA, 53, 173. [6] Ehlers et al. (1993) GCA, 56, 3733. [7] Colson (1992) Nature, 357, 65. [8] Capobianco and Amelin (1993) GCA, 56 (in press).

Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC.

PubMed

Halim, Cheryl E; Short, Stephen A; Scott, Jason A; Amal, Rose; Low, Gary

2005-10-17

A leaching model was developed using the United States Geological Survey public domain PHREEQC geochemical package to simulate the leaching of Pb, Cd, As, and Cr from cementitious wastes. The model utilises both kinetic terms and equilibrium thermodynamics of key compounds and provides information on leachate and precipitate speciation. The model was able to predict the leaching of Pb, Cd, As, and Cr from cement in the presence of both simple (0.1 and 0.6M acetic acid) and complex municipal landfill leachates. Heavy metal complexation by the municipal landfill leachate was accounted for by the introduction of a monoprotic organic species into the model. The model indicated Pb and As were predominantly incorporated within the calcium silicate hydrate matrix while a greater portion of Cd was seen to exist as discrete particles in the cement pores and Cr (VI) existed mostly as free CrO4(2-) ions. Precipitation was found to be the dominant mechanism controlling heavy metal solubility with carbonate and silicate species governing the solubility of Pb and carbonate, silicate and hydroxide species governing the solubility of Cd. In the presence of acetic acid, at low pH values Pb and Cd acetate complexes were predominant whereas, at high pH values, hydroxide species dominated. At high pH values, the concentration of As in the leachate was governed by the solubility of Ca3(AsO4)2 with the presence of carbonate alkalinity competing with arsenate for Ca ions. In the presence of municipal landfill leachate, Pb and Cd organic complexes dominated the heavy metal species in solution. The reduction of As and Cr in municipal landfill leachate was crucial for determining aqueous speciation, with typical municipal landfill conditions providing the reduced forms of As and Cr.

Enzyme stabilization by glass-derived silicates in glass-exposed aqueous solutions

USGS Publications Warehouse

Ives, J.A.; Moffett, J.R.; Arun, P.; Lam, D.; Todorov, T.I.; Brothers, A.B.; Anick, D.J.; Centeno, J.; Namboodiri, M.A.A.; Jonas, W.B.

2010-01-01

Objectives: To analyze the solutes leaching from glass containers into aqueous solutions, and to show that these solutes have enzyme activity stabilizing effects in very dilute solutions. Methods: Enzyme assays with acetylcholine esterase were used to analyze serially succussed and diluted (SSD) solutions prepared in glass and plastic containers. Aqueous SSD preparations starting with various solutes, or water alone, were prepared under several conditions, and tested for their solute content and their ability to affect enzyme stability in dilute solution. Results: We confirm that water acts to dissolve constituents from glass vials, and show that the solutes derived from the glass have effects on enzymes in the resultant solutions. Enzyme assays demonstrated that enzyme stability in purified and deionized water was enhanced in SSD solutions that were prepared in glass containers, but not those prepared in plastic. The increased enzyme stability could be mimicked in a dose-dependent manner by the addition of silicates to the purified, deionized water that enzymes were dissolved in. Elemental analyses of SSD water preparations made in glass vials showed that boron, silicon, and sodium were present at micromolar concentrations. Conclusions: These results show that silicates and other solutes are present at micromolar levels in all glass-exposed solutions, whether pharmaceutical or homeopathic in nature. Even though silicates are known to have biological activity at higher concentrations, the silicate concentrations we measured in homeopathic preparations were too low to account for any purported in vivo efficacy, but could potentially influence in vitro biological assays reporting homeopathic effects. ?? 2009 The Faculty of Homeopathy.

The Effect of Pressure on Siderophile-Element (Ni, Co, Mo, W, and P) Metal-Silicate Partition Coefficients

NASA Astrophysics Data System (ADS)

Righter, K.; Drake, M. J.

1995-09-01

Quantification of the effect of pressure on siderophile element metal-silicate partition coefficients (D) is essential in modelling the accretion histories of the the Earth and terrestrial planets [1], as metal-silicate equilibria may have been set over a range of pressures [2]. We report siderophile element partition coefficients from metal-silicate equilibrium experiments done at 10 and 15 kb, and 1300 degrees C. These new results show that metal-silicate partition coefficients for Ni (Fig. 1), Co, and P decrease with increasing pressure (at constant T and relative fO(sub)2), while those for Mo and W increase. Experiments were done in a 1/2" piston cylinder apparatus, with T, P and fO(sub)2 controlled and monitored as described in a previous study [3]. Synthetic basalt [see 3] powder, doped with 5 wt% levels of either MoO3, WO3 or apatite, was loaded into Fe54Ni29Co17 or Fe64Ni36 tubing, which was closed either by welding or plugging the open ends with small, tapered caps of the same alloy composition. The samples were quenched after 4 to 6 hrs. The metal and glass in the run products are then analyzed by electron microprobe to obtain a solid metal/liquid silicate (SM/LS) partition coefficient for a given element (D = wt% element in metal/ wt% element in glass). For several experiments, NiS was added as a sulfur source, and thus stabilizing a sulfur-bearing metallic liquid. For these experiments, both solid metal/ liquid silicate and liquid metal/ liquid silicate (LM/LS) partition coefficients are reported (Table 1). In order to isolate the effect of pressure on siderophile element partition coefficients, we have compared our results at high pressures to calculated 1 bar values at the same T and fO(sub)2 as our experiments (based on experiments of [4 - 11]; see results for Ni in Fig. 1; data from [3] and this study). The effect of pressure and other intensive variables on metal-silicate D's can be quantified using the thermodynamically-based relation: lnD (metal/silicate) = a/T + b + clnfO(sub)2 + dln(1-2X(sub)S) + e(P-1)/T. (1) Values for a, b, c, d and e were determined by multiple linear regression of the 1 bar experimental data cited above, together with data from this study and available high pressure experimental data [3, 12 - 16]. Equation 1 can be used to predict the abundances of the siderophile elements in a planetary mantle that has undergone a metal separation event, at a specific T, P, fO(sub)2 and metal sulfur content. Such calculations for Mars indicate that metal segregation in the Martian mantle (based on SNC meteorite analyses) may have occurred at low pressures, in agreement with the conclusions of several other studies [17, 18, 19]. Similar calculations for Earth indicate that the upper mantle abundances of the siderophile elements are unlikely to have been set by simple metal-silicate equilibrium at pressures less than 100 kb. References: [1] Drake M. J. (1989) Z. Naturforsch., 44a, 883-890. [2] Newsom H. (1992] LPI Tech. Rpt. 92-03, 42-43. [3] Righter K. et al. (1995) LPS XXVI, 1169-1170. [4] Hillgren V. J. (1993) Ph.D. Thesis, Univ. of Arizona, Tucson. [5] Capobianco C. J. and Amelin A. (1994) GCA, 58, 125-140. [6] Schmitt et al. (1989) GCA, 53, 173-186. [7] Newsom H. and Drake M. J. (1982) GCA, 46, 2483-2489. [8] Newsom H. and Drake M. J. (1983) GCA, 47, 93-100. [9] Lodders K. and Palme H. (1991) EPSL, 113, 311-324. [10] Jones J. H. and Drake M. J. (1986) Nature, 322, 221-228. [11] Holzheid A. et al. (1994) GCA, 58, 1975-1981. [12] Thibault Y. and Walter M. J. (1994) GCA, 59, 991-1002. [13] Hillgren V. J. et al. (1994) Science, 264, 1442-1445. [14] Walker D. et al. (1993) Science, 262, 1858-1861. [15] Peach C. L. and Mathez E. A. (1993) GCA, 57, 3013-3032. [16] Seifert et al. (1988) GCA, 52, 603-616. [17] Drake M. J. et al. (1995) LPS XXVI, 345-346. [18] Gaetani G. A. and Grove T. L. (1995) LPS XXVI, 437-438. [19] Treiman A. H. et al. (1986) GCA, 50, 1071-1091. Acknowledgment: NASA Grant NAGW 3348 Table 1 shows a summary of experimental results.

Calcium silicate-based drug delivery systems.

PubMed

Zhu, Ying-Jie; Guo, Xiao-Xuan; Sham, Tsun-Kong

2017-02-01

Compared with other inorganic materials such as silica, metal oxides, noble metals and carbon, calcium silicate-based materials, especially nanostructured calcium silicate materials, have high biocompatibility, bioactivity and biodegradability, high specific surface area, nanoporous/hollow structure, high drug-loading capacity, pH-responsive drug release behavior and desirable drug release properties, and thus they are promising for the application in drug delivery. Calcium silicate-based drug delivery systems have a long drug-release time, which can significantly prolong the therapeutic effect of drugs. Another advantage of calcium silicate-based drug delivery systems is their pH-responsive drug release property, which can act as an ideal platform for targeted drug delivery. Areas covered: In recent years, studies have been carried out on calcium silicate-based drug delivery systems, and important results and insights have been documented. This article is not intended to offer a comprehensive review on the research on calcium silicate-based drug delivery systems, but presents some examples reported in the literature, and includes new insights obtained by tracking the interactions between drug molecules and calcium silicate carriers on the molecular level using the synchrotron-based X-ray spectroscopy. Expert opinion: Finally, our opinions on calcium silicate-based drug delivery systems are provided, and several research directions for the future studies are proposed.

Highly Siderophile Elements in Pallasites and Diogenites, Including the New Pallasite, CMS 04071

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Humayun, M.; Righter, K.

2006-01-01

Pallasites are long thought to represent a metallic core-silicate mantle boundary, where the IIIAB irons are linked to the crystallization history of the metallic fraction, and the HED meteorites may be linked to the silicate fraction. However, measurement of trace elements in individual metallic and silicate phases is necessary in order to fully under-stand the petrogenetic history of pallasites, as well as any magmatic processes which may link pallasites to both IIIAB irons and HED meteorites. In order to achieve this objective, abundances of a suite of elements were measured, including the highly siderophile elements (HSEs), in kamacite, taenite, troilite, schreibersite, chromite and olivine for the pallasites Admire, Imilac, Springwater, CMS 04071. In the diogenites GRO 95555, LAP 91900, and MET 00436, metal, sulfide, spinel, pyroxene, and silica were individually measured.

View planetary differentiation process through high-resolution 3D imaging

NASA Astrophysics Data System (ADS)

Fei, Y.

2011-12-01

Core-mantle separation is one of the most important processes in planetary evolution, defining the structure and chemical distribution in the planets. Iron-dominated core materials could migrate through silicate mantle to the core by efficient liquid-liquid separation and/or by percolation of liquid metal through solid silicate matrix. We can experimentally simulate these processes to examine the efficiency and time of core formation and its geochemical signatures. The quantitative measure of the efficiency of percolation is usually the dihedral angle, related to the interfacial energies of the liquid and solid phases. To determine the true dihedral angle at high pressure and temperatures, it is necessary to measure the relative frequency distributions of apparent dihedral angles between the quenched liquid metal and silicate grains for each experiment. Here I present a new imaging technique to visualize the distribution of liquid metal in silicate matrix in 3D by combination of focus ion beam (FIB) milling and high-resolution SEM image. The 3D volume rendering provides precise determination of the dihedral angle and quantitative measure of volume fraction and connectivity. I have conducted a series of experiments using mixtures of San Carlos olivine and Fe-S (10wt%S) metal with different metal-silicate ratios, up to 25 GPa and at temperatures above 1800C. High-quality 3D volume renderings were reconstructed from FIB serial sectioning and imaging with 10-nm slice thickness and 14-nm image resolution for each quenched sample. The unprecedented spatial resolution at nano scale allows detailed examination of textural features and precise determination of the dihedral angle as a function of pressure, temperature and composition. The 3D reconstruction also allows direct assessment of connectivity in multi-phase matrix, providing a new way to investigate the efficiency of metal percolation in a real silicate mantle.

Effect of temperature on hydration kinetics and polymerization of tricalcium silicate in stirred suspensions of CaO-saturated solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grant, Steven A.; Boitnott, Ginger E.; Korhonen, Charles J.

2006-04-15

Tricalcium silicate was hydrated at 274, 278, 283, 298, and 313 K in stirred suspensions of saturated CaO solutions under a nitrogen-gas atmosphere until the end of deceleratory period. The suspension conductivities and energy flows were measured continuously. The individual reaction rates for tricalcium silicate dissolution, calcium silicate hydrate precipitation, and calcium hydroxide precipitation were calculated from these measurements. The results suggest that the proportion of tricalcium silicate dissolved was determined by the rate of tricalcium silicate dissolution and the time to very rapid calcium hydroxide precipitation. The time to very rapid calcium hydroxide precipitation was more sensitive to changesmore » in temperature than was the rate of tricalcium silicate dissolution, so that the proportion of tricalcium silicate hydration dissolved by the deceleratory period increased with decreasing temperature. The average chain length of the calcium silicate hydrate ascertained by magic-angle spinning nuclear magnetic resonance spectroscopy increased with increasing temperature.« less

Experimental partitioning of Zr, Ti, and Nb between silicate liquid and a complex noble metal alloy and the partitioning of Ti between perovskite and platinum metal

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1993-01-01

El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.

An Interconnected Network of Core-Forming Melts Produced by Shear Deformation

NASA Technical Reports Server (NTRS)

Bruhn, D.; Groebner, N.; Kohlstedt, D. L.

2000-01-01

The formation mechanism of terrestrial planetary is still poorly understood, and has been the subject of numerous experimental studies. Several mechanisms have been proposed by which metal-mainly iron with some nickel-could have been extracted from a silicate mantle to form the core. Most recent models involve gravitational sinking of molten metal or metal sulphide through a partially or fully molten mantle that is often referred to as a'magma ocean. Alternative models invoke percolation of molten metal along an interconnected network (that is, porous flow) through a solid silicate matrix. But experimental studies performed at high pressures have shown that, under hydrostatic conditions, these melts do not form an interconnected network, leading to the widespread assumption that formation of metallic cores requires a magma ocean. In contrast, here we present experiments which demonstrate that shear deformation to large strains can interconnect a significant fraction of initially isolated pockets of metal and metal sulphide melts in a solid matrix of polycrystalline olivine. Therefore, in a dynamic (nonhydrostatic) environment, percolation remains a viable mechanism for the segregation and migration of core-forming melts in a solid silicate mantle.

Metal/sulfide-silicate intergrowth textures in EL3 meteorites: Origin by impact melting on the EL parent body

NASA Astrophysics Data System (ADS)

van Niekerk, Deon; Keil, Klaus

2011-10-01

We document the petrographic setting and textures of Fe,Ni metal, the mineralogy of metallic assemblages, and the modal mineral abundances in the EL3 meteorites Asuka (A-) 881314, A-882067, Allan Hills 85119, Elephant Moraine (EET) 90299/EET 90992, LaPaz Icefield 03930, MacAlpine Hills (MAC) 02635, MAC 02837/MAC 02839, MAC 88136, Northwest Africa (NWA) 3132, Pecora Escarpment 91020, Queen Alexandra Range (QUE) 93351/QUE 94321, QUE 94594, and higher petrologic type ELs Dar al Gani 1031 (EL4), Sayh al Uhaymir 188 (EL4), MAC 02747 (EL4), QUE 94368 (EL4), and NWA 1222 (EL5). Large metal assemblages (often containing schreibersite and graphite) only occur outside chondrules and are usually intergrown with silicate minerals (euhedral to subhedral enstatite, silica, and feldspar). Sulfides (troilite, daubréelite, and keilite) are also sometimes intergrown with silicates. Numerous authors have shown that metal in enstatite chondrites that are interpreted to have been impact melted contains euhedral crystals of enstatite. We argue that the metal/sulfide-silicate intergrowths in the ELs we studied were also formed during impact melting and that metal in EL3s thus does not retain primitive (i.e., nebular) textures. Likewise, the EL4s are also impact-melt breccias. Modal abundances of metal in the EL3s and EL4s range from approximately 7 to 30 wt%. These abundances overlap or exceed those of EL6s, and this is consistent either with pre-existing heterogeneity in the parent body or with redistribution of metal during impact processes.

Contribution of early impact events to metal-silicate separation, thermal annealing, and volatile redistribution: Evidence in the Pułtusk H chondrite

NASA Astrophysics Data System (ADS)

Krzesińska, Agata M.

2017-11-01

Three-dimensional X-ray tomographic reconstructions and petrologic studies reveal voluminous accumulations of metal in Pułtusk H chondrite. At the contact of these accumulations, the chondritic rock is enriched in troilite. The rock contains plagioclase-rich bands, with textures suggesting crystallization from melt. Unusually large phosphates are associated with the plagioclase and consist of assemblages of merrillite, and fluorapatite and chlorapatite. The metal accumulations were formed by impact melting, rapid segregation of metal-sulfide melt and the incorporation of this melt into the fractured crater basement. The impact most likely occurred in the early evolution of the H chondrite parent body, when post-impact heat overlapped with radiogenic heat. This enabled slow cooling and separation of the metallic melt into metal-rich and sulfide-rich fractions. This led to recrystallization of chondritic rock in contact with the metal accumulations and the crystallization of shock melts. Phosphorus was liberated from the metal and subsumed by the silicate shock melt, owing to oxidative conditions upon slow cooling. The melt was also a host for volatiles. Upon further cooling, phosphorus reacted with silicates leading to the formation of merrillite, while volatiles partitioned into the residual halogen-rich, dry fluid. In the late stages, the fluid altered merrillite to patchy Cl/F-apatite. The above sequence of alterations demonstrates that impact during the early evolution of chondritic parent bodies might have contributed to local metal segregation and silicate melting. In addition, postshock conditions supported secondary processes: compositional/textural equilibration, redistribution of volatiles, and fluid alterations.

Effect of silicate ions on electrode overvoltage

NASA Technical Reports Server (NTRS)

Gras, J. M.; Seite, C.

1979-01-01

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.

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Choi, Y.; Pando, K.

2011-01-01

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Pozzolanic filtration/solidification of radionuclides in nuclear reactor cooling water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Englehardt, J.D.; Peng, C.

1995-12-31

Laboratory studies to investigate the feasibility of one- and two-step processes for precipitation/coprecipitating radionuclides from nuclear reactor cooling water, filtering with pozzolanic filter aid, and solidifying, are reported in this paper. In the one-step process, ferrocyanide salt and excess lime are added ahead of the filter, and the resulting filter cake solidifies by a pozzolanic reaction. The two-step process involves addition of solidifying agents subsequent to filtration. It was found that high surface area diatomaceous synthetic calcium silicate powders, sold commercially as functional fillers and carriers, adsorb nickel isotopes from solution at neutral and slightly basic pH. Addition of themore » silicates to cooling water allowed removal of the tested metal isotopes (nickel, iron, manganese, cobalt, and cesium) simultaneously at neutral to slightly basic pH. Lime to diatomite ratio was the most influential characteristic of composition on final strength tested, with higher lime ratios giving higher strength. Diatomaceous earth filter aids manufactured without sodium fluxes exhibited higher pozzolanic activity. Pozzolanic filter cake solidified with sodium silicate and a ratio of 0.45 parts lime to 1 part diatomite had compressive strength ranging from 470 to 595 psi at a 90% confidence level. Leachability indices of all tested metals in the solidified waste were acceptable. In light of the typical requirement of removing iron and desirability of control over process pH, a two-step process involving addition of Portland cement to the filter cake may be most generally applicable.« less

Constraining the Depth of the Martian Magma Ocean during Core Formation using Element Partitioning

NASA Astrophysics Data System (ADS)

Wijbrans, Ineke; Tronche, Elodie; van Westrenen, Wim

2010-05-01

The depth of a planetary magma ocean places first order constraints on the thermal state of a young planet. For the Earth, the depth of the magma ocean is mostly constrained by the pressure-temperature conditions at which Fe-rich metal last equilibrated with the bulk silicate Earth (BSE). These equilibration conditions are thought to correspond to the conditions at the terrestrial magma ocean floor, as this is where the metal ponds before sinking to the core. This depth is estimated by combining the BSE contents of siderophile (iron-loving) elements with metal-silicate partition coefficients (D) at high temperatures and pressures [e.g. 1]. The extent and depth of a magma ocean on Mars are hotly debated. In the case of Mars, the sulphur content of the core is significantly higher than for Earth (10-16 wt% sulphur [2]). The presence of sulphur has been shown to have an effect on the metal-silicate partitioning of some siderophile elements [3], but the current data set is insufficient to be of use for direct application to Martian conditions. We have started an experimental programme to constrain siderophile element partition coefficients for Ni and Co between metal and silicate as a function of temperature, pressure and sulphur content in the metal-alloy. For the silicate composition we used a newly proposed bulk silicate Mars (BSM) [4]. We chose the above-mentioned siderophile elements because their BSM concentrations are reasonably known from studies of Martian meteorites. Our aim is to derive new constraints on the depth of the Martian magma ocean and the chemistry accompanying Martian core formation. Experimental methods: The starting material consisted of a 1:1 mixture of silicate glass + quench crystals in the FeO-CaO-MgO-Al2O3-SiO2 (FCMAS) system with a composition based on [4], and metal consisting of FeS, Fe, Ni, Co, FeP3. Four different metal compositions were used with sulphur contents of 0, 5, 15 and 25wt% respectively. Experiments were made in an end-loaded piston-cylinder using graphite-lined Pt capsules. Experiments were performed at 1, 2 and 3 GPa, and at temperatures of 1600 and 1650 °C, for 5hrs. Electron microprobe was used to determine the concentration of major and minor elements in each phase. Results: Preliminary results show that the sulfur content has an effect on the siderophile element partitioning, even within this small range of pressures and temperatures. With these experiments made with realistic conditions for a Martian magma ocean, we will present a new parameterization of metal-silicate D (Ni and Co) depending on pressure, temperature and sulfur content. References: [1] Righter (2003) Ann. Rev. Earth Planet. Sci. 31, 135-174 [2] Schubert (1990) JGR 95, 14095-14104. [3] Jana and Walker (1997) GCA 61, 5255-5277. [4] Khan and Connolly (2008) JGR, 113, E07003.

Lunar and Planetary Science XXXV: Terrestrial Planets: Building Blocks and Differentiation

NASA Technical Reports Server (NTRS)

2004-01-01

The session "Terrestrial Planets: Building Blocks and Differentiation: included the following topics:Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS; Meteoritic Constraints on Collision Rates in the Primordial Asteroid Belt and Its Origin; New Constraints on the Origin of the Highly Siderophile Elements in the Earth's Upper Mantle; Further Lu-Hf and Sm-Nd Isotopic Data on Planetary Materials and Consequences for Planetary Differentiation; A Deep Lunar Magma Ocean Based on Neodymium, Strontium and Hafnium Isotope Mass Balance Partial Resetting on Hf-W System by Giant Impacts; On the Problem of Metal-Silicate Equilibration During Planet Formation: Significance for Hf-W Chronometry ; Solid Metal-Liquid Metal Partitioning of Pt, Re, and Os: The Effect of Carbon; Siderophile Element Abundances in Fe-S-Ni-O Melts Segregated from Partially Molten Ordinary Chondrite Under Dynamic Conditions; Activity Coefficients of Silicon in Iron-Nickel Alloys: Experimental Determination and Relevance for Planetary Differentiation; Reinvestigation of the Ni and Co Metal-Silicate Partitioning; Metal/Silicate Paritioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition; and Closure of the Fe-S-Si Liquid Miscibility Gap at High Pressure and Its Implications for Planetary Core Formation.

Phospho-silicate and silicate layers modified by hydroxyapatite particles

NASA Astrophysics Data System (ADS)

Rokita, M.; Brożek, A.; Handke, M.

2005-06-01

Common used metal materials do not ensure good connection between an implant and biological neighbourhood. Covering implants by thin silicate or phosphate layers enable to improve biological properties of implants and create conditions for producing the non-concrete bonding between the implant and tissue. The project includes preparing silicate sols of different concentrations and proper (powder) fraction of synthetic as well as natural ox hydroxyapatite, depositing the sol mixed with hydroxyapatite onto the base material (metal, ceramic carbon) and heat treatment. Our work includes also preparation of phospho-silicate layers deposited onto different base materials using sol-gel method. Deposited sols were prepared regarding composition, concentration and layer heat treatment conditions. The prepared layers are examined to determine their phase composition (XRD, IR spectroscopy methods), density and continuity (scanning microscopy with EDX methods). Biological activity of layers was evaluated by means of estimation of their corrosive resistance in synthetic body fluids ('in vitro' method) and of bone cells growth on the layers surface. Introducing hydroxyapatite to the layer sol should improve connection between tissue and implant as well as limit the disadvantageous, corrosive influence of implant material (metal) on the tissue.

Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Malouta, A.; Lee, C.-T.

2017-01-01

Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

Synthesis of non-siliceous mesoporous oxides.

PubMed

Gu, Dong; Schüth, Ferdi

2014-01-07

Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

Non-fibrous inorganic particles in bronchoalveolar lavage fluid of pottery workers.

PubMed Central

Falchi, M; Paoletti, L; Mariotta, S; Giosue, S; Guidi, L; Biondo, L; Scavalli, P; Bisetti, A

1996-01-01

AIM: To study the actual exposure of pottery workers to silica particles, as their risk of silicosis is potentially high because of the presence of inhalable crystalline silica particles in the workplace. METHODS: Nine pottery workers underwent bronchoalveolar lavage. The recovered fluid was analysed for cytological and mineralogical content by analytical transmission electron microscopy. The data were compared with those obtained from a control group composed of seven patients with sarcoidosis and six patients with haemoptysis. RESULTS: Cytological results showed a similar profile in exposed workers and controls, whereas in patients with sarcoidosis a lymphocytic alveolitis was found. Microanalysis of the particulate identified the presence of silicates, CRSs, and metals. Pottery workers had higher numbers of total particles and CRSs, and had a higher silicate/metal ratio. In five workers, the presence of zirconium silicate was also detected. Patients with sarcoidosis had the lowest number of particles, and an inverted silicate/metal ratio. CONCLUSION: Microanalysis by transmission electron microscope can provide useful information to assess occupational exposure to dusts. PMID:9038801

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals - II. Application to Fe2+ --> Ti4+ charge transfer transitions in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1987-01-01

A molecular orbital description, based on Xα-Scattered wave calculations on a (FeTiO10)14− cluster, is given for Fe2+ → Ti4+ charge transfer transitions in minerals. The calculated energy for the lowest Fe2+ → Ti4+ metal-metal charge transfer transition is 18040 cm−1 in reasonable agreement with energies observed in the optical spectra of Fe-Ti oxides and silicates. As in the case of Fe2+ → Fe3+ charge transfer in mixed-valence iron oxides and silicates, Fe2+ → Ti4+ charge transfer is associated with Fe-Ti bonding across shared polyhedral edges. Such bonding results from the overlap of the Fe(t 2g ) and Ti(t 2g ) 3d orbitals.

Size distributions and aerodynamic equivalence of metal chondrules and silicate chondrules in Acfer 059

NASA Technical Reports Server (NTRS)

Skinner, William R.; Leenhouts, James M.

1993-01-01

The CR2 chondrite Acfer 059 is unusual in that the original droplet shapes of metal chondrules are well preserved. We determined separate size distributions for metal chondrules and silicate chondrules; the two types are well sorted and have similar size distributions about their respective mean diameters of 0.74 mm and 1.44 mm. These mean values are aerodynamically equivalent for the contrasting densities, as shown by calculated terminal settling velocities in a model solar nebula. Aerodynamic equivalence and similarity of size distributions suggest that metal and silicate fractions experienced the same sorting process before they were accreted onto the parent body. These characteristics, together with depletion of iron in Acfer 059 and essentially all other chondrites relative to primitive CI compositions, strongly suggest that sorting in the solar nebula involved a radial aerodynamic component and that sorting and siderophile depletion in chondrites are closely related.

Effect of natural fiber types and sodium silicate coated on natural fiber mat/PLA composites: Tensile properties and rate of fire propagation

NASA Astrophysics Data System (ADS)

Thongpin, C.; Srimuk, J.; hipkam, N.; Wachirapong, P.

2015-07-01

In this study, 3 types of natural fibres, i.e. jute, sisal and abaca, were plain weaved to fibre mat. Before weaving, the fibres were treated with 5% NaOH to remove hemi cellulose and lignin. The weaving was performed by hand using square wooden block fit with nails for weaving using one and two types of natural fibres as weft and warp fibre to produce natural fibre mat. The fibre mat was also impregnated in sodium silicate solution extracted from rich husk ash. The pH of the solution was adjusted to pH 7 using H2SO4 before impregnation. After predetermined time, sodium silicate was gelled and deposited on the mat. The fabric mat and sodium silicate coated mat were then impregnated with PLA solution to produce prepreg. Dried pepreg was laminated with PLA sheet using compressing moulding machine to obtain natural fibre mat/PLA composite. The composite containing abaca aligned in longitudinal direction with respect to tension force enhanced Young's modulus more than 300%. Fibre mat composites with abaca aligned in longitudinal direction also showed tensile strength enhancement nearly 400% higher than neat PLA. After coating with sodium silicate, the tensile modulus of the composites was found slightly increased. The silicate coating was disadvantage on tensile strength of the composite due to the effect of sodium hydroxide solution that was used as solvent for silicate extraction from rice husk ash. However, sodium silicate could retard rate of fire propagation about 50%compare to neat PLA and about 10% reduction compared to fibre mat composites without sodium silicate coated fibre mat.

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

NASA Technical Reports Server (NTRS)

Sibille, L.; Gavira-Gallardo, J. A.; Hourlier-Bahloul, D.

2004-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil similar JSC-1 in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. Characterization of the precursor molecules and efforts to further concentrate and hydrolyze the products to obtain gel materials will be presented for evaluation as ceramic precursors.

Synthesis of Sol-Gel Precursors for Ceramics from Lunar and Martian Soil Simulars

NASA Technical Reports Server (NTRS)

Sibille, L.; Gavira-Gallardo, J. A.; Hourlier-Bahloul, D.

2003-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report initial results on the production of sol-gel precursors for ceramic products using mineral resources available in martian or lunar soil. The presence of SiO2, TiO2, and Al2O3 in both martian (44 wt.% SiO2, 1 wt.% TiO2,7 wt.% Al2O3) and lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from lunar and martian soil simulars. Clear solutions of sol-gel precursors have been obtained by dissolution of silica from lunar soil simular in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Similarly, sol-gel solutions produced from martian soil simulars reveal higher contents of iron oxides. The elemental composition and structure of the precursor molecules were characterized. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors.

Encapsulation of aluminium in geopolymers produced from metakaolin

NASA Astrophysics Data System (ADS)

Kuenzel, C.; Neville, T. P.; Omakowski, T.; Vandeperre, L.; Boccaccini, A. R.; Bensted, J.; Simons, S. J. R.; Cheeseman, C. R.

2014-04-01

Magnox swarf contaminated with trace levels of Al metal is an important UK legacy waste originated from the fuel rod cladding system used in Magnox nuclear power stations. Composite cements made from Portland cement and blast furnace slag form a potential encapsulation matrix. However the high pH of this system causes the Al metal to corrode causing durability issues. Geopolymers derived from metakaolin are being investigated as an alternative encapsulation matrix for Magnox swarf waste and the corrosion kinetics and surface interactions of Al with metakaolin geopolymer are reported in this paper. It is shown that the pH of the geopolymer paste can be controlled by the selection of metakaolin and the sodium silicate solution used to form the geopolymer. A decrease in pH of the activation solution reduces corrosion of the Al metal and increases the stability of bayerite and gibbsite layers formed on the Al surface. The bayerite and gibbsite act as a passivation layer which inhibits further corrosion and mitigates H2 generation. The research shows that optimised metakaolin geopolymers have potential to be used to encapsulate legacy Magnox swarf wastes.

Extraction of trace metals from fly ash

DOEpatents

Blander, M.; Wai, C.M.; Nagy, Z.

1983-08-15

A process is described for recovering silver, gallium and/or other trace metals from a fine grained industrial fly ash associated with a process for producing phosphorous. The fly ash has a silicate base and contains surface deposits of the trace metals as oxides, chlorides or the like. The process is carried out by contacting the fly ash with AlCl/sub 3/ in an alkali halide melt to react the trace metals with the AlCl/sub 3/ to form compositions soluble in the melt and a residue containing the silicate and aluminum oxide or other aluminum precipitate, and separating the desired trace metal or metals from the melt by electrolysis or other separation techniques.

Extraction of trace metals from fly ash

DOEpatents

Blander, Milton; Wai, Chien M.; Nagy, Zoltan

1984-01-01

A process for recovering silver, gallium and/or other trace metals from a fine grained industrial fly ash associated with a process for producing phosphorous, the fly ash having a silicate base and containing surface deposits of the trace metals as oxides, chlorides or the like, with the process being carried out by contacting the fly ash with AlCl.sub.3 in an alkali halide melt to react the trace metals with the AlCl.sub.3 to form compositions soluble in the melt and a residue containing the silicate and aluminum oxide or other aluminum precipitate, and separating the desired trace metal or metals from the melt by electrolysis or other separation techniques.

The effect of thermal and organic additive in morphology of ceramic based silicate

NASA Astrophysics Data System (ADS)

Ginting, J.; Bangun, N.; Sembiring, H. Br; Putri, N. K.

2017-04-01

M-Silicate (M = Mg, Ca) has been prepared by exchange metal reaction from M-Chloride salts and sodium silicate. The resulting white solid of chloride salts then heated at 700, 800, 900 and 1000 °C. Due to increase the porosity of M-Silicate, 1,2-propanediol, oleic acid and glycerol were added, then formed M-silicates were heated at 800 °C. Then, obtained white solid M-Silicates were characterized by Scanning Electron Microscopy (SEM). SEM images show the variance of surface morphology when the temperature increases. The addition of organic compounds is involved in surface modification.

Unusual olivine and pyroxene composition in interplanetary dust and unequilibrated ordinary chondrites

NASA Technical Reports Server (NTRS)

Klock, W.; Mckay, D. S.; Thomas, K. L.; Palme, H.

1989-01-01

The presence, in both a number of interplanetary dust particles (IDPs) and in meteorite matrices, of olivine and orthopyroxene grains, low in FeO but containing up to 5 wt pct MnO, is reported. The majority of olivines and pyroxenes in meteorites contain less than 0.5 wt pct MnO. The presence of these low-iron, manganese-enriched (LIME) olivines and pyroxenes in IDPs and meteorites may indicate a link between the origin and history of IDPs and the matrix material of primitive meteorites. The origin of the LIME silicates could be explained by condensation from a gas of solar composition. Forsterite is the first major silicate phase to condense from a solar nebula gas, and Mn, which is not stable as a metal under solar nebula conditions, would condense at about 1100 K as Mn2SiO4 in solid solution with forsterite.

Chemistry and Ni-isotope composition of ureilites and their components

NASA Astrophysics Data System (ADS)

Gabriel, A. D.; Quitté, G.; Pack, A.

2008-09-01

Ureilites are olivine-pigeonite bearing achondrites with interstitial carbonaceous material and metal. The latter is present as <1 μm metal inclusions in reduced rims of silicate grains, 5-20 μm spherical inclusions in clear silicate grains, and in association with interstitial carbonaceous material. We have studied the composition of metal and silicates in 9 ureilites with a fayalite content of Fa2 to Fa21. Vein metal contains 3.7 to 5.4 wt% Ni and 0.35 to 0.54 wt% Co. Cobalt and Ni contents in vein metal and fayalite in olivine do not correlate. Mass balance calculations assuming a chondritic parent body yield a metal core with 7 to 11 wt% Ni and 0.3 to 0.55 wt% Co. Thermodynamic calculations of Fe-Ni and Fe-Co exchange between olivine and vein metal show that vein metal cannot be in equilibrium with the olivine at any temperature. We conclude that the vein metal is genetically not linked to the ureilite olivine and may have been injected into the parent body by an impactor. Recently published data show a deficit in 60Ni of - 0.24+/-0.02 ɛ-units for various achondrites including ureilites [1]. This has been interpreted as evidence for a late injection of 60Fe after formation of these achondrites. However, our chemical data for vein metal, which is the dominant Ni host in ureilites, demonstrate that bulk Ni isotope data have little meaning with respect to the formation of ureilite silicates. In this work we present Ni isotope data for bulk samples but also vein material and the silicate phase of 4 ureilites (ALHA77257, EET87157, EET96041, Kenna). Bulk ureilites have a ɛ60 between -0.05+/-0.12 and 0.08+/-0.12; the vein metal gives ɛ60 = -0.05+/-0.13 to 0.11+/-0.16. No resolvable deficit in ɛ60 was found, in disagreement with results reported in Bizzarro et al. (2007). The vein material and the bulk samples have, within uncertainty, the same isotopic composition, confirming that the global Ni budget is controlled by the vein material. In ureilite silicates ɛ60 varies from -0.77+/-0.31 to -0.12+/-0.21. Due to the high Fe/Ni ratio of silicates, clear excesses of 60Ni (at least several ɛ-units) are expected if they formed early in the solar system. This is not observed. There is thus no evidence for life 60Fe in ureilites, which may be interpreted in different ways: either 60Fe was injected at a later time into the protoplanetary disk as suggested by [1] (but this is difficult to reconcile with data obtained in other meteorites [2]), or several isotopically distinct reservoirs co-existed at the beginning of the solar system. The isotopic difference between vein material and silicates rather supports the second hypothesis, even if further studies are required to confirm it. It may also be that the Fe-Ni system has been disturbed at a later stage after formation of ureilites. References [1] Bizzarro M. et al. 2007. Science 316 (5828), 1178- 1181. [2] Quitté G. et al. 2007. LPSC 38, abstract #1900.

An interconnected network of core-forming melts produced by shear deformation

PubMed

Bruhn; Groebner; Kohlstedt

2000-02-24

The formation mechanism of terrestrial planetary cores is still poorly understood, and has been the subject of numerous experimental studies. Several mechanisms have been proposed by which metal--mainly iron with some nickel--could have been extracted from a silicate mantle to form the core. Most recent models involve gravitational sinking of molten metal or metal sulphide through a partially or fully molten mantle that is often referred to as a 'magma ocean'. Alternative models invoke percolation of molten metal along an interconnected network (that is, porous flow) through a solid silicate matrix. But experimental studies performed at high pressures have shown that, under hydrostatic conditions, these melts do not form an interconnected network, leading to the widespread assumption that formation of metallic cores requires a magma ocean. In contrast, here we present experiments which demonstrate that shear deformation to large strains can interconnect a significant fraction of initially isolated pockets of metal and metal sulphide melts in a solid matrix of polycrystalline olivine. Therefore, in a dynamic (non-hydrostatic) environment, percolation remains a viable mechanism for the segregation and migration of core-forming melts in a solid silicate mantle.

Silicate Inclusions in IAB Irons: Correlations Between Metal Composition and Inclusion Properties, and Inferences for Their Origin

NASA Astrophysics Data System (ADS)

Benedix, G. K.; McCoy, T. J.; Keil, K.

1995-09-01

IAB irons are the largest group of iron meteorites, exhibit a large range of siderophile element concentrations in their metal, and commonly contain silicate inclusions with roughly chondritic composition. They are closely related to IIICD irons [1,2] and their inclusions resemble winonaites [3]. It has been suggested that IAB's and IIICD's formed in individual impact melt pools [4,2] on a common parent body. However, it has also been suggested that fractional crystallization [5,6] of a S-saturated core could produce the observed siderophile element trends. Metal composition is correlated with silicate inclusion mineralogy in IIICD's [1], indicating reactions between solid silicates and the metallic magma in a core. These trends observed in IIICD's differ from those in IAB's, suggesting different parent bodies. A bi-modal grouping, based primarily on mineralogy and mineral abundances, was suggested for IAB inclusions [7]. However, recent recoveries of several new silicate-bearing IAB's, along with the emergence of new ideas on their origins, prompted a comprehensive study to document more fully the range of inclusions within IAB irons, to examine possible correlations between the compositions of the metallic host and the silicate inclusions, and to elucidate the origin of IAB irons. We are studying troilite-graphite-silicate inclusions in 24 IAB irons with Ni concentrations ranging from 6.6-25.0%. These include Odessa and Copiapo types [7], newly recovered meteorites (e.g., Lueders [8]) and meteorites with extreme Ni contents (e.g., Jenny's Creek, 6.8%; San Cristobal, 25.0% [9]). The inclusions exhibit a range of textures from recrystallized to partial melts (e.g., Caddo County [10]). Rigorous classification [7] is hampered by heterogeneities between group meteorites, between different samples of distinct meteorites, and within individual inclusions. While intergroup heterogeneities make comparisons between the suite of IAB's somewhat difficult, some general trends do exist. Inclusion mineralogy progresses from graphite-troilite nodules in low Ni IAB's, to silicate-dominated inclusions in high Ni IAB's. With increasing Ni abundance in the metal, systematic variations are found in several properties. Two groups are delineated on a Ni vs Fa content plot and both are positively correlated with Ni content. Graphite abundance noticeably decreases with increasing Ni content [7]. Graphite location also varies with Ni: graphite is primarily found interstitial to the silicates in low Ni IAB's, but is located at metal-silicate boundaries in those with higher Ni abundances. With increasing Ni, daubreelite disappears. Inclusion shape also varies [7]: more angular inclusions are associated with low Ni, while more rounded inclusions exist at high Ni contents. These systematic changes suggest interaction between the silicate inclusions and an evolving metallic magma. Troilite and graphite abundances may be related to early nucleation on silicates, hence their depletion in high Ni (later crystallizing) irons. The presence of abundant graphite creates reducing conditions which would result in the formation of daubreelite. Conditions become more oxidizing with loss of graphite, evidenced by lack of daubreelite and more FeO-rich silicates in high Ni irons. Although an overall trend exists, the story is complicated by heterogeneities. Significant variations are found between paired samples (e.g., Toluca and Tacubaya), as well as within individual inclusions (daubreelite and chromite in same inclusion). Local oxidation conditions may be controlled by graphite abundance. Heterogeneities within specific meteorites need documentation. Most of the inclusions exhibit similar textural (metamorphic) features, but a few show evidence of partial melting and melt migration, further complicating the parent body history. While a variety of processes (oxidation-reduction, metamorphism, partial melting) affected the inclusions during formation, systematic changes observed here indicate that the silicates were interacting with a single evolving metallic magma. We suggest that the requirement for a common system is more compatible with core formation [5,6] than with impact-melt pools [2,4]. References: [1] McCoy T. J. et al. (1993) Meteoritics, 28, 552-560. [2] Choi B.-G. et al. (1995) GCA, 59, 593-612. [3] Benedix G. K. et al. (1995) LPS XXVI, 99-100. [4] Wasson J. T. et al. (1980) Z. Naturforsch., 35a, 781-795. [5] Kracher A. (1982) GRL, 9, 412-415. [6] Kracher A. (1985) Proc. LPSC 15th, in JGR, 90, C689-C698. [7] Bunch T. E. et al. (1970) Contrib. Mineral. Petrol., 25, 297-340. [8] McCoy et al. (1995) Meteoritics, in preparation. [9] Scott E. R. D. and Bild R. W. (1974) GCA, 38, 1379-1391. [10] Takeda H. et al. (1993) Meteoritics, 28, 447.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate differentiation processes, such as partial mantle melting and crystal fractionation, can cause stable Cr isotopic fractionation on Earth and other planetary bodies.

Formation of Metal and Silicate Globules in Gujba: A New Bencubbin-like Meteorite Fall

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.; Clayton, Robert N.; Mayeda, Toshiko; Grady, Monica; Verchovsky, Alexander B.; Eugster, Otto; Lorenzetti, Silvio

2006-01-01

Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

Evidence of cross-cutting and redox reaction in Khatyrka meteorite reveals metallic-Al minerals formed in outer space.

PubMed

Lin, Chaney; Hollister, Lincoln S; MacPherson, Glenn J; Bindi, Luca; Ma, Chi; Andronicos, Christopher L; Steinhardt, Paul J

2017-05-09

We report on a fragment of the quasicrystal-bearing CV3 carbonaceous chondrite Khatyrka recovered from fine-grained, clay-rich sediments in the Koryak Mountains, Chukotka (Russia). We show higher melting-point silicate glass cross-cutting lower melting-point Al-Cu-Fe alloys, as well as unambiguous evidence of a reduction-oxidation reaction history between Al-Cu-Fe alloys and silicate melt. The redox reactions involve reduction of FeO and SiO 2 to Fe and Fe-Si metal, and oxidation of metallic Al to Al 2 O 3 , occurring where silicate melt was in contact with Al-Cu-Fe alloys. In the reaction zone, there are metallic Fe and Fe-Si beads, aluminous spinel rinds on the Al-Cu-Fe alloys, and Al 2 O 3 enrichment in the silicate melt surrounding the alloys. From this and other evidence, we demonstrate that Khatyrka must have experienced at least two distinct events: first, an event as early as 4.564 Ga in which the first Al-Cu-Fe alloys formed; and, second, a more recent impact-induced shock in space that led to transformations of and reactions between the alloys and the meteorite matrix. The new evidence firmly establishes that the Al-Cu-Fe alloys (including quasicrystals) formed in outer space in a complex, multi-stage process.

High Performance Multifunctional Corrosion Inhibitors Especially for Combining at 20 to 50 Weight Percent with Soap or Paint.

DTIC Science & Technology

1987-12-22

zinc sulfate and ben- Coad Pefert i esrcent) zotriazole (BT) are also required. The alkali metal can 5 Component Broad Preferred Ingredients (percent)b...Nitrate .05 .0 .40 glucose 0.072 Silicate .002 .01 .04 smmomum sulfate 4.00 potamium phosphate 0.175 20 Phosphate .003 .005 .02MET .0061 .003 .012...potsium sulfate 0.134 tions 2 and 3 are recommended for use in aggressive solutions such as are found in the bilge areas of aircraft. FIG. 6

Preliminary results of sulfide melt/silicate wetting experiments in a partially melted ordinary chondrite

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, John H.

1994-01-01

Recently, mechanisms for core formation in planetary bodies have received considerable attention. Most current theories emphasize the need for large degrees of silicate partial melting to facilitate the coalescence and sinking of sulfide-metal liquid blebs through a low strength semi-crystalline silicate mush. This scenario is based upon observations that sulfide-metal liquid tends to form circular blebs in partially molten meteorites during laboratory experiments. However, recent experimental work by Herpfer and Larimer indicates that some sulfide-Fe liquids have wetting angles at and slightly below 60 deg in an olivine aggregate, implying an interconnected melt structure at any melt fraction. Such melt interconnectivity provides a means for gravitational compaction and extraction of the majority of a sulfide liquid phase in small planetary bodies without invoking large degrees of silicate partial melting. Because of the important ramifications of these results, we conducted a series of experiments using H-chondrite starting material in order to evaluate sulfide-liquid/silicate wetting behavior in a more complex natural system.

A carbon-rich region in Miller Range 091004 and implications for ureilite petrogenesis

NASA Astrophysics Data System (ADS)

Day, James M. D.; Corder, Christopher A.; Cartigny, Pierre; Steele, Andrew M.; Assayag, Nelly; Rumble, Douglas; Taylor, Lawrence A.

2017-02-01

Ureilite meteorites are partially melted asteroidal-peridotite residues, or more rarely, cumulates that can contain greater than three weight percent carbon. Here we describe an exceptional C-rich lithology, composed of 34 modal % large (up to 0.8 mm long) crystalline graphite grains, in the Antarctic ureilite meteorite Miller Range (MIL) 091004. This C-rich lithology is embedded within a silicate region composed dominantly of granular olivine with lesser quantities of low-Ca pyroxene, and minor FeNi metal, high-Ca pyroxene, spinel, schreibersite and troilite. Petrological evidence indicates that the graphite was added after formation of the silicate region and melt depletion. Associated with graphite is localized reduction of host olivine (Fo88-89) to nearly pure forsterite (Fo99), which is associated with FeNi metal grains containing up to 11 wt.% Si. The main silicate region is typical of ureilite composition, with highly siderophile element (HSE) abundances ∼0.3 × chondrite, 187Os/188Os of 0.1260-0.1262 and Δ17O of -0.81 ± 0.16‰. Mineral trace-element analyses reveal that the rare earth elements (REE) and the HSE are controlled by pyroxene and FeNi metal phases in the meteorite, respectively. Modeling of bulk-rock REE and HSE abundances indicates that the main silicate region experienced ∼6% silicate and >50% sulfide melt extraction, which is at the lower end of partial melt removal estimated for ureilites. Miller Range 091004 demonstrates heterogeneous distribution of carbon at centimeter scales and a limited range in Mg/(Mg + Fe) compositions of silicate grain cores, despite significant quantities of carbon. These observations demonstrate that silicate rim reduction was a rapid disequilibrium process, and came after silicate and sulfide melt removal in MIL 091004. The petrography and mineral chemistry of MIL 091004 is permissive of the graphite representing late-stage C-rich melt that pervaded silicates, or carbon that acted as a lubricant during anatexis and impact disruption in the parent body. Positive correlation of Pt/Os ratios with olivine core compositions, but a wide range of oxygen isotope compositions, indicates that ureilites formed from a compositionally heterogeneous parent body that experienced variable sulfide and metal melt-loss that is most pronounced in relatively oxidized ureilites with Δ17O between -1.5 and ∼0‰.

Pyrolytic Synthesis of Carbon Nanotubes from Sucrose on a Mesoporous Silicate

NASA Technical Reports Server (NTRS)

Abdel-Fattah, Tarek; Siochi, Mia; Crooks, Roy

2005-01-01

Multiwall carbon nanotubes were synthesized from sucrose by a pyrolytic technique using mesoporous MCM-41 silicate templates without transition metal catalysts. The Nanotubes were examined in the carbon/silicate composite and after dissolution of the silicate. High resolution transmission electron microscopy study of the multiwall nanotubes showed them to be 15 nm in diameter, 200 nm in length and close-ended. There was variation in crystallinity with some nanotubes showing disordered wall structures.

Differentiation of Asteroid 4 Vesta: Core Formation by Iron Rain in a Silicate Magma Ocean

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Mittlefehldt, David W.

2017-01-01

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft while orbiting asteroid 4 Vesta, suggest that Vesta resembles H chondrites in bulk chemical composition, possible with about 25 percent of a CM-chondrite like composition added in. For this model, the core is 15 percent by mass (or 8 percent by volume) of the asteroid, with a composition of 73.7 percent by weight Fe, 16.0 percent by weight S, and 10.3 percent by weight Ni. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. The combination of the melting phase relationships for the silicate and metal phases, together with the moderately siderophile element concentrations together require that complete melting of the metal phase occurred (temperature is greater than1350 degrees Centigrade), along with substantial (greater than 40 percent) melting of the silicate material. Thus, core formation on Vesta occurs as iron rain sinking through a silicate magma ocean.

Polysilicate binding for silicate paints

NASA Astrophysics Data System (ADS)

Ivanovna, Loganina Valentina; Nikolaevna, Kislitsyna Svetlana; Bisengalievich, Mazhitov Yerkebulan

2018-06-01

It was suggested, that the polysilicate solutions obtained by mixing liquid glass and silicic acid sol as a binder in the manufacture of silicate paints. Information is provided on the structure and a property of the sodium polysilicate binder is presented. It has been found that the addition of silica powder to a liquid glass causes gelling in the course of time. It has been established that the introduction of the sol (increasing the silicate module) contributes to an increase in the fraction of high-polymer fractions of silicic anion, with the increase in the sol content of the polymer form of silica increasing. The research results the structure of sols and polysilicate solutions by the method of violation of total internal reflection. By the method of IR spectroscopy, the molybdate method established the presence of silica in the polysilicate binder polymeric varieties, which provides an increase in the stability of silicate coatings.

Metal-Silicate Segregation in Asteroidal Meteorites

NASA Technical Reports Server (NTRS)

Herrin, Jason S.; Mittlefehldt, D. W.

2006-01-01

A fundamental process of planetary differentiation is the segregation of metal-sulfide and silicate phases, leading eventually to the formation of a metallic core. Asteroidal meteorites provide a glimpse of this process frozen in time from the early solar system. While chondrites represent starting materials, iron meteorites provide an end product where metal has been completely concentrated in a region of the parent asteroid. A complimentary end product is seen in metal-poor achondrites that have undergone significant igneous processing, such as angrites, HED's and the majority of aubrites. Metal-rich achondrites such as acapulcoite/lodranites, winonaites, ureilites, and metal-rich aubrites may represent intermediate stages in the metal segregation process. Among these, acapulcoite-lodranites and ureilites are examples of primary metal-bearing mantle restites, and therefore provide an opportunity to observe the metal segregation process that was captured in progress. In this study we use bulk trace element compositions of acapulcoites-lodranites and ureilites for this purpose.

Growth dynamics and composition of tubular structures in a reaction-precipitation system

NASA Astrophysics Data System (ADS)

Pagano, Jason John

Self-organization in reaction precipitation systems occurs in many physical, chemical, biological, and geological systems. In particular, chemical reactions provide a wealth of examples for this intriguing process. Permanent tubular structures arise from the interplay of chemical and transport phenomena such as diffusion and fluid flow. These astonishing tubular structures are prevalent throughout nature. Examples include black smokers at hydrothermal vents, silica tubes in setting cement, soda-straw stalactites in caves, and biological structures such as the outer skeleton of certain algae. In this work, the aim is to establish and understand a laboratory scale model by examining the, seemingly simple, precipitation reaction between sodium silicate and copper sulfate as well as zinc sulfate. The tubular precipitation structures in so-called silica gardens are known to many scientists and non-scientists alike. However, little is known regarding their growth dynamics and chemical composition. We devised an injection technique which provides control over parameters that are not accessible in the classic silica garden system. For the example of cupric sulfate injection into waterglass solution, we identify three distinct growth regimes (jetting, popping, and budding) and study their concentration dependent transitions. Here we describe the composition and morphology of the tube material using techniques such as electron microscopy and vibrational spectroscopy. Specifically, we find that the tube wall consists of metal hydroxide that is stabilized by a thin, exterior silica layer. After synthesis the tubes can be further modified by using chemical and/or physical means. A second study aims to understand tubule formation under "reverse" conditions. More specifically, waterglass is being injected into lighter cupric sulfate solution. In these experiments, single, downward growing precipitation tubes are created. Four distinct growth regimes are observed and their stability in terms of flow rate and cupric sulfate concentration is investigated. Three of these growth regimes (reverse jetting, reverse popping, and reverse budding) resemble the same behavior for the injection of cupric sulfate into silicate solution. However, the reverse conditions studied herein reveal one novel regime in which the tube is limited by repetitive fracturing. The lengths of the broken-off tube segments and times between subsequent break-off events can be described by log-normal distributions. We also discuss the development of a method for synthesizing highly linear precipitation tubes via gas bubble injection and templating. In this method, an aqueous metal salt is injected into a large reservoir of waterglass. Systematic measurements show that the size of the bubble governs the tube radius. According to this radius, the system selects its growth velocity following volume conservation of the injected metal salt solution. Moreover, scanning electron microscopy reveals intricate ring patterns on the walls. We also show evidence for the existence of minimal and maximal tube radius. Lastly, we report the collapse of tubes at high concentrations of silicate solution, yielding twisted ribbon-like structures. Critical radii and tube collapse are discussed in terms of simple competing forces. Concluding, the latter study suggests that one can create interesting geometries and the possible production of speciality materials. Furthermore, we extend our results toward other metals. This study reveals that silica-supported zinc hydroxide walls can be reacted to form zinc oxide. The chemically activated walls are composed of zinc oxide nanoparticles that can be used for technical applications.

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Fast accretion of the Earth with a late Moon-forming giant impact

PubMed Central

Yu, Gang; Jacobsen, Stein B.

2011-01-01

Constraints on the formation history of the Earth are critical for understanding of planet formation processes. 182Hf-182W chronometry of terrestrial rocks points to accretion of Earth in approximately 30 Myr after the formation of the solar system, immediately followed by the Moon-forming giant impact (MGI). Nevertheless, some N-body simulations and 182Hf-182W and 87Rb-87Sr chronology of some lunar rocks have been used to argue for a later formation of the Moon at 52 to > 100 Myr. This discrepancy is often explained by metal-silicate disequilibrium during giant impacts. Here we describe a model of the 182W isotopic evolution of the accreting Earth, including constraints from partitioning of refractory siderophile elements (Ni, Co, W, V, and Nb) during core formation, which can explain the discrepancy. Our modeling shows that the concentrations of the siderophile elements of the mantle are consistent with high-pressure metal-silicate equilibration in a terrestrial magma ocean. Our analysis shows that the timing of the MGI is inversely correlated with the time scale of the main accretion stage of the Earth. Specifically, the earliest time the MGI could have taken place right at approximately 30 Myr, corresponds to the end of main-stage accretion at approximately 30 Myr. A late MGI (> 52 Myr) requires the main stage of the Earth’s accretion to be completed rapidly in < 10.7 ± 2.5 Myr. These are the two end member solutions and a continuum of solutions exists in between these extremes. PMID:22006299

Fast accretion of the earth with a late moon-forming giant impact.

PubMed

Yu, Gang; Jacobsen, Stein B

2011-10-25

Constraints on the formation history of the Earth are critical for understanding of planet formation processes. (182)Hf-(182)W chronometry of terrestrial rocks points to accretion of Earth in approximately 30 Myr after the formation of the solar system, immediately followed by the Moon-forming giant impact (MGI). Nevertheless, some N-body simulations and (182)Hf-(182)W and (87)Rb-(87)Sr chronology of some lunar rocks have been used to argue for a later formation of the Moon at 52 to > 100 Myr. This discrepancy is often explained by metal-silicate disequilibrium during giant impacts. Here we describe a model of the (182)W isotopic evolution of the accreting Earth, including constraints from partitioning of refractory siderophile elements (Ni, Co, W, V, and Nb) during core formation, which can explain the discrepancy. Our modeling shows that the concentrations of the siderophile elements of the mantle are consistent with high-pressure metal-silicate equilibration in a terrestrial magma ocean. Our analysis shows that the timing of the MGI is inversely correlated with the time scale of the main accretion stage of the Earth. Specifically, the earliest time the MGI could have taken place right at approximately 30 Myr, corresponds to the end of main-stage accretion at approximately 30 Myr. A late MGI (> 52 Myr) requires the main stage of the Earth's accretion to be completed rapidly in < 10.7 ± 2.5 Myr. These are the two end member solutions and a continuum of solutions exists in between these extremes.

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

Geochemical Constraints on Core Formation in the Earth

NASA Technical Reports Server (NTRS)

Jones, John H.; Drake, Michael J.

1986-01-01

New experimental data on the partitioning of siderophile and chalcophile elements among metallic and silicate phases may be used to constrain hypotheses of core formation in the Earth. Three current hypotheses can explain gross features of mantle geochemistry, but none predicts siderophile and chalcophile element abundances to within a factor of two of observed values. Either our understanding of metal-silicate interactions and/or our understanding of the early Earth requires revision.

Effect of Silicon on Activity Coefficients of P, Bi, Cd, Sn, and Ag in Liquid Fe-Si, and Implications for Core Formation

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Ross, D. K.; Righter, M.; Lapen, T. J.

2018-01-01

Cores of differentiated bodies (Earth, Mars, Mercury, Moon, Vesta) contain light elements such as S, C, Si, and O. We have previously measured small effects of Si on Ni and Co, and larger effects on Mo, Ge, Sb, As metal/silicate partitioning. The effect of Si on metal-silicate partitioning has been quantified for many siderophile elements, but there are a few key elements for which the effects are not yet quantified. Here we report new experiments designed to quantify the effect of Si on the partitioning of Bi, Cd, Sn, Ag, and P between metal and silicate melt. The results will be applied to Earth, Mars, Moon, and Vesta, for which we have good constraints on the mantle Bi, Cd, Sn, Ag, and P concentrations from mantle and/or basalt samples.

Late metal-silicate separation on the IAB parent asteroid: Constraints from combined W and Pt isotopes and thermal modelling

NASA Astrophysics Data System (ADS)

Hunt, Alison C.; Cook, David L.; Lichtenberg, Tim; Reger, Philip M.; Ek, Mattias; Golabek, Gregor J.; Schönbächler, Maria

2018-01-01

The short-lived 182Hf-182W decay system is a powerful chronometer for constraining the timing of metal-silicate separation and core formation in planetesimals and planets. Neutron capture effects on W isotopes, however, significantly hamper the application of this tool. In order to correct for neutron capture effects, Pt isotopes have emerged as a reliable in-situ neutron dosimeter. This study applies this method to IAB iron meteorites, in order to constrain the timing of metal segregation on the IAB parent body. The ε182W values obtained for the IAB iron meteorites range from -3.61 ± 0.10 to -2.73 ± 0.09. Correlating εiPt with ε182W data yields a pre-neutron capture ε182W of -2.90 ± 0.06. This corresponds to a metal-silicate separation age of 6.0 ± 0.8 Ma after CAI for the IAB parent body, and is interpreted to represent a body-wide melting event. Later, between 10 and 14 Ma after CAI, an impact led to a catastrophic break-up and subsequent reassembly of the parent body. Thermal models of the interior evolution that are consistent with these estimates suggest that the IAB parent body underwent metal-silicate separation as a result of internal heating by short-lived radionuclides and accreted at around 1.4 ± 0.1 Ma after CAIs with a radius of greater than 60 km.

Solubility of tungsten in a haplobasaltic melt as a function of temperature and oxygen fugacity

NASA Astrophysics Data System (ADS)

Ertel, W.; O'Neill, H. St. C.; Dingwell, D. B.; Spettel, B.

1996-04-01

The solubility of tungsten (W) in a haplobasaltic melt has been determined as a function of oxygen fugacity in the temperature range 1300-1500°C using the mechanically assisted equilibrium technique of Dingwell et al. (1994), and at 1600-1700°C by the wire loop method. Quenched samples were analysed for W by using ICP-AES as well as INAA, and sample major element compositions were checked by electron microprobe. W concentrations ranged from 20 ppm to 17 wt%, and the solution of WO 2 in the melt may be described by Henry's Law up to remarkably high concentrations (e.g., 14 wt% at 1500°C). W dissolves in the melt with a quadrivalent (4+) formal oxidation state over the entire range of oxygen fugacity and temperature investigated. The solubility of W decreases strongly with increasing temperature at constant oxygen fugacity. The solubility data have been used to calculate trace distribution coefficients for W between Fe-rich metal and silicate melt, using literature values for the activity coefficient of W in liquid Fe. Comparison of our data with the distribution coefficients for Mo calculated from the analogous Mo solubility data of Holzheid et al. (1994) shows that the ratio of the metal-silicate distribution coefficient DMomet/sil/ DWmet/sil remains very high (~10 3) at all T-fO 2 conditions. However, in the Earth's mantle, Mo is relatively more depleted than W only by a factor of three. The relative abundances of W and Mo in the Earth's mantle cannot, therefore, be explained by core formation from a homogeneously accreted Earth whatever the temperature at which metal/silicate equilibrium may have ocurred might have been. Their abundances may be quantitatively accounted for by a heterogeneous accretion model such as that of O'Neill (1991).

The redox potential of boron nitride and implications for its use as a crucible material in experimental petrology

NASA Technical Reports Server (NTRS)

Wendlandt, R. F.; Huebner, J. S.; Harrison, W. J.

1982-01-01

The suitability of boron nitride for use as a crucible material in silicate and oxygen-bearing metal sulfide systems has been investigated. Boron nitride is unsatisfactory for use with many silicate systems because its presence in combination with a source of oxygen establishes the oxygen fugacity at values below that of the assemblage quartz + fayalite + iron, reducing transition metal ions such as Ni(2+) and Fe(2+) to the metallic state. B2O3, resulting from the oxidation of BN, acts as a flux to promote formation of melt.

The Sm-Nd systematics of silicate inclusions in iron meteorites: Results from Caddo (IAB)

NASA Technical Reports Server (NTRS)

Stewart, Brian W.; Papanastassiou, D. A.; Wasserburg, G. J.

1993-01-01

The timing of events leading to the formation of silicate-rich and metal-rich regions in planetesimals remains an important problem in the study of planetary formation and differentiation in the early solar system. The IAB irons are especially important as they are considered to represent a magmatic differentiation series. Iron meteorites present a particular challenge for chronological studies, due to the relative paucity of phases serving as hosts for radioactive parent-daughter nuclides. Recent work using the Re-Os system, following on the pioneering work by Herr et al. and Luck and Allegre, appears promising, but investigators up to now have concentrated on whole rock isochrons. Silicate clasts enclosed within iron meteorites can provide information about the chronology and thermal history of irons. Extensive work on Rb-Sr, K-Ar, and I-Xe has been reported on silicate inclusions in iron meteorites. We report the initial results from our Sm-Nd study of an inclusion with the Caddo IAB iron, the first Sm-Nd isotopic study of a silicate clast embedded within an iron meteorite. Our results include measurements of the standard long-lived Sm-147/Nd-143 (tau = 152 AE) system, as well as the shorter-lived SM-146/Nd-142 (tau = 0.149 AE) system, which has been shown to be very useful in deciphering the history of the early solar system. The Caddo silicate clast was described by Palme et al., who kindly provided us with a major part of the inclusion. The inclusion is coarse-grained consisting predominantly of olivine, clinopyroxene, and plagioclase, with lesser amounts of orthopyroxene, Fe-Ni metal, sulfide, and phosphate. The relatively large grain size (up to 3 mm) and 120 degree grain boundaries suggest extensive metamorphism at high temperatures. Based on study of a thin section, there is evidence for metal invading along grain boundaries in some regions of the inclusion, suggesting that the Fe-Ni metal was molten when the silicate clast was incorporated. Metamorphic recrystallization may have occurred during this event.

Metal/Silicate Partitioning of W, Ge, Ga and Ni: Dependence on Silicate Melt Composition

NASA Astrophysics Data System (ADS)

Singletary, S.; Drake, M. J.

2004-12-01

Metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle (Drake and Righter, 2002; Jones and Drake, 1986; Righter et al. 1997). The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. In this work, we investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid. Experiments were performed in the Experimental Geochemistry Laboratory at the University of Arizona utilizing a non-end loaded piston cylinder apparatus with a barium carbonate pressure medium. Starting materials were created by combining the mafic and silicic compositions of Jaeger and Drake (2000) with Fe powder (~25 wt% of the total mixture) to achieve metal saturation. Small amounts of W, Ge, Ga2O3 and NiO powder (less than 2 wt% each) were also added to the starting compositions. The experiments were contained in a graphite capsule and performed with temperature and pressure fixed at 1400ºC and 1.5 GPa. Experimental run products were analyzed with the University of Arizona Cameca SX50 electron microprobe with four wavelength dispersive spectrometers and a PAP ZAF correction program. All experiments in our set are saturated with metal and silicate liquid, indicating that oxygen fugacity is below IW. Several of the runs also contain a gallium-rich spinel as an additional saturating phase. Quench phases are also present in the silicate liquid in all runs. The experimentally produced liquids have nbo/t values (calculated using the method of Mills, 1993) that range from 1.10 to 2.97. These values are higher than those calculated for the liquids in the Jaeger and Drake (2000) study. The higher nbo/t values are due to uptake of Fe by the melt. The initial silicate composition contained no FeO, however the experimentally produced silicate liquids contained from 15 to 26 wt % FeO. We find that W is incompatible over the range of compositions used in this study. However, W compatibility increases as melts become more silicic, with D(W) = 0.0005 at nbo/t = 2.97 and D(W) = 0.09 at nbo/t = 1.1. The slope of the best fit line for the W data when plotted in nbo/t vs Log D space is -1.22 and close to the value of -1.34 found by Jaeger and Drake (2000). Ge is compatible at all compositions and follows a similar pattern to that of W becoming more compatible with decreasing nbo/t (D(Ge)= 14 at nbo/t = 2.97 and D(Ge) = 100 at nbo/t = 1.1). Ni and Ga display essentially flat slopes within the error of our analysis, with D(Ni) = 395 at nbo/t = 2.97 and D(Ni) = 870 at nbo/t 1.10 and D(Ga) = 0.08 at nbo/t = 2.97 and D(Ga) = 0.02 at nbo/t = 1.1. A second series of experiments is in progress to verify these data and extend the study to lower values of nbo/t. References: Drake, M.J. and Righter, K. (2002) Nature, v. 416, 39-44; Jones, J.H. and Drake, M.J. (1986) Nature, v. 323, 470-471; Righter, K., et al. (1997) Physics Earth and Planet. Int., v. 100, 115-134; Jaeger, W.L. and Drake, M.J. (2000) Geo. Cosmo. Acta, v. 64, 3887-3895; Mills, K.C. (1993) ISIJ International, v. 33, 148-155.

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate.

PubMed

Tommaseo, C E; Kersten, M

2002-07-01

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.

Metal-silicate partitioning of U: Implications for the heat budget of the core and evidence for reduced U in the mantle

NASA Astrophysics Data System (ADS)

Chidester, Bethany A.; Rahman, Zia; Righter, Kevin; Campbell, Andrew J.

2017-02-01

Earth's core might require an internal heat source, such as radioactive decay, to explain the presence of the magnetic field through geologic time. To investigate whether U would be an important heat source in the core, we performed metal-silicate partitioning experiments of U at P-T (up to 67 GPa and 5400 K) conditions more relevant to a magma ocean scenario than has previously been reported. This study finds the partitioning of U to be strongly dependent on ƒO2, temperature, the S content of the metal and the SiO2 content of the silicate during core-mantle differentiation. Differentiation at mean conditions of 42-58 GPa and 3900-4200 K would put 1.4-3.5 ppb U (2-8 wt% S) in the core, amounting to a maximum of 1.4 (+1/-0.7) TW of heat 4.5 billion years ago. This is likely not enough heat to mitigate early widespread mantle melting. It was also found that U likely exists in the 2+ oxidation state in silicate melts in the deep Earth, a state which has not been previously observed in nature.

Mineralogical basis for the interpretation of multi-element (ICP-AES), oxalic acid, and aqua regia partial digestions of stream sediments for reconnaissance exploration geochemistry

USGS Publications Warehouse

Church, S.E.; Mosier, E.L.; Motooka, J.M.

1987-01-01

We have applied partial digestion procedures, primarily oxalic acid and aqua regia leaches, to several regional geochemical reconnaissance studies carried out using Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) analytical methods. We have chosen to use these two acids because the oxalic acid primarily attacks those compounds formed during secondary geochemical processes, whereas aqua regia will digest the primary sulfide phases as well as secondary phases. Application of the partial digestion technique has proven superior to total digestion because the concentration of metals in hydromorphic compounds and the sulfides is enhanced relative to the metals bound in the unattacked silicate phases. The aqua regia digestion attacks and leaches metals from the mafic chain silicates and the phyllosilicates (coordination number of VI or more), yielding a characteristic geochemical signature, but does not leach appreciable metal from many other silicates. In order to interpret the results from these leach studies, we have initiated an investigation of a large suite of hand-picked mineral separates. The study includes analyses of about two hundred minerals representing the common rock-forming minerals as well as end-member compositions of various silicates, oxides, sulfides, carbonates, sulfates, and some vanadates, molybdates, tungstates, and phosphates. The objective of this study is to evaluate the effect of leaching by acids of particular lattice sites in specific mineral structures. ?? 1987.

Combining Sequential Extractions and X-ray Absorption Spectroscopy for Quantitative and Qualitative Zinc Speciation in Soil

NASA Astrophysics Data System (ADS)

Bauer, Tatiana; Minkina, Tatiana; Batukaev, Abdulmalik; Nevidomskaya, Dina; Burachevskaya, Marina; Tsitsuashvili, Viktoriya; Urazgildieva, Kamilya

2017-04-01

The combined use of X-ray absorption spectrometry and extractive fractionation is an effective approach for studying the interaction of metal ions with soil compounds and identifying the phases-carriers of metals in soil and their stable fixation. These studies were carried out using the technique of X-ray absorption spectroscopy and chemical extractive fractionation. In a model experiment the samples taken in Calcic Chernozem were artificially contaminated with higher portion of Zn(NO3)2 (2000 mg/kg). The metal were incubated in soil samples for 2 year. The samples of soil mineral and organic phases (calcite, kaolinite, bentonite, humic acids) were saturated with Zn2+ from a solution of nitrate salts of metal. The total content of Zn in soil and soil various phases was determined using the X-ray fluorescence method. Extended X-ray absorption fine structure (EXAFS) Zn was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation. Sequential fractionation of Zn in soil conducted by Tessier method (Tessier et al., 1979) which determining 5 fractions of metals in soil: exchangeable, bound to Fe-Mn oxide, bound to carbonate, bound to the organic matter, and bound to silicate (residual). This methodology has so far more than 4000 citations (Web of Science), which demonstrates the popularity of this approach. Much Zn compounds are contained in uncontaminated soils in stable primary and secondary silicates inherited from the parental rocks (67% of the total concentrations in all fractions), which is a regional trait of soils in the fore-Caucasian plain. Extracted fractionation of metal compounds in soil samples, artificially contaminated with Zn salts, indicates the priority holding of Zn2+ ions by silicates, carbonates and Fe-Mn oxides. The Zn content significantly increases in the exchangeable fraction. Atomic structure study of the soil various phases saturated with Zn2+ ion by using (XANES) X-ray absorption spectroscopy allowed the determination of mechanism of metal ions interaction with soil phases and the resulting types of chemical bonds. Interaction with soil components modifies the electron structure of the metal ions themselves. The soil contamination with Zn is accompanied by decreasing the stable connection between metal and soil components. Interacting with humic acids in chernozem, the Zn2+ ion is coordinated by functional groups and ligands and forms unstable outer-sphere complexes. Zinc included into octahedral structures of layered minerals and hydro(oxides) can be inner-and outer-sphere adsorbed. The Zn2+ ions enable to replace Ca2+ ions in octahedral positions being coordinated with carbonate ions as ligands, thus forming absorbed complexes at the surface of mineral calcite. This work was supported by grant of the Russian Scientific Foundation № 16-14-10217.

Metal-silicate partitioning of Co, Ni, V, Cr, Si, and O up to 100 GPa and 5500 K: Implications for core formation

NASA Astrophysics Data System (ADS)

Fischer, R. A.; Campbell, A. J.; Frost, D. J.; Harries, D.; Langenhorst, F.; Miyajima, N.; Pollok, K.; Rubie, D. C.

2013-12-01

During core formation, metal and silicate of accreted bodies equilibrated with the proto-Earth in a series of partitioning reactions, characterized by average (or time-intregrated) partition coefficients that can be calculated assuming a bulk Earth that is chondritic in nonvolatile elements [e.g. 1]. Comparisons to experimentally-measured partition coefficients allow constraints on the time-integrated conditions of core-mantle equilibration [e.g. 2-7], providing valuable input into more complex chemical models of Earth's evolution [8]. Partitioning has been studied extensively in the multi-anvil press [e.g. 3, 7], but very few studies extend to pressures above ~25 GPa [e.g. 2, 5-6]. In this study, we measure the metal-silicate partitioning of Co, Ni, V, Cr, Si, and O at higher pressures and temperatures. Thin foils of Fe-rich alloy doped with trace elements were loaded in a diamond anvil cell between layers of (Mg,Fe)2SiO4. Samples were laser-heated to melt the metal and silicate. After decompression, samples were cut parallel to the compression axis into sections ~100 nm thick with a focused ion beam (FIB). Chemical analyses of all elements except oxygen in the coexisting metal, silicate, and oxide were performed using energy dispersive X-ray spectroscopy (EDXS) in a transmission electron microscope (TEM). Later, samples were further thinned by FIB to ~60 nm and analyzed by electron energy loss spectroscopy (EELS) in a TEM to determine the Fe/O ratio of the metal. Analysis was performed on a suite of six experiments from pressures of 25, 31, 43, 57, 58, and 100 GPa and temperatures above the silicate liquidus, up to 5500 K. Our results are generally consistent with the recent findings of [5-6], although our log(KD) values for cobalt are ~0.1-0.2 log units lower. Some of our experiments contain carbon in the metal which may affect the partitioning of some elements. The metal in the experiment from 100 GPa and 5500 K contains 9 wt% silicon and an estimated 11 wt% oxygen, which is a significantly higher percentage of light elements than the Earth's outer core is thought to contain [e.g. 1]. Using our results, we develop a model for metal/silicate exchange during core formation, the light element composition of the core, and possible chemical reactions at the core-mantle boundary. [1] McDonough, W.F. (2003) Treatise on Geochemistry, Vol. 2, pp 547-568. [2] Bouhifd, M.A. and A.P. Jephcoat (2011) Earth Planet. Sci. Lett. 307, 341-348. [3] Mann, U., D.J. Frost, and D.C. Rubie (2009) Geochim. Cosmochim. Acta 73, 7360-7386. [4] Righter, K. et al. (2010) Earth Planet. Sci. Lett. 291, 1-9. [5] Siebert, J. et al. (2012) Earth Planet. Sci. Lett. 321-322, 189-197. [6] Siebert, J. et al. (2013) Science 339, 1194-1197. [7] Wade, J., and B.J. Wood (2005) Earth Planet. Sci. Lett. 236, 78-95. [8] Rubie, D.C. et al. (2011) Earth Planet. Sci. Lett. 301, 31-42.

Exfoliation restacking route to Au nanoparticle-clay nanohybrids

NASA Astrophysics Data System (ADS)

Paek, Seung-Min; Jang, Jae-Up; Hwang, Seong-Ju; Choy, Jin-Ho

2006-05-01

A novel gold-pillared aluminosilicate (Au-PILC) were synthesized with positively charged gold nanoparticles capped by mercaptoammonium and exfoliated silicate layers. Gold nanoparticles were synthesized by NaBH4 reduction of AuCl4- in the presence of N,N,N-Trimethyl (11-mercaptoundecyl)ammonium (HS(CH2)11NMe3+) protecting ligand in an aqueous solution, and purified by dialysis. The resulting positively charged and water-soluble gold nanoparticles were hybridized with exfoliated silicate sheets by electrostatic interaction. The formation of Au clay hybrids could be easily confirmed by the powder X-ray diffraction with the increased basal spacing of clay upon insertion of Au nanoparticles. TEM image clearly revealed that the Au particles with an average size of 4 nm maintain their structure even after intercalation. The Au nanoparticles supported by clay matrix were found to be thermally more stable, suggesting that the Au nanoparticles were homogeneously protected with clay nanoplates. The present synthetic route could be further applicable to various hybrid systems between metal nanoparticles and clays.

Glass corrosion in natural environments

NASA Technical Reports Server (NTRS)

Thorpe, Arthur N.; Barkatt, Aaron

1992-01-01

Experiments carried out during the progress period are summarized. Experiments carried out involving glass samples exposed to solutions of Tris have shown the appearance of 'spikes' upon monitoring glass dissolution as a function of time. The periodic 'spikes' observed in Tris-based media were interpreted in terms of cracking due to excessive stress in the surface region of the glass. Studies of the interactions of silicate glasses with metal ions in buffered media were extended to systems containing Al. Caps buffer was used to establish the pH. The procedures used are described and the results are given. Preliminary studies were initiated as to the feasibility of adding a slowly dissolving solid compound of the additive to the glass-water system to maintain a supply of dissolved additive. It appears that several magnesium compounds have a suitable combination of solubility and affinity towards silicate glass surfaces to have a pronounced retarding effect on the extraction of uranium from the glass. These preliminary findings raise the possibility that introducing a magnesium source into geologic repositories for nuclear waste glass in the form of a sparingly soluble Mg-based backfill material may cause a substantial reduction in the extent of long-term glass corrosion. The studies described also provide mechanistic understanding of the roles of various metal solutes in the leachant. Such understanding forms the basis for developing long-term predictions of nuclear waste glass durability under repository conditions. From what is known about natural highly reduced glasses such as tektites, it is clear that iron is dissolved as ferrous iron with little or no ferric iron. The reducing conditions were high enough to cause metallic iron to exsolve out of the glass in the form of submicroscopic spherules. As the nuclear waste glass is much less reduced, a study was initiated on other natural glasses in addition to the nuclear waste glass. Extensive measurements were carried out on these glasses in order to characterize their magnetic properties. Results of these studies are described.

Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth

NASA Technical Reports Server (NTRS)

Nickodem, K.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2012-01-01

There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.

Equilibrium Tin Isotope Fractionation during Metal-Sulfide-Silicate Differentiation: A Nuclear Resonant Inelastic X-ray Scattering Approach

NASA Astrophysics Data System (ADS)

Roskosz, M.; Amet, Q.; Fitoussi, C.; Laporte, D.; Hu, M. Y.; Alp, E. E.

2016-12-01

Metal-silicate differentiation was recently addressed through the insight of the isotopic composition of siderophile elements (mainly Fe, Si and Cr isotopes) of planetary and extraterrestrial bodies. A key limitation of this approach is however the knowledge of equilibrium fractionation factors between coexisting phases (metal alloys, silicates and sulfides) used to interpret data on natural samples. These properties are difficult to determine experimentally. In this context, tin is generally classified as a chalcophile element but it is also siderophile and volatile. We applied a synchrotron-based method to circumvent difficulties related to determination of equilibrium isotope fractionation. The nuclear resonant inelastic x-ray scattering (NRIXS) was used to measure the phonon excitation spectrum and then to derive the force constant and finally the fractionation factors of Sn-bearing geomaterials. Spectroscopic measurements were carried out at room pressure at Sector 30-ID (APS, USA). A range of Fe-Ni alloys, rhyolitic and basaltic glasses and iron sulfides containing isotopically enriched 119Sn were synthesized. The tin content and the redox conditions prevailing during the synthesis were varied. The data evaluation was carried out using PHOENIX and SciPhon programs. A strong effect of both the redox state and the tin content was measured. In addition, the composition of the silicate glasses was found to be another important factor determining the tin isotope metal-silicate-sulfide fractionation factors. Our results are consistent with trends previously observed in the case of iron isotopes [1,2]. We will discuss the implications of our experimental results in terms of tin isotope planetary signatures. References: [1] Dauphas et al. (2014), EPSL, 398, 127-140; [2] Roskosz et al. (2015), GCA, 169, 184-199.

Core segregation mechanism and compositional evolution of terretrial planets

NASA Astrophysics Data System (ADS)

Petford, N.; Rushmer, T.

2009-04-01

A singular event in the formation of the earth and terrestrial planets was the separation iron-rich melt from mantle silicate to form planetary cores. On Earth, and by implication other rocky planets, this process induced profound internal chemical fractionation, with siderophile elements (Ni, Co, Au, Pt, W, Re) following Fe into the core, leaving the silicate crust and mantle with strong depletions of these elements relative to primitive planetary material. Recent measurements of radiogenic 182W anomalies in the silicate Earth, Mars and differentiated meteorites imply that planetesimals segregated metallic cores within a few Myr of the origin of the solar system. Various models have been put forward to explain the physical nature of the segregation mechanism (Fe-diapirs, ‘raining' through a magma ocean), and more recently melt flow via fractures. In this contribution we present the initial results of a numerical study into Fe segregation in a deforming silicate matrix that captures the temperature-dependent effect of liquid metal viscosity on the transport rate. Flow is driven by pressure gradients associated with impact deformation in a growing planetesimal and the fracture geometry is constrained by experimental data on naturally deformed H6 chondrite. Early results suggest that under dynamic conditions, fracture-driven melt flow can in principle be extremely rapid, leading to a significant draining of the Fe-liquid metal and siderophile trace element component on a timescale of hours to days. Fluid transport in planetesimals where deformation is the driving force provides an attractive and simple way of segregating Fe from host silicate as both precursor and primary agent of core formation. The potential for flow of metal-rich melt to induce local magnetic anomalies will also be addressed.

Sensitivities of Earth's core and mantle compositions to accretion and differentiation processes

NASA Astrophysics Data System (ADS)

Fischer, Rebecca A.; Campbell, Andrew J.; Ciesla, Fred J.

2017-01-01

The Earth and other terrestrial planets formed through the accretion of smaller bodies, with their core and mantle compositions primarily set by metal-silicate interactions during accretion. The conditions of these interactions are poorly understood, but could provide insight into the mechanisms of planetary core formation and the composition of Earth's core. Here we present modeling of Earth's core formation, combining results of 100 N-body accretion simulations with high pressure-temperature metal-silicate partitioning experiments. We explored how various aspects of accretion and core formation influence the resulting core and mantle chemistry: depth of equilibration, amounts of metal and silicate that equilibrate, initial distribution of oxidation states in the disk, temperature distribution in the planet, and target:impactor ratio of equilibrating silicate. Virtually all sets of model parameters that are able to reproduce the Earth's mantle composition result in at least several weight percent of both silicon and oxygen in the core, with more silicon than oxygen. This implies that the core's light element budget may be dominated by these elements, and is consistent with ≤1-2 wt% of other light elements. Reproducing geochemical and geophysical constraints requires that Earth formed from reduced materials that equilibrated at temperatures near or slightly above the mantle liquidus during accretion. The results indicate a strong tradeoff between the compositional effects of the depth of equilibration and the amounts of metal and silicate that equilibrate, so these aspects should be targeted in future studies aiming to better understand core formation conditions. Over the range of allowed parameter space, core and mantle compositions are most sensitive to these factors as well as stochastic variations in what the planet accreted as a function of time, so tighter constraints on these parameters will lead to an improved understanding of Earth's core composition.

Experimental constraints on Earth's core formation

NASA Astrophysics Data System (ADS)

Bouhifd, Mohamed Ali

2017-04-01

The Earth contains a Fe-rich metallic core that segregated from the primitive silicate mantle very early in its 4.5 billion year history. One major consequence of this segregation is the depletion of the Earth's mantle from the siderophile elements "high core affinity" relative to primitive solar system abundances. The way in which siderophile elements partition between metal and silicate depends strongly on pressure (P), temperature (T), oxygen fugacity (fO2) and chemical compositions of both metal and silicate phases. In the present presentation, I will discuss the experimental results of metal-silicate partitioning of Ni and Co that show a marked change with increasing pressure (e.g. Bouhifd and Jephcoat, 2011; Siebert et al., 2012; Fischer et al., 2015 for the most recent studies). This behavior coincides with a change in the coordination of silicon (in a basaltic melt composition) from 4-fold coordination under ambient conditions to 6-fold coordination at about 35 GPa, indicating that melt compressibility may controls siderophile-element partitioning (Sanloup et al., 2013). I will also discuss the impact of Earth's core formation on "lithophile" elements such as Sm, Nd, Ta and Nb (e.g. Bouhifd et al. 2015; Cartier et al., 2014), as well as the impact of sulphur on the behavior of various elements during core formation (e.g. Boujibar et al., 2014; Wohlers and Wood, 2015). By combining the metal-silicate partitioning data from siderophile, lithophile and chalcophile elements I will present and discuss the most plausible conditions for Earth's core formation. References Bouhifd and Jephcoat (2011) EPSL, 307, 341-348. Bouhifd et al. (2015) EPSL 413, 158-166. Boujibar et al. (2014) EPSL 391, 42-54. Cartier et al. (2014) Nature Geoscience, 7, 573-576. Fischer et al. (2015) GCA 167, 177-194. Sanloup et al. (2013) Nature, 503, 104-107. Siebert et al. (2012) EPSL 321-322, 189-197. Wohlers and Wood (2015) Nature 520, 337-340.

Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

NASA Astrophysics Data System (ADS)

Kiefer, W. S.; Mittlefehldt, D. W.

2017-07-01

Initially small liquid metal drops must grow to about 10 cm in size before sinking through the convecting silicate magma ocean to form a core. The required magma temperature is consistent with moderately siderophile element abundances in eucrites.

Shock recovery analogs and the origin of mesosiderites. [Abstract only

NASA Technical Reports Server (NTRS)

Rowan, L. R.

1994-01-01

The origin of mesosiderites, which consist of approximately equal-weight proportions of Fe-Ni metal and silicates (gabbros, basalts, orthopyroxenites, dunites), remains an interesting and complex problem in meteoritics. There is general agreement that multiple impact events were probably involved in the formation of these brecciated stony-iron meteorites, but given the heterogeneity of mesosiderites, additional processes have been invoked to explain the unique and intricate textural and compositional makeup of mesosiderites. We conducted a series of shock recovery experiments to test the impact event(s) scenario. The results indicated significant similarities between the shocked analogs and many mesosiderites. We have compared our analogs with a suite of thin sections of Barea mesosiderite. I have conducted a series of flash heating experiments in which equal-weight proportions of gabbro and stainless steel (SS304) powders were compressed into small charges and heated under reducing conditions for short times. These experiments were used to bracket localized, peak postshock temperatures in our analog shots and to compare the mixing relations between the silicate and metal. The shock recovery experiments used porous metal-silicate powder starting mixtures, therefore our experiments are most analogous to an impact scenario where the target is an asteroidal regolith surface composed of a loose mixture of Fe-Ni metal and heterogeneous silicates. Analog experiments may really describe a secondary impact process similar to the late-stage, localized impact melting event. This leaves one of the crucial questions about mesosiderite genesis unanswered, namely what is the source of the Fe-Ni metal that is so intimately distributed in these meteorites?

Treatment of fly ash for use in concrete

DOEpatents

Boxley, Chett [Park City, UT; Akash, Akash [Salt lake City, UT; Zhao, Qiang [Natick, MA

2012-05-08

A process for treating fly ash to render it highly usable as a concrete additive. A quantity of fly ash is obtained that contains carbon and which is considered unusable fly ash for concrete based upon foam index testing. The fly ash is mixed with an activator solution sufficient to initiate a geopolymerization reaction and for a geopolymerized fly ash. The geopolymerized fly ash is granulated. The geopolymerized fly ash is considered usable fly ash for concrete according to foam index testing. The geopolymerized fly ash may have a foam index less than 35% of the foam index of the untreated fly ash, and in some cases less than 10% of the foam index of the untreated fly ash. The activator solution may contain an alkali metal hydroxide, carbonate, silicate, aluminate, or mixtures thereof.

Treatment of fly ash for use in concrete

DOEpatents

Boxley, Chett; Akash, Akash; Zhao, Qiang

2013-01-08

A process for treating fly ash to render it highly usable as a concrete additive. A quantity of fly ash is obtained that contains carbon and which is considered unusable fly ash for concrete based upon foam index testing. The fly ash is mixed with an activator solution sufficient to initiate a geopolymerization reaction and for a geopolymerized fly ash. The geopolymerized fly ash is granulated. The geopolymerized fly ash is considered usable fly ash for concrete according to foam index testing. The geopolymerized fly ash may have a foam index less than 35% of the foam index of the untreated fly ash, and in some cases less than 10% of the foam index of the untreated fly ash. The activator solution may contain an alkali metal hydroxide, carbonate, silicate, aluminate, or mixtures thereof.

The Activity of Trace Metals in Aqueous Systems and the Effect of Corrosion Control Inhibitors

DTIC Science & Technology

1975-10-01

corrosion product on metallic zinc 49 Uncombined slilica as quartz or cristobalite forms by the hydrothermal alteration of solid zilicates or by direct... hydrothermally . The com- position of the solids are dependent on temperature and pressure as well as on the relative concentrations of the dissolved...of the few anhydrous simple silicates formed hydrotherm - ally. The sodium silicates, Na2SiO 3 and BNa 2Si205, are somewhat soluble in high temperature

Watson: A new link in the IIE iron chain

NASA Technical Reports Server (NTRS)

Olsen, Edward; Davis, Andrew; Clarke, Roy S., Jr.; Schultz, Ludolf; Weber, Hartwig W.; Clayton, Robert; Mayeda, Toshiko; Jarosewich, Eugene; Sylvester, Paul; Grossman, Lawrence

1994-01-01

Watson, which was found in 1972 in South Australia, contains the largest single silicate rock mass seen in any known iron meteorite. A comprehensive study has been completed on this unusual meteorite: petrography, metallography, analyses of the silicate inclusion (whole rock chemical analysis, INAA, RNAA, noble gases, and oxygen isotope analysis) and mineral compositions (by electron microprobe and ion microprobe). The whole rock has a composition of an H-chondrite minus the normal H-group metal and troilite content. The oxygen isotope composition is that of the silicates in the IIE iron meteorites and lies along an oxygen isotope fractionation line with the H-group chondrites. Trace elements in the metal confirm Watson is a new IIE iron. Whole rock Watson silicate shows an enrichment in K and P (each approximately 2X H-chondrites). The silicate inclusion has a highly equilibrated igneous (peridotite-like) texture with olivine largely poikilitic within low-Ca pyroxene: olivine (Fa20), opx (Fs17Wo3), capx (Fs9Wo14)(with very fine exsolution lamellae), antiperthite feldspar (An1-3Or5) with less than 1 micron exsolution lamellae (An1-3Or greater than 40), shocked feldspar with altered stoichiometry, minor whitlockite (also a poorly characterized interstitial phosphate-rich phase) and chromite, and only traces of metal and troilite. The individual silicate minerals have normal chondritic REE patterns, but whitlockite has a remarkable REE pattern. It is very enriched in light REE (La is 720X C1, and Lu is 90X C1, as opposed to usual chonditic values of approximately 300X and 100-150X, respectively) with a negative Eu anomaly. The enrichment of whole rock K is expressed both in an unusually high mean modal Or content of the feldspar, Or13, and in the presence of antiperthite.

Smyer H-Chondrite Impact-Melt Breccia and Evidence for Sulfur Vaporization

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

2002-01-01

Smyer is an H-chondrite impact-melt breccia containing approx.20 vol% 0.5- to 13-mm-thick silicate-rich melt veins surrounding unmelted subrounded chondritic clasts up to 7 cm in maximum dimension. At the interface between some of the melt veins and chondritic clasts, there are troilite-rich regions consisting of unmelted. crushed 0.2- to 140-micron-size angular silicate grains and chondrule fragments surrounded by troilite and transected by thin troilite veins. Troilite fills every available fracture in the silicates. including some as thin as 0.1 microns. Little metallic Fe-Ni is present in these regions: the FeS/Fe modal ratio ranges from -25: 1 to approx.500: 1, far higher than the eutectic weight ratio of 7.5: 1. The texture of these regions indicates that the sulfide formed from a fluid of very low viscosity. The moderately high viscosity (0.2 poise) and large surface tension of liquid FeS, its inability to wet silicate grain surfaces at low oxygen fugacities. and the supereutectic FeS/Fe ratios in the troilite-rich regions indicate that the fluid was a vapor. It seems likely that during the shock event that melted Smyer, many silicates adjacent to the melt veins were crushed. Upon release of shock pressure. some of the troilite evaporated and dissociated. Molecules of S2 were transported and condensed into fractures and around tiny silicate grains: there, they combined with Fe from small adjacent metallic Fe-Ni grains to form troilite. The Ni content at the edges of some of these metal grains increased significantly; Co from these Ni-rich grains diffused into nearby kamacite. Impact-induced S volatilization may have played a major role in depleting the surface of 433 Eros (and other chondritic asteroids) in S.

Redox systematics of a magma ocean with variable pressure-temperature gradients and composition.

PubMed

Righter, K; Ghiorso, M S

2012-07-24

Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO(2)), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO(2) that is based on the ratio of Fe and FeO [called "ΔIW (ratio)" hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO(2) + O(2) = Fe(2)SiO(4) to calculate absolute fO(2) and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO(2) in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO(2) may evolve from high to low fO(2) during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account.

The Origin of Chondrites: Metal-Silicate Separation Experiments Under Microgravity Conditions, Experiment 2

NASA Technical Reports Server (NTRS)

Moore, S. R.; Franzen, M.; Benoit, P. H.; Sears, D. W. G.; Holley, A.; Myers, M.; Godsey, R.; Czlapinski, J.

2003-01-01

Chondrites are categorized into different groups by several properties, including the metal-to-silicate ratio. Various processes have been suggested to produce distinct metal/silicate ratios, some based on sorting in the early solar nebular and others occurring after accretion on the parent body. Huang et al. suggested that a weak gravitational field accompanied by degassing, could result in metal/silicate separation on parent bodies. We suggest that asteroids were volatile-rich, at least early in their histories. Spectroscopic evidence from asteroid surfaces indicates that one-third of all asteroids maybe rich in clays and hydrated minerals, similar to carbonaceous chondrites. Internal and/or external heating could have caused volatiles to evaporate and pass through a surface dust layer. Spacecraft images of asteroids show they have a thick regoliths. Housen, and Asphaug and Nolan proposed that even a 10 km diameter asteroid could potentially have a significant regolith. Grain size and grain density sorting could occur in the unconsolidated layer by the process known as fluidization. This process occurs when an upward stream of gas is passed through a bed of particles which are lifted against a gravitational force. Fluidization is commonly used commercially to sort particulates. This type of behavior is based upon the bed, as a whole, and differs from aerodynamic sorting. Two sets of reduced gravity experiments were conducted during parabolic flights aboard NASA's KC-135 aircraft. The first experiment employed 310 tubes of 2.5 cm diameter, containing mixtures of sand and metal grains. A gas source was used to fluidize the mixture at reduced gravity conditions and mixtures were analyzed after the flight. However, this experiment did not allow a description of the fluidization as a function of gravity. A second experiment was conducted on the KC-135 aircraft in the summer of 2001, consisting of two Plexiglas cylinders containing a metal/silicate mixture, and video cameras to record the experiment on tape. Here we summarize this experiment and discusses the implications for metalsilicate separation on asteroid bodies.

Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.

Germanium geochemistry and mineralogy

USGS Publications Warehouse

Bernstein, L.R.

1985-01-01

Germanium is enriched in the following geologic environments: 1. (1) iron meteorites and terrestrial iron-nickel; 2. (2) sulfide ore deposits, particularly those hosted by sedimentary rocks; 3. (3) iron oxide deposits; 4. (4) oxidized zones of Ge-bearing sulfide deposits; 5. (5) pegmatites, greisens, and skarns; and 6. (6) coal and lignitized wood. In silicate melts, Ge is highly siderophile in the presence of native iron-nickel; otherwise, it is highly lithophile. Among silicate minerals, Ge is concentrated in those having less polymerized silicate tetrahedra such as olivine and topaz. In deposits formed from hydrothermal solutions, Ge tends to be enriched mostly in either sulfides or in fluorine-bearing phases; it is thus concentrated both in some hydrothermal sulfide deposits and in pegmatites, greisens, and skarns. In sulfide deposits that formed from solutions having low to moderate sulfur activity, Ge is concentrated in sphalerite in amounts up to 3000 ppm. Sulfide deposits that formed from solutions having higher sulfur activity allowed Ge to either form its own sulfides, particularly with Cu, or to substitute for As, Sn, or other metals in sulfosalts. The Ge in hydrothermal fluids probably derives from enrichment during the fractional crystallization of igneous fluids, or is due to the incorporation of Ge from the country rocks, particularly from those containing organic material. Germanium bonds to lignin-derivative organic compounds that are found in peat and lignite, accounting for its common concentration in coals and related organic material. Germanium is precipitated from water together with iron hydroxide, accounting for its concentration in some sedimentary and supergene iron oxide deposits. It also is able to substitute for Fe in magnetite in a variety of geologic environments. In the oxidized zone of Ge-bearing sulfide deposits, Ge is concentrated in oxides, hydroxides, and hydroxy-sulfates, sometimes forming its own minerals. It is particularly enriched in some iron- and manganese-bearing oxides and hydroxides, including goethite (up to 5300 ppm) and hematite (up to 7000 ppm). ?? 1985.

Solubility, Partitioning, and Speciation of Carbon in Shallow Magma Oceans of Terrestrial Planets Constrained by High P-T Experiments

NASA Astrophysics Data System (ADS)

Chi, H.; Dasgupta, R.; Shimizu, N.

2011-12-01

Deep planetary volatile cycles have a critical influence on planetary geodynamics, atmospheres, climate, and habitability. However, the initial conditions that prevailed in the early, largely molten Earth and other terrestrial planets, in terms of distribution of volatiles between various reservoirs - metals, silicates, and atmosphere - remains poorly constrained. Here we investigate the solubility, partitioning, and speciation of carbon-rich volatile species in a shallow magma ocean environment, i.e., in equilibrium with metallic and silicate melts. A series of high pressure-temperature experiments using a piston cylinder apparatus were performed at 1-3 GPa, 1500-1800 °C on synthetic basaltic mixtures + Fe-Ni metal powders contained in graphite capsules. All the experiments produced glassy silicate melt pool in equilibrium with quenched metal melt composed of dendrites of cohenite and kamacite. Major element compositions of the resulting phases and the carbon content of metallic melts were analyzed by EPMA at NASA-JSC. Carbon and hydrogen concentrations of basaltic glasses were determined using Cameca IMS 1280 SIMS at WHOI and speciation of dissolved volatiles was constrained using FTIR and Raman spectroscopy at Rice University. Based on the equilibria - FeO (silicate melt) = Fe (metal alloy melt) + 1/2O2, we estimate the oxygen fugacity of our experiments in the range of ΔIW of -1 to -2. FTIR analysis on doubly polished basaltic glass chips suggests that the concentrations of dissolved CO32- or molecular CO2 are negligible in graphite and metal saturated reduced conditions, whereas the presence of dissolved OH- is evident from the asymmetric peak at 3500 cm-1. Collected Raman spectra of basaltic glasses in the frequency range of 200-4200 cm-1 suggest that hydrogen is present both as dissolved OH- species (band at 3600 cm-1) and as molecular H2 (band near 4150 cm-1) for all of our experiments. Faint peaks near 2915 cm-1 and consistent peaks near 740 cm-1 suggest that possible carbon species in our reduced glasses are likely minor CH4 and Si-C, respectively and are consistent with the recent solubility studies at reduced conditions [1,2]. Carbon solubility (calibrated using 12C/30Si) at graphite saturation in our reduced basaltic glasses is only in the range 20-100 ppm C, with H2O contents in the range of 0.2-0.7 wt.%. In contrast to the low dissolved carbon concentration in the basaltic silicate melts, carbon solubility in quenched metallic melts vary in the range of 5-7 wt.%. Our preliminary work indicates that the solubility of carbon in reduced basaltic melts relevant for early magma conditions may be several orders of magnitude lower compared to the solubility of carbon in modern terrestrial basalts. This coupled with significant solubility of carbon in Fe-Ni metallic melt suggests that most of magma ocean carbon was likely partitioned into deep metallic melts. Further metal-silicate experiments with more depolymerized basaltic melts of variable compositions are underway and will be presented. [1] Kadik et al. JPetrol 45, 1297-1310, 2004; [2] Kadik et al. Geochem Int 44, 33-47, 2006.

Mineralogical Characterization of Fe-Bearing AGB and Supernova Silicate Grains From the Queen Alexandra Range 99177 Meteorite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.

2017-01-01

Spectroscopic observations of the circumstellar envelopes of evolved O-rich stars indicate the dust is mostly amorphous silicate with olivine-like compositions. Spectral modeling suggests these grains are Fe-rich [Mg/(Mg+Fe) 0.5], but it is not known whether the Fe is distributed within the silicate matrix or exists as metal inclusions. In contrast, the crystalline silicates are inferred to be extremely Mg-rich [Mg/(Mg+Fe) > 0.95]. The mineralogies and chemical compositions of dust in supernova (SN) remnants are not as well constrained, but abundant silicates of olivine-like and enstatite-like compositions have been fit to the infrared emission features. Silicates in the interstellar medium (ISM) are >99% amor-phous and Fe-bearing. The dearth of crystalline silicates in the ISM requires that some amorphization or destruction mechanisms process these grains.

A Model for Siderophile Element Distribution in Planetary Differentiation

NASA Technical Reports Server (NTRS)

Humayun, M.; Rushmer, T.; Rankenburg, K.; Brandon, A. D.

2005-01-01

Planetary differentiation begins with partial melting of small planetesimals. At low degrees of partial melting, a sulfur-rich liquid segregates by physical mechanisms including deformation-assisted porous flow. Experimental studies of the physical mechanisms by which Fe-S melts segregate from the silicate matrix of a molten H chondrite are part of a companion paper. Geochemical studies of these experimental products revealed that metallic liquids were in equilibrium with residual metal in the H chondrite matrix. This contribution explores the geochemical signatures produced by early stages of core formation. Particularly, low-degree partial melt segregation of Fe-S liquids leaves residual metal in the silicate matrix. Some achondrites appear to be residues of partial melting, e.g., ureilites, which are known to contain metal. The metal in these achondrites may show a distinct elemental signature. To quantify the effect of sulfur on siderophile element contents of residual metal we have developed a model based on recent parametrizations of equilibrium solid metal-liquid metal partitioning experiments.

Reflectance spectra of 'featureless' materials and the surface mineralogies of M- and E-class asteroids

NASA Technical Reports Server (NTRS)

Cloutis, Edward A.; Smith, Dorian G.; Lambert, Richard St. J.; Gaffey, Michael J.

1990-01-01

In a search for diagnostic spectral parameters which can be used to distinguish different materials on the surface of asteroids and to provide information on the detection limits for mafic silicates, the 0.3- to 2.6-micron reflectance spectra of meteoritic enstatite (nearly pure MgSiO3), iron meteorite metal, magnetite, and amorphous carbon as well as various mixtures of these materials with mafic silicates were examined. Results are presented on the dependence of the spectral detectability of mafic silicates associated with metal, carbon, and magnetite on the particle sizes of the phases, their chemistries, crystal structures, and abundances. It is shown that the observational data for a representative M-class asteroid, (16) Psyche, are largely consistent with a fine-grained metal-rich surface assemblage, whereas data for the E-class asteroid (44) Nysa indicate that its surface is composed of fine-grained material similar to enstatite achondrites, with a small amount of material comparable to the chondritic inclusions found in the Cumberland Falls aubrite.

Study on Microstructure and Electrochemical Corrosion Behavior of PEO Coatings Formed on Aluminum Alloy

NASA Astrophysics Data System (ADS)

Xiang, N.; Song, R. G.; Li, H.; Wang, C.; Mao, Q. Z.; Xiong, Y.

2015-12-01

Plasma electrolytic oxidation (PEO) treated 6063 aluminum alloy was applied in a silicate- and borate-based alkaline solution. The microstructure and electrochemical corrosion behavior were studied by scanning electron microscopy, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization techniques. The results showed that the silicate-based PEO coating was of a denser structure compared with that of borate-based PEO coating. In addition, the silicate-based PEO coating was composed of more phased (Al9Si) than borate-based PEO coating. The results of corrosion test indicated that the silicate-based PEO coating provided a superior protection to 6063 aluminum alloy substrate, while borate-based PEO coating with a porous structure showed an inferior conservancy against corrosive electrolyte. Furthermore, the EIS tests proved that both coatings were capable to resist the aggressive erosion in 0.5 M NaCl solution after 72 h of immersion. However, the borate-based PEO coating could not provide sufficient protection to the substrate after 72-h immersion in 1 M NaCl solution.

Quantitative analysis of major elements in silicate minerals and glasses by micro-PIXE

USGS Publications Warehouse

Campbell, J.L.; Czamanske, G.K.; MacDonald, L.; Teesdale, W.J.

1997-01-01

The Guelph micro-PIXE facility has been modified to accommodate a second Si(Li) X-ray detector which records the spectrum due to light major elements (11 ??? Z ??? 20) with no deleterious effects from scattered 3 MeV protons. Spectra have been recorded from 30 well-characterized materials, including a broad range of silicate minerals and both natural and synthetic glasses. Sodium is mobile in some of the glasses, but not in the studied mineral lattices. The mean value of the instrumental constant H for each of the elements Mg, Al, and Si in these materials is systematically 6-8% lower than the H-value measured for the pure metals. Normalization factors are derived which permit the matrix corrections requisite for trace-element measurements in silicates to be based upon pure metal standards for Mg, Al and Si, supplemented by well-established, silicate mineral standards for the elements Na, K and Ca. Rigorous comparisons of electron microprobe and micro-PIXE analyses for the entire, 30-sample suite demonstrate the ability of micro-PIXE to produce accurate analysis for the light major elements in silicates. ?? 1997 Elsevier Science B.V.

Effect of silicate module of water glass on rheological parameters of poly(sodium acrylate)/sodium silicate hydrogels

NASA Astrophysics Data System (ADS)

Mastalska-Popiawska, J.; Izak, P.

2017-01-01

The poly(sodium acrylate)/sodium silicate hydrogels were synthesized in the presence of sodium thiosulphate and potassium persulphate as the redox initiators and N,N’-methylene-bisacrylamide as the cross-linking monomer. 20 wt% aqueous solution of sodium acrylate was polymerized together with water glass with different silicate modules (M) from 1.74 to 2.29, in three mass ratio of the monomer solution to the water glass 2:1, 1:1 and 1:2. Such obtained hybrid composites were rheologically tested using the oscillation method. It allowed to designate the crossover point during polymerization, as well as to define the viscoelastic properties of the casted hydrogel samples one week after the reaction. The obtained results of the oscillation measurements showed that cross-linking reaction proceeds very quickly and the lower the silicate module is, the process starts faster. After the completion of the reaction the silicate-polymer hydrogels are strongly elastic materials and the highest elasticity characterizes systems with the mass ratio 1:2, i.e. with the highest water glass content.

Source apportionment of aerosol particles near a steel plant by electron microscopy.

PubMed

Ebert, Martin; Müller-Ebert, Dörthe; Benker, Nathalie; Weinbruch, Stephan

2012-12-01

The size, morphology and chemical composition of 37,715 individual particles collected over 22 sampling days in the vicinity of a large integrated steel production were studied by scanning and transmission electron microscopy. Based on the morphology, chemistry and beam stability the particles were classified into the following fourteen groups: silicates, sea salt, calcium sulfates, calcium carbonates, carbonate-silicate mixtures, sulfate-silicate mixtures, iron oxides, iron mixtures, metal oxide-metals, complex secondary particles, soot, Cl-rich particles, P-rich particles, and other particles. The majority of iron oxide (≈85%) and metal oxide-metal (≈70%) particles as well as ≈20% of the silicate particles are fly ashes from high temperature processes. The emissions from the steel work are dominated by iron oxide particles. For source apportionment, seven source categories and two sectors of local wind direction (industrial and urban background) were distinguished. In both sectors PM₁₀ consists of four major source categories: 35% secondary, 20% industrial, 17% soil and 16% soot in the urban background sector compared to 45% industrial, 20% secondary, 13% soil, and 9% soot in the industrial sector. As the secondary and the soot components are higher in the urban background sector than in the industrial sector, it is concluded that both components predominantly originate from urban background sources (traffic, coal burning, and domestic heating). Abatement measures should not only focus on the steel work but should also include the urban background aerosol.

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil.

PubMed

Gu, Hai-Hong; Qiu, Hao; Tian, Tian; Zhan, Shu-Shun; Deng, Teng-Hao-Bo; Chaney, Rufus L; Wang, Shi-Zhong; Tang, Ye-Tao; Morel, Jean-Louis; Qiu, Rong-Liang

2011-05-01

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40gkg(-1)) and steel slag (3 and 6gkg(-1)) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils. Copyright © 2011 Elsevier Ltd. All rights reserved.

CHEMICAL STABILIZATION OF MIXED ORGANIC AND METAL COMPOUNDS - EPA SITE PROGRAM DEMONSTRATION OF THE SILICATE TECHNOLOGY CORPORATION PROCESS

EPA Science Inventory

In November 1990, the Silicate Technology Corporation`s (STC) proprietary process for treating soil contaminated with toxic semivolatile organic and inorganic contaminants was evaluated in a Superfund Innovative Technology Evaluation (SITE) field demonstration at the Selma Pressu...

Veins in Silicates of IIE Iron Mont Dieu II: Melt Migration Caused by Impact?

NASA Astrophysics Data System (ADS)

Van Roosbroek, N.; Debaille, V.; Pittarello, L.; Hecht, L.; Claeys, Ph.

2014-09-01

Mont Dieu II is a ~450kg meteorite classified as IIE iron. The primitive silicate inclusions can be linked to the H-chondrites. Thick metal veins with angular clasts crosscut these inclusions and could point to an impact-melt migration formation.

Mapping the Spatial Distribution of Metal-Bearing Oxides in VY Canis Majoris

NASA Astrophysics Data System (ADS)

Burkhardt, Andrew; Booth, S. Tom; Remijan, Anthony; Carroll, Brandon; Ziurys, Lucy M.

2015-06-01

The formation of silicate-based dust grains is not well constrained. Despite this, grain surface chemistry is essential to modern astrochemical formation models. In carbon-poor stellar envelopes, such as the red hypergiant VY Canis Majoris (VY CMa), metal-bearing oxides, the building blocks of silicate grains, dominate the grain formation, and thus are a key location to study dust chemistry. TiO_2, which was only first detected in the radio recently (Kaminski et al., 2013a), has been proposed to be a critical molecule for silicate grain formation, and not oxides containing more abundant metals (eg. Si, Fe, and Mg) (Gail and Sedlmayr, 1998). In addition, other molecules, such as SO_2, have been found to trace shells produced by numerous outflows pushing through the expanding envelope, resulting in a complex velocity structure (Ziurys et al., 2007). With the advanced capabilities of ALMA, it is now possible to individually resolve the velocity structure of each of these outflows and constrain the underlying chemistry in the region. Here, we present high resolution maps of rotational transitions of several metal-bearing oxides in VY CMa from the ALMA Band 7 and Band 9 Science Verification observations. With these maps, the physical parameters of the region and the formation chemistry of metal-bearing oxides will be studied.

Long-term adequacy of metal resources

USGS Publications Warehouse

Singer, D.A.

1977-01-01

Although the earth's crust contains vast quantities of metals, extraction technologies and associated costs are inextricably bound to three fundamental geological factors - the amount of metal available in the earth's crust in each range of grades, the mineralogical form and chemical state of the metal, and the spatial distribution of the metal. The energy required to recover a given amount of metal increases substantially as grade declines. Most metal is produced from sulphide or oxide minerals, whereas most metal in the crust may be locked in the structures of the more refractory silicates. Recovery from silicate minerals could require orders of magnitude more energy than that used at present as also could exploitation of small, widely scattered or thin, deeply buried deposits. Although specific information on the fundamental factors is not available, each factor must in turn tend to further restrict exploitation. Independence of average grade and tonnage for many deposit types further reduces the availability of rock as a source of metal. In the long term, effects of these factors will be large increases in price for many metals. ?? 1977.

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

The Thermal States of Accreting Planets: From Mars-like Embryos to a MAD Earth

NASA Astrophysics Data System (ADS)

Stewart, S. T.; Lock, S. J.

2015-12-01

The thermal states of rocky planets can vary widely during the process of accretion. The thermal structure affects several major processes on the growing planet, including the mechanics of core formation, pressure-temperature conditions for metal-silicate equilibration, mixing, and atmospheric erosion. Because impact energy is distributed heterogeneously, accretional energy is preferentially deposited in the gravitationally re-equilibrated outer layers of the planet for both small and giant impacts. The resulting stably stratified structure inhibits complete mixing within the mantle. Initially, the specific energy of giant impacts between Mars-mass embryos leads to melting of the mantle. However, as planet formation progresses, the specific energies of giant impacts increase and can drive the mantle into a transient supercritical state. In the hottest regions of the planet, metal and silicates are miscible, and metal exsolution occurs as the structure cools. The cooling time of the supercritical structure is typically longer than the timescale for metal segregation to the core. Thus, these high temperature excursions during planet formation are significant for understanding metal-silicate equilibration. Furthermore, when a supercritical planet is also rapidly rotating, the mantle, atmosphere and disk (MAD) form a continuous dynamic and thermodynamic structure. Lunar origin by condensation from a MAD Earth can explain the major characteristics of the Moon (Lock et al., this meeting). One of the greatest uncertainties in understanding the thermal states of planets during accretion is the changing composition and mass of the atmosphere. After the dispersal of the solar nebula, the thermal boundary condition imposed by the atmosphere can vary between silicate vapor and condensed ices. The coupled problem of atmospheric origin and planetary accretion can be used to constrain the many uncertainties in the growth and divergence of the terrestrial planets in our solar system.

Establishing the interfacial nano-structure and elemental composition of homeopathic medicines based on inorganic salts: a scientific approach.

PubMed

Temgire, Mayur Kiran; Suresh, Akkihebbal Krishnamurthy; Kane, Shantaram Govind; Bellare, Jayesh Ramesh

2016-05-01

Extremely dilute systems arise in homeopathy, which uses dilution factors 10(60), 10(400) and also higher. These amounts to potencies of 30c, 200c or more, those are far beyond Avogadro's number. There is extreme skepticism among scientists about the possibility of presence of starting materials due to these high dilutions. This has led modern scientists to believe homeopathy may be at its best a placebo effect. However, our recent studies on 30c and 200c metal based homeopathic medicines clearly revealed the presence of nanoparticles of starting metals, which were found to be retained due to the manufacturing processes involved, as published earlier.(9,10) Here, we use HR-TEM and STEM techniques to study medicines arising from inorganic salts as starting materials. We show that the inorganic starting materials are present as nano-scale particles in the medicines even at 1 M potency (having a large dilution factor of 10(2000)). Thus this study has extended our physicochemical studies of metal based medicines to inorganic based medicines, and also to higher dilution. Further, we show that the particles develop a coat of silica: these particles were seen embedded in a meso-microporous silicate layer through interfacial encapsulation. Similar silicate coatings were also seen in metal based medicines. Thus, metal and inorganic salt based homeopathic medicines retain the starting material as nanoparticles encapsulated within a silicate coating. On the basis of these studies, we propose a universal microstructural hypothesis that all types of homeopathic medicines consist of silicate coated nano-structures dispersed in the solvent. Copyright © 2015 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

High Pressure and Temperature Core Formation as an Alternative to the "Late Veneer" Hypothesis

NASA Technical Reports Server (NTRS)

Righter, Kevin; Pando, K.; Humayun, M.; Danielson, L.

2011-01-01

The highly siderophile elements (HSE; Re, Au and the Platinum Group Elements - Pd Pt, Rh, Ru, Ir, Os) are commonly utilized to constrain accretion processes in terrestrial differentiated bodies due to their affinity for FeNi metal [1]. These eight elements exhibit highly siderophile behavior, but nonetheless have highly diverse metal-silicate partition coefficients [2]. Therefore the near chondritic relative concentrations of HSEs in the terrestrial and lunar mantles, as well as some other bodies, are attributed to late accretion rather than core formation [1]. Evaluation of competing theories, such as high pressure metal-silicate partitioning or magma ocean hypotheses has been hindered by a lack of relevant partitioning data for this group of eight elements. In particular, systematic studies isolating the effect of one variable (e.g. temperature or melt compositions) are lacking. Here we undertake new experiments on all eight elements, using Fe metal and FeO-bearing silicate melts at fixed pressure, but variable temperatures. These experiments, as well as some additional planned experiments should allow partition coefficients to be more accurately calculated or estimated at the PT conditions and compositions at which core formation is thought to have occurred.

Thermal Constraints from Siderophile Trace Elements in Acapulcoite-Lodranite Metals

NASA Technical Reports Server (NTRS)

Herrin, Jason S.; Mittlefehldt, D. W.; Humayun, M.

2006-01-01

A fundamental process in the formation of differentiated bodies is the segregation of metal-sulfide and silicate phases, leading to the formation of a metallic core. The only known direct record of this process is preserved in some primitive achondrites, such as the acapulcoite-lodranites. Meteorites of this clan are the products of thermal metamorphism of a chondritic parent. Most acapulcoites have experienced significant partial melting of the metal-sulfide system but not of silicates, while lodranites have experienced partial melting and melt extraction of both. The clan has experienced a continuum of temperatures relevant to the onset of metal mobility in asteroidal bodies and thus could yield insight into the earliest stages of core formation. Acapulcoite GRA 98028 contains relict chondrules, high modal sulfide/metal, has the lowest 2-pyroxene closure temperature, and represents the least metamorphosed state of the parent body among the samples examined. Comparison of the metal-sulfide component of other clan members to GRA 98028 can give an idea of the effects of metamorphism.

Chemical evidence for differentiation, evaporation and recondensation from silicate clasts in Gujba

NASA Astrophysics Data System (ADS)

Oulton, Jonathan; Humayun, Munir; Fedkin, Alexei; Grossman, Lawrence

2016-03-01

The silicate and metal clasts in CB chondrites have been inferred to form as condensates from an impact-generated vapor plume between a metal-rich body and a silicate body. A detailed study of the condensation of impact-generated vapor plumes showed that the range of CB silicate clast compositions could not be successfully explained without invoking a chemically differentiated target. Here, we report the most comprehensive elemental study yet performed on CB silicates with 32 silicate clasts from nine slices of Gujba analyzed by laser ablation inductively coupled plasma mass spectrometry for 53 elements. Like in other studies of CBs, the silicate clasts are either barred olivine (BO) or cryptocrystalline (CC) in texture. In major elements, the Gujba silicate clasts ranged from chondritic to refractory enriched. Refractory element abundances ranged from 2 to 10 × CI, with notable anomalies in Ba, Ce, Eu, and U abundances. The two most refractory-enriched BO clasts exhibited negative Ce anomalies and were depleted in U relative to Th, characteristic of volatilization residues, while other BO clasts and the CC clasts exhibited positive Ce anomalies with excess U (1-3 × CI), and Ba (1-6 × CI) anomalies indicating re-condensation of ultra-refractory element depleted vapor. The Rare Earth Elements (REE) also exhibit light REE (LREE) enrichment or depletion in several clasts with a range of (La/Sm)CI of 0.9-1.8. This variation in the LREE is essentially impossible to accomplish by processes involving vapor-liquid or vapor-solid exchange of REE, and appears to have been inherited from a differentiated target. The most distinctive evidence for inherited chemical differentiation is observed in highly refractory element (Sc, Zr, Nb, Hf, Ta, Th) systematics. The Gujba clasts exhibit fractionations in Nb/Ta that correlate positively with Zr/Hf and span the range known from lunar and Martian basalts, and exceed the range in Zr/Hf variation known from eucrites. Variations of highly incompatible refractory elements (e.g., Th) against less incompatible elements (e.g., Zr, Sr, Sc) are not chondritic, but exhibit distinctly higher Th abundances requiring a differentiated crust to be admixed with depleted mantle in ratios that are biased to higher crust/mantle ratios than in a chondritic body. The possibility that these variations are due to admixture of refractory inclusion-debris into normal chondritic matter is raised but cannot be definitively tested because existing ;bulk; analyses of CAIs carry artifacts of unrepresentative sampling. The inferences drawn from the compositions of Gujba silicate clasts, here, complement what has been inferred from the compositions of metallic clasts, but provide surprisingly detailed insight into the structure of the target. Evidence that metal and silicate in CB chondrites both formed from impact-generated vapor plumes, taken together with recent work on metallic nodules in E chondrites, and on ordinary chondrites, indicates that chondrule formation occurs by this mechanism quite widely. However, the nature of the impact on the CB body is quite different than the popular conceptions of impact of partially or wholly molten chondritic bodies and the younger (5 Ma) age of CB chondrules is consistent with origin in a disk with more evolved targets and impactors gravitationally perturbed by nascent planets.

Characterization of iron-phosphate-silicate chemical garden structures.

PubMed

Barge, Laura M; Doloboff, Ivria J; White, Lauren M; Stucky, Galen D; Russell, Michael J; Kanik, Isik

2012-02-28

Chemical gardens form when ferrous chloride hydrate seed crystals are added or concentrated solutions are injected into solutions of sodium silicate and potassium phosphate. Various precipitation morphologies are observed depending on silicate and phosphate concentrations, including hollow plumes, bulbs, and tubes. The growth of precipitates is controlled by the internal osmotic pressure, fluid buoyancy, and membrane strength. Additionally, rapid bubble-led growth is observed when silicate concentrations are high. ESEM/EDX analysis confirms compositional gradients within the membranes, and voltage measurements across the membranes during growth show a final potential of around 150-200 mV, indicating that electrochemical gradients are maintained across the membranes as growth proceeds. The characterization of chemical gardens formed with iron, silicate, and phosphate, three important components of an early earth prebiotic hydrothermal system, can help us understand the properties of analogous structures that likely formed at submarine alkaline hydrothermal vents in the Hadean-structures offering themselves as the hatchery of life. © 2011 American Chemical Society

Alkali-metal silicate binders and methods of manufacture

NASA Technical Reports Server (NTRS)

Schutt, J. B. (Inventor)

1979-01-01

A paint binder is described which uses a potassium or sodium silicate dispersion having a silicon dioxide to alkali-metal oxide mol ratio of from 4.8:1 to 6.0:1. The binder exhibits stability during both manufacture and storage. The process of making the binder is predictable and repeatable and the binder may be made with inexpensive components. The high mol ratio is achieved with the inclusion of a silicon dioxide hydrogel. The binder, which also employs a silicone, is in the final form of a hydrogel sol.

Primitive material surviving in chondrites - Mineral grains

NASA Astrophysics Data System (ADS)

Steele, Ian M.

Besides chondrules and various kinds of polymineralic inclusion, carbonaceous chondrites commonly contain, embedded in their matrices, isolated grains of mafic silicates and metallic iron. Most of the silicate grains probably originated in chondrules, but some appear to predate chondrule formation and may have formed as individual grains in the solar nebula. If that was the case, their compositions suggest some departure from equilibrium condensation from a gas of solar composition. Metal-grain compositions are broadly suggestive of nebular formation but the exact nature of the conditions in which they were formed remains problematical.

Lowering the environmental impact of high-kappa/ metal gate stack surface preparation processes

NASA Astrophysics Data System (ADS)

Zamani, Davoud

ABSTRACT Hafnium based oxides and silicates are promising high-κ dielectrics to replace SiO2 as gate material for state-of-the-art semiconductor devices. However, integrating these new high-κ materials into the existing complementary metal-oxide semiconductor (CMOS) process remains a challenge. One particular area of concern is the use of large amounts of HF during wet etching of hafnium based oxides and silicates. The patterning of thin films of these materials is accomplished by wet etching in HF solutions. The use of HF allows dissolution of hafnium as an anionic fluoride complex. Etch selectivity with respect to SiO2 is achieved by appropriately diluting the solutions and using slightly elevated temperatures. From an ESH point of view, it would be beneficial to develop methods which would lower the use of HF. The first objective of this study is to find new chemistries and developments of new wet etch methods to reduce fluoride consumption during wet etching of hafnium based high-κ materials. Another related issue with major environmental impact is the usage of large amounts of rinsing water for removal of HF in post-etch cleaning step. Both of these require a better understanding of the HF interaction with the high-κ surface during the etching, cleaning, and rinsing processes. During the rinse, the cleaning chemical is removed from the wafers. Ensuring optimal resource usage and cycle time during the rinse requires a sound understanding and quantitative description of the transport effects that dominate the removal rate of the cleaning chemicals from the surfaces. Multiple processes, such as desorption and re-adsorption, diffusion, migration and convection, all factor into the removal rate of the cleaning chemical during the rinse. Any of these processes can be the removal rate limiting process, the bottleneck of the rinse. In fact, the process limiting the removal rate generally changes as the rinse progresses, offering the opportunity to save resources. The second objective of this study is to develop new rinse methods to reduce water and energy usage during rinsing and cleaning of hafnium based high-κ materials in single wafer-cleaning tools. It is necessary to have a metrology method which can study the effect of all process parameters that affect the rinsing by knowing surface concentration of contaminants in patterned hafnium based oxides and silicate wafers. This has been achieved by the introduction of a metrology method at The University of Arizona which monitors the transport of contaminant concentrations inside micro- and nano- structures. This is the only metrology which will be able to provide surface concentration of contaminants inside hafnium based oxides and silicate micro-structures while the rinsing process is taking place. The goal of this research is to study the effect of various process parameters on rinsing of patterned hafnium based oxides and silicate wafers, and modify a metrology method for end point detection.

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

NASA Astrophysics Data System (ADS)

Jin, Lixin; Williams, Erika L.; Szramek, Kathryn J.; Walter, Lynn M.; Hamilton, Stephen K.

2008-02-01

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition. Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO 2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg 2+/Ca 2+ ratio of 0.4. Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca 2+ and Mg 2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg 2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.

Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts

NASA Astrophysics Data System (ADS)

Anenburg, Michael; Mavrogenes, John A.

2016-11-01

Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed, nanonuggets cannot be removed by oxidation or dissolution, but only by PGM coarsening. Sulfur-poor PGE ore deposits commonly contain more PGE than permitted by existing estimates of equilibrium solubility in silicate melts. This is commonly explained by initial scavenging of PGE by sulfide liquids followed by S-loss, but evidence for S-loss is not conclusive. We suggest that nanonuggets may be a means to transport PGE from source regions to form ore deposits, followed by direct PGM crystallisation from silicate melt without intermediate concentration by sulfide liquids.

The chlorine abundance of Earth: Implications for a habitable planet

NASA Astrophysics Data System (ADS)

Sharp, Z. D.; Draper, D. S.

2013-05-01

The Cl, Br and I contents of Earth are depleted by a factor of 10 relative to predicted values from chondritic and solar abundances. Possible explanations for the apparent discrepancy include (1) unrecognized sequestration of Cl in the core, (2) a much higher nebular volatility than normally presumed or (3) a preferential loss of the heavy halogens during planetary accretion. We tested the first assumption by conducting high pressure-temperature equilibration experiments between silicate and metal. At 15 GPa and 1900 °C, the DCl(metal-silicate) value for Cl is less than 0.007, indicating that the core is not a significant reservoir for Cl. The concentration of Cl in all chondritic classes follows a depletion trend very similar to that of Na and Mn, arguing against a low condensation temperature for Cl. Instead, we propose that the depletion of the heavy halogens is due to their unique hydrophilic behavior. Almost half of Earth's Cl and Br inventory resides in the ocean and evaporites, demonstrating the unique affinity for aqueous solutions for these elements. During planetary accretion, there would have been a strong sequestration of halogens into the crustal reservoir. 'Collisional erosion' during planetary accretion provides a mechanism that would uniquely strip the heavy halogens out of an accreting Earth. Had such loss not occurred, the salinity of the oceans would be 10× the present value, and complex life would probably never have evolved.

Bismuth silicate glass containing heavy metal oxide as a promising radiation shielding material

NASA Astrophysics Data System (ADS)

Elalaily, Nagia A.; Abou-Hussien, Eman M.; Saad, Ebtisam A.

2016-12-01

Optical and FTIR spectroscopic measurements and electron paramagnetic resonance (EPR) properties have been utilized to investigate and characterize the given compositions of binary bismuth silicate glasses. In this work, it is aimed to study the possibility of using the prepared bismuth silicate glasses as a good shielding material for γ-rays in which adding bismuth oxide to silicate glasses causes distinguish increase in its density by an order of magnitude ranging from one to two more than mono divalent oxides. The good thermal stability and high density of the bismuth-based silicate glass encourage many studies to be undertaken to understand its radiation shielding efficiency. For this purpose a glass containing 20% bismuth oxide and 80% SiO2 was prepared using the melting-annealing technique. In addition the effects of adding some alkali heavy metal oxides to this glass, such as PbO, BaO or SrO, were also studied. EPR measurements show that the prepared glasses have good stability when exposed to γ-irradiation. The changes in the FTIR spectra due to the presence of metal oxides were referred to the different housing positions and physical properties of the respective divalent Sr2+, Ba2+ and Pb2+ ions. Calculations of optical band gap energies were presented for some selected glasses from the UV data to support the probability of using these glasses as a gamma radiation shielding material. The results showed stability of both optical and magnetic spectra of the studied glasses toward gamma irradiation, which validates their irradiation shielding behavior and suitability as the radiation shielding candidate materials.

Igneous petrology of the new ureilites Nova 001 and Nullarbor 010

NASA Technical Reports Server (NTRS)

Triman, Allan H.; Berkley, John L.

1994-01-01

The Nova 001 (= Nuevo Mercurio (b)) and Nullarbor 010 meteorites are ureilites, both of which contain euhedral graphite crystals. The bulk of the meteorites are olivine (Fo79) and pyroxenes (Wo9En73Fs18, Wo3En77Fs20), with a few percent graphite and minor amounts of troilite, Ni-Fe metal, and possibly diamond. The rims of olivine grains are reduced (to Fo91) and contain abundant blebs of Fe metal. Silicate mineral grains are equant, anhedral, up to 2 mm across, and lack obvious preferred orientations. Euhedral graphite crystals (to 1 mm x 0.3 mm) are present at silicate grain boundaries, along boundaries and protruding into the silicates, and entirely within silicate mineral grains. Graphite euhedra are also present as radiating clusters and groups of parallel plates grains embedded in olivine; no other ureilite has comparable graphite textures. Minute lumps within graphite grains are possible diamond, inferred to be a result of shock. Other shock effects are limited to undulatory extinction and fracturing. Both ureilites have been weathered significantly. Considering their similar mineralogies, identical mineral compositions, and identical unusual textures, Nova 001 and Nullarbor 010 are probably paired. Based on olivine compositions, Nova 001 and Nullarbor 010 are in Group 1 (FeO-rich) of Berkley et al. (1980). Silicate mineral compositions are consistent with those of others known ureilites. The presence of euhedral graphite crystals within the silicate minerals is consistent with an igneous origin, and suggests that large proportions of silicate magma were present locally and crystallized in situ.

Determination of chlorine in silicate rocks

USGS Publications Warehouse

Peck, L.C.

1959-01-01

In a rapid accurate method for the determination of chlorine in silicate rocks, the rock powder is sintered with a sodium carbonate flux containing zinc oxide and magnesium carbonate. The sinter cake is leached with water, the resulting solution is filtered, and the filtrate is acidified with nitric acid. Chlorine is determined by titrating this solution with mercuric nitrate solution using sodium nitroprusside as the indicator. The titration is made in the dark with a beam of light shining through the solution. The end point of the titration is found by visually comparing the intensity of this beam of light with that of a similar beam of light in a reference solution.

Leakage conduction behavior in electron-beam-cured nanoporous silicate films

NASA Astrophysics Data System (ADS)

Liu, Po-Tsun; Tsai, T. M.; Chang, T. C.

2005-05-01

This letter explores the application of electron-beam curing on nanoporous silicate films. The electrical conduction mechanism for the nanoporous silicate film cured by electron-beam radiation has been studied with metal-insulator-semiconductor capacitors. Electrical analyses over a varying temperature range from room temperature to 150°C provide evidence for space-charge-limited conduction in the electron-beam-cured thin film, while Schottky-emission-type leaky behavior is seen in the counterpart typically cured by a thermal furnace. A physical model consistent with electrical analyses is also proposed to deduce the origin of conduction behavior in the nanoporous silicate thin film.

Highly siderophile elements were stripped from Earth’s mantle by iron sulfide segregation

NASA Astrophysics Data System (ADS)

Rubie, David C.; Laurenz, Vera; Jacobson, Seth A.; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K.; Frost, Daniel J.

2016-09-01

Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth’s core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the “Hadean matte”) stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neumann, W.; Kruijer, T. S.; Breuer, D.

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182Hf- 182W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here in this paper, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively latemore » time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1–0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.« less

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

DOE PAGES

Neumann, W.; Kruijer, T. S.; Breuer, D.; ...

2018-02-01

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182Hf- 182W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here in this paper, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively latemore » time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1–0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.« less

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

NASA Astrophysics Data System (ADS)

Neumann, W.; Kruijer, T. S.; Breuer, D.; Kleine, T.

2018-02-01

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182Hf-182W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively late time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1-0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.

Nitrogen partitioning during core-mantle differentiation

NASA Astrophysics Data System (ADS)

Speelmanns, I. M.; Schmidt, M. W.; Liebske, C.

2016-12-01

This study investiagtes nitrogen partitioing between metal and silicate melts as relevant for core segregation during the accretion of planetesimals into the Earth. On present day Earth, N belongs to the most important elements, as it is one of the key constituents of our atmosphere and forms the basis of life. However, the geochemistry of N, i.e. its distribution and isotopic fractionation between Earth's deep reservoirs is not well constrained. In order to determine the partitioning behaviour of N, a centrifuging piston cylinder was used to euqilibrate and then gravitationally separate metal-silicate melt pairs at 1250 °C, 1 GPa over the range of oxygen fugacities thought to have prevailied druing core segreagtion (IW-4 to IW). Complete segregation of the two melts was reached within 3 hours at 1000 g, the interface showing a nice meniscus The applied double capsule technique, using an outer metallic and inner non-metallic (mostly graphite) capsule, minimizes volatile loss over the course of the experiment compared to single non-metallic capsules. The two quenched melts were cut apart, cleaned at the outside and N concentrations of the melts were analysed on bulk samples by an elemental analyser. Nevertheless, the low amount of sample material and the N yield in the high pressure experiments required the developement of new analytical routines. Despite these experimental and analytical difficulties, we were able to determine a DNmetal/silicateof 13±0.25 at IW-1, N partitioning into the core froming metal. The few availible literature data [1],[2] suggest that N changes its compatibility favoring the silicate melt or magma ocean at around IW-2.5. In order to asses how much N may effectively be contained in the core and the silicate Earth, experiments characterizing N behaviour over the entire range of core formation condtitions are well under way. [1] Kadik et al., (2011) Geochemistry International 49.5: 429-438. [2] Roskosz et al., (2013) GCA 121: 15-28.

Regularities in Low-Temperature Phosphatization of Silicates

NASA Astrophysics Data System (ADS)

Savenko, A. V.

2018-01-01

The regularities in low-temperature phosphatization of silicates are defined from long-term experiments on the interaction between different silicate minerals and phosphate-bearing solutions in a wide range of medium acidity. It is shown that the parameters of the reaction of phosphatization of hornblende, orthoclase, and labradorite have the same values as for clayey minerals (kaolinite and montmorillonite). This effect may appear, if phosphotization proceeds, not after silicate minerals with a different structure and composition, but after a secondary silicate phase formed upon interaction between silicates and water and stable in a certain pH range. Variation in the parameters of the reaction of phosphatization at pH ≈ 1.8 is due to the stability of the silicate phase different from that at higher pH values.

Ultrasonic Monitoring of the Interaction between Cement Matrix and Alkaline Silicate Solution in Self-Healing Systems.

PubMed

Ait Ouarabi, Mohand; Antonaci, Paola; Boubenider, Fouad; Gliozzi, Antonio S; Scalerandi, Marco

2017-01-07

Alkaline solutions, such as sodium, potassium or lithium silicates, appear to be very promising as healing agents for the development of encapsulated self-healing concretes. However, the evolution of their mechanical and acoustic properties in time has not yet been completely clarified, especially regarding their behavior and related kinetics when they are used in the form of a thin layer in contact with a hardened cement matrix. This study aims to monitor, using linear and nonlinear ultrasonic methods, the evolution of a sodium silicate solution interacting with a cement matrix in the presence of localized cracks. The ultrasonic inspection via linear methods revealed that an almost complete recovery of the elastic and acoustic properties occurred within a few days of healing. The nonlinear ultrasonic measurements contributed to provide further insight into the kinetics of the recovery due to the presence of the healing agent. A good regain of mechanical performance was ascertained through flexural tests at the end of the healing process, confirming the suitability of sodium silicate as a healing agent for self-healing cementitious systems.

Constraints on cosmic silicates

NASA Astrophysics Data System (ADS)

Ossenkopf, V.; Henning, Th.; Mathis, J. S.

1992-08-01

Observational determinations of opacities of circumstellar silicates, relative to the peak value near 10 microns, are used to estimate the optical constants n and k, the real and imaginary parts of the index of refraction. Circumstellar dust is modified by processing within the interstellar medium. This leads to higher band strengths and a somewhat larger ratio of the opacities at the 18 and 10-micron peaks, compared with circumstellar silicates. By using an effective-medium theory, we calculate the effects of small spherical inclusions of various materials (various oxides, sulfides, carbides, amorphous carbon, and metallic iron) upon silicate opacities. Some of these can increase the absorption coefficient k in the 2-8 micron region appreciably, as is needed to reconcile laboratory silicate opacities with observations of both the interstellar medium and envelopes around late-type stars. We give tables of two sets of optical constants for warm oxygen-deficient and cool oxygen-rich silicates, representative for circumstellar and interstellar silicates. The required opacity in the 2-8 micron region is provided by iron and magnetite.

Fracture-induced flow and liquid metal transport during core formation

NASA Astrophysics Data System (ADS)

Jones, V.; Petford, N.; Rushmer, T.; Wertheim, D.

2008-12-01

The most important event in the early history of the earth was the separation of its iron-rich core. Core formation induced profound chemical fractionations and extracted into the core most of Earth's iron and siderophile elements (Ni, Co, Au, Pt, W, Re), leaving the silicate crust and mantle with strong depletions of these elements relative to primitive planetary material. Recent measurements of radiogenic 182W anomalies in the silicate Earth, Mars and differentiated meteorites imply that planetesimals segregated metallic cores within a few Myr of the origin of the solar system. Various models have been put forward to explain the physical nature of the segregation mechanism (Fe-diapirs, 'raining' through a magma ocean), and more recently melt flow via fractures. In this contribution we present the initial results of a numerical study into Fe segregation in a deforming silicate matrix that captures the temperature-dependent effect of liquid metal viscosity on the transport rate. Flow is driven by pressure gradients associated with impact deformation in a growing planetesimal and the fracture geometry is constrained by experimental data on naturally deformed H6 chondrite. Early results suggest that under dynamic conditions, fracture-driven melt flow can in principle be extremely rapid, leading to a significant draining of the Fe-liquid metal and siderophile trace element component on a timescale of hours to days. Fluid transport in planetesimals where deformation is the driving force provides an attractive and simple way of segregating Fe from host silicate as both precursor and primary agent of core formation

Cr-Free Metallic-Ceramic Coatings

DTIC Science & Technology

2014-11-01

Comparable to Aluminum-Chromate/ Phosphate Humidity Resistance Galvanic Corrosion Resistance Nov. 2014 ASETSDefense 2014, Fort Myer, VA...Aluminum-Silicate Comparable to Aluminum-Chromate/ Phosphate  Humidity, Galvanic Corrosion , Heat/Salt Resistance  Adhesion & Compatibility...WP-TR-2007-4069, Sept. 2006 Sealed Aluminum-Silicate Not Comparable to Sealed Aluminum-Chromate/ Phosphate in PEWG Evaluation  Corrosion

Process for sequestering carbon dioxide and sulfur dioxide

DOEpatents

Maroto-Valer, M Mercedes [State College, PA; Zhang, Yinzhi [State College, PA; Kuchta, Matthew E [State College, PA; Andresen, John M [State College, PA; Fauth, Dan J [Pittsburgh, PA

2009-10-20

A process for sequestering carbon dioxide, which includes reacting a silicate based material with an acid to form a suspension, and combining the suspension with carbon dioxide to create active carbonation of the silicate-based material, and thereafter producing a metal salt, silica and regenerating the acid in the liquid phase of the suspension.

Uranium, thorium and REE partitioning into sulfide liquids at high pressure and high temperature: Implications for reduced, S-rich planetary bodies

NASA Astrophysics Data System (ADS)

Wohlers, A.; Wood, B. J.

2017-12-01

Based on models of the young solar nebula it is likely that the inner planets went through an early reduced phase of accretion with high metal/silicate ratio and low volatile element contents. Mercury is an existing example of a large planetary embryo with these characteristics but also with a very high S content. In order to investigate the geochemical evolution of Mercury-like bodies we experimentally determined the partitioning of lithophile elements (U, Th, Eu, Sm, Nd, Zr, La, Ce, Yb) between sulfide liquid, low-S metals and silicate melt at 1.5 GPa and 1400-2100˚C. Our results, when combined with those of Wohlers and Wood (2015) show that under highly reducing conditions (FeOsilicate<1wt%) U, Sm, Nd and other lithophile elements partition strongly into FeS liquids relative to silicate melts. The dependences of D's on the FeS contents of the metal and FeO contents of the silicate may be understood in terms of exchange reactions: UO2 + 2FeS = 2FeO + US2silicate sulfide silicate sulfideHigh concentrations of FeSmetal and low FeO contents of the silicate melts drive the reaction to the right, yielding high US2 in the sulfide and high DU. A second effect which raises DU (and other lithophile D's) is the S content of the silicate melt. The latter increases rapidly at low FeO contents and reaches 11wt %. This greatly reduces the activity coefficient of FeO, displacing the reaction further to the right. At 1.5GPa and 1400˚C we obtain sulfide-silicate partitioning with DNd/DSm 1.4 and DTh 0.1DU. As temperature increases to 2100˚C, DNd/DSm declines to 1.0 and DTh/DU increases to 0.3. We estimated the effects of accreting a reduced sulfur-rich component (with FeS core) added to early Earth. The results at 1400˚C imply the possibility of a significant ( 11ppm) 142Nd anomaly in silicate Earth and the addition of >8 ppb U to the core, but require an unreasonably high Th/U of silicate Earth (4.54). Results at 2100˚C lead to a 142Nd anomaly of 0 but addition of such a reduced sulfur-rich body could add up to 10 ppb of U to the core, together with 21 ppb Th. This combination would generate 3 TW of the energy required for the geodynamo. In this case, the Th/U ratio of silicate Earth would be 4.3, within the range of some estimates. Wohlers A. & Wood B.J. (2015) A Mercury-like component of early Earth yield uranium in the core and high mantle Nd142. Nature 520, 337-340

Young Pb-Isotopic Ages of Chondrules in CB Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Amelin, Yuri; Krot, Alexander N.

2005-01-01

CB (Bencubbin-type) carbonaceous chondrites differ in many ways from more familiar CV and CO carbonaceous chondrites and from ordinary chondrites. CB chondrites are very rich in Fe-Ni metal (50-70 vol%) and contain magnesian silicates mainly as angular to sub-rounded clasts (or chondrules) with barred olivine (BO) or cryptocrystalline (CC) textures. Both metal and silicates appear to have formed by condensation. The sizes of silicate clasts vary greatly between the two subgroups of CB chondrites: large (up to one cm) in CB(sub a) chondrites, and typically to much much less than 1 mm in CB(sub b) chondrites. The compositional and mineralogical differences between these subgroups and between the CB(sub s) and other types of chondrites suggest different environment and possibly different timing of chondrule formation. In order to constrain the timing of chondrule forming processes in CB(sub s) and understand genetic relationship between their subgroups, we have determined Pb-isotopic ages of silicate material from the CB(sub a) chondrite Gujba and CB(sub b) chondrite Hammadah al Hamra 237 (HH237 hereafter).

SEPARATION BY ADSORPTION

DOEpatents

Lowe, C.S.

1959-06-16

Separation of Pu from fission products by adsorption on hydrous aluminum silicate is described. The Pu in a HNO/sub 3/ solution is oxidized to the hexavalent state and contacted with the silicate which adsorbs fission products. (T.R.H.)

Redox systematics of a magma ocean with variable pressure-temperature gradients and composition

PubMed Central

Righter, K.; Ghiorso, M. S.

2012-01-01

Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO2), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO2 that is based on the ratio of Fe and FeO [called “ΔIW (ratio)” hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO2 + O2 = Fe2SiO4 to calculate absolute fO2 and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO2 in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO2 may evolve from high to low fO2 during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account. PMID:22778438

Characteristics and environmental aspects of slag: a review

USGS Publications Warehouse

Piatak, Nadine M.; Parsons, Michael B.; Seal, Robert R.

2015-01-01

The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

Method and product for phosphosilicate slurry for use in dentistry and related bone cements

DOEpatents

Wagh, Arun S.; Primus, Carolyn

2006-08-01

The present invention is directed to magnesium phosphate ceramics and their methods of manufacture. The composition of the invention is produced by combining a mixture of a substantially dry powder component with a liquid component. The substantially dry powder component comprises a sparsely soluble oxide powder, an alkali metal phosphate powder, a sparsely soluble silicate powder, with the balance of the substantially dry powder component comprising at least one powder selected from the group consisting of bioactive powders, biocompatible powders, fluorescent powders, fluoride releasing powders, and radiopaque powders. The liquid component comprises a pH modifying agent, a monovalent alkali metal phosphate in aqueous solution, the balance of the liquid component being water. The use of calcined magnesium oxide as the oxide powder and hydroxylapatite as the bioactive powder produces a self-setting ceramic that is particularly suited for use in dental and orthopedic applications.

Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaefer, Laura; Petaev, M. I.; Sasselov, Dimitar D.

We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on themore » metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.« less

Asteroid (16) Psyche: Evidence for a silicate regolith from spitzer space telescope spectroscopy

NASA Astrophysics Data System (ADS)

Landsman, Zoe A.; Emery, Joshua P.; Campins, Humberto; Hanuš, Josef; Lim, Lucy F.; Cruikshank, Dale P.

2018-04-01

Asteroid (16) Psyche is a unique, metal-rich object belonging to the "M" taxonomic class. It may be a remnant protoplanet that has been stripped of most silicates by a hit-and-run collision. Because Psyche offers insight into the planetary formation process, it is the target of NASA's Psyche mission, set to launch in 2023. In order to constrain Psyche's surface properties, we have carried out a mid-infrared (5-14 μm) spectroscopic study using data collected with the Spitzer Space Telescope's Infrared Spectrograph. Our study includes two observations covering different rotational phases. Using thermophysical modeling, we find that Psyche's surface is smooth and likely has a thermal inertia Γ = 5-25 J/m2/K/s1/2 and bolometric emissivity ɛ = 0.9, although a scenario with ɛ = 0.7 and thermal inertia up to 95 J/m2/K/s1/2 is possible if Psyche is somewhat larger than previously determined. The smooth surface is consistent with the presence of a metallic bedrock, which would be more ductile than silicate bedrock, and thus may not readily form boulders upon impact events. From comparisons with laboratory spectra of silicate and meteorite powders, Psyche's 7-14 μm emissivity spectrum is consistent with the presence of fine-grained (< 75 μm) silicates on Psyche's surface. We conclude that Psyche is likely covered in a fine silicate regolith, which may also contain iron grains, overlying an iron-rich bedrock.

Chronology and Petrology of Silicates From IIE Iron Meteorites: Evidence of a Complex Parent Body Evolution

NASA Technical Reports Server (NTRS)

Bogard, Donald D.; Garrison, Daniel H.; McCoy, Timothy J.

1999-01-01

IIE iron meteorites contain silicate inclusions whose characteristics suggest a parent body similar to that of H-chondrites. However, these silicates show a wide range of alteration, ranging from Netschadvo and Techado, whose inclusions are little altered. to highly differentiated silicates like-those in Kodaikanal, Weekeroo Station and Colomera, which have lost metal and sulfur and are enriched in feldspar. We find these inclusions to show varying degrees of shock alteration. Because only a limited amount of data on - isotopic ages of HE silicates were available, we made Ar-39 - Ar-40 age determinations of Watson, Techado, miles Colomera, and Sombrerete. Watson has an Ar-Ar age of 3.653 +/- 0.012 Gyr, similar to previously reported ages for Kodaikanal and Netschadvo. We suggest that the various determined radiometric ages of these three meteorites were probably reset by a common impact event. The space exposure ages for these three meteorites are also similar to each other and are considerably younger than exposure ages of other IIEs. Ar-39 - Ar-40 ages inferred for the other four meteorites analyzed are considerably older than Watson and are: Techado =4.49 +/- 0.01 Gyr, Miles =4.412 +/- 0.016 Gyr, Colomera =4.469 +/- 0.012 Gyr, and Sombrerete =4.535 +/- 0.005 Gyr. These ages are in fair agreement with previously reported Rb-Sr isochron ages for Colomera and Weekeroo Station. Although several mechanisms to form HE meteorites previously were suggested, it is not obvious that a single mechanism could produce a suite of meteorites with very different degrees of silicate differentiation and with isotopic ages that differ by >0.8 Gyr. We suggest that those IIEs with older isotopic ages are a product of partial melting and differentiation within the parent body, followed by mixing of silicate and metal while both were relatively hot. Netschadvo and Watson may have formed by this same process or by impact mixing about 4.5 Gyr ago, but their isotopic ages were subsequently reset by shock heating. Kodaikanal apparently is required to have formed more recently, in which case impact melting and differentiation seems the only viable process. We see no compelling reasons to believe that IIE silicate and metal derived from different parent bodies or that the parent body of IIEs was the same as that of H-chondrites.

Volcanic Metal Emissions and Implications for Geochemical Cycling and Mineralization

NASA Astrophysics Data System (ADS)

Edmonds, M.; Mather, T. A.

2016-12-01

Volcanoes emit substantial fluxes of metals to the atmosphere in volcanic gas plumes in the form of aerosol, adsorbed onto silicate particles and even in some cases as gases.. A huge database of metal emissions has been built over the preceding decades, which shows that volcanoes emit highly volatile metals into the atmosphere, such as As, Bi, Cd, Hg, Re, Se, Tl, among others. Understanding the cycling of metals through the Solid Earth system has importance for tackling a wide range of Earth Science problems, e.g. (1) the environmental impacts of metal emissions; (2) the sulfur and metal emissions of volcanic eruptions; (3) the behavior of metals during subduction and slab devolatilization; (4) the influence of redox on metal behavior in subduction zones; (5) the partitioning of metals between magmatic vapor, brines and melts; and (6) the relationships between volcanism and ore deposit formation. It is clear, when comparing the metal composition and flux in the gases and aerosols emitted from volcanoes, that they vary with tectonic setting. These differences allow insights into how the magmatic vapor was generated and how it interacted with melts and sulfides during magma differentiation and decompression. Hotspot volcanoes (e.g. Kilauea, Hawaii; volcanoes in Iceland) outgas a metal suite that mirrors the sulfide liquid-silicate melt partitioning behaviors reconstructed from experiments (as far as they are known), suggesting that the aqueous fluids (that will later be outgassed from the volcano) receive metals directly from oxidation of sulfide liquids during degassing and ascent of magmas towards the surface. At arc volcanoes, the gaseous fluxes of metals are typically much higher; and there are greater enrichments in elements that partition strongly into vapor or brine from silicate melts such as Cu, Au, Zn, Pb, W. We collate and present data on volcanic metal emissions from volcanoes worldwide and review the implications of the data array for metal cycling through subduction, the potential link between the rise of plate tectonics, metal outgassing and biology, and what we can understand about metal sequestration into ore deposits from volcanic emissions.

Antimicrobial activity of sodium hypochlorite-based irrigating solutions.

PubMed

Poggio, Claudio; Arciola, Carla Renata; Dagna, Alberto; Chiesa, Marco; Sforza, Dario; Visai, Livia

2010-09-01

The objective of the present study was the in vitro evaluation of the antimicrobial activity of three different NaOCl-based endodontic irrigating solutions: a 5.25% conventional sodium hypochlorite solution; and two new irrigating solutions, a 5.25% sodium hypochlorite solution with the addition of a proteolytic enzyme and a surfactant; and a 5.25% sodium hypochlorite gel with inorganic silicate. Enterococcus faecalis, Staphylococcus aureus and Streptococcus mutans strains were selected to evaluate the antimicrobial activity of the endodontic irrigating solutions by the agar disc diffusion test. Paper disks were saturated with each one of the tested solutions (at room temperature and pre-warmed at 45°C) and placed onto culture agar-plates pre-adsorbed with bacterial cells and further incubated for 24 h at 37°C. The growth inhibition zones around each irrigating solution were recorded and compared for each bacterial strain. The results were significantly different among the tested irrigating solutions: 5.25% sodium hypochlorite solution produced the highest inhibition areas; 5.25% sodium hypochlorite solution with a proteolytic enzyme and a surfactant, and 5.25% sodium hypochlorite gel with inorganic silicate showed the lowest zones of inhibition. Even if all tested irrigating solution possessed antibacterial activity versus all tested bacterial strains, 5.25% sodium hypochlorite solution with a proteolytic enzyme and a surfactant, and 5.25% sodium hypochlorite gel with inorganic silicate showed lower in vitro efficacy than 5.25% conventional sodium hypochlorite solution.

Nitrogen partitioning during Earth's accretion and core-mantle differentiation

NASA Astrophysics Data System (ADS)

Speelmanns, I. M.; Schmidt, M. W.; Liebske, C.

2017-12-01

On present day Earth, N is one of the key constituents of our atmosphere and forms the basis of life. However, the deep Earth geochemistry of N, i.e. its distribution and isotopic fractionation between Earth's deep reservoirs is not well constrained. This study investigates nitrogen partitioning between metal and silicate melts as relevant for core segregation during the accretion of planetesimals into the Earth. We have determined N-partitioning coefficients over a wide range of temperatures (1250-2000 °C), pressures (15-35 kbar) and oxygen fugacity's, the latter in the relevant range of core segregation (IW-5 to IW). Centrifuging piston cylinders were used to equilibrate and then gravitationally separate metal-silicate melt pairs. Separation of the two melts is necessary to avoid micro nugget contamination in the silicate melt at reducing conditions < IW-2.5. Complete segregation of the two melts was reached within 1 to 3 hours at 1000 g and 1600-1250 °C respectively, the interface showing a proper meniscus. The applied double capsule technique in all experiments, using an outer metallic (Pt) and inner non-metallic capsule (graphite or Al2O3), minimizes N-loss over the course of the experiments compared to single non-metallic capsules. The two quenched melts were cut apart mechanically, cleaned at the outside, their N concentrations were then analysed on bulk samples by an elemental analyser, the low abslute masses requiring careful development of analytical routines. Despite these difficulties, we were able to determine a DNmetal/silicate of 13±0.3 at IW-1 decreasing to 2.0±0.2 at IW-5.5, at 1250°C and 15 kbar, N partitioning into the core forming metal. Increasing temperature dramatically lowers the DNmetal/silicate to e.g. 0.5±0.15 at IW-4, during early core formation N was hence mildly incompatible in the metal. The results suggest that under magma ocean conditions (> 2000 oC and fO2 IW-2.5), N-partition coefficents were within a factor of 2 of unity. Hence, N did not partition into the core, which should contain negliligible quantities of N. The few available literature data [1],[2],[3] support N changing compatibility with decreasing fO2. [1] Kadik et al., (2011) Geochem Int 49.5: 429-438. [2] Roskosz et al., (2013) GCA 121: 15-28. [3] Dalou et al., (2017) EPSL 458: 141-151

Observations of impact-induced molten metal-silicate partitioning

NASA Technical Reports Server (NTRS)

Rowan, Linda R.; Ahrens, Thomas J.

1994-01-01

Observations of molten mid-ocean ridge basalt (MORB)-molybdenum (Mo) interactions produced by shock experiments provide insight into impact and differentiation processes involving metal-silicate partitioning. Analysis of fragments recovered from experiments (achieving MORB liquid shock pressures from 0.8 to 6 GPa) revealed significant changes in the composition of the MORB and Mo due to reaction of the silicate and metal liquids on a short time scale (less than 13 s). The FeO concentration of the shocked liquid decreases systematically with increasing pressure. In fact, the most highly shocked liquid (6 GPa) contains only 0.1 wt% FeO compared to an initial concentration of 9 wt% in the MORB. We infer from the presence of micrometer-sized Fe-, Si- and Mo-rich metallic spheres in the shocked glass that the Fe and Si oxides in the MORB were reduced in an estimated oxygen fugacity of 10(exp -17) bar and subsequently alloyed with the Mo. The in-situ reduction of FeO in the shocked molten basalt implies that shock-induced reduction of impact melt should be considered a viable mechanism for the formation of metallic phases. Similar metallic phases may form during impact accretion of planets and in impacted material found on the lunar surface and near terrestrial impact craters. In particular, the minute, isolated Fe particles found in lunar soils may have formed by such a process. Furthermore, the metallic spheres within the shocked glass have a globular texture similar to the textures of metallic spheroids from lunar samples and the estimated, slow cooling rate of less than or equal to 140 C/s for our spheres is consistent with the interpretation that the lunar spheroids formed by slow cooling within a melted target.

Chondritic Meteorites: Nebular and Parent-Body Formation Processes

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Lindstrom, David (Technical Monitor)

2002-01-01

It is important to identify features in chondrites that formed as a result of parent-body modification in order to disentangle nebular and asteroidal processes. However, this task is difficult because unmetamorphosed chondritic meteorites are mixtures of diverse components including various types of chondrules, chondrule fragments, refractory and mafic inclusions, metal-sulfide grains and fine-grained matrix material. Shocked chondrites can contain melt pockets, silicate-darkened material, metal veins, silicate melt veins, and impact-melt-rock clasts. This grant paid for several studies that went far in helping to distinguish primitive nebular features from those produced during asteroidal modification processes.

Microanalytical study of some cosmic dust discovered in sea-floor sediments in China

NASA Technical Reports Server (NTRS)

Shijie, Z.; Hanchang, P.; Zhong, Y.

1984-01-01

The study of cosmic dust can provide useful data in the investigation of the origin of the Earth and the evolution of celestial bodies. Three types of cosmic dust (ferriginous, siliceous, and glassy) were discovered in the seafloor sediments near China. Their chemical composition and microstructure were examined by X-ray diffraction, fractography, and electron microscopy. The major mineral in an iron-containing cosmic dust is magnetite. The silicate spheres contain sundry metals and metal oxides. Glassy microtektites are similar in composition to tektites, and are found in all the major meteorite areas worldwide.

Silicic Acid and Beer Consumption Reverses the Metal Imbalance and the Prooxidant Status Induced by Aluminum Nitrate in Mouse Brain.

PubMed

González-Muñoz, María José; Garcimartán, Alba; Meseguer, Isabel; Mateos-Vega, Carmen José; Orellana, José María; Peña-Fernández, Antonio; Benedí, Juana; Sánchez-Muniz, Francisco J

2017-01-01

Emerging evidence suggests that by affecting mineral balance, aluminum (Al) may enhance some events associated with neurodegenerative diseases. To examine the effect of Al(NO3)3 exposure on brain Al, cooper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), silicon (Si), and zinc (Zn) levels, and the metal-change implication in brain oxidant and inflammatory status. Four groups of six-week-old male NMRI mice were treated for three months: i) controls, administrated with deionized water; ii) Al, which received Al(NO3)3; iii) Al+silicic acid, which were given Al(NO3)3 plus silicic acid; and iv) Al+beer, which received Al(NO3)3 plus beer. Brain Al and TBARS levels and TNFα and GPx expressions increased, while Cu, Mn, and Zn levels, and catalase and CuZn-SOD expression decreased (at least, p < 0.05) in Al versus control animals. Al, Si, and TBARS levels and TNFα expression decreased (p < 0.05) in Al+silicic acid and Al+beer specimens while Cu, Mn, and Zn levels and antioxidant expression increased versus the Al group. Brain Al levels correlated negatively with those of Cu, Fe, Mn, and Zn, and catalase, CuZn-SOD, and GPx enzyme expressions but positively with Si and TBARS levels and TNFα expression. Two components of the principal component analysis (PCA) explained 71.2% of total data variance (p < 0.001). PCA connected the pro-oxidant markers with brain Al content, while brain Zn and Cu levels were closer to antioxidant enzyme expression. Administration of Al(NO3)3 induced metal imbalance, inflammation, and antioxidant status impairment in the brain. Those effects were blocked to a significant extent by silicic acid and beer administration.

Siderophile Volatile Element Partitioning during Core Formation.

NASA Astrophysics Data System (ADS)

Loroch, D. C.; Hackler, S.; Rohrbach, A.; Klemme, S.

2017-12-01

Since the nineteen sixties it is known, that the Earth's mantle is depleted relative to CI chondrite in numerous elements as a result of accretion and core-mantle differentiation. Additionally, if we take the chondritic composition as the initial solar nebular element abundances, the Earth lacks 85 % of K and up to 98 % of other volatiles. However one potentially very important group of elements has received considerably less attention in this context and these elements are the siderophile but volatile elements (SVEs). SVEs perhaps provide important information regarding the timing of volatile delivery to Earth. Especially for the SVEs the partitioning between metal melt and silicate melt (Dmetal/silicate) at core formation conditions is poorly constrained, never the less they are very important for most of the core formation models. This study is producing new metal-silicate partitioning data for a wide range of SVEs (S, Se, Te, Tl, Ag, As, Au, Cd, Bi, Pb, Sn, Cu, Ge, Zn, In and Ga) with a focus on the P, T and fO2dependencies. The initial hypothesis that we are aiming to test uses the accretion of major portions of volatile elements while the core formation was still active. The key points of this study are: - What are the effects of P, T and fO2 on SVE metal-silicate partioning? - What is the effect of compositional complexity on SVE metal-silicate partioning? - How can SVE's D-values fit into current models of core formation? The partitioning experiments will be performed using a Walker type multi anvil apparatus in a pressure range between 10 and 20 GPa and temperatures of 1700 up to 2100 °C. To determine the Dmetal/silicate values we are using a field emission high-resolution JEOL JXA-8530F EPMA for major elements and a Photon Machines Analyte G2 Excimer laser (193 nm) ablation system coupled to a Thermo Fisher Element 2 single-collector ICP-MS (LA-ICP-MS) for the trace elements. We recently finished the first sets of experiments and can provide the corresponding datasets. Based on the general understanding of Dmetal/silicate values we expect to depend on the composition, in this particular case this means a variation in sulfur and carbon content of the core composition, and also a change of the redox conditions. The major goal however is to derive a model of core formation on Earth that includes and also explains the SVEs.

Radiogenic Xenon-129 in Silicate Inclusions in the Campo Del Cielo Iron Meteorite

NASA Technical Reports Server (NTRS)

Meshik, A.; Kurat, G.; Pravdivtseva, O.; Hohenberg, C. M.

2004-01-01

Iron meteorites present a challenge for the I-Xe dating technique because it is usually the inclusions, not metal, that contain radiogenic xenon and iodine. Silicate inclusions are frequent in only types IAB and IIE, and earlier studies of irons have demonstrated that I-Xe system can survive intact in these inclusions preserving valuable age information. Our previous studies of the I-Xe record in pyroxene grains from Toluca iron suggested an intriguing relationship between apparent I-Xe ages and (Mg+Fe)/Fe ratios. The I-Xe system in K-feldspar inclusions from Colomera (IIE) had the fingerprint of slow cooling, with an indicated cooling rate of 2-4 C/Ma. Here we present studies of the iodine-xenon system in a silicate-graphite-metal (SiGrMet) inclusion of the IA Campo del Cielo iron meteorite from the collection of the Museum of Natural History in Vienna.

Iron metal production in silicate melts through the direct reduction of Fe/II/ by Ti/III/, Cr/II/, and Eu/II/. [in lunar basalts

NASA Technical Reports Server (NTRS)

Schreiber, H. D.; Balazs, G. B.; Shaffer, A. P.; Jamison, P. L.

1982-01-01

The production of metallic iron in silicate melts by chemical reactions of Ti(3+), Cr(2+), and Eu(2+) with Fe(2+) is demonstrated under experimental conditions in a simplified basaltic liquid. These reactions form a basis for interpreting the role of isochemical valency exchange models in explanations for the reduced nature of lunar basalts. The redox couples are individually investigated in the silicate melt to ascertain reference redox ratios that are independent of mutual interactions. These studies also provide calibrations of spectral absorptions of the Fe(2+) and Ti(2+) species in these glasses. Subsequent spectrophotometric analyses of Fe(2+) and Ti(2+) in glasses doped with both iron and titanium and of Fe(2+) in glasses doped with either iron and chromium or iron and europium ascertain the degree of mutual interactions in these dual-doped glasses.

Dust in a Type Ia Supernova Progenitor: Spitzer Spectroscopy of Kepler's Supernova Remnant

NASA Technical Reports Server (NTRS)

Williams, Brian J.; Borkowski, Kazimierz; Reynolds, Stephen P.; Ghavamian, Parviz; Blair, William P.; Long, Knox S.; Sankrit, Ravi

2012-01-01

Characterization of the relatively poorly-understood progenitor systems of Type Ia supernovae is of great importance in astrophysics, particularly given the important cosmological role that these supernovae play. Kepler's Supernova Remnant, the result of a Type Ia supernova, shows evidence for an interaction with a dense circumstellar medium (CSM), suggesting a single-degenerate progenitor system. We present 7.5-38 micron IR spectra of the remnant, obtained with the Spitzer Space Telescope, dominated by emission from warm dust. Broad spectral features at 10 and 18 micron, consistent with various silicate particles, are seen throughout. These silicates were likely formed in the stellar outflow from the progenitor system during the AGB stage of evolution, and imply an oxygen-rich chemistry. In addition to silicate dust, a second component, possibly carbonaceous dust, is necessary to account for the short-wavelength IRS and IRAC data. This could imply a mixed chemistry in the atmosphere of the progenitor system. However, non-spherical metallic iron inclusions within silicate grains provide an alternative solution. Models of collisionally-heated dust emission from fast shocks (> 1000 km/s) propagating into the CSM can reproduce the majority of the emission associated with non-radiative filaments, where dust temperatures are approx 80-100 K, but fail to account for the highest temperatures detected, in excess of 150 K. We find that slower shocks (a few hundred km/s) into moderate density material (n(sub o) approx 50-100 / cubic cm) are the only viable source of heating for this hottest dust. We confirm the finding of an overall density gradient, with densities in the north being an order of magnitude greater than those in the south.

Determination of silver, bismuth, cadmium, copper, lead, and zinc in geologic materials by atomic absorption spectrometry with tricaprylylmethylammonium chloride

USGS Publications Warehouse

Viets, J.G.

1978-01-01

Interferences commonly encountered in the determination of silver, bismuth, cadmium, copper, lead, and zinc at crustal abundance levels are effectively eliminated using a rapid, sensitive, organic extraction technique. A potassium chlorate-hydrochloric acid digestion solubilizes the metals not tightly bound in the silicate lattice of rocks, soils, and stream sediments. The six metals are selectively extracted into a 10% Aliquat 336-MIBK organic phase in the presence of ascorbic acid and potassium iodide. Metals in the organic extract are determined by flame atomic absorption spectrometry to the 0.02-ppm level for silver, cadmium, copper, and zinc and to the 0.2-ppm level for bismuth and lead with a maximum relative standard deviation of 18.8% for known reference samples. An additional hydrofluoric acid digestion may be used to determine metals substituted in the silicate lattice.

Polymer/Silicate Nanocomposites Used to Manufacture Gas Storage Tanks With Reduced Permeability

NASA Technical Reports Server (NTRS)

Campbell, Sandi G.; Johnston, Chris

2004-01-01

Over the past decade, there has been considerable research in the area of polymer-layered silicate nanocomposites. This research has shown that the dispersion of small amounts of an organically modified layered silicate improves the polymer strength, modulus, thermal stability, and barrier properties. There have been several reports on the dispersion of layered silicates in an epoxy matrix. Potential enhancements to the barrier properties of epoxy/silicate nanocomposites make this material attractive for low permeability tankage. Polymer matrix composites (PMCs) have several advantages for cryogenic storage tanks. They are lightweight, strong, and stiff; therefore, a smaller fraction of a vehicle's potential payload capacity is used for propellant storage. Unfortunately, the resins typically used to make PMC tanks have higher gas permeability than metals. This can lead to hydrogen loss through the body of the tank instead of just at welds and fittings. One approach to eliminate this problem is to build composite tanks with thin metal liners. However, although these tanks provide good permeability performance, they suffer from a substantial mismatch in the coefficient of thermal expansion, which can lead to failure of the bond between the liner and the body of the tank. Both problems could be addressed with polymersilicate nanocomposites, which exhibit reduced hydrogen permeability, making them potential candidates for linerless PMC tanks. Through collaboration with Northrop Grumman and Michigan State University, nanocomposite test tanks were manufactured for the NASA Glenn Research Center, and the helium permeability was measured. An organically modified silicate was prepared at Michigan State University and dispersed in an epoxy matrix (EPON 826/JeffamineD230). The epoxy/silicate nanocomposites contained either 0 or 5 wt% of the organically modified silicate. The tanks were made by filament winding carbon fibers with the nanocomposite resin. Helium permeability was measured by Northrop Grumman, showing that the leak rate/day of the nanocomposite matrix tank was approximately 80-percent less than that of the neat epoxy matrix tank.

The solubility of platinum in silicate melt under reducing conditions: Results from experiments without metal inclusions

NASA Astrophysics Data System (ADS)

Bennett, N. R.; Brenan, J. M.; Koga, K. T.

2014-05-01

The solubility of Pt in silicate melt was investigated at conditions of 2073-2573 K, 2 GPa and ˜IW -1.5 to +3.5. These are the first measurements of Pt solubility under conditions more reducing than the iron-wüstite buffer (IW) which are demonstrably free from contamination by metal-inclusions. Pt solubility increases with increasing temperature and decreasing oxygen fugacity. The ability of carbon to enhance Pt solubility under reducing conditions (3500 K. Under these conditions however, the estimated Pt/Os ratio is ˜40,000 times higher than that estimated for the PUM (Brandon et al., 2006). Instead, the PUM composition is generated most readily by metal-silicate equilibrium at more modest temperatures (˜3100 K), followed by a late accretion of chondritic material subsequent to core formation.

Prediction of equilibrium parameters of adsorption of lead (II) ions onto diatomite

NASA Astrophysics Data System (ADS)

Salman, Taylan; Ardalı, Yüksel; Gamze Turan, N.

2013-04-01

Heavy metals from industrial wastewaters are one of the most important environmental issues to be solved today. Due to their toxicity and nonbiodegradable nature, heavy metals cause environmental and public health problems. Various techniques have been developed to remove heavy metals from aqueous solutions. These include chemical precipitation, reverse osmosis, ion Exchange and adsorption. Among them, adsorption is considered to be a particularly competitive and effective process for the removal of heavy metals from aqueous solutions. There is growing interest in using low cost, commercially available materials for the adsorption of heavy metals. Diatomite is a siliceous sedimentary rock having an amorphous form of silica (SiO2. nH2O) containing a small amount of microcrystalline material. It has unique combination of physical and chemical properties such as high porosity, high permeability, small particle size, large surface area, and low thermal conductivity. In addition, it is available in Turkey and in various locations around the world. Therefore, diatomite has been successfully used as adsorbent for the removal of heavy metals. The aim of the study is to investigate the adsorption properties of diatomite. The equilibrium adsorption data were applied to the Langmuir, Freundlich and Dubinin-Radushkevic (D-R) isotherm models. Adsorption experiments were performed under batch process, using Pb (II) initial concentration, pH of solution and contact time as variables. The results demonstrated that the adsorption of Pb (II) was strongly dependent on pH of solution. The effect of pH on adsorption of Pb(II) on diatomite was conducted by varying pH from 2 to 12 at 20 oC. In the pH range of 2.0-4.0, the adsorption percentage increases slightly as the pH increasing. At pH>4, the adsorption percentage decreases with increasing pH because hydrolysis product and the precipitation begin to play an important role in the sorption of Pb (II). At pH4, the maximum adsorption capacity of diatomite was found as 26.158 mg/g. The adsorption isotherms of Pb (II) on diatomite can be described well by the Freundlich model. The high adsorption capacity of diatomite makes it suitable low-cost material in the removal of Pb (II) from aqueous solutions.

Distribution, microfabric, and geochemical characteristics of siliceous rocks in central orogenic belt, China: implications for a hydrothermal sedimentation model.

PubMed

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Gao, Le; Yang, Zhijun; Zhou, Yongzhang; He, Junguo; Liang, Jin; Zhou, Liuyu; Voudouris, Panagiotis Ch

2014-01-01

Marine siliceous rocks are widely distributed in the central orogenic belt (COB) of China and have a close connection to the geological evolution and metallogenesis. They display periodic distributions from Mesoproterozoic to Jurassic with positive peaks in the Mesoproterozoic, Cambrian--Ordovician, and Carboniferous--Permian and their deposition is enhanced by the tensional geological settings. The compressional regimes during the Jinning, Caledonian, Hercynian, Indosinian, and Yanshanian orogenies resulted in sudden descent in their distribution. The siliceous rocks of the Bafangshan-Erlihe ore deposit include authigenic quartz, syn-depositional metal sulphides, and scattered carbonate minerals. Their SiO2 content (71.08-95.30%), Ba (42.45-503.0 ppm), and ΣREE (3.28-19.75 ppm) suggest a hydrothermal sedimentation origin. As evidenced by the Al/(Al + Fe + Mn), Sc/Th, (La/Yb) N, and (La/Ce) N ratios and δCe values, the studied siliceous rocks were deposited in a marginal sea basin of a limited ocean. We suggest that the Bafangshan-Erlihe area experienced high- and low-temperature stages of hydrothermal activities. The hydrothermal sediments of the former stage include metal sulphides and silica, while the latter was mainly composed of silica. Despite the hydrothermal sedimentation of the siliceous rocks, minor terrigenous input, magmatism, and biological activity partly contributed to geochemical features deviating from the typical hydrothermal characteristics.

Distribution, Microfabric, and Geochemical Characteristics of Siliceous Rocks in Central Orogenic Belt, China: Implications for a Hydrothermal Sedimentation Model

PubMed Central

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Gao, Le; Yang, Zhijun; Zhou, Yongzhang; He, Junguo; Liang, Jin; Zhou, Liuyu; Voudouris, Panagiotis Ch.

2014-01-01

Marine siliceous rocks are widely distributed in the central orogenic belt (COB) of China and have a close connection to the geological evolution and metallogenesis. They display periodic distributions from Mesoproterozoic to Jurassic with positive peaks in the Mesoproterozoic, Cambrian—Ordovician, and Carboniferous—Permian and their deposition is enhanced by the tensional geological settings. The compressional regimes during the Jinning, Caledonian, Hercynian, Indosinian, and Yanshanian orogenies resulted in sudden descent in their distribution. The siliceous rocks of the Bafangshan-Erlihe ore deposit include authigenic quartz, syn-depositional metal sulphides, and scattered carbonate minerals. Their SiO2 content (71.08–95.30%), Ba (42.45–503.0 ppm), and ΣREE (3.28–19.75 ppm) suggest a hydrothermal sedimentation origin. As evidenced by the Al/(Al + Fe + Mn), Sc/Th, (La/Yb)N, and (La/Ce)N ratios and δCe values, the studied siliceous rocks were deposited in a marginal sea basin of a limited ocean. We suggest that the Bafangshan-Erlihe area experienced high- and low-temperature stages of hydrothermal activities. The hydrothermal sediments of the former stage include metal sulphides and silica, while the latter was mainly composed of silica. Despite the hydrothermal sedimentation of the siliceous rocks, minor terrigenous input, magmatism, and biological activity partly contributed to geochemical features deviating from the typical hydrothermal characteristics. PMID:25140349

Processing lunar soils for oxygen and other materials

NASA Technical Reports Server (NTRS)

Knudsen, Christian W.; Gibson, Michael A.

1992-01-01

Two types of lunar materials are excellent candidates for lunar oxygen production: ilmenite and silicates such as anorthite. Both are lunar surface minable, occurring in soils, breccias, and basalts. Because silicates are considerably more abundant than ilmenite, they may be preferred as source materials. Depending on the processing method chosen for oxygen production and the feedstock material, various useful metals and bulk materials can be produced as byproducts. Available processing techniques include hydrogen reduction of ilmenite and electrochemical and chemical reductions of silicates. Processes in these categories are generally in preliminary development stages and need significant research and development support to carry them to practical deployment, particularly as a lunar-based operation. The goal of beginning lunar processing operations by 2010 requires that planning and research and development emphasize the simplest processing schemes. However, more complex schemes that now appear to present difficult technical challenges may offer more valuable metal byproducts later. While they require more time and effort to perfect, the more complex or difficult schemes may provide important processing and product improvements with which to extend and elaborate the initial lunar processing facilities. A balanced R&D program should take this into account. The following topics are discussed: (1) ilmenite--semi-continuous process; (2) ilmenite--continuous fluid-bed reduction; (3) utilization of spent ilmenite to produce bulk materials; (4) silicates--electrochemical reduction; and (5) silicates--chemical reduction.

Sol-Gel Precursors for Ceramics from Minerals Simulating Soils from the Moon and Mars

NASA Technical Reports Server (NTRS)

Sibille, Laurent; Gavira-Gallardo, Jose-Antonio; Hourlier-Bahloul, Djamila

2003-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report some preliminary results on the production of sol-gel precursors for ceramic products using mineral resources available in Martian or Lunar soil. The presence of SiO2, TiO2, and A12O3 in both Martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and Lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from Lunar and Martian simulant soils. Clear sol-gel precursors have been obtained by dissolution of silica from Lunar simulant soil in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Thermogravimetric Analysis and X-ray Photoelectron Spectroscopy were used to characterize the elemental composition and structure of the precursor molecules. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors. In the second set of experiments, we used the same starting materials to synthesize silicate esters in acidified alcohol mixtures. Preliminary results indicate the presence of silicon alkoxides in the product of distillation.

Partitioning of carbon between Fe-rich alloy melt and silicate melt in a magma ocean - Implications for the abundance and origin of volatiles in Earth, Mars, and the Moon

NASA Astrophysics Data System (ADS)

Chi, Han; Dasgupta, Rajdeep; Duncan, Megan S.; Shimizu, Nobumichi

2014-08-01

The budget and origin of carbon in Earth and other terrestrial planets are debated and one of the key unknowns is the fate of carbon during early planetary processes including accretion, core formation, and magma ocean (MO) crystallization. Here we determine, experimentally, the solubility of carbon in coexisting Fe-Ni alloy melt and basaltic silicate melt in shallow MO conditions, i.e., at 1-3 GPa, 1500-1800 °C. Oxygen fugacity of the experiments, estimated based on Fe (in metallic alloy melt)-FeO (in silicate melt) equilibrium, varied between ∼IW-0.4 and IW-1.0, where IW refers to the oxygen fugacity imposed by the coexistence of iron and wüstite. Four different starting mixes, each with 7:3 silicate:metal mass ratio and silicate melt NBO/T (estimated proportion of non-bridging oxygen with respect to tetrahedral cations; NBO/T=2×/total OT -4, where T = Si + Ti + Al + Cr + P) ranging from 0.81 to 1.54 were studied. Concentrations of carbon in the alloy melt were determined using electron microprobe whereas carbon contents of quenched basaltic glasses were determined using secondary ionization mass spectrometry (SIMS). Identification of carbon and hydrogen-bearing species in silicate glasses was performed using Raman and Fourier Transformed Infrared (FTIR) spectroscopy. Our results show that carbon in the metallic melt varies between 4.4 wt.% and 7.4 wt.% and increases with increasing temperature and modestly with increasing pressure but decreases with increasing Ni content of the alloy melt. Carbon concentration in the silicate melts, on the other hand, varies from 11 ± 1 ppm to 111 ± 7 ppm and is negatively correlated with pressure but positively correlated with temperature, the NBO/T, the oxygen fugacity and the water content of the silicate melts. Raman and FTIR results show that at our experimental conditions, carbon in silicate melt is dissolved both as hydrogenated species and CO32-. The calculated carbon partition coefficient DCmetal/silicate varies from 510 ± 53 to 5369 ± 217 and varies systematically as a function of P, T, fO2, water content, the composition of the silicate melt (expressed using NBO/T), and Ni content of alloy melt (XNi). The range of DCmetal/silicate measured in our study with carbonated and hydrogenated carbon species in silicate melt is similar to that reported in the literature for experiments where carbonyl complexes are the chief carbon species in silicate melts. A parameterization was derived using the data from this and existing studies such as lnDCmetal/silicate=a/T+b·P/T+c·ln(fO2)+d·(NBO/T)+e·ln(1-XNi)+f where a = -33,510, b = 1357, c = -0.596, d = -1.182, e = 4.15, f = 13.38, the temperature is in Kelvin, and the pressure is in gigapascal. Using this parameterization and the estimated conditions for the base of the MOs, the average DCmetal/silicate value for Earth, Mars, and the Moon can be predicted. The deep MO of Earth is predicted to cause the strongest depletion of its silicate carbon budget, closely followed by Mars with intermediate depth MO, and then the Moon with a shallow MO. We predict that the lunar mantle carbon budget, similar to that of the Earth’s present-day upper mantle, might have been set by equilibrium core-mantle fractionation in MO; whereas for Earth, later processes such as ingassing from a proto-atmosphere and late-stage accretion of volatile-rich material was necessary for delivery of carbon and other volatiles. Finally, the comparison of our measured and predicted value of DCmetal/silicate for terrestrial MO with similar constraints on DNmetal/silicate from the literature suggests that the apparent depletion of nitrogen relative to carbon for the bulk silicate Earth and the Earth’s upper mantle is unlikely to be caused by preferential partitioning of nitrogen to alloy melt during core formation.

Influence of the type of aqueous sodium silicate on the stabilization and rheology of kaolin clay suspensions

NASA Astrophysics Data System (ADS)

Izak, Piotr; Ogłaza, Longin; Mozgawa, Włodzimierz; Mastalska-Popławska, Joanna; Stempkowska, Agata

2018-05-01

To avoid agglomeration and sedimentation of grains, ceramic slurries should be modified by stabilizers in order to increase the electrostatic interactions between the dispersed particles. In this study we present the spectral analysis of aqueous sodium silicates obtained by different synthesis methods and their influence on the rheological properties of kaolin based slurries. Infrared and Raman spectra can be used to describe the structure of silicate structural units present in aqueous sodium silicates. It was confirmed that the best stabilization results possess aqueous sodium silicates of the silicate moduli of about 2 and the optimal concentration of the used fluidizer is 0.3 wt% to the kaolin clay dry mass. One of the most important conclusions is that the synthesis method of the fluidizer has no significant effect on its stabilization properties but used medium does create adequate stabilization mechanism depending on the silicate structures present in the sodium silicate solution.

Novel Experimental Simulations of the Atmospheric Injection of Meteoric Metals

NASA Astrophysics Data System (ADS)

Gómez Martín, J. C.; Bones, D. L.; Carrillo-Sánchez, J. D.; James, A. D.; Trigo-Rodríguez, J. M.; Fegley, B., Jr.; Plane, J. M. C.

2017-02-01

A newly developed laboratory, Meteoric Ablation Simulator (MASI), is used to test model predictions of the atmospheric ablation of interplanetary dust particles (IDPs) with experimental Na, Fe, and Ca vaporization profiles. MASI is the first laboratory setup capable of performing time-resolved atmospheric ablation simulations, by means of precision resistive heating and atomic laser-induced fluorescence detection. Experiments using meteoritic IDP analogues show that at least three mineral phases (Na-rich plagioclase, metal sulfide, and Mg-rich silicate) are required to explain the observed appearance temperatures of the vaporized elements. Low melting temperatures of Na-rich plagioclase and metal sulfide, compared to silicate grains, preclude equilibration of all the elemental constituents in a single melt. The phase-change process of distinct mineral components determines the way in which Na and Fe evaporate. Ca evaporation is dependent on particle size and on the initial composition of the molten silicate. Measured vaporized fractions of Na, Fe, and Ca as a function of particle size and speed confirm differential ablation (I.e., the most volatile elements such as Na ablate first, followed by the main constituents Fe, Mg, and Si, and finally the most refractory elements such as Ca). The Chemical Ablation Model (CABMOD) provides a reasonable approximation to this effect based on chemical fractionation of a molten silicate in thermodynamic equilibrium, even though the compositional and geometric description of IDPs is simplistic. Improvements in the model are required in order to better reproduce the specific shape of the elemental ablation profiles.

Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy

PubMed Central

2009-01-01

Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (± 0.1) × 10-5 s-1 for a solution:solid of 10:1 and 1.6 (± 0.8) × 10-4 s-1 for a solution:solid of 5:1 (batch mode; T = 150°C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at δiso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (± 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR. PMID:19144195

Calcium and magnesium isotope systematics in rivers draining the Himalaya-Tibetan-Plateau region: Lithological or fractionation control?

NASA Astrophysics Data System (ADS)

Tipper, Edward T.; Galy, Albert; Bickle, Mike J.

2008-02-01

In rivers draining the Himalaya-Tibetan-Plateau region, the 26Mg/ 24Mg ratio has a range of 2‰ and the 44Ca/ 42Ca ratio has a range of 0.6‰. The average δ26Mg values of tributaries from each of the main lithotectonic units (Tethyan Sedimentary Series (TSS), High Himalayan Crystalline Series (HHCS) and Lesser Himalayan Series (LHS)) are within 2 standard deviation analytical uncertainty (0.14‰). The consistency of average riverine δ26Mg values is in contrast to the main rock types (limestone, dolostone and silicate) which range in their average δ26Mg values by more than 2‰. Tributaries draining the dolostones of the LHS differ in their δ44Ca values compared to tributaries from the TSS and HHCS. The chemistry of these river waters is strongly influenced by dolostone (solute Mg/Ca close to unity) and both δ26Mg (-1.31‰) and δ44Ca (0.64‰) values are within analytical uncertainty of the LHS dolostone. These are the most elevated δ44Ca values in rivers and rock reported so far demonstrating that both riverine and bedrock δ44Ca values may show greater variability than previously thought. Although rivers draining TSS limestone have the lowest δ26Mgandδ44Ca values at -1.41 and 0.42‰, respectively, both are offset to higher values compared to bedrock TSS limestone. The average δ26Mg value of rivers draining mainly silicate rock of the HHCS is -1.25‰, lower by 0.63‰ than the average silicate rock. These differences are consistent with a fractionation of δ26Mg values during silicate weathering. Given that the proportion of Mg exported from the Himalaya as solute Mg is small, the difference in 26Mg/ 24Mg ratios between silicate rock and solute Mg reflects the 26Mg/ 24Mg isotopic fractionation factor ( αsilicate-dissolvedMg) between silicate and dissolved Mg during incongruent silicate weathering. The value of αsilicate-dissolvedMg of 0.99937 implies that in the TSS, solute Mg is primarily derived from silicate weathering, whereas the source of Ca is overwhelmingly derived from carbonate weathering. The average δ44Ca value in HHCS rivers is within uncertainty of silicate rock at 0.39‰. The widespread hot springs of the High Himalaya have an average δ26Mg value of -0.46‰ and an average δ44Ca value of 0.5‰, distinct from riverine values for δ26Mg but similar to riverine δ44Ca values. Although rivers draining each major rock type have δ44Ca and δ26Mg values in part inherited from bedrock, there is no correlation with proxies for carbonate or silicate lithology such as Na/Ca ratios, suggesting that Ca and Mg are in part recycled. However, in spite of the vast contrast in vegetation density between the arid Tibetan Plateau and the tropical Lesser Himalaya, the isotopic fractionation factor for Ca and Mg between solute and rocks are not systematically different suggesting that vegetation may only recycle a small amount of Ca and Mg in these catchments. The discrepancy between solute and solid Ca and Mg isotope ratios in these rivers from diverse weathering environments highlight our lack of understanding concerning the origin and subsequent path of Ca and Mg, bound as minerals in rock, and released as cations in rivers. The fractionation of Ca and Mg isotope ratios may prove useful for tracing mechanisms of chemical alteration. Ca isotope ratios of solute riverine Ca show a greater variability than previously acknowledged. The variability of Ca isotope ratios in modern rivers will need to be better quantified and accounted for in future models of global Ca cycling, if past variations in oceanic Ca isotope ratios are to be of use in constraining the past carbon cycle.

Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

NASA Astrophysics Data System (ADS)

Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

2016-12-01

In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.

Alkali Silicate Vehicle Forms Durable, Fireproof Paint

NASA Technical Reports Server (NTRS)

Schutt, John B.; Seindenberg, Benjamin

1964-01-01

The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

Typhoon impacts on chemical weathering source provenance of a High Standing Island watershed, Taiwan

NASA Astrophysics Data System (ADS)

Meyer, Kevin J.; Carey, Anne E.; You, Chen-Feng

2017-10-01

Chemical weathering source provenance changes associated with Typhoon Mindulle (2004) were identified for the Choshui River Watershed in west-central Taiwan using radiogenic Sr isotope (87Sr/86Sr) and major ion chemistry analysis of water samples collected before, during, and following the storm event. Storm water sampling over 72 h was conducted in 3 h intervals, allowing for novel insight into weathering regime changes in response to intense rainfall events. Chemical weathering sources were determined to be bulk silicate and disseminated carbonate minerals at the surface and silicate contributions from deep thermal waters. Loss on ignition analysis of collected rock samples indicate disseminated carbonate can compose over 25% by weight of surface mineralogy, but typically makes up ∼2-3% of watershed rock. 87Sr/86Sr and major element molar ratios indicate that Typhoon Mindulle caused a weathering regime switch from normal flow incorporating a deep thermal signature to that of a system dominated by surface weathering. The data suggest release of silicate solute rich soil pore waters during storm events, creating a greater relative contribution of silicate weathering to the solute load during periods of increased precipitation and runoff. Partial depletion of this soil solute reservoir and possible erosion enhanced carbonate weathering lead to increased importance of carbonates to the weathering regime as the storm continues. Major ion data indicate that complex mica weathering (muscovite, biotite, illite, chlorite) may represent an important silicate weathering pathway in the watershed. Deep thermal waters represent an important contribution to river solutes during normal non-storm flow conditions. Sulfuric acid sourced from pyrite weathering is likely a major weathering agent in the Choshui River watershed.

ACFER 182/207/214 A Metal-rich, Volatile-poor Chondritic Meteorite, Similar to ALH85085

NASA Astrophysics Data System (ADS)

Palme, H.; Spettel, B.

1992-07-01

The unique Antarctic meteorite ALH85085 was the first chondritic meteorite to contain a significant excess of metallic Fe and associated siderophile elements (e.g., Grossman et al. 1988, Wasson and Kallemeyn 1990). Recently three Sahara meteorites, Acfer 182/207/214, apparently belonging to the same fall, were shown to be chemically and mineralogically very similar to ALHA85085, although minor textural differences appear to exclude a common origin with ALH85085. A mineralogical description and chemical composition of Acfer182/207/214 (henceforth ACFER182) are given in Bischoff et al. (1992). These authors suggested designating ALH85085 and ACFER182 as HH-chondrites reflecting high total Fe and high metal. The Fe/Mg-ratio of ACFER182 is 1.7 times that of CI-chondrites. All metals more refractory than Fe have similar enrichment factors, i.e., non-volatile metals occur in chondritic proportions, except for a slightly lower W enrichment. Metals more volatile than Fe are strongly depleted, with the depletion sequence closely following decreasing condensation temperatures. CI-normalized abundances are: Fe(1.92), Au(1.33), As(1.04), Cu(0.62), Ga(0.38), and the chalcophile Se(0.17). Lithophiles, more refractory than Mg, but including Mg and Cr, also occur in CI-abundance ratios (e.g., Sc/Mg in ACFER182 is 1.05xCI), although their absolute abundances are lower than those of metals. More volatile lithophile elements (Mn, Zn, etc.) decrease in abundance with decreasing condensation temperatures, just as the metals. The parallel (metal and silicate) decrease in moderately volatile element abundances with condensation temperatures suggests a similar nebular history for metal and silicate and is readily understood in a model where nebular gas is continually removed during condensation (Wasson and Chou 1974). Actual mixing of silicate and metal, i.e., agglomeration of silicate and metal grains in non-chondritic proportions (with 70% metal excess) could have occurred at relatively low temperatures, after the chondrule-forming process had transformed silicate grains into chondrules and fine metal grains into coarser metal. Partial loss of volatiles during chondrule formation or reheating of a metal-silicate assemblage with high volatile element abundances are very unlikely to produce the observed depletion sequence as argued by Grossman et al. (1988) for ALH85085. In addition, experiments on artificially heated meteorites produce losses of volatiles that are strongly dependent on fO(sub)2 and are incompatible with the patterns observed in ACFER182 (Wulf and Palme 1991). For example, the observed depletion of Mn in Acfer182 is 0.35 (i.e., 65 % are not condensed). However, Mn loss was never observed in the heating experiments, while large losses of Ga, Se, and Zn were found at temperatures up to 1300 degrees C. At temperatures required for Mn-volatilisation most other moderately volatiles would be quantitatively removed. However, the delicate pattern of moderate volatiles excludes ACFER182 as being a simple mixture of volatile-rich and volatile-poor material. Chemically, ACFER182 and ALHA85085 are related to CR-chondrites. These meteorites follow a trend of increasingly lower contents of volatile elements (e.g., Se, Zn) with decreasing contents of refractory element contents (e.g., Sc), opposite to the major trend in carbonaceous chondrites (from CI to CV). The ACFER182 and ALH85085 meteorites with their low Zn and Se contents and their low Sc abundances appear to form an endmember of this trend. Additional similarities with CR-meteorites in texture, mineralogy, and O, C, and N isotopic compositions (Bischoff et al. 1992; Prinz and Weisberg 1992 and references therein) may indicate that these meteorites are not as unique as originally thought. References: Bischoff A., Palme H., Schultz L., Weber D., Weber H.W. and Spettel B. (submitted to Geochim. Cosmochim. Acta 1992). Grossman J.N., Rubin A.E., MacPherson G.J. (1988) Earth Planet. Sci. Lett. 91, 33-54. Prinz M. and Weisberg M.K. (1992) Lunar. Planet. Sci. (abstract) 23, 1109. Wasson J.T. and Chou C.L. (1974) Meteoritics 9, 69-84. Wasson J.T. and Kallemeyn G.W. (1990) Earth Planet. Sci. Lett. 101, 148-161. Wulf A.-V. and Palme H.(1991) Lunar. Planet. Sci. (abstract) 22, 1527.

OXIDATION-RESISTANT COATING ON ARTICLES OF YTTRIUM METAL

DOEpatents

Wilder, D.R.; Wirkus, C.D.

1963-11-01

A process for protecting yttrium metal from oxidation by applying thereto and firing thereon a liquid suspension of a fritted ground silicate or phosphate glass plus from 5 to 35% by weight of CeO/sub 2/ is presented. (AEC)

The Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses: Results from W L-Edge Xanes Measurements

NASA Technical Reports Server (NTRS)

Danielson, Lisa R.; Righter, K.; Sutton S.; Newville, M.; Le, L.

2007-01-01

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted approx. 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies (figure 1) are inconsistent on whether W occurs as W(4+) or W(6+).

Properties of zirconium silicate and zirconium-silicon oxynitride high-k dielectric alloys for advanced microelectronic applications: Chemical and electrical characterizations

NASA Astrophysics Data System (ADS)

Ju, Byongsun

2005-11-01

As the microelectronic devices are aggressively scaled down to the 1999 International Technology Roadmap, the advanced complementary metal oxide semiconductor (CMOS) is required to increase packing density of ultra-large scale integrated circuits (ULSI). High-k alternative dielectrics can provide the required levels of EOT for device scaling at larger physical thickness, thereby providing a materials pathway for reducing the tunneling current. Zr silicates and its end members (SiO2 and ZrO2) and Zr-Si oxynitride films, (ZrO2)x(Si3N 4)y(SiO2)z, have been deposited using a remote plasma-enhanced chemical vapor deposition (RPECVD) system. After deposition of Zr silicate, the films were exposed to He/N2 plasma to incorporate nitrogen atoms into the surface of films. The amount of incorporated nitrogen atoms was measured by on-line Auger electron spectrometry (AES) as a function of silicate composition and showed its local minimum around the 30% silicate. The effect of nitrogen atoms on capacitance-voltage (C-V) and leakage-voltage (J-V) were also investigated by fabricating metal-oxide-semiconductor (MOS) capacitors. Results suggested that incorporating nitrogen into silicate decreased the leakage current in SiO2-rich silicate, whereas the leakage increased in the middle range of silicate. Zr-Si oxynitride was a pseudo-ternary alloy and no phase separation was detected by x-ray photoelectron spectroscopy (XPS) analysis up to 1100°C annealing. The leakage current of Zr-Si oxynitride films showed two different temperature dependent activation energies, 0.02 eV for low temperature and 0.3 eV for high temperature. Poole-Frenkel emission was the dominant leakage mechanism. Zr silicate alloys with no Si3N4 phase were chemically separated into the SiO2 and ZrO2 phase as annealed above 900°C. While chemical phase separation in Zr silicate films with Si 3N4 phase (Zr-Si oxynitride) were suppressed as increasing the amount of Si3N4 phase due to the narrow bonding network m Si3N4 phase. (3.4 bonds/atom for Si3 N4 network, 2.67 bonds/atom for SiO2 network).

Development of Aerogel Molds for Metal Casting Using Lunar and Martian Regolith

NASA Technical Reports Server (NTRS)

2003-01-01

In the last few years NASA has set new priorities for research and development of technologies necessary to enable long-term presence on the Moon and Mars. Among these key technologies is what is known as in situ resource utilization, which defines all conceivable usage of mineral, liquid, gaseous, or biological resources on a visited planet. In response to this challenge, we have been focusing on developing and demonstrating the manufacturing of a specific product using Lunar and Martian soil simulants (i.e., a mold for the casting of metal and alloy parts) which will be an indispensable tool for the survival of outposts on the Moon and Mars. In addition, our purpose is to demonstrate the feasibility of using mesoporous materials such as aerogels to serve as efficient casting molds for high quality components in propulsion and other aerospace applications. The first part of the project consists of producing aerogels from the in situ resources available in Martian and Lunar soil. The approach we are investigating is to use chemical processes to solubilize silicates using organic reagents at low temperatures and then use these as precursors in the formation of aerogels for the fabrication of metal casting molds. One set of experiments consists of dissolving silica sources in basic ethylene glycol solution to form silicon glycolates. When ground silica aerogel was used as source material, a clear solution of silicon glycolate was obtained and reacted to form a gel thus proving the feasibility of this approach. The application of this process to Lunar and Martian simulants did not result in the formation of a gel; further study is in progress. In the second method acidified alcohol is reacted with the simulants to form silicate esters. Preliminary results indicate the presence of silicon alkoxide in the product distillation. However, no gel has been obtained so further characterization is ongoing. In the second part of the project, the focus has been on developing a series of aerogel plates suitable for thin plate metal casting and ingot metal castings. The influence of aerogels on thin wall metal castings was studied by placing aerogel plates into the cavities of thin sections of resin bonded sand molds. An 1 based commercial alloy ( 356) containing 7 percent Si was poured into these molds. Post-solidification studies provide evidence that aerogel inserts significantly reduce the cooling rate during solidification. The advantage of a lower rate using aerogel inserts was reflected in the reduction of casting defects such as shrinkage porosity. Quantitative results support the hypothesis that using aerogels as a mold material can offer definite advantages when used as casting thin sections. As a separate effort, silica aerogel with cylindrical cavities have been prepared and will be evaluated for casting commercial alloys.

High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung

2016-04-15

Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absencemore » of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer structure with the alkali metal cations within and between the layers. The third one adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. - Highlights: • Three new mixed-alkali metals uranyl silicates were synthesized by high-T, high-P hydrothermal method and structurally. • Two compounds adopt a layer structure and the third one has a 3D framework structure. • The 3D framework structure contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si.« less

Constraints on Ureilite Petrogenesis and Carbon-Metal-Silicate Equilibria on the UPB

NASA Astrophysics Data System (ADS)

Goodrich, C. A.; Holloway, J. R.

1992-07-01

The most important constraints on models of ureilite petrogenesis are 1) Ureilites have lost a basaltic complement (they are ultramafic, extremely depleted in plagiophile elements, enriched in HREE, and have negative Eu anomalies and superchondritic Ca/Al ratios). 2) Ureilites experienced long equilibration times at high T (indicated by coarse grain size, extreme homogeneity of core crystals, correlations between olivine and pyroxene compositions, and metamorphic-like textures), followed by rapid cooling (indicated by structural features of pyroxene and narrow reduction rims on olivine). 3) Ureilites are probably residues (based on mass balance) but partly crystallized from melts. 4) Ureilites are derived from a minimum of six reservoirs that were distinct in oxygen isotopic composition and did not equilibrate with one another (this is consistent with the observation that olivine and pyroxene cores do not show correlations of mg with MnO, Cr2O3, Sm/Eu or Lu/Eu). 5) There is a correlation between oxygen isotopic composition and mg ratio in ureilites. Similar correlations are observed for Allende chondrules and group means of H3-L3-LL3 chondrites (Fig. 1), and are argued to result from nebular processes [1]. 6) If graphite-metal-silicate-CO/CO2 equilibrium was established during melting, then mg ratios of ureilites were determined by depth because CCO redox reactions are strongly pressure-dependent. Cohenite-bearing metallic spherule inclusions in the silicates and euhedral shapes of large graphite crystals in low-shock ureilites have been taken as evidence of equilibrium. Olivine reduction rims, highly variable interstitial metal compositions, and a lack of correlation between mg and metal content argue against equilibrium. 7) Ureilites either lost a low melting-T metal fraction or gained a refractory-rich metal component. (they have high abundances of siderophile elements but show fractionation between [Os, Ir, W, Re] and [Ni, Ga, Ge, Au]). 8) Primordial noble gases were retained in some carbon phases. 9) Ureilites formed at ~4.55 Ga but both Sm-Nd and Rb-Sr isotopic systematics have been subsequently disturbed. Constraints 1-4 are best met if ureilites are partial melt residues produced by ~25% equilibrium partial melting on an oxygen-isotopically heterogeneous parent body in >=6 distinct melting zones. If there was no global magma ocean, km-sized melting zones would not equilibrate oxygen with one another in 10 m.y. Constraints 5 and 6 appear difficult to reconcile. If the UPB inherited a nebular oxygen isotope-mg correlation how could this correlation have survived partial melting? If the melting zones all experienced approximately the same degree of melting (Mn/Mg, Cr/Mg, and HRE provide evidence for this), and silicate equilibria determined mg, then the original correlation may simply have shifted to higher mg, consistent with the position of the ureilite trend relative to the Allende trends (Fig. 1). However, if mg was depth-dependent then it is unlikely that any oxygen isotope-mg correlation would remain. Also, noble gases in carbon would be lost (violating constraint 8) during carbon redox reactions. All constraints would be better met if graphite-metal-silicate-CO/CO2 equilibrium was not established during partial melting. If graphite was primary but a CO/CO2 fluid phase was not present then there would have been no pressure/depth dependence of fO(sub)2. As long as the pressure was sufficiently high (~100-200 bars) to stabilize the most ferroan ureilite (Fo 76) then the more magnesian ureilites would have been stable in the presence of graphite and metal. On the other hand, constraints 7, 8, and 9 could be neatly met if most of the carbon was not primary but a carbon-metal-noble gas assemblage was added as a late component to the ultramafic rocks. The cohenite-bearing metallic spherules are rare and tiny (10-50 micrometers) compared to interstitial metal (mm-sized irregular grains). They appear to have been droplets of immiscible, hypereutectic Fe(Ni)-C liquids that were trapped by crystallizing silicates. In contrast, the interstitial metal and graphite show no evidence of having been a liquid Fe-C alloy and their confinement to grain boundaries and reduction rims is consistent with late addition. Goodrich and Berkley (2) argued that the spherules were carbon-saturated at 1200-1225 degrees C and therefore that the silicate liquid must have contained graphite. However, in the Fe-C system the stable graphite liquidus is much steeper than the metastable cohenite liquidus, and although these alloys were cohenite-saturated, they were not graphite-saturated. Hence, the silicate magma probably did not contain graphite and carbon was not the dominant control on fO(sub)2. Thus, it may be possible to reconcile the main constraints on ureilite petrogenesis without high pressures. [1] R.N. Clayton & T.K. Mayeda (1988] GCA 52, 1313. [2] C.A. Goodrich & J.L. Berkely (1986) GCA 50, 681.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure

PubMed Central

Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

2017-01-01

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

Simple technology for recycling phosphate from wastewater to farmland in rural areas.

PubMed

Ohtake, Hisao; Okano, Kenji; Kunisada, Masashi; Takano, Hiroyuki; Toda, Masaya

2018-01-01

A simple technology for phosphate (P i ) recovery has been developed using a bifunctional adsorption-aggregation agent. The bifunctional agent was prepared by soaking calcium silicates in hydrochloric acid solution. Importantly, recyclable calcium silicates were available almost free of charge from the cement industry and also from the steel industry. The acid treatment was essential not only for enhancing the ability of calcium silicates to remove P i from aqueous solution but also for enabling the high settleability of removed P i . On-site experiments using a mobile plant showed that approximately 80% P i could be recovered from anaerobic sludge digestion liquor at a wastewater treatment plant. This technology has the potential to offer a simple, compact service for recycling P i from wastewater to farmland in rural areas.

VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

USGS Publications Warehouse

Newman, S.; Lowenstern, J. B.

2002-01-01

We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

V OLATILEC ALC: a silicate melt-H 2O-CO 2 solution model written in Visual Basic for excel

NASA Astrophysics Data System (ADS)

Newman, Sally; Lowenstern, Jacob B.

2002-06-01

We present solution models for the rhyolite-H 2O-CO 2 and basalt-H 2O-CO 2 systems at magmatic temperatures and pressures below ˜5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within Microsoft ® Excel (Office'98 and 2000). The series of macros, entitled V OLATILEC ALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H 2O and CO 2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H 2O and CO 2 vapors at magmatic temperatures. The basalt-H 2O-CO 2 macros in V OLATILEC ALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar.

Pyroxene Pallasites: A New Pallasite Grouplet

NASA Astrophysics Data System (ADS)

Boesenberg, J. S.; Prinz, M.; Weisberg, M. K.; Davis, A. M.; Clayton, R. N.; Mayeda, T. K.; Wasson, J. T.

1995-09-01

A new pallasite grouplet, the pyroxene pallasites, consisting of the meteorites Vermillion and Y8451, has been identified by petrologic, trace element, and oxygen isotopic data. Vermillion is a new 27 kg find from central Kansas with a texture that differs from main group (MG) and Eagle Station (ES) pallasites and consists of about (vol. %) 86 FeNi metal and 14 silicates. The silicates are interspersed with metal along bands up to 1.5 cm wide within the metal host. These bands contain micron to cm-sized silicates, including rounded to subrounded olivine (up to 1.5 cm), as well as orthopyroxene, chromite, and merrillite. Y8451, previously described in [1], is texturally similar to MG pallasites and consists of FeNi metal, rounded to subangular olivine (up to 1 cm), pyroxene, chromite, and merrillite. Modally, Vermillion silicates consist of (vol. %) about 93 olivine, 5 opx, 1.5 chromite, 0.5 merrillite, while Y8451 silicates consist of about 94 olivine, 4.8 opx, 1.1 cpx, and 0.1 merrillite. Vermillion olivine (Fo(sub)(87.0-88.9)) is comparable to MG pallasite olivine [2], while that of Y8451 (Fo(sub)(88.8-89.8)) is slightly more magnesian than MG [1]. Vermillion pyroxene (En(sub)(86-88.5) Wo(sub)(0.5-2.5)) typically occurs along the rims of smaller olivine grains, although larger pyroxene inclusions (up to 1 mm) of the same composition are sometimes found within olivine grains. Y8451 has two types of opx, a lower-Ca opx (En(sub)(89.1) Wo(sub)(0.6)) with 0.3 wt% CaO, and a higher-Ca opx (En(sub)(87.6-88.1) Wo(sub)(1.9-2.3)) with 1 wt% CaO; the lower-Ca opx coexists with cpx (En(sub)(51.5-51.8) Wo(sub)(43.7-44.1)). The higher-Ca opx has a smoothly fractionated REE pattern increasing from 0.3 x CI for La to 2.5 x CI for Lu, with no Eu anomaly, and does not appear to be in equilibrium with cpx, which has a fairly flat REE pattern at about 5 x CI (Fig. 1). The lower-Ca opx, however, is in equilibrium with cpx. Merrillites in Y8451 and Vermillion have relatively flat LREE (2 x CI) patterns, with HREE increasing to near 100 x CI in Lu, and do not appear to be in equilibrium with the higher-Ca opx or cpx. FeNi metal in Vermillion has a fine octahedrite texture and contains 65 micrograms/g Cr, 4.9 mg/g Co, 75 mg/g Ni, 130 micrograms/g Cu, 44 micrograms/g Ga, 13 micrograms/g As, 0.7 micrograms/g W, 1.9 micrograms/g Ir, and 1.4 micrograms/g Au. The metal is ungrouped and differs from MG or ES pallasite metal. Y8451 metal has not yet been analyzed. Oxygen isotopic compositions of olivine are similar in Vermillion (delta^(18)O=2.24, delta^(17)O=0.40, Delta^(17)O=-0.76) and Y8451 (delta^(18)O=2.26, delta^(17)O=0.41, Delta^(17)O=-0.77) and plot (Fig. 2) below the MG pallasite mass fractionation line (Delta^(17)O=-0.32). Pyroxene pallasites are clearly resolved from MG pallasites, as well as the acapulcoite-lodranite, and IAB-IIICD-winonaite groups. Conclusions: (1) Pyroxene pallasites constitute a new pallasite subgroup. (2) Application of the two-pyroxene thermometer [2] to Y8451 indicates an equilibration temperature of about 1000 degrees C. (3) The disequilibrium between silicates and phosphates is consistent with formation of merrillite by subsolidus reaction between metal and silicate where merrillite inherits the REE patterns of the olivine and orthopyroxene that probably formed as cumulates from a chondritic melt [3]. (4) The higher-Ca opx may be a xenocryst because of its disequilibrium pattern with the coexisting silicates. (5) The presence of pyroxene coexisting with olivine in pyroxene pallasites, in contrast to olivine alone in MG pallasites, may indicate a lower temperature of crystal accumulation for the pyroxene pallasites, assuming they both started from a similar chondritic melt. (6) The presence of three pallasite groups or grouplets may be indicative of three parent bodies, with only the MG pallasites related to the HED group. (7) Whatever the cause of the unusual metal-silicate relations in pallasites, this situation must have occurred in three different settings. References: [1] Yanai K. and Kojima H. (1995) Proc. NIPR Symp. Antarc. Meteorites, 8, 1-10. [2] Lindsley D. H. and Andersen D. J. (1983) Proc. LPSC 13th, in JGR, 88, A887-A906. [3] Davis A. M. and Olsen E. J. (1991) Nature, 353, 637-640.

Novel Experimental Simulations of the Atmospheric Injection of Meteoric Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gómez Martín, J. C.; Bones, D. L.; Carrillo-Sánchez, J. D.

2017-02-20

A newly developed laboratory, Meteoric Ablation Simulator (MASI), is used to test model predictions of the atmospheric ablation of interplanetary dust particles (IDPs) with experimental Na, Fe, and Ca vaporization profiles. MASI is the first laboratory setup capable of performing time-resolved atmospheric ablation simulations, by means of precision resistive heating and atomic laser-induced fluorescence detection. Experiments using meteoritic IDP analogues show that at least three mineral phases (Na-rich plagioclase, metal sulfide, and Mg-rich silicate) are required to explain the observed appearance temperatures of the vaporized elements. Low melting temperatures of Na-rich plagioclase and metal sulfide, compared to silicate grains, precludemore » equilibration of all the elemental constituents in a single melt. The phase-change process of distinct mineral components determines the way in which Na and Fe evaporate. Ca evaporation is dependent on particle size and on the initial composition of the molten silicate. Measured vaporized fractions of Na, Fe, and Ca as a function of particle size and speed confirm differential ablation (i.e., the most volatile elements such as Na ablate first, followed by the main constituents Fe, Mg, and Si, and finally the most refractory elements such as Ca). The Chemical Ablation Model (CABMOD) provides a reasonable approximation to this effect based on chemical fractionation of a molten silicate in thermodynamic equilibrium, even though the compositional and geometric description of IDPs is simplistic. Improvements in the model are required in order to better reproduce the specific shape of the elemental ablation profiles.« less

Silicate release from glass for pharmaceutical preparations.

PubMed

Bohrer, Denise; Bortoluzzi, Fabiana; Nascimento, Paulo Cícero; Carvalho, Leandro Machado; Ramirez, Adrian Gustavo

2008-05-01

Glass is made of polymeric silica and other minor components, which are necessary for turning the silica into a material more easily moldable and resistant to temperature changes. Glass containers for pharmaceutical usage are classified according to their resistance to a chemical attack, a test carried out in the presence of water and heat. The test is designed to show the released alkalinity, a variable dependent on the amount of sodium oxide, one of the minor components added to the glass mass. In this work, the release of silica from glass by action of constituents from pharmaceutical formulations was investigated. The study included products used in large volumes and usually stored in glass containers. Solutions of amino acids, electrolytes, glucose, oligoelements and others such as heparin and sodium bicarbonate were individually stored in glass containers and heated at 121 degrees C for 30min, as in the water attack test. The test was also carried out only with water, where the pH varied from 2 to 12. The released silicate was measured either by photometry or atomic absorption spectrometry, depending on the nature of the sample. The results showed that silicate is released during the heating cycle even if the contact is with pure water only. The pH exerts a considerable influence on the release, being that the higher the pH, the higher the silica dissolved. An elevated pH, however, is not the only factor responsible for silica dissolution. While in the solutions of NaCl, KCl, Mg Cl2 and ZnSO4 and in most of the amino acids, the concentration of silicate was as high as in pure water (0.1-1.0mg Si/L). In the solutions of sodium acetate, bicarbonate and gluconate, its concentration was much higher, over 30mg Si/L. These results were confirmed by the analysis of commercial products, where in solutions of amino acids the level of silicate ranged from 0.14 to 0.19mg Si/L. On the other hand, calcium gluconate, sodium bicarbonate and potassium phosphate presented silicate levels from 1 to 4mg/L. Although silica is not considered a toxic substance for humans, it is necessary to be aware of its presence in solutions for parenteral nutrition due to the direct introduction into the bloodstream and the large volume usually administrated, even to pre-term infants.

Phosphorus Elimination at Sodium Silicate from Quartz Sand Roasted with Complexation using Chitosan-EDTA

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Ramelan, A. H.; Suharty, N. S.; Handayani, M.; Firdiyono, F.; Sulistiyono, E.; Munawaroh, H.; Sari, P. P.; Kristiawan, Y. R.

2018-03-01

A phosphorus elimination from sodium silicate solution has been studied. Phosphorus elimination was performed by adding chitosan-EDTA to remove cation phosphorus. Characterization of chitosan-EDTA material was performed using FT-IR, while the decreasing level of phosphorus content was analyzed by quantitative analysis using spectrophotometer UV-Vis refers to SNI 06-6989-2004. The results showed that the content of the sodium silicate can be reduced up to 67.1% through Chitosan-EDTA complexation with phosphorus.

Application of electrochemical methods in corrosion and battery research

NASA Astrophysics Data System (ADS)

Sun, Zhaoli

Various electrochemical methods have been applied in the development of corrosion protection methods for ammonia/water absorption heat pumps and the evaluation of the stability of metallic materials in Li-ion battery electrolyte. Rare earth metal salts (REMSs) and organic inhibitors have been evaluated for corrosion protection of mild steel in the baseline solution of 5 wt% NH 3 + 0.2 wt% NaOH to replace the conventionally used toxic chromate salt inhibitors. Cerium nitrate provided at least comparable corrosion inhibition efficiency as dichromate in the baseline solution at 100°C. The cerium (IV) oxide formed on mild steel through the cerating process exhibited increasing corrosion protection for mild steel with prolonged exposure time in the hot baseline solution. The optimum cerating process was found to be first cerating in a solution of 2.3 g/L CeCl3 + 4.4 wt% H2O2 + appropriate additives for 20 minutes at pH 2.2 at room temperature with 30 minutes solution aging prior to use, then sealing in 10% sodium (meta) silicate or sodium molybdate at 50°C for 30 minutes. Yttrium salts provided less corrosion protection for mild steel in the baseline solution than cerium salts. Glycerophosphate was found to be a promising chromate-free organic inhibitor for mild steel; however, its thermostability in hot ammonia/water solutions has not been confirmed yet. The stability of six metallic materials used in Li-ion batteries has been evaluated in 1M lithium hexafluorophosphate (LiPF6) dissolved in a 1:1 volume mixture of ethylene carbonate and diethyl carbonate at 37°C in a dry-box. Aluminum is the most stable material, while Copper is active under anodic potentials and susceptible to localized corrosion and galvanic corrosion. The higher the concentration of the alloying elements Al and/or V in a titanium alloy, the higher was the stability of the titanium alloy in the battery electrolyte. 90Pt-10Ir can cause decomposition of the electrolyte resulting in a low stable potential window.

An iridium-rich iron micrometeorite with silicate inclusions from the Moon

NASA Technical Reports Server (NTRS)

Jolliff, Bradley L.; Korotev, Randy L.; Haskin, Larry A.

1993-01-01

We have found a 0.1 mg iron micrometeorite containing meteoritic silicate inclusions in an agglutinate from 2-2.5 cm deep in regolith core 60014. The metal is 93 percent iron, 6.5 percent nickel, 0.5 percent cobalt, approximately 150 ppm iridium, and less than 2 ppm gold. Although the Ir concentration is higher than that reported previously for any iron meteorite group, it lies on the extrapolation to low Ni and high Ir concentrations of several meteorite groups on Ni,Ir plots (groups 2C,D,E, and 3AB,E,F). Tiny, subrounded silicate inclusions comprise low-Ca pyroxene (En83), olivine (FO80), and albitic and potassic feldspars, as mixtures of minerals or glasses. Minor phases include oldhamite (CaS) and, tentatively, hercynite (FeAl2O4). The inclusions have pyroxene FeO/MnO of approximately 25 and olivine FeO/MnO of 40-60. In comparison with known iron meteorites, the inclusions are most similar to those in type 2E, e.g., Weekeroo Station, Colomera, and Kodaikanal. As far as we know, this is the first observation of an iron meteorite with silicate inclusions from a lunar sample. No metal fragments with meteoritic, nonmetallic inclusions were reported in several previous, exhaustive studies of soil particles.

Multilayer article having stabilized zirconia outer layer and chemical barrier layer

NASA Technical Reports Server (NTRS)

Bansal, Narottam P. (Inventor); Lee, Kang N. (Inventor)

2004-01-01

A multilayer article includes a substrate that includes at least one of a ceramic compound and a Si-containing metal alloy. An outer layer includes stabilized zirconia. Intermediate layers are located between the outer layer and the substrate and include a mullite-containing layer and a chemical barrier layer. The mullite-containing layer includes 1) mullite or 2) mullite and an alkaline earth metal aluminosilicate. The chemical barrier layer is located between the mullite-containing layer and the outer layer. The chemical barrier layer includes at least one of mullite, hafnia, hafnium silicate and rare earth silicate (e.g., at least one of RE.sub.2 SiO.sub.5 and RE.sub.2 Si.sub.2 O.sub.7 where RE is Sc or Yb). The multilayer article is characterized by the combination of the chemical barrier layer and by its lack of a layer consisting essentially of barium strontium aluminosilicate between the mullite-containing layer and the chemical barrier layer. Such a barium strontium aluminosilicate layer may undesirably lead to the formation of a low melting glass or unnecessarily increase the layer thickness with concomitant reduced durability of the multilayer article. In particular, the chemical barrier layer may include at least one of hafnia, hafnium silicate and rare earth silicate.

Mesosiderites on Vesta: A Hyperspectral VIS-NIR Investigation

NASA Technical Reports Server (NTRS)

Palomba, E.; Longobardo, A.; DeSanctis, M. C.; Mittlefehldt, D. W.; Ammannito, E.; Capaccioni, F.; Capria, M. T.; Frigeri, A.; Tosi, F.; Zambon, F.;

The effect of impeller type on silica sol formation in laboratory scale agitated tank

NASA Astrophysics Data System (ADS)

Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul; Dewa, Restu Mulya; Machmudah, Siti; Widiyastuti, Winardi, Sugeng

2016-02-01

The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cation resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.

The effect of impeller type on silica sol formation in laboratory scale agitated tank

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul

2016-02-08

The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cationmore » resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.« less

Oxygen and iron production by electrolytic smelting of lunar soil

NASA Technical Reports Server (NTRS)

Colson, R. O.; Haskin, L. A.

1991-01-01

Oxygen, present in abundance in nearly all lunar materials, can theoretically be extracted by molten silicate electrolysis from any known lunar rock. Derivation of oxygen by this method has been amply demonstrated experimentally in silicate melts of a variety of compositions. This work can be divided into three categories: (1) measurement of solubilities of metals (atomic) in silicate melts; (2) electrolysis experiments under various conditions of temperature, container material, electrode configuration, current density, melt composition, and sample mass (100 to 2000 mg) measuring energy required and character of resulting products; and (3) theoretical assessment of compositional requirements for steady state operations of an electrolysis cell.

Interaction of water vapor with silicate glass surfaces: Mass-spectrometric investigations

NASA Astrophysics Data System (ADS)

Kudriavtsev, Yu.; Asomoza-Palacio, R.; Manzanilla-Naim, L.

2017-05-01

The secondary ion mass-spectroscopy technique was used to study the results of hydration of borosilicate, aluminosilicate, and soda-lime silicate glasses in 1H2 18O water vapor containing 97% of the isotope 18O. It is shown that hydration of the surface of the soda-lime silicate glass occurs as a result of the ion-exchange reaction with alkali metals. In the case of borosilicate and aluminosilicate glasses, water molecules decompose on the glass surface, with the observed formation of hydrogenated layer in the glass being the result of a solid-state chemical reaction—presumably, with the formation of hydroxides from aluminum and boron oxides.

The effect of oxygen fugacity on the partitioning of nickel and cobalt between olivine, silicate melt, and metal

NASA Technical Reports Server (NTRS)

Ehlers, Karin; Grove, Timothy L.; Sisson, Thomas W.; Recca, Steven I.; Zervas, Deborah A.

1992-01-01

The effect of oxygen fugacity, f(O2), on the partitioning behavior of Ni and Co between olivine, silicate melt, and metal was investigated in the CaO-MgO-Al2O3-SiO2-FeO-Na2O system, an analogue of a chondrule composition from an ordinary chondrite. The conditions were 1350 C and 1 atm, with values of f(O2) varying between 10 exp -5.5 and 10 exp -12.6 atm (i.e., the f(O2) range relevant for crystal/liquid processes in terrestrial planets and meteorite parent bodies). Results of chemical analysis showed that the values of the Ni and Co partitioning coefficients begin to decrease at values of f(O2) that are about 3.9 log units below the nickel-nickel oxide and cobalt-cobalt oxide buffers, respectively, near the metal saturation for the chondrule analogue composition.

Iron Isotope Constraints on Planetesimal Core Formation

NASA Astrophysics Data System (ADS)

Jordan, M.; Young, E. D.

2016-12-01

The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured iron isotope ratios in a suite of iron meteorites representing a large range of degrees of fractional crystallization. We find no clear variation in 57Fe/54Fe among these samples.

Microstructural Study of an 18-O-Poor Presolar Silicate Grain from The Meteorite Hills 00426 Cr2 Chondrite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Messenger, S.

2017-01-01

The majority of presolar silicate and oxide grains derive from low-mass red giant and asymptotic giant branch (AGB) stars of approximately solar metallicity (Z). A small subclass of presolar O-rich grains (less than 7%) is thought to originate from stars having lower-than-solar Z. These "Group 3" [1] grains have depletions in 18O and 17O that typically fall along or above the Galactic chemical evolution (GCE) line. Other Group 3 grains show greater 17O than 18O depletions and most likely have supernova (SN) origins. Owing to their rarity, only two Group 3 silicates have been mineralogically examined in detail [2, 3]. Here we present a mineralogical study of a Group 3 presolar silicate to explore its formation conditions and interstellar history.

Processing of metal and oxygen from lunar deposits

NASA Technical Reports Server (NTRS)

Acton, Constance F.

1992-01-01

On the moon, some whole rocks may be ores for abundant elements, such as oxygen, but beneficiation will be important if metallic elements are sought from raw lunar dirt. In the extraction process, a beneficiated metallic ore, such as an oxide, sulfide, carbonate, or silicate mineral, is converted to reduced metal. A variety of plausible processing technologies, which includes recovery of meteoritic iron, and processing of lunar ilmenite, are described in this report.

The W-W02 Oxygen Fugacity Buffer at High Pressures and Temperatures: Implications for f02 Buffering and Metal-silicate Partitioning

NASA Technical Reports Server (NTRS)

Shofner, G. A.; Campbell, A. J.; Danielson, L.; Righter, K.

2013-01-01

Oxygen fugacity (fO2) controls multivalent phase equilibria and partitioning of redox-sensitive elements, and it is important to understand this thermodynamic parameter in experimental and natural systems. The coexistence of a metal and its oxide at equilibrium constitutes an oxygen buffer which can be used to control or calculate fO2 in high pressure experiments. Application of 1-bar buffers to high pressure conditions can lead to inaccuracies in fO2 calculations because of unconstrained pressure dependencies. Extending fO2 buffers to pressures and temperatures corresponding to the Earth's deep interior requires precise determinations of the difference in volume (Delta) V) between the buffer phases. Synchrotron x-ray diffraction data were obtained using diamond anvil cells (DAC) and a multi anvil press (MAP) to measure unit cell volumes of W and WO2 at pressures and temperatures up to 70 GPa and 2300 K. These data were fitted to Birch-Murnaghan 3rd-order thermal equations of state using a thermal pressure approach; parameters for W are KT = 306 GPa, KT' = 4.06, and aKT = 0.00417 GPa K-1. Two structural phase transitions were observed for WO2 at 4 and 32 GPa with structures in P21/c, Pnma and C2/c space groups. Equations of state were fitted for these phases over their respective pressure ranges yielding the parameters KT = 190, 213, 300 GPa, KT' = 4.24, 5.17, 4 (fixed), and aKT = 0.00506, 0.00419, 0.00467 GPa K-1 for the P21/c, Pnma and C2/c phases, respectively. The W-WO2 buffer (WWO) was extended to high pressure by inverting the W and WO2 equations of state to obtain phase volumes at discrete pressures (1-bar to 100 GPa, 1 GPa increments) along isotherms (300 to 3000K, 100 K increments). The slope of the absolute fO2 of the WWO buffer is positive with increasing temperature up to approximately 70 GPa and is negative above this pressure. The slope is positive along isotherms from 1000 to 3000K with increasing pressure up to at least 100 GPa. The WWO buffer is at a higher fO2 than the IW buffer at pressures lower than 40 GPa, and the magnitude of this difference decreases at higher pressures. This qualitatively indicates an increasingly lithophile character for W at higher pressures. The WWO buffer was quantitatively applied to W metal-silicate partitioning by using the WWO-IW buffer difference in combination with literature data on W metal-silicate partitioning to model the exchange coefficient (KD) for the Fe-W exchange reaction. This approach captures the pressure dependence of W metal-silicate partitioning using the WWO-IW buffer difference and models the activities of the components in the silicate and metallic phases using an expression of the Gibbs excess energy of mixing. Calculation of KD along a peridotite liquidus predicts a decrease in W siderophility at higher pressures that supports the qualitative behavior predicted by the WWO-IW buffer difference, and agrees with findings of others. Comparing the competing effects of temperature and pressure on W metal-silicate partitioning, our results indicate that pressure exerts a greater effect.

Adsorption of Cu2+ to biomass ash and its modified product.

PubMed

Xu, Lei; Cui, Hongbiao; Zheng, Xuebo; Liang, Jiani; Xing, Xiangyu; Yao, Lunguang; Chen, Zhaojin; Zhou, Jing

2017-04-01

Ash produced by biomass power plants has great potential for the removal of heavy metal ions from aqueous solution. The pollution of toxic heavy metals to water is a worldwide environmental problem. Discharges containing copper, in particular, are strictly controlled because the excessive copper can cause serious harm to the environment and human health. This work aims to investigate the adsorption characteristics of copper ions in aqueous solution by biomass ash and the modified products, and to evaluate their potential application in water pollution control. The biomass ash was modified with a mesoporous siliceous material and functionalized with 3-aminopropyltriethoxysilane. The surface properties of the biomass ash and the new matrix were studied to evaluate their adsorption property for Cu 2+ ions at different pHs, initial metal concentrations and the thermodynamic and kinetic were studied. The chemical and morphological properties of this modified material are analyzed; the specific surface area of the modified biomass ash was nine times that of the initial ash. Both of the two materials showed a strong affinity for Cu 2+ , and the Langmuir model could best represent the adsorption characteristics of Cu 2+ on the two kinds of materials. The adsorption capacity of copper on the material increased with the increase of pH and pH 6 was the optimum pH. Thermodynamic analysis results showed that the adsorption of Cu 2+ was spontaneous and endothermic in nature. The adsorptions of Cu 2+ onto the modified biomass ash followed pseudo-second-order kinetics.

Polymeric, Metallic, and Other Glasses in Introductory Chemistry

ERIC Educational Resources Information Center

Hawkes, Stephen J.

2008-01-01

Non-ceramic glasses are not adequately discussed in introductory chemistry. Such glasses include polycarbonate, which many corrective lenses are made of, amber, enamel, gelatin, hard candy, coal, refrigerated glycerol, and metallic glasses that have been marketed in recent decades. What is usually discussed in elementary texts is siliceous glass,…

The biological effect of asbestos exposure is dependent on changes in iron homeostasis

EPA Science Inventory

Abstract Functional groups on the surface of fibrous silicates can complex iron. We tested the postulate that 1) asbestos complexes and sequesters host cell iron resulting in a disruption of metal homeostasis and 2) this loss of essential metal results in an oxidative stress and...

HSE Abundances in Angrites and HEDs: Core-Mantle Equilibration or Late Accretion Addition of a Chondritic Component

NASA Astrophysics Data System (ADS)

Rai, N.; Downes, H.; Smith, C. L.

2016-08-01

Using metal-silicate partitioning of HSEs together with their mantle abundances in Vesta and the APB respectively, we test whether formation of a metallic core could have led to the observed abundances of the HSEs, in the mantles of these bodies.

The inhibitory effects of potassium chloride versus potassium silicate application on (137)Cs uptake by rice.

PubMed

Fujimura, Shigeto; Yoshioka, Kunio; Ota, Takeshi; Ishikawa, Tetsuya; Sato, Makoto; Satou, Mutsuto

2016-03-01

After the accident at the Fukushima Dai-ichi Nuclear Power Plant owned by the Tokyo Electric Power Company on 11 March 2011, potassium fertilizer was applied to agricultural fields in the southern Tohoku and northern Kanto regions of Japan to reduce the uptake of radiocesium by crops. In this study, we examined the effects of two types of potassium fertilizers, potassium chloride (a readily available potassium fertilizer) and potassium silicate (a slow-release potassium fertilizer), as well as a split application of potassium, on the accumulation of (137)Cs by rice plants in two pot experiments. The (137)Cs concentrations in the brown rice and in the above-ground plants were significantly lower after potassium chloride application than after potassium silicate application. The potassium ion (K(+)) concentrations in soil solutions sampled 9 and 21 d after transplanting were significantly higher for the potassium chloride application than for the potassium silicate application. The K(+) concentrations in soil solutions observed in the application of potassium silicate were similar to those in the treatment when no potassium was applied. This finding indicates that the application of potassium silicate did not sufficiently increase the available K(+) for rice plants in the soil, which led to a greater uptake of (137)Cs after the potassium silicate application than after the application of potassium chloride. The (137)Cs concentration in brown rice was higher in the split application of potassium fertilizer with the second application at the full heading stage than that without split application and the split application with the second application before heading. Copyright © 2016 Elsevier Ltd. All rights reserved.

How Deep and Hot was Earth's Magma Ocean? Combined Experimental Datasets for the Metal-silicate Partitioning of 11 Siderophile Elements - Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd

NASA Technical Reports Server (NTRS)

Righter, Kevin

2008-01-01

Since approximately 1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients (D) for siderophile (iron-loving) elements are much different than those measured at low PT conditions. The high PT data have been used to argue for a magma ocean during growth of the early Earth. Initial conclusions were based on experiments and calculations for a small number of elements such as Ni and Co. However, for many elements only a limited number of experimental data were available then, and they only hinted at values of metal-silicate D's at high PT conditions. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements. At the same time several different models have been advanced to explain the siderophile elements in the earth's mantle: a) intermediate depth magma ocean; 25-30 GPa, b) deep magma ocean; up to 50 GPa, and c) early reduced and later oxidized magma ocean. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to update the predictive expressions outlined by Righter et al. (1997) with new experimental data from the last decade, test the predictive ability of these expressions against independent datasets (there are more data now to do this properly), and to apply the resulting expressions to the siderophile element patterns in Earth's upper mantle. The predictive expressions have the form: lnD = alnfO2 + b/T + cP/T + d(1Xs) + e(1Xc) + SigmafiXi + g These expressions are guided by the thermodynamics of simple metal-oxide equilibria that control each element, include terms that mimic the activity coefficients of each element in the metal and silicate, and quantify the effect of variable oxygen fugacity. Preliminary results confirm that D(Ni) and D(Co) converge at pressures near 25-30 GPa and approximately 2200 K, and show that D(Pd) and D(Cu) become too low at the PT conditions of the deepest models. Furthermore, models which force fit V and Cr mantle concentrations by metal-silicate equilibrium overlook the fact that at early Earth mantle fO2, these elements will be more compatible in Mg-perovskite and (Fe,Mg)O than in metal. Thus an intermediate depth magma ocean, at 25-30 GPa, 2200 K, and at IW-2, can explain more mantle siderophile element concentrations than other models.

Constraints on silicates formation in the Si-Al-Fe system: Application to hard deposits in steam generators of PWR nuclear reactors

NASA Astrophysics Data System (ADS)

Berger, Gilles; Million-Picallion, Lisa; Lefevre, Grégory; Delaunay, Sophie

2015-04-01

Introduction: The hydrothermal crystallization of silicates phases in the Si-Al-Fe system may lead to industrial constraints that can be encountered in the nuclear industry in at least two contexts: the geological repository for nuclear wastes and the formation of hard sludges in the steam generator of the PWR nuclear plants. In the first situation, the chemical reactions between the Fe-canister and the surrounding clays have been extensively studied in laboratory [1-7] and pilot experiments [8]. These studies demonstrated that the high reactivity of metallic iron leads to the formation of Fe-silicates, berthierine like, in a wide range of temperature. By contrast, the formation of deposits in the steam generators of PWR plants, called hard sludges, is a newer and less studied issue which can affect the reactor performance. Experiments: We present here a preliminary set of experiments reproducing the formation of hard sludges under conditions representative of the steam generator of PWR power plant: 275°C, diluted solutions maintained at low potential by hydrazine addition and at alkaline pH by low concentrations of amines and ammoniac. Magnetite, a corrosion by-product of the secondary circuit, is the source of iron while aqueous Si and Al, the major impurities in this system, are supplied either as trace elements in the circulating solution or by addition of amorphous silica and alumina when considering confined zones. The fluid chemistry is monitored by sampling aliquots of the solution. Eh and pH are continuously measured by hydrothermal Cormet© electrodes implanted in a titanium hydrothermal reactor. The transformation, or not, of the solid fraction was examined post-mortem. These experiments evidenced the role of Al colloids as precursor of cements composed of kaolinite and boehmite, and the passivation of amorphous silica (becoming unreactive) likely by sorption of aqueous iron. But no Fe-bearing was formed by contrast to many published studies on the Fe-clay interactions in the nuclear waste storage, and by contrast with basic thermodynamic predictions. Conclusion: The Fe-clays and steam generators contexts imply relatively close aqueous environments: hydrothermal, reduced, diluted, neutral to slightly alkaline. The main difference is the status of iron: ferric/ferrous (magnetite) in the steam generators, metallic in the Fe-clay experiments. The concentration of aqueous iron when supplied by magnetite is low and does not allow its incorporation in secondary phases. By contrast, aqueous ferrous iron released by the corrosion of steel is not limited by the source, rather by the sink, and produces Fe-rich silicates. This example illustrates the discrepancy between complex mineral reactions and oversimplified predictions when sorption/passivation and nucleation/growth constraints are ignored. Reference: [1] Lanson et al. (2012) Amer. Min. 97, 864-871. [2] Lantenois et al. (2005) Clays & Clay Min. 53, 597-612. [3] Mosser-Ruck et al. (2010) Clays & Clay Min. 58, 280-291. [4] Perronnet et al. (2008) App. Clay Sci. 38, 187-202. [5] Osacky et al. (2010) App. Clay Sci. 50, 237-244. [6] Guillaume et al. (2003) Clay Min. 38, 281-302. [7] Rivard et al. (2013) Amer. Mineral. 98, 163-180. [8] Svensson and Hansen (2013) Clays & Clay Min. 61, 566-579.

Contrasting Effects of Carbon and Sulfur on Fe-Isotope Fractionation between Metal and Silicate Melt during Planetary Core Formation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.

2015-12-01

There are numerous studies that show well-resolved Fe isotope fractionations in igneous materials from different planetary bodies. Potential explanations for these fractionations include a non-chondritic bulk planetary Fe isotopic composition, and equilibrium fractionation between Fe-alloys or minerals and silicate melts during planetary differentiation, mantle melting, or fractional crystallization. This is further complicated by the fact that these processes are not mutually exclusive, making the interpretation of Fe isotope data a complex task. Here we present new experimental results investigating the effect of C on Fe isotope fractionation between molten peridotite and an Fe-alloy. Experiments were conducted at 1 GPa and 1850° C for 0.5 - 3 hours on a mixture of an 54Fe-spiked peridotite and Fe-metal with and without Ni metal in an end-loaded piston cylinder at the Geophysical Laboratory. Carbon saturation was achieved with a graphite capsule, and resulted in C contents of the Fe-alloy in our experiments ranging from 3.8 - 4.9 wt. %. The metal and silicate phases from half of each experiment were separated manually and dissolved in concentrated acids. Iron was separated from matrix elements by anion exchange chromatagraphy. Iron-isotopic compositions were determined with the Nu Plasma II MC-ICP-MS at GL. The other half of each experiment was used for quantitative microbeam analysis. Equilibrium was assessed with a time series and the three-isotope exchange method. The Ni-free experiments resulted in no resolvable Fe isotope fractionation between the Fe-C-alloy and molten silicate. This is in contrast to the results of Shahar et al. (2015) which showed a fractionation for Δ57Fe of ~0.18 ‰ between a peridotite and an Fe-alloy with a similar S abundance to C in these experiments. The one experiment thus far that contained Ni (~4 wt. % in the alloy) showed a resolvable fractionation between the Fe-Ni-C alloy and silicate of ~0.10 ‰. Shahar et al. found a similar magnitude fractionation to our Ni bearing experiment in experiments with no C or S. The difference in temperature (1650° C in Shahar et al. vs. 1850° C here) may be partially responsible for these discrepancies. Ongoing experiments will further investigate the effects of C and other light elements on Fe isotope fractionation during core segregation.

Influence of Sodium Silicate/Sodium Alginate Additives on Discharge Performance of Mg-Air Battery Based on AZ61 Alloy

NASA Astrophysics Data System (ADS)

Ma, Jingling; Wang, Guangxin; Li, Yaqiong; Li, Wuhui; Ren, Fengzhang

2018-04-01

The application of Mg-air batteries is limited due to passivation and self-corrosion of anode alloys in electrolyte. In effort of solving this problem, the present work studied the influence of sodium silicate (SS)/sodium alginate (SA) on electrochemical behaviors of AZ61 alloy in NaCl solution by circle potentiodynamic polarization and galvanostatic discharge. The corrosion morphology and discharge product were examined by scanning electron microscopy (SEM) and x-ray diffraction (XRD). Results have shown that sodium silicate/sodium alginate inhibitors have an apparent effect on the self-corrosion of AZ61 alloy without affecting its discharge performance. The discharge capacity and the anodic utilization for Mg-air battery in a 0.6 M NaCl + 0.01 M SS +0.04 M SA solution are measured to be 1397 mAhg-1 and 48.2%, respectively. Electrochemical impedance spectroscopy (EIS) and SEM investigation have confirmed that the sodium silicate/sodium alginate inhibitor can obviously decrease the self-corrosion of AZ61 alloy. SEM and XRD diffraction examinations suggest that the inhibiting mechanism is due to the formation of a compact and "cracked mud" layer. AZ61 alloy can be used as the anode for Mg-air battery in a solution of 0.6 M NaCl + 0.01 M SS +0.04 M SA.

Influence of Sodium Silicate/Sodium Alginate Additives on Discharge Performance of Mg-Air Battery Based on AZ61 Alloy

NASA Astrophysics Data System (ADS)

Ma, Jingling; Wang, Guangxin; Li, Yaqiong; Li, Wuhui; Ren, Fengzhang

2018-05-01

The application of Mg-air batteries is limited due to passivation and self-corrosion of anode alloys in electrolyte. In effort of solving this problem, the present work studied the influence of sodium silicate (SS)/sodium alginate (SA) on electrochemical behaviors of AZ61 alloy in NaCl solution by circle potentiodynamic polarization and galvanostatic discharge. The corrosion morphology and discharge product were examined by scanning electron microscopy (SEM) and x-ray diffraction (XRD). Results have shown that sodium silicate/sodium alginate inhibitors have an apparent effect on the self-corrosion of AZ61 alloy without affecting its discharge performance. The discharge capacity and the anodic utilization for Mg-air battery in a 0.6 M NaCl + 0.01 M SS +0.04 M SA solution are measured to be 1397 mAhg-1 and 48.2%, respectively. Electrochemical impedance spectroscopy (EIS) and SEM investigation have confirmed that the sodium silicate/sodium alginate inhibitor can obviously decrease the self-corrosion of AZ61 alloy. SEM and XRD diffraction examinations suggest that the inhibiting mechanism is due to the formation of a compact and "cracked mud" layer. AZ61 alloy can be used as the anode for Mg-air battery in a solution of 0.6 M NaCl + 0.01 M SS +0.04 M SA.

Possible Gems and Ultra-Fine Grained Polyphase Units in Comet Wild 2.

NASA Technical Reports Server (NTRS)

Gainsforth, Z.; Butterworth, A. L.; Jilly-Rehak, C. E.; Westphal, A. J.; Brownlee, D. E.; Joswiak, D.; Ogliore, R. C.; Zolensky, M. E.; Bechtel, H. A.; Ebel, D. S.;

Early metal-silicate differentiation during planetesimal formation revealed by acapulcoite and lodranite meteorites

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Corder, Christopher A.; Tait, Kim T.; Marti, Kurt; Assayag, Nelly; Cartigny, Pierre; Rumble, Doug; Taylor, Lawrence A.

2017-11-01

In order to establish the role and expression of silicate-metal fractionation in early planetesimal bodies, we have conducted a highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundance and 187Re-187Os study of acapulcoite-lodranite meteorites. These data are reported with new petrography, mineral chemistry, bulk-rock major and trace element geochemistry, and oxygen isotopes for Acapulco, Allan Hills (ALHA) 81187, Meteorite Hills (MET) 01195, Northwest Africa (NWA) 2871, NWA 4833, NWA 4875, NWA 7474 and two examples of transitional acapulcoite-lodranites, Elephant Moraine (EET) 84302 and Graves Nunataks (GRA) 95209. These data support previous studies that indicate that these meteorites are linked to the same parent body and exhibit limited degrees (<2-7%) of silicate melt removal. New HSE and osmium isotope data demonstrate broadly chondritic relative and absolute abundances of these elements in acapulcoites, lower absolute abundances in lodranites and elevated (>2 × CI chondrite) HSE abundances in transitional acapulcoite-lodranite meteorites (EET 84302, GRA 95209). All of the meteorites have chondritic Re/Os with measured 187Os/188Os ratios of 0.1271 ± 0.0040 (2 St. Dev.). These geochemical characteristics imply that the precursor material of the acapulcoites and lodranites was broadly chondritic in composition, and were then heated and subject to melting of metal and sulfide in the Fe-Ni-S system. This resulted in metallic melt removal and accumulation to form lodranites and transitional acapulcoite-lodranites. There is considerable variation in the absolute abundances of the HSE, both among samples and between aliquots of the same sample, consistent with both inhomogeneous distribution of HSE-rich metal, and of heterogeneous melting and incomplete mixing of silicate material within the acapulcoite-lodranite parent body. Oxygen isotope data for acapulcoite-lodranites are also consistent with inhomogeneous melting and mixing of accreted components from different nebular sources, and do not form a well-defined mass-dependent fractionation line. Modeling of HSE inter-element fractionation suggests a continuum of melting in the Fe-Ni-S system and partitioning between solid metal and sulfur-bearing mineral melt, where lower S contents in the melt resulted in lower Pt/Os and Pd/Os ratios, as observed in lodranites. The transitional meteorites, EET 84302 and GRA 95209, exhibit the most elevated HSE abundances and do not follow modelled Pt/Os and Pd/Os solid metal-liquid metal partitioning trends. We interpret this to reflect metal melt pooling into domains that were sampled by these meteorites, suggesting that they may originate from deeper within the acapulcoite-lodranite parent body, perhaps close to a pooled metallic 'core' region. Petrographic examination of transitional samples reveals the most extensive melting, pooling and networking of metal among the acapulcoite-lodranite meteorites. Overall, our results show that solid metal-liquid metal partitioning in the Fe-Ni-S system in primitive achondrites follows a predictable sequence of limited partial melting and metal melt pooling that can lead to significant HSE inter-element fractionation effects in proto-planetary materials.

Effects of atmospheric composition on apparent activation energy of silicate weathering: I. Model formulation

NASA Astrophysics Data System (ADS)

Kanzaki, Yoshiki; Murakami, Takashi

2018-07-01

We have developed a weathering model to comprehensively understand the determining factors of the apparent activation energy of silicate weathering in order to better estimate the silicate-weathering flux in the Precambrian. The model formulates the reaction rate of a mineral as a basis, then the elemental loss by summing the reaction rates of whole minerals, and finally the weathering flux from a given weathering profile by integrating the elemental losses along the depth of the profile. The rate expressions are formulated with physicochemical parameters relevant to weathering, including solution and atmospheric compositions. The apparent activation energies of silicate weathering are then represented by the temperature dependences of the physicochemical parameters based on the rate expressions. It was found that the interactions between individual mineral-reactions and the compositions of solution and atmosphere are necessarily accompanied by those of temperature-dependence counterparts. Indeed, the model calculates the apparent activation energy of silicate weathering as a function of the temperature dependence of atmospheric CO2 (Δ HCO2‧) . The dependence of the apparent activation energy of silicate weathering on Δ HCO2‧ may explain the empirical dependence of silicate weathering on the atmospheric composition. We further introduce a compensation law between the apparent activation energy and the pre-exponential factor to obtain the relationship between the silicate-weathering flux (FCO2), temperature and the apparent activation energy. The model calculation and the compensation law enable us to predict FCO2 as a function of temperature, once Δ HCO2‧ is given. The validity of the model is supported by agreements between the model prediction and observations of the apparent activation energy and FCO2 in the modern weathering systems. The present weathering model will be useful for the estimation of FCO2 in the Precambrian, for which Δ HCO2‧ can be deduced from the greenhouse effect of atmospheric CO2.

Experimental, in-situ carbon solution mechanisms and isotope fractionation in and between (C-O-H)-saturated silicate melt and silicate-saturated (C-O-H) fluid to upper mantle temperatures and pressures

NASA Astrophysics Data System (ADS)

Mysen, Bjorn

2017-02-01

Our understanding of materials transport processes in the Earth relies on characterizing the behavior of fluid and melt in silicate-(C-O-H) systems at high temperature and pressure. Here, Raman spectroscopy was employed to determine structure of and carbon isotope partitioning between melts and fluids in alkali aluminosilicate-C-O-H systems. The experimental data were recorded in-situ while the samples were at equilibrium in a hydrothermal diamond anvil cell at temperatures and pressures to 825 °C and >1300 MPa, respectively. The carbon solution equilibrium in both (C-O-H)-saturated melt and coexisting, silicate-saturated (C-O-H) fluid is 2CO3 + H2O + 2Qn + 1 = 2HCO3 + 2Qn. In the Qn-notation, the superscript, n, is the number of bridging oxygen in silicate structural units. At least one oxygen in CO3 and HCO3 groups likely is shared with silicate tetrahedra. The structural behavior of volatile components described with this equilibrium governs carbon isotope fractionation factors between melt and fluid. For example, the ΔH equals 3.2 ± 0.7 kJ/mol for the bulk 13C/12C exchange equilibrium between fluid and melt. From these experimental data, it is suggested that at deep crustal and upper mantle temperatures and pressures, the δ13C-differences between coexisting silicate-saturated (C-O-H) fluid and (C-O-H)-saturated silicate melts may change by more than 100‰ as a function of temperature in the range of magmatic processes. Absent information on temperature and pressure, the use of carbon isotopes of mantle-derived magma to derive isotopic composition of magma source regions in the Earth's interior, therefore, should be exercised with care.

Mineral dissolution and precipitation in carbonate dominated terranes assessed using Mg isotopes

NASA Astrophysics Data System (ADS)

Tipper, E.; Calmels, D.; Gaillardet, J.; Galy, A.

2013-12-01

Carbonate weathering by carbonic acid consumes atmospheric CO2 during mineral dissolution, fixing it as aqueous bicarbonate over millennial time-scales. Ocean acidification has increased the solubility of CO2 in seawater by changing the balance of pH to alkalinity (the oceanic reservoir of carbon). This has lengthened the time-scale for CO2 sequestration by carbonate weathering to tens of thousands of years. At a global scale, the net consumption of CO2 is at least equal to that from silicate weathering, but there is far less work on carbonate weathering compared to silicate weathering because it has generally been assumed to be CO2 neutral on geological time-scales. Carbonate rocks are more readily dissolved than silicate rocks, meaning that their dissolution will likely respond much more rapidly to global environmental change when compared with the dissolution of silicate minerals. Although far less concentrated than Ca in many carbonates, Mg substitutes for Ca and is more concentrated than any other metal ion. Tracing the behavior of Mg in river waters, using Mg stable isotopes (26Mg/24Mg ratio expressed as delta26Mg in per mil units) is therefore a novel way to understand the complex series of dissolution/precipitation reactions that govern solute concentrations of Ca and Mg, and hence CO2 transfer by carbonate weathering. We present new Mg isotope data on a series of river and spring waters from the Jura mountains in North-East France. The stratigraphic column is relatively uniform throughout the Jura mountains and is dominated by limestones. As the limestone of the Jura Mountains were deposited in high-energy shallow water environments (shore line, lagoon and coral reefs), they are usually clay and organic poor. The delta26Mg of the local rocks is very constant at circa -4permil. The delta26Mg of the river waters is also fairly constant, but offset from the rock at -2.5permil. This is an intriguing observation because the dissolution of limestones is expected to be congruent, meaning that the Mg released to solutes during mineral dissolution should have the same composition as the host rock. Some of this difference is likely accounted for by atmospheric deposition or cyclic inputs, but this cannot account for all of the 1.5permil shift between rock and water. It is plausible that some of the difference is explained by trace levels of Mg-silicate dissolution (with a delta26Mg of circa 0permil), but equally carbonate precipitation and attendant Mg isotope fractionation could theoretically account for the difference between rock and water. The various plausible explications will be discussed, as well as the implications of the data for better understanding carbonate weathering.

Molybdenum Valence in Basaltic Silicate Melts

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

2010-01-01

The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

Geology and hydrothermal alteration at the Madh adh Dhahab epithermal precious-metal deposit, Kingdom of Saudi Arabia

USGS Publications Warehouse

Doebrich, J.L.; LeAnderson, J.P.

1984-01-01

Vein-related alteration consisting of quartz-sericite-pyrite, chloritic, argillic, and silicic halos was superimposed on broad zones of pervasive silicic, potassic, and argillic alteration that surrounds the rhyolite intrusive body. Quartz-sericite-pyrite alteration associated with the earliest stage of mineralization was followed by broad, pervasive, stratigraphically controlled potassic alteration. Subsequent mineralization was accompanied by quartz-sericitepyrite alteration and was followed by the main stage of mineralization that formed strong chloritic alteration halos. Development of broad zones and halos of argillic alteration also may have been related to the main stage of mineralization. Development of silicic halos was characteristic of the late stages of mineralization. Broad, pervasive propylitic alteration was then superimposed on all alteration types and represents cooling and inward encroachment of the hydrothermal system. All alteration, except the early silicic alteration is interpreted to have been related to circulating meteoric fluids heated by the rhyolite.

A Circum-terrestrial Compositional Filter

NASA Technical Reports Server (NTRS)

Chapman, C. R.; Greenberg, R.

1985-01-01

A major question about the moon is its under abundance of iron. It is the purpose of this research to understand whether a metal-silicate fractionation of heliocentrically orbiting bodies can be achieved through collisional interactions with a circum-terrestrial swarm. Rates of diffusion are investigated and the mutual collisional destruction within the population is examined. The interactions of these differentiated planetesimals and their collisional products (both silicate mantle fragments and iron cores) with a swarm of Earth orbiting lunesimals (perhaps ejecta from the Earth) of km scale, totaling a mass of order 0.1 lunar mass, extending out 10 or 20 Earth radii are considered. It is found that such a small near Earth population of lunesimals can filter out silicate rich material, while passing iron cores, and form a moon composed partly of terrestrial material, but more substantially of the captured silicate rich portions of the planetesimals.

The adsorption kinetics of metal ions onto different microalgae and siliceous earth.

PubMed

Schmitt, D; Müller, A; Csögör, Z; Frimmel, F H; Posten, C

2001-03-01

In the present work the adsorption kinetics of the six metal ions aluminum, zinc, mercury, lead, copper, and cadmium onto living microalgae were measured. The freshwater green microalga Scenedesmus subspicatus, the brackish water diatom Cyclotella cryptica, the seawater diatom Phaeodactylum tricornutum, and the seawater red alga Porphyridium purpureum were the subject of investigation. In most cases the adsorption rate of the metals could be well described by using the equation of the Langmuir adsorption rate expression. Inverse parameter estimation allowed the determination of the rate constants of the adsorption process and the maximum metal content of the algae. The highest values for the rate constant were obtained for Porphyridium purpureum followed by Phaeodactylum tricornutum. High values for the maximum content were obtained for Cyclotella cryptica and Scenedesmus subspicatus. The maximum rate constant was 24.21 h-1 for the adsorption of Hg to Porphyridium purpureum whereas the maximum metal content (0.243 g g-1) was obtained for Zn on Cyclotella cryptica. A comparison of these values with those obtained for the mineral siliceous earth exhibiting low maximum content and high adsorption rates reveals that the mechanism of adsorption onto the algae is a mixture of adsorption and accumulation.

Geopolymerisation of fly ashes with waste aluminium anodising etching solutions.

PubMed

Ogundiran, M B; Nugteren, H W; Witkamp, G J

2016-10-01

Combined management of coal combustion fly ash and waste aluminium anodising etching solutions using geopolymerisation presents economic and environmental benefits. The possibility of using waste aluminium anodising etching solution (AES) as activator to produce fly ash geopolymers in place of the commonly used silicate solutions was explored in this study. Geopolymerisation capacities of five European fly ashes with AES and the leaching of elements from their corresponding geopolymers were studied. Conventional commercial potassium silicate activator-based geopolymers were used as a reference. The geopolymers produced were subjected to physical, mechanical and leaching tests. The leaching of elements was tested on 28 days cured and crushed geopolymers using NEN 12457-4, NEN 7375, SPLP and TCLP leaching tests. After 28 days ambient curing, the geopolymers based on the etching solution activator showed compressive strength values between 51 and 84 MPa, whereas the commercial potassium silicate based geopolymers gave compressive strength values between 89 and 115 MPa. Based on the regulatory limits currently associated with the used leaching tests, all except one of the produced geopolymers (with above threshold leaching of As and Se) passed the recommended limits. The AES-geopolymer geopolymers demonstrated excellent compressive strength, although less than geopolymers made from commercial activator. Additionally, they demonstrated low element leaching potentials and therefore can be suitable for use in construction works. Copyright © 2016. Published by Elsevier Ltd.

Properties of ambient cured blended alkali activated cement concrete

NASA Astrophysics Data System (ADS)

Talha Junaid, M.

2017-11-01

This paper presents results of the development and strength properties of ambient-cured alkali activated geopolymer concrete (GPC). The study looks at the strength properties, such as compressive strength, splitting tensile strength, and elastic modulus of such concretes and its dependency on various parameters. The parameters studied in this work are the type and proportions of pre-cursor materials, type of activator and their respective ratios and the curing time. Two types of pre-cursor material; low calcium fly ash (FA) and ground granulated blast furnace slag (GGBFS) were activated using different proportions of sodium silicate and sodium hydroxide solutions. The results indicate that ambient cured geopolymer concrete can be manufactured to match strength properties of ordinary Portland cement concrete (OPC). The strength properties of GPC are dependent on the type and ratio of activator and the proportion of GGBFS used. Increasing the percentage of GGBFS increased the compressive and tensile strengths, while reducing the setting time of the mix. The effect of GGBFS on strength was more pronounced in mixes that contained sodium silicate as activator solution. Unlike OPC, ambient-cured GPC containing sodium silicate gain most of their strength in the first 7 days and there is no change in strength thereafter. However, GPC mixes not containing sodium silicate only achieve a fraction of their strength at 7 days and extended curing is required for such concretes to gain full strength. The results also indicate that the elastic modulus values of GPC mixes without sodium silicate are comparable to OPC while mixes with sodium silicate have elastic modulus values much lower than ordinary concrete.

Alteration, adsorption and nucleation processes on clay-water interfaces: Mechanisms for the retention of uranium by altered clay surfaces on the nanometer scale

NASA Astrophysics Data System (ADS)

Schindler, Michael; Legrand, Christine A.; Hochella, Michael F.

2015-03-01

Nano-scale processes on the solid-water interface of clay minerals control the mobility of metals in the environment. These processes can occur in confined pore spaces of clay buffers and barriers as well as in contaminated sediments and involve a combination of alteration, adsorption and nucleation processes of multiple species and phases. This study characterizes nano-scale processes on the interface between clay minerals and uranyl-bearing solution near neutral pH. Samples of clay minerals with a contact pH of ∼6.7 are collected from a U mill and mine tailings at Key Lake, Saskatchewan, Canada. The tailings material contains Cu-, As-, Co-, Mo-, Ni-, Se-bearing polymetallic phases and has been deposited with a surplus of Ca(OH)2 and Na2CO3 slaked lime. Small volumes of mill-process solutions containing sulfuric acid and U are occasionally discharged onto the surface of the tailings and are neutralized after discharge by reactions with the slaked lime. Transmission electron microscopy (TEM) in combination with the focused ion beam (FIB) technique and other analytical methods (SEM, XRD, XRF and ICP-OES) are used to characterize the chemical and mineralogical composition of phases within confined pore spaces of the clay minerals montmorillonite and kaolinite and in the surrounding tailings material. Alteration zones around the clay minerals are characterized by different generations of secondary silicates containing variable proportions of adsorbed uranyl- and arsenate-species and by the intergrowth of the silicates with the uranyl-minerals cuprosklodowskite, Cu[(UO2)2(SiO3OH)2](H2O)6 and metazeunerite, Cu[(UO2)(AsO4)2](H2O)8. The majority of alteration phases such as illite, illite-smectite, kaolinite and vermiculite have been most likely formed in the sedimentary basin of the U-ore deposit and contain low amounts of Fe (<5 at.%). Iron-enriched Al-silicates or illite-smectites (Fe >10 at.%) formed most likely in the limed tailings at high contact pH (∼10.5) and their structure is characterized by a low degree of long-range order. Adsorption of U and nucleation of metazeunerite and cuprosklodowskite are strongly controlled by the presence of the adsorbed oxy-anion species arsenate and silica on the Fe-enriched silicates. Heterogeneous nucleation of nano-crystals of the uranyl minerals occurs most likely on adsorption sites of binary uranyl-, arsenate- and silica-complexes as well as on ternary uranyl-arsenate or uranyl-silicate complexes. The uranyl minerals occur as aggregates of misoriented nano-size crystals and are the result of supersaturated solutions and a high number of nucleation sites that prevented the formation of larger crystals through Oswald ripening. The results of this study provide an understanding of interfacial nano-scale processes between uranyl species and altered clay buffers in a potential Nuclear Waste repository as similar alteration conditions of clays may occur in a multi-barrier system.

Hydration and leaching characteristics of cement pastes made from electroplating sludge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ying-Liang; Sustainable Environment Research Center, National Cheng Kung University, No. 1, University Rd., Tainan City 70101, Taiwan; Ko, Ming-Sheng

2011-06-15

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the {sup 29}Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, includingmore » nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic {beta}-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability.« less

Online differentiation of mineral phase in aerosol particles by ion formation mechanism using a LAAP-TOF single-particle mass spectrometer

NASA Astrophysics Data System (ADS)

Marsden, Nicholas A.; Flynn, Michael J.; Allan, James D.; Coe, Hugh

2018-01-01

Mineralogy of silicate mineral dust has a strong influence on climate and ecosystems due to variation in physiochemical properties that result from differences in composition and crystal structure (mineral phase). Traditional offline methods of analysing mineral phase are labour intensive and the temporal resolution of the data is much longer than many atmospheric processes. Single-particle mass spectrometry (SPMS) is an established technique for the online size-resolved measurement of particle composition by laser desorption ionisation (LDI) followed by time-of-flight mass spectrometry (TOF-MS). Although non-quantitative, the technique is able to identify the presence of silicate minerals in airborne dust particles from markers of alkali metals and silicate molecular ions in the mass spectra. However, the differentiation of mineral phase in silicate particles by traditional mass spectral peak area measurements is not possible. This is because instrument function and matrix effects in the ionisation process result in variations in instrument response that are greater than the differences in composition between common mineral phases.In this study, we introduce a novel technique that enables the differentiation of mineral phase in silicate mineral particles by ion formation mechanism measured from subtle changes in ion arrival times at the TOF-MS detector. Using a combination of peak area and peak centroid measurements, we show that the arrangement of the interstitial alkali metals in the crystal structure, an important property in silicate mineralogy, influences the ion arrival times of elemental and molecular ion species in the negative ion mass spectra. A classification scheme is presented that allowed for the differentiation of illite-smectite, kaolinite and feldspar minerals on a single-particle basis. Online analysis of mineral dust aerosol generated from clay mineral standards produced mineral fractions that are in agreement with bulk measurements reported by traditional XRD (X-ray diffraction) analysis.

Na, Rb and Cs partitioning between metal, silicate and sulfide: Implications for volatile depletion in terrestrial planets

NASA Astrophysics Data System (ADS)

Boujibar, A.; Fei, Y.; Du, Z.; Righter, K.; Bullock, E. S.

2017-12-01

Inner Solar System materials are known for their depletion in volatile elements, including the moderately volatile alkalis: Na, K, Rb, and Cs. The origin of this depletion is still uncertain, as several processes could have been involved, during the nebular condensation or planetary accretion. Volatile depletion is commonly estimated through comparison of alkali concentrations relatively to those of chondrites, assuming they remain in planetary mantles during core segregation. However, experimental studies show that substantial K can partition into metals that are enriched in sulfur and oxygen. Several models have also suggested that sulfides may have played an important role during episodes of sulfide segregation from a crystallizing magma ocean (sulfide matte) or accretion of S-rich planetary embryos. For Mercury, a sulfide layer could be present between core and mantle, due to immiscibility between Si-rich and S-rich metals. Therefore, here we investigate whether alkali elements (Na, Cs and Rb) could be partly sequestered in planetary cores during their differentiation. We conducted experiments at high pressure and temperature (1 to 5 GPa and up to 1900 °C) to determine partition coefficients of Na, Rb and Cs between metal and silicate. Our results show that pressure, temperature, sulfur and oxygen in metals enhance the partitioning of Na, Rb and Cs into metals, as previously found for K. For all three investigated alkalis (Na, Rb and Cs), we found a maximum partition coefficient of 1 between sulfides containing 13 wt% O and silicate melt. Therefore, S-rich cores or sulfide layers formed due to immiscibility in Fe-S-O systems could have acted as important geochemical reservoirs for alkali elements. Using our experimental data and different assumptions on initial bulk abundances, we evaluate volatile depletion in terrestrial planets, by comparing resulting mantle alkali concentrations after core segregation, with actual concentrations in the Earth's mantle.

Modifying Silicates for Better Dispersion in Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi

2005-01-01

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

The role of ophiolite in metallogeny of the Sikhote-Alin region

NASA Astrophysics Data System (ADS)

Kazachenko, V. T.; Perevoznikova, E. V.; Lavrik, S. N.; Skosareva, N. V.

2012-06-01

Metalliferous sediments of the Triassic siliceous formation of the Sikhote-Alin (manganese-silicate rocks and cherts with dispersed rhodochrosite, silicate-magnetite ores, and jasper) and skarns of the Dalnegorsk and Olginsk ore districts were initially the wash away products (Late Anisian-end of the Triassic) of the lateritic weathering crust on ophiolite in the islands. Manganese, iron, and other metals were deposited in the sediments of both lagoons (present-day, skarns) and island water areas (manganese-silicate and siliceousrhodochrosite rocks, silicate-magnetite ores, and jasper). Skarns contain boric and polymetallic ores thus indicating the occurrence of both shallow (periodically drying up) and quite deep (with hydrogen sulfide contamination zones) lagoons. Lead was deposited in protoliths of the skarn deposits in lagoons from the beginning of the Carboniferous to the beginning of the Late Anisian (initial island submergence). Tin, tin-leadzinc (with Ag), and silver-lead-zinc (with Sn and Au) vein deposits (Late Cretaceous-Paleogene) of the Taukha and Zhuravlevka Terrains contain lead deposited in the sediments flanking the islands of water areas with the hydrogen sulfide contamination zones, in the Carboniferous-Permian and Triassic metalliferous sediments.

Thermochemistry of Silicates

NASA Technical Reports Server (NTRS)

Costa, Gustavo; Jacobson, Nathan

2015-01-01

The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

Alkali-Activated Aluminium-Silicate Composites as Insulation Materials for Industrial Application

NASA Astrophysics Data System (ADS)

Dembovska, L.; Bajare, D.; Pundiene, I.; Bumanis, G.

2015-11-01

The article reports on the study of thermal stability of alkali-activated aluminium- silicate composites (ASC) at temperature 800-1100°C. ASC were prepared by using calcined kaolinite clay, aluminium scrap recycling waste, lead-silicate glass waste and quartz sand. As alkali activator, commercial sodium silicate solution modified with an addition of sodium hydroxide was used. The obtained alkali activation solution had silica modulus Ms=1.67. Components of aluminium scrap recycling waste (aluminium nitride (AlN) and iron sulphite (FeSO3)) react in the alkali media and create gases - ammonia and sulphur dioxide, which provide the porous structure of the material [1]. Changes in the chemical composition of ASC during heating were identified and quantitatively analysed by using DTA/TG, dimension changes during the heating process were determined by using HTOM, pore microstructure was examined by SEM, and mineralogical composition of ASC was determined by XRD. The density of ASC was measured in accordance with EN 1097-7. ASC with density around 560 kg/m3 and heat resistance up to 1100°C with shrinkage less than 5% were obtained. The intended use of this material is the application as an insulation material for industrial purposes at elevated temperatures.

Ni, Cu, Au, and platinum-group element contents of sulphides associated with intraplate magmatism: A synthesis

USGS Publications Warehouse

Barnes, S.-J.; Zientek, M.L.; Severson, M.J.

1997-01-01

The tectonic setting of intraplate magmas, typically a plume intersecting a rift, is ideal for the development of Ni - Cu - platinum-group element-bearing sulphides. The plume transports metal-rich magmas close to the mantle - crust boundary. The interaction of the rift and plume permits rapid transport of the magma into the crust, thus ensuring that no sulphides are lost from the magma en route to the crust. The rift may contain sediments which could provide the sulphur necessary to bring about sulphide saturation in the magmas. The plume provides large volumes of mafic magma; thus any sulphides that form can collect metals from a large volume of magma and consequently the sulphides will be metal rich. The large volume of magma provides sufficient heat to release large quantities of S from the crust, thus providing sufficient S to form a large sulphide deposit. The composition of the sulphides varies on a number of scales: (i) there is a variation between geographic areas, in which sulphides from the Noril'sk - Talnakh area are the richest in metals and those from the Muskox intrusion are poorest in metals; (ii) there is a variation between textural types of sulphides, in which disseminated sulphides are generally richer in metals than the associated massive and matrix sulphides; and (iii) the massive and matrix sulphides show a much wider range of compositions than the disseminated sulphides, and on the basis of their Ni/Cu ratio the massive and matrix sulphides can be divided into Cu rich and Fe rich. The Cu-rich sulphides are also enriched in Pt, Pd, and Au; in contrast, the Fe-rich sulphides are enriched in Fe, Os, Ir, Ru, and Rh. Nickel concentrations are similar in both. Differences in the composition between the sulphides from different areas may be attributed to a combination of differences in composition of the silicate magma from which the sulphides segregated and differences in the ratio of silicate to sulphide liquid (R factors). The higher metal content of the disseminated sulphides relative to the massive and matrix sulphides may be due to the fact that the disseminated sulphides equilibrated with a larger volume of magma than massive and matrix sulphides. The difference in composition between the Cu- and Fe-rich sulphides may be the result of the fractional crystallization of monosulphide solid solution from a sulphide liquid, with the Cu-rich sulphides representing the liquid and the Fe-rich sulphides representing the cumulate.

Deformation of a crystalline olivine aggregate containing two immiscible liquids: Implications for early core-mantle differentiation

NASA Astrophysics Data System (ADS)

Cerantola, V.; Walte, N. P.; Rubie, D. C.

2015-05-01

Deformation-assisted segregation of metallic and sulphidic liquid from a solid peridotitic matrix is a process that may contribute to the early differentiation of small planetesimals into a metallic core and a silicate mantle. Here we present results of an experimental study using a simplified system consisting of a polycrystalline Fo90-olivine matrix containing a small percentage of iron sulphide and a synthetic primitive MORB melt, in order to investigate whether the silicate melt enhances the interconnection and segregation of FeS liquid under deformation conditions at varying strain rates. The experiments have been performed at 2 GPa, 1450 °C and strain rates between 1 ×10-3s-1 to 1 ×10-5s-1. Our results show that the presence of silicate melt actually hinders the migration and segregation of sulphide liquid by reducing its interconnectivity. At low to moderate strain rates the sulphide liquid pockets preserved a roundish shape, showing the liquid behavior is governed mainly by surface tension rather than by differential stress. Even at the highest strain rates, insignificant FeS segregation and interconnection were observed. On the other hand the basaltic melt was very mobile during deformation, accommodating part of the strain, which led to its segregation from the matrix at high bulk strains leaving the sulphide liquid stranded in the olivine matrix. Hence, we conclude that deformation-induced percolation of sulphide liquid does not contribute to the formation of planetary cores after the silicate solidus is overstepped. A possible early deformation enhanced core-mantle differentiation after overstepping the Fe-S solidus is not possible between the initial formation of silicate melt and the formation of a widespread magma ocean.

Method for extracting metals from aqueous waste streams for long term storage

DOEpatents

Chaiko, D.J.

1995-03-07

A liquid-liquid extraction method for removing metals and hydrous metal colloids from waste streams is provided wherein said waste streams are contacted with a solvent system containing a water-in-oil microemulsion wherein the inverted micelles contain the extracted metal. A silicon alkoxide, either alone or in combination with other metal alkoxide compounds is added to the water-in-oil microemulsion, thereby allowing encapsulation of the extracted metal within a silicon oxide network. Lastly, the now-encapsulated metal is precipitated from the water-in-oil microemulsion phase to yield aggregates of metal-silicate particles having average individual particle sizes of approximately 40 nanometers. 2 figs.

Method for extracting metals from aqueous waste streams for long term storage

DOEpatents

Chaiko, D.J.

1993-01-01

A liquid-liquid extraction method for removing metals and hydrous metal colloids from waste streams is provided wherein said waste streams are contacted with a solvent system containing a water-in-oil microemulsion wherein the inverted micelles contain the extracted metal. A silicon alkoxide, either alone or in combination with other metal alkoxide compounds is added to the water-in-oil microemulsion, thereby allowing encapsulation of the extracted metal within a silicon oxide network. Lastly, the now-encapsulated metal is precipitated from the water-in-oil microemulsion phase to yield aggregates of metal-silicate particles having average. individual particle sizes of approximately 40 manometers.

Method for extracting metals from aqueous waste streams for long term storage

DOEpatents

Chaiko, David J.

1995-01-01

A liquid--liquid extraction method for removing metals and hydrous metal colloids from waste streams is provided wherein said waste streams are contacted with a solvent system containing a water-in-oil microemulsion wherein the inverted micelles contain the extracted metal. A silicon alkoxide, either alone or in combination with other metal alkoxide compounds is added to the water-in-oil microemulsion, thereby allowing encapsulation of the extracted metal within a silicon oxide network. Lastly, the now-encapsulated metal is precipitated from the water-in-oil microemulsion phase to yield aggregates of metal-silicate particles having average individual particle sizes of approximately 40 nanometers.

Cesium distribution and phases in proxy experiments on the incineration of radioactively contaminated waste from the Fukushima area.

PubMed

Saffarzadeh, Amirhomayoun; Shimaoka, Takayuki; Kakuta, Yoshitada; Kawano, Takashi

2014-10-01

After the March 11, 2011 Tohoku earthquake and Fukushima I Nuclear Power Plant accident, incineration was initially adopted as an effective technique for the treatment of post-disaster wastes. Accordingly, considerable amounts of radioactively contaminated residues were immediately generated through incineration. The level of radioactivity associated with radiocesium in the incineration ash residues (bottom ash and fly ash) became significantly high (several thousand to 100,000 Bq/kg) as a result of this treatment. In order to understand the modes of occurrence of radiocesium, bottom ash products were synthesized through combusting of refuse-derived fuel (RDF) with stable Cs salts in a pilot incinerator. Microscopic and microanalytical (SEM-EDX) techniques were applied and the following Cs categories were identified: low and high concentrations in the matrix glass, low-level partitioning into some newly-formed silicate minerals, partitioning into metal-sulfide compounds, and occurring in newly-formed Cs-rich minerals. These categories that are essentially silicate-bound are the most dominant forms in large and medium size bottom ash particles. It is expected that these achievements provide solutions to the immobilization of radiocesium in the incineration ash products contaminated by Fukushima nuclear accident. Copyright © 2014 Elsevier Ltd. All rights reserved.

(Ar-39)-(Ar-40) dating of mesosiderites - Evidence for major parent body disruption less than 4 Ga ago

NASA Technical Reports Server (NTRS)

Bogard, D. D.; Jordan, J. L.; Garrison, D. H.; Mittlefehldt, D.

1990-01-01

The (Ar-39) (Ar-40) chronologies were determined for 14 different mesosiderites representing the full range of classification according to recrystallization, and these chronologies were compared with analogous data for other meteorite types and for lunar highland rocks. Results of Ar-Ar chronologies indicate the history of a degassing of Ar due to a major thermal event that occurred less than 3.9 Ga ago; this event is not the metal-silicate mixing event, which is known to have occurred earlier than 4.4 Ga ago. It is suggested that a major collisional disruption-reassembly event less than 3.9 Ga ago took place, leaving the metal-silicate breccias buried under tens of kilometers of rubble, where they cooled slowly through the Ar closure temperatures.

Euhedral metallic-Fe-Ni grains in extraterrestrial samples

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

1993-01-01

Metallic Fe-Ni is rare in terrestrial rocks, being largely restricted to serpentinized peridotites and volcanic rocks that assimilated carbonaceous material. In contrast, metallic Fe-Ni is nearly ubiquitous among extraterrestrial samples (i.e., meteorites, lunar rocks, and interplanetary dust particles). Anhedral grains are common. For example, in eucrites and lunar basalts, most of the metallic Fe-Ni occurs interstitially between silicate grains and thus tends to have irregular morphologies. In many porphyritic chondrules, metallic Fe-Ni and troilite form rounded blebs in the mesostasis because their precursors were immiscible droplets. In metamorphosed ordinary chondrites, metallic Fe-Ni and troilite form coarse anhedral grains. Some of the metallic Fe-Ni and troilite grains has also been mobilized and injected into fractures in adjacent silicate grains where local shock-reheating temperatures reached the Fe-FeS eutectic (988 C). In interplanetary dust particles metallic Fe-Ni most commonly occurs along with sulfide as spheroids and fragments. Euhedral metallic Fe-Ni grains are extremely rare. Several conditions must be met before such grains can form: (1) grain growth must occur at free surfaces, restricting euhedral metallic Fe-Ni grains to systems that are igneous or undergoing vapor-deposition; (2) the metal (+/-) sulfide assemblage must have an appropriate bulk composition so that taenite is the liquidus phase in igneous systems or the stable condensate phase in vapor-deposition systems; and (3) metallic Fe-Ni grains must remain underformed during subsequent compaction, thermal metamorphism, and shock. Because of these restrictions, the occurrence of euhedral metallic Fe-Ni grains in an object can potentially provide important petrogenetic information. Despite its rarity, euhedral metallic Fe-Ni occurs in a wide variety of extraterrestrial materials. Some of these materials formed in the solar nebula; others formed on parent body surfaces by meteoroid impacts.

[Flotation and extraction spectrophotometric determination of trace silicate in water].

PubMed

Di, J; Liu, Q; Li, W

2000-12-01

In HCl solution, silicate reacted with molybdate ammonium to produce silicomolibdic, then a yellow compound which was produced from the oxidation of TMB was simultaneously isolated to benzene phase by flotation and then isolated to dimethylsulfoxideformic acid by extraction. The compound gives a high absorption at 458 nm. The apparent molar absorptivity is 1.26 x 10(5) L.mol-1.cm-1. In the range of 0.02-1 mg.L-1 Si obeys Beer's law. The proposed method which combines with enrichment and measurement is simple, rapid, selective and convenient to determine silicate in water with satisfied results.

Heavy metal distribution in organic and siliceous marine sponge tissues measured by square wave anodic stripping voltammetry.

PubMed

Illuminati, S; Annibaldi, A; Truzzi, C; Scarponi, G

2016-10-15

May sponge spicules represent a "tank" to accumulate heavy metals? In this study we test this hypothesis determining the distribution of Cd, Pb and Cu concentrations between organic and siliceous tissues in Antarctic Demospongia (Sphaerotylus antarcticus, Kirkpatrikia coulmani and Haliclona sp.) and in the Mediterranean species Petrosia ficiformis. Results show that although, in these sponges, spicules represent about 80% of the mass content, the accumulation of pollutant is lower in the spicules than in the corresponding organic fraction. The contribution of tissues to the total sponge content of Cd, Pb and Cu is respectively 99%, 82% and 97% for Antarctic sponges and 96%, 95% and 96% for P. ficiformis, similar in polar and temperate organisms. These results pave the way to a better understanding of the role of marine sponges in uptaking heavy metals and to their possible use as monitor of marine ecosystems, recommend by the Water Framework Directive. Copyright © 2016 Elsevier Ltd. All rights reserved.

Research on the use of space resources

NASA Technical Reports Server (NTRS)

Carroll, W. F. (Editor)

1983-01-01

The second year of a multiyear research program on the processing and use of extraterrestrial resources is covered. The research tasks included: (1) silicate processing, (2) magma electrolysis, (3) vapor phase reduction, and (4) metals separation. Concomitant studies included: (1) energy systems, (2) transportation systems, (3) utilization analysis, and (4) resource exploration missions. Emphasis in fiscal year 1982 was placed on the magma electrolysis and vapor phase reduction processes (both analytical and experimental) for separation of oxygen and metals from lunar regolith. The early experimental work on magma electrolysis resulted in gram quantities of iron (mixed metals) and the identification of significant anode, cathode, and container problems. In the vapor phase reduction tasks a detailed analysis of various process concepts led to the selection of two specific processes designated as ""Vapor Separation'' and ""Selective Ionization.'' Experimental work was deferred to fiscal year 1983. In the Silicate Processing task a thermophysical model of the casting process was developed and used to study the effect of variations in material properties on the cooling behavior of lunar basalt.

Constraints on Nubular Electromagnetic Pulses

NASA Astrophysics Data System (ADS)

Eisenhour, D. D.; Buseck, P. R.

1993-07-01

Chondritic meteorites contain an abundance of silicate minerals with opaque inclusions of oxides, sulfides, and metals. These host silicates interact differently from their enclosed opaques to electromagnetic (EM) radiation; specifically, silicates are inefficient at absorbing EM energy in the visible and near infrared while metals, sulfides, and Fe oxides absorb strongly in this frequency range. In the presence of a strong electromagnetic pulse (EMP), this preferential absorption leads to the selective heating of the opaque inclusions and can produce unique textures ("dirty snowballs": intimate, ~spherical intergrowths of silicate and opaque minerals with radii of < 1 to 10 micrometers) that record the passage of the EMP. Many chondrules, CAIs, and isolated silicate grains within chondritic meteorites exhibit these unique features, suggesting that strong EMPs were common in the early solar nebula [1]. Here we discuss new constraints on nebular EMPs obtained from both experimental simulations and calculations of radiative heat transport. To test the feasibility of producing "dirty snowball" textures by EMP heating, olivines and pyroxenes containing metal and sulfide inclusions were heated with a 10 watt, argon-ion, CW laser operated at 514 nm. Comparisons between meteoritic "dirty snowball" textures and experimentally produced textures confirm the ability to produce the meteoritic textures by EMP heating and suggest heating times and fluxes of 0.25 to 10 seconds and 10^9 to 10^10 ergs cm^-2 sec^-1. Fluxes less than 10^9 ergs cm^-2 sec^-1 were insufficient to melt metal and sulfide inclusions, while fluxes greater than 10^10 ergs cm^-2 sec^-1 resulted in complete melting of metal, sulfide, and silicates. The experimentally determined heating time scales suggest that radiative equilibrium was reached in the "dirty snowball" formation process, indicating that the range of observed textures is controlled by cooling rates. Calculations of radiative absorption and emission allow further constraints to be placed on the EMPs responsible for "dirty snowball" formation. The absorption and emission efficiencies of grains in a blackbody radiation field were determined by calculating Planck mean cross sections for olivine, pyroxene, and iron as a function of grain size [2,3]. This information was combined with conductive heat flow calculations to determine the behavior of olivine and pyroxene grains with small inclusions of metal. Results indicate that "dirty snowball" formation results only over a narrow flux range for a given multiphase assemblage, with higher fluxes required for smaller, more transparent, or more refractory grains. For a 100-mm olivine chondrule containing a 10-micrometer "dirty snowball," the required flux is ~9 +- 1 x 10^8 ergs cm^-2 sec^-1, with a minimum pulse duration of 4 seconds (assuming an initial grain temperature of 500 K prior to heating). These values are in good agreement with experimentally determined values. The results show that pulses energetic enough to create "dirty snowballs" are also capable of producing the total melting required for chondrule formation with only slight increases in flux, or with only marginally different grain properties (e.g., more opaque inclusions, lower melting points, higher absorption cross sections). Because of the temperature and grain size dependence of the Planck mean cross sections of silicates, an EMP of the type described above will selectively melt larger aggregates and individual grains (>100 micrometer) while leaving smaller aggregates and grains unmelted. Therefore, natural products of EMP heating are: 1) the formation of chondrules in a sustained dusty environment, 2) a paucity of small chondrules, and 3) residual grains relatively unaffected by the EMPs. References: [1] Eisenhour D. D. and Buseck P. R. (1993) LPSC XXIV, 435-436. [2] Falk S. W. and Scalo J. M. (1975) Ap. J., 202, 690-695. [3] Gilman R. C. (1974) Ap. J. Supp., 268, 28, 397-403.

Do Mesosiderites Reside on 4 VESTA? an Assessment Based on Dawn Grand Data

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Prettyman, T. H.; Reedy, R. C.; Beck, A. W.; Blewett, D. T.; Gaffey, M. J.; Lawrence, D. J.; McCoy, T. J.; McSween, H. Y., Jr.; Toplis, J. J.

2012-01-01

Almost a century ago, simple petrographic observations were used to suggest a close genetic link between eucrites and the silicates in mesosiderites [1]. Mesosiderites are composed of roughly equal proportions of silicates that are very similar in mineralogy and texture to howardites, and Fe, Ni metal (Fig. 1) [2]. This similarity has led some to conclude that mesosiderites come from the howardite, eucrite and diogenite (HED) parent asteroid [3, 4]. Subsequent petrologic study demonstrated a number of differences between mesosiderite silicates and HEDs that are more plausibly explained as requiring separate parent asteroids [5]. However, HEDs and mesosiderites are identical in oxygen isotopic composition, and this has been used to argue for a common parent 4 Vesta [6].

EVIDENCE FOR TWO-STAGE MELTING IN THE BRAHIN PALLASITE PARENT BODY

NASA Astrophysics Data System (ADS)

Sonzogni, Y.; Devouard, B.; Provost, A.; Devidal, J.

2009-12-01

We identified two types of melt inclusions in olivine crystals from the Brahin main-group pallasite, similar to those described in [1, 2]. Both types are abundant and coexist within a same olivine grain. The first type are isolated, 1-10 µm large, elongated to tubular, and oriented along the [001] axis of the olivine host (as determined by EBSD). These inclusions are phosphate-rich, typically made of stanfieldite, a bubble, often phosphoran olivine (21-32 wt% P2O5), plus occasional minute phases including metal-sulfide blebs and daubreelite. These isolated inclusions look primary, but microprobe mapping of P revealed the scars of former fractures joining these inclusions. The second type are 2-dimensional arrays of abundant chromite inclusions (<100 µm) and metal-sulfide assemblages (<50 µm). Typical metal-sulfide inclusions contain metal (kamacite and/or taenite ) + troilite + phosphoran olivine (6-24 wt% P2O5) + occasional minute grains of withlockite, shreibersite, daubreelite, and silica. These 2D arrays show the same morphological features that characterize secondary inclusions and healed fractures in olivine xenocrysts and other terrestrial minerals. Discussion: The phosphoran olivines are known in pallasites [3] but to our knowledge it is the first description of this mineral in inclusions. We identify this phase as olivine based on its steochiometry, (Mg,Fe,Ca)4-x(Si1-xPx)2O8, and its structure (as evidenced by EBSD). The value of 32 wt% P2O5 is the highest of all P-rich olivines reported so far [3, 4, 5, 6]. Such high P contents suggest an extended solid solution between olivine and chopinite [7]. Melt inclusions in Brahin seem to record two distinct HT events. According to phase diagrams, a single silicate melt enriched in P might be sufficient to form these phosphate-rich inclusions at T < 1200°C. On the contrary, at least two immiscible melts are required to form the secondary inclusions: a silicate-chromite melt and a metal-sulfide one. The abundance of chromite requires temperatures > ca. 1800°C in order to accommodate Cr in the silicate melt. It seems likely that these secondary inclusions result from a shock that took place while the stony-iron assembly of the Brahin pallasite was already formed. On the other hand, the lack of metal-sulfide associated with the phosphate-rich inclusions may imply that the iron part of the Brahin pallasite was not present when these inclusions were formed. References: [1] Buseck P.R. 1977. Geochimica and Cosmochimica Acta 41:711-740. [2] Koviazin S.V. and Podgornykh N.M. 2006. 37th Lunar and Planetary Science Conference pp. 1235-1236. [3] Buseck P.R. and Clark J. 1984. Mineralogical Magazine 48:229-235. [4] Agrell S.O. et al. 1998. Mineralogical Magazine 62:265-269. [5] Tropper P. et al. 2004. European Journal of Mineralogy 16:631-640. [6] Boesenberg J.S. et al. 2004. 35th Lunar and Planetary Science Conference pp. 1366-1367. [7] Grew E.S. et al. 2007. European Journal of Mineralogy 19:229-245.

Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals and industrial wastes as a Novel Carbon Capture and Storage Technology

NASA Astrophysics Data System (ADS)

Park, A. H. A.

2014-12-01

Increasing concentration of CO2 in the atmosphere is attributed to rising consumption of fossil fuels around the world. The development of solutions to reduce CO2 emissions to the atmosphere is one of the most urgent needs of today's society. One of the most stable and long-term solutions for storing CO2 is via carbon mineralization, where minerals containing metal oxides of Ca or Mg are reacted with CO2 to produce thermodynamically stable Ca- and Mg-carbonates that are insoluble in water. Carbon mineralization can be carried out in-situ or ex-situ. In the case of in-situ mineralization, the degree of carbonation is thought to be limited by both mineral dissolution and carbonate precipitation reaction kinetics, and must be well understood to predict the ultimate fate of CO2 within geological reservoirs. While the kinetics of in-situ mineral trapping via carbonation is naturally slow, it can be enhanced at high temperature and high partial pressure of CO2. The addition of weak organic acids produced from food waste has also been shown to enhance mineral weathering kinetics. In the case of the ex-situ carbon mineralization, the role of these ligand-bearing organic acids can be further amplified for silicate mineral dissolution. Unfortunately, high mineral dissolution rates often lead to the formation of a silica-rich passivation layer on the surface of silicate minerals. Thus, the use of novel solvent mixture that allows chemically catalyzed removal of this passivation layer during enhanced Mg-leaching surface reaction has been proposed and demonstrated. Furthermore, an engineered biological catalyst, carbonic anhydrase, has been developed and evaluated to accelerate the hydration of CO2, which is another potentially rate-limiting step of the carbonation reaction. The development of these novel catalytic reaction schemes has significantly improved the overall efficiency and sustainability of in-situ and ex-situ mineral carbonation technologies and allowed direct capture and storage of CO2 from mixture gas streams eliminating the energy-intensive solvent regeneration and CO2 compression steps.

The importance of sulfur for the behavior of highly-siderophile elements during Earth's differentiation

NASA Astrophysics Data System (ADS)

Laurenz, Vera; Rubie, David C.; Frost, Daniel J.; Vogel, Antje K.

2016-12-01

The highly siderophile elements (HSEs) are widely used as geochemical tracers for Earth's accretion and core formation history. It is generally considered that core formation strongly depleted the Earth's mantle in HSEs, which were subsequently replenished by a chondritic late veneer. However, open questions remain regarding the origin of suprachondritic Ru/Ir and Pd/Ir ratios that are thought to be characteristic for the primitive upper mantle. In most core-formation models that address the behavior of the HSEs, light elements such as S entering the core have not been taken into account and high P-T experimental data for S-bearing compositions are scarce. Here we present a comprehensive experimental study to investigate the effect of increasing S concentration in the metal on HSE metal-silicate partitioning at 2473 K and 11 GPa. We show that the HSEs become less siderophile with increasing S concentrations in the metal, rendering core-forming metal less efficient in removing the HSEs from the mantle if S is present. Furthermore, we investigated the FeS sulfide-silicate partitioning of the HSEs as a function of pressure (7-21 GPa) and temperature (2373-2673 K). The sulfide-silicate partition coefficient for Pt increases strongly with P, whereas those for Pd, Ru and Ir all decrease. The combined effect is such that above ∼20 GPa Ru becomes less chalcophile than Pt, which is opposite to their behavior in the metal-silicate system where Ru is always more siderophile than Pt. The newly determined experimental results are used in a simple 2-stage core formation model that takes into account the effect of S on the behavior of the HSEs during core formation. Results of this model show that segregation of a sulfide liquid to the core from a mantle with substantial HSE concentrations plays a key role in reproducing Earth's mantle HSE abundances. As Ru and Pd are less chalcophile than Pt and Ir at high P-T, some Ru and Pd remain in the mantle after sulfide segregation. Addition of the late veneer then raised the concentrations of all HSE to their current levels. Suprachondritic Ru/Ir and Pd/Ir ratios of the mantle can thus be explained by a combination of sulfide segregation together with the addition of a late veneer without the need to invoke unknown chondritic material.

The distribution and composition characteristics of siliceous rocks from Qinzhou Bay-Hangzhou Bay joint belt, South China: constraint on the tectonic evolution of plates in South China.

PubMed

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Zhou, Yongzhang; Yang, Zhijun; He, Junguo; Liang, Jin; Zhou, Liuyu

2013-01-01

The Qinzhou Bay-Hangzhou Bay joint belt is a significant tectonic zone between the Yangtze and Cathaysian plates, where plentiful hydrothermal siliceous rocks are generated. Here, the authors studied the distribution of the siliceous rocks in the whole tectonic zone, which indicated that the tensional setting was facilitating the development of siliceous rocks of hydrothermal genesis. According to the geochemical characteristics, the Neopalaeozoic siliceous rocks in the north segment of the Qinzhou Bay-Hangzhou Bay joint belt denoted its limited width. In comparison, the Neopalaeozoic Qinzhou Bay-Hangzhou Bay joint belt was diverse for its ocean basin in the different segments and possibly had subduction only in the south segment. The ocean basin of the north and middle segments was limited in its width without subduction and possibly existed as a rift trough that was unable to resist the terrigenous input. In the north segment of the Qinzhou Bay-Hangzhou Bay joint belt, the strata of hydrothermal siliceous rocks in Dongxiang copper-polymetallic ore deposit exhibited alternative cycles with the marine volcanic rocks, volcanic tuff, and metal sulphide. These sedimentary systems were formed in different circumstances, whose alternative cycles indicated the release of internal energy in several cycles gradually from strong to weak.

Effects of an iron-silicon material, a synthetic zeolite and an alkaline clay on vegetable uptake of As and Cd from a polluted agricultural soil and proposed remediation mechanisms.

PubMed

Yao, Aijun; Wang, Yani; Ling, Xiaodan; Chen, Zhe; Tang, Yetao; Qiu, Hao; Ying, Rongrong; Qiu, Rongliang

2017-04-01

Economic and highly effective methods of in situ remediation of Cd and As polluted farmland in mining areas are urgently needed. Pot experiments with Brassica chinensis L. were carried out to determine the effects of three soil amendments [a novel iron-silicon material (ISM), a synthetic zeolite (SZ) and an alkaline clay (AC)] on vegetable uptake of As and Cd. SEM-EDS and XRD analyses were used to investigate the remediation mechanisms involved. Amendment with ISM significantly reduced the concentrations of As and Cd in edible parts of B. chinensis (by 84-94 % and 38-87 %, respectively), to levels that met food safety regulations and was much lower than those achieved by SZ and AC. ISM also significantly increased fresh biomass by 169-1412 % and 436-731 % in two consecutive growing seasons, while SZ and AC did not significantly affect vegetable growth. Correlation analysis suggested that it was the mitigating effects of ISM on soil acidity and on As and Cd toxicity, rather than nutrient amelioration, that contributed to the improvement in plant growth. SEM-EDS analysis showed that ISM contained far more Ca, Fe and Mn than did SZ or AC, and XRD analysis showed that in the ISM these elements were primarily in the form of silicates, oxides and phosphates that had high capacities for chemisorption of metal(loid)s. After incubation with solutions containing 800 mg L -1 AsO 4 2- or Cd 2+ , ISM bound distinctly higher levels of As (6.18 % in relative mass percent by EDS analysis) and Cd (7.21 % in relative mass percent by EDS analysis) compared to SZ and AC. XRD analysis also showed that ISM facilitated the precipitation of Cd 2+ as silicates, phosphates and hydroxides, and that arsenate combined with Fe, Al, Ca and Mg to form insoluble arsenate compounds. These precipitation mechanisms were much more active in ISM than in SZ or AC. Due to the greater pH elevation caused by the abundant calcium silicate, chemisorption and precipitation mechanisms in ISM treatments could be further enhanced. That heavy metal(loid)s fixation mechanisms of ISM ensure the remediation more irreversible and more resilient to environmental changes. With appropriate application rate and proper nutrients supplement, the readily available and economic ISM is a very promising amendment for safe crop production on multi-metal(loids) polluted soils.

Precipitated Silica from Pumice and Carbon Dioxide Gas (Co2) in Bubble Column Reactor

NASA Astrophysics Data System (ADS)

Dewati, R.; Suprihatin, S.; Sumada, K.; Muljani, S.; Familya, M.; Ariani, S.

2018-01-01

Precipitated silica from silica and carbon dioxide gas has been studied successfully. The source of silica was obtained from pumice stone while precipitation process was carried out with carbon dioxide gas (CO2). The sodium silicate solution was obtained by extracting the silica from pumice stone with sodium hydroxide (NaOH) solution and heated to 100 °C for 1 h. The carbon dioxide gas is injected into the aqueous solution of sodium silicate in a bubble column reactor to form precipitated silica. m2/g. The results indicate that the products obtained are precipitate silica have surface area in the range of 100 - 227 m2/g, silica concentration more than 80%, white in appearance, and silica concentration reached 90% at pH 7.

Surface protected lithium-metal-oxide electrodes

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho

2016-04-05

A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

Paleomagnetic evidence for dynamo activity driven by inward crystallisation of a metallic asteroid

NASA Astrophysics Data System (ADS)

Bryson, James F. J.; Weiss, Benjamin P.; Harrison, Richard J.; Herrero-Albillos, Julia; Kronast, Florian

2017-08-01

The direction in which a planetary core solidifies has fundamental implications for the feasibility and nature of dynamo generation. Although Earth's core is outwardly solidifying, the cores of certain smaller planetary bodies have been proposed to inwardly solidify due to their lower central pressures. However, there have been no unambiguous observations of inwardly solidified cores or the relationship between this solidification regime and planetary magnetic activity. To address this gap, we present the results of complimentary paleomagnetic techniques applied to the matrix metal and silicate inclusions within the IVA iron meteorites. This family of meteorites has been suggested to originate from a planetary core that had its overlaying silicate mantle removed by collisions during the early solar system. This process is thought to have produced a molten ball of metal that cooled rapidly and has been proposed to have inwardly solidified. Recent thermal evolution models of such a body predict that it should have generated an intense, multipolar and time-varying dynamo field. This field could have been recorded as a remanent magnetisation in the outer, cool layers of a solid crust on the IVA parent core. We find that the different components in the IVA iron meteorites display a range of paleomagnetic fidelities, depending crucially on the cooling rate of the meteorite. In particular, silicate inclusions in the quickly cooled São João Nepomuceno meteorite are poor paleomagnetic recorders. On the other hand, the matrix metal and some silicate subsamples from the relatively slowly cooled Steinbach meteorite are far better paleomagnetic recorders and provide evidence of an intense (≳100 μT) and directionally varying (exhibiting significant changes on a timescale ≲200 kyr) magnetic field. This is the first demonstration that some iron meteorites record ancient planetary magnetic fields. Furthermore, the observed field intensity, temporal variability and dynamo lifetime are consistent with thermal evolution models of the IVA parent core. Because the acquisition of remanent magnetisation by some IVA iron meteorites require that they cooled below their Curie temperature during the period of dynamo activity, the magnetisation carried by Steinbach also provides strong evidence favouring the inward solidification of its parent core.

Catching Constrains on the Parent Body Genesis of Mesosiderites and a Possible Link to HED (Howardite-Eucrite-Diogenite) Meteorites - A New Hope?

NASA Technical Reports Server (NTRS)

Baecker, B.; Cohen, Barbara A.

2016-01-01

Mesosiderites (MES) are a group of enigmatic stony-iron meteorites exhibiting fragmental matrix breccias and irregular textures; e.g. [1-3]. Mesosiderites contain roughly equal volumes metal (Fe-Ni) and silicates often intimately mixed together (Fig.1). The silicates mostly consist of basaltic, gabbroic, and pyroxenitic components, and appear similar to eucrites and howardites; [4-8]. But unlike HEDs - and other differentiated parent body meteorite groups e.g. ureilites - mesosiderites contain high metal abundances. Several studies have been published to reveal the processes leading to the formation of mesosiderites and attempt to classifiy them [1], [2], [10-15]. Because the silicate inclusions in mesosiderites are often strongly metamorphosed after formation, it is difficult to assess the origin of the silicates and implications for the differentiation process of their parent body [15-17]. Several workers have advanced a formation hypothesis for the mesosiderites where an impact between differentiated bodies occurred prior to 4.47 Ga ago (e.g. [13,18], which could explain the possible incomplete dispersal of the colliding bodies due to their low cosmic ray exposure ages and their special thermal history. However, [13] discuss and favor the model for formation of mesosiderites with the collision of two differentiated bodies, along with disruption events and gravitational re-assembly. The mesosiderites have numerous gabbroid melt clasts with anomalous rare-earth- element (REE) - especially positive Eu - values [19, 20]. HEDs do not show the same. However, the heating mechanisms of both mesosiderites and HED's are puzzling. Mesosiderites are remarkable, they consist of a mix of basalts, which are only found on or near planetary surfaces and undifferentiated metal [1,2]. The probable model is that an asteroid containing a metallic magma impacted onto a second asteroid covered with basalt [18,21]. The mix was then buried under an insulating regolith, and cooled slowly. During cooling and at low temperatures the redox reactions continued to occur and proceed (J.T. Wasson; in pers. comm. 2015).

9 CFR 95.26 - Railroad cars, trucks, boats, aircraft and other means of conveyance, equipment or containers...

Code of Federal Regulations, 2014 CFR

2014-01-01

... proportion of 1 pound to 3 gallons of water. (2) Sodium carbonate (4 percent) plus sodium silicate (0.1 percent) in the proportion of 1 pound of sodium carbonate plus sodium silicate to 3 gallons of water. (3) Sodium hydroxide (Lye) prepared in a fresh solution in the proportion of not less than 1 pound...

9 CFR 95.26 - Railroad cars, trucks, boats, aircraft and other means of conveyance, equipment or containers...

Code of Federal Regulations, 2012 CFR

2012-01-01

... proportion of 1 pound to 3 gallons of water. (2) Sodium carbonate (4 percent) plus sodium silicate (0.1 percent) in the proportion of 1 pound of sodium carbonate plus sodium silicate to 3 gallons of water. (3) Sodium hydroxide (Lye) prepared in a fresh solution in the proportion of not less than 1 pound...

9 CFR 95.26 - Railroad cars, trucks, boats, aircraft and other means of conveyance, equipment or containers...

Code of Federal Regulations, 2013 CFR

2013-01-01

... proportion of 1 pound to 3 gallons of water. (2) Sodium carbonate (4 percent) plus sodium silicate (0.1 percent) in the proportion of 1 pound of sodium carbonate plus sodium silicate to 3 gallons of water. (3) Sodium hydroxide (Lye) prepared in a fresh solution in the proportion of not less than 1 pound...

Fluoride-containing nanoporous calcium-silicate MTA cements for endodontics and oral surgery: early fluorapatite formation in a phosphate-containing solution.

PubMed

Gandolfi, M G; Taddei, P; Siboni, F; Modena, E; Ginebra, M P; Prati, C

2011-10-01

To test the chemical-physical properties and apatite-forming ability of experimental fluoride-doped calcium silicate cements designed to create novel bioactive materials for use in endodontics and oral surgery. A thermally treated calcium silicate cement (wTC) containing CaCl(2) 5%wt was modified by adding NaF 1%wt (FTC) or 10%wt (F10TC). Cements were analysed by environmental scanning electron microscopy with energy-dispersive X-ray analysis, IR and micro-Raman spectroscopy in wet conditions immediately after preparation or after ageing in a phosphate-containing solution (Dulbecco's phosphate-buffered saline). Calcium and fluoride release and pH of the storage solution were measured. The results obtained were analysed statistically (Tukey's HSD test and two-way anova). The formation of calcium phosphate precipitates (spherulites) was observed on the surface of 24 h-aged cements and the formation of a thick bone-like B-type carbonated apatite layer (biocoating) on 28 day-aged cements. The rate of apatite formation was FTC>F10TC>wTC. Fluorapatite was detected on FTC and F10TC after 1 day of ageing, with a higher fluoride content on F10TC. All the cements released calcium ions. At 5 and 24 h, the wTC had the significantly highest calcium release (P<0.001) that decreased significantly over the storage time. At 3-28 days, FTC and F10TC had significantly higher calcium release than wTC (P<0.05). The F10TC had the significantly highest fluoride release at all times (P<0.01) that decreased significantly over storage time. No significant differences were observed between FTC and wTC. All the cements had a strong alkalinizing activity (OH(-) release) that remained after 28 days of storage. The addition of sodium fluoride accelerated apatite formation on calcium silicate cements. Fluoride-doped calcium silicate cements had higher bioactivity and earlier formation of fluorapatite. Sodium fluoride may be introduced in the formulation of mineral trioxide aggregate cements to enhance their biological behaviour. F-doped calcium silicate cements are promising bone cements for clinical endodontic use. © 2011 International Endodontic Journal.

Efficient removal of sulfur hexafluoride (SF6) through reacting with recycled electroplating sludge.

PubMed

Zhang, Jia; Zhou, Ji Zhi; Liu, Qiang; Qian, Guangren; Xu, Zhi Ping

2013-06-18

This paper reports that recycled electroplating sludge is able to efficiently remove greenhouse gas sulfur hexafluoride (SF6). The removal process involves various reactions of SF6 with the recycled sludge. Remarkably, the sludge completely removed SF6 at a capacity of 1.10 mmol/g (SF6/sludge) at 600 °C. More importantly, the evolved gases were SO2, SiF4, and a limited amount of HF, with no toxic SOF4, SO2F2, or SF4 being detected. These generated gases can be readily captured and removed by NaOH solution. The reacted solids were further found to be various metal fluorides, thus revealing that SF6 removal takes place by reacting with various metal oxides and silicate in the sludge. Moreover, the kinetic investigation revealed that the SF6 reaction with the sludge is a first-order chemically controlled process. This research thus demonstrates that the waste electroplating sludge can be potentially used as an effective removal agent for one of the notorious greenhouse gases, SF6.

Effect of pressure on ore mineral solubilities under hydrothermal conditions.

USGS Publications Warehouse

Hemley, J.J.; Cygan, G.L.; d'Angelo, W. M.

1986-01-01

The combined solubilities of Fe, Zn and Pb sulphides were determined at elevated P and T in chloride solutions buffered in pH by a silicate assemblage of quartz monzonite composition plus added muscovite, and buffered in fS2 and fO2 by the assemblage pyrite-pyrrhotite-magnetite. Higher T and higher chloride concentration favour higher metal solubilities, but the P effect is opposite. At 500oC, 0.5 kbar and 1 M total chloride, Fe, Zn, Pb solubilities were 8500, 4300 and 8700 ppm, respectively, whereas at 1 kbar they were 4200, 2400 and 2600 ppm, and at 2 kbar, 1700, 800 and 1200 ppm. The P effect is of considerable importance to problems of ore-mineral transport; the metal could be carried over long distances on a decreasing P gradient so long as the T decreases were sufficient; this condition could be approximated by a near-adiabatic transport cooling path. Such a condition is probably common for hydrothermal processes involving fairly deep-seated sources of heat and mineral components.-L.C.H.

COORDINATED ANALYSES OF PRESOLAR GRAINS IN THE ALLAN HILLS 77307 AND QUEEN ELIZABETH RANGE 99177 METEORITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ann N.; Nittler, Larry R.; Alexander, Conel M. O'D.

2010-08-10

We report the identification of presolar silicates ({approx}177 ppm), presolar oxides ({approx}11 ppm), and one presolar SiO{sub 2} grain in the Allan Hills (ALHA) 77307 chondrite. Three grains having Si-isotopic compositions similar to SiC X and Z grains were also identified, though the mineral phases are unconfirmed. Similar abundances of presolar silicates ({approx}152 ppm) and oxides ({approx}8 ppm) were also uncovered in the primitive CR chondrite Queen Elizabeth Range (QUE) 99177, along with 13 presolar SiC grains and one presolar silicon nitride. The O-isotopic compositions of the presolar silicates and oxides indicate that most of the grains condensed in low-massmore » red giant and asymptotic giant branch stars. Interestingly, unlike presolar oxides, few presolar silicate grains have isotopic compositions pointing to low-metallicity, low-mass stars (Group 3). The {sup 18}O-rich (Group 4) silicates, along with the few Group 3 silicates that were identified, likely have origins in supernova outflows. This is supported by their O- and Si-isotopic compositions. Elemental compositions for 74 presolar silicate grains were determined by scanning Auger spectroscopy. Most of the grains have non-stoichiometric elemental compositions inconsistent with pyroxene or olivine, the phases commonly used to fit astronomical spectra, and have comparable Mg and Fe contents. Non-equilibrium condensation and/or secondary alteration could produce the high Fe contents. Transmission electron microscopic analysis of three silicate grains also reveals non-stoichiometric compositions, attributable to non-equilibrium or multistep condensation, and very fine scale elemental heterogeneity, possibly due to subsequent annealing. The mineralogies of presolar silicates identified in meteorites thus far seem to differ from those in interplanetary dust particles.« less

Artificial Weathering as a Function of CO2 Injection in Pahang Sandstone Malaysia: Investigation of Dissolution Rate in Surficial Condition

PubMed Central

Jalilavi, Madjid; Zoveidavianpoor, Mansoor; Attarhamed, Farshid; Junin, Radzuan; Mohsin, Rahmat

2014-01-01

Formation of carbonate minerals by CO2 sequestration is a potential means to reduce atmospheric CO2 emissions. Vast amount of alkaline and alkali earth metals exist in silicate minerals that may be carbonated. Laboratory experiments carried out to study the dissolution rate in Pahang Sandstone, Malaysia, by CO2 injection at different flow rate in surficial condition. X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDX), Atomic Absorption Spectroscopy (AAS) and weight losses measurement were performed to analyze the solid and liquid phase before and after the reaction process. The weight changes and mineral dissolution caused by CO2 injection for two hours CO2 bubbling and one week' aging were 0.28% and 18.74%, respectively. The average variation of concentrations of alkaline earth metals in solution varied from 22.62% for Ca2+ to 17.42% for Mg2+, with in between 16.18% observed for the alkali earth metal, potassium. Analysis of variance (ANOVA) test is performed to determine significant differences of the element concentration, including Ca, Mg, and K, before and after the reaction experiment. Such changes show that the deposition of alkali and alkaline earth metals and the dissolution of required elements in sandstone samples are enhanced by CO2 injection. PMID:24413195

Artificial weathering as a function of CO2 injection in Pahang Sandstone Malaysia: investigation of dissolution rate in surficial condition.

PubMed

Jalilavi, Madjid; Zoveidavianpoor, Mansoor; Attarhamed, Farshid; Junin, Radzuan; Mohsin, Rahmat

2014-01-13

Formation of carbonate minerals by CO2 sequestration is a potential means to reduce atmospheric CO2 emissions. Vast amount of alkaline and alkali earth metals exist in silicate minerals that may be carbonated. Laboratory experiments carried out to study the dissolution rate in Pahang Sandstone, Malaysia, by CO2 injection at different flow rate in surficial condition. X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDX), Atomic Absorption Spectroscopy (AAS) and weight losses measurement were performed to analyze the solid and liquid phase before and after the reaction process. The weight changes and mineral dissolution caused by CO2 injection for two hours CO2 bubbling and one week' aging were 0.28% and 18.74%, respectively. The average variation of concentrations of alkaline earth metals in solution varied from 22.62% for Ca(2+) to 17.42% for Mg(2+), with in between 16.18% observed for the alkali earth metal, potassium. Analysis of variance (ANOVA) test is performed to determine significant differences of the element concentration, including Ca, Mg, and K, before and after the reaction experiment. Such changes show that the deposition of alkali and alkaline earth metals and the dissolution of required elements in sandstone samples are enhanced by CO2 injection.

Alkali activation of recovered fuel-biofuel fly ash from fluidised-bed combustion: Stabilisation/solidification of heavy metals.

PubMed

Yliniemi, Juho; Pesonen, Janne; Tiainen, Minna; Illikainen, Mirja

2015-09-01

Recovered fuel-biofuel fly ash from a fluidized bed boiler was alkali-activated and granulated with a sodium-silicate solution in order to immobilise the heavy metals it contains. The effect of blast-furnace slag and metakaolin as co-binders were studied. Leaching standard EN 12457-3 was applied to evaluate the immobilisation potential. The results showed that Ba, Pb and Zn were effectively immobilised. However, there was increased leaching after alkali activation for As, Cu, Mo, Sb and V. The co-binders had minimal or even negative effect on the immobilisation. One exception was found for Cr, in which the slag decreased leaching, and one was found for Cu, in which the slag increased leaching. A sequential leaching procedure was utilized to gain a deeper understanding of the immobilisation mechanism. By using a sequential leaching procedure it is possible fractionate elements into watersoluble, acid-soluble, easily-reduced and oxidisable fractions, yielding a total 'bioavailable' amount that is potentially hazardous for the environment. It was found that the total bioavailable amount was lower following alkali activation for all heavy metals, although the water-soluble fraction was higher for some metals. Evidence from leaching tests suggests the immobilisation mechanism was chemical retention, or trapping inside the alkali activation reaction products, rather than physical retention, adsorption or precipitation as hydroxides. Copyright © 2015 Elsevier Ltd. All rights reserved.

Artificial Weathering as a Function of CO2 Injection in Pahang Sandstone Malaysia: Investigation of Dissolution Rate in Surficial Condition

NASA Astrophysics Data System (ADS)

Jalilavi, Madjid; Zoveidavianpoor, Mansoor; Attarhamed, Farshid; Junin, Radzuan; Mohsin, Rahmat

2014-01-01

Formation of carbonate minerals by CO2 sequestration is a potential means to reduce atmospheric CO2 emissions. Vast amount of alkaline and alkali earth metals exist in silicate minerals that may be carbonated. Laboratory experiments carried out to study the dissolution rate in Pahang Sandstone, Malaysia, by CO2 injection at different flow rate in surficial condition. X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDX), Atomic Absorption Spectroscopy (AAS) and weight losses measurement were performed to analyze the solid and liquid phase before and after the reaction process. The weight changes and mineral dissolution caused by CO2 injection for two hours CO2 bubbling and one week' aging were 0.28% and 18.74%, respectively. The average variation of concentrations of alkaline earth metals in solution varied from 22.62% for Ca2+ to 17.42% for Mg2+, with in between 16.18% observed for the alkali earth metal, potassium. Analysis of variance (ANOVA) test is performed to determine significant differences of the element concentration, including Ca, Mg, and K, before and after the reaction experiment. Such changes show that the deposition of alkali and alkaline earth metals and the dissolution of required elements in sandstone samples are enhanced by CO2 injection.

Determination of total tin in silicate rocks by graphite furnace atomic absorption spectrometry

USGS Publications Warehouse

Elsheimer, H.N.; Fries, T.L.

1990-01-01

A method is described for the determination of total tin in silicate rocks utilizing a graphite furnace atomic absorption spectrometer with a stabilized-temperature platform furnace and Zeeman-effect background correction. The sample is decomposed by lithium metaborate fusion (3 + 1) in graphite crucibles with the melt being dissolved in 7.5% hydrochloric acid. Tin extractions (4 + 1 or 8 + 1) are executed on portions of the acid solutions using a 4% solution of tricotylphosphine oxide in methyl isobutyl ketone (MIBK). Ascorbic acid is added as a reducing agent prior to extraction. A solution of diammonium hydrogenphosphate and magnesium nitrate is used as a matrix modifier in the graphite furnace determination. The limit of detection is > 10 pg, equivalent to > 1 ??g l-1 of tin in the MIBK solution or 0.2-0.3 ??g g-61 in the rock. The concentration range is linear between 2.5 and 500 ??g l-1 tin in solution. The precision, measured as relative standard deviation, is < 20% at the 2.5 ??g l-1 level and < 7% at the 10-30 ??g l-1 level of tin. Excellent agreement with recommended literature values was found when the method was applied to the international silicate rock standards BCR-1, PCC-1, GSP-1, AGV-1, STM-1, JGb-1 and Mica-Fe. Application was made to the determination of tin in geological core samples with total tin concentrations of the order of 1 ??g g-1 or less.

Constraining the Material that Formed the Moon: The Origin of Lunar V, CR, and MN Depletions

NASA Technical Reports Server (NTRS)

Chabot, N. L.; Agee, C. B.

2002-01-01

The mantles of the Earth and Moon are similarly depleted in V, Cr, and Mn relative to chondritic values. Core formation deep within the Earth was suggested by as the origin of the depletions. Following Earth's core formation, the Moon was proposed to have inherited its mantle from the depleted mantle of the Earth by a giant impact event. This theory implied the Moon was primarily composed of material from the Earth's mantle. Recent systematic metal-silicate experiments of V, Cr, and Mn evaluated the behavior of these elements during different core formation scenarios. The study found that the V, Cr, and Mn depletions in the Earth could indeed be explained by core formation. The conditions of core formation necessary to deplete V, Cr, and Mn in the Earth's mantle were consistent with the deep magma ocean proposed to account for the Earth's mantle abundances of Ni and Co. Using the parameterizations of for the metal-silicate partition coefficients (D) of V, Cr, and Mn, we investigate here the conditions needed to match the depletions in the silicate Moon and determine if such conditions could have been present on the giant impactor.

Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?

NASA Technical Reports Server (NTRS)

Rankenburg, K.; Brandon, A. D.; Humayun, M.

2005-01-01

Ureilites are an enigmatic group of primitive carbon-bearing achondrites of ultramafic composition. The majority of the 143 ureilite meteorites consist primarily of olivine and pyroxene (and occasionally chromite) [1]. They are coarse-grained, slowly cooled, and depleted in incompatible lithophile elements. Minor amounts of dark interstitial material consisting of carbon, metal, sulfides, and fine-grained silicates occur primarily along silicate grain boundaries, but also intrude the silicates along fractures and cleavage planes. Variable degrees of impact shock features have also been imparted on ureilites. The prevailing two origins proposed for these rocks are either as melting residues of carbonaceous chondritic material [2], [3], or alternatively, derivation as mineral cumulates from such melts [4], [5], [6]. It has recently been proposed that ureilites are the residues of a smelting event, i.e. residues of a partial melting event under highly reducing conditions, where a solid Fe-bearing phase reacts with a melt and carbon to form Fe metal and carbon monoxide [7]. Rapid, localized extraction and loss of the basaltic component into space resulting from high eruption velocities could preserve unequilibrated oxygen isotopes and produce the observed olivine-pyroxene residues via 25-30% partial melting of chondritic-like precursor material.

Doped Calcium Silicate Ceramics: A New Class of Candidates for Synthetic Bone Substitutes

PubMed Central

No, Young Jung; Li, Jiao Jiao; Zreiqat, Hala

2017-01-01

Doped calcium silicate ceramics (DCSCs) have recently gained immense interest as a new class of candidates for the treatment of bone defects. Although calcium phosphates and bioactive glasses have remained the mainstream of ceramic bone substitutes, their clinical use is limited by suboptimal mechanical properties. DCSCs are a class of calcium silicate ceramics which are developed through the ionic substitution of calcium ions, the incorporation of metal oxides into the base binary xCaO–ySiO2 system, or a combination of both. Due to their unique compositions and ability to release bioactive ions, DCSCs exhibit enhanced mechanical and biological properties. Such characteristics offer significant advantages over existing ceramic bone substitutes, and underline the future potential of adopting DCSCs for clinical use in bone reconstruction to produce improved outcomes. This review will discuss the effects of different dopant elements and oxides on the characteristics of DCSCs for applications in bone repair, including mechanical properties, degradation and ion release characteristics, radiopacity, and biological activity (in vitro and in vivo). Recent advances in the development of DCSCs for broader clinical applications will also be discussed, including DCSC composites, coated DCSC scaffolds and DCSC-coated metal implants. PMID:28772513

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

NASA Technical Reports Server (NTRS)

Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

2016-01-01

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

NASA Technical Reports Server (NTRS)

Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

2016-01-01

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approx.576-867 C. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Metallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120deg triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3+, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung

2008-01-01

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Hydration and leaching characteristics of cement pastes made from electroplating sludge.

PubMed

Chen, Ying-Liang; Ko, Ming-Sheng; Lai, Yi-Chieh; Chang, Juu-En

2011-06-01

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the (29)Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability. Copyright © 2011 Elsevier Ltd. All rights reserved.

Metal-silicate partitioning and the light element in the core (Invited)

NASA Astrophysics Data System (ADS)

Wood, B. J.; Wade, J.; Tuff, J.

2009-12-01

Most attempts to constrain the concentrations of “light” elements in the Earth’s core rely either on cosmochemical arguments or on arguments based on the densities and equations of state of Fe-alloys containing the element of concern. Despite its utility, the latter approach yields a wide range of permissible compositions and hence weak constraints. The major problem with the cosmochemical approach is that the abundances in the bulk Earth of all the candidate “light” elements- H, C, O, Si and S are highly uncertain because of their volatile behavior during planetary accretion. In contrast, refractory elements appear to be in approximately CI chondritic relative abundances in the Earth. This leads to the potential for using the partitioning of refractory siderophile elements between the mantle and core to constrain the concentrations of light elements in the core. Recent experimental metal-silicate partitioning data, coupled with mantle abundances of refractory siderophile elements (e.g. Wade and Wood, EPSL v.236, 78—95,2005; Kegler et. al. EPSL v.268, 28-40,2008) have shown that the core segregated from the mantle under high pressure conditions (~40 GPa). If a wide range of elements, from very siderophile, (e.g. Mo) through moderately (Ni, Co, W) to weakly siderophile (V, Cr, Nb, Si) are considered, the Earth also appears to have become more oxidized during accretion. Metal-silicate partitioning of some elements is also sensitive to the light element content of the metal. For example, Nb and W partitioning depend strongly on carbon, Mo on silicon and Cr on sulfur. Given the measured mantle abundances of the refractory elements, these observations enable the Si and C contents of the core to be constrained at ~5% and <2% respectively while partitioning is consistent with a cosmochemically-estimated S content of ~2%.

Modelling of Equilibrium Between Mantle and Core: Refractory, Volatile, and Highly Siderophile Elements

NASA Technical Reports Server (NTRS)

Righter, K.; Danielson, L.; Pando, K.; Shofner, G.; Lee, C. -T.

2013-01-01

Siderophile elements have been used to constrain conditions of core formation and differentiation for the Earth, Mars and other differentiated bodies [1]. Recent models for the Earth have concluded that the mantle and core did not fully equilibrate and the siderophile element contents of the mantle can only be explained under conditions where the oxygen fugacity changes from low to high during accretion and the mantle and core do not fully equilibrate [2,3]. However these conclusions go against several physical and chemical constraints. First, calculations suggest that even with the composition of accreting material changing from reduced to oxidized over time, the fO2 defined by metal-silicate equilibrium does not change substantially, only by approximately 1 logfO2 unit [4]. An increase of more than 2 logfO2 units in mantle oxidation are required in models of [2,3]. Secondly, calculations also show that metallic impacting material will become deformed and sheared during accretion to a large body, such that it becomes emulsified to a fine scale that allows equilibrium at nearly all conditions except for possibly the length scale for giant impacts [5] (contrary to conclusions of [6]). Using new data for D(Mo) metal/silicate at high pressures, together with updated partitioning expressions for many other elements, we will show that metal-silicate equilibrium across a long span of Earth s accretion history may explain the concentrations of many siderophile elements in Earth's mantle. The modeling includes refractory elements Ni, Co, Mo, and W, as well as highly siderophile elements Au, Pd and Pt, and volatile elements Cd, In, Bi, Sb, Ge and As.

Synthesis, integration, and characterization of metal oxide films as alternative gate dielectric materials

NASA Astrophysics Data System (ADS)

Lin, You-Sheng

ZrO2 and HfO2 were investigated in this study to replace SiO2 as the potential gate dielectric materials in metal-oxide-semiconductor field effect transistors. ZrO2 and HfO2 films were deposited on p-type Si (100) wafers by an atomic layer chemical vapor deposition (ALCVD) process using zirconium (IV) t-butoxide and hafnium (IV) t-butoxide as the metal precursors, respectively. Oxygen was used alternatively with these metal alkoxide precursors into the reactor with purging and evacuation in between. The as-deposited ZrO2 and HfO2 films were stoichiometric and uniform based on X-ray photoemission spectroscopy and ellipsometry measurements. X-ray diffraction analysis indicated that the deposited films were amorphous, however, the high-resolution transmission electron microscopy showed an interfacial layer formation on the silicon substrate. Time-of-flight secondary ion mass spectrometry and medium energy ion scattering analysis showed significant intermixing between metal oxides and Si, indicating the formation of metal silicates, which were confirmed by their chemical etching resistance in HF solutions. The thermal stability of ZrO2 and HfO2 thin films on silicon was examined by monitoring their decomposition temperatures in ultra-high vacuum, using in-situ synchrotron radiation ultra-violet photoemission spectroscopy. The as-deposited ZrO2 and HfO2 thin films were thermally stable up to 880°C and 950°C in vacuum, respectively. The highest achieveable dielectric constants of as-deposited ZrO 2 and HfO2 were 21 and 24, respectively, which were slightly lower than the reported dielectric constants of bulk ZrO2 and HfO 2. These slight reductions in dielectric constants were attributed to the formation of the interfacial metal silicate layers. Very small hysteresis and interface state density were observed for both metal oxide films. Their leakage currents were a few orders of magnitude lower than that of SiO 2 at the same equivalent oxide thickness. NMOSFETs were also fabricated with the as-deposited metal oxide films, and reasonable ID-V D and IG-VG results were obtained. The electron mobilities were high from devices built using a plasma etching process to pattern the metal oxide films. However, they can be degraded if an HF wet etching process was used due to the large contact resistences. Upon oxygen annealing, the formation of SiOx at the interface improved the thermal stability of the as-deposited metal oxide films, however, lower overall dielectric constant and higher leakage current were observed. Upon ammonia annealing, the formation of SiOxNy improved not only the thermal stability but also reduced the leakage current. However, the overall dielectric constant of the film was still reduced due to the formation of the additional interfacial layer.

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

NASA Technical Reports Server (NTRS)

Gaetani, Glenn A.; Grove, Timothy L.

1997-01-01

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Effects of pH and anions on the sorption of selenium ions onto magnetite.

PubMed

Kim, Seung Soo; Min, Je Ho; Lee, Jae Kwang; Baik, Min Hoon; Choi, Jong-Won; Shin, Hyung Seon

2012-02-01

This study analyzes the influence of carbonate and silicate, which are generally abundant in granitic groundwater, on the sorption of selenium ions onto magnetite in order to understand the behaviors of selenium in a radioactive waste repository. Selenite was sorbed onto magnetite very well below pH 10, but silicate and carbonate hindered the sorption of selenite onto magnetite. On the other hand, little selenate was sorbed onto magnetite in neutral and weak alkaline solutions of 0.02 M NaNO(3) or NaClO(4), matching the ionic strength in a granitic groundwater, even though silicate or carbonate was not contained in the solutions. The surface complexation constants between selenite and magnetite were obtained by using a geochemical program, FITEQL 4.0, from the experimental data, and the formation of an inner-sphere surface complex such as =FeOSeO(2)(-) was suggested for the sorption of selenite onto magnetite from the diffuse double layer model calculation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Femtosecond laser-induced refractive index modification in multicomponent glasses

NASA Astrophysics Data System (ADS)

Bhardwaj, V. R.; Simova, E.; Corkum, P. B.; Rayner, D. M.; Hnatovsky, C.; Taylor, R. S.; Schreder, B.; Kluge, M.; Zimmer, J.

2005-04-01

We present a comprehensive study on femtosecond laser-induced refractive index modification in a wide variety of multicomponent glasses grouped as borosilicate, aluminum-silicate, and heavy-metal oxide glasses along with lanthanum-borate and sodium-phosphate glasses. By using high-spatial resolution refractive index profiling techniques, we demonstrate that under a wide range of writing conditions the refractive index modification in multicomponent glasses can be positive, negative, or nonuniform, and exhibits a strong dependence on the glass composition. With the exception of some aluminum-silicate glasses all other glasses exhibited a negative/nonuniform index change. We also demonstrate direct writing of waveguides in photosensitive Foturan® glass with a femtosecond laser without initiating crystallization by thermal treatment. Upon ceramization of lithium-aluminum-silicate glasses such as Foturan®, Zerodur®, and Robax® we observe switching of laser-induced refractive index change from being positive to negative. The measured transmission losses in the waveguides at 1550nm agree with the index profile measurements in alkali-free aluminum-silicate glasses.

Size determination of gold nanoparticles in silicate glasses by UV-Vis spectroscopy

NASA Astrophysics Data System (ADS)

Ali, Shahid; Khan, Younas; Iqbal, Yaseen; Hayat, Khizar; Ali, Muhammad

2017-01-01

A relatively easier and more accurate method for the determination of average size of metal nanoparticles/aggregates in silicate glasses based on ultraviolet visible (UV-Vis) spectra fitted with the Mie and Mie-Gans models was reported. Gold ions were diffused into sodalime silicate and borosilicate glasses by field-assisted solid-state ion-exchange technique using the same experimental parameters for both glasses. Transmission electron microscopy was performed to directly investigate the morphology and distribution of the dopant nanoparticles. UV-Vis spectra of the doped glasses showed broad surface plasmon resonance peaks in their fingerprint regions, i.e., at 525 and 500 nm for sodalime silicate and borosilicate glass matrices, respectively. These spectra were fitted with the Mie model for spherical nanoparticles and the Mie-Gans model for spheroidal nanoparticles. Although both the models were developed for colloidal nanoparticles, the size of the nanoparticles/aggregates calculated was accurate to within ˜10% in both the glass matrices in comparison to the size measured directly from the transmission electron microscope images.

An Earth-sized exoplanet with a Mercury-like composition

NASA Astrophysics Data System (ADS)

Santerne, A.; Brugger, B.; Armstrong, D. J.; Adibekyan, V.; Lillo-Box, J.; Gosselin, H.; Aguichine, A.; Almenara, J.-M.; Barrado, D.; Barros, S. C. C.; Bayliss, D.; Boisse, I.; Bonomo, A. S.; Bouchy, F.; Brown, D. J. A.; Deleuil, M.; Delgado Mena, E.; Demangeon, O.; Díaz, R. F.; Doyle, A.; Dumusque, X.; Faedi, F.; Faria, J. P.; Figueira, P.; Foxell, E.; Giles, H.; Hébrard, G.; Hojjatpanah, S.; Hobson, M.; Jackman, J.; King, G.; Kirk, J.; Lam, K. W. F.; Ligi, R.; Lovis, C.; Louden, T.; McCormac, J.; Mousis, O.; Neal, J. J.; Osborn, H. P.; Pepe, F.; Pollacco, D.; Santos, N. C.; Sousa, S. G.; Udry, S.; Vigan, A.

2018-05-01

Earth, Venus, Mars and some extrasolar terrestrial planets1 have a mass and radius that is consistent with a mass fraction of about 30% metallic core and 70% silicate mantle2. At the inner frontier of the Solar System, Mercury has a completely different composition, with a mass fraction of about 70% metallic core and 30% silicate mantle3. Several formation or evolution scenarios are proposed to explain this metal-rich composition, such as a giant impact4, mantle evaporation5 or the depletion of silicate at the inner edge of the protoplanetary disk6. These scenarios are still strongly debated. Here, we report the discovery of a multiple transiting planetary system (K2-229) in which the inner planet has a radius of 1.165 ± 0.066 Earth radii and a mass of 2.59 ± 0.43 Earth masses. This Earth-sized planet thus has a core-mass fraction that is compatible with that of Mercury, although it was expected to be similar to that of Earth based on host-star chemistry7. This larger Mercury analogue either formed with a very peculiar composition or has evolved, for example, by losing part of its mantle. Further characterization of Mercury-like exoplanets such as K2-229 b will help to put the detailed in situ observations of Mercury (with MESSENGER and BepiColombo8) into the global context of the formation and evolution of solar and extrasolar terrestrial planets.

Metal-silicate fractionation in the surface dust layers of accreting planetesimals: Implications for the formation of ordinary chondrites and the nature of asteroid surfaces

NASA Astrophysics Data System (ADS)

Huang, Shaoxiong; Akridge, Glen; Sears, Derek W. G.

Some of the most primitive solar system materials available for study in the laboratory are the ordinary chondrites, the largest meteorite class. The size and distribution of the chondrules (silicate beads) and metal, which leads to the definition of the H, L, and LL classes, suggest sorting before or during aggregation. We suggest that meteorite parent bodies (probably asteroids) had thick dusty surfaces during their early evolution that were easily mobilized by gases evolving from their interiors. Density and size sorting would have occurred in the surface layers as the upward drag forces of the gases (mainly water) acted against the downward force of gravity. The process is analogous to the industrially important process of fluidization and sorting in pyroclastic volcanics. We calculate that gas flow velocities and gas fluxes for the regolith of an asteroid-sized object heated by the impact of accreting objects or by 26Al would have been sufficient for fluidization. It can also explain, quantitatively in some cases, the observed metal-silicate sorting of ordinary chondrites, which has long been ascribed to processes occurring in the primordial solar nebula. Formation of the chondrites in the thick dynamic regolith is consistent with the major properties of chondritic meteorites (i.e., redox state, petrologic type, cooling rate, matrix abundance). These ideas have implications for the nature of asteroid surfaces and the virtual lack of asteroids with ordinary chondrite-like surfaces.

Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs

NASA Technical Reports Server (NTRS)

Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.

2006-01-01

Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.

Improving the electrical properties of lanthanum silicate films on ge metal oxide semiconductor capacitors by adopting interfacial barrier and capping layers.

PubMed

Choi, Yu Jin; Lim, Hajin; Lee, Suhyeong; Suh, Sungin; Kim, Joon Rae; Jung, Hyung-Suk; Park, Sanghyun; Lee, Jong Ho; Kim, Seong Gyeong; Hwang, Cheol Seong; Kim, HyeongJoon

2014-05-28

The electrical properties of La-silicate films grown by atomic layer deposition (ALD) on Ge substrates with different film configurations, such as various Si concentrations, Al2O3 interfacial passivation layers, and SiO2 capping layers, were examined. La-silicate thin films were deposited using alternating injections of the La[N{Si(CH3)3}2]3 precursor with O3 as the La and O precursors, respectively, at a substrate temperature of 310 °C. The Si concentration in the La-silicate films was further controlled by adding ALD cycles of SiO2. For comparison, La2O3 films were also grown using [La((i)PrCp)3] and O3 as the La precursor and oxygen source, respectively, at the identical substrate temperature. The capacitance-voltage (C-V) hysteresis decreased with an increasing Si concentration in the La-silicate films, although the films showed a slight increase in the capacitance equivalent oxide thickness. The adoption of Al2O3 at the interface as a passivation layer resulted in lower C-V hysteresis and a low leakage current density. The C-V hysteresis voltages of the La-silicate films with Al2O3 passivation and SiO2 capping layers was significantly decreased to ∼0.1 V, whereas the single layer La-silicate film showed a hysteresis voltage as large as ∼1.0 V.

CONDUCT AN INVESTIGATION OF CIGUATERA POISON

DTIC Science & Technology

Research on ciguatera toxin has resulted in the development of an efficient method for extracting the toxin from the musculature of fish. Procedures...solution and adsorption of ciguatera toxin on silicic ac d. More precise fractionation of ciguatera toxin is accomplished on a silicic acid column...developed in stepwise fashion by ether containing small percentages of methanol.As a method for fractionation and as the basis for a test for ciguatera

The thermodynamic activity of ZnO in silicate melts

NASA Astrophysics Data System (ADS)

Reyes, R. A.; Gaskell, D. R.

1983-12-01

The activity of ZnO in ZnO-SiO2 and CaO-ZnO-SiO2 melts has been measured at 1560 °C using a transpiration technique with CO-CO2 mixtures as the carrier gas. The activities of ZnO in dilute solution in 42 wt pct SiO2-38 wt pct CaO-20 wt pct A12O3 in the range 1400° to 1550 °C and in 62 wt pct SiO2-23.3 wt pct CaO-14.7 wt pct A12O3 at 1550 °C have also been measured. The measured free energies of formation of ZnO-SiO2 melts are significantly more negative than published estimated values and this, together with the behavior observed in the system CaO-Al2O3-SiO2, indicate that ZnO is a relatively basic oxide. The results are discussed in terms of the polymerization model of binary silicate melts and ideal silicate mixing in ternary silicate melts. The behavior of ZnO in dilute solution in CaO-Al2O3-SiO2 melts is discussed in terms of the possibility of the fluxing of ZnO by iron blast furnace slags.

Iron Speciation in Minerals and Melts at High Pressure: Implications for the Redox Evolution of the Early Mantle

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.; Miyajima, N.

2016-12-01

During the differentiation of the early Earth, the silicates of the mantle must have been in equilibrium with core-forming metal iron, as indicated by the depletion of siderophile elements from the mantle. Studies of ancient rocks suggest that by at least 3.9 Ga, the upper mantle was 4-5 log units more oxidized than metal saturation implies (Delano 2001). The process(es) by which the mantle was oxidized is unclear, but has implications for the timing of accretion, differentiation, and volatile delivery to the early Earth, as well as evolution of the early atmosphere. One plausible oxidation mechanism is suggested by the tendency of high-pressure silicate minerals to favor Fe3+ over Fe2+ in their structures, even at metal saturation. This preference in the lower mantle mineral bridgmanite has been proposed to drive the disproportionation reaction of FeO to form Fe­2O3 and iron metal (Frost and McCammon 2008). We have performed experiments at the Ru-RuO2 fO2 buffer which show that silicate melts may mirror this behavior and Fe3+ may be stabilized with pressure for a constant fO2; by 21 GPa, the previously observed trend of Fe3+ decreasing with pressure (O'Neill, 2006) reverses and ferric iron content had increased. If this is also the case at lower oxygen fugacities, FeO disproportionation may have occurred at the base of an early magma ocean, establishing a redox gradient similar to what is presumed for the mantle today. Here we report results of further multianvil and diamond anvil cell experiments exploring the plausibility of FeO disproportionation driving mantle oxidation. Experiments investigating Fe speciation in high pressure melts at variable fO2 will be discussed along with results of diamond anvil cell experiments investigating ferric iron content of lower mantle minerals at metal saturation.

The Evolution of Land Plants and the Silicate Weathering Feedback

NASA Astrophysics Data System (ADS)

Ibarra, D. E.; Caves Rugenstein, J. K.; Bachan, A.; Baresch, A.; Lau, K. V.; Thomas, D.; Lee, J. E.; Boyce, C. K.; Chamberlain, C. P.

2017-12-01

It has long been recognized that the advent of vascular plants in the Paleozoic must have changed silicate weathering and fundamentally altered the long-term carbon cycle. Efforts to quantify these effects have been formulated in carbon cycle models that are, in part, calibrated by weathering studies of modern plant communities. In models of the long-term carbon cycle, plants play a key role in controlling atmospheric CO2, particularly in the late Paleozoic. We test the impact of some established and recent theories regarding plant-enhanced weathering by coupling a one-dimensional vapor transport model to a reactive transport model of silicate weathering. In this coupled model, we evaluate consequences of plant evolutionary innovation that have not been mechanistically incorporated into most existing models: 1) the role of evolutionary shifts in plant transpiration in enhancing silicate weathering by increasing downwind transport and recycling of water vapor to continental interiors; 2) the importance of deeply-rooted plants and their associated microbial communities in increasing soil CO2 and weathering zone length scales; and, 3) the cumulative effect of these processes. Our modeling approach is framed by energy/supply constraints calibrated for minimally vegetated-, vascular plant forested-, and angiosperm-worlds. We find that the emergence of widespread transpiration and associated inland vapor recycling approximately doubles weathering solute concentrations when deep-rooted vascular plants (Devonian-Carboniferous) fully replace a minimally vegetated (pre-Devonian) world. The later evolution of angiosperms (Cretaceous and Cenozoic) and subsequent increase in transpiration fluxes increase weathering solute concentrations by approximately an additional 20%. Our estimates of the changes in weatherability caused by land plant evolution are of a similar magnitude, but explained with new process-based mechanisms, than those used in existing carbon cycle models. We suggest a feedback where the increase in solute concentrations is compensated by a decrease in runoff and temperature, permitting lower steady-state atmospheric pCO2. Consequently, plants have increased the strength of the climatic feedback on silicate weathering since the late Paleozoic.

How Mercury can be the most reduced terrestrial planet and still store iron in its mantle

NASA Astrophysics Data System (ADS)

Malavergne, Valérie; Cordier, Patrick; Righter, Kevin; Brunet, Fabrice; Zanda, Brigitte; Addad, Ahmed; Smith, Thomas; Bureau, Hélène; Surblé, Suzy; Raepsaet, Caroline; Charon, Emeline; Hewins, Roger H.

2014-05-01

Mercury is notorious as the most reduced planet with the highest metal/silicate ratio, yet paradoxically data from the MESSENGER spacecraft show that its iron-poor crust is high in sulfur (up to ˜6 wt%, ˜80× Earth crust abundance) present mainly as Ca-rich sulfides on its surface. These particularities are simply impossible on the other terrestrial planets. In order to understand the role played by sulfur during the formation of Mercury, we investigated the phase relationships in Mercurian analogs of enstatite chondrite-like composition experimentally under conditions relevant to differentiation of Mercury (˜1 GPa and 1300-2000 °C). Our results show that Mg-rich and Ca-rich sulfides, which both contain Fe, crystallize successively from reduced silicate melts upon cooling below 1550 °C. As the iron concentration in the reduced silicates stays very low (≪1 wt%), these sulfides represent new host phases for both iron and sulfur in the run products. Extrapolated to Mercury, these results show that Mg-rich sulfide crystallization provides the first viable and fundamental means for retaining iron as well as sulfur in the mantle during differentiation, while sulfides richer in Ca would crystallize at shallower levels. The distribution of iron in the differentiating mantle of Mercury was mainly determined by its partitioning between metal (or troilite) and Mg-Fe-Ca-rich sulfides rather than by its partitioning between metal (or troilite) and silicates. Moreover, the primitive mantle might also be boosted in Fe by a reaction at the core mantle boundary (CMB) between Mg-rich sulfides of the mantle and FeS-rich outer core materials to produce (Fe, Mg)S. The stability of Mg-Fe-Ca-rich sulfides over a large range of depths up to the surface of Mercury would be consistent with sulfur, calcium and iron abundances measured by MESSENGER.

Kinetics of apatite formation on a calcium-silicate cement for root-end filling during ageing in physiological-like phosphate solutions.

PubMed

Gandolfi, Maria Giovanna; Taddei, Paola; Tinti, Anna; De Stefano Dorigo, Elettra; Rossi, Piermaria Luigi; Prati, Carlo

2010-12-01

The bioactivity of calcium silicate mineral trioxide aggregate (MTA) cements has been attributed to their ability to produce apatite in presence of phosphate-containing fluids. This study evaluated surface morphology and chemical transformations of an experimental accelerated calcium-silicate cement as a function of soaking time in different phosphate-containing solutions. Cement discs were immersed in Dulbecco's phosphate-buffered saline (DPBS) or Hank's balanced salt solution (HBSS) for different times (1-180 days) and analysed by scanning electron microscopy connected with an energy dispersive X-ray analysis (SEM-EDX) and micro-Raman spectroscopy. SEM-EDX revealed Ca and P peaks after 14 days in DPBS. A thin Ca- and P-rich crystalline coating layer was detected after 60 days. A thicker multilayered coating was observed after 180 days. Micro-Raman disclosed the 965-cm(-1) phosphate band at 7 days only on samples stored in DPBS and later the 590- and 435-cm(-1) phosphate bands. After 60-180 days, a layer approximately 200-900 μm thick formed displaying the bands of carbonated apatite (at 1,077, 965, 590, 435 cm(-1)) and calcite (at 1,088, 713, 280 cm(-1)). On HBSS-soaked, only calcite bands were observed until 90 days, and just after 180 days, a thin apatite-calcite layer appeared. Micro-Raman and SEM-EDX demonstrated the mineralization induction capacity of calcium-silicate cements (MTAs and Portland cements) with the formation of apatite after 7 days in DPBS. Longer time is necessary to observe bioactivity when cements are immersed in HBSS.

Pulsed deposition of silicate films

NASA Astrophysics Data System (ADS)

He, W.; Solanki, R.; Conley, J. F.; Ono, Y.

2003-09-01

A sequential pulsed process is utilized for deposition of nonstoichiometric silicate films without employing an oxidizing agent. The metal precursors were HfCl4, AlCl3, and ZrCl4, as well as Hf(NO3)4 and the silicon source was tris(tert-butoxy)silanol. Unlike atomic layer deposition, the growth per cycle was several monolayers thick, where the enhancement in growth was due to a catalytic reaction. The bulk and electrical properties of these films are similar to those of silicon dioxide. Silicon carbide devices coated with these films show good insulating characteristics.

Perspectives on Magmatic Differentiation of Mercury

NASA Astrophysics Data System (ADS)

Charlier, B.; Namur, O.; Cartier, C.

2018-05-01

Silicate/metal liquid immiscibility, crystallization of a magma ocean, partial melting of mantle rocks, and surface crystallization have shaped Mercury as we know it today. We review these processes based on high-T experiments at reducing conditions.

Thermodynamics of rock forming crystalline solutions

NASA Technical Reports Server (NTRS)

Saxena, S. K.

1971-01-01

Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.

The Distribution and Composition Characteristics of Siliceous Rocks from Qinzhou Bay-Hangzhou Bay Joint Belt, South China: Constraint on the Tectonic Evolution of Plates in South China

PubMed Central

Li, Hongzhong; Zhai, Mingguo; Zhang, Lianchang; Zhou, Yongzhang; Yang, Zhijun; He, Junguo; Liang, Jin; Zhou, Liuyu

2013-01-01

The Qinzhou Bay-Hangzhou Bay joint belt is a significant tectonic zone between the Yangtze and Cathaysian plates, where plentiful hydrothermal siliceous rocks are generated. Here, the authors studied the distribution of the siliceous rocks in the whole tectonic zone, which indicated that the tensional setting was facilitating the development of siliceous rocks of hydrothermal genesis. According to the geochemical characteristics, the Neopalaeozoic siliceous rocks in the north segment of the Qinzhou Bay-Hangzhou Bay joint belt denoted its limited width. In comparison, the Neopalaeozoic Qinzhou Bay-Hangzhou Bay joint belt was diverse for its ocean basin in the different segments and possibly had subduction only in the south segment. The ocean basin of the north and middle segments was limited in its width without subduction and possibly existed as a rift trough that was unable to resist the terrigenous input. In the north segment of the Qinzhou Bay-Hangzhou Bay joint belt, the strata of hydrothermal siliceous rocks in Dongxiang copper-polymetallic ore deposit exhibited alternative cycles with the marine volcanic rocks, volcanic tuff, and metal sulphide. These sedimentary systems were formed in different circumstances, whose alternative cycles indicated the release of internal energy in several cycles gradually from strong to weak. PMID:24302882

Connecting the Interstellar Gas and Dust Properties in Distant Galaxies Using Quasar Absorption Systems

NASA Technical Reports Server (NTRS)

Aller, Monique C.; Dwek, Eliahu; Kulkarni, Varsha P.; York, Donald G.; Welty, Daniel E.; Vladilo, Giovanni; Som, Debopam; Lackey, Kyle; Dwek, Eli; Beiranvand, Nassim;

Kinetics and mechanisms of the conversion of silicate (45S5), borate, and borosilicate glasses to hydroxyapatite in dilute phosphate solutions.

PubMed

Huang, Wenhai; Day, Delbert E; Kittiratanapiboon, Kanisa; Rahaman, Mohamed N

2006-07-01

Bioactive glasses with controllable conversion rates to hydroxyapatite (HA) may provide a novel class of scaffold materials for bone tissue engineering. The objective of the present work was to comprehensively characterize the conversion of a silicate bioactive glass (45S5), a borate glass, and two intermediate borosilicate glass compositions to HA in a dilute phosphate solution at 37 degrees Celsius. The borate glass and the borosilicate glasses were derived from the 45S5 glass by fully or partially replacing the SiO(2) with B(2)O(3). Higher B(2)O(3) content produced a more rapid conversion of the glass to HA and a lower pH value of the phosphate solution. Whereas the borate glass was fully converted to HA in less than 4 days, the silicate (45S5) and borosilicate compositions were only partially converted even after 70 days, and contained residual SiO(2) in a Na-depleted core. The concentration of Na(+) in the phosphate solution increased with reaction time whereas the PO(4) (3-) concentration decreased, both reaching final limiting values at a rate that increased with the B(2)O(3) content of the glass. However, the Ca(2+) concentration in the solution remained low, below the detection limit of atomic absorption, throughout the reaction. Immersion of the glasses in a mixed solution of K(2)HPO(4) and K(2)CO(3) produced a carbonate-substituted HA but the presence of the K(2)CO(3) had little effect on the kinetics of conversion to HA. The kinetics and mechanisms of the conversion process of the four glasses to HA are compared and used to develop a model for the process.

Isomorphic introduction of d(0) transition metals to mesoporous silica

NASA Astrophysics Data System (ADS)

Morey, Mark Sanson

1998-12-01

Early transition metals (Ti, V, Zr, Mo, W) have been incorporated in the mesoporous silicate system by hydrothermal and post-synthesis treatments. The materials were studied by diffraction, adsorption and spectroscopic techniques and were found to have catalytic, halogenation activity toward organic substrates at neutral pH. Intense interest has been shown in the new class of silica-based, mesoporous materials due to their high potential for catalytic applications. Their synthesis occurs via a cooperative self-assembly of surfactant/silicate pairs to form numerous, extended network structures upon silicate condensation based on liquid crystal phases of surfactant/water systems. Surfactant micelle removal by calcination generates a well defined pore system with a narrow pore size distribution. Of these phases, the cubic MCM-48 form possesses a high surface area (1200-1500msp2/g), a 3-D array of pores, and a large pore diameter (20-100A) so that selectivity for large (>10A kinetic diameter) molecules is possible. For this work, the MCM-48 phase was chosen since its branched, bi-continuous pore array would be less likely to clog during use than a one dimensional array. Two techniques for transition metal incorporation are compared consisting of hydrothermal and post-synthesis treatment. A brief description of an attempt to synthesize mesoporous molybdena will be included. The first approach consists of combining various metal and Si precursors in the starting gel, while exploring a broad region of the multi-component phase diagram. The second pathway involves grafting metal species on a pure silica, MCM-48 support by anchoring them to surface silanols using reactive metal alkoxides. Bulk structural characterization by X-ray powder diffraction and nitrogen adsorption shows that the pore structure is maintained after incorporation of metal species by both methods. Spectroscopic methods (FTIR/RAMAN and UV/VIS) are used to gain insight into the local metal/silica environments. The post-synthesis and grafted materials have been shown to exhibit activity in the bromination of large, organic molecules such as phenol red at neutral pH and is a first for a non-biological system. In nature, vanadium bromoperoxidase accomplishes this task, effectively producing brominated, marine natural products with interesting pharmacological properties. The five metals were meticulously chosen based on their well known oxidative properties and ease of incorporation into the silica matrix. A discussion of the relative rates of halogenation will be based on the metal's ability to coordinate and activate peroxide ligands.

Hf-W chronology of CR chondrites: Implications for the timescales of chondrule formation and the distribution of 26Al in the solar nebula

NASA Astrophysics Data System (ADS)

Budde, Gerrit; Kruijer, Thomas S.; Kleine, Thorsten

2018-02-01

Renazzo-type carbonaceous (CR) chondrites are distinct from most other chondrites in having younger chondrule 26Al-26Mg ages, but the significance of these ages and whether they reflect true formation times or spatial variations of the 26Al/27Al ratio within the solar protoplanetary disk are a matter of debate. To address these issues and to determine the timescales of metal-silicate fractionation and chondrule formation in CR chondrites, we applied the short-lived 182Hf-182W chronometer to metal, silicate, and chondrule separates from four CR chondrites. We also obtained Mo isotope data for the same samples to assess potential genetic links among the components of CR chondrites, and between these components and bulk chondrites. All investigated samples plot on a single Hf-W isochron and constrain the time of metal-silicate fractionation in CR chondrites to 3.6 ± 0.6 million years (Ma) after the formation of Ca-Al-rich inclusions (CAIs). This age is indistinguishable from a ∼3.7 Ma Al-Mg age for CR chondrules, suggesting not only that metal-silicate fractionation and chondrule formation were coeval, but also that these two processes were linked to each other. The good agreement of the Hf-W and Al-Mg ages, combined with concordant Hf-W and Al-Mg ages for angrites and CV chondrules, provides strong evidence for a disk-wide, homogeneous distribution of 26Al in the early solar system. As such, the young Al-Mg ages for CR chondrules do not reflect spatial 26Al/27Al heterogeneities but indicate that CR chondrules formed ∼1-2 Ma later than chondrules from most other chondrite groups. Metal and silicate in CR chondrites exhibit distinct nucleosynthetic Mo and W isotope anomalies, which are caused by the heterogeneous distribution of the same presolar s-process carrier. These data suggest that the major components of CR chondrites are genetically linked and therefore formed from a single reservoir of nebular dust, most likely by localized melting events within the solar protoplanetary disk. Taken together, the chemical, isotopic, and chronological data for components of CR chondrites imply a close temporal link between chondrule formation and chondrite accretion, indicating that the CR chondrite parent body is one of the youngest meteorite parent bodies. The relatively late accretion of the CR parent body is consistent with its isotopic composition (for instance the elevated 15N/14N) that suggests a formation at a larger heliocentric distance, probably beyond the orbit of Jupiter. As such, the accretion age of the CR chondrite parent body of ∼3.6 Ma after CAI formation provides the earliest possible time at which Jupiter's growth could have led to scattering of carbonaceous meteorite parent bodies from beyond its orbit into the inner solar system.

Properties of Tricalcium Silicate Sealers.

PubMed

Khalil, Issam; Naaman, Alfred; Camilleri, Josette

2016-10-01

Sealers based on tricalcium silicate cement aim at an interaction of the sealer with the root canal wall, alkalinity with potential antimicrobial activity, and the ability to set in a wet field. The aim of this study was to characterize and investigate the properties of a new tricalcium silicate-based sealer and verify its compliance to ISO 6876 (2012). A new tricalcium silicate-based sealer (Bio MM; St Joseph University, Beirut, Lebanon), BioRoot RCS (Septodont, St Maure de Fosses, France), and AH Plus (Dentsply, DeTrey, Konstanz, Germany) were investigated. Characterization using scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction analysis was performed. Furthermore, sealer setting time, flow, film thickness, and radiopacity were performed following ISO specifications. pH and ion leaching in solution were assessed by pH analysis and inductively coupled plasma. Bio MM and BioRoot RCS were both composed of tricalcium silicate and tantalum oxide in Bio MM and zirconium oxide in BioRoot RCS. In addition, the Bio MM contained calcium carbonate and a phosphate phase. The inorganic components of AH Plus were calcium tungstate and zirconium oxide. AH Plus complied with the ISO norms for both flow and film thickness. BioRoot RCS and Bio MM exhibited a lower flow and a higher film thickness than that specified for sealer cements in ISO 6876. All test sealers exhibited adequate radiopacity. Bio MM interacted with physiologic solution, thus showing potential for bioactivity. Sealer properties were acceptable and comparable with other sealers available clinically. Copyright © 2016 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

NASA Astrophysics Data System (ADS)

Amelina, Anna; Grinberg, Evgenii

A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used for producing of thin coats on ceramics and metallic surfaces.

Composite materials for thermal energy storage

NASA Astrophysics Data System (ADS)

Benson, D. K.; Burrows, R. W.; Shinton, Y. D.

1985-01-01

A composite material for thermal energy storage based upon polyhydric alcohols, such as pentaerythritol, trimethylol ethane (also known as pentaglycerine), neopentyl glycol and related compounds including trimethylol propane, monoaminopentaerythritol, diamino-pentaerythritol and tris(hydroxymethyl)acetic acid, separately or in combinations, which provide reversible heat storage through crystalline phase transformations are discussed. These PCM's do not become liquid during use and are in contact with at least one material selected from the group consisting of metals, carbon, siliceous, plastic, cellulosic, natural fiber, artificial fiber, concrete, gypsum, porous rock, and mixtures thereof. Particulate additions such as aluminum or graphite powders, as well as metal and carbon fibers can also be incorporated therein. Particulate and/or fibrous additions can be introduced into molten phase change materials which can then be cast into various shapes. After the phase change materials have solidified, the additions will remain dispersed throughout the matrix of the cast solid. The polyol is in contact with at least one material selected from the group consisting of metals, carbon, siliceous, plastic, cellulosic, natural fiber, artificial fiber, concrete, gypsum, and mixtures thereof.

Effective work function engineering for a TiN/XO(X = La, Zr, Al)/SiO{sub 2} stack structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Dongjin, E-mail: dongjin0710.lee@samsung.com; Lee, Jieun; Jung, Kyoungho

In this study, we demonstrated that work function engineering is possible over a wide range (+200 mV to −430 mV) in a TiN/XO (X = La, Zr, or Al)/SiO{sub 2} stack structures. From ab initio simulations, we selected the optimal material for the work function engineering. The work function engineering mechanism was described by metal diffusion into the TiN film and silicate formation in the TiN/SiO{sub 2} interface. The metal doping and the silicate formation were confirmed by transmission electron microscopy and energy dispersive spectroscopy line profiling, respectively. In addition, the amount of doped metal in the TiN film depended on the thickness ofmore » the insertion layer XO. From the work function engineering technique, which can control a variety of threshold voltages (Vth), an improvement in transistors with different V{sub th} values in the TiN/XO/SiO{sub 2} stack structures is expected.« less

Composite materials for thermal energy storage

DOEpatents

Benson, David K.; Burrows, Richard W.; Shinton, Yvonne D.

1986-01-01

The present invention discloses composite material for thermal energy storage based upon polyhydric alcohols, such as pentaerythritol, trimethylol ethane (also known as pentaglycerine), neopentyl glycol and related compounds including trimethylol propane, monoaminopentaerythritol, diamino-pentaerythritol and tris(hydroxymethyl)acetic acid, separately or in combinations, which provide reversible heat storage through crystalline phase transformations. These phase change materials do not become liquid during use and are in contact with at least one material selected from the group consisting of metals, carbon siliceous, plastic, cellulosic, natural fiber, artificial fiber, concrete, gypsum, porous rock, and mixtures thereof. Particulate additions, such as aluminum or graphite powders, as well as metal and carbon fibers can also be incorporated therein. Particulate and/or fibrous additions can be introduced into molten phase change materials which can then be cast into various shapes. After the phase change materials have solidified, the additions will remain dispersed throughout the matrix of the cast solid. The polyol is in contact with at least one material selected from the group consisting of metals, carbon siliceous, plastic, cellulosic, natural fiber, artificial fiber, concrete, gypsum, and mixtures thereof.

Composite materials for thermal energy storage

DOEpatents

Benson, D.K.; Burrows, R.W.; Shinton, Y.D.

1985-01-04

A composite material for thermal energy storage based upon polyhydric alcohols, such as pentaerythritol, trimethylol ethane (also known as pentaglycerine), neopentyl glycol and related compounds including trimethylol propane, monoaminopentaerythritol, diamino-pentaerythritol and tris(hydroxymethyl)acetic acid, separately or in combinations, which provide reversible heat storage through crystalline phase transformations. These PCM's do not become liquid during use and are in contact with at least one material selected from the group consisting of metals, carbon, siliceous, plastic, cellulosic, natural fiber, artificial fiber, concrete, gypsum, porous rock, and mixtures thereof. Particulate additions such as aluminum or graphite powders, as well as metal and carbon fibers can also be incorporated therein. Particulate and/or fibrous additions can be introduced into molten phase change materials which can then be cast into various shapes. After the phase change materials have solidified, the additions will remain dispersed throughout the matrix of the cast solid. The polyol is in contact with at least one material selected from the group consisting of metals, carbon, siliceous, plastic, cellulosic, natural fiber, artificial fiber, concrete, gypsum, and mixtures thereof.

Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lassinantti Gualtieri, Magdalena, E-mail: magdalena.gualtieri@unimore.it; Romagnoli, Marcello; Pollastri, Simone

2015-01-15

Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for constructionmore » purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties. -- Highlights: •Geopolymerization of laterite is promising for fabrication of building materials. •Both phosphoric acid and alkaline sodium silicate solution can be used for activation. •Thermally activated redox properties of the inorganic polymers were observed.« less

Experimental constraints on heating and cooling rates of refractory inclusions in the early solar system

NASA Technical Reports Server (NTRS)

Boynton, W. V.; DRAKE; HILDEBRAND; JONES; LEWIS; TREIMAN; WARK

1987-01-01

The refractory inclusions in carbonaceous chondrites were the subject of considerable interest since their discovery. These inclusions contain minerals that are predicted to be some of the earliest condensates from the solar nebula, and contain a plethora of isotopic anomalies of unknown origin. Of particular interest are those coarse-grained inclusions that contain refractory metal particles (Fe, Ni, Pt, Ru, Os Ir). Experimental studies of these inclusions in terrestrial laboratories are, however, complicated because the dense particles tend to settle out of a molten or partially molten silicate material. Heating experiments in the Space Station technology and microgravity in order to observe the effects of metal nuggets (which may act as heterogeneous nucleation sites) on nucleation rates in silicate systems and to measure simultaneously the relative volatilization rate of siderophile and lithophile species. Neither experiment is possible in the terrestrial environment.

Experimental evidence of {alpha}-olefin readsorption in Fischer-Tropsch synthesis on ruthenium-supported ETS-10 titanium silicate catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bianchi, C.L.; Ragaini, V.

1997-05-01

Fischer-Tropsch synthesis seems to develop the following two consecutive paths: a primary process that involves the formation of {alpha}-olefin products and a secondary process leading to the production of branched isomers and paraffins and requiring the readsorption of primary {alpha}-olefin products. It was already shown by Iglesia et al. that such readsorption steps are of fundamental importance for Ru catalysts and that they occur due to the slow diffusive removal of {alpha}-olefins when the molecular size increases, this resulting in a long intraparticle residence time. In the present paper {alpha}-olefins readsorption was enhanced by changing the metal distribution inside themore » pores of a titanium silicate (ETS-10), modified by ion exchange with alkali metal ions, used as a support for Ru-based catalysts. 24 refs., 5 figs., 3 tabs.« less

Metal-silicate thermochemistry at high temperature - Magma oceans and the 'excess siderophile element' problem of the earth's upper mantle

NASA Technical Reports Server (NTRS)

Capobianco, Christopher J.; Jones, John H.; Drake, Michael J.

1993-01-01

Low-temperature metal-silicate partition coefficients are extrapolated to magma ocean temperatures. If the low-temperature chemistry data is found to be applicable at high temperatures, an important assumption, then the results indicate that high temperature alone cannot account for the excess siderophile element problem of the upper mantle. For most elements, a rise in temperature will result in a modest increase in siderophile behavior if an iron-wuestite redox buffer is paralleled. However, long-range extrapolation of experimental data is hazardous when the data contains even modest experimental errors. For a given element, extrapolated high-temperature partition coefficients can differ by orders of magnitude, even when data from independent studies is consistent within quoted errors. In order to accurately assess siderophile element behavior in a magma ocean, it will be necessary to obtain direct experimental measurements for at least some of the siderophile elements.

High temperature crystal field spectra of transition metal-bearing minerals - Relevance to remote-sensed spectra of planetary surfaces

NASA Technical Reports Server (NTRS)

Parkin, K. M.; Burns, R. G.

1980-01-01

It is pointed out that transition metal ions in silicate minerals, glasses, and crystalline and amorphous oxyhydroxides and salts contribute to the visible-near infrared spectral profiles of planetary surfaces. Investigations are conducted to obtain spectral information which might be helpful in the interpretation of the remote-sensed spectra of planetary surfaces. A description is presented of the results of high temperature crystal field spectral measurements of a variety of heated minerals containing Cr(3+), Fe(3+), Fe(++), and Mn(++) ions in different coordination symmetries, taking into account a correlation of the temperature-induced variations with those previously observed for octahedrally coordinated Fe(++)-bearing silicates. The employed experimental methods are also discussed, giving attention to the preparation of the samples, the determination of the absorption spectra, electron microprobe analyses, and the curve fitting procedure.

Effect of Silicon on Activity Coefficients of P, Bl, CD, SN, and AG in Liquid Fe-Si, and Implications for Differentiation and Core Formation

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.; Ross, D. K.

2017-01-01

Cores of differentiated bodies (Earth, Mars, Mercury, Moon, Vesta) contain light elements such as S, C, Si, and O. We have previously measured small effects of Si on metal-silicate partitioning of Ni and Co [1,2], and larger effects for Mo, Ge, Sb, As [2]. The effect of Si on many siderophile elements could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of Bi, Cd, Sn, Ag, and P between metal and silicate melt. The results will be applied to Earth, Mars, Mercury, Moon, and Vesta, for which we have excellent constraints on the mantle Bi, Cd, Sn, Ag, and P concentrations from mantle and/or basalt samples.

Rhenium-osmium isotope systematics of Group 2A and Group 4A iron meteorites

NASA Technical Reports Server (NTRS)

Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

1993-01-01

We are investigating the Re-Os isotope systematics of two groups of magmatic iron meteorites (2A, 4A) in an attempt to establish precise 'total rock' isochrons by the Re-Os system. The Re-187/Os-187 isotope system is recognized as a method by which the ages of iron meteorites can be directly determined and that can provide information on the timing of FeNi segregation and core formation in planetesimals. The Re-Os isotope system permits the direct absolute dating of the metal phase in iron meteorites. Indirect dating of iron meteorites has been achieved in the past through the Rb-Sr, K-Ar, and most recently, Sm-Nd for silicate inclusions, where present. Relative dating has been obtained directly by extensive studies of the short-lived system Pd-107/Ag-107 for the metal and sulfide phases and indirectly using I-129/Xe-129 in silicate and sulfide inclusions.

Spectroscopic evidence for organic diacid complexation with dissolved silica in aqueous systems—I. Oxalic acid

USGS Publications Warehouse

Marley, N.A.; Bennett, P.; Janecky, D.R.; Gaffney, J.S.

1989-01-01

Increased solubility of quartz and mobilization in contaminated groundwater due to the complexation with dissolved organic acids has been recently proposed [Bennett and Siegel, Nature326, 684–686 (1987)]. Using laser Raman and Fourier transform infrared spectroscopies, we have examined mixed solutions of oxalic and silicic acids at near neutral pH in the tenth molar concentration ranges in an attempt to directly observe the proposed organo-silicate complexes.In both laser Raman and infrared spectra, product bands were observed that indicate an oxalate/silicic acid ester is being formed in the reaction. These data support the observation that organic diacids can lead to enhanced solubility of quartz in hydrogeological systems.

Relationships between CO 2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

DOE PAGES

Winnick, Matthew J.; Maher, Kate

2018-01-27

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profilesmore » under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2(y =kx n)where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.« less

Relationships between CO 2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winnick, Matthew J.; Maher, Kate

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profilesmore » under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2(y =kx n)where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.« less

Relationships between CO2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

NASA Astrophysics Data System (ADS)

Winnick, Matthew J.; Maher, Kate

2018-03-01

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. We test this theoretical scaling relationship against reactive transport simulations of chemical weathering profiles under open- and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO2 (y = kxn) where n is dependent on reaction stoichiometry and k is dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO2 at low values and approach open-system scaling at high pCO2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.

Ion-Doped Silicate Bioceramic Coating of Ti-Based Implant

PubMed Central

Mohammadi, Hossein; Sepantafar, Mohammadmajid

2016-01-01

Titanium and its alloy are known as important load-bearing biomaterials. The major drawbacks of these metals are fibrous formation and low corrosion rate after implantation. The surface modification of biomedical implants through various methods such as plasma spray improves their osseointegration and clinical lifetime. Different materials have been already used as coatings on biomedical implant, including calcium phosphates and bioglass. However, these materials have been reported to have limited clinical success. The excellent bioactivity of calcium silicate (Ca-Si) has been also regarded as coating material. However, their high degradation rate and low mechanical strength limit their further coating application. Trace element modification of (Ca-Si) bioceramics is a promising method, which improves their mechanical strength and chemical stability. In this review, the potential of trace element-modified silicate coatings on better bone formation of titanium implant is investigated. PMID:26979401

Natural occurrence and significance of fluids indicating high pressure and temperature

USGS Publications Warehouse

Roedder, E.

1981-01-01

Most natural minerals have formed from a fluid phase such as a silicate melt or a saline aqueous solution. Fluid inclusions are tiny volumes of such fluids that were trapped within the growing crystals. These inclusions can provide valuable but sometimes ambiguous data on the temperature, pressure, and composition of these fluids, many of which are not available from any other source. They also provide "visual autoclaves" in which it is possible to watch, through the microscope, the actual phase changes take place as the inclusions are heated. This paper reviews the methods of study and the results obtained, mainly on inclusions formed from highly concentrated solutions, at temperatures ???500??C. Many such fluids have formed as a result of immiscibility with silicate melt in igneous or high-temperature metamorphic rocks. These include fluids consisting of CO2, H2O, or hydrosaline melts that were <50% H2O. From the fluid inclusion evidence it is clear that a boiling, very hot, very saline fluid was present during the formation of most of the porphyry copper deposits in the world. Similarly, from the inclusion evidence it is clear that early (common) pegmatites formed from essentially silicate melts and that the late, rare-element-bearing and chamber-type pegmatites formed from a hydrosaline melt or a more dilute water solution. The evidence on whether this change in composition from early to late solutions was generally continuous or involved immiscibility is not as clear. ?? 1981.

Estimation of weathering rates and CO2 drawdown based on solute load: Significance of granulites and gneisses dominated weathering in the Kaveri River basin, Southern India

NASA Astrophysics Data System (ADS)

Pattanaik, J. K.; Balakrishnan, S.; Bhutani, R.; Singh, P.

2013-11-01

The solute load of the Kaveri River (South India) and its tributaries draining diverse Precambrian terrains during pre-monsoon and monsoon periods was determined. Using average annual flow, total drainage area and atmospheric input corrected major ion concentrations of these rivers chemical weathering rates, annual fluxes of different ionic species to the ocean and CO2 consumption rates were estimated. Bicarbonate is the most dominant ion (27-79% of anion budget) in all the river samples collected during monsoon period followed by Ca2+, whereas, in case of pre-monsoon water samples Na+ is the most dominant ion (in meq/l). Two approaches were adopted to estimate silicate and carbonate weathering rates in the drainage basin. At Musuri silicate weathering rate (SWR) is 9.44 ± 0.29 tons/km2/a and carbonate weathering rate (CWR) is 1.46 ± 0.16 tons/km2/a. More than 90% of the total ionic budget is derived from weathering of silicates in the Kaveri basin. CO2 consumption rate in the basin for silicate weathering FCO2sil is 3.83 ± 0.12 × 105 mol/km2/a (upper limit), which is comparable with the Himalayan rivers at upper reaches. For carbonate weathering (FCO2carb) CO2 consumption rate is 0.15 ± 0.03 × 105 mol/km2/a in the Kaveri basin. The lower limit of CO2 consumption rate corrected for H2SO4 during silicate and carbonate weathering is FCO2sil is 3.24 × 1005 mol/km2/a and FCO2carb 0.13 × 105 mol/km2/a respectively. CO2 sequestered due to silicate weathering in the Kaveri basin is 25.41 (±0.82) × 109 mol/a which represents 0.21 (±0.01)% of global CO2 drawdown. This may be due to tropical climatic condition, high rainfall during both SW and NE monsoon and predominance of silicate rocks in the Kaveri basin.

Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production

PubMed Central

Rau, Greg H.; Carroll, Susan A.; Bourcier, William L.; Singleton, Michael J.; Smith, Megan M.; Aines, Roger D.

2013-01-01

We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 105-fold increase in OH− concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH− initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification. PMID:23729814

To probe a core

NASA Astrophysics Data System (ADS)

2017-04-01

Hidden under many kilometres of silicate mantle material, the cores of Earth and other planets are hard to investigate. The Psyche spacecraft, designed to visit a metal body that may be a core stripped of its mantle, could bring a close-up view.

The composition of Earth's core from equations of state, metal-silicate partitioning, and core formation modeling

NASA Astrophysics Data System (ADS)

Fischer, Rebecca; Campbell, Andrew; Ciesla, Fred

2016-04-01

The Earth accreted in a series of increasingly large and violent collisions. Simultaneously, the metallic core segregated from the silicate mantle, acquiring its modern composition through high pressure (P), high temperature (T) partitioning reactions. Here we present a model that couples these aspects of early planetary evolution, building on recent accretion simulations and metal-silicate partitioning experiments, constrained by density measurements of Fe-rich alloys. Previously, the equations of state of FeO, Fe-9Si, Fe-16Si, and FeSi were measured to megabar pressures and several thousand K using a laser-heated diamond anvil cell. With these equations of state, we determined that the core's density can be reproduced through the addition of 11.3 +/- 0.6 wt% silicon or 8.1 +/- 1.1 wt% oxygen to an Fe-Ni alloy (Fischer et al., 2011, 2014). Metal-silicate partitioning experiments of Ni, Co, V, Cr, Si, and O have been performed in a diamond anvil cell to 100 GPa and 5700 K, allowing the effects of P, T, and composition on the partitioning behaviors of these elements to be parameterized (Fischer et al., 2015; Siebert et al., 2012). Here we apply those experimental results to model Earth's core formation, using N-body simulations to describe the delivery, masses, and original locations of planetary building blocks (Fischer and Ciesla, 2014). As planets accrete, their core and mantle compositions are modified by high P-T reactions with each collision (Rubie et al., 2011). For partial equilibration of the mantle at 55% of the evolving core-mantle boundary pressure and the liquidus temperature, we find that the core contains 5.4 wt% Si and 1.9 wt% O. This composition is consistent with the seismologically-inferred density of Earth's core, based on comparisons to our equations of state, and indicate that the core cannot contain more than ~2 wt% S or C. Earth analogues experience 1.2 +/- 0.2 log units of oxidation during accretion, due to both the effects of high P-T partitioning and the temporal evolution of the Earth's feeding zone. This modeling can reveal the relative importance of various accretion and differentiation processes to core composition, highlighting targets for future experimental and numerical studies.

The Influence of Oxygen and Sulfur on Uranium Partitioning Into the Core

NASA Astrophysics Data System (ADS)

Moore, R. D., Jr.; Van Orman, J. A.; Hauck, S. A., II

2017-12-01

Uranium, along with K and Th, may provide substantial long-term heating in planetary cores, depending on the magnitude of their partitioning into the metal during differentiation. In general, non-metallic light elements are known to have a large influence on the partitioning of trace elements, and the presence of sulfur is known to enhance the partitioning of uranium into the metal. Data from the steelmaking literature indicate that oxygen also enhances the solubility of oxygen in liquid iron alloys. Here we present experimental data on the partitioning of U between immiscible liquids in the Fe-S-O system, and use these data along with published metal-silicate partitioning data to calibrate a quantitative activity model for U in the metal. We also determined partition coefficients for Th, K, Nb, Nd, Sm, and Yb, but were unable to fully constrain activity models for these elements with available data. A Monte Carlo fitting routine was used to calculate U-S, U-O, and U-S-O interaction coefficients, and their associated uncertainties. We find that the combined interaction of uranium with sulfur and oxygen is predominant, with S and O together enhancing the solubility of uranium to a far greater degree than either element in isolation. This suggests that uranium complexes with sulfite or sulfate species in the metal. For a model Mars core composition containing 14 at% S and 5 at% O, the metal/silicate partition coefficient for U is predicted to be an order of magnitude larger than for a pure Fe-Ni core.

Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

NASA Astrophysics Data System (ADS)

Verdolotti, Letizia; Liguori, Barbara; Capasso, Ilaria; Caputo, Domenico; Lavorgna, Marino; Iannace, Salvatore

2014-05-01

Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a "meringue" type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (˜500 Kg/m3) with good cellular structure and mechanical properties were obtained by combining the "meringue" approach with the use of the chemical blowing agent based on Si.

L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

2008-01-01

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

Application of X-ray photoelectron spectroscopy to the analysis of stainless-steel welding aerosols

NASA Astrophysics Data System (ADS)

Tandon, R. K.; Payling, R.; Chenhall, B. E.; Crisp, P. T.; Ellis, J.; Baker, R. S.

1985-02-01

Aerosol particles ("fume") from manual metal arc welding of stainless steel with E316L-16 electrodes were analysed by X-ray photoelectron spectroscopy. The inherent complexity of the particles required the use of a wide range of experimental techniques. These included IR spectrophotometry, TGA/DTA, XRF, XRD, AAS and electron microprobe analysis. The surface of the fume particles comprised ≈ 50 at% NaF and KF, ≈ 8 at.% soluble (probably K) chromate, ≈ 30 at% SiO 2 and several at.% transition-metal oxides, hydroxides or silicates. The fluorides and chromates were removed by washing to reveal a surface which was predominantly SiO 2 (≈ 60 at%) with the remainder comprising of transition-metal oxides, silicates and fluorides. Approximately 6 at% F remained on the surface of the water-washed particles, presumably as transition-metal fluoro-complexes. The water-soluble fraction of the fume contained K +, Na +, F - and CrO 2-4 ions in the mole ratio 5:5:4:3. When aerosol particles are deposited in lung tissues, water-soluble constituents would be expected to dissolve rapidly. In view of the suspected carcinogenicity of stainless steel welding fume, a bio-medical study of the combined effects of F - and CrO 2-4 ions on lung tissue is warranted.

Sol-gel method for encapsulating molecules

DOEpatents

Brinker, C. Jeffrey; Ashley, Carol S.; Bhatia, Rimple; Singh, Anup K.

2002-01-01

A method for encapsulating organic molecules, and in particular, biomolecules using sol-gel chemistry. A silica sol is prepared from an aqueous alkali metal silicate solution, such as a mixture of silicon dioxide and sodium or potassium oxide in water. The pH is adjusted to a suitably low value to stabilize the sol by minimizing the rate of siloxane condensation, thereby allowing storage stability of the sol prior to gelation. The organic molecules, generally in solution, is then added with the organic molecules being encapsulated in the sol matrix. After aging, either a thin film can be prepared or a gel can be formed with the encapsulated molecules. Depending upon the acid used, pH, and other processing conditions, the gelation time can be from one minute up to several days. In the method of the present invention, no alcohols are generated as by-products during the sol-gel and encapsulation steps. The organic molecules can be added at any desired pH value, where the pH value is generally chosen to achieve the desired reactivity of the organic molecules. The method of the present invention thereby presents a sufficiently mild encapsulation method to retain a significant portion of the activity of the biomolecules, compared with the activity of the biomolecules in free solution.

Compositional effects on Si–OH bond length in hydrous silicates with implications for trends in the SiOH acidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zarubin, Dmitri P., E-mail: dmitri.zarubin@mtu-net.ru

2014-04-01

Theoretical calculations of the structure and Brønsted acidity of SiOH groups in silica clusters have never addressed the question if these vary with the degree of SiOH deprotonation. In this connection, a statistical analysis is presented of Si–OH bond lengths in crystalline hydrogen silicates with well-determined structures with a special emphasis placed on effects of the silicate composition. It is found that among hydrogen silicates of large cations with low charges the Si–OH bonds are always longer than terminal Si–O bonds in the same anion and correlate in length with the anionic charge per tetrahedron. The findings are explained bymore » steric limitations on charge balancing at oxygen atoms by hydrogen bonds and/or cations. It is suggested that similar limitations and imbalances may underlie the well-known trends in the Brønsted acidity of silicic acids and silicas in aqueous media: decreased acidity with increased SiOH deprotonation and increased acidity with increased tetrahedra connectivity. - Graphical abstract: Si–OH bonds in crystalline silicates lengthen with the anionic charge per tetrahedron, which is in parallel with the well-known trend of decreased acidity of silicic acids and silicas in solution with increased degree of deprotonation. - Highlights: • Si–OH bonds in alkali hydrogen silicates are always longer than terminal Si–O bonds. • Si–OH bonds in silicates lengthen with the anionic charge per tetrahedron. • The Si–OH bond elongation results from inherent underbonding of terminal O atoms. • The longer the Si–OH bond, the less acidic the OH group is.« less

Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

2016-07-22

Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruentmore » dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.« less

Structural and elemental analysis of bottom sediments from the Paraíba do Sul River (SE, Brazil) by analytical microscopy

NASA Astrophysics Data System (ADS)

Miguens, Flávio Costa; Oliveira, Martha Lima de; Ferreira, Amanda de Oliveira; Barbosa, Laís Rodrigues; Melo, Edésio José Tenório de; Carvalho, Carlos Eduardo Veiga de

2016-03-01

The Paraíba do Sul River (PSR) is a medium-sized river that flows through the Minas Gerais, São Paulo and Rio de Janeiro Brazilian states the three most developed states in Brazil. Industrial parks and cities have historically been established along the river basin. The waters of PSR are used in agriculture, industry and human consumption of over 20 million people, including Rio de Janeiro City. Furthermore, the river receives effluent from these activities: agricultural runoff, industrial waste, and domestic sewage. Therefore, PSR has been considered polluted, particularly by heavy metals. In order to assess heavy metals in bottom sediments grains of the PSR, to infer their elemental composition, and to characterize individual sediment grains morphology, a non-destructive methodology - X-ray microanalyses (Scanning Electron Microscope coupled to Energy Dispersive X-rays Spectrometer/SEM/EDS) - was used. Heavy metals - Cr, Mn, Ni, Cu, Zn, Zr, Ag, Ba, Au, La, Ce, Nd, Th, Y, Sn, Os and Pb - were detected by SEM/EDS in bottom sediment grains from PSR, predominantly in grains with equivalent diameter ≤10 μm. They occurred as silicates, oxides (hydro-oxides), sulfides, carbonates, sulfates, phosphates and chlorides. All detected heavy metals occurred as, at least, one kind of soluble metal compound, mainly due to ionic exchange from silicates, with the exception of Ag, which was chloride, sulfate or metallic as Os, Au and Pb. These results corroborate heavy metal PSR pollution and food chain risk, considering that near-shore continental shelf is free of heavy metals contamination. Our results also give support to the hypothesis that the PSR estuary can act as a trap for these elements.

Aqueous Silicate Polymers: An Alternative to `Supercritical' Fluids as Transport Agents in Subduction Zones

NASA Astrophysics Data System (ADS)

Mannig, C. E.

2005-12-01

The chemistry of subduction-zone fluids is complicated by melt-vapor miscibility and the existence of critical end-points in rock-H2O systems. It is commonly assumed that fluids in subduction zones attain properties intermediate in composition between hydrous silicate liquid and H2O, and that such fluids possess enhanced material transport capabilities. However, the relevance of supercritical, intermediate fluids to subduction zones presents four problems. (1) Albite-H2O is typically used as an analogue system, but the favorable position of its critical curve is not representative; critical curves for polymineralic subduction-zone lithologies lie at substantially higher P. (2) Even if albite-H2O is relevant, jadeite may interfere because of its different solubility and the positive clapeyron slope of its solidus, which points to liquid-structure changes that could cause reappearance of the liquid+vapor field. (3) Critical curves are features of very H2O-rich compositions; low-porosity, H2O-poor natural systems will coexist with intermediate fluids only over a narrow PT interval. (4) Intermediate fluids are expected only over short length scales because their migration will likely result in compositional shifts via reaction and mineral precipitation in the mantle wedge. Although supercritical, intermediate fluids are probably relatively unimportant in subduction zones, they reflect a chemical process that may hold the key to understanding high- P mass transfer. Miscibility in melt-vapor systems is a consequence of polymerization of dissolved components, primarily Si ± Al, Na and Ca. This behavior yields, e.g., aqueous Si-Si, Si-Al, Si-Na-Al, and Si-Ca oxide dimers and other multimers of varying stoichiometry (silicate polymers), even in subcritical, dilute, H2O-rich vapor. Silicate polymers in subcritical aqueous solutions have been inferred from high- P mineral-solubility experiments. The abundance of these species at high P shows that the chemistry of aqueous fluids in subduction-zones differs fundamentally from the more familiar ionic solutions of the upper crust. This has important consequences for minor element transport. Measurements of Fe, phosphorous and Ti solubility reveal that dissolved concentrations rise with increased aqueous albite content at fixed P and T, with maximum enhancements exceeding 10X at melt saturation. Subcritical silicate polymerization thus permits transport of low solubility components via their substitution into sites on aqueous multimers constructed of "polymer formers" such as Na, Al, and Si, even in dilute solutions. The partitioning of elements between the bulk fluid, the polymer network, and the rock matrix likely controls the overall compositional evolution of subduction-zone fluids. Because they form over a wider PT and bulk X range, subcritical silicate polymers in dilute solutions are likely responsible for more mass transfer in subduction zones than intermediate, supercritical fluids.

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K. M.; Danielson, L. R.

2015-01-01

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented.

Investigations on Heat Treatment of a High-Speed Steel Roll

NASA Astrophysics Data System (ADS)

Fu, Hanguang; Qu, Yinhu; Xing, Jiandong; Zhi, Xiaohui; Jiang, Zhiqiang; Li, Mingwei; Zhang, Yi

2008-08-01

High-carbon high-speed steels (HSS) are very abrasion-resistant materials primarily due to their high hardness MC-type carbide and high hardness martensitic matrix. The effects of quenching and tempering treatment on the microstructure, mechanical properties, and abrasion resistance of centrifugal casting high-carbon HSS roll were studied. Different microstructures and mechanical properties were obtained after the quenching and tempering temperatures of HSS roll were changed. With air-cooling and sodium silicate solution cooling, when the austenitizing temperature reaches 1273 K, the metallic matrix all transforms into the martensite. Afterwards, the eutectic carbides dissolve into the metallic matrix and their continuous network distribution changes into the broken network. The second hardening temperature of high-carbon HSS roll is around 793 K. No significant changes in tensile strength and elongation percentage are observed unless the tempering temperature is beyond 753 K. The tensile strength increases obviously and the elongation percentage decreases slightly beyond 753 K. However, the tensile strength decreases and the elongation percentage increases when the tempering temperature exceeds 813 K. When the tempering temperature excels 773 K, the impact toughness has a slight decrease. Tempering at 793-813 K, high-carbon HSS roll presents excellent abrasion resistance.

Calc-silicate mineralization in active geothermal systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bird, D.K.; Schiffman, P.; Elders, W.A.

The detailed study of calc-silicate mineral zones and coexisting phase relations in the Cerro Prieto geothermal system were used as examples for thermodynamic evaluation of phase relations among minerals of variable composition and to calculate the chemical characteristics of hydrothermal solutions compatible with the observed calc-silicate assemblages. In general there is a close correlation between calculated and observed fluid compositions. Calculated fugacities of O{sub 2} at about 320{degrees}C in the Cerro Prieto geothermal system are about five orders of magnitude less than that at the nearby Salton Sea geothermal system. This observation is consistent with the occurrence of Fe{sup 3+}more » rich epidotes in the latter system and the presence of prehnite at Cerro Prieto.« less

The solubility of gold in silicate melts: First results

NASA Technical Reports Server (NTRS)

Borisov, A.; Palme, H.; Spettel, B.

1993-01-01

The effects of oxygen fugacity and temperature on the solubility of Au in silicate melts were determined. Pd-Au alloys were equilibrated with silicate of anorthite-diopside eutectic composition at different T-fO2 conditions. The behavior of Au was found to be similar to that of Pd reported recently. Au solubilities for alloys with 30 to 40 at. percent Au decrease at 1400 C from 12 ppm in air to 160 ppb at a log fO2 = -8.7. The slope of the log(Me-solubility) vs. log(fO2) curve is close to 1/4 for Au and the simultaneously determined Pd suggesting a formal valence of Au and Pd of 1+. Near the IW buffer Pd and Au solubilities become even less dependent on fO2 perhaps reflecting the presence of some metallic Au and Pd.

Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

USGS Publications Warehouse

Wanty, Richard B.; De Giudici, G.; Onnis, P.; Rutherford, D.; Kimball, B.A.; Podda, F.; Cidu, R.; Lattanzi, P.; Medas, D.

2013-01-01

n southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals remain low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silicate.

Experimental modeling of the interaction of subducted carbonates and sulfur with mantle silicates

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Sobolev, N. V.

2016-09-01

Experimental studies in the system Fe,Ni-olivine-carbonate-S ( P = 6.3 GPa, T = 1050-1550°C, t = 40-60 h) aimed at modeling of the interaction of subducted carbonates and sulfur with rocks of the silicate mantle and at investigation of the likely mechanism of the formation of mantle sulfides were performed. It is shown that an association of olivine + orthopyroxene + magnesite + pyrite coexisting with a sulfur melt/fluid with dissolved Fe, Ni, and O is formed at T ≤ 1250°C. An association of low-Fe olivine, orthopyroxene, and magnesite and two immiscible melts of the carbonate and S-Fe-Ni-O compositions are formed at T ≥ 1350°C. It is shown that the reduced S-bearing fluids may transform silicates and carbonates, extract metals from the solid-phase matrix, and provide conditions for generation of sulfide melts.

Production of magnesium metal

DOEpatents

Blencoe, James G [Harriman, TN; Anovitz, Lawrence M [Knoxville, TN; Palmer, Donald A [Oliver Springs, TN; Beard, James S [Martinsville, VA

2012-04-10

A process of producing magnesium metal includes providing magnesium carbonate, and reacting the magnesium carbonate to produce a magnesium-containing compound and carbon dioxide. The magnesium-containing compound is reacted to produce magnesium metal. The carbon dioxide is used as a reactant in a second process. In another embodiment of the process, a magnesium silicate is reacted with a caustic material to produce magnesium hydroxide. The magnesium hydroxide is reacted with a source of carbon dioxide to produce magnesium carbonate. The magnesium carbonate is reacted to produce a magnesium-containing compound and carbon dioxide. The magnesium-containing compound is reacted to produce magnesium metal. The invention also relates to the magnesium metal produced by the processes described herein.

Highly spatially resolved structural and optical investigation of Bi nanoparticles in Y-Er disilicate thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scarangella, A.; Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia 64, 95123 Catania; Amiard, G.

2016-08-08

Er-containing silicon compatible materials have been widely used as infrared emitters for microphotonics application. In this field, the additional introduction of a proper sensitizer permits to increase the Er excitation cross sections, thus increasing its optical efficiency. This work aims to investigate the influence of a post-transition metal, bismuth, on the optical properties of erbium-yttrium disilicate thin films synthesized by magnetron co-sputtering. After thermal treatments at 1000 °C in O{sub 2} or N{sub 2} environment, the presence of small precipitates, about 6 nm in diameter, was evidenced by transmission electron microscopy analyses. The spatially resolved chemical nature of the nanoparticles was discernedmore » in the Si and O rich environments by means of scanning transmission electron microscopy–energy dispersive X-ray and scanning transmission electron microscopy–electron energy loss spectroscopy analyses performed with nanometric resolution. In particular, metallic Bi nanoparticles were stabilized in the N{sub 2} environment, being strongly detrimental for the Er emission. A different scenario was instead observed in O{sub 2}, where the formation of Bi silicate nanoparticles was demonstrated with the support of photoluminescence excitation spectroscopy. In particular, a broad band peaked at 255 nm, correlated to the excitation band of Bi silicate nanoparticles, was identified in Er excitation spectrum. Thus Bi silicate clusters act as sensitizer for Er ions, permitting to improve Er emission up to 250 times with respect to the resonant condition. Moreover, the Er decay time increases in the presence of the Bi silicate nanoparticles that act as cages for Er ions. These last results permit to further increase Er optical efficiency in the infrared range, suggesting (Bi + Er)-Y disilicate as a good candidate for applications in microphotonics.« less

Paleomagnetism of a primitive achondrite parent body: The acapulcoite-lodranites

NASA Astrophysics Data System (ADS)

Schnepf, N. R.; Weiss, B. P.; Andrade Lima, E.; Fu, R. R.; Uehara, M.; Gattacceca, J.; Wang, H.; Suavet, C. R.

2014-12-01

Primitive achondrites are a recently recognized meteorite grouping with textures and compositions intermediate between unmelted meteorites (chondrites) and igneous meteorites (achondrites). Their existence demonstrates prima facie that some planetesimals only experienced partial rather than complete melting. We present the first paleomagnetic measurements of acapulcoite-lodranite meteorites to determine the existence and intensity of ancient magnetic fields on their parent body. Our paleomagnetic study tests the hypothesis that their parent body had an advecting metallic core, with the goal of providing one of the first geophysical constraints on its large-scale structure and the extent of interior differentiation. In particular, by analyzing samples whose petrologic textures require an origin on a partially differentiated body, we will be able to critically test a recent proposal that some achondrites and chondrite groups could have originated on a single body (Weiss and Elkins-Tanton 2013). We analyzed samples of the meteorites Acapulco and Lodran. Like other acapulcoites and lodranites, these meteorites are granular rocks containing large (~0.1-0.3 mm) kamacite and taenite grains along with similarly sized silicate crystals. Many silicate grains contain numerous fine (1-10 μm) FeNi metal inclusions. Our compositional measurements and rock magnetic data suggest that tetrataenite is rare or absent. Bulk paleomagnetic measurements were done on four mutually oriented bulk samples of Acapulco and one bulk sample of Lodran. Alternating field (AF) demagnetization revealed that the magnetization of the bulk samples is highly unstable, likely due to the large (~0.1-0.3 mm) interstitial kamacite grains throughout the samples. To overcome this challenge, we are analyzing individual ~0.2 mm mutually oriented silicate grains extracted using a wire saw micromill. Preliminary SQUID microscopy measurements of a Lodran silicate grain suggest magnetization stable to AF levels of at least 25-40 mT.

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Messenger, Scott R.; Nguyen, A.; Ito, M.; Rahman, Z.

2010-01-01

The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average 230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

Silicates Eroded under Simulated Martian Conditions Effectively Kill Bacteria—A Challenge for Life on Mars

PubMed Central

Bak, Ebbe N.; Larsen, Michael G.; Moeller, Ralf; Nissen, Silas B.; Jensen, Lasse R.; Nørnberg, Per; Jensen, Svend J. K.; Finster, Kai

2017-01-01

The habitability of Mars is determined by the physical and chemical environment. The effect of low water availability, temperature, low atmospheric pressure and strong UV radiation has been extensively studied in relation to the survival of microorganisms. In addition to these stress factors, it was recently found that silicates exposed to simulated saltation in a Mars-like atmosphere can lead to a production of reactive oxygen species. Here, we have investigated the stress effect induced by quartz and basalt abraded in Mars-like atmospheres by examining the survivability of the three microbial model organisms Pseudomonas putida, Bacillus subtilis, and Deinococcus radiodurans upon exposure to the abraded silicates. We found that abraded basalt that had not been in contact with oxygen after abrasion killed more than 99% of the vegetative cells while endospores were largely unaffected. Exposure of the basalt samples to oxygen after abrasion led to a significant reduction in the stress effect. Abraded quartz was generally less toxic than abraded basalt. We suggest that the stress effect of abraded silicates may be caused by a production of reactive oxygen species and enhanced by transition metal ions in the basalt leading to hydroxyl radicals through Fenton-like reactions. The low survivability of the usually highly resistant D. radiodurans indicates that the effect of abraded silicates, as is ubiquitous on the Martian surface, would limit the habitability of Mars as well as the risk of forward contamination. Furthermore, the reactivity of abraded silicates could have implications for future manned missions, although the lower effect of abraded silicates exposed to oxygen suggests that the effects would be reduced in human habitats. PMID:28955310

Silicates Eroded under Simulated Martian Conditions Effectively Kill Bacteria-A Challenge for Life on Mars.

PubMed

Bak, Ebbe N; Larsen, Michael G; Moeller, Ralf; Nissen, Silas B; Jensen, Lasse R; Nørnberg, Per; Jensen, Svend J K; Finster, Kai

2017-01-01

The habitability of Mars is determined by the physical and chemical environment. The effect of low water availability, temperature, low atmospheric pressure and strong UV radiation has been extensively studied in relation to the survival of microorganisms. In addition to these stress factors, it was recently found that silicates exposed to simulated saltation in a Mars-like atmosphere can lead to a production of reactive oxygen species. Here, we have investigated the stress effect induced by quartz and basalt abraded in Mars-like atmospheres by examining the survivability of the three microbial model organisms Pseudomonas putida, Bacillus subtilis , and Deinococcus radiodurans upon exposure to the abraded silicates. We found that abraded basalt that had not been in contact with oxygen after abrasion killed more than 99% of the vegetative cells while endospores were largely unaffected. Exposure of the basalt samples to oxygen after abrasion led to a significant reduction in the stress effect. Abraded quartz was generally less toxic than abraded basalt. We suggest that the stress effect of abraded silicates may be caused by a production of reactive oxygen species and enhanced by transition metal ions in the basalt leading to hydroxyl radicals through Fenton-like reactions. The low survivability of the usually highly resistant D. radiodurans indicates that the effect of abraded silicates, as is ubiquitous on the Martian surface, would limit the habitability of Mars as well as the risk of forward contamination. Furthermore, the reactivity of abraded silicates could have implications for future manned missions, although the lower effect of abraded silicates exposed to oxygen suggests that the effects would be reduced in human habitats.

Determination of 17O-excess of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW).

PubMed

Tanaka, Ryoji; Nakamura, Eizo

2013-01-30

Oxygen triple isotope compositions give key information for understanding physical processes during isotopic fractionation between the geo-, hydro-, bio-, and atmosphere. For detailed discussion of these topics, it is necessary to determine precise (17)O-excess values of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW). Water was fluorinated in an electrically heated Ni-metal tube into which water and BrF(5) were loaded for the quantitative extraction of oxygen. Silicate/oxide minerals were fluorinated by heating with a CO(2) laser in an atmosphere of BrF(5). The extracted oxygen was purified and isotope ratios of the oxygen triple isotope compositions were determined using a Finnigan MAT253 isotope ratio mass spectrometer. The oxygen triple isotope compositions of meteoric water and terrestrial silicate/oxide minerals fall on statistically distinguishable fractionation lines, defined as [ln(δ(17)O + 1) = λln(δ(18) O + 1) + Δ], where λ and Δ correspond to the slope and intercept, respectively. The fractionation line for meteoric water has λ = 0.5285 ± 0.0005 and Δ = 0.03 ± 0.02‰ and for terrestrial silicate/oxide minerals has λ = 0.5270 ± 0.0005 and Δ = -0.070 ± 0.005‰, at the 95% confidence limit. All the analyzed terrestrial silicate/oxide minerals including internationally accepted reference materials (NBS-28, UWG-2, and San Carlos olivine) have a negative (17)O-excess with respect to VSMOW. We propose that it is necessary to specify if the determined δ(17)O values of terrestrial and extraterrestrial samples are expressed as the difference from VSMOW or the terrestrial silicate mineral-corrected value. Copyright © 2012 John Wiley & Sons, Ltd.

Hydrogeochemistry and microbiology of mine drainage: An update

USGS Publications Warehouse

Nordstrom, D. Kirk; Blowes, D.W; Ptacek, C.J.

2015-01-01

The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality.

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2010-01-01

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Thermochemistry of dense hydrous magnesium silicates

NASA Technical Reports Server (NTRS)

Bose, Kunal; Burnley, Pamela; Navrotsky, Alexandra

1994-01-01

Recent experimental investigations under mantle conditions have identified a suite of dense hydrous magnesium silicate (DHMS) phases that could be conduits to transport water to at least the 660 km discontinuity via mature, relatively cold, subducting slabs. Water released from successive dehydration of these phases during subduction could be responsible for deep focus earthquakes, mantle metasomatism and a host of other physico-chemical processes central to our understanding of the earth's deep interior. In order to construct a thermodynamic data base that can delineate and predict the stability ranges for DHMS phases, reliable thermochemical and thermophysical data are required. One of the major obstacles in calorimetric studies of phases synthesized under high pressure conditions has been limitation due to the small (less than 5 mg) sample mass. Our refinement of calorimeter techniques now allow precise determination of enthalpies of solution of less than 5 mg samples of hydrous magnesium silicates. For example, high temperature solution calorimetry of natural talc (Mg(0.99) Fe(0.01)Si4O10(OH)2), periclase (MgO) and quartz (SiO2) yield enthalpies of drop solution at 1044 K to be 592.2 (2.2), 52.01 (0.12) and 45.76 (0.4) kJ/mol respectively. The corresponding enthalpy of formation from oxides at 298 K for talc is minus 5908.2 kJ/mol agreeing within 0.1 percent to literature values.

Single-Crystal Material on Non-Single-Crystalline Substrate

DTIC Science & Technology

1999-02-01

point frit or solder glass can be deposited on a surface and bonded to a second surface using pressure and temperature. A sodium silicate material...interface. A metal or silicide at the bonding interface may be advantageous fQr electrical current conduction across the interface. 10 Applications...substrate, or a silicide or metal to aid bonding and vertical electrical current conduction. In some cases, it is difficult to polish the non- single

The mineralogy of ordinary chondrites and implications for asteroid spectrophotometry

NASA Technical Reports Server (NTRS)

Mcsween, Harry Y., Jr.; Bennett, Marvin E., III; Jarosewich, Eugene

1991-01-01

Published data from bulk chemical analyses of 94 ordinary chondrites are compiled in a table of normative mineralogy and discussed in detail. Significant variations in olivine, pyroxene, and metal abundance ratios are found within each chondrite class and attributed to redox processes superimposed on initial differences in metal/silicate ratios. The use of the diagrams constructed here to predict the mineralogic characteristics of asteroids on the basis of spectrophotometric observations is suggested.

Metal/silicate partitioning of Pt and the origin of the "late veneer"

NASA Astrophysics Data System (ADS)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

Highly siderophile elements (HSEs) are perfect tools for investigating core forming processes in planetary bodies due to their Fe-loving (siderophile) geochemical behavior. Tremendous scientific effort was invested into this field during the past 10 years - mostly in 1 atm experiments. However, little is known about their high-pressure geochemistry and partitioning behavior between core and mantle forming phases. This knowledge is essential to distinguish between equilibrium (Magma Ocean) and non-equilibrium (heterogeneous accretion, late veneer) models for the accretion history for the early Earth. We therefore chose to investigate the partitioning behavior of Pt up to pressures of 140 kbar (14 GPa) and temperatures of 1950°C. The used melt composition - identical to melt systems used in 1 atm experiments - is the eutectic composition of Anorthite-Diopside (AnDi), a pseudo-basalt. A series of runs were performed which were internaly buffered by the piston cylinder apparatus, and were followed by duplicate experiments buffered in the AnDi-C-CO2 system. These experiments constitute reversals since they approach equilibrium from an initially higher and lower Pt solubility (8 ppm in the non-buffered runs, and essentially Pt free in the buffered runs). Experimental charges were encapsulated in Pt capsules which served as source for Pt. Experiments up to 20 kbar were performed in a Quickpress piston cylinder apparatus, while experiments at higher pressures were performed in a Walker-type (Tucson, AZ) and a Kawai-type (Misasa, Japan) multi anvil apparatus. Time series experiments were performed in piston-cylinder runs to determine minimum run durations for the achievement of equilibrium, and to guarantee high-quality partitioning data. 6 hours was found to be sufficient to obtain equilibrium. In practice, all experiments exceeded 12 hours to assure equilibrium. In a second set of runs the temperature dependence of the partitioning behavior of Pt was investigated between the melting point of the 1 atm, AnDi system and the melting point of the Pt capsule material. Over 150 piston cylinder and 12 multi anvil experiments have been performed. Pt solubility is only slightly dependent on temperature, decreasing between 1800 and 1400°C by less than an order of magnitude. In consequence, the partitioning behavior of Pt is mostly determined by its oxygen fugacity dependence, which has only been determined in 1 atm experiments. At 10 kbar, metal/silicate partition coefficients (D's) decrease by about 3 orders of magnitude. The reason for this is not understood, but might be attributed to a first order phase transition as found for, e.g., SiO2 or H2O. Above 10 kbar any increase in pressure does not lead to any further significant decrease in partition coefficients. Solubilities stay roughly constant up to 140 kbar. Abundances of moderately siderophile elements were possibly established by metal/silicate equilibrium in a magma ocean. These results for Pt suggest that the abundances of HSEs were most probably established by the accretion of a chondritic veneer following core formation, as metal/silicate partition coefficients are too high to be consistent with metal/silicate equilibrium in a magma ocean.

Testing the Late-Veneer hypothesis with selenium isotopes

NASA Astrophysics Data System (ADS)

Labidi, J.; Koenig, S.; Bennett, N.; Kurzawa, T.; Aierken, E.; Shahar, A.; Schoenberg, R.

2016-12-01

Selenium (Se) is a siderophile element displaying an excess abundance in Earth's mantle compared to experimental predictions [1], which may be attributed to the Late-Veneer. As Se is also volatile, testing the late-veneer addition of Se can constrain the origin of other volatile elements on Earth. Here we combine high-precision Se isotope measurements of metal-silicate partitioning experiments and chondrites to assess whether planetary differentiation could leave a measurable Se isotopic signature on planetary mantles. We performed Se isotopic measurements of 5 metal-silicate partitioning experiments and 20 chondrites of all major classes. Experiments were conducted at 1 GPa and 1650 C for 1 to 4 hours using the piston-cylinder apparatus at Carnegie's Geophysical Laboratory. After wet chemistry, data were obtained on a ThermoFisher Scientific™ NeptunePlus MC-ICP-MS at the University of Tübingen with a 74Se/77Se double spike technique. δ82/76Se values are given relative to NIST SRM-3149 and the external reproducibility calculated from duplicate meteorite analyses is ≤ 0.1‰ (2 s.d.). Chondrites vary over a 0.8‰ range of δ82/76Se values. CIs and CMs show evidence for heavier 82Se/76Se ratios, likely due to mixing processes in the proto-planetary nebula. When these isotopically heavier meteorites are excluded, remaining chondrites have δ82/76Se values varying over a 0.3‰ range, within uncertainty of previous results [2]. We suggest that these chondrites may be used to estimate a δ82/76Se value of bulk planets. At the conditions of our experiments, the partition coefficients for Se log Dmetal-silicate range from 0.7±0.1 to 1.9±0.1, consistent with previous work [1]. A small but resolvable Se isotopic fractionation was observed: 82Se/76Se ratios were enriched by ≤ 0.5‰ in the silicates relative to the metals. Thus, given current uncertainties for Se isotopic measurements, marginal differences between planetary mantles and chondrites may be resolved. [1] Rose-Weston et al. 2009, GCA, 73(15), 4598-4615. [2] Vollstaedt et al. 2016, 450, 372-380.

The Effect of Pressure on Iron Speciation in Silicate Melts at a Fixed Oxygen Fugacity: The Possibility of a Redox Profile Through a Terrestrial Magma Ocean

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.

2017-12-01

As terrestrial planets accreted, mantle silicates equilibrated with core-forming metallic iron, which would have imposed a mantle oxygen fugacity below the iron-wüstite oxygen buffer. Throughout Earth's history, however, the oxygen fugacity of at least the accessible portions of the upper mantle has been 4-5 orders of magnitude higher. The process that caused the rapid increase in the redox state of the mantle soon after core formation is unclear. Here we test the possibility that pressure stabilises ferric iron in silicate melts, as has been observed in silicate minerals. A deep magma ocean, which would have likely existed towards the end of accretion, could then develop a gradient in oxygen fugacity for a fixed ferric-ferrous ratio as a result of pressure. We have equilibrated an andesitic melt with a Ru-RuO2 buffer in a multianvil press between 5 and 24 GPa. Further experiments were performed on the same melt in equilibrium with iron metal. The recovered melts were then analysed using Mössbauer spectroscopy to determine the ferric/ferrous ratio. The results show that for the Ru-RuO2 buffer at lower pressures, the ferric iron content decreases with pressure, due to a positive volume change of the reaction FeO + 1/4O2 = FeO1.5. Ferric iron content also appears to be sensitive to water content at lower pressures. However, above 15 GPa this trend apparently reverses and the ferric iron content increases with pressure. This reversal in pressure dependence would drive the oxygen fugacity of a deep magma ocean with a fixed ferric/ferrous ratio down with increasing depth. This would create a redox gradient, where the magma ocean could potentially be in equilibrium with metallic iron at its base but more oxidised in its shallower regions. Crystallisation of this magma ocean could render an upper mantle oxygen fugacity similar to that in the Earth's accessible mantle today.

The role of surface chemical analysis in a study to select replacement processes for TCA vapor degreasing

NASA Technical Reports Server (NTRS)

Lesley, Michael W.; Davis, Lawrence E.; Moulder, John F.; Carlson, Brad A.

1995-01-01

The role of surface-sensitive chemical analysis (ESCA, AES, and SIMS) in a study to select a process to replace 1, 1, 1-trichloroethane (TCA) vapor degreasing as a steel and aluminum bonding surface preparation method is described. The effort was primarily concerned with spray-in-air cleaning processes involving aqueous alkaline and semi-aqueous cleaners and a contamination sensitive epoxy-to-metal bondline. While all five cleaners tested produced bonding strength results equal to or better than those produced by vapor degreasing, the aqueous alkaline cleaners yielded results which were superior to those produced by the semi-aqueous cleaners. The main reason for the enhanced performance appears to be a silicate layer left behind by the aqueous alkaline cleaners. The silicate layer increases the polarity of the surface and enhances epoxy-to-metal bonding. On the other hand, one of the semi-aqueous cleaners left a nonpolar carbonaceous residue which appeared to have a negative effect on epoxy-to-metal bonding. Differences in cleaning efficiency between cleaners/processes were also identified. These differences in surface chemistry, which were sufficient to affect bonding, were not detected by conventional chemical analysis techniques.

Iron (III) Matrix Effects on Mineralization and Immobilization of Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cynthia-May S. Gong; Tyler A. Sullens; Kenneth R. Czerwinski

2006-01-01

Abstract - A number of models for the Yucca Mountain Project nuclear waste repository use studies of actinide sorption onto well-defined iron hydroxide materials. In the case of a waste containment leak, however, a complex interaction between dissolved waste forms and failed containment vessel components can lead to immediate precipitation of migratory iron and uranyl in the silicate rich near-field environment. Use of the Fe(III) and UO22+ complexing agent acetohydroxamic acid (AHA) as a colorimetric agent for visible spectrophotometry is well-known. Using the second derivative of these spectra a distinct shift in iron complexation in the presence of silicate ismore » seen that is not seen with uranyl or alone. Silica also decreases the ability of uranyl and ferric solutions to absorb hydroxide, hastening precipitation. These ferric silicate precipitates are highly amorphous and soluble. Precipitates formed in the presence of uranyl below ~1 mol% exhibit lower solubility than precipitates from up to 50 mol % and of uranyl silicates alone.« less

Late Reduction Textures in Almahata Sitta Ureilite

NASA Technical Reports Server (NTRS)

Herrin, J. S.; Le, L.; Zolensky, M. E.; Ito, M.; Jenniskens, P.; Shaddad, M. H.

2009-01-01

The Almahata Sitta ureilite, derived from asteroid 2008 TC3, consists of many individual fragments recovered from the Nubian dessert strewn field [1]. Like most ureilites, it contains abundant carbon and exhibits examples of disequilibrium textures that record a late reduction event accompanied by rapid cooling (tens of degC/h) from high temperatures (1150-1300 C). Variations in Fe/Mg of silicate minerals are accompanied by variations in Fe/Mn, indicating loss of Fe into metal [2]. In coarser-grained fragments of Almahata Sitta, olivine exhibits irregular high mg# rims in contact with networks of interstitial metal 5- 20 microns in typical thickness. This is a common ureilite texture thought to be driven by the reaction of graphite to a CO gas phase and the concurrent reduction of FeO in olivine to Fe metal, with excess silica going primarily into pyroxene (2MgFeSiO4 + C approaches MgSiO4 + MgSiO3 + 2Fe + CO) [3, see also 4,5,6]. Other fragments of Almahata Sitta exhibit anomalous textures such as fine grain size, high porosity, and abundant graphite. Within these fragments pyroxene locally exhibits high-mg# rims in contact with metal and a discreet silica phase, suggesting that the reduction mechanism MgFeSi2O6 + C approaches MgSiO3 + Fe + SiO2 + CO. Metals in Almahata Sitta are particularly unaltered in comparison to ureilite finds. Variations in minor and trace element composition of this metal might partly result from localized dilution as iron is supplied by reduction of silicates.

Supported transition metal catalysts for para- to ortho-hydrogen conversion

NASA Technical Reports Server (NTRS)

Brooks, Christopher J.; Wang, Wei; Eyman, Darrell P.

1994-01-01

The main goal of this study was to develop and improve on existing catalysts for the conversion of ortho- to para-hydrogen. Starting with a commercially available Air Products nickel silicate, which had a beta value of 20, we were trying to synthesize catalysts that would be an improvement to AP. This was accomplished by preparing silicates with various metals as well as different preparation methods. We also prepared supported ruthenium catalysts by various techniques using several metal precursors to improve present technology. What was also found was that the activation conditions prior to catalytic testing was highly important for both the silicates and the supported ruthenium catalysts. While not the initial focus of the research, we made some interesting observations into the adsorption of H2 on ruthenium. This helped us to get a better understanding of how ortho- to para-H2 conversion takes place, and what features in a catalyst are important to optimize activity. Reactor design was the final area in which some interesting conclusions were drawn. As discussed earlier, the reactor catalyst bed must be constructed using straight 1/8 feet OD stainless steel tubing. It was determined that the use of 1/4 feet OD tubing caused two problems. First, the radius from the center of the bed to the wall was too great for thermal equilibrium. Since the reaction of ortho- to para-H2 is exothermic, the catalyst bed center was warmer than the edges. Second, the catalyst bed was too shallow using a 1/4 feet tube. This caused reactant blow-by which was thought to decrease the measured activity when the flow rate was increased. The 1/8 feet tube corrected both of these concerns.

Materials properties of hafnium and zirconium silicates: Metal interdiffusion and dopant penetration studies

NASA Astrophysics Data System (ADS)

Quevedo Lopez, Manuel Angel

Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050°C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixO y are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford Backscattering Spectroscopy (RBS), Heavy Ion RBS (HI-RBS), X-ray Photoelectron Spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM), and Time of Flight and Dynamic Secondary Ion Mass Spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixO y films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSi xOyNz films.

ToF-SIMS images and spectra of biomimetic calcium silicate-based cements after storage in solutions simulating the effects of human biological fluids

NASA Astrophysics Data System (ADS)

Torrisi, A.; Torrisi, V.; Tuccitto, N.; Gandolfi, M. G.; Prati, C.; Licciardello, A.

2010-01-01

ToF-SIMS images were obtained from a section of a tooth, obturated by means of a new calcium-silicate based cement (wTCF) after storage for 1 month in a saline solutions (DPBS), in order to simulate the body fluid effects on the obturation. Afterwards, ToF-SIMS spectra were obtained from model samples, prepared by using the same cement paste, after storage for 1 month and 8 months in two different saline solutions (DPBS and HBSS). ToF-SIMS spectra were also obtained from fluorine-free cement (wTC) samples after storage in HBSS for 1 month and 8 months and used for comparison. It was found that the composition of both the saline solution and the cement influenced the composition of the surface of disks and that longer is the storage greater are the differences. Segregation phenomena occur both on the cement obturation of the tooth and on the surface of the disks prepared by using the same cement. Indirect evidences of formation of new crystalline phases are supplied.

High-compactness coating grown by plasma electrolytic oxidation on AZ31 magnesium alloy in the solution of silicate-borax

NASA Astrophysics Data System (ADS)

Shen, M. J.; Wang, X. J.; Zhang, M. F.

2012-10-01

A ceramic coating was formed on the surface of AZ31 magnesium alloy by plasma electrolytic oxidation (PEO) in the silicate solution with and without borax doped. The composition, morphology, elements and roughness as well as mechanical property of the coating were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and reciprocal-sliding tribometer. The results show that the PEO coating is mainly composed of magnesia. When using borax dope, boron element is permeating into the coating and the boron containing phase exist in the form of amorphous. In addition, the microhardness and compactness of the PEO coating are improved significantly due to doped borax.

Nitrogen solubility in the deep mantle and the origin of Earth's primordial nitrogen budget

NASA Astrophysics Data System (ADS)

Yoshioka, Takahiro; Wiedenbeck, Michael; Shcheka, Svyatoslav; Keppler, Hans

2018-04-01

The solubility of nitrogen in the major minerals of the Earth's transition zone and lower mantle (wadsleyite, ringwoodite, bridgmanite, and Ca-silicate perovskite) coexisting with a reduced, nitrogen-rich fluid phase was measured. Experiments were carried out in multi-anvil presses at 14 to 24 GPa and 1100 to 1800 °C close to the Fe-FeO buffer. Starting materials were enriched in 15N and the nitrogen concentrations in run products were measured by secondary ion mass spectrometry. Observed nitrogen (15N) solubilities in wadsleyite and ringwoodite typically range from 10 to 250 μg/g and strongly increase with temperature. Nitrogen solubility in bridgmanite is about 20 μg/g, while Ca-silicate perovskite incorporates about 30 μg/g under comparable conditions. Partition coefficients of nitrogen derived from coexisting phases are DNwadsleyite/olivine = 5.1 ± 2.1, DNringwoodite/wadsleyite = 0.49 ± 0.29, and DNbridgmanite/ringwoodite = 0.24 (+ 0.30 / - 0.19). Nitrogen solubility in the solid, iron-rich metal phase coexisting with the silicates was also measured and reached a maximum of nearly 1 wt.% 15N at 23 GPa and 1400 °C. These data yield a partition coefficient of nitrogen between iron metal and bridgmanite of DNmetal/bridgmanite ∼ 98, implying that in a lower mantle containing about 1% of iron metal, about half of the nitrogen still resides in the silicates. The high nitrogen solubility in wadsleyite and ringwoodite may be responsible for the low nitrogen concentrations often observed in ultradeep diamonds from the transition zone. Overall, the solubility data suggest that the transition zone and the lower mantle have the capacity to store at least 33 times the mass of nitrogen presently residing in the atmosphere. By combining the nitrogen solubility data in minerals with data on nitrogen solubility in silicate melts, mineral/melt partition coefficients of nitrogen can be estimated, from which the behavior of nitrogen during magma ocean crystallization can be modeled. Such models show that if the magma ocean coexisted with a primordial atmosphere having a nitrogen partial pressure of just a few bars, several times the current atmospheric mass of nitrogen must have been trapped in the deep mantle. It is therefore plausible that the apparent depletion of nitrogen relative to other volatiles in the near-surface reservoirs reflects the storage of a larger reservoir of nitrogen in the solid Earth. Dynamic exchange between these reservoirs may have induced major fluctuations of bulk atmospheric pressure over Earth's history.

Microstructure and mechanical properties of stainless steel/calcium silicate composites manufactured by selective laser melting.

PubMed

Zheng, Zeng; Wang, Lianfeng; Jia, Min; Cheng, Lingyu; Yan, Biao

2017-02-01

Selective laser melting (SLM) is raised as one kind of additive manufacturing (AM) which is based on the discrete-stacking concept. This technique can fabricate advanced composites with desirable properties directly from 3D CAD data. In this research, 316L stainless steel (316L SS) and different fractions of calcium silicate (CaSiO 3 ) composites (weight fractions of calcium silicate are 0%, 5%,10% and 15%, respectively) were prepared by SLM technique with a purpose to develop biomedical metallic materials. The relative density, tensile, microhardness and elastic modulus of the composites were tested, their microstructures and fracture morphologies were observed using optical microscope (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the addition of CaSiO 3 particles influenced the microstructure and mechanical properties of specimens significantly. The CaSiO 3 precipitates from the overlap of adjacent tracks and became the origin of the defects. The tensile strength of specimens range 320-722MPa. The microhardness and elastic modulus are around 250HV and 215GPa respectively. These composites were ductile materials and the fracture mode of the composites was mixed mode of ductile and brittle fracture. The 316L SS/CaSiO 3 composites can be a potential biomedical metallic materials in the medical field. Copyright © 2016. Published by Elsevier B.V.

Polyamorphic Transformations in Fe-Ni-C Liquids: Implications for Chemical Evolution of Terrestrial Planets: Fe-Ni-C liquid structural change

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, Xiaojing; Chen, Bin; Wang, Jianwei

During the formation of the Earth's core, the segregation of metallic liquids from silicate mantle should have left behind evident geochemical imprints on both the mantle and the core. Some distinctive geochemical signatures of the mantle-derived rocks likely own their origin to the metal-silicate differentiation of the primitive Earth, setting our planet apart from undifferentiated meteorites as well as terrestrial planets or moons isotopically and compositionally. Understanding the chemical evolution of terrestrial planetary bodies requires knowledge on properties of both liquid iron alloys and silicates equilibrating under physicochemical conditions pertinent to the deep magma ocean. Here we report experimental andmore » computational results on the pressure-induced structural evolution of iron-nickel liquids alloyed with carbon. Our X-ray diffraction experiments up to 7.3 gigapascals (GPa) demonstrate that Fe-Ni (Fe90Ni10) liquids alloyed with 3 and 5 wt % carbon undergo a polyamorphic liquid structure transition at approximately 5 GPa. Corroborating the experimental observations, our first-principles molecular dynamic calculations reveal that the structural transitions result from the marked prevalence of three-atom face-sharing polyhedral connections in the liquids at >5 GPa. The structure and polyamorphic transitions of liquid iron-nickel-carbon alloys govern their physical and chemical properties and may thus cast fresh light on the chemical evolution of terrestrial planets and moons.« less

Polyamorphic Transformations in Fe-Ni-C Liquids: Implications for Chemical Evolution of Terrestrial Planets

NASA Astrophysics Data System (ADS)

Lai, Xiaojing; Chen, Bin; Wang, Jianwei; Kono, Yoshio; Zhu, Feng

2017-12-01

During the formation of the Earth's core, the segregation of metallic liquids from silicate mantle should have left behind evident geochemical imprints on both the mantle and the core. Some distinctive geochemical signatures of the mantle-derived rocks likely own their origin to the metal-silicate differentiation of the primitive Earth, setting our planet apart from undifferentiated meteorites as well as terrestrial planets or moons isotopically and compositionally. Understanding the chemical evolution of terrestrial planetary bodies requires knowledge on properties of both liquid iron alloys and silicates equilibrating under physicochemical conditions pertinent to the deep magma ocean. Here we report experimental and computational results on the pressure-induced structural evolution of iron-nickel liquids alloyed with carbon. Our X-ray diffraction experiments up to 7.3 gigapascals (GPa) demonstrate that Fe-Ni (Fe90Ni10) liquids alloyed with 3 and 5 wt % carbon undergo a polyamorphic liquid structure transition at approximately 5 GPa. Corroborating the experimental observations, our first-principles molecular dynamic calculations reveal that the structural transitions result from the marked prevalence of three-atom face-sharing polyhedral connections in the liquids at >5 GPa. The structure and polyamorphic transitions of liquid iron-nickel-carbon alloys govern their physical and chemical properties and may thus cast fresh light on the chemical evolution of terrestrial planets and moons.

Rb3In(H2O)Si5O13: a novel indium silicate with a CdSO4-topological-type structure.

PubMed

Hung, Ling-I; Wang, Sue-Lein; Chen, Chia-Yi; Chang, Bor-Chen; Lii, Kwang-Hwa

2005-05-02

A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.

Core Formation and Evolution of Asteroid 4 Vesta

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Mittlefehldt, David W.

2014-01-01

The howardites, eucrites, and diogenites (HEDs) are a suite of related meteorite types that formed by igneous and impact processes on the same parent body. Multiple lines of evidence, including infrared spectroscopy of the asteroid belt and the petrology and geochemistry of the HEDs, suggest that the asteroid 4 Vesta is the parent body for the HEDs. Observations by NASA's Dawn spacecraft mission strongly support the conclusion that the HEDs are from Vesta. The abundances of the moderately siderophile elements Ni, Co, Mo, W, and P in eucrites require that most or all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. These observations place important constraints on the mode and timescale of core formation on Vesta. Possible core formation mechanisms include porous flow, which potentially could occur prior to initiation of silicate melting, and metallic rain in a largely molten silicate magma ocean. Once the core forms, convection within the core could possible sustain a magnetic dynamo for a period of time. We consider each process in turn.

Origin of the terrestrial planets and the moon.

PubMed

Taylor, S R

1996-03-01

Our ideas about the origin and evolution of the solar system have advanced significantly as a result of the past 25 years of space exploration. Metal-sulfide-silicate partitioning seems to have been present in the early dust components of the solar nebula, prior to chondrule formation. The inner solar nebula was depleted in volatile elements by early solar activity. The early formation of the gas giant, Jupiter, affected the subsequent development of inner solar system and is responsible for the existence of the asteroid belt, and the small size of Mars. The Earth and the other terrestrial planets accreted in a gas-free environment, mostly from volatile-depleted planetesimals which were already differentiated into metallic cores and silicate mantles. The origin of the Moon by a single massive impact with a body larger than Mars explains the angular momentum, orbital characteristics and unique nature of the Earth-Moon system. The density and chemical differences between the Earth and Moon are accounted for by deriving the Moon from the mantle of the impactor.

The Earth's core formation: Constraints imposed by partitioning behaviour of Germanium and Copper.

NASA Astrophysics Data System (ADS)

Kegler, P.; Holzheid, A.; Palme, H.

2006-12-01

The abundances of the siderophile (metal-seeking) elements in the present Earth mantle are the result of the core formation in the early Earth. It is commonly assumed that the concentrations of the siderophile elements in the Earth mantle, especially of Ni and Co, can be explained by metal-silicate equilibrium at the base of a deep magma ocean during the core forming event [1,2], assuming values of Ni and Co metal-silicate partition coefficients at the bottom of a magma ocean that are identical to the Ni and Co core-mantle ratios (Ni:~39; pressure, where both partition coefficients have the same value, does exist within the Earth upper mantle [3,4]. In order to better constrain the origin of the siderophile elements in the upper mantle of the Earth we expanded our study and determined high pressure and high temperature metal/silicate partition coefficients of Ge and Cu (Dmet/sil = concentration of, e.g., Ge in metal / concentration of, e.g., Ge in silicate). The experiments were performed with Fe97Ge3 and Fe97Cu3 alloys. The metals were equilibrated with a synthetic basaltic melt (same composition as in [3,4]) within a pressure range from 0.5 to 2.5 GPa and at a temperature of 1450°C. The partition coefficients of both elements decrease within the investigated pressure range and at an oxygen fugacity of 1.4 log units more reduced than the Fe-FeO buffer (Dmet/sil at 0.5 GPa: Ge 5475, Cu 49; Dmet/sil at 2.5 GPa: Ge 4057, Cu 42). Although the pressure range covered by our experiments is narrow and extrapolations to pressures relevant to upper mantle conditions are therefore not very robust, it is still obvious that Dmet/sil of Ge and Cu at conditions at the bottom of a magma ocean would not be equal to their core/mantle ratios (Ge: 26; Cu: 6). These findings, in addition to the earlier results of Ni and Co, question the hypothesis of a simple single stage magma ocean. However, other models like inefficient core formation [5], heterogeneous accretion [6-7], or self oxidation of the Earth mantle with a multiple stage magma ocean [8,9] might be alternative hypotheses to explain the siderophile element abundances in the Earth mantle. [1] Li &Agee 1996 Nature, 381, 686-689. [2] Bouhifd &Jephcoat 2003. EPSL, 209, 245-255. [3] Kegler et al. 2004 LPSC XXXV, 1632. [4] Kegler et al. 2005 LPSC XXXVI, 2030. [5] Jones & Drake 1986 Nature 322, 221- 228. [6] Ringwood 1984 Proc.R.Soc.London, A395, 1-46. [7] Wanke et al. 1984 In: Archean geochemistry (ed. A. Kroener ) pp 1-24. [8] Frost et al. 2004 Nature, 428, 409-412. [9] Wade &Wood 2005 EPSL, 236, 78-95.

Low-voltage bendable pentacene thin-film transistor with stainless steel substrate and polystyrene-coated hafnium silicate dielectric.

PubMed

Yun, Dong-Jin; Lee, Seunghyup; Yong, Kijung; Rhee, Shi-Woo

2012-04-01

The hafnium silicate and aluminum oxide high-k dielectrics were deposited on stainless steel substrate using atomic layer deposition process and octadecyltrichlorosilane (OTS) and polystyrene (PS) were treated improve crystallinity of pentacene grown on them. Besides, the effects of the pentacene deposition condition on the morphologies, crystallinities and electrical properties of pentacene were characterized. Therefore, the surface treatment condition on dielectric and pentacene deposition conditions were optimized. The pentacene grown on polystyrene coated high-k dielectric at low deposition rate and temperature (0.2-0.3 Å/s and R.T.) showed the largest grain size (0.8-1.0 μm) and highest crystallinity among pentacenes deposited various deposition conditions, and the pentacene TFT with polystyrene coated high-k dielectric showed excellent device-performance. To decrease threshold voltage of pentacene TFT, the polystyrene-thickness on high-k dielectric was controlled using different concentration of polystyrene solution. As the polystyrene-thickness on hafnium silicate decreases, the dielectric constant of polystyrene/hafnium silicate increases, while the crystallinity of pentacene grown on polystyrene/hafnium silicate did not change. Using low-thickness polystyrene coated hafnium silicate dielectric, the high-performance and low voltage operating (<5 V) pentacene thin film transistor (μ: ~2 cm(2)/(V s), on/off ratio, >1 × 10(4)) and complementary inverter (DC gains, ~20) could be fabricated.

Composition characteristics and regularities of dissolving of hydroxyapatite materials obtained in water solutions with varied content of silicate ions

NASA Astrophysics Data System (ADS)

Solonenko, A. P.

2018-01-01

Research aimed at developing new bioactive materials for the repair of defects in bone tissues, do not lose relevance due to the strengthening of the regenerative approach in medicine. From this point of view, materials based on calcium phosphates, including silicate ions, consider as one of the most promising group of substances. Methods of synthesis and properties of hydroxyapatite doped with various amounts of SiO4 4- ions are described in literature. In the present work synthesis of a solid phase in the systems Ca(NO3)2 - (NH4)2HPO4 - Na2SiO3 - NH4OH - H2O (Cca/CP = 1.70) performed with a wide range of sodium silicate additive concentration (y = CSi/CP = 0 ÷ 5). It is established that under the studied conditions at y ≥ 0.3 highly dispersed poorly crystallized apatite containing isomorphic impurities of CO3 2- and SiO4 4- precipitates in a mixture with calcium hydrosilicate and SiO2. It is shown that the resulting composites can gradually dissolve in physiological solution and initiate passive formation of the mineral component of hard tissues.

Effect of clayey groundwater on the dissolution rate of SON68 simulated nuclear waste glass at 70 °C

NASA Astrophysics Data System (ADS)

De Echave, T.; Tribet, M.; Jollivet, P.; Marques, C.; Gin, S.; Jégou, C.

2018-05-01

To predict the long-term behavior of high-level radioactive waste glass, it is necessary to study aqueous dissolution of the glass matrix under geological repository conditions. The present article focuses on SON68 (an inactive surrogate of the R7T7 glass) glass alteration in synthetic clayey groundwater at 70 °C. Experiments in deionized water as reference were also performed in the same conditions. Results are in agreement with those of previous studies showing that magnesium present in the solution is responsible for higher glass alteration. This effect is transient and pH-dependent: Once all the magnesium is consumed, the glass alteration rate diminishes. Precipitation of magnesium silicate of the smectite group seems to be the main factor for the increased glass alteration. A pH threshold of 7.5-7.8 was found, above which precipitation of these magnesium silicates at 70 °C is possible. TEM observations reveal that magnesium silicates grow at the expense of the passivating gel, which partly dissolves, forming large pores which increase mass transfer between the reacting glass surface and the bulk solution.

Bioassembled layered silicate-metal nanoparticle hybrids.

PubMed

Drummy, Lawrence F; Jones, Sharon E; Pandey, Ras B; Farmer, B L; Vaia, Richard A; Naik, Rajesh R

2010-05-01

Here we report on the bioenabled assembly of layered nanohybrids using peptides identified with regard to their affinity to the nanoparticle surface. A dodecamer peptide termed M1, determined from a phage peptide display library, was found to bind to the surface of a layered aluminosilicate (montmorillonite, MMT). Fusion of a metal binding domain to the M1 peptide or the M1 peptide by itself was able to direct the growth of metal nanoparticles, such as gold and cobalt-platinum, respectively, on the MMT. This method of producing hybrid nanoclay materials will have utility in catalytic, optical, biomedical, and composite materials applications.

Thermal evolution and core formation of planetesimals

NASA Astrophysics Data System (ADS)

Suwa, Taichi; Nagahara, Hiroko

2017-04-01

Planetesimals did not get an adequate thermal energy by accretion to form large scale magma ocean because of smaller radii, masses, gravity and accretion energy, however, there are various evidences for the presence of core in planetesimals: 4-Vesta has a core and non-magmatic iron meteorites were segregated metal in bodies that did not experience silicate melting. It has been pointed out that accretion time of planetesimals controls melting and differentiation, because short lived nuclides are plausible heat source. Other factors such as radiative cooling from the surface and thermal conductivity, would also affect thermal evolution of planetesimals. Furthermore, percolation of Fe-S melt through silicate matrix is controlled by the porosity and grain size of silicates and dihedral angle between the melt and silicates. Therefore, the interior structure of planetesimals should be considered by taking the accretion, growth, and thermal evolution of the interior simultaneously. We make a numerical simulation with a spherical 1D model on the basis of the model by Neuman, which is a non-stationary heat conduction equation. We specifically pay attention to the process at temperatures between eutectic temperature Fe-FeS (1213K) and silicate solidus (1425K) and the surface tension of the melt that governs percolation. The model contains three free parameters, formation time, accretion duration, and final size of the planetesimals. The results show that the interior structure can be divided to four types: Type A is undifferentiated, Type B is differentiated to core and mantle of which core was formed by Fe-S melt percolation, Type C is partially differentiated to FeS core and mantle, where mantle retains residual Fe metal, and Type D is differentiated to core and mantle by metal separation in silicate magma. Type A would correspond to the parent bodies of chondrites, and Type B (and Type C?) core would be the source of non-magmatic iron meteorites. Type D would be parent bodies for 4 Vesta and angrites. The conditions for the four types of planetesimals are throuly investigated as a function of the three parameters, accretion time, accreting duration, and palnetesimal size. We found that the planetesimal interior is strongly controlled by the formation time: planetesimals formed after 3 Ma after CAIs would be undifferentiated (Type A) regardless of the planetary size, whereas most of them formed within 1 Ma are Type D (differentiated bodies with magmatically formed core). Types B and C bodies are preferentially formed between 1 and 3 Ma after CAIs. Longer accretion duration tends to be resulted in formation of Types A, B and C. The present work predicts the planetesimal interior structure if we know the formation age with the isotopic measurements of samples and the size of the body, which would be a very powerful tool for future explorations of small bodies except for very small (< 20 km) bodies.

Geochemistry of ferromanganese nodule-sediment pairs from Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Pattan, J. N.; Parthiban, G.

2011-01-01

Fourteen ferromanganese nodule-sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule-sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo - (307, 273), Ni - (71, 125), Mn - (64, 87), Cu - (43, 80), Co - (23, 75), Pb - (15, 24), Zn - (9, 11) and V - (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation ( r ⩾ 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.

Phosphate-Silicate Inclusions in Chaunskij: How Diverse are They?

NASA Astrophysics Data System (ADS)

Petaev, M. I.; Clarke, R. S., Jr.; Jarosewich, E.; Lipschutz, M. E.; Wang, M.-S.; Davis, A. M.; Steele, I. M.; Olsen, E. J.; Wood, J. A.

1993-07-01

The Chaunskij meteorite was found in 1985 and was recently classified as the most highly metamorphosed, shock-modified, and metal-rich mesosiderite [1]. It contains ~10 vol% mono- and polymineralic troilite-phosphate-silicate inclusions, micrometers to centimeters in size. Metal in Chaunskij displays a mesosiderite structure and is described in some detail in an accompanying paper [2]. Here we present new data on polymineralic inclusions that shed additional light on their origin. Two dominant silicate lithologies have been found in the inclusions. One, making up the largest inclusion (2.2 x 1.7 cm), consists of a fine-grained (20-30 micrometers) aggregate of anhedral pyroxene, subhedral plagioclase laths, and silica, with larger poikilitic grains of the first two minerals. Whitlockite is minor. Textures vary from microophitic to xenoblastic. This lithology, called "igneous," also contains rare primary clasts enriched in pyroxene, whose boundaries are almost unresolvable from the ground mass in transmitted light. The second, "metamorphic" lithology occurs as separate small inclusions and as larger areas in intimate contact with the "igneous" lithology in the largest inclusion. This lithology is a fine-grained (typically 30-50 micrometers) xenoblastic intergrowth of low-Ca pyroxene, whitlockite, and cordierite, with rare larger porphyritic grains of the first two minerals. Porphyritic pyroxene grain edges are generally irregular, indicative of reaction with the ground mass. Plagioclase is present only as a rare accessory mineral. Minor minerals in both lithologies are silica, kamacite, taenite, troilite, chromite, ilmenite, and rutile. Rare grains of pyrophanite, zircon, alabandite, stanfieldite, and a graftonite-farringtonite mineral are also present in the inclusions. Mineral compositions of small inclusions are more diverse than those characteristic of the "igneous" and "metamorphic" lithologies. Many of them consist of cordierite, pyroxene, and whitlockite intergrowths, with or without silica and opaque minerals. However, some inclusions do not match the mineralogies of "igneous" or "metamorphic" lithologies. They consist of cordierite only (inclusion #1-10); cordierite and silica (#1-18); silica, whitlockite, and troilite with minor Al-rich chromite and rare pyroxene (#4- 5A); plagioclase and whitlockite (#4-5D); and silica and whitlockite (#4-6E). Mineral compositions vary considerably both between and within all inclusions. No systematic differences between separate inclusions were found. Compositions of pyroxene and plagioclase match those of mesosideritic minerals. The chromite and ilmenite display systematic variations in MgO, MnO, Al(sub)2O(sub)3 and V(sub)2O(sub)3 contents, suggestive of a precursor material consisting of a series of basaltic rocks. The bulk chemical composition of the largest silicate inclusion, recalculated to the silicate fraction only, is very close to that of eucrites and mesosiderites except for a large enrichment in P and volatile chalcophiles. Major-element and REE chemistry and bulk mineralogy point to cumulate eucrites as the precursor of the silicate inclusions. This precursor was apparently slightly fractionated during the remelting event inferred by the structure of the "igneous" lithology. The "metamorphic" lithology apparently was formed due to reaction between silicates and phosphorus dissolved in the metal: Px + An + P + O --> Cord + Q + Whit. This reaction took place under ~700 degrees C and ~4 kbar [3] in the interior of the Chaunskij parent body. Compositions and textures of small inclusions suggest that the metamorphic reaction took place before the incorporation of the inclusions into the piece of metal making up the Chaunskij main mass. References: [1] Petaev M. I. et al. (1993) LPS XXIV, 1131-1132. [2] Clarke R. S. Jr. et al., this volume. [3] Petaev M. I. et al. (1992) Meteoritics, 27, 276-277.

What can the Hf–W System tell Us About the Mechanism and Timing of Earth's Core Formation?

NASA Astrophysics Data System (ADS)

Fischer, R. A.; Nimmo, F.; O'Brien, D. P.

2018-05-01

Strong tradeoff between effects of depth and extent of metal-silicate equilibration and formation timescale on the Hf-W system. Whole mantle equilibration requires k = 0.4. Later formation times require less equilibration to match Earth's anomaly.

Mineral resource of the month: zirconium and hafnium

USGS Publications Warehouse

Gambogi, Joseph

2007-01-01

Zirconium and hafnium are corrosion-resistant metals that are grouped in the same family as titanium on the periodic table. The two elements commonly occur in oxide and silicate minerals and have significant economic importance in everything from ink, ceramics and golf shoes to nuclear fuel rods.

Effect of silicon on activity coefficients of siderophile elements (Au, Pd, Pt, P, Ga, Cu, Zn, and Pb) in liquid Fe: Roles of core formation, late sulfide matte, and late veneer in shaping terrestrial mantle geochemistry

NASA Astrophysics Data System (ADS)

Righter, K.; Pando, K.; Humayun, M.; Waeselmann, N.; Yang, S.; Boujibar, A.; Danielson, L. R.

2018-07-01

Earth's core contains ∼10% of a light element that may be a combination of Si, S, C, O or H, with Si potentially being the major light element. Metal-silicate partitioning of siderophile elements can place important constraints on the P-T-fO2 and composition of the early Earth, but the effect of Si alloyed in Fe liquids is unknown for many of these elements. In particular, the effect of Si on the partitioning of highly siderophile elements (Au, Re and PGE) is virtually unknown. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Au, Pd, and Pt, and the volatile siderophile elements P, Ga, Cu, Zn, and Pb at variable Si content of metal, and 1600 °C and 1 GPa. From our experiments we derive epsilon interaction parameters between these elements and Si in Fe metallic liquids. The new parameters are used to update an activity model for trace siderophile elements in Fe alloys; Si causes large variation in the magnitude of activity coefficients of these elements in FeSi liquids. Because the interaction parameters are all positive, Si causes a decrease in their metal/silicate partition coefficients. We combine these new activity results with experimental studies of Au, Pd, Pt, P, Ga, Cu, Zn and Pb, to derive predictive expressions for metal/silicate partition coefficients which can then be applied to Earth. The expressions are applied to two scenarios for continuous accretion of Earth; specifically for constant and increasing fO2 during accretion. The results indicate that mantle concentrations of P, Ga, Cu, Zn, and Pb can be explained by metal-silicate equilibrium during accretion of the Earth where Earth's early magma ocean deepens to pressures of 40-60 GPa. Au, Pd, and Pt, on the other hand become too high in the mantle in such a scenario, and require a later removal mechanism, rather than an addition as traditionally argued. A late reduction event that removes 0.5% metal from a shallow magma ocean can lower the Au, Pd, and Pt contents to values near the current day BSE. On the other hand, removal of 0.2-1.0% of a late sulfide-rich matte to the core would lower the Au, Pd, and Pt concentrations in the mantle, but not to chondritic relative concentrations observed in the BSE. If sulfide matte is called upon to remove HSEs, they must be later added via a late veneer to re-establish the high and chondritic relative PUM concentrations. These results suggest that although accretion and core formation (involving a Si, S, and C-bearing metallic liquid) were the primary processes establishing many of Earth's mantle volatile elements and HSE, a secondary removal process is required to establish HSEs at their current and near-chondritic relative BSE levels. Mn and P - two siderophile elements that are central to biochemical processes (photosynthesis and triphosphates, respectively) - have significant and opposite interactions with FeSi liquids, and their mantle concentrations would be notably different if Earth had a Si-free core.

Nutritional differentiation among populations of the mediterranean shrub Dittrichia viscosa (Asteraceae) in siliceous and calcareous habitats.

PubMed

Wacquant, J P; Picard, J Baus

1992-10-01

Dittrichia (ex Inula) viscosa is a ruderal species that has recently become an invading plant in the northwest Mediterranean basin. A previous study failed to demonstrate the occurrence of morphologically differentiated ecotypes among populations of the species but suggested the existence of nutritional ecotypes. This latter possibility is examined here by comparing the ability of plants from contrasting habitats to control cation accumulation balance. Dittrichia viscosa plants, from eight siliceous habitats and nine calcareous habitats of southern France and neighbouring Spain and Italy, were cloned and grown together hydroponically with a solution simulating an acid soil with an aluminium constraint. Two independent hydroponic units containing solution supplemented with two levels of Al were used (2 Al levels x17 populations x3 genotypes x3 replicates). The growth and cation content (K, Ca, Mg and Na) of plant shoots and the chemical composition of the soil of each habitat were analysed. At the high Al level (1.1MM), populations differed in K, Ca and Mg plant proportions. Two groups could be distinguished: one containing all but one siliceous populations and the other containing all but one calcareous populations. Plants of the siliceous group accumulated proportionally more K and less Ca, and had better growth, than plants of the calcareous group, in the same way as calcifuge and calcicole species when grown on acid soil. At the lowest Al level (0.37MM), differences between siliceous and calcareous populations were less marked. The results suggest that differences in the ability of plants to control K and Ca balance, which appear to be of adaptive significance, could have arisen through selection, and that Dittrichia viscosa has evolved calcifuge and calcicole nutritional ecotypes in siliceous and calcareous habitats respectively. Various degrees of calcifugy, and to a lesser extent of calcicoly, can thus be suggested to occur among the studied populations, some in relation to the intensity of mineral stress in the natural habitats. So far, only functional traits have provided evidence of ecotypic differentiations within Dittrichia viscosa.

Investigations on the Crystal-Chemical Behavior of Transition-Metal-Bearing Aluminosilicate Garnet Solid Solutions Using 27Al and 29Si NMR Spectroscopy

NASA Astrophysics Data System (ADS)

Palke, A. C.; Geiger, C. A.; Stebbins, J. F.

2015-12-01

The petrological importance of silicate garnet is derived from the presence of three distinct cation sites of varying size and coordination number. This allows for a wide range of trace, minor, and major element substitutions. However, a full and precise crystal-chemical understanding of the nature of transition metals in garnet is not at hand. Possible mechanisms of various charge-balanced substitutions (e.g. octahedral Ti4+ or tetrahedral Al3+) and the structural state of solid solutions (i.e. short- to long-range ordering) need study. We report on ongoing efforts in these directions using 27Al and 29Si Magic-Angle Spinning Nuclear Magnetic Resonance (MAS-NMR) spectroscopy. Early work on synthetic and natural Fe- and Mn-bearing pyrope- and grossular-rich garnets focused on the effect these paramagnetic transition metals have in measuring and interpreting NMR spectra. These results have been expanded with NMR measurements on synthetic pyrope-rich garnets containing other paramagnetic transition metals including Cr3+, V3+, Co2+, and Ni2+ as well as diamagnetic Ti4+. NMR peaks are severely broadened in the presence of even small concentrations of Cr3+, Mn2+, and Fe3+ leading to a loss of spectral resolution. On the other hand, the spectra of garnet containing V3+, Fe2+, Co2+, and Ni2+ have better resolution and show separate paramagnetically shifted NMR peaks. In some cases, crystal-chemical information can be obtained because of the large frequency separations between the NMR peaks that can be assigned to various local atomic configurations around Al and Si. Furthermore, the 27Al NMR spectrum of a synthetic pyrope garnet with about 2% diamagnetic Ti4+ on the octahedral site showed the absence of any tetrahedral Al3+, which rules out the substitution mechanism VITi + IVAl = VIAl + IVSi in the solid solution. Our NMR investigations on garnet are now being made at the exploratory level. We think that NMR spectra of diamagnetic garnet can provide information on a number of crystal-chemical properties. Spectra of garnet containing various paramagnetic transition elements can also, in some cases, give local structural information. With a better understanding of paramagnetic effects in NMR spectroscopy, this type of study can possibly be expanded to other geologically important paramagnetic minerals and phases.

30Ar-40Ar Ages of Silicates from IIE Iron Meteorites

NASA Astrophysics Data System (ADS)

Garrison, D. H.; Bogard, D. D.

1995-09-01

Several IIE iron meteorites contain small silicate inclusions, dispersed within metal, which suggest formation by a common process involving different degrees of heating and silicate fractionation from a chondrite-like parent (see discussion and references in McCoy [1]). The isotope chronology of IIE meteorites addresses two major questions concerning their origin. How many formation events are required, and do the isotopic ages also represent the times of silicate differentiation in some meteorites, or do they represent later impact heating events? We have determined ^39Ar-^40Ar ages of whole silicate samples of Watson, Techado, and Miles [1]. Although each meteorite gives a complex Ar age spectrum, each spectrum gives a well-defined age plateau over a significant (55-65%) portion of the total ^39Ar release. The ^39Ar-^40Ar degassing ages derived are 3.656 +/-0.005 Ga for Watson, 4.482 +/-0.025 Ga for Techado, and 4.408 +/-0.011 Ga for Miles (one-sigma errors). Absolute ages have an additional ^-0.5% uncertainty arising from the hornblende age monitor used. None of our Ar-Ar spectra show any significant evidence for an age older than those given, and only Miles shows modest evidence for recent diffusive loss of ^40Ar (affecting ^-10% of the ^39Ar release). Previous studies of Kodaikanal gave these ages: Rb-Sr = 3.7 +/-0.1 Ga [2], Pb-Pb = 3.676 +/-0.003 Ga [3], and K-^40Ar = 3.5 Ga [4]. Netschaevo gave a ^39Ar-^40Ar age of 3.74 Ga +/-0.03 Ga [5], and Watson gave a K-^40Ar age of 3.5 Ga [6]. (Some ages have been adjusted for changes in decay and irradiation constants.) All three meteorites suggest a common formation age of ^-3.70 +/-0.05 Ga. The ^39Ar-^40Ar age for Techado is identical to a ^39Ar-^40Ar age of 4.49 +/-0.03 Ga reported for Weekeroo Station [5] and to a Rb-Sr age of 4.51 Ga for Colomera [7]. These ages resemble ^39Ar-^40Ar ages of unshocked ordinary chondrites, and suggest that metal-silicate mixing and cooling to closure for Ar diffusion occurred early in parent body history. The ^39Ar-^40Ar age for Miles, however, appears slightly younger and is similar to Rb-Sr ages for Weekeroo Station of ^-4.28-4.39 Ga [8, 9]. Young isotopic ages do not obviously correlate with the degree of melting and silicate fractionation, except that three of four dated IIEs showing significant fractionation give older ages. Totally unrelated events may have melted and fractionated similar silicates to produce comparable mixtures with IIE metal at both ^-4.5 and ^-3.7 Ga ago. This requires at least the younger event to have been an impact, possibly related to impact chronometer resetting observed in lunar highland rocks and HED meteorites near this time. However, petrologic data suggest that IIE meteorites may also represent a suite of samples that responded in different degrees to a single, early mixing event [1]. This explanation suggests that isotopic ages of Watson, Netschaevo, and Kodaikanal were reset by strong impact heating, possibly involving melting of individual silicate clasts, in one or more events long after their initial formation. Impacts may also explain the apparent younger ages observed for Miles and Weekeroo Station. A problem for the origin of IIEs in a single, early event is the apparent requirement from initial ^87Sr/^86Sr of Kodaikanal that the Rb/Sr ratio was increased significantly at a time near 3.7 Ga [2]. Whether such fractionation could occur within or across shock-melted silicate inclusions [10] deserves further consideration. References: [1] McCoy, this volume. [2] Burnett and Wasserburg (1967) EPSL, 2, 397. [3] Gopel et al. (1985) Nature, 317, 341. [4] Bogard et al. (1969) EPSL, 5, 273. [5] Niemeyer (1980) GCA, 44, 33. [6] Olsen et al. (1994) Meteoritics, 29, 200. [7] Sanz et al. (1970) GCA, 34, 1227. [8] Burnett and Wasserburg (1967) EPSL, 2, 397. [9] Evensen et al. (1979) LPS X, 376. [10] Bence and Burnett (1969) GCA, 33, 387.

In vitro bioactivity of novel tricalcium silicate ceramics.

PubMed

Zhao, Wenyuan; Chang, Jiang; Wang, Junying; Zhai, Wanyin; Wang, Zheng

2007-05-01

In this study, bone-like apatite-formation ability of tricalcium silicate (Ca(3)SiO(5)) ceramics in simulated body fluid (SBF) was evaluated and the in vitro degradability was investigated by soaking in Ringer's solution. The effect of ionic products from Ca(3)SiO(5) dissolution on osteobalsts proliferation was investigated. The result indicated that hydroxyapatite (HA) was formed on the surface of the Ca(3)SiO(5) ceramics after soaking in SBF for 1 day, and Ca(3)SiO(5) ceramics could degraded in Ringer's solution. The Si ions from Ca(3)SiO(5) dissolution at certain concentration range significantly stimulated osteoblasts proliferation. Our results show that Ca(3)SiO(5) ceramics possess bone-like apatite-formation ability and degradability, and can release soluble ionic products to stimulate cell proliferation.

Bonelike apatite formation on ethylene-vinyl alcohol copolymer modified with silane coupling agent and calcium silicate solutions.

PubMed

Oyane, Ayako; Kawashita, Masakazu; Nakanishi, Kazuki; Kokubo, Tadashi; Minoda, Masahiko; Miyamoto, Takeaki; Nakamura, Takashi

2003-05-01

An ethylene-vinyl alcohol copolymer (EVOH) was treated with a silane coupling agent and calcium silicate solutions, and then soaked in a simulated body fluid (SBF) with ion concentrations approximately equal to those of human blood plasma. A smooth and uniform bonelike apatite layer was successfully formed on both the EVOH plate and the EVOH-knitted fibers in SBF within 2 days. Part of the structure of the resulting apatite-EVOH fiber composite was similar to that of natural bone. If this kind of composite can be fabricated into a three-dimensional structure similar to natural bone, the resultant composite is expected to exhibit both mechanical properties analogous to those of natural bone and bone-bonding ability. Hence, it has great potential as a bone substitute. Copyright 2003 Elsevier Science Ltd.

Developing a novel magnesium glycerophosphate/silicate-based organic-inorganic composite cement for bone repair.

PubMed

Ding, Zhengwen; Li, Hong; Wei, Jie; Li, Ruijiang; Yan, Yonggang

2018-06-01

Considering that the phospholipids and glycerophosphoric acid are the basic materials throughout the metabolism of the whole life period and the bone is composed of organic polymer collagen and inorganic mineral apatite, a novel self-setting composite of magnesium glycerophosphate (MG) and di-calcium silicate(C2S)/tri-calcium silicate(C3S) was developed as bio-cement for bone repair, reconstruction and regeneration. The composite was prepared by mixing the MG, C2S and C3S with the certain ratios, and using the deionized water and phosphoric acid solution as mixed liquid. The combination and formation of the composites was characterized by FTIR, XPS and XRD. The physicochemical properties were studied by setting time, compressive strength, pH value, weight loss in the PBS and surface change by SEM-EDX. The biocompatibility was evaluated by cell culture in the leaching solution of the composites. The preliminary results showed that when di- and tri-calcium silicate contact with water, there are lots of Ca(OH) 2 generated making the pH value of solution is higher than 9 which is helpful for the formation of hydroxyapatite(HA) that is the main bone material. The new organic-inorganic self-setting bio-cements showed initial setting time is ranged from 20 min to 85 min and the compressive strength reached 30 MPa on the 7th days, suitable as the bone fillers. The weight loss was 20% in the first week, and 25% in the 4th week. Meanwhile, the new HA precipitated on the composite surface during the incubation in the SBF showed bioactivity. The cell cultured in the leaching liquid of the composite showed high proliferation inferring the new bio-cement has good biocompatibility to the cells. Copyright © 2018 Elsevier B.V. All rights reserved.

FTIR spectra of the solid solutions (Na0.88K0.12)VO3, (Na0.5K0.5)VO3, and Na(V0.66P0.34)O3

NASA Astrophysics Data System (ADS)

de Waal, D.; Heyns, A. M.

1992-03-01

It is known that three different solid solutions, (Na0.88K0.12)VO3, (Na0.5K0.5)VO3 and Na(V0.66P0.34)O3, form in the (Na,K)(V,P)O3 system. These compounds all have monoclinic crystal structures similar to the pure alkali metal metavanadates containing small cations, e.g. Li+ and Na+ (Space group C2/c). Metavanadates with large cations like K+, Rb+, C+s and NH+4 form orthorhombic crystals, space group Pbcm. All those are structurally related to the silicate pyroxenes. Na(V0.66P0.34)O3 and (Na0.88K0.12)VO3 have the same modified diopside structure as (alpha) - NaVO3 while (Na0.5K0.5)VO3 adopts the true diopside structure. The infrared spectra of the three solid solutions are reported here in comparison with those of (alpha) -NaVO3 and KVO3. The results are also correlated with those obtained in two independent high pressure Raman studies of NH4VO3 and RbVO3 as the introduction of a larger cation like K+ should increase the pressure in the structure.

High temperature sorbents for oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor)

1994-01-01

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C comprising a porous alumina silicate support, such as zeolite, containing from 1 to 10 percent by weight of ion exchanged transition metal, such as copper or cobalt ions, and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum is described. The activation temperature, oxygen sorption, and reducibility are all improved by the presence of the platinum activator.

What Should the FeO Content of a Terrestrial Planet Be?

NASA Technical Reports Server (NTRS)

Jones, John H.

2013-01-01

Basalts from the Earth, the Moon, Mars, and Vesta are strongly depleted in elements that prefer to reside in the metallic state (siderophile elements). Therefore, it is believed that all these bodies have metallic cores. We do not yet have siderophile element analyses of venusian or mercurian basalts, but we assume that Venus, too, as a terrestrial planet, has a metallic core. For the Earth, Moon, Mercury, and Mars, the moments-of-inertia of these bodies are consistent with metallic cores of various sizes. Because Venus rotates so slowly, it may be difficult to determine the moment-of-inertia of Venus in order to confirm this assumption. However, despite many possible complexities, it seems likely that most of the major and minor terrestrial planets have experienced some sort of metal/silicate equilibration, and we will use this as a boundary condition. One immediate contrast between the Earth and Moon is the difference in FeO content between lunar and terrestrial basalts. Both bodies presumably formed near 1 AU and formed from the same feeding zone of planetesimals, judging by their oxygen isotopes [13]. If, for example, the Moon formed from the Earth by a giant impact, then this event must have occurred before high-pressure equilibria had the opportunity to deplete the Earth s mantle in FeO. Alternatively, the bulk silicate Moon may be dominated by material from the impactor. Regardless, it would be useful to know the pressures where FeO incorporation into a metallic core is not of interest. If the Giant Impact hypothesis is correct, this should set an upper limit for the size of the proto-Earth at the time of the impact.

3D Observation of GEMS by Electron Tomography

NASA Technical Reports Server (NTRS)

Matsuno, Junya; Miyake, Akira; Tsuchiyama, Akira; Nakamura-Messenger, Keiko; Messenger, Scott

2014-01-01

Amorphous silicates in chondritic porous interplanetary dust particles (CP-IDPs) coming from comets are dominated by glass with embedded metal and sulfides (GEMS). GEMS grains are submicron-sized rounded objects (typically 100-500) nm in diameter) with anaometer-sized (10-50 nm) Fe-Ni metal and sulfide grains embedded in an amorphous silicate matrix. Several formation processes for GEMS grains have been proposed so far, but these models are still being debated [2-5]. Bradley et al. proposed that GEMS grains are interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk and that they are amorphiation products of crystalline silicates in the interstellar medium by sputter-deposition of cosmic ray irradiation, similar to space weathering [2,4]. This consideration is based on the observation of nano-sized crystals (approximately 10 nm) called relict grains in GEMS grains and their shapes are pseudomorphs to the host GEMS grains. On the other hand, Keller and Messenger proposed that most GEMS formed in the protoplanetary disk as condensates from high temperature gas [3,5]. This model is based on the fact that most GEMS grains have solar isotopic compositions and have extremely heterogeneous and non-solar elemental compositions. Keller and Messenger (2011) also reported that amorphous silicates in GEMS grains are surrounded by sulfide grains, which formed as sulfidization of metallic iron grains located on the GEMS surface. The previous studies were performed with 2D observation by using transmission electron microscopy (TEM) or scanning TEM (STEM). In order to understand the structure of GEMS grains described above more clearly, we observed 3D structure of GEMS grains by electron tomography using a TEM/STEM (JEM-2100F, JEOL) at Kyoto University. Electron tomography gives not only 3D structures but also gives higher spatial resolution (approximately a few nm) than that in conventional 2D image, which is restricted by sample thickness ) approx. or greater than 50 nm). Three cluster IDPs (L2036AA5 cluster4, L2009L8 cluster 13 and W726A2) were used for the observations. ID W726A2 was collected without silicon oil, which is ordinary used to collect IDPs, so this sample has no possibility of contaminations caused by silicon oil or solvent to rinse it [6]. The samples were embedded in epoxy risin and sliced into ultrathin sections (50-300 nm) using an ultramicotome. The sections were observed by BF-TEM and HAADF-STEM (high angle annular dark field-scanning TEM) modes. Images were obtained by rotating the sample tilt angle over a range of +/- 65 deg in 1 deg steps. The obtained images were reconstructed to slice images. Mineral phases in the slice images were estimated by comparing with a 2D elemental map obtained by an EDS (energy dispersive X-ray spectroscopy) system equipped in the TEM/STEM. Careful examination of the slice images confirmed that iron grains are embedded in the amorphous silicate matrix of the GEMS grains, but sulfide grains were mainly present on the surface of the amorphous silicate. These results are consistent with the model that GEMS grains formed as condensates [3,5], although more data are needed to conclude the origin of GEMS grains. The present study is the first successful example adapting the electron tomography to the IDPs. This type of analysis will be important for planetary material sciences in the future.

Iodine-Xenon Systematics of Mineral Separates from the Ordinary Chondrite Allegan and the Acapulcoite Dhofar 125

NASA Astrophysics Data System (ADS)

Schönbächler, M.; Theis, K. J.; Crowther, S. A.; Gilmour, J. D.

2014-09-01

We present I-Xe data for mineral separates from Allegan (H5) and Dhofar 125 (acapulcoite). Metals show younger ages (4500-4550 Ma) than silicates (Allegan:4563-4566 Ma and Dhofar 125: 4557.1 ± 0.5 Ma) for both meteorites.

Evaluation of Metal Partitioning and Mobility in a Sulfidic Mine Tailing Pile under Oxic and Anoxic Conditions

EPA Science Inventory

Mining-influenced water emanating from mine tailings and potentially contaminating surface water and groundwater is one of the most important environmental issues linked to the mining industry. In this study, two subsets of Callahan Mine tailings (mainly comprised of silicates, ...

Silicate petrography and origin of the mesosiderites: a preliminary investigation of their relationships to the howardite-eurite-diogenite suite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Floran, R. J

1978-04-01

Results are reported from a petrographic study of 20 mesosiderites that reveals that most contain a complex assemblage of mineral, lithic, and metal clasts. Mineral fragments dominate the clast population and consist primarily of orthopyroxene, plagioclase, and olivine.

Investigation and Development of Methods to Increase the Dispersibility of Aluminum Metal Power

DTIC Science & Technology

1977-01-01

Tullanox-500 remain intact. A fourth material investigated as a possible deagglomerating agent was Micro- Cel ( Johns - Manville , Inc. ). This material is...20 percent Johns - Manville Micro-Cel (calcium silicate), (3) 20 percent Baker & Adamson, Code 1551, activated carbon, (4) 2 percent Cabot Cab-O-Sil

Nanoscale assembly of lanthanum silica with dense and porous interfacial structures.

PubMed

Ballinger, Benjamin; Motuzas, Julius; Miller, Christopher R; Smart, Simon; Diniz da Costa, João C

2015-02-03

This work reports on the nanoscale assembly of hybrid lanthanum oxide and silica structures, which form patterns of interfacial dense and porous networks. It was found that increasing the molar ratio of lanthanum nitrate to tetraethyl orthosilicate (TEOS) in an acid catalysed sol-gel process alters the expected microporous metal oxide silica structure to a predominantly mesoporous structure above a critical lanthanum concentration. This change manifests itself by the formation of a lanthanum silicate phase, which results from the reaction of lanthanum oxide nanoparticles with the silica matrix. This process converts the microporous silica into the denser silicate phase. Above a lanthanum to silica ratio of 0.15, the combination of growth and microporous silica consumption results in the formation of nanoscale hybrid lanthanum oxides, with the inter-nano-domain spacing forming mesoporous volume. As the size of these nano-domains increases with concentration, so does the mesoporous volume. The absence of lanthanum hydroxide (La(OH)3) suggests the formation of La2O3 surrounded by lanthanum silicate.

Earth's core-mantle boundary - Results of experiments at high pressures and temperatures

NASA Technical Reports Server (NTRS)

Knittle, Elise; Jeanloz, Raymond

1991-01-01

Laboratory experiments document that liquid iron reacts chemically with silicates at high pressures (above 2.4 x 10 to the 10th Pa) and temperatures. In particular, (Mg,Fe)SiO3 perovskite, the most abundant mineral of earth's lower mantle, is expected to react with liquid iron to produce metallic alloys (FeO and FeSi) and nonmetallic silicates (SiO2 stishovite and MgSiO3 perovskite) at the pressures of the core-mantle boundary, 14 x 10 to the 10th Pa. The experimental observations, in conjunction with seismological data, suggest that the lowermost 200 to 300 km of earth's mantle, the D-double-prime layer, may be an extremely heterogeneous region as a result of chemical reactions between the silicate mantle and the liquid iron alloy of earth's core. The combined thermal-chemical-electrical boundary layer resulting from such reactions offers a plausible explanation for the complex behavior of seismic waves near the core-mantle boundary and could influence earth's magnetic field observed at the surface.

Brinicles as a case of inverse chemical gardens.

PubMed

Cartwright, Julyan H E; Escribano, Bruno; González, Diego L; Sainz-Díaz, C Ignacio; Tuval, Idan

2013-06-25

Brinicles are hollow tubes of ice from centimeters to meters in length that form under floating sea ice in the polar oceans when dense, cold brine drains downward from sea ice to seawater close to its freezing point. When this extremely cold brine leaves the ice, it freezes the water it comes into contact with: a hollow tube of ice-a brinicle-growing downward around the plume of descending brine. We show that brinicles can be understood as a form of the self-assembled tubular precipitation structures termed chemical gardens, which are plantlike structures formed on placing together a soluble metal salt, often in the form of a seed crystal, and an aqueous solution of one of many anions, often silicate. On one hand, in the case of classical chemical gardens, an osmotic pressure difference across a semipermeable precipitation membrane that filters solutions by rejecting the solute leads to an inflow of water and to its rupture. The internal solution, generally being lighter than the external solution, flows up through the break, and as it does so, a tube grows upward by precipitation around the jet of internal solution. Such chemical-garden tubes can grow to many centimeters in length. In the case of brinicles, on the other hand, in floating sea ice we have porous ice in a mushy layer that filters out water, by freezing it, and allows concentrated brine through. Again there is an osmotic pressure difference leading to a continuing ingress of seawater in a siphon pump mechanism that is sustained as long as the ice continues to freeze. Because the brine that is pumped out is denser than the seawater and descends rather than rises, a brinicle is a downward-growing tube of ice, an inverse chemical garden.

Non-conductive nanomaterial enhanced electrochemical response in stripping voltammetry: The use of nanostructured magnesium silicate hollow spheres for heavy metal ions detection.

PubMed

Xu, Ren-Xia; Yu, Xin-Yao; Gao, Chao; Jiang, Yu-Jing; Han, Dong-Dong; Liu, Jin-Huai; Huang, Xing-Jiu

2013-08-06

Nanostructured magnesium silicate hollow spheres, one kind of non-conductive nanomaterials, were used in heavy metal ions (HMIs) detection with enhanced performance for the first time. The detailed study of the enhancing electrochemical response in stripping voltammetry for simultaneous detection of ultratrace Cd(2+), Pb(2+), Cu(2+) and Hg(2+) was described. Electrochemical properties of modified electrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The operational parameters which have influence on the deposition and stripping of metal ions, such as supporting electrolytes, pH value, and deposition time were carefully studied. The anodic stripping voltammetric performance toward HMIs was evaluated using square wave anodic stripping voltammetry (SWASV) analysis. The detection limits achieved (0.186nM, 0.247nM, 0.169nM and 0.375nM for Cd(2+), Pb(2+), Cu(2+) and Hg(2+)) are much lower than the guideline values in drinking water given by the World Health Organization (WHO). In addition, the interference and stability of the modified electrode were also investigated under the optimized conditions. An interesting phenomenon of mutual interference between different metal ions was observed. Most importantly, the sensitivity of Pb(2+) increased in the presence of certain concentrations of other metal ions, such as Cd(2+), Cu(2+) and Hg(2+) both individually and simultaneously. The proposed electrochemical sensing method is thus expected to open new opportunities to broaden the use of SWASV in analysis for detecting HMIs in the environment. Copyright © 2013 Elsevier B.V. All rights reserved.

Mountain ranges, climate and weathering. Do orogens strengthen or weaken the silicate weathering carbon sink?

NASA Astrophysics Data System (ADS)

Maffre, Pierre; Ladant, Jean-Baptiste; Moquet, Jean-Sébastien; Carretier, Sébastien; Labat, David; Goddéris, Yves

2018-07-01

The role of mountains in the geological evolution of the carbon cycle has been intensively debated for the last decades. Mountains are thought to increase the local physical erosion, which in turns promotes silicate weathering, organic carbon transport and burial, and release of sulfuric acid by dissolution of sulfides. In this contribution, we explore the impact of mountain ranges on silicate weathering. Mountains modify the global pattern of atmospheric circulation as well as the local erosion conditions. Using an IPCC-class climate model, we first estimate the climatic impact of mountains by comparing the present day climate with the climate when all the continents are assumed to be flat. We then use these climate output to calculate weathering changes when mountains are present or absent, using standard expression for physical erosion and a 1D vertical model for rock weathering. We found that large-scale climate changes and enhanced rock supply by erosion due to mountain uplift have opposite effect, with similar orders of magnitude. A thorough testing of the weathering model parameters by data-model comparison shows that best-fit parameterizations lead to a decrease of weathering rate in the absence of mountain by about 20%. However, we demonstrate that solutions predicting an increase in weathering in the absence of mountain cannot be excluded. A clear discrimination between the solutions predicting an increase or a decrease in global weathering is pending on the improvement of the existing global databases for silicate weathering. Nevertheless, imposing a constant and homogeneous erosion rate for models without relief, we found that weathering decrease becomes unequivocal for very low erosion rates (below 10 t/km2/yr). We conclude that further monitoring of continental silicate weathering should be performed with a spatial distribution allowing to discriminate between the various continental landscapes (mountains, plains …).

From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water.

PubMed

Wang, Wenbo; Tian, Guangyan; Zong, Li; Zhou, Yanmin; Kang, Yuru; Wang, Qin; Wang, Aiqin

2017-01-01

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline (CTC) were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite (IS) clay, sodium silicate and magnesium sulfate as the starting materials. In this process, IS clay was "teared up" and then "rebuilt" as new porous silicate adsorbent with high specific surface area of 363.52m 2 /g (about 8.7 folds higher than that of IS clay) and very negative Zeta potential (-34.5mV). The inert SiOSi (Mg, Al) bonds in crystal framework of IS were broken to form Si(Al) O - groups with good adsorption activity, which greatly increased the adsorption sites served for holding much CTC molecules. Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81mg/g of CTC (only 159.7mg/g for raw IS clay) and remove 99.3% (only 46.5% for raw IS clay) of CTC from 100mg/L initial solution (pH3.51; adsorption temperature 30°C; adsorbent dosage, 3g/L). The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model, Temkin equation and pseudo second-order kinetic model. The mesopore adsorption, electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties. As a whole, the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC. Copyright © 2016. Published by Elsevier B.V.

Psyche: The Science of a Metal World

NASA Astrophysics Data System (ADS)

Elkins-Tanton, L. T.

2016-12-01

(16) Psyche is a large metallic asteroid orbiting in the outer main belt at 3 AU. Psyche's metal composition is indicated by high radar albedo, thermal inertia, and density. Models show that among the accretionary collisions early in the solar system, some destructive "hit and run" impacts could strip the silicate mantle from differentiated bodies. This is the leading hypothesis for Psyche's formation: it is a bare planetesimal core. It is the only one we can explore for substantial information about a metal core (other metallic asteroids are far smaller and not roughly spherical). If our observations indicate that it is not a core, Psyche may instead be highly reduced, primordial metal-rich materials that accreted closer to the Sun, and never melted. Psyche is also a Discovery-class mission, selected for a Step 2 concept study, to investigate this metal body. The Psyche investigation has three broad goals: Understand a previously unexplored building block of planet formation: iron cores. Look inside the terrestrial planets, including Earth, by directly examining the interior of a differentiated body, which otherwise could not be seen. Explore a new type of world. For the first time, examine a world made not of rock, ice, or gas, but of metal. We will meet our science objectives with three domestic high heritage instruments and radio science: Multispectral imagers with clear and seven color filters map surface morphology and reveal the distribution of residual mantle silicates. A gamma-ray and neutron spectrometer determines elemental composition, particularly the concentrations of iron, nickel, silicon, and potassium. Dual fluxgate magnetometers, in a gradiometer configuration, characterize the magnetic field. Radio science maps the gravity field sufficiently to differentiate among core-formation hypotheses. New models for magnetic dynamo generation and solidification of planetesimal cores make testable predictions for geophysical measurements, and lead as well to predictions about tectonics and surface compositions. In this presentation we will show how measurements from these flight instruments can confirm or disprove hypotheses for Psyche's formation and evolution.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-04-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-05-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Long term mechanical properties of alkali activated slag

NASA Astrophysics Data System (ADS)

Zhu, J.; Zheng, W. Z.; Xu, Z. Z.; Leng, Y. F.; Qin, C. Z.

2018-01-01

This article reports a study on the microstructural and long-term mechanical properties of the alkali activated slag up to 180 days, and cement paste is studied as the comparison. The mechanical properties including compressive strength, flexural strength, axis tensile strength and splitting tensile strength are analyzed. The results showed that the alkali activated slag had higher compressive and tensile strength, Slag is activated by potassium silicate (K2SiO3) and sodium hydroxide (NaOH) solutions for attaining silicate modulus of 1 using 12 potassium silicate and 5.35% sodium hydroxide. The volume dosage of water is 35% and 42%. The results indicate that alkali activated slag is a kind of rapid hardening and early strength cementitious material with excellent long-term mechanical properties. Single row of holes block compressive strength, single-hole block compressive strength and standard solid brick compressive strength basically meet engineering requirements. The microstructures of alkali activated slag are studied by X-ray diffraction (XRD). The hydration products of alkali-activated slag are assured as hydrated calcium silicate and hydrated calcium aluminate.

High angular resolution N-band observation of the silicate carbon star IRAS08002-3803 with the VLTI/MIDI instrument . Dusty environment spatially resolved

NASA Astrophysics Data System (ADS)

Ohnaka, K.; Driebe, T.; Hofmann, K.-H.; Leinert, Ch.; Morel, S.; Paresce, F.; Preibisch, Th.; Richichi, A.; Schertl, D.; Schöller, M.; Waters, L. B. F. M.; Weigelt, G.; Wittkowski, M.

2006-01-01

We present the results of N-band spectro-interferometric observations of the silicate carbon star IRAS08002-3803 with the MID-infrared Interferometric instrument (MIDI) at the Very Large Telescope Interferometer (VLTI) of the European Southern Observatory (ESO). The observations were carried out using two unit telescopes (UT2 and UT3) with projected baseline lengths ranging from 39 to 47 m. Our observations of IRAS08002-3803 have spatially resolved the dusty environment of a silicate carbon star for the first time and revealed an unexpected wavelength dependence of the angular size in the N band: the uniform-disk diameter is found to be constant and 36 mas (72 Rstar) between 8 and 10 μm, while it steeply increases longward of 10 μm to reach 53 mas (106 Rstar) at 13 μm. Model calculations with our Monte Carlo radiative transfer code show that neither spherical shell models nor axisymmetric disk models consisting of silicate grains alone can simultaneously explain the observed wavelength dependence of the visibility and the spectral energy distribution (SED). We propose that the circumstellar environment of IRAS08002-3803 may consist of two grain species coexisting in the disk: silicate and a second grain species, for which we consider amorphous carbon, large silicate grains, and metallic iron grains. Comparison of the observed visibilities and SED with our models shows that such disk models can fairly - though not entirely satisfactorily - reproduce the observed SED and N-band visibilities. Our MIDI observations and the radiative transfer calculations lend support to the picture where oxygen-rich material around IRAS08002-3803 is stored in a circumbinary disk surrounding the carbon-rich primary star and its putative low-luminosity companion.

Effects of thin-film accelerated carbonation on steel slag leaching.

PubMed

Baciocchi, R; Costa, G; Polettini, A; Pomi, R

2015-04-09

This paper discusses the effects of accelerated carbonation on the leaching behaviour of two types of stainless steel slags (electric arc furnace and argon oxygen decarburisation slag). The release of major elements and toxic metals both at the natural pH and at varying pH conditions was addressed. Geochemical modelling of the eluates was used to theoretically describe leaching and derive information about mineralogical changes induced by carbonation. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases; geochemical modelling indicated that the Ca/Si ratio of Ca-controlling minerals shifted from ∼ 1 for the untreated slag to 0.5-0.67 for the carbonated samples, thus showing that the carbonation process left some residual Ca-depleted silicate phases while the extracted Ca precipitated in the form of carbonate minerals. For toxic metals the changes in leaching induced by carbonation appeared to be mainly related to the resulting pH changes, which were as high as ∼ 2 orders of magnitude upon carbonation. Depending on the specific shape of the respective solubility curves, the extent of leaching of toxic metals from the slag was differently affected by carbonation. Copyright © 2014 Elsevier B.V. All rights reserved.

The influence of heavy metals on the polymorphs of dicalcium silicate in the belite-rich clinkers produced from electroplating sludge.

PubMed

Chen, Ying-Liang; Shih, Pai-Haung; Chiang, Li-Choung; Chang, Yi-Kuo; Lu, Hsing-Cheng; Chang, Juu-En

2009-10-15

The purpose of this study is to utilize an electroplating sludge for belite-rich clinker production and to observe the influence of heavy metals on the polymorphs of dicalcium silicate (C(2)S). Belite-rich clinkers prepared with 0.5-2% of NiO, ZnO, CuO, and Cr(2)O(3) were used to investigate the individual effects of the heavy metals in question. The Reference Intensity Ratio (RIR) method was employed to determine the weight fractions of gamma-C(2)S and beta-C(2)S in the clinkers, and their microstructures were examined by the transmission electron microscopy (TEM). The results showed that nickel, zinc, and chromium have positive effects on beta-C(2)S stabilization (Cr(3+)>Ni(2+)>Zn(2+)), whereas copper has a negative effect. The addition of up to 10% electroplating sludge did not have any negative influence on the formation of C(2)S. It was observed that gamma-C(2)S decreased while beta-C(2)S increased with a rise in the addition of the electroplating sludge. Moreover, nickel and chromium mainly contributed to stabilizing beta-C(2)S in the belite-rich clinkers produced from the electroplating sludge.

Porous, S-bearing silica in metal-sulfide nodules and in the interchondrule clastic matrix in two EH3 chondrites

NASA Astrophysics Data System (ADS)

Lehner, S. W.; Németh, P.; Petaev, M. I.; Buseck, P. R.

2017-11-01

Two new occurrences of porous, S-bearing, amorphous silica are described within metal-sulfide nodules (MSN) and as interchondrule patches in EH3 chondrites SAH 97072 and ALH 84170. This porous amorphous material, which was first reported from sulfide-bearing chondrules, consists of sinewy SiO2-rich areas containing S with minor Na or Ca as well as Fe, Mg, and Al. Some pores contain minerals including pyrite, pyrrhotite, and anhydrite. Most pores appear vacant or contain unidentified material that is unstable under analytical conditions. Niningerite, olivine, enstatite, albite, and kumdykolite occur enclosed within porous silica patches. Porous silica is commonly interfingered with cristobalite suggesting its amorphous structure resulted from high-temperature quenching. We interpret the S-bearing porous silica to be a product of silicate sulfidation, and the Na, Ca, Fe, Mg, and Al detectable within this material are chemical residues of sulfidized silicates and metal. The occurrence of porous silica in the cores of MSN, which are considered to be pre-accretionary objects, suggests the sulfidizing conditions occurred prior to final parent-body solidification. Ubiquitous S-bearing porous silica among sulfide-bearing chondrules, MSN, and in the interchondrule clastic matrix, suggests that similar sulfidizing conditions affected all the constituents of these EH3 chondrites.

An early geodynamo driven by exsolution of mantle components from Earth’s core

PubMed Central

Badro, James; Siebert, Julien; Nimmo, Francis

2016-01-01

Terrestrial core formation occurred in the early molten Earth by gravitational segregation of immiscible metal and silicate melts, stripping iron-loving elements from the silicate mantle to the metallic core1–3, and leaving rock-loving components behind. Here we performed experiments showing that at high enough temperature, Earth’s major rock-loving component, magnesium oxide, can also dissolve in core-forming metallic melts. Our data clearly point to a dissolution reaction, and are in agreement with recent DFT calculations4. Using core formation models5, we further show that a high-temperature event during Earth’s accretion (such as the Moon-forming giant impact6) can contribute significant amounts of magnesium to the early core. As it subsequently cools, the ensuing exsolution7 of buoyant magnesium oxide generates a substantial amount of gravitational energy. This energy is comparable to if not significantly higher than that produced by inner core solidification8 — the primary driver of the Earth’s current magnetic field9–11. Since the inner core is too young12 to explain the existence of an ancient field prior to ~1 billion years, our results solve the conundrum posed by the recent paleomagnetic observation13 of an ancient field at least 3.45 Gyr old. PMID:27437583

Petrography and Geochemistry of Metals in Almahata Sitta Ureilites

NASA Technical Reports Server (NTRS)

Ross, A. J.; Herrin, J. S.; Mittlefehldt, D. W.; Downes, H.; Smith, C. L.; Lee, M. R.; Jones, A. P.; Jenniskens, P.; Shaddad, M. H,

2011-01-01

Ureilites are ultramafic achondrites, predominantly composed of olivine and pyroxenes with accessory carbon, metal and sulfide. The majority of ureilites are believed to represent the mantle of the ureilite parent body (UPB) [1]. Although ureilites have lost much of their original metal [2], the metal that remains retains a record of the formative processes. Almahata Sitta is predominantly composed of unbrecciated ureilites with a wide range of silicate compositions [3,4]. As a fall it presents a rare opportunity to examine fresh ureilite metal in-situ, and analyzing their highly siderophile element (HSE) ratios gives clues to their formation. Bulk siderophile element analyses of Almahata Sitta fall within the range observed in other ureilites [5]. We have examined the metals in seven ureilitic samples of Almahata Sitta (AS) and one associated chondrite fragment (AS#25).

Sillica Gel-Amine from Geothermal Sludge

NASA Astrophysics Data System (ADS)

Muljani, S.; Pujiastuti, C.; Wicaksono, P.; Lutfianingrum, R.

2018-01-01

Silica Gel-Amine (SGA) has been made from geothermal sludge by grafting amine method. Sodium silicate solution is prepared by extracted geothermal sludge powder using sodium hidroxide solution then acidification in the range of pH 5 - 9 by using tartaric acid 1N. The grafting process uses 1 ml of ammonia solution and 10 ml of toluene at a rate of 0.1 ml min-1 accompanied by a reflux process. The amine grafting is done in two methods. The first method is grafting amine in silicate solution and the second method is grafting amine in washed gel. Product SGA was confirmed by FTIR, TGA-DTG and BET characterization. The results show that the pH affects the amount of amine that is grafted onto silica gel. Differences in grafting method affect the size of the pore and surface area. SGA product prepared by grafting washed gel at pH 8 have pore diameter of 12.06 nm, surface area of 173.44 m2g-1, and mass of decomposed amine compound 0.4 mg. In the presence of amine groups on the silica gel surface, these adsorbents may be able to selectively adsorb CO2 gas from natural gas.

Silica and Pyroxene in IVA Irons; Possible Formation of the IVA Magma by Impact Melting and Reduction of L-LL-Chondrite Materials Followed by Crystallization and Cooling

NASA Technical Reports Server (NTRS)

Wasson, John T.; Matsunami, Yoshiyuki; Rubin, Alan E.

2006-01-01

Group IVA is a large magmatic group of iron meteorites. The mean DELTA O-17 (= delta O-17 - 0.52(raised dot) delta O-18) of the silicates is approx. plus or minus 1.2%o, similar to the highest values in L chondrites and the lowest values in LL chondrites; delta O-18 values are also in the L/LL range. This strongly suggests that IVA irons formed by melting L-LL parental material, but the mean Ni content of IVA irons (83 mg/g) is much lower than that of a presumed L-LL parent (approx. 170 mg/g) and the low-Ca pyroxene present in two IVA meteorites is Fs13, much lower than the Fs20-29 values in L and LL chondrites. Thus, formation from L-LL precursors requires extensive addition of metallic Fe, probably produced by reduction of FeS and FeO. Group IVA also has S/Ni, Ga/Ni, and Ge/Ni ratios that are much lower than those in L-LL chondrites or any chondrite group that preserves nebular compositions, implying loss of these volatile elements during asteroidal processing. We suggest that these reduction and loss processes occurred near the surface of the asteroid during impact heating, and resulted partly from reduction by C, and partly from the thermal dissociation of FeS and FeO with loss of O and S. The hot (approx. 1770 K) low-viscosity melt quickly moved through channels in the porous asteroid to form a core. Two members of the IVA group, Sao Joao Nepomuceno (hereafter, SJN) and Steinbach, contain moderate amounts of orthopyroxene and silica, and minor amounts of low-Ca clinopyroxene. Even though SJN formed after approx. 26% crystallization and Steinbach formed after approx. 77% Crystallization of the IVA core, both could have originated within several tens of meters of the core-mantle interface if 99% of the crystallization occurred from the center outwards. Two other members of the group (Gibeon and Bishop Canyon) contain tabular tridymite, which we infer to have initially formed as veins deposited from a cooling SiO-rich vapor. The silicates were clearly introduced into IVA irons after the initial magma crystallized. Because the y-iron crystals in SJN are typically about 5 cm across, an order of magnitude smaller than in IVA irons that do not contain massive silicates, we infer that the metal was in the gamma-iron field when the silicates were injected. The SJN and Steinbach silicate compositions are near the low-Ca-pyroxene/silica eutectic compositions. We suggest that a tectonic event produced a eutectic-like liquid and injected it together with unmelted pyroxene grains into fissures in the solid metal core. Published estimates of IVA metallographic cooling rates range from 20 to 3000 K/Ma, leading to a hypothesized breakup of the core during a major impact followed by scrambling of the core and mantle debris [Haack, H., Scott, E.R.D., Love, S.G., Brearley, A. 1996. Thermal histories of IVA stony-iron and iron meteorites: evidence for asteroid fragmentation and reaccretion. Geochim. Cosmochim. Acta 60, 3103-3113]. This scrambling model is physically implausible and cannot explain the strong correlation of estimated cooling rates with metal composition. Previous workers concluded that the low-Ca clinopyroxene in SJN and Steinbach formed from protopyroxene by quenching at a cooling rate of 10(sup 12) K/Ma, and suggested that this also supported an impact-scrambling model. This implausible spike in cooling rate by a factor of 10(sup 10) can be avoided if the low-Ca clinopyroxene were formed by a late shock event that converted orthopyroxene to clinopyroxene followed by minimal growth in the clinopyroxene field, probably because melt was also produced. We suggest that metallographic cooling-rate estimates (e.g., based on island taenite) giving similar values throughout the metal compositional range are more plausible, and that the IVA parent asteroid can be modeled by monotonic cooling followed by a high-temperature impact event that introduced silicates into the metal and a low-temperature impact event that partially converted thopyroxene into low-Ca clinopyroxene.

LA-ICP-MS Study of Trace Elements in the Chanuskij Metal

NASA Technical Reports Server (NTRS)

Petaev, Michail I.

2005-01-01

This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.

Are modern geothermal waters in northwest Nevada forming epithermal gold deposits?

USGS Publications Warehouse

Breit, George N.; Hunt, Andrew G.; Wolf, Ruth E.; Koenig, Alan E.; Fifarek, Richard; Coolbaugh, Mark F.

2010-01-01

Hydrothermal systems currently are active near some gold deposits in northwestern Nevada. Possible links of these modern systems to gold mineralization were evaluated by chemically and isotopically analyzing water samples from the Brady, Dixie Valley, Humboldt House, San Emidio-Empire, Soda Lake, and Wabuska geothermal areas. In addition, quartz veins from Humboldt House and the adjacent Florida Canyon Mine were analyzed to compare ore and gangue phases with those predicted to form from proximal hydrothermal fluids.Nearly all water samples are alkali-chloride-type. Total dissolved solids range from 800 to 3900 mg/L, and pH varies from 5.6 to 7.8. Geochemical modeling with SOLVEQ, WATCH, and CHILLER predict the precipitation of silica in all systems during cooling. Anhydrite, calcite, barite, pyrite, base-metal sulfides, and alumino-silicates are variably saturated at calculated reservoir temperatures and also precipitate during boiling/cooling of some fluids. Measured dissolved gold concentrations are low (<0.2μg/L), but are generally consistent with contents predicted by equilibrium of sampled solutions with elemental gold at reservoir temperatures.  Although the modern geothermal waters can precipitate ore minerals, the low gold and other ore metal concentrations require very large fluid volumes to form a deposit of economic interest.

Transfer of volatiles and metals from mafic to felsic magmas in composite magma chambers: An experimental study

NASA Astrophysics Data System (ADS)

Guo, Haihao; Audétat, Andreas

2017-02-01

In order to determine the behavior of metals and volatiles during intrusion of mafic magma into the base of silicic, upper crustal magma chambers, fluid-rock partition coefficients (Dfluid/rock) of Li, B, Na, S, Cl, K, Mn, Fe, Rb, Sr, Ba, Ce, Cu, Zn, Ag, Cd, Mo, As, Se, Sb, Te, W, Tl, Pb and Bi were determined experimentally at 2 kbar and 850 °C close to the solidus of mafic magma. In a first step, volatile-bearing mafic glasses were prepared by melting a natural basaltic trachyandesite in the presence of volatile-bearing fluids at 1200 °C/10 kbar in piston cylinder presses. The hydrous glasses were then equilibrated in subsequent experiments at 850 °C/2 kbar in cold-seal pressure vessels, which caused 80-90% of the melt to crystallize. After 0.5-2.0 days of equilibration, the exsolved fluid was trapped by means of in-situ fracturing in the form of synthetic fluid inclusions in quartz. Both the mafic rock residue and the fluid inclusions were subsequently analyzed by laser-ablation ICP-MS for major and trace elements. Reverse experiments were conducted by equilibrating metal-bearing aqueous solutions with rock powder and then trapping the fluid. In two additional experiments, information on relative element mobilities were obtained by reacting fluids that exsolved from crystallizing mafic magma with overlying silicic melts. The combined results suggest that under the studied conditions S, Cl, Cu, Se, Br, Cd and Te are most volatile (Dfluid/rock >10), followed by Li, B, Zn, As, Ag, Sb, Cs, W, Tl, Pb and Bi (Dfluid/rock = 1-10). Less volatile are Na, Mg, K, Ca, Mn, Fe, Rb, Sr, Mo and Rb (Dfluid/rock 0.1-1), and the least fluid-mobile elements are Al, Si, Ti, Zr, Ba and Ce (Dfluid/rock <0.1). This trend is broadly consistent with relative element volatilities determined on natural high-temperature fumarole gases, although some differences exist. Based on the volatility data and measured mineral-melt and sulfide-melt partition coefficients, volatile fluxing in felsic natural samples may be identified by Cu, Se, Te and Cd-enrichment in magmatic sulfides, and by As, Se, Cd and Bi-enrichment in magmatic apatite.

Metal endowment reflected in chemical composition of silicates and sulfides of mineralized porphyry copper systems, Urumieh-Dokhtar magmatic arc, Iran

NASA Astrophysics Data System (ADS)

Zarasvandi, Alireza; Rezaei, Mohsen; Raith, Johann G.; Pourkaseb, Houshang; Asadi, Sina; Saed, Madineh; Lentz, David R.

2018-02-01

The present work attempts to discriminate between the geochemical features of magmatic-hydrothermal systems involved in the early stages of mineralization in high grade versus low grade porphyry copper systems, using chemical compositions of silicate and sulfide minerals (i.e., plagioclase, biotite, pyrite and chalcopyrite). The data indicate that magmatic plagioclase in all of the porphyry copper systems studied here has high An% and Al content with a significant trend of evolution toward AlAl3SiO8 and □Si4O8 endmembers, providing insight into the high melt water contents of the parental magmas. Comparably, excess Al and An% in the high grade deposits appears to be higher than that of selected low grade deposits, representing a direct link between the amounts of exsolving hydrothermal fluids and the potential of metal endowment in porphyry copper deposits (PCDs). Also, higher Al contents accompanied by elevated An% are linked to the increasing intensity of disruptive alteration (phyllic) in feldspars from the high grade deposits. As calculated from biotite compositions, chloride contents are higher in the exsolving hydrothermal fluids that contributed to the early mineralization stages of highly mineralized porphyry systems. However, as evidenced by scattered and elevated log (fH2O)/(fHF) and log (fH2O)/(fHCl) values, chloride contents recorded in biotite could be influenced by post potassic fluids. Geothermometry of biotite associated with the onset of sulfide mineralization indicates that there is a trend of increasing temperature from high grade to low grade porphyry systems. Significantly, this is coupled with a sharp change in copper content of pyrite assemblages precipitated at the early stages of mineralization such that Cu decreased with increasing temperature. Based on EMPA and detailed WDS elemental mapping, trace elements do not exhibit complex compositional zoning or solid solution in the sulfide structure. Nevertheless, significant amounts of Cu and Au are contained in pyrite assemblages as micro- to nano-sized inclusions, especially in the high grade fertile porphyry deposits. However, unexpectedly high concentrations of Te, Se, and Re may be associated with early stage of sulfide mineralization, especially when there is no epithermal lithocap. This may highlight the significance of trace metals partitioning in the sulfides formed at the early stages of mineralization in PCDs.

Composition of Impact Melt Debris from the Eltanin Impact Strewn Field, Bellingshausen Sea

NASA Technical Reports Server (NTRS)

Kyte, Frank T.

2002-01-01

The impact of the km-sized Eltanin asteroid into the Bellingshausen Sea produced mm- to cm-sized vesicular impact melt-rock particles found in sediment cores across a large area of the ocean floor. These particles are composed mainly of olivine and glass with minor chromite and traces of NiFe-sulfides. Some particles have inclusions of unmelted mineral and rock fragments from the precursor asteroid. Although all samples of melt rock examined have experienced significant alteration since their deposition in the late Pliocene, a significant portion of these particles have interiors that remain pristine and can be used to estimate the bulk composition of the impact melt. The bulk composition of the melt-rock particles is similar to the composition of basaltic meteorites such as howardites or mesosiderite silicates, with a contribution from seawater salts and a siderophile-rich component. There is no evidence that the Eltanin impact melt contains a significant terrestrial silicate component that might have been incorporated by mixing of the projectile with oceanic crust. If terrestrial silicates were incorporated into the melt, then their contribution must be much less than 10 wt%. Since excess K, Na, and CI are not present in seawater proportions, uptake of these elements into the melt must have been greatest for K and least for CI, producing a K/CI ratio about 4 times that in seawater. After correcting for the seawater component, the bulk composition of the Eltanin impact melt provides the best estimate of the bulk composition of the Eltanin asteroid. Excess Fe in the impact melt, relative to that in howardites, must be from a significant metal phase in the parent asteroid. Although the estimated Fe:Ni:Ir ratios (8:1:4 x 10(exp -5)) are similar to those in mesosiderite metal nodules (10:1:6 x 10(exp -5), excess Co and Au by factors of about 2 and 10 times, respectively, imply a metal component distinct from that in typical mesosiderites. An alternative interpretation, that siderophiles have been highly fractionated from a mesosiderite source, would require loss of about 90% of the original metal from the impact melt and the sediments, and is unsupported by any observational data. More likely, the excess Fe in the melt rocks is 'representative of the amount of metal in the impacting asteroid, which is estimated to be 4+/- 1 wt%.

Chemical reactivity parameters (HSAB) applied to magma evolution and ore formation

NASA Astrophysics Data System (ADS)

Vigneresse, Jean-Louis

2012-11-01

Magmas are commonly described through the usual content of 10 major oxides. This requires a complex dimensional plot. Concepts of hard-soft acid-base (HSAB) interactions allow estimating chemical reactivity of elements, such as electronegativity, i.e. the chemical potential changed of sign, hardness and electrophilicity. For complex system, those values result from equalization methods, i.e. the equalization of the respective chemical potentials, or from ab-initio computations through density functional theory (DFT). They help to characterize silicate magmas by a single value describing their reactivity. Principles of minimum electrophilicity (mEP), maximum hardness (MHP) and minimum polarizability (mPP) indicate trends towards regions of higher stability. Those parameters are plotted within a fitness landscape diagram, highlighting toward which principle reactions trend. Major oxides, main minerals and magmas determine the respective fields in which evolve natural rocks. Three poles are identified, represented by silica and alkalis, whereas oxidation forms the third trend. Mantle-derived rocks show a large variation in electrophilicity compared to hardness. They present all characters of a closed chemical system, being simply described by the free Gibbs energy. Conversely, rocks contaminated within the continental crust show a large variation in hardness between a silica pole and an alkaline, defining two separate trends. The trends show the character of an open chemical system, requiring a Grand Potential description (i.e. taking into account the difference in chemical potential). The terms open and closed systems refer to thermodynamical description, implying contamination for the crust and recycling for the mantle. The specific role of alkalis contrasts with other cations, pointing to their behavior in modifying silicate polymer structures. A second application deals with the reactivity of the melt and its fluid phase. It leads to a better understanding on the mechanisms that control sequestration and transport of metals within the different phases during igneous activity. Based on high gas/melt partitioning for metals and similar reactivity, the gaseous phase is more attractive for metals than silicate melts. The presence of halogens in the fluid phase tends to reinforce hardness, making the fluid phase attractive for hard metals such as Sn or W. Conversely, the presence of S decreases hardness of the fluid phase that becomes attractive for soft metals such as Au, Ag and Cu.

Evidence for a Late Reducing Event in IAB-Silicate Inclusions

NASA Astrophysics Data System (ADS)

Seckendorff, V. V.; O'Neill, H. St. C.; Zipfel, J.; Palme, H.

1992-07-01

Coexisting orthopyroxene (opx) and olivine (ol) in silicate inclusions of IAB-iron meteorites have different Fe/(Fe+Mg) ratios. Ferrosilite (fs) contents of opx are higher than fayalite contents (fa) of ol (e.g., Bunch and Keil 1970). Non-ideal solid solution of fs in opx and/or fa in ol is generally assumed. We reinvestigated the equilibrium Fe-Mg distribution between coexisting ol+opx in the system MgO-FeO-SiO2 (von Seckendorff and O'Neill 1992). Reversal experiments at high- Mg compositions were performed from 900 to 1600 degrees C at 16 and 20 kbar using a barium borosilicate flux. The data could be fitted to a simple thermodynamic model with ol and opx treated as regular solutions and this model was found to describe satisfactorily the literature data extending down to 700 degrees C. For Fe/(Fe+Mg) between 0.05 to 0.15 we find KD^ol-opx close to one from 1600 to 700 degrees C, virtually independent of pressure and temperature. Fig. 1 shows experimental results at the Mg-rich end. Error bars mark 1-sigma standard deviations. Ol is in all cases more Fe-rich than coexisting opx, except for a single run at 1000 degrees C that probably did not reach equilibrium because of slow reaction kinetics. Two calculated distribution curves (1300, 700 degrees C at 16 kbar) lie close together indicating the absence of any significant temperature dependence of the exchange reaction at the Mg- rich end of the system. IAB-silicate inclusions plot outside the range of experimental data (Fig. 1). Although some previous models for Fe-Mg exchange between ol and opx (e.g., Sack 1980) extrapolate to KD<1 at temperatures near 500 degrees C, such models reproduce the experimental data (700 to 1600 degrees C) less well, than our updated model. In addition, temperatures at 500 degrees C are probably too low to allow Fe diffusion in opx. Two pyroxene equilibration temperatures of IAB-silicate inclusions are around 900-1000 degrees C suggesting a similar closure temperature for Fe diffusion in opx. Because of this and because of the essentially temperature-independent Fe-Mg distribution between ol and opx from 1600 to 700 degrees C, we conclude that the Fe-Mg distribution between ol and opx in IAB-silicate inclusion does not reflect thermodynamic equilibrium. As Fe-diffusion in ol is faster than in opx, redistribution of Fe in ol should have occurred at a temperature below the closure temperature for Fe-diffusion in opx. We suggest that FeO in ol was reduced to Fe metal by some species such as C, P, S, etc. A lower limit for the temperature of the reducing event is provided by Ca-zoning in ol, which develops below 650 degrees C (Kohler et al. 1991). Since strong FeO zoning in ol is absent, reduction of FeO in ol should have occurred above 650 degrees C, assuming similar diffusion coefficients for Ca and Fe in ol. References: Bunch T.E. and Keil K. (1970) Contrib. Mineral. Petrol. 25, 297-340. Kohler T., Palme H. and Brey G. (1991) N. Jb. Miner. Mh. 9, 423-431. Sack R.O. (1980) Contrib. Mineral. Petrol. 71, 257-269. v. Seckendorff V. and O'Neill H.St.C. (1992) Contr. Min. Petrol. (submitted).

Paleomagnetic Evidence for Partial Differentiation of the Silicate-Bearing IIE Iron Meteorite Parent Body

NASA Astrophysics Data System (ADS)

Maurel, C.; Bryson, J. F. J.; Weiss, B. P.; Scholl, A.

2016-12-01

The identification of dozens of petrologically diverse chondritic and achondritic meteoritic groups indicates that a diversity of planetesimals formed in the early solar system. It is commonly thought that planetesimals formed as either unmelted or else fully differentiated bodies, implying that chondrites and achondrites cannot have originated on a single body. However, it has been suggested that partially melted bodies with chondritic crusts and achondritic interiors may also have formed. This alternative proposal is supported by the recent identification of post-accretional remanent magnetization in CV, H chondrites, and also possibly in CM chondrites, which has been interpreted as possible evidence for a core dynamo on their parent bodies. Other piece of evidence suggesting the existence of partially differentiated bodies is the existence of the silicate-bearing IIE iron meteorites. The IIEs are composed of a Fe-Ni alloy matrix containing a mixture of chondritic, primitive achondritic, and chondritic silicate inclusions that likely formed on a single parent body. Therefore, IIEs may sample all three putative layers of a layered, partially differentiated body. On the other hand, the siderophile element compositions of the matrix metal demonstrate that it is not the product of fractional crystallization of a molten core. This suggests that the matrix metal is derived from isolated reservoirs of metal in the mantle and/or crust. It is unknown whether a large-scale metallic core, not represented by known meteorite samples, also formed on the same parent planetesimal. We can search for evidence of a molten, advecting core by assessing whether IIE irons contain remanent magnetization produced by a core dynamo. With this goal, we studied the paleomagnetism of a cloudy zone (CZ) interface in the Fe-Ni matrix of the IIE iron Colomera using X-ray photoelectron emission microscopy (XPEEM). Our initial results suggest that a steady, intense magnetic field was present during the gradual formation of the CZ. This may indicate the existence of an advecting core on the IIE parent body, which would support the hypothesis of a partially differentiated structure. We are continuing to test this conclusion with further XPEEM measurements on Colomera and other IIE irons.