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.

Metal-rich RRc Stars in the Carnegie RR Lyrae Survey

NASA Astrophysics Data System (ADS)

Sneden, Christopher; Preston, George W.; Kollmeier, Juna A.; Crane, Jeffrey D.; Morrell, Nidia; Prieto, José L.; Shectman, Stephen A.; Skowron, Dorota M.; Thompson, Ian B.

2018-01-01

We describe and employ a stacking procedure to investigate abundances derived from the low signal-to-noise ratio spectra obtained in the Carnegie RR Lyrae Survey (CARRS). We find iron metallicities that extend from [Fe/H] ∼ ‑2.5 to values at least as large as [Fe/H] ∼ ‑0.5 in the 274-spectrum CARRS RRc data set. We consider RRc sample contamination by high amplitude solar metallicity δ Scuti stars (HADS) at periods less than 0.3 days, where photometric discrimination between RRc and δ Scuti stars has proven to be problematic. We offer a spectroscopic discriminant, the well-marked overabundance of heavy elements, principally [Ba/H], that is a common, if not universal, characteristic of HADS of all periods and axial rotations. No bona fide RRc stars known to us have verified heavy-element overabundances. Three out of 34 stars in our sample with [Fe/H] > ‑0.7 exhibit anomalously strong features of Sr, Y, Zr, Ba, and many rare earths. However, carbon is not enhanced in these three stars, and we conclude that their elevated n-capture abundances have not been generated in interior neutron-capture nucleosynthesis. Contamination by HADS appears to be unimportant, and metal-rich RRc stars occur in approximately the same proportion in the Galactic field as do metal-rich RRab stars. An apparent dearth of metal-rich RRc is probably a statistical fluke. Finally, we show that RRc stars have a similar inverse period–metallicity relationship as has been found for RRab stars.

The Toxicological Geochemistry of Dusts, Soils, and Other Earth Materials: Insights From In Vitro Physiologically-based Geochemical Leach Tests

NASA Astrophysics Data System (ADS)

Plumlee, G. S.; Ziegler, T. L.; Lamothe, P.; Meeker, G. P.; Sutley, S.

2003-12-01

Exposure to mineral dusts, soils, and other earth materials results in chemical reactions between the materials and different body fluids that include, depending upon the exposure route, lung fluids, gastrointestinal fluids, and perspiration. In vitro physiologically-based geochemical leach tests provide useful insights into these chemical reactions and their potential toxicological implications. We have conducted such leach tests on a variety of earth materials, including asbestos, volcanic ash, dusts from dry lake beds, mine wastes, wastes left from the roasting of mercury ores, mineral processing wastes, coal dusts and coal fly ash, various soils, and complex dusts generated by the World Trade Center collapse. Size-fractionated samples of earth materials that have been well-characterized mineralogically and chemically are reacted at body temperature (37 C) for periods from 2 hours up to multiple days with various proportions of simulated lung, gastric, intestinal, and/or plasma-based fluids. Results indicate that different earth materials may have quite different solubility and dissolution behavior in vivo, depending upon a) the mineralogic makeup of the material, and b) the exposure route. For example, biodurable minerals such as asbestos and volcanic ash particles, whose health effects result because they dissolve very slowly in vivo, bleed off low levels of trace metals into the simulated lung fluids; these include metals such as Fe and Cr that are suspected by health scientists of contributing to the generation of reactive oxygen species and resulting DNA damage in vivo. In contrast, dry lake bed dusts and concrete-rich dusts are highly alkaline and bioreactive, and cause substantial pH increases and other chemical changes in the simulated body fluids. Many of the earth materials tested contain a variety of metals that can be quite soluble (bioaccessible), depending upon the material and the simulated body fluid composition. For example, due to their acidic pH and high chloride concentrations, simulated gastric fluids are most efficient at solubilizing metals such as Hg, Pb, Zn, and others that form strong chloride complexes; although these metals tend to partially reprecipitate in the near-neutral simulated intestinal fluids, complexes with organic ligands (i.e., amino and carboxylic acids) enhance their solubility. These metals are also quite soluble in near-neutral, protein-rich plasma-based fluids because they form strong complexes with the proteins. In contrast, metalloids that form oxyanion species (such as As, Cr, Mo, W) are commonly more soluble in near-neutral pH simulated lung fluids than in simulated gastric fluids.

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.

The deep structure of a sea-floor hydrothermal deposit

USGS Publications Warehouse

Zierenberg, R.A.; Fouquet, Y.; Miller, D.J.; Bahr, J.M.; Baker, P.A.; Bjerkgard, T.; Brunner, C.A.; Duckworth, R.C.; Gable, R.; Gieskes, J.; Goodfellow, W.D.; Groschel-Becker, H. M.; Guerin, G.; Ishibashi, J.; Iturrino, G.; James, R.H.; Lackschewitz, K.S.; Marquez, L.L.; Nehlig, P.; Peter, J.M.; Rigsby, C.A.; Schultheiss, P.; Shanks, Wayne C.; Simoneit, B.R.T.; Summit, M.; Teagle, D.A.H.; Urbat, M.; Zuffa, G.G.

1998-01-01

Hydrothermal circulation at the crests of mid-ocean ridges plays an important role in transferring heat from the interior of the Earth. A consequence of this hydrothermal circulation is the formation of metallic ore bodies known as volcanic-associated massive sulphide deposits. Such deposits, preserved on land, were important sources of copper for ancient civilizations and continue to provide a significant source of base metals (for example, copper and zinc). Here we present results from Ocean Drilling Program Leg 169, which drilled through a massive sulphide deposit on the northern Juan de Fuca spreading centre and penetrated the hydrothermal feeder zone through which the metal-rich fluids reached the sea floor. We found that the style of feeder-zone mineralization changes with depth in response to changes in the pore pressure of the hydrothermal fluids and discovered a stratified zone of high-grade copper-rich replacement mineralization below the massive sulphide deposit. This copper-rich zone represents a type of mineralization not previously observed below sea-floor deposits, and may provide new targets for land-based mineral exploration.

New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

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

Li, Yuwei; Zhang, Lijun; Singh, David J.

The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

DOE PAGES

Li, Yuwei; Zhang, Lijun; Singh, David J.

2017-10-16

The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

Fractionation of rhenium from osmium during noble metal alloy formation in association with sulfides: Implications for the interpretation of model ages in alloy-bearing magmatic rocks

NASA Astrophysics Data System (ADS)

Fonseca, Raúl O. C.; Brückel, Karoline; Bragagni, Alessandro; Leitzke, Felipe P.; Speelmanns, Iris M.; Wainwright, Ashlea N.

2017-11-01

Although Earth's continental crust is thought to derive from melting of the Earth's mantle, how the crust has formed and the timing of its formation are not well understood. The main difficulty in understanding how the crust was extracted from the Earth's mantle is that most isotope systems recorded in mantle rocks have been disturbed by crustal recycling, metasomatic activity and dilution of the signal by mantle convection. In this regard, important age constraints can be obtained from Re-Os model ages in platinum group minerals (PGM), as Re-poor and Os-rich PGM show evidence of melting events up to 4.1 Ga. To constrain the origin of the Re-Os fractionation and Os isotope systematics of natural PGM, we have investigated the linkage between sulfide and PGM grains of variable composition via a series of high-temperature experiments carried out at 1 bar. We show that with the exception of laurite, all experimentally-produced PGM, in particular Pt3Fe (isoferroplatinum) and Pt-Ir metal grains, are systematically richer in Re than their sulfide precursors and will develop radiogenic 187Os /188Os signatures over time relative to their host base metal sulfides. Cooling of an PGM-saturated sulfide assemblage shows a tendency to amplify the extent of Re-Os fractionation between PGM and the different sulfide phases present during cooling. Conversely, laurite grains (RuS2) are shown to accept little to no Re in them and their Os isotope composition changes little over time as a result. Laurite is therefore the PGM that provides the most robust Re-depletion ages in mantle lithologies. Our results are broadly consistent with observations made on natural PGM, where laurites are systematically less radiogenic than Pt-rich PGM. These experimental results highlight the need for the acquisition of large datasets for both mantle materials and ophiolite-derived detrital grains that include measurements of the Os isotope composition of minerals rich in highly siderophile elements at the grain scale (i.e. PGM and base metal sulfides). Only with such datasets is it possible to identify past episodes of mantle melting.

Stability of iron-rich magnesiowüstite in Earth's lower mantle

NASA Astrophysics Data System (ADS)

Ohta, K.; Fujino, K.; Kuwayama, Y.; Kondo, T.; Shimizu, K.; Ohishi, Y.

2012-12-01

At ambient conditions, MgO periclase and FeO wüstite form a solid solution (Mg1-xFex)O, named ferropericlase (x ≤ 0.5) and magnesiowüstite (x > 0.5). (Mg1-xFex)O ferropericlase is considered to be a major component of Earth's lower mantle, and may play an important role for its structure and dynamics. Iron-rich magnesiowüstite also needs to be considered because of possible iron enrichment at the core-mantle boundary region [e.g., Nomura et al., 2011]. Recent laser-heated diamond anvil cell experiments on FeO revealed that NaCl-type (B1) structured FeO underwent an insulator-metal transition at about 70 GPa and 1800 K without any structural transformation [Fischer et al., 2011; Ohta et al., 2012]. These results imply that the metallic B1 FeO would require a two-phase field for the MgO-FeO binary system due to different chemical bonding between insulating MgO and metallic FeO. We performed simultaneous electrical conductivity and x-ray diffraction measurements on (Mg0.20Fe0.80)O and (Mg0.05Fe0.95)O magnesiowüstite up to 140 GPa and 2100 K, and then examined recovered samples by using analytical transmission electron microprobe. We obtained some evidences for the dissociation of (Mg0.05Fe0.95)O into lighter and heavier phases than starting material occurring above 70 GPa and 1900 K, which is most likely due to the metallization of FeO component. On the other hand, we did not observe such dissociation and metallization in (Mg0.20Fe0.80)O. Observed dissociation in (Mg0.05Fe0.95)O might contribute to the heterogeneity in seismic wave and electrical conductivity at the Earth's core-mantle boundary region.

Were micrometeorites a source of prebiotic molecules on the early Earth?

PubMed

Maurette, M; Brack, A; Kurat, G; Perreau, M; Engrand, C

1995-03-01

"Interplanetary Dust Particles" with sizes approximately 10 micrometers collected in the stratosphere (IDPs), as well as much larger "giant" micrometeorites retrieved from Antarctic ice melt water (AMMs), are mostly composed of unequilibrated assemblages of minerals, thus being related to primitive unequilibrated meteorites. Two independent evaluations of the mass flux of micrometeorites measuring approximately 50 micrometers to approximately 200 micrometers, recovered from either the Greenland or the Antarctic ice sheets have been reported (approximately 20,000 tons/a). A comparison with recent evaluation of the flux of meteorites reaching the Earth's surface (up to masses of 10,000 tons), indicates that micrometeorites represent about 99.5% of the extraterrestrial material falling on the Earth's surface each year. As they show carbon concentrations exceeding that of the most C-rich meteorite (Orgueil), they are the major contributors of extraterrestrial C-rich matter accreting to the Earth today. Moreover they are complex microstructured aggregates of grains. They contain not only a variety of C-rich matter, such as a new "dirty" magnetite phase enriched in P, S, and minor elements, but also a diversity of potential catalysts (hydrous silicates, oxides, sulfides and metal grains of Fe/Ni composition, etc.). They could have individually functioned on the early Earth, as "micro-chondritic-reactors" for the processing of prebiotic organic molecules in liquid water. Future progress requires the challenging development of meaningful laboratory simulation experiments, and a better understanding of the partial reprocessing of micrometeorites in the atmosphere.

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.

Origins of ultralow velocity zones through slab-derived metallic melt

PubMed Central

Liu, Jiachao; Li, Jie; Smith, Jesse S.

2016-01-01

Understanding the ultralow velocity zones (ULVZs) places constraints on the chemical composition and thermal structure of deep Earth and provides critical information on the dynamics of large-scale mantle convection, but their origin has remained enigmatic for decades. Recent studies suggest that metallic iron and carbon are produced in subducted slabs when they sink beyond a depth of 250 km. Here we show that the eutectic melting curve of the iron−carbon system crosses the current geotherm near Earth’s core−mantle boundary, suggesting that dense metallic melt may form in the lowermost mantle. If concentrated into isolated patches, such melt could produce the seismically observed density and velocity features of ULVZs. Depending on the wetting behavior of the metallic melt, the resultant ULVZs may be short-lived domains that are replenished or regenerated through subduction, or long-lasting regions containing both metallic and silicate melts. Slab-derived metallic melt may produce another type of ULVZ that escapes core sequestration by reacting with the mantle to form iron-rich postbridgmanite or ferropericlase. The hypotheses connect peculiar features near Earth's core−mantle boundary to subduction of the oceanic lithosphere through the deep carbon cycle. PMID:27143719

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.

Heavy Metal - Exploring a magnetised metallic asteroid

NASA Astrophysics Data System (ADS)

Wahlund, J.-E.; Andrews, D. J.

2017-09-01

We propose an ESA/M5 spacecraft mission to orbit and explore (16) Psyche - the largest M-class metallic asteroid in the main belt. Recent estimates of the shape, 279×232×189 km and mass, 2.7×1019 kg of (16) Psyche make it one of the largest and densest of asteroids, 4.5 g cm-3, and together with the high surface radar reflectivity and the spectral data measured from Earth it is consistent with a bulk composition rich in iron-nickel. (16) Psyche orbits the Sun with semi-major axis 2.9 AU, 3º inclination, and is as yet unexplored in-situ.

Heavy Metal - Exploring a magnetised metallic asteroid

NASA Astrophysics Data System (ADS)

Wahlund, Jan-Erik; Andrews, David; Futaana, Yoshifumi; Masters, Adam; Thomas, Nicolas; De Sanctis, Maria Cristina; Herique, Alain; Retherford, Kurt; Tortora, Paolo; Trigo-Rodriguez, Joseph; Ivchenko, Nickolay; Simon, Sven

2017-04-01

We propose a spacecraft mission (Heavy Metal) to orbit and explore (16) Psyche - the largest M-class metallic asteroid in the main belt. Recent estimates of the shape, 279×232×189 km and mass, 2.7×10(19) kg make it one of the largest and densest of asteroids, and together with the high surface radar reflectivity and the spectral data measured from Earth it is consistent with a bulk composition rich in iron-nickel. The M5 mission Heavy Metal will investigate if (16) Psyche is the exposed metallic core of a planetesimal, formed early enough to melt and differentiate. High-resolution mapping of the surface in optical, IR, UV and radar wavebands, along with the determination of the shape and gravity field will be used to address the formation and subsequent evolution of (16) Psyche, determining the origin of metallic asteroids. It is conceivable that a cataclysmic collision with a second body led to the ejection of all or part of the differentiated core of the parent body. Measurements at (16) Psyche therefore provide a possibility to directly examine an iron-rich planetary core, similar to that expected at the center of all the major planets including Earth. A short-lived dynamo producing a magnetic field early in the life of (16) Psyche could have led to a remnant field (of tens of micro Tesla) being preserved in the body today. (16) Psyche is embedded in the variable flow of the solar wind. Whereas planetary magnetospheres and induced magnetospheres are the result of intense dynamo fields and dense conductive ionospheres presenting obstacles to the solar wind, (16) Psyche may show an entirely new 'class' of interaction as a consequence of its lack of a significant atmosphere, the extremely high bulk electrical conductivity of the asteroid, and the possible presence of intense magnetic fields retained in iron-rich material. The small characteristic scale of (16) Psyche ( 200 km) firmly places any solar wind interaction in the "sub-MHD" scale, in which kinetic plasma effects must be considered. Heavy Metal will investigate if (16) Psyche has an extended magnetosphere by mapping the local plasma density, composition, energy state and dynamics around the body, along with the magnetic field. By accurately mapping any internally retained magnetic field of (16) Psyche, we will address the origin of any magnetization (the possible remains of an early magnetic dynamo). The Heavy Metal spacecraft will be launched from Earth with an Ariane 6.2 rocket in the time window 2029 - 2031, and by using electric propulsion, along with a possible gravity assist manoeuvre by Mars, arrive at (16) Psyche some 4 - 4.5 years later. The S/C is then planned to orbit the body for a period of 1 year, and release a CubeSat for close up studies.

High contents of rare earth elements (REEs) in stream waters of a Cu-Pb-Zn mining area.

PubMed

Protano, G; Riccobono, F

2002-01-01

Stream waters draining an old mining area present very high rare earth element (REE) contents, reaching 928 microg/l as the maximum total value (sigmaREE). The middle rare earth elements (MREEs) are usually enriched with respect to both the light (LREEs) and heavy (HREEs) elements of this group, producing a characteristic "roof-shaped" pattern of the shale Post-Archean Australian Shales-normalized concentrations. At the Fenice Capanne Mine (FCM), the most important base metal mine of the study area, the REE source coincides with the mine tailings, mostly the oldest ones composed of iron-rich materials. The geochemical history of the REEs released into Noni stream from wastes in the FCM area is strictly determined by the pH, which controls the REE speciation and in-stream processes. The formation of Al-rich and mainly Fe-rich flocs effectively scavenges the REEs, which are readily and drastically removed from the solution when the pH approaches neutrality. Leaching experiments performed on flocs and waste materials demonstrate that Fe-oxides/oxyhydroxides play a key role in the release of lanthanide elements into stream waters. The origin of the "roof-shaped" REE distribution pattern as well as the peculiar geochemical behavior of some lanthanide elements in the aqueous system are discussed.

Temperate Earth-sized planets transiting a nearby ultracool dwarf star

NASA Astrophysics Data System (ADS)

Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M.; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam J.; Triaud, Amaury H. M. J.; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K.; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

2016-05-01

Star-like objects with effective temperatures of less than 2,700 kelvin are referred to as ‘ultracool dwarfs’. This heterogeneous group includes stars of extremely low mass as well as brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15 per cent of the population of astronomical objects near the Sun. Core-accretion theory predicts that, given the small masses of these ultracool dwarfs, and the small sizes of their protoplanetary disks, there should be a large but hitherto undetected population of terrestrial planets orbiting them—ranging from metal-rich Mercury-sized planets to more hospitable volatile-rich Earth-sized planets. Here we report observations of three short-period Earth-sized planets transiting an ultracool dwarf star only 12 parsecs away. The inner two planets receive four times and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Our data suggest that 11 orbits remain possible for the third planet, the most likely resulting in irradiation significantly less than that received by Earth. The infrared brightness of the host star, combined with its Jupiter-like size, offers the possibility of thoroughly characterizing the components of this nearby planetary system.

Temperate Earth-sized planets transiting a nearby ultracool dwarf star.

PubMed

Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam J; Triaud, Amaury H M J; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

2016-05-12

Star-like objects with effective temperatures of less than 2,700 kelvin are referred to as 'ultracool dwarfs'. This heterogeneous group includes stars of extremely low mass as well as brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15 per cent of the population of astronomical objects near the Sun. Core-accretion theory predicts that, given the small masses of these ultracool dwarfs, and the small sizes of their protoplanetary disks, there should be a large but hitherto undetected population of terrestrial planets orbiting them--ranging from metal-rich Mercury-sized planets to more hospitable volatile-rich Earth-sized planets. Here we report observations of three short-period Earth-sized planets transiting an ultracool dwarf star only 12 parsecs away. The inner two planets receive four times and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Our data suggest that 11 orbits remain possible for the third planet, the most likely resulting in irradiation significantly less than that received by Earth. The infrared brightness of the host star, combined with its Jupiter-like size, offers the possibility of thoroughly characterizing the components of this nearby planetary system.

Lunar-derived titanium alloys for hydrogen storage

NASA Technical Reports Server (NTRS)

Love, S.; Hertzberg, A.; Woodcock, G.

1992-01-01

Hydrogen gas, which plays an important role in many projected lunar power systems and industrial processes, can be stored in metallic titanium and in certain titanium alloys as an interstitial hydride compound. Storing and retrieving hydrogen with titanium-iron alloy requires substantially less energy investment than storage by liquefaction. Metal hydride storage systems can be designed to operate at a wide range of temperatures and pressures. A few such systems have been developed for terrestrial applications. A drawback of metal hydride storage for lunar applications is the system's large mass per mole of hydrogen stored, which rules out transporting it from earth. The transportation problem can be solved by using native lunar materials, which are rich in titanium and iron.

Structure and magnetic properties of RE{sub 2}CuIn{sub 3} (RE=Ce, Pr, Nd, Sm and Gd)

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

Tyvanchuk, Yuriy B.; Szytula, Andrzej; Zarzycki, Arkadiusz

2008-12-15

The ternary copper indides RE{sub 2}CuIn{sub 3}{identical_to}RECu{sub 0.5}In{sub 1.5} (RE=Ce, Pr, Nd, Sm and Gd) were synthesized from the elements in sealed tantalum tubes in an induction furnace. They crystallize with the CaIn{sub 2}-type structure, space group P6{sub 3}/mmc, with a statistical occupancy of copper and indium on the tetrahedral substructure. These indides show homogeneity ranges RECu{sub x}In{sub 2-x}. Single crystal structure refinements were performed for five crystals: CeCu{sub 0.66}In{sub 1.34} (a=479.90(7) pm, c=768.12(15) pm), PrCu{sub 0.52}In{sub 1.48} (a=480.23(7) pm, c=759.23(15) pm), NdCu{sub 0.53}In{sub 1.47} (a=477.51(7) pm, c=756.37(15) pm), SmCu{sub 0.46}In{sub 1.54} (a=475.31(7) pm, c=744.77(15) pm), and GdCu{sub 0.33}In{sub 1.67}more » (a=474.19(7), c=737.67(15) pm). Temperature-dependent susceptibility measurements show antiferromagnetic ordering at T{sub N}=4.7 K for Pr{sub 2}CuIn{sub 3} and Nd{sub 2}CuIn{sub 3} and 15 K for Sm{sub 2}CuIn{sub 3}. Fitting of the susceptibility data of the samarium compound revealed an energy gap {delta}E=39.7(7) K between the ground and the first excited levels. - Graphical abstract: The CaIn{sub 2}-type structure of Sm{sub 2}CuIn{sub 3}.« less

Microphysical Modeling of Mineral Clouds in GJ1214 b and GJ436 b: Predicting Upper Limits on the Cloud-top Height

NASA Astrophysics Data System (ADS)

Ohno, Kazumasa; Okuzumi, Satoshi

2018-05-01

The ubiquity of clouds in the atmospheres of exoplanets, especially of super-Earths, is one of the outstanding issues for the transmission spectra survey. Understanding the formation process of clouds in super-Earths is necessary to interpret the observed spectra correctly. In this study, we investigate the vertical distributions of particle size and mass density of mineral clouds in super-Earths using a microphysical model that takes into account the vertical transport and growth of cloud particles in a self-consistent manner. We demonstrate that the vertical profiles of mineral clouds significantly vary with the concentration of cloud condensation nuclei and atmospheric metallicity. We find that the height of the cloud top increases with increasing metallicity as long as the metallicity is lower than the threshold. If the metallicity is larger than the threshold, the cloud-top height no longer increases appreciably with metallicity because coalescence yields larger particles of higher settling velocities. We apply our cloud model to GJ1214 b and GJ436 b, for which recent transmission observations suggest the presence of high-altitude opaque clouds. For GJ436 b, we show that KCl particles can ascend high enough to explain the observation. For GJ1214 b, by contrast, the height of KCl clouds predicted from our model is too low to explain its flat transmission spectrum. Clouds made of highly porous KCl particles could explain the observations if the atmosphere is highly metal-rich, and hence the particle microstructure might be a key to interpret the flat spectrum of GJ1214 b.

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.

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.

Complete phase diagram of rare-earth nickelates from first-principles

NASA Astrophysics Data System (ADS)

Varignon, Julien; Grisolia, Mathieu N.; Íñiguez, Jorge; Barthélémy, Agnès; Bibes, Manuel

2017-12-01

The structural, electronic and magnetic properties of AMO3 perovskite oxides, where M is a 3d transition metal, are highly sensitive to the geometry of the bonds between the metal-d and oxygen-p ions (through octahedra rotations and distortions) and to their level of covalence. This is particularly true in rare-earth nickelates RNiO3 that display a metal-insulator transition with complex spin orders tunable by the rare-earth size, and are on the border line between dominantly ionic (lighter elements) and covalent characters (heavier elements). Accordingly, computing their ground state is challenging and a complete theoretical description of their rich phase diagram is still missing. Here, using first-principles simulations, we successfully describe the electronic and magnetic experimental ground state of nickelates. We show that the insulating phase is characterized by a split of the electronic states of the two Ni sites (i.e., resembling low-spin 4+ and high-spin 2+) with a concomitant shift of the oxygen-2p orbitals toward the depleted Ni cations. Therefore, from the point of view of the charge, the two Ni sites appear nearly identical whereas they are in fact distinct. Performing such calculations for several nickelates, we built a theoretical phase diagram that reproduces all their key features, namely a systematic dependence of the metal-insulator transition with the rare-earth size and the crossover between a second to first order transition for R = Pr and Nd. Finally, our results hint at strategies to control the electronic and magnetic phases of perovskite oxides by fine tuning of the level of covalence.

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.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

PubMed

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

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.

Temperate Earth-sized planets transiting a nearby ultracool dwarf star

PubMed Central

Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M.; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam; Triaud, Amaury H. M. J.; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K.; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

2017-01-01

Stellar-like objects with effective temperatures of 2700K and below are referred to as “ultracool dwarfs”1. This heterogeneous group includes both extremely low-mass stars and brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15% of the stellar-like objects in the vicinity of the Sun2. Based on the small masses and sizes of their protoplanetary disks3,4, core-accretion theory for ultracool dwarfs predicts a large, but heretofore undetected population of close-in terrestrial planets5, ranging from metal-rich Mercury-sized planets6 to more hospitable volatile-rich Earth-sized planets7. Here we report the discovery of three short-period Earth-sized planets transiting an ultracool dwarf star 12 parsecs away using data collected by the TRAPPIST8 telescope as part of an ongoing prototype transit survey9. The inner two planets receive four and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star10. Eleven orbits remain possible for the third planet based on our data, the most likely resulting in an irradiation significantly smaller than Earth's. The infrared brightness of the host star combined with its Jupiter-like size offer the possibility of thoroughly characterizing the components of this nearby planetary system. PMID:27135924

Siderophile Element Constraints on the Conditions of Core Formation in Mars

NASA Technical Reports Server (NTRS)

Righter, K.; Humayun, M.

2012-01-01

Siderophile element concentrations in planetary basalts and mantle samples have been used to estimate conditions of core formation for many years and have included applications to Earth, Moon, Mars and asteroid 4 Vesta [1]. For Earth, we have samples of mantle and a diverse collection of mantle melts which have provided a mature understanding of the how to reconstruct the concentration of siderophile elements in mantle materials, from only concentrations in surficial basalt (e.g., [2]). This approach has led to the consensus views that Earth underwent an early magma ocean stage to pressures of 40-50 GPa (e.g., [3,4]), Moon melted extensively and formed a small (approx. 2 mass %) metallic core [5], and 4 Vesta contains a metallic core that is approximately 18 mass % [6,7]. Based on new data from newly found meteorites, robotic spacecraft, and experimental partitioning studies, [8] showed that eight siderophile elements (Ni, Co, Mo, W, Ga, P, V and Cr) are consistent with equilibration of a 20 mass% S-rich metallic core with the mantle at pressures of 14 +/- 3 GPa. We aim to test this rather simple scenario with additional analyses of meteorites for a wide range of siderophile elements, and application of new experimental data for the volatile siderophile and highly siderophile elements.

Alkali and alkaline earth metal salts of tetrazolone: structurally interesting and excellently thermostable.

PubMed

He, Piao; Wu, Le; Wu, Jin-Ting; Yin, Xin; Gozin, Michael; Zhang, Jian-Guo

2017-07-04

Tetrazolone (5-oxotetrazole) was synthesized by a moderate strategy through three steps (addition, cyclization and catalytic hydrogenation) avoiding the unstable intermediate diazonium, as reported during the previous preparation. Alkali and alkaline earth metal salts with lithium (1), sodium (2), potassium (3), rubidium (4) caesium (5), magnesium (6), calcium (7), strontium (8) and barium (9) were prepared and fully characterized using elemental analysis, IR and NMR spectroscopy, DSC and TG analysis. All metal salts were characterized via single-crystal X-ray diffraction. They crystallize in common space groups with high densities ranging from 1.479 (1) to 3.060 g cm -3 (5). Furthermore, the crystal structures of 7, 8 and 9 reveal interesting porous energetic coordination polymers with strong hydrogen bond interactions. All new salts have good thermal stabilities with decomposition temperature between 215.0 °C (4) and 328.2 °C (7), significantly higher than that of the reported nitrogen-rich salt neutral tetrazolone. The sensitivities towards impact and friction were tested using standard methods, and all the tetrazolone-based compounds investigated can be classified into insensitive. The flame test of these metal salts supports their potential use as perchlorate-free pyrotechnics or eco-friendly insensitive energetic materials.

Wide-band-gap, alkaline-earth-oxide semiconductor and devices utilizing same

DOEpatents

Abraham, Marvin M.; Chen, Yok; Kernohan, Robert H.

1981-01-01

This invention relates to novel and comparatively inexpensive semiconductor devices utilizing semiconducting alkaline-earth-oxide crystals doped with alkali metal. The semiconducting crystals are produced by a simple and relatively inexpensive process. As a specific example, a high-purity lithium-doped MgO crystal is grown by conventional techniques. The crystal then is heated in an oxygen-containing atmosphere to form many [Li].degree. defects therein, and the resulting defect-rich hot crystal is promptly quenched to render the defects stable at room temperature and temperatures well above the same. Quenching can be effected conveniently by contacting the hot crystal with room-temperature air.

Earth Observations taken by the Expedition 22 Crew

NASA Image and Video Library

2010-01-14

ISS022-E-026137 (14 Jan. 2010) --- Open Pit Mines in southern Arizona are featured in this image photographed by an Expedition 22 crew member on the International Space Station. The State of Arizona is the United States? largest producer of the metal copper, primarily mined from ore bodies known as porphyry copper deposits. Copper is a good conductor of electricity and heat, and is a vital element of virtually all of our electronic devices and components. A porphyry copper deposit is a geological structure formed by crystal-rich magma moving upwards through pre-existing rock layers. As the magma cools and crystallizes, it forms an igneous rock with large crystals embedded in a fine-grained matrix, known as porphyry. Hot fluids circulate through the magma and surrounding rocks via fractures, depositing copper-bearing and other minerals in characteristic spatial patterns that signal the nature of the ore body to a geologist. The most common approach to extracting metal-bearing ore from a porphyry copper deposit is by open-pit mining. For more details, please refer to http://earth.jsc.nasa.gov/EarthObservatory/OpenPitMinesSouthernArizona.htm.

Yttrium and rare earth stabilized fast reactor metal fuel

DOEpatents

Guon, Jerold; Grantham, LeRoy F.; Specht, Eugene R.

1992-01-01

To increase the operating temperature of a reactor, the melting point and mechanical properties of the fuel must be increased. For an actinide-rich fuel, yttrium, lanthanum and/or rare earth elements can be added, as stabilizers, to uranium and plutonium and/or a mixture of other actinides to raise the melting point of the fuel and improve its mechanical properties. Since only about 1% of the actinide fuel may be yttrium, lanthanum, or a rare earth element, the neutron penalty is low, the reactor core size can be reduced, the fuel can be burned efficiently, reprocessing requirements are reduced, and the nuclear waste disposal volumes reduced. A further advantage occurs when yttrium, lanthanum, and/or other rare earth elements are exposed to radiation in a reactor, they produce only short half life radioisotopes, which reduce nuclear waste disposal problems through much shorter assured-isolation requirements.

Clouds and hazes in exoplanets and brown dwarfs

NASA Astrophysics Data System (ADS)

Morley, Caroline Victoria

The formation of clouds significantly alters the spectra of cool substellar atmospheres from terrestrial planets to brown dwarfs. In cool planets like Earth and Jupiter, volatile species like water and ammonia condense to form ice clouds. In hot planets and brown dwarfs, iron and silicates instead condense, forming dusty clouds. Irradiated methane-rich planets may have substantial hydrocarbon hazes. During my dissertation, I have studied the impact of clouds and hazes in a variety of substellar objects. First, I present results for cool brown dwarfs including clouds previously neglected in model atmospheres. Model spectra that include sulfide and salt clouds can match the spectra of T dwarf atmospheres; water ice clouds will alter the spectra of the newest and coldest brown dwarfs, the Y dwarfs. These sulfide/salt and ice clouds potentially drive spectroscopic variability in these cool objects, and this variability should be distinguishable from variability caused by hot spots. Next, I present results for small, cool exoplanets between the size of Earth and Neptune. They likely have sulfide and salt clouds and also have photochemical hazes caused by stellar irradiation. Vast resources have been dedicated to characterizing the handful of super Earths and Neptunes accessible to current telescopes, yet of the planets smaller than Neptune studied to date, all have radii in the near-infrared consistent with being constant in wavelength, likely showing that these small planets are consistently enshrouded in thick hazes and clouds. For the super Earth GJ 1214b, very thick, lofted clouds of salts or sulfides in high metallicity (1000x solar) atmospheres create featureless transmission spectra in the near-infrared. Photochemical hazes also create featureless transmission spectra at lower metallicities. For the Neptune-sized GJ 436b, its thermal emission and transmission spectra combine indicate a high metallicity atmosphere, potentially heated by tides and affected by disequilibrium chemistry. I show that despite the challenges, there are promising avenues for understanding small planets: by observing thermal emission and reflected light, we can break the degeneracies and con- strain the atmospheric compositions. These future observations will provide rich diagnostics of molecules and clouds in small planets.

Resources of Near-Earth Space: Abstracts

NASA Technical Reports Server (NTRS)

1991-01-01

The objectives are by theory, experiment, and bench-level testing of small systems, to develop scientifically-sound engineering processes and facility specifications for producing propellants and fuels, construction and shielding materials, and life support substances from the lithospheres and atmospheres of lunar, planetary, and asteroidal bodies. Current emphasis is on the production of oxygen, other usefull gases, metallic, ceramic/composite, and related byproducts from lunar regolith, carbonaceous chrondritic asteroids, and the carbon dioxide rich Martian atmosphere.

Water abundance and accretion history of terrestrial planets

NASA Technical Reports Server (NTRS)

Waenke, H.; Dreibus, G.

1994-01-01

According to a widespread believe, Earth's water was either added in form of a late volatile-rich veneer or as we have argued repeatedly that of all the water which was added to the Earth only that portion remained which was added towards the end of accretion when the mean oxygen fugacity of the accreting material became so high that metallic iron could not exist any longer. Prior to this moment, all the water in the latter scenario would have been used up for the oxidation of iron. Fe + H2O yields FeO + H2. Huge quantities of hydrogen would continuously be produced in this scenario which escaped. In the same moment the hydrogen on its way to the surface would lead to an efficient degassing of the growing Earth's mantle. The fact that - assuming C1 abundances - the amount of iridium in the Earth's mantle agrees, within a factor of two with the total water inventory of the Earth's mantle and crust is taken as evidence for the validity of such a scenario. In both scenarios, the Earth's mantle would remain dry and devoid of other volatiles. Some species soluble in metallic iron like carbon and hydrogen will probably partly enter the core in some portions. It is generally assumed that today a considerable portion of the earth's total water inventory resides in the mantle. It is also clear that over the history of the Earth the water of the Earth's oceans has been recycled many times through the mantle. This is the consequence of plate subduction. In a similar way mantle convection was probably responsible to being water into the originally dry mantle. As a consequence, today the Earth is wet both inside and outside.

β-Decay Half-Lives of 110 Neutron-Rich Nuclei across the N=82 Shell Gap: Implications for the Mechanism and Universality of the Astrophysical r Process.

PubMed

Lorusso, G; Nishimura, S; Xu, Z Y; Jungclaus, A; Shimizu, Y; Simpson, G S; Söderström, P-A; Watanabe, H; Browne, F; Doornenbal, P; Gey, G; Jung, H S; Meyer, B; Sumikama, T; Taprogge, J; Vajta, Zs; Wu, J; Baba, H; Benzoni, G; Chae, K Y; Crespi, F C L; Fukuda, N; Gernhäuser, R; Inabe, N; Isobe, T; Kajino, T; Kameda, D; Kim, G D; Kim, Y-K; Kojouharov, I; Kondev, F G; Kubo, T; Kurz, N; Kwon, Y K; Lane, G J; Li, Z; Montaner-Pizá, A; Moschner, K; Naqvi, F; Niikura, M; Nishibata, H; Odahara, A; Orlandi, R; Patel, Z; Podolyák, Zs; Sakurai, H; Schaffner, H; Schury, P; Shibagaki, S; Steiger, K; Suzuki, H; Takeda, H; Wendt, A; Yagi, A; Yoshinaga, K

2015-05-15

The β-decay half-lives of 110 neutron-rich isotopes of the elements from _{37}Rb to _{50}Sn were measured at the Radioactive Isotope Beam Factory. The 40 new half-lives follow robust systematics and highlight the persistence of shell effects. The new data have direct implications for r-process calculations and reinforce the notion that the second (A≈130) and the rare-earth-element (A≈160) abundance peaks may result from the freeze-out of an (n,γ)⇄(γ,n) equilibrium. In such an equilibrium, the new half-lives are important factors determining the abundance of rare-earth elements, and allow for a more reliable discussion of the r process universality. It is anticipated that universality may not extend to the elements Sn, Sb, I, and Cs, making the detection of these elements in metal-poor stars of the utmost importance to determine the exact conditions of individual r-process events.

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.

An abundance of small exoplanets around stars with a wide range of metallicities.

PubMed

Buchhave, Lars A; Latham, David W; Johansen, Anders; Bizzarro, Martin; Torres, Guillermo; Rowe, Jason F; Batalha, Natalie M; Borucki, William J; Brugamyer, Erik; Caldwell, Caroline; Bryson, Stephen T; Ciardi, David R; Cochran, William D; Endl, Michael; Esquerdo, Gilbert A; Ford, Eric B; Geary, John C; Gilliland, Ronald L; Hansen, Terese; Isaacson, Howard; Laird, John B; Lucas, Philip W; Marcy, Geoffrey W; Morse, Jon A; Robertson, Paul; Shporer, Avi; Stefanik, Robert P; Still, Martin; Quinn, Samuel N

2012-06-13

The abundance of heavy elements (metallicity) in the photospheres of stars similar to the Sun provides a 'fossil' record of the chemical composition of the initial protoplanetary disk. Metal-rich stars are much more likely to harbour gas giant planets, supporting the model that planets form by accumulation of dust and ice particles. Recent ground-based surveys suggest that this correlation is weakened for Neptunian-sized planets. However, how the relationship between size and metallicity extends into the regime of terrestrial-sized exoplanets is unknown. Here we report spectroscopic metallicities of the host stars of 226 small exoplanet candidates discovered by NASA's Kepler mission, including objects that are comparable in size to the terrestrial planets in the Solar System. We find that planets with radii less than four Earth radii form around host stars with a wide range of metallicities (but on average a metallicity close to that of the Sun), whereas large planets preferentially form around stars with higher metallicities. This observation suggests that terrestrial planets may be widespread in the disk of the Galaxy, with no special requirement of enhanced metallicity for their formation.

Iron-Terephthalate Coordination Network Thin Films Through In-Situ Atomic/Molecular Layer Deposition.

PubMed

Tanskanen, A; Karppinen, M

2018-06-12

Iron terephthalate coordination network thin films can be fabricated using the state-of-the-art gas-phase atomic/molecular layer deposition (ALD/MLD) technique in a highly controlled manner. Iron is an Earth-abundant and nonhazardous transition metal, and with its rich variety of potential applications an interesting metal constituent for the inorganic-organic coordination network films. Our work underlines the role of the metal precursor used when aiming at in-situ ALD/MLD growth of crystalline inorganic-organic thin films. We obtain crystalline iron terephthalate films when FeCl 3 is employed as the iron source whereas depositions based on the bulkier Fe(acac) 3 precursor yield amorphous films. The chemical composition and structure of the films are investigated with GIXRD, XRR, FTIR and XPS.

Recovering heavy rare earth metals from magnet scrap

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

Ott, Ryan T.; McCallum, Ralph W.; Jones, Lawrence L.

A method of treating rare earth metal-bearing permanent magnet scrap, waste or other material in a manner to recover the heavy rare earth metal content separately from the light rare earth metal content. The heavy rare earth metal content can be recovered either as a heavy rare earth metal-enriched iron based alloy or as a heavy rare earth metal based alloy.

Metal loading levels influence on REE distribution on humic acid: Experimental and Modelling approach

NASA Astrophysics Data System (ADS)

Marsac, R.; Davranche, M.; Gruau, G.; Dia, A.

2009-04-01

In natural organic-rich waters, rare earth elements (REE) speciation is mainly controlled by organic colloids such as humic acid (HA). Different series of REE-HA complexation experiments performed at several metal loading (REE/C) displayed two pattern shapes (i) at high metal loading, a middle-REE (MREE) downward concavity, and (ii) at low metal loading, a regular increase from La to Lu (e.g. Sonke and Salters, 2006; Pourret et al., 2007). Both REE patterns might be related to REE binding with different surface sites on HA. To understand REE-HA binding, REE-HA complexation experiments at various metals loading were carried out using ultrafiltration combined with ICP-MS measurements, for the 14 REE simultaneously. The patterns of the apparent coefficients of REE partition between HA and the inorganic solution (log Kd) evolved regularly according to the metal loading. The REE patterns presented a MREE downward concavity at low loading and a regular increase from La to Lu at high loading. The dataset was modelled with Model VI by adjusting two specific parameters, log KMA, the apparent complexation constant of HA low affinity sites and DLK2, the parameter increasing high affinity sites binding strength. Experiments and modelling provided evidence that HA high affinity sites controlled the REE binding with HA at low metal loading. The REE-HA complex could be as multidentate complexes with carboxylic or phenolic sites or potentially with sites constituted of N, P or S as donor atoms. Moreover, these high affinity sites could be different for light and heavy REE, because heavy REE have higher affinity for these sites, in low density, and could saturate them. These new Model VI parameter sets allowed the prediction of the REE-HA pattern shape evolution on a large range of pH and metal loading. According to the metal loading, the evolution of the calculated REE patterns was similar to the various REE pattern observed in natural acidic organic-rich waters (pH<7 and DOC>10 mg L-1). As a consequence, the metal loading could be the key parameter controlling the REE pattern in organic-rich waters.

Partitioning of Oxygen During Core Formation on Earth and Mars

NASA Astrophysics Data System (ADS)

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

2003-12-01

Core formation on Earth and Mars involved the physical separation of Fe-Ni metal alloy from silicate, most likely in deep magma oceans. Although core-formation models explain many aspects of mantle geochemistry, they do not account for large differences between the compositions of the mantles of Earth ( ˜8 wt% FeO) and Mars ( ˜18 wt% FeO) or the much smaller mass fraction of the Martian core. Here we explain these differences using new experimental results on the solubility of oxygen in liquid Fe-Ni alloy, which we have determined at 5-23 GPa, 2100-2700 K and variable oxygen fugacities using a multianvil apparatus. Oxygen solubility increases with increasing temperature and oxygen fugacity and decreases with increasing pressure. Thus, along a high temperature adiabat (e.g. after formation of a deep magma ocean on Earth), oxygen solubility is high at depths up to about 2000 km but decreases strongly at greater depths where the effect of high pressure dominates. For modeling oxygen partitioning during core formation, we assume that Earth and Mars both accreted from oxidized chondritic material with a silicate fraction initially containing around 18 wt% FeO. In a terrestrial magma ocean, 1200-2000 km deep, high temperatures resulted in the extraction of FeO from the silicate magma ocean, due to the high solubility of oxygen in the segregating metal, leaving the mantle with its present FeO content of ˜8 wt%. Lower temperatures of a Martian magma ocean resulted in little or no extraction of FeO from the mantle, which thus remained unchanged at about 18 wt%. The mass fractions of segregated metal are consistent with the mass fraction of the Martian core being small relative to that of the Earth. FeO extracted from the Earth's magma ocean by segregating core-forming liquid may have contributed to chemical heterogeneities in the lowermost mantle, a FeO-rich D'' layer and the light element budget of the core.

A molecular cross-linking approach for hybrid metal oxides.

PubMed

Jung, Dahee; Saleh, Liban M A; Berkson, Zachariah J; El-Kady, Maher F; Hwang, Jee Youn; Mohamed, Nahla; Wixtrom, Alex I; Titarenko, Ekaterina; Shao, Yanwu; McCarthy, Kassandra; Guo, Jian; Martini, Ignacio B; Kraemer, Stephan; Wegener, Evan C; Saint-Cricq, Philippe; Ruehle, Bastian; Langeslay, Ryan R; Delferro, Massimiliano; Brosmer, Jonathan L; Hendon, Christopher H; Gallagher-Jones, Marcus; Rodriguez, Jose; Chapman, Karena W; Miller, Jeffrey T; Duan, Xiangfeng; Kaner, Richard B; Zink, Jeffrey I; Chmelka, Bradley F; Spokoyny, Alexander M

2018-04-01

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO 2 , to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as 'molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B 12 (OH) 12 ] 2- . This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO 2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

A molecular cross-linking approach for hybrid metal oxides

NASA Astrophysics Data System (ADS)

Jung, Dahee; Saleh, Liban M. A.; Berkson, Zachariah J.; El-Kady, Maher F.; Hwang, Jee Youn; Mohamed, Nahla; Wixtrom, Alex I.; Titarenko, Ekaterina; Shao, Yanwu; McCarthy, Kassandra; Guo, Jian; Martini, Ignacio B.; Kraemer, Stephan; Wegener, Evan C.; Saint-Cricq, Philippe; Ruehle, Bastian; Langeslay, Ryan R.; Delferro, Massimiliano; Brosmer, Jonathan L.; Hendon, Christopher H.; Gallagher-Jones, Marcus; Rodriguez, Jose; Chapman, Karena W.; Miller, Jeffrey T.; Duan, Xiangfeng; Kaner, Richard B.; Zink, Jeffrey I.; Chmelka, Bradley F.; Spokoyny, Alexander M.

2018-03-01

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as `molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2-. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

Ca(2+) -complex stability of GAPAGPLIVPY peptide in gas and aqueous phase, investigated by affinity capillary electrophoresis and molecular dynamics simulations and compared to mass spectrometric results.

PubMed

Nachbar, Markus; El Deeb, Sami; Mozafari, Mona; Alhazmi, Hassan A; Preu, Lutz; Redweik, Sabine; Lehmann, Wolf Dieter; Wätzig, Hermann

2016-03-01

Strong, sequence-specific gas-phase bindings between proline-rich peptides and alkaline earth metal ions in nanoESI-MS experiments were reported by Lehmann et al. (Rapid Commun. Mass Spectrom. 2006, 20, 2404-2410), however its relevance for physiological-like aqueous phase is uncertain. Therefore, the complexes should also be studied in aqueous solution and the relevance of the MS method for binding studies be evaluated. A mobility shift ACE method was used for determining the binding between the small peptide GAPAGPLIVPY and various metal ions in aqueous solution. The findings were compared to the MS results and further explained using computational methods. While the MS data showed a strong alkaline earth ion binding, the ACE results showed nonsignificant binding. The proposed vacuum state complex also decomposed during a molecular dynamic simulation in aqueous solution. This study shows that the formed stable peptide-metal ion adducts in the gas phase by ESI-MS does not imply the existence of analogous adducts in the aqueous phase. Comparing peptide-metal ion interaction under the gaseous MS and aqueous ACE conditions showed huge difference in binding behavior. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A volatile rich Earth's core?

NASA Astrophysics Data System (ADS)

Morard, G.; Antonangeli, D.; Andrault, D.; Nakajima, Y.

2017-12-01

The composition of the Earth's core is still an open question. Although mostly composed of iron, it contains impurities that lower its density and melting point with respect to pure Fe. Knowledge of the nature and abundance of light elements (O, S, Si, C or H) in the core has major implications for establishing the bulk composition of the Earth and for building the model of Earth's differentiation. Geochemical models of the Earth's formation point out that its building blocks were depleted in volatile elements compared to the chondritic abundance, therefore light elements such as S, H or C cannot be the major elements alloyed with iron in the Earth's core. However, such models should be compatible with the comparison of seismic properties of the Earth's core and physical properties of iron alloys under extreme conditions, such as sound velocity or density of solid and liquid. The present work will discuss the recent progress for compositional model issued from studies of phase diagrams and elastic properties of iron alloys under core conditions and highlight the compatibility of volatile elements with observed properties of the Earth's core, in potential contradiction with models derived from metal-silicate partitioning experiments.

Evolution of electronic structure across the rare-earth RNiO 3 series

DOE PAGES

Freeland, John W.; van Veenendaal, Michel; Chakhalian, Jak

2015-07-31

Here, the perovksite rare-earth nickelates, RNiO 3 (R = La… Lu), are a class of materials displaying a rich phase-diagram of metallic and insulating phases associated with charge and magnetic order. Being in the charge transfer regime, Ni 3+ in octahedral coordination displays a strong hybridization with oxygen to form 3d-2p mixed states, which results in a strong admixture of 3d 8L_ into 3d 7, where L_ denotes a hole on the oxygen. To understand the nature of this strongly hybridized ground state, we present a detailed study of the Ni and O electronic structure using high-resolution soft X-ray absorptionmore » spectroscopy (XAS). Through a comparison of the evolution of the XAS line-shape at Ni L- and O K-edges across the phase diagram, we explore the changes in the electronic signatures in connection with the insulating and metallic phases that support the idea of hybridization playing a fundamental role.« less

Particle size dependence of alkali and alkaline earth metal enrichment in marine aerosols from Bermuda

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

Hoffman, E.J.; Hoffman, G.L.; Duce, R.A.

1980-10-20

Three cascade impactor samples were collected from a 20-m-high tower on the southeastern coast of Bermuda. These samples were analyzed for Na, K, Ca, Mg, and Fe by atomic absorption spectrophotometry. When the alkali-alkakine earth metal concentrations are corrected for a soil-derived component, utilizing the atmospheric Fe concentrations, Mg, Ca, and Na are found to be present in the same relative abundances as in seawater for all particle sizes sampled. Potassium also shows no deviation from a bulk seawater composition for particles with radii greater than approx.0.5 ..mu..m. However, excess K above that expected from either a bulk seawater ormore » soil source is observed on particles with radii less than approx.0.5 ..mu..m. While oceanic chemical fractionation processes during bubble bursting may be responsible for this excess small particle K, it is most likely due to long-range transport of K-rich particles of terrestrial vegetative origin.« less

Behaviour of Rare Earth Elements during the Earth's core formation

NASA Astrophysics Data System (ADS)

Faure, Pierre; Bouhifd, Mohamed Ali; Boyet, Maud; Hammouda, Tahar; Manthilake, Geeth

2017-04-01

Rare Earth Elements (REE) are classified in the refractory group, which means that they have a high temperature condensation and their volatility-controlled fractionation is limited to high-temperature processes. Anomalies have been measured for Eu, Yb and Sm, which are the REE with the lowest condensation temperatures in CAIs and chondrules (e.g. [1]). REE are particularly abundant in the sulfides of enstatite chondrites, 100 to 1000 times the CI value [e.g. 2,3], proving that these elements are not strictly lithophile under extremely reducing conditions. However by investigating experimentally the impact of Earth's core formation on the behavior of Sm and Nd, we have shown the absence of fractionation between Sm and Nd during the segregation of the metallic phase [4]. Recently, Wohlers and Wood [5] proposed that Nd and Sm could be fractionated in presence of a S-rich alloy phase. However, their results were obtained at pressure and temperature conditions below the plausible conditions of the Earth's core formation. Clearly, large pressure range needs to be covered before well-constrained model can be expected. Furthermore, our preliminary metal-silicate partitioning results show that Ce and Eu have higher metal/silicate partition coefficients than their neighboring elements, and that the presence of sulphur enhances the relative difference between partition coefficients. In this presentation, we will present and discuss new metal-silicate partition coefficients of all REE at a deep magma ocean at pressures ranging from those of the uppermost upper mantle ( 5 GPa) to a maximum pressure expected in the range of 20 GPa, temperatures ranging from 2500 to about 3000 K, and oxygen fugacities within IW-1 to IW-5 (1 to 5 orders of magnitude lower than the iron-wüstite buffer). We will discuss the effect of S, as well as the effect of H2O on the behaviour of REE during the Earth's core formation: recent models suggest that contrary to currently accepted beliefs, the presence of water during the formation of metallic core of terrestrial planets is very plausible [e.g. 6-8]. References [1] Pack et al. (2004) Science 303, 997-1000. [2] Crozaz and Lundberg (1995) Geochim. Cosmochim. Acta 59, 3817-3831. [3] Gannoun et al. (2011) Geochim. Cosmochim. Acta 75, 3269-3289. [4] Bouhifd et al. (2015) Earth Planet. Sci. Lett. 413, 158-166. [5] Wohlers and Wood (2015) Nature 520, 337-340. [6] Marty (2012) Earth Planet. Sci. Lett. 313-314, 56-66. [7] Morbidelli et al. (2000) Meteor. Planet. Sci. 1320, 1309-1320. [8] Sarafian et al. (2014 Science 346, 623-626.

Spent NiMH batteries-The role of selective precipitation in the recovery of valuable metals

NASA Astrophysics Data System (ADS)

Bertuol, Daniel Assumpção; Bernardes, Andréa Moura; Tenório, Jorge Alberto Soares

The production of electronic equipment, such as computers and cell phones, and, consequently, batteries, has increased dramatically. One of the types of batteries whose production and consumption has increased in recent times is the nickel metal hydride (NiMH) battery. This study evaluated a hydrometallurgical method of recovery of rare earths and a simple method to obtain a solution rich in Ni-Co from spent NiMH batteries. The active materials from both electrodes were manually removed from the accumulators and leached. Several acid and basic solutions for the recovery of rare earths were evaluated. Results showed that more than 98 wt.% of the rare earths were recovered as sulfate salts by dissolution with sulfuric acid, followed by selective precipitation at pH 1.2 using sodium hydroxide. The complete process, precipitation at pH 1.2 followed by precipitation at pH 7, removed about 100 wt.% of iron and 70 wt.% of zinc from the leaching solution. Results were similar to those found in studies that used solvent extraction. This method is easy, economic, and does not pose environmental threats of solvent extraction.

Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

DOEpatents

Ellis, Timothy W.; Schmidt, Frederick A.

1995-08-01

Method of treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation.

AN ANCIENT EXTRASOLAR SYSTEM WITH FIVE SUB-EARTH-SIZE PLANETS

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

Campante, T. L.; Davies, G. R.; Chaplin, W. J.

The chemical composition of stars hosting small exoplanets (with radii less than four Earth radii) appears to be more diverse than that of gas-giant hosts, which tend to be metal-rich. This implies that small, including Earth-size, planets may have readily formed at earlier epochs in the universe's history when metals were more scarce. We report Kepler spacecraft observations of Kepler-444, a metal-poor Sun-like star from the old population of the Galactic thick disk and the host to a compact system of five transiting planets with sizes between those of Mercury and Venus. We validate this system as a true five-planetmore » system orbiting the target star and provide a detailed characterization of its planetary and orbital parameters based on an analysis of the transit photometry. Kepler-444 is the densest star with detected solar-like oscillations. We use asteroseismology to directly measure a precise age of 11.2 ± 1.0 Gyr for the host star, indicating that Kepler-444 formed when the universe was less than 20% of its current age and making it the oldest known system of terrestrial-size planets. We thus show that Earth-size planets have formed throughout most of the universe's 13.8 billion year history, leaving open the possibility for the existence of ancient life in the Galaxy. The age of Kepler-444 not only suggests that thick-disk stars were among the hosts to the first Galactic planets, but may also help to pinpoint the beginning of the era of planet formation.« less

Scandium Terminal Imido Chemistry.

PubMed

Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

2018-02-20

Research into transition metal complexes bearing multiply bonded main-group ligands has developed into a thriving and fruitful field over the past half century. These complexes, featuring terminal M═E/M≡E (M = transition metal; E = main-group element) multiple bonds, exhibit unique structural properties as well as rich reactivity, which render them attractive targets for inorganic/organometallic chemists as well as indispensable tools for organic/catalytic chemists. This fact has been highlighted by their widespread applications in organic synthesis, for example, as olefin metathesis catalysts. In the ongoing renaissance of transition metal-ligand multiple-bonding chemistry, there have been reports of M═E/M≡E interactions for the majority of the metallic elements of the periodic table, even some actinide metals. In stark contrast, the largest subgroup of the periodic table, rare-earth metals (Ln = Sc, Y, and lanthanides), have been excluded from this upsurge. Indeed, the synthesis of terminal Ln═E/Ln≡E multiple-bonding species lagged behind that of the transition metal and actinide congeners for decades. Although these species had been pursued since the discovery of a rare-earth metal bridging imide in 1991, such a terminal (nonpincer/bridging hapticities) Ln═E/Ln≡E bond species was not obtained until 2010. The scarcity is mainly attributed to the energy mismatch between the frontier orbitals of the metal and the ligand atoms. This renders the putative terminal Ln═E/Ln≡E bonds extremely reactive, thus resulting in the formation of aggregates and/or reaction with the ligand/environment, quenching the multiple-bond character. In 2010, the stalemate was broken by the isolation and structural characterization of the first rare-earth metal terminal imide-a scandium terminal imide-by our group. The double-bond character of the Sc═N bond was unequivocally confirmed by single-crystal X-ray diffraction. Theoretical investigations revealed the presence of two p-d π bonds between the scandium ion and the nitrogen atom of the imido ligand and showed that the dianionic [NR] 2- imido ligand acts as a 2σ,4π electron donor. Subsequent studies of the scandium terminal imides revealed highly versatile and intriguing reactivity of the Sc═N bond. This included cycloaddition toward various unsaturated bonds, C-H/Si-H/B-H bond activations and catalytic hydrosilylation, dehydrofluorination of fluoro-substituted benzenes/alkanes, CO 2 and H 2 activations, activation of elemental selenium, coordination with other transition metal halides, etc. Since our initial success in 2010, and with contributions from us and across the community, this young, vibrant research field has rapidly flourished into one of the most active frontiers of rare-earth metal chemistry. The prospect of extending Ln═N chemistry to other rare-earth metals and/or different metal oxidation states, as well as exploiting their stoichiometric and catalytic reactivities, continues to attract research effort. Herein we present an account of our investigations into scandium terminal imido chemistry as a timely summary, in the hope that our studies will be of interest to this readership.

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

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

Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

DOEpatents

Ellis, T.W.; Schmidt, F.A.

1995-08-01

A method is described for treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation. 2 figs.

Carbon and oxygen abundances in cool metal-rich exoplanet hosts: A case study of the C/O ratio of 55 Cancri

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

Teske, Johanna K.; Cunha, Katia; Schuler, Simon C.

2013-12-01

The super-Earth exoplanet 55 Cnc e, the smallest member of a five-planet system, has recently been observed to transit its host star. The radius estimates from transit observations, coupled with spectroscopic determinations of mass, provide constraints on its interior composition. The composition of exoplanetary interiors and atmospheres are particularly sensitive to elemental C/O ratio, which to first order can be estimated from the host stars. Results from a recent spectroscopic study analyzing the 6300 Å [O I] line and two C I lines suggest that 55 Cnc has a carbon-rich composition (C/O = 1.12 ± 0.09). However, oxygen abundances derivedmore » using the 6300 Å [O I] line are highly sensitive to a Ni I blend, particularly in metal-rich stars such as 55 Cnc ([Fe/H] =0.34 ± 0.18). Here, we further investigate 55 Cnc's composition by deriving the carbon and oxygen abundances from these and additional C and O absorption features. We find that the measured C/O ratio depends on the oxygen lines used. The C/O ratio that we derive based on the 6300 Å [O I] line alone is consistent with the previous value. Yet, our investigation of additional abundance indicators results in a mean C/O ratio of 0.78 ± 0.08. The lower C/O ratio of 55 Cnc determined here may place this system at the sensitive boundary between protoplanetary disk compositions giving rise to planets with high (>0.8) versus low (<0.8) C/O ratios. This study illustrates the caution that must applied when determining planet host star C/O ratios, particularly in cool, metal-rich stars.« less

A seismologically consistent compositional model of Earth's core.

PubMed

Badro, James; Côté, Alexander S; Brodholt, John P

2014-05-27

Earth's core is less dense than iron, and therefore it must contain "light elements," such as S, Si, O, or C. We use ab initio molecular dynamics to calculate the density and bulk sound velocity in liquid metal alloys at the pressure and temperature conditions of Earth's outer core. We compare the velocity and density for any composition in the (Fe-Ni, C, O, Si, S) system to radial seismological models and find a range of compositional models that fit the seismological data. We find no oxygen-free composition that fits the seismological data, and therefore our results indicate that oxygen is always required in the outer core. An oxygen-rich core is a strong indication of high-pressure and high-temperature conditions of core differentiation in a deep magma ocean with an FeO concentration (oxygen fugacity) higher than that of the present-day mantle.

Geogenic Factors as Drivers of Microbial Community Diversity in Soils Overlying Polymetallic Deposits.

PubMed

Reith, Frank; Zammit, Carla M; Pohrib, Rebecca; Gregg, Adrienne L; Wakelin, Steven A

2015-11-01

This study shows that the geogenic factors landform, lithology, and underlying mineral deposits (expressed by elevated metal concentrations in overlying soils) are key drivers of microbial community diversity in naturally metal-rich Australian soils with different land uses, i.e., agriculture versus natural bushland. One hundred sixty-eight soil samples were obtained from two metal-rich provinces in Australia, i.e., the Fifield Au-Pt field (New South Wales) and the Hillside Cu-Au-U rare-earth-element (REE) deposit (South Australia). Soils were analyzed using three-domain multiplex terminal-restriction-fragment-length-polymorphism (M-TRFLP) and PhyloChip microarrays. Geogenic factors were determined using field-mapping techniques and analyses of >50 geochemical parameters. At Fifield, microbial communities differed significantly with geogenic factors and equally with land use (P < 0.05). At Hillside, communities in surface soils (0.03- to 0.2-m depth) differed significantly with landform and land use (P < 0.05). Communities in deeper soils (>0.2 m) differed significantly with lithology and mineral deposit (P < 0.05). Across both sites, elevated metal contents in soils overlying mineral deposits were selective for a range of bacterial taxa, most importantly Acidobacteria, Bacilli, Betaproteobacteria, and Epsilonproteobacteria. In conclusion, long-term geogenic factors can be just as important as land use in determining soil microbial community diversity. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Geogenic Factors as Drivers of Microbial Community Diversity in Soils Overlying Polymetallic Deposits

PubMed Central

Zammit, Carla M.; Pohrib, Rebecca; Gregg, Adrienne L.; Wakelin, Steven A.

2015-01-01

This study shows that the geogenic factors landform, lithology, and underlying mineral deposits (expressed by elevated metal concentrations in overlying soils) are key drivers of microbial community diversity in naturally metal-rich Australian soils with different land uses, i.e., agriculture versus natural bushland. One hundred sixty-eight soil samples were obtained from two metal-rich provinces in Australia, i.e., the Fifield Au-Pt field (New South Wales) and the Hillside Cu-Au-U rare-earth-element (REE) deposit (South Australia). Soils were analyzed using three-domain multiplex terminal-restriction-fragment-length-polymorphism (M-TRFLP) and PhyloChip microarrays. Geogenic factors were determined using field-mapping techniques and analyses of >50 geochemical parameters. At Fifield, microbial communities differed significantly with geogenic factors and equally with land use (P < 0.05). At Hillside, communities in surface soils (0.03- to 0.2-m depth) differed significantly with landform and land use (P < 0.05). Communities in deeper soils (>0.2 m) differed significantly with lithology and mineral deposit (P < 0.05). Across both sites, elevated metal contents in soils overlying mineral deposits were selective for a range of bacterial taxa, most importantly Acidobacteria, Bacilli, Betaproteobacteria, and Epsilonproteobacteria. In conclusion, long-term geogenic factors can be just as important as land use in determining soil microbial community diversity. PMID:26341204

Recovery of rare earths from spent NdFeB magnets of wind turbine: Leaching and kinetic aspects.

PubMed

Kumari, Aarti; Sinha, Manish Kumar; Pramanik, Swati; Sahu, Sushanta Kumar

2018-05-01

Increasing demands of rare earth (RE) metals for advanced technological applications coupled with the scarcity of primary resources have led to the development of processes to treat secondary resources like scraps or end of life products that are often rich in such metals. Spent NdFeB magnet may serve as a potential source of rare earths containing around ∼30% of neodymium and other rare earths. In the present investigation, a pyro-hydrometallurgical process has been developed to recover rare earth elements (Nd, Pr and Dy) from the spent wind turbine magnet. The spent magnet is demagnetized and roasted at 1123 K to convert rare earths and iron to their respective oxides. Roasting of the magnet not only provides selectivity, but enhances the leaching efficiency also. The leaching of the roasted sample with 0.5 M hydrochloric acid at 368 K, 100 g/L pulp density and 500 rpm for 300 min selectively recovers the rare earth elements almost quantitatively leaving iron oxide in the residue. Leaching of rare earth elements with hydrochloric acid follows the mixed controlled kinetic model with activation energy (E a ) of 30.1 kJ/mol in the temperature range 348-368 K. The leaching mechanism is further established by characterizing the leach residues obtained at different time intervals by scanning electron microscopy- energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Individual rare earth elements from the leach solution containing 16.8 g/L of Nd, 3.8 g/L Pr, 0.28 g/L of Dy and other minor impurity elements could be separated by solvent extraction. However, mixed rare earth oxide of 99% purity was produced by oxalate precipitation followed by roasting. The leach residue comprising of pure hematite has a potential to be used as pigment or can find other applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Solidification studies of nanocrystalline and quasicrystalline materials from the undercooled state

NASA Astrophysics Data System (ADS)

Croat, Thomas Kevin

2001-07-01

Nanocrystallization occurring during metallic glass devitrification is studied in Zr-Al-Ni-Cu bulk metallic glasses (BMGs) and Al-RE-TM (RE = rare-earth, TM = transition metal) metallic glasses. The importance of transient nucleation in BMG devitrification was established by a direct transmission electron microscopy (TEM) measurement of the grain density in two-stage annealed samples. TEM examination of low temperature annealed BMGs also suggest that amorphous phase separation is occurring prior to crystallization. Nanocrystallization of rapidly quenched Al-RE-Ni glasses was preceded by the compositional segregation of the initially homogeneous glass into Al-rich and solute-rich regions (mainly nickel-enriched) on a ≈50--100 nm length scale, suggesting amorphous phase separation. This pre-existing compositional modulation on a nanometer scale leads naturally to the development of nanocrystals. The average rare earth radius (rRE) in Al-RE-Ni alloys was altered by co-substitution of chemically similar rare earth elements. In glasses with smaller r RE, nucleation of alpha-Al occurred preferentially near the boundaries of the phase-separated regions. However, phase separation did not universally lead to alpha-Al nanocrystallization; glasses with larger rRE crystallized to metastable intermetallic phases with a 50--100 nm grain size. Kinetic analysis of the alpha-Al crystallization was performed using isothermal DSC, yielding abnormally low Avrami exponents (n = 1.0--1.5); these values were found to be consistent with the observed transformation using a model that considers the overlapping diffusion fields of the alpha-Al grains during growth within the phase separated region. Containerless solidification experiments on Ti-based quasicrystal-forming alloys have been performed using various techniques, including drop-tube solidification, electromagnetic levitation (EML) and electrostatic levitation (ESL). In Ti-Fe-Si-O, the alpha-1/1 quasicrystal approximant phase is found to nucleate directly from the liquid over the range TixFe94-xSi 4(SiO2)2 with 67 < x < 69 in EML experiments. Both the alpha-1/1 phase in Ti-Fe-Si-O and the C14 Laves phase in Ti-Zr-Ni have lower relative undercoolings than nearby crystal phases. This presumably reflects the structural similarity between these polytetrahedral phases and the undercooled liquid, which leads to smaller nucleation barriers and lower maximum undercoolings.

Haze production rates in super-Earth and mini-Neptune atmosphere experiments

NASA Astrophysics Data System (ADS)

Hörst, Sarah M.; He, Chao; Lewis, Nikole K.; Kempton, Eliza M.-R.; Marley, Mark S.; Morley, Caroline V.; Moses, Julianne I.; Valenti, Jeff A.; Vuitton, Véronique

2018-04-01

Numerous Solar System atmospheres possess photochemically generated hazes, including the characteristic organic hazes of Titan and Pluto. Haze particles substantially impact atmospheric temperature structures and may provide organic material to the surface of a world, potentially affecting its habitability. Observations of exoplanet atmospheres suggest the presence of aerosols, especially in cooler (<800 K), smaller (<0.3× Jupiter's mass) exoplanets. It remains unclear whether the aerosols muting the spectroscopic features of exoplanet atmospheres are condensate clouds or photochemical hazes1-3, which is difficult to predict from theory alone4. Here, we present laboratory haze simulation experiments that probe a broad range of atmospheric parameters relevant to super-Earth- and mini-Neptune-type planets5, the most frequently occurring type of planet in our galaxy6. It is expected that photochemical haze will play a much greater role in the atmospheres of planets with average temperatures below 1,000 K (ref. 7), especially those planets that may have enhanced atmospheric metallicity and/or enhanced C/O ratios, such as super-Earths and Neptune-mass planets8-12. We explored temperatures from 300 to 600 K and a range of atmospheric metallicities (100×, 1,000× and 10,000× solar). All simulated atmospheres produced particles, and the cooler (300 and 400 K) 1,000× solar metallicity (`H2O-dominated' and CH4-rich) experiments exhibited haze production rates higher than our standard Titan simulation ( 10 mg h-1 versus 7.4 mg h-1 for Titan13). However, the particle production rates varied greatly, with measured rates as low as 0.04 mg h-1 (for the case with 100× solar metallicity at 600 K). Here, we show that we should expect great diversity in haze production rates, as some—but not all—super-Earth and mini-Neptune atmospheres will possess photochemically generated haze.

Haze production rates in super-Earth and mini-Neptune atmosphere experiments

NASA Astrophysics Data System (ADS)

Hörst, Sarah M.; He, Chao; Lewis, Nikole K.; Kempton, Eliza M.-R.; Marley, Mark S.; Morley, Caroline V.; Moses, Julianne I.; Valenti, Jeff A.; Vuitton, Véronique

2018-03-01

Numerous Solar System atmospheres possess photochemically generated hazes, including the characteristic organic hazes of Titan and Pluto. Haze particles substantially impact atmospheric temperature structures and may provide organic material to the surface of a world, potentially affecting its habitability. Observations of exoplanet atmospheres suggest the presence of aerosols, especially in cooler (<800 K), smaller (<0.3× Jupiter's mass) exoplanets. It remains unclear whether the aerosols muting the spectroscopic features of exoplanet atmospheres are condensate clouds or photochemical hazes1-3, which is difficult to predict from theory alone4. Here, we present laboratory haze simulation experiments that probe a broad range of atmospheric parameters relevant to super-Earth- and mini-Neptune-type planets5, the most frequently occurring type of planet in our galaxy6. It is expected that photochemical haze will play a much greater role in the atmospheres of planets with average temperatures below 1,000 K (ref. 7), especially those planets that may have enhanced atmospheric metallicity and/or enhanced C/O ratios, such as super-Earths and Neptune-mass planets8-12. We explored temperatures from 300 to 600 K and a range of atmospheric metallicities (100×, 1,000× and 10,000× solar). All simulated atmospheres produced particles, and the cooler (300 and 400 K) 1,000× solar metallicity (`H2O-dominated' and CH4-rich) experiments exhibited haze production rates higher than our standard Titan simulation ( 10 mg h-1 versus 7.4 mg h-1 for Titan13). However, the particle production rates varied greatly, with measured rates as low as 0.04 mg h-1 (for the case with 100× solar metallicity at 600 K). Here, we show that we should expect great diversity in haze production rates, as some—but not all—super-Earth and mini-Neptune atmospheres will possess photochemically generated haze.

A molecular cross-linking approach for hybrid metal oxides

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

Jung, Dahee; Saleh, Liban A. M.; Berkson, Zachariah J.

Developing methods to create hybrid materials to maximize their transformative capabilities has been the subject of significant interest. In particular, several key methods have been developed to manipulate earth abundant metal oxides such as TiO 2 to produce hybrid materials with improved or new properties relevant to a broad spectrum of applications. Here, we introduce a new approach we refer to as “molecular doping”, whereby a hybrid molecular boron oxide material is formed from polyhedral boron cluster precursors of the type [B 12(OH) 12] 2-. This new approach is enabled by the inherent robustness of the boron cluster molecular buildingmore » block, which is compatible with harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, we show how this material can be successfully interfaced with TiO 2, resulting in boron-rich hybrid materials with unprecedented photophysical and electrochemical properties.« less

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates.

PubMed

Middey, S; Meyers, D; Kareev, M; Cao, Yanwei; Liu, X; Shafer, P; Freeland, J W; Kim, J-W; Ryan, P J; Chakhalian, J

2018-04-13

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO_{3}. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions. Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. This designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates

NASA Astrophysics Data System (ADS)

Middey, S.; Meyers, D.; Kareev, M.; Cao, Yanwei; Liu, X.; Shafer, P.; Freeland, J. W.; Kim, J.-W.; Ryan, P. J.; Chakhalian, J.

2018-04-01

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO3 . Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions. Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. This designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.

Effect of oxygen content of Nd-Fe-B sintered magnet on grain boundary diffusion process of DyH2 dip-coating

NASA Astrophysics Data System (ADS)

Bae, Kyoung-Hoon; Lee, Seong-Rae; Kim, Hyo-Jun; Lee, Min-Woo; Jang, Tae-Suk

2015-11-01

We investigated the effect of oxygen content on the microstructural and magnetic properties of a DyH2 dip-coated Nd-Fe-B sintered magnet. When the magnet had a low oxygen content (1500 ppm), the volume and size of the rare-earth-rich oxide (Nd-Dy-O) phase was reduced, and a uniform and continuous thin Nd-rich grain boundary phase (GBP) was well developed. The grain boundary diffusion depth of Dy increased from 200 to 350 μm with decreasing oxygen content from ˜3000 to 1500 ppm. The coercivity of the low-oxygen magnet increased from 19.98 to 23.59 kOe after grain boundary diffusion process (GBDP) while the remanence reduction was minimized. The formation of an fcc-NdOx Nd-rich phase in the high-oxygen magnet hindered the formation of a Nd-rich triple-junction phase and GBP. In contrast, a metallic dhcp-Nd phase, which was closely related to coercivity enhancement after GBDP, was formed in the low-oxygen magnet.

Chondritic Mn/Na ratio and limited post-nebular volatile loss of the Earth

NASA Astrophysics Data System (ADS)

Siebert, Julien; Sossi, Paolo A.; Blanchard, Ingrid; Mahan, Brandon; Badro, James; Moynier, Frédéric

2018-03-01

The depletion pattern of volatile elements on Earth and other differentiated terrestrial bodies provides a unique insight as to the nature and origin of planetary building blocks. The processes responsible for the depletion of volatile elements range from the early incomplete condensation in the solar nebula to the late de-volatilization induced by heating and impacting during planetary accretion after the dispersion of the H2-rich nebular gas. Furthermore, as many volatile elements are also siderophile (metal-loving), it is often difficult to deconvolve the effect of volatility from core formation. With the notable exception of the Earth, all the differentiated terrestrial bodies for which we have samples have non-chondritic Mn/Na ratios, taken as a signature of post-nebular volatilization. The bulk silicate Earth (BSE) is unique in that its Mn/Na ratio is chondritic, which points to a nebular origin for the depletion; unless the Mn/Na in the BSE is not that of the bulk Earth (BE), and has been affected by core formation through the partitioning of Mn in Earth's core. Here we quantify the metal-silicate partitioning behavior of Mn at deep magma ocean pressure and temperature conditions directly applicable to core formation. The experiments show that Mn becomes more siderophile with increasing pressure and temperature. Modeling the partitioning of Mn during core formation by combining our results with previous data at lower P-T conditions, we show that the core likely contains a significant fraction (20 to 35%) of Earth's Mn budget. However, we show that the derived Mn/Na value of the bulk Earth still lies on the volatile-depleted end of a trend defined by chondritic meteorites in a Mn/Na vs Mn/Mg plot, which tend to higher Mn/Na with increasing volatile depletion. This suggests that the material that formed the Earth recorded similar chemical fractionation processes for moderately volatile elements as chondrites in the solar nebula, and experienced limited post nebular volatilization.

Implications for Core Formation of the Earth from High Pressure-Temperature Au Partitioning Experiments

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Sharp, T. G.; Hervig, R. L.

2005-01-01

Siderophile elements in the Earth.s mantle are depleted relative to chondrites. This is most pronounced for the highly siderophile elements (HSEs), which are approximately 400x lower than chondrites. Also remarkable is the relative chondritic abundances of the HSEs. This signature has been interpreted as representing their sequestration into an iron-rich core during the separation of metal from silicate liquids early in the Earth's history, followed by a late addition of chondritic material. Alternative efforts to explain this trace element signature have centered on element partitioning experiments at varying pressures, temperatures, and compositions (P-T-X). However, first results from experiments conducted at 1 bar did not match the observed mantle abundances, which motivated the model described above, a "late veneer" of chondritic material deposited on the earth and mixed into the upper mantle. Alternatively, the mantle trace element signature could be the result of equilibrium partitioning between metal and silicate in the deep mantle, under P-T-X conditions which are not yet completely identified. An earlier model determined that equilibrium between metal and silicate liquids could occur at a depth of approximately 700 km, 27(plus or minus 6) GPa and approximately 2000 (plus or minus 200) C, based on an extrapolation of partitioning data for a variety of moderately siderophile elements obtained at lower pressures and temperatures. Based on Ni-Co partitioning, the magma ocean may have been as deep as 1450 km. At present, only a small range of possible P-T-X trace element partitioning conditions has been explored, necessitating large extrapolations from experimental to mantle conditions for tests of equilibrium models. Our primary objective was to reduce or remove the additional uncertainty introduced by extrapolation by testing the equilibrium core formation hypothesis at P-T-X conditions appropriate to the mantle.

Cosmological quantum chromodynamics, neutron diffusion, and the production of primordial heavy elements

NASA Technical Reports Server (NTRS)

Applegate, J. H.; Hogan, Craig J.; Scherrer, R. J.

1988-01-01

A simple one-dimensional model is used to describe the evolution of neutron density before and during nucleosynthesis in a high-entropy bubble left over from the cosmic quark-hadron phase transition. It is shown why cosmic nucleosynthesis in such a neutron-rich environment produces a surfeit of elements heavier than lithium. Analytical and numerical techniques are used to estimate the abundances of carbon, nitrogen, and heavier elements up to Ne-22. A high-density neutron-rich region produces enough primordial N-14 to be observed in stellar atmospheres. It shown that very heavy elements may be created in a cosmological r-process; the neutron exposure in the neutron-rich regions is large enough for the Ne-22 to trigger a catastrophic r-process runaway in which the quantity of heavy elements doubles in much less than an expansion time due to fission cycling. A primordial abundance of r-process elements is predicted to appear as an excess of rare earth elements in extremely metal-poor stars.

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.

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.

High-pressure phase relation of KREEP basalts: A clue for finding the lost Hadean crust?

NASA Astrophysics Data System (ADS)

Gréaux, Steeve; Nishi, Masayuki; Tateno, Shigehiko; Kuwayama, Yasuhiro; Hirao, Naohisa; Kawai, Kenji; Maruyama, Shigenori; Irifune, Tetsuo

2018-01-01

The phase relations, mineral chemistry and density of KREEP basalt were investigated at pressures of 12-125 GPa and temperatures up to 2810 K by a combination of large volume multi-anvil press experiments and in situ synchrotron X-ray diffraction measurements in a laser-heated diamond anvil cell. Our results showed that grossular-rich majorite garnet, liebermannite and Al-bearing stishovite are dominant in the upper-to-middle part of the upper mantle while in the lowermost transition zone a dense Ti-rich CaSiO3 perovskite exsoluted from the garnet, which becomes more pyropic with increasing pressure. At lower mantle conditions, these minerals transform into an assemblage of bridgmanite, Ca-perovskite, Al-stishovite, the new aluminium-rich (NAL) phase and the calcium-ferrite type (CF) phase. At pressures higher than 50 GPa, NAL phase completely dissolved into the CF phase, which becomes the main deposit of alkali metals in the lower mantle. The density of KREEP estimated from phase compositions obtained by energy dispersive X-ray spectroscopy (EDS) in scanning (SEM) and transmission (TEM) electron microscopes, was found substantially denser than pyrolite suggesting that the Earth primordial crust likely subducted deep into the Earth's mantle after or slightly before the final solidification of magma ocean at 4.53 Ga. Radiogenic elements U, Th and 40K which were abundant in the final residue of magma ocean were brought down along the subduction of the primordial crust and generate heat by decay after the settlement of the primordial crust on top of the CMB, suggesting the non-homogeneous distribution of radiogenic elements in the Hadean mantle with implications for the thermal history of the Earth.

Ordered porous mesostructured materials from nanoparticle-block copolymer self-assembly

DOEpatents

Warren, Scott; Wiesner, Ulrich; DiSalvo, Jr., Francis J

2013-10-29

The invention provides mesostructured materials and methods of preparing mesostructured materials including metal-rich mesostructured nanoparticle-block copolymer hybrids, porous metal-nonmetal nanocomposite mesostructures, and ordered metal mesostructures with uniform pores. The nanoparticles can be metal, metal alloy, metal mixture, intermetallic, metal-carbon, metal-ceramic, semiconductor-carbon, semiconductor-ceramic, insulator-carbon or insulator-ceramic nanoparticles, or combinations thereof. A block copolymer/ligand-stabilized nanoparticle solution is cast, resulting in the formation of a metal-rich (or semiconductor-rich or insulator-rich) mesostructured nanoparticle-block copolymer hybrid. The hybrid is heated to an elevated temperature, resulting in the formation of an ordered porous nanocomposite mesostructure. A nonmetal component (e.g., carbon or ceramic) is then removed to produce an ordered mesostructure with ordered and large uniform pores.

The Impact of Clouds and Hazes in Substellar Atmospheres

NASA Astrophysics Data System (ADS)

Morley, Caroline; Fortney, Jonathan J.; Marley, Mark S.

2016-01-01

The formation of clouds significantly alters the spectra of cool substellar atmospheres from terrestrial planets to brown dwarfs. In cool planets like Earth and Jupiter, volatile species like water and ammonia condense to form ice clouds. In hot planets and brown dwarfs, iron and silicates instead condense, forming dusty clouds. Irradiated methane-rich planets may have substantial hydrocarbon hazes. During my thesis, I have studied the impact of clouds and hazes in a variety of substellar objects. First, I present results for cool brown dwarfs including clouds previously neglected in model atmospheres. Model spectra that include sulfide and salt clouds can match the spectra of T dwarf atmospheres; water ice clouds will alter the spectra of the newest and coldest brown dwarfs, the Y dwarfs. These sulfide/salt and ice clouds potentially drive spectroscopic variability in these cool objects, and this variability should be distinguishable from variability caused by hot spots.Next, I present results for small, cool exoplanets between the size of Earth and Neptune, so-called super Earths. They likely have sulfide and salt clouds and also have photochemical hazes caused by stellar irradiation. Vast resources have been dedicated to characterizing the handful of super Earths accessible to current telescopes, yet of the planets smaller than Neptune studied to date, all have radii in the near-infrared consistent with being constant in wavelength, likely showing that these small planets are consistently enshrouded in thick hazes and clouds. Very thick, lofted clouds of salts or sulfides in high metallicity (1000× solar) atmospheres create featureless transmission spectra in the near-infrared. Photochemical hazes with a range of particle sizes also create featureless transmission spectra at lower metallicities. I show that despite these challenges, there are promising avenues for understanding this class of small planets: by observing the thermal emission and reflectivity of small planets, we can break the degeneracies and better constrain the atmospheric compositions. These observations may provide rich diagnostics of molecules and clouds in small planets, in contrast to the limited success to date.

Cometary dust in Antarctic ice and snow: Past and present chondritic porous micrometeorites preserved on the Earth's surface

NASA Astrophysics Data System (ADS)

Noguchi, Takaaki; Ohashi, Noriaki; Tsujimoto, Shinichi; Mitsunari, Takuya; Bradley, John P.; Nakamura, Tomoki; Toh, Shoichi; Stephan, Thomas; Iwata, Naoyoshi; Imae, Naoya

2015-01-01

Chondritic porous interplanetary dust particles (CP IDPs) collected in the stratosphere are regarded as possibly being cometary dust, and are therefore the most primitive solar system material that is currently available for analysis in laboratories. In this paper we report the discovery of more than 40 chondritic porous micrometeorites (CP MMs) in the surface snow and blue ice of Antarctica, which are indistinguishable from CP IDPs. The CP MMs are botryoidal aggregates, composed mainly of sub-micrometer-sized constituents. They contain two components that characterize them as CP IDPs: enstatite whiskers and GEMS (glass with embedded metal and sulfides). Enstatite whiskers appear as <2-μm-long acicular objects that are attached on, or protrude from the surface, and when included in the interior of the CP MMs are composed of a unit-cell scale mixture of clino- and ortho-enstatite, and elongated along the [100] direction. GEMS appear as 100-500 nm spheroidal objects containing <50 nm Fe-Ni metal and Fe sulfide. The CP MMs also contain low-iron-manganese-enriched (LIME) and low-iron-chromium-enriched (LICE) ferromagnesian silicates, kosmochlor (NaCrSi2O6)-rich high-Ca pyroxene, roedderite (K, Na)2Mg5Si12O30, and carbonaceous nanoglobules. These components have previously been discovered in primitive solar system materials such as the CP IDPs, matrices of primitive chondrites, phyllosilicate-rich MMs, ultracarbonaceous MMs, and cometary particles recovered from the 81P/Wild 2 comet. The most outstanding feature of these CP MMs is the presence of kosmochlor-rich high-Ca pyroxene and roedderite, which suggest that they have building blocks in common with CP IDPs and cometary dust particles and therefore suggest a possible cometary origin of both CP MMs and CP IDPs. It is therefore considered that CP MMs are CP IDPs that have fallen to Earth and have survived the terrestrial environment.

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

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

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

DOE PAGES

Du, Mao -Hua; Singh, David J.; Zhang, Lijun; ...

2016-04-19

Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn 2O 3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn 2O 3 andmore » BaSn 2O 3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO 3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn 2O 3) to 3.15 (SrSn 2O 3) eV, and hole effective masses ranging from 0.87 (BaSn 2O 3) to above 6.0 (SrSn 2O 3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.« less

Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

PubMed

Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

2009-01-01

Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

Large magnetic anisotropy predicted for rare-earth-free F e 16 - x C o x N 2 alloys

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

Zhao, Xin; Wang, Cai -Zhuang; Yao, Yongxin

Structures and magnetic properties of Fe 16–xCo xN 2 are studied using adaptive genetic algorithm and first-principles calculations. We show that substituting Fe with Co in Fe 16N 2 with a Co/Fe ratio ≤1 can greatly improve the magnetic anisotropy of the material. The magnetocrystalline anisotropy energy from first-principles calculations reaches 3.18 MJ/m 3 (245.6 μeV per metal atom) for Fe 12Co 4N 2, much larger than that of Fe 16N 2, and is one of the largest among the reported rare-earth-free magnets. From our systematic crystal structure searches, we show that there is a structure transition from tetragonal Femore » 16N 2 to cubic Co 16N 2 in Fe 16–xCo xN 2 as the Co concentration increases, which can be well explained by electron counting analysis. As a result, different magnetic properties between the Fe-rich (x ≤ 8) and Co-rich (x > 8) Fe 16–xCo xN 2 is closely related to the structural transition.« less

Large magnetic anisotropy predicted for rare-earth-free F e 16 - x C o x N 2 alloys

DOE PAGES

Zhao, Xin; Wang, Cai -Zhuang; Yao, Yongxin; ...

2016-12-23

Structures and magnetic properties of Fe 16–xCo xN 2 are studied using adaptive genetic algorithm and first-principles calculations. We show that substituting Fe with Co in Fe 16N 2 with a Co/Fe ratio ≤1 can greatly improve the magnetic anisotropy of the material. The magnetocrystalline anisotropy energy from first-principles calculations reaches 3.18 MJ/m 3 (245.6 μeV per metal atom) for Fe 12Co 4N 2, much larger than that of Fe 16N 2, and is one of the largest among the reported rare-earth-free magnets. From our systematic crystal structure searches, we show that there is a structure transition from tetragonal Femore » 16N 2 to cubic Co 16N 2 in Fe 16–xCo xN 2 as the Co concentration increases, which can be well explained by electron counting analysis. As a result, different magnetic properties between the Fe-rich (x ≤ 8) and Co-rich (x > 8) Fe 16–xCo xN 2 is closely related to the structural transition.« less

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

Origins of ultralow velocity zones through slab-derived metallic melt

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

Liu, Jiachao; Li, Jie; Hrubiak, Rostislav

2016-05-03

Understanding the ultralow velocity zones (ULVZs) places constraints on the chemical composition and thermal structure of deep Earth and provides critical information on the dynamics of large-scale mantle convection, but their origin has remained enigmatic for decades. Recent studies suggest that metallic iron and carbon are produced in subducted slabs when they sink beyond a depth of 250 km. Here we show that the eutectic melting curve of the iron-carbon system crosses the current geotherm near Earth’s core-mantle boundary, suggesting that dense metallic melt may form in the lowermost mantle. If concentrated into isolated patches, such melt could produce themore » seismically observed density and velocity features of ULVZs. Depending on the wetting behavior of the metallic melt, the resultant ULVZs may be short-lived domains that are replenished or regenerated through subduction, or long-lasting regions containing both metallic and silicate melts. Slab-derived metallic melt may produce another type of ULVZ that escapes core sequestration by reacting with the mantle to form iron-rich post-bridgmanite or ferropericlase. The hypotheses connect peculiar features near Earth’s core-mantle boundary to subduction of the oceanic lithosphere through the deep carbon cycle.« less

A Paleoarchean coastal hydrothermal field inhabited by diverse microbial communities: the Strelley Pool Formation, Pilbara Craton, Western Australia.

PubMed

Sugitani, K; Mimura, K; Takeuchi, M; Yamaguchi, T; Suzuki, K; Senda, R; Asahara, Y; Wallis, S; Van Kranendonk, M J

2015-11-01

The 3.4-Ga Strelley Pool Formation (SPF) at the informally named 'Waterfall Locality' in the Goldsworthy greenstone belt of the Pilbara Craton, Western Australia, provides deeper insights into ancient, shallow subaqueous to possibly subaerial ecosystems. Outcrops at this locality contain a thin (<3 m) unit of carbonaceous and non-carbonaceous cherts and silicified sandstones that were deposited in a shallow-water coastal environment, with hydrothermal activities, consistent with the previous studies. Carbonaceous, sulfide-rich massive black cherts with coniform structures up to 3 cm high are characterized by diverse rare earth elements (REE) signatures including enrichment of light [light rare earth elements (LREE)] or middle rare earth elements and by enrichment of heavy metals represented by Zn. The massive black cherts were likely deposited by mixing of hydrothermal and non-hydrothermal fluids. Coniform structures in the cherts are characterized by diffuse laminae composed of sulfide particles, suggesting that unlike stromatolites, they were formed dominantly through physico-chemical processes related to hydrothermal activity. The cherts yield microfossils identical to previously described carbonaceous films, small and large spheres, and lenticular microfossils. In addition, new morphological types such as clusters composed of large carbonaceous spheroids (20-40 μm across each) with fluffy or foam-like envelope are identified. Finely laminated carbonaceous cherts are devoid of heavy metals and characterized by the enrichment of LREE. This chert locally contains conical to domal structures characterized by truncation of laminae and trapping of detrital grains and is interpreted as siliceous stromatolite formed by very early or contemporaneous silicification of biomats with the contribution of silica-rich hydrothermal fluids. Biological affinities of described microfossils and microbes constructing siliceous stromatolites are under investigation. However, this study emphasizes how diverse the microbial community in Paleoarchean coastal hydrothermal environment was. We propose the diversity is at least partially due to the availability of various energy sources in this depositional environment including reducing chemicals and sunlight. © 2015 John Wiley & Sons Ltd.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

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.

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.

Flex-flame burner and combustion method

DOEpatents

Soupos, Vasilios; Zelepouga, Serguei; Rue, David M.; Abbasi, Hamid A.

2010-08-24

A combustion method and apparatus which produce a hybrid flame for heating metals and metal alloys, which hybrid flame has the characteristic of having an oxidant-lean portion proximate the metal or metal alloy and having an oxidant-rich portion disposed above the oxidant lean portion. This hybrid flame is produced by introducing fuel and primary combustion oxidant into the furnace chamber containing the metal or metal alloy in a substoichiometric ratio to produce a fuel-rich flame and by introducing a secondary combustion oxidant into the furnace chamber above the fuel-rich flame in a manner whereby mixing of the secondary combustion oxidant with the fuel-rich flame is delayed for a portion of the length of the flame.

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, W.E.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Pierce, R.D.

1992-08-25

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800 C to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein. 1 figure.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, William E.; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800.degree. C. to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein.

Iron-carbonate interaction at Earth's core-mantle boundary

NASA Astrophysics Data System (ADS)

Dorfman, S. M.; Badro, J.; Nabiei, F.; Prakapenka, V.; Gillet, P.

2015-12-01

Carbon storage and flux in the deep Earth are moderated by oxygen fugacity and interactions with iron-bearing phases. The amount of carbon stored in Earth's mantle versus the core depends on carbon-iron chemistry at the core-mantle boundary. Oxidized carbonates subducted from Earth's surface to the lowermost mantle may encounter reduced Fe0 metal from disproportionation of Fe2+ in lower mantle silicates or mixing with the core. To understand the fate of carbonates in the lowermost mantle, we have performed experiments on sandwiches of single-crystal (Ca0.6Mg0.4)CO3 dolomite and Fe foil in the laser-heated diamond anvil cell at lower mantle conditions of 49-110 GPa and 1800-2500 K. Syntheses were conducted with in situ synchrotron X-ray diffraction to identify phase assemblages. After quench to ambient conditions, samples were sectioned with a focused Ga+ ion beam for composition analysis with transmission electron microscopy. At the centers of the heated spots, iron melted and reacted completely with the carbonate to form magnesiowüstite, iron carbide, diamond, magnesium-rich carbonate and calcium carbonate. In samples heated at 49 and 64 GPa, the two carbonates exhibit a eutectoid texture. In the sample heated at 110 GPa, the carbonates form rounded ~150-nm-diameter grains with a higher modal proportion of interspersed diamonds. The presence of reduced iron in the deep lower mantle and core-mantle boundary region will promote the formation of diamonds in carbonate-bearing subducted slabs. The complete reaction of metallic iron to oxides and carbides in the presence of mantle carbonate supports the formation of these phases at the Earth's core-mantle boundary and in ultra-low velocity zones.

New permanent magnets

NASA Astrophysics Data System (ADS)

Müller, K.-H.; Krabbes, G.; Fink, J.; Gruß, S.; Kirchner, A.; Fuchs, G.; Schultz, L.

2001-05-01

Permanent magnets play an important role and are widely spread in daily-life applications. Due to their very low costs, large availability of the row materials and their high chemical stability, hard ferrites are still dominant in the permanent magnet market although their relatively poor magnetic properties are a distinct disadvantage. Today's high-performance magnets are mostly made from Nd 2Fe 14B. The aim of research is to combine the large spontaneous magnetization of 3d metals with strong anisotropy fields known from rare-earth transition-metal compounds and, at the same time, to maintain a high value of the Curie temperature. However, the number of iron-rich rare-earth intermetallics is very limited and, consequently, not much success can be noted in this field for the last 10 years. One alternative concept is to use magnetic fields trapped in type II superconductors where much higher fields can be achieved compared to conventional rare-earth magnets. Very recently, we obtained a trapped field as high as 14.4 T in a melt-textured YBCO bulk sample of a few centimeters in diameter. This is the highest value ever achieved in a bulk superconductor. The trapped field of a superconductor is not governed by the Laplace equation and, therefore, levitation works without any additional (active) stabilization. The disadvantage of these magnets is their low working temperature (of liquid nitrogen and below).

Production method for making rare earth compounds

DOEpatents

McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

Production method for making rare earth compounds

DOEpatents

McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

Physical properties of the planet Mercury

NASA Technical Reports Server (NTRS)

Clark, Pamela E.

1988-01-01

The global physical properties of Mercury are summarized with attention given to its figure and orbital parameters. The combination of properties suggests that Mercury has an extensive iron-rich core, possibly with a still-functioning dynamo, which is 42 percent of the interior by volume. Mercury's three major axes are comparable in size, indicating that the planet is a triaxial ellipsoid rather than an oblate spheroid. In terms of the domination of its surface by an intermediate plains terrane, it is more Venus- or Mars-like; however, due to the presence of a large metallic magnetic core, its interior may be more earth-like.

Human mining activity across the ages determines the genetic structure of modern brown trout (Salmo trutta L.) populations

PubMed Central

Paris, Josephine R; King, R Andrew; Stevens, Jamie R

2015-01-01

Humans have exploited the earth's metal resources for thousands of years leaving behind a legacy of toxic metal contamination and poor water quality. The southwest of England provides a well-defined example, with a rich history of metal mining dating to the Bronze Age. Mine water washout continues to negatively impact water quality across the region where brown trout (Salmo trutta L.) populations exist in both metal-impacted and relatively clean rivers. We used microsatellites to assess the genetic impact of mining practices on trout populations in this region. Our analyses demonstrated that metal-impacted trout populations have low genetic diversity and have experienced severe population declines. Metal-river trout populations are genetically distinct from clean-river populations, and also from one another, despite being geographically proximate. Using approximate Bayesian computation (ABC), we dated the origins of these genetic patterns to periods of intensive mining activity. The historical split of contemporary metal-impacted populations from clean-river fish dated to the Medieval period. Moreover, we observed two distinct genetic populations of trout within a single catchment and dated their divergence to the Industrial Revolution. Our investigation thus provides an evaluation of contemporary population genetics in showing how human-altered landscapes can change the genetic makeup of a species. PMID:26136823

Does the linear conversion between calcium infrared triplet and metallicity of globular clusters in early-type galaxies hold in the whole range of metallicity?

NASA Astrophysics Data System (ADS)

Chung, Chul; Yoon, Suk-Jin; Lee, Young-Wook; Lee, Sang-Yoon

2015-01-01

The calcium infrared triplet (CaT) is one of the prominent absorption features in the infrared wavelength regime. Recently, these absorption features have been getting attention in the prediction of metallicity of globular clusters (GCs) in early-type galaxies (ETGs) because of its strong sensitivity to the metallicity and calcium abundance of a star. However, based on our population synthesis model for CaT, we find that measuring metallicity directly from CaT is inaccurate because the formation mechanism of Ca II ionised line is very inefficient in the cool stars which are abundant in metal-rich stellar populations. This characteristics of Ca II ionised line make the CaT-metallicity relation to converge around 8 angstrom in the metal-rich regime. This is why the metallicity of simple stellar populations, such as GCs, greater than [Fe/H]~-0.5 is unreliable when the linear conversion between CaT and metallicity is applied to derive metallicity. In addition, we have successfully simulated the metal-rich CaT peaks found in GCs in ETGs by using the nonlinear CaT-metallicity relation in the metal-rich regime. This can also explain the difference between color and CaT distributions of GCs in various ETGs. Based on these results, we suggest that CaT is not a good metallicity indicator for the metal-rich stellar populations.

Designing solid-liquid interphases for sodium batteries

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

Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid–electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport,more » comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.« less

In situ studies of oxide nucleation, growth, and transformation using slow electrons

NASA Astrophysics Data System (ADS)

Flege, Jan Ingo; Grinter, David C.

2018-05-01

Surface processes such as metal oxidation and metal oxide growth invariably influence the physical and chemical properties of materials and determine their interaction with their surroundings and hence their functionality in many technical applications. On a fundamental level, these processes are found to be governed by a complex interplay of thermodynamic variables and kinetic constraints, resulting in a rich variety of material-specific phenomena. In this review article, we discuss recent results and insights on transition metal oxidation and rare-earth oxide growth acquired by low-energy electron microscopy and related techniques. We demonstrate that the use of in situ surface sensitive methods is a prerequisite to gaining a deeper understanding of the underlying concepts and the mechanisms responsible for the emerging oxide structure and morphology. Furthermore, examples will be provided on how structural and chemical modifications of the oxide films and nanostructures can be followed in real-time and analyzed in terms of local reactivity and cooperative effects relevant for heterogeneous model catalysis.

Designing solid-liquid interphases for sodium batteries

DOE PAGES

Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin; ...

2017-10-12

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid–electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport,more » comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.« less

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates

DOE PAGES

Middey, S.; Meyers, D.; Kareev, M.; ...

2018-04-09

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO 3. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions.more » Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. In conclusion, this designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.« less

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates

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

Middey, S.; Meyers, D.; Kareev, M.

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO 3. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions.more » Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. In conclusion, this designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.« less

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Phase Transformations and Metallization of Magnesium Oxide at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

McWilliams, R. Stewart; Spaulding, Dylan K.; Eggert, Jon H.; Celliers, Peter M.; Hicks, Damien G.; Smith, Raymond F.; Collins, Gilbert W.; Jeanloz, Raymond

2012-12-01

Magnesium oxide (MgO) is representative of the rocky materials comprising the mantles of terrestrial planets, such that its properties at high temperatures and pressures reflect the nature of planetary interiors. Shock-compression experiments on MgO to pressures of 1.4 terapascals (TPa) reveal a sequence of two phase transformations: from B1 (sodium chloride) to B2 (cesium chloride) crystal structures above 0.36 TPa, and from electrically insulating solid to metallic liquid above 0.60 TPa. The transitions exhibit large latent heats that are likely to affect the structure and evolution of super-Earths. Together with data on other oxide liquids, we conclude that magmas deep inside terrestrial planets can be electrically conductive, enabling magnetic field-producing dynamo action within oxide-rich regions and blurring the distinction between planetary mantles and cores.

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 1: Constituent quantities and correlations

USGS Publications Warehouse

Cravotta, C.A.

2008-01-01

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s-1, with a median of 18.4 L s-1. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-??m pore-size filter) SO4 (34-2000), Fe (0.046-512), Mn (0.019-74), and Al (0.007-108) varied widely. Predominant metalloid elements were Si (2.7-31.3 mg L-1), B ( C > P = N = Se) were not elevated in the CMD samples compared to average river water or seawater. Compared to seawater, the CMD samples also were poor in halogens (Cl > Br > I > F), alkalies (Na > K > Li > Rb > Cs), most alkaline earths (Ca > Mg > Sr), and most metalloids but were enriched by two to four orders of magnitude with Fe, Al, Mn, Co, Be, Sc, Y and the lanthanide rare-earth elements, and one order of magnitude with Ni and Zn. The ochre samples collected at a subset of 10 sites in 2003 were dominantly goethite with minor ferrihydrite or lepidocrocite. None of the samples for this subset contained schwertmannite or was Al rich, but most contained minor aluminosilicate detritus. Compared to concentrations in global average shale, the ochres were rich in Fe, Ag, As and Au, but were poor in most other metals and rare earths. The ochres were not enriched compared to commercial ore deposits mined for Au or other valuable metals. Although similar to commercial Fe ores in composition, the ochres are dispersed and present in relatively small quantities at most sites. Nevertheless, the ochres could be valuable for use as pigment.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, James B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, J.B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass, CA, USA, in 1949, was significant because it led to the production of commercial quantities of rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

Effects of Rare Earth Metals on Steel Microstructures

PubMed Central

Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Kuo, Chia-Liang; Su, Yen-Hao; Chen, Shin-Hau; Lin, Kuan-Ju; Hsieh, Ping-Hung; Hwang, Weng-Sing

2016-01-01

Rare earth metals are used in semiconductors, solar cells and catalysts. This review focuses on the background of oxide metallurgy technologies, the chemical and physical properties of rare earth (RE) metals, the background of oxide metallurgy, the functions of RE metals in steelmaking, and the influences of RE metals on steel microstructures. Future prospects for RE metal applications in steelmaking are also presented. PMID:28773545

40 CFR 421.276 - Pretreatment standards for new sources.

Code of Federal Regulations, 2014 CFR

2014-07-01

... GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals... wastewater pollutants in primary rare earth metals process wastewater introduced into a POTW shall not exceed the following values: (a) Dryer vent water quench and scrubber. PSNS for the Primary Rare Earth Metals...

40 CFR 421.276 - Pretreatment standards for new sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

... GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals... wastewater pollutants in primary rare earth metals process wastewater introduced into a POTW shall not exceed the following values: (a) Dryer vent water quench and scrubber. PSNS for the Primary Rare Earth Metals...

40 CFR 421.276 - Pretreatment standards for new sources.

Code of Federal Regulations, 2013 CFR

2013-07-01

... GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals... wastewater pollutants in primary rare earth metals process wastewater introduced into a POTW shall not exceed the following values: (a) Dryer vent water quench and scrubber. PSNS for the Primary Rare Earth Metals...

40 CFR 421.276 - Pretreatment standards for new sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

... GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals... wastewater pollutants in primary rare earth metals process wastewater introduced into a POTW shall not exceed the following values: (a) Dryer vent water quench and scrubber. PSNS for the Primary Rare Earth Metals...

40 CFR 421.276 - Pretreatment standards for new sources.

Code of Federal Regulations, 2012 CFR

2012-07-01

... GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals... wastewater pollutants in primary rare earth metals process wastewater introduced into a POTW shall not exceed the following values: (a) Dryer vent water quench and scrubber. PSNS for the Primary Rare Earth Metals...

Thermochemistry and Photochemistry in Thick Atmospheres on Super Earths and Mini Neptunes

NASA Astrophysics Data System (ADS)

Hu, R.; Seager, S.

2013-12-01

Dectection and characterization of low-mass exoplanets is poised to accelerate in the coming decade. Some low-mass exoplanets, namely super Earths and some mini Neptunes, will likely have thick atmospheres that are not H2-dominated. We have developed a photochemistry-thermochemistry model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H2-dominated atmospheres and non-H2-dominated atmospheres. Using this model, we have simulated the molecular composition of thick atmospheres on warm and hot super Earths/mini Neptunes, and classified thick atmospheres into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres, depending on the hydrogen abundance and the carbon to oxygen abundance ratio. We find that carbon has to be in the form of CO2 rather than CH4 or CO in an H2-depleted water-dominated thick atmosphere, and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to formation of unsaturated hydrocarbons. For future observations, we find for GJ 1214b that (1) C2H2 features at 1.0 and 1.5 μm in transmission are diagnostic for hydrocarbon-rich atmospheres; (2) a constraint on the thermal emission at 4.5 μm could differentiate water-rich atmospheres versus hydrocarbon-rich atmospheres; (3) a detection of water-vapor features and a confirmation of nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. For a hot super Earth like 55 Cnc e, the diagnostic features of water-rich atmospheres (H2O) and the diagnostic features of hydrocarbon-rich atmospheres (CO and C2H2) are well separated in transmission spectra at 0.6-5 μm, which would enable straightforward characterization. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Theoretical transmission spectra and thermal emission spectra of non-H2-dominated atmospheres on GJ 1214b based on photochemistry-thermochemistry simulations in comparison with current observations. The simulated spectra are for an hydrogen abundance of 0.5 and a variety of carbon to oxygen ratios ranging from oxygen rich to carbon rich. The atmospheric scenarios with different carbon to oxygen ratios can be constrained via the spectral features of their hallmark molecules.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Jacobsen, Stein; Sasselov, Dimitar D.

2015-01-01

We propose to use evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called 'late veneer'. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. We plan to build an integrative model of Earth-like planets from the bottom up. We would like to infer their chemical compositions from their mass-radius relations and their host stars' elemental abundances, and understand the origins of volatile contents (especially water) on their surfaces, and thereby shed light on the origins of life on them.

Electroluminescence color tuning between green and red from metal-oxide-semiconductor devices fabricated by spin-coating of rare-earth (terbium + europium) organic compounds on silicon

NASA Astrophysics Data System (ADS)

Matsuda, Toshihiro; Hattori, Fumihiro; Iwata, Hideyuki; Ohzone, Takashi

2018-04-01

Color tunable electroluminescence (EL) from metal-oxide-semiconductor devices with the rare-earth elements Tb and Eu is reported. Organic compound liquid sources of (Tb + Ba) and Eu with various Eu/Tb ratios from 0.001 to 0.4 were spin-coated on an n+-Si substrate and annealed to form an oxide insulator layer. The EL spectra had only peaks corresponding to the intrashell Tb3+/Eu3+ transitions in the spectral range from green to red, and the intensity ratio of the peaks was appropriately tuned using the appropriate Eu/Tb ratios in liquid sources. Consequently, the EL emission colors linearly changed from yellowish green to yellowish orange and eventually to reddish orange on the CIE chromaticity diagram. The gate current +I G current also affected the EL colors for the medium-Eu/Tb-ratio device. The structure of the surface insulator films analyzed by cross-sectional transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis, and X-ray photoelectron spectroscopy (XPS) has four layers, namely, (Tb4O7 + Eu2O3), [Tb4O7 + Eu2O3 + (Tb/Eu/Ba)SiO x ], (Tb/Eu/Ba)SiO x , and SiO x -rich oxide. The EL mechanism proposed is that electrons injected from the Si substrate into the SiO x -rich oxide and Tb/Eu/Ba-silicate layers become hot electrons accelerated in a high electric field, and then these hot electrons excite Tb3+ and Eu3+ ions in the Tb4O7/Eu2O3 layers resulting in EL emission from Tb3+ and Eu3+ intrashell transitions.

METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

DOEpatents

Baker, R.D.; Hayward, B.R.

1963-01-01

>This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

Isotopes as clues to the origin and earliest differentiation history of the Earth.

PubMed

Jacobsen, Stein B; Ranen, Michael C; Petaev, Michael I; Remo, John L; O'Connell, Richard J; Sasselov, Dimitar D

2008-11-28

Measurable variations in (182)W/(183)W, (142)Nd/(144)Nd, (129)Xe/(130)Xe and (136)XePu/(130)Xe in the Earth and meteorites provide a record of accretion and formation of the core, early crust and atmosphere. These variations are due to the decay of the now extinct nuclides (182)Hf, (146)Sm, (129)I and (244)Pu. The (l82)Hf-(182)W system is the best accretion and core-formation chronometer, which yields a mean time of Earth's formation of 10Myr, and a total time scale of 30Myr. New laser shock data at conditions comparable with those in the Earth's deep mantle subsequent to the giant Moon-forming impact suggest that metal-silicate equilibration was rapid enough for the Hf-W chronometer to reliably record this time scale. The coupled (146)Sm-(147)Sm chronometer is the best system for determining the initial silicate differentiation (magma ocean crystallization and proto-crust formation), which took place at ca 4.47Ga or perhaps even earlier. The presence of a large (129)Xe excess in the deep Earth is consistent with a very early atmosphere formation (as early as 30Myr); however, the interpretation is complicated by the fact that most of the atmospheric Xe may be from a volatile-rich late veneer.

Cluster expansion modeling and Monte Carlo simulation of alnico 5–7 permanent magnets

DOE PAGES

Nguyen, Manh Cuong; Zhao, Xin; Wang, Cai -Zhuang; ...

2015-03-05

The concerns about the supply and resource of rare earth (RE) metals have generated a lot of interests in searching for high performance RE-free permanent magnets. Alnico alloys are traditional non-RE permanent magnets and have received much attention recently due their good performance at high temperature. In this paper, we develop an accurate and efficient cluster expansion energy model for alnico 5–7. Monte Carlo simulations using the cluster expansion method are performed to investigate the structure of alnico 5–7 at atomistic and nano scales. The alnico 5–7 master alloy is found to decompose into FeCo-rich and NiAl-rich phases at lowmore » temperature. The boundary between these two phases is quite sharp (~2 nm) for a wide range of temperature. The compositions of the main constituents in these two phases become higher when the temperature gets lower. Both FeCo-rich and NiAl-rich phases are in B2 ordering with Fe and Al on α-site and Ni and Co on β-site. The degree of order of the NiAl-rich phase is much higher than that of the FeCo-rich phase. In addition, a small magnetic moment is also observed in NiAl-rich phase but the moment reduces as the temperature is lowered, implying that the magnetic properties of alnico 5–7 could be improved by lowering annealing temperature to diminish the magnetism in NiAl-rich phase. Furthermore, the results from our Monte Carlo simulations are consistent with available experimental results.« less

Cluster expansion modeling and Monte Carlo simulation of alnico 5-7 permanent magnets

NASA Astrophysics Data System (ADS)

Nguyen, Manh Cuong; Zhao, Xin; Wang, Cai-Zhuang; Ho, Kai-Ming

2015-03-01

The concerns about the supply and resource of rare earth (RE) metals have generated a lot of interests in searching for high performance RE-free permanent magnets. Alnico alloys are traditional non-RE permanent magnets and have received much attention recently due their good performance at high temperature. In this paper, we develop an accurate and efficient cluster expansion energy model for alnico 5-7. Monte Carlo simulations using the cluster expansion method are performed to investigate the structure of alnico 5-7 at atomistic and nano scales. The alnico 5-7 master alloy is found to decompose into FeCo-rich and NiAl-rich phases at low temperature. The boundary between these two phases is quite sharp (˜2 nm) for a wide range of temperature. The compositions of the main constituents in these two phases become higher when the temperature gets lower. Both FeCo-rich and NiAl-rich phases are in B2 ordering with Fe and Al on α-site and Ni and Co on β-site. The degree of order of the NiAl-rich phase is much higher than that of the FeCo-rich phase. A small magnetic moment is also observed in NiAl-rich phase but the moment reduces as the temperature is lowered, implying that the magnetic properties of alnico 5-7 could be improved by lowering annealing temperature to diminish the magnetism in NiAl-rich phase. The results from our Monte Carlo simulations are consistent with available experimental results.

Magnesium transport extraction of transuranium elements from LWR fuel

DOEpatents

Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.

Fe-Ni metal in primitive chondrites: Indicators of classification and metamorphic conditions for ordinary and CO chondrites

USGS Publications Warehouse

Kimura, M.; Grossman, J.N.; Weisberg, M.K.

2008-01-01

We report the results of our petrological and mineralogical study of Fe-Ni metal in type 3 ordinary and CO chondrites, and the ungrouped carbonaceous chondrite Acfer 094. Fe-Ni metal in ordinary and CO chondrites occurs in chondrule interiors, on chondrule surfaces, and as isolated grains in the matrix. Isolated Ni-rich metal in chondrites of petrologic type lower than type 3.10 is enriched in Co relative to the kamacite in chondrules. However, Ni-rich metal in type 3.15-3.9 chondrites always contains less Co than does kamacite. Fe-Ni metal grains in chondrules in Semarkona typically show plessitic intergrowths consisting of submicrometer kamacite and Ni-rich regions. Metal in other type 3 chondrites is composed of fine- to coarse-grained aggregates of kamacite and Ni-rich metal, resulting from metamorphism in the parent body. We found that the number density of Ni-rich grains in metal (number of Ni-rich grains per unit area of metal) in chondrules systematically decreases with increasing petrologic type. Thus, Fe-Ni metal is a highly sensitive recorder of metamorphism in ordinary and carbonaceous chondrites, and can be used to distinguish petrologic type and identify the least thermally metamorphosed chondrites. Among the known ordinary and CO chondrites, Semarkona is the most primitive. The range of metamorphic temperatures were similar for type 3 ordinary and CO chondrites, despite them having different parent bodies. Most Fe-Ni metal in Acfer 094 is martensite, and it preserves primary features. The degree of metamorphism is lower in Acfer 094, a true type 3.00 chondrite, than in Semarkona, which should be reclassified as type 3.01. ?? The Meteoritical Society, 2008.

How Irreversible Heat Transport Processes Drive Earth's Interdependent Thermal, Structural, and Chemical Evolution Providing a Strongly Heterogeneous, Layered Mantle

NASA Astrophysics Data System (ADS)

Hofmeister, A.; Criss, R. E.

2013-12-01

Because magmatism conveys radioactive isotopes plus latent heat rapidly upwards while advecting heat, this process links and controls the thermal and chemical evolution of Earth. We present evidence that the lower mantle-upper mantle boundary is a profound chemical discontinuity, leading to observed heterogeneities in the outermost layers that can be directly sampled, and construct an alternative view of Earth's internal workings. Earth's beginning involved cooling via explosive outgassing of substantial ice (mainly CO) buried with dust during accretion. High carbon content is expected from Solar abundances and ice in comets. Reaction of CO with metal provided a carbide-rich core while converting MgSiO3 to olivine via oxidizing reactions. Because thermodynamic law (and buoyancy of hot particles) indicates that primordial heat from gravitational segregation is neither large nor carried downwards, whereas differentiation forced radioactive elements upwards, formation of the core and lower mantle greatly cooled the Earth. Reference conductive geotherms, calculated using accurate and new thermal diffusivity data, require that heat-producing elements are sequestered above 670 km which limits convection to the upper mantle. These irreversible beginnings limit secular cooling to radioactive wind-down, permiting deduction of Earth's inventory of heat-producing elements from today's heat flux. Coupling our estimate for heat producing elements with meteoritic data indicates that Earth's oxide content has been underestimated. Density sorting segregated a Si-rich, peridotitic upper mantle from a refractory, oxide lower mantle with high Ca, Al and Ti contents, consistent with diamond inclusion mineralogy. Early and rapid differentiation means that internal temperatures have long been buffered by freezing of the inner core, allowing survival of crust as old as ca.4 Ga. Magmatism remains important. Melt escaping though stress-induced fractures in the rigid lithosphere imparts a lateral component and preferred direction to upper mantle circulation. Mid-ocean magma production over ca. 4 Ga has deposited a slab volume at 670 km that is equivalent to the transition zone, thereby continuing differentiation by creating a late-stage chemical discontinuity near 400 km. This ongoing process has generated the observed lateral and vertical heterogeneity above 670 km.

A model for osmium isotopic evolution of metallic solids at the core-mantle boundary

NASA Astrophysics Data System (ADS)

Humayun, Munir

2011-03-01

Some plumes are thought to originate at the core-mantle boundary, but geochemical evidence of core-mantle interaction is limited to Os isotopes in samples from Hawaii, Gorgona (89 Ma), and Kostomuksha (2.7 Ga). The Os isotopes have been explained by physical entrainment of Earth's liquid outer core into mantle plumes. This model has come into conflict with geophysical estimates of the timing of core formation, high-pressure experimental determinations of the solid metal-liquid metal partition coefficients (D), and the absence of expected 182W anomalies. A new model is proposed where metallic liquid from the outer core is partially trapped in a compacting cumulate pile of Fe-rich nonmetallic precipitates (FeO, FeS, Fe3Si, etc.) at the top of the core and undergoes fractional crystallization precipitating solid metal grains, followed by expulsion of the residual metallic liquid back to the outer core. The Os isotopic composition of the solids and liquids in the cumulate pile is modeled as a function of the residual liquid remaining and the emplacement age using 1 bar D values, with variable amounts of oxygen (0-10 wt %) as the light element. The precipitated solids evolve Os isotope compositions that match the trends for Hawaii (at an emplacement age of 3.5-4.5 Ga; 5%-10% oxygen) and Gorgona (emplacement age < 1.5 Ga; 0%-5% oxygen). The Fe-rich matrix of the cumulate pile dilutes the precipitated solid metal decoupling the Fe/Mn ratio from Os and W isotopes. The advantages to using precipitated solid metal as the Os host include a lower platinum group element and Ni content to the mantle source region relative to excess iron, miniscule anomalies in 182W (<0.1 ɛ), and no effects for Pb isotopes, etc. A gradual thermomechanical erosion of the cumulate pile results in incorporation of this material into the base of the mantle, where mantle plumes subsequently entrain it. Fractional crystallization of metallic liquids within the CMB provides a consistent explanation of both Os isotope correlations, Os-W isotope systematics, and Fe/Mn evidence for core-mantle interaction over the entire Hawaiian source.

Rare Earth Metals: Resourcefulness and Recovery

NASA Astrophysics Data System (ADS)

Wang, Shijie

2013-10-01

When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

Comparative Transcriptomic Analysis of the Response of Dunaliella acidophila (Chlorophyta) to Short-Term Cadmium and Chronic Natural Metal-Rich Water Exposures.

PubMed

Puente-Sánchez, Fernando; Olsson, Sanna; Aguilera, Angeles

2016-10-01

Heavy metals are toxic compounds known to cause multiple and severe cellular damage. However, acidophilic extremophiles are able to cope with very high concentrations of heavy metals. This study investigated the stress response under natural environmental heavy metal concentrations in an acidophilic Dunaliella acidophila. We employed Illumina sequencing for a de novo transcriptome assembly and to identify changes in response to high cadmium concentrations and natural metal-rich water. The photosynthetic performance was also estimated by pulse amplitude-modulated (PAM) fluorescence. Transcriptomic analysis highlights a number of processes mainly related to a high constitutive expression of genes involved in oxidative stress and response to reactive oxygen species (ROS), even in the absence of heavy metals. Photosynthetic activity seems to be unaltered under short-term exposition to Cd and chronic exposure to natural metal-rich water, probably due to an increase in the synthesis of structural photosynthetic components preserving their functional integrity. An overrepresentation of Gene Ontology (GO) terms related to metabolic activities, transcription, and proteosomal catabolic process was observed when D. acidophila grew under chronic exposure to natural metal-rich water. GO terms involved in carbohydrate metabolic process, reticulum endoplasmic and Golgi bodies, were also specifically overrepresented in natural metal-rich water library suggesting an endoplasmic reticulum stress response.

Ionic Transport Through Metal-Rich Organic Coatings

DTIC Science & Technology

2016-08-19

COVERED October 2013-Septermber 2015 4. TITLE AND SUBTITLE Ionic Transport Through Metal-Rich Organic Coatings 5a. CONTRACT NUMBER 5b. GRANT...NOTES 14. ABSTRACT Organic coatings are commonly used on aircraft and in the automotive industry to protect against corrosive environments. Although...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal-rich organic (MRO) coatings. Following design

Ionic Transport Through Metal-Rich Organic Coatings

DTIC Science & Technology

2016-08-19

COVERED October 2013-Septermber 2015 4. TITLE AND SUBTITLE Ionic Transport Through Metal-Rich Organic Coatings 5a. CONTRACT NUMBER 5b. GRANT...14. ABSTRACT Organic coatings are commonly used on aircraft and in the automotive industry to protect against corrosive environments. Although...volume (MPV) percent, solvent polarity, and resin molecular weight impact corrosion protection of metal-rich organic (MRO) coatings. Following design of

Assessment of radionuclide and metal contamination in a thorium rich area in Norway.

PubMed

Popic, Jelena Mrdakovic; Salbu, Brit; Strand, Terje; Skipperud, Lindis

2011-06-01

The Fen Central Complex in southern Norway, a geologically well investigated area of magmatic carbonatite rocks, is assumed to be among the world largest natural reservoirs of thorium ((232)Th). These rocks, also rich in iron (Fe), niobium (Nb), uranium ((238)U) and rare earth elements (REE), were mined in several past centuries. Waste locations, giving rise to enhanced levels of both radionuclides and metals, are now situated in the area. Estimation of radionuclide and metal contamination of the environment and radiological risk assessment were done in this study. The average outdoor gamma dose rate measured in Fen, 2.71 μGy h(-1), was significantly higher than the world average dose rate of 0.059 μGy h(-1). The annual exposure dose from terrestrial gamma radiation, related to outdoor occupancy, was in the range 0.18-9.82 mSv. The total activity concentrations of (232)Th and (238)U in soil ranged from 69 to 6581 and from 49 to 130 Bq kg(-1), respectively. Enhanced concentrations were also identified for metals, arsenic (As), lead (Pb), chromium (Cr) and zinc (Zn), in the vicinity of former mining sites. Both radionuclide and heavy metal concentrations suggested leaching, mobilization and distribution from rocks into the soil. Correlation analysis indicated different origins for (232)Th and (238)U, but same or similar for (232)Th and metals As, Cr, Zn, nickel (Ni) and cadmium (Cd). The results from in situ size fractionation of water demonstrated radionuclides predominately present as colloids and low molecular mass (LMM) species, being potentially mobile and available for uptake in aquatic organisms of Norsjø Lake. Transfer factors, calculated for different plant species, showed the highest radionuclide accumulation in mosses and lichens. Uptake in trees was, as expected, lower. Relationship analysis of (232)Th and (238)U concentrations in moss and soil samples showed a significant positive linear correlation.

Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

PubMed

Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

2016-10-12

The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically engineered microbial powders revealed unique adsorption behaviors of the rare earth metal ions.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Sasselov, Dimitar; Jacobsen, Stein

2015-08-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet’s rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called “late veneer”. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet’s surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars’ elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, L.; Jacobsen, S. B.; Sasselov, D. D.

2015-12-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called "late veneer". The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars' elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

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.

Phase composition and magnetic properties in nanocrystalline permanent magnets based on misch-metal

NASA Astrophysics Data System (ADS)

Ma, Q.; Wang, J.; Zhang, Z. Y.; Zhang, X. F.; Liu, F.; Liu, Y. L.; Jv, X. M.; Li, Y. F.; Wang, G. F.

2017-09-01

The magnetic properties and phase composition of magnets based on misch-metal (MM) with nominal composition of MM13+xFe84-xB6.5 with x = 0.5, 1, 1.5, 2 and 2.5 using melt-spinning method were investigated. For x = 1.5, it could exhibit best magnetic properties (Hcj = 753.02 kA m-1, (BH)max = 70.77 kJ m-3). X-ray diffraction and energy dispersive spectroscopy show that the multi hard magnetic phase of RE2Fe14B (RE = La, Ce, Pr, Nd) existed in the magnets. The domain wall pinning effect and the exchange coupling interaction between grains are dependent on the abnormal RE-rich phase composition. Optimizing the phase constitution is necessary to improve magnetic properties in MM-Fe-B magnets for utilizing the rare earth resource in a balanced manner.

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‰.

Geochemistry, Nd-Pb Isotopes, and Pb-Pb Ages of the Mesoproterozoic Pea Ridge Iron Oxide-Apatite–Rare Earth Element Deposit, Southeast Missouri

USGS Publications Warehouse

Ayuso, Robert A.; Slack, John F.; Day, Warren C.; McCafferty, Anne E.

2016-01-01

Iron oxide-apatite and iron oxide-copper-gold deposits occur within ~1.48 to 1.47 Ga volcanic rocks of the St. Francois Mountains terrane near a regional boundary separating crustal blocks having contrasting depleted-mantle Sm-Nd model ages (TDM). Major and trace element analyses and Nd and Pb isotope data were obtained to characterize the Pea Ridge deposit, improve identification of exploration targets, and better understand the regional distribution of mineralization with respect to crustal blocks. The Pea Ridge deposit is spatially associated with felsic volcanic rocks and plutons. Mafic to intermediate-composition rocks are volumetrically minor. Data for major element variations are commonly scattered and strongly suggest element mobility. Ratios of relatively immobile elements indicate that the felsic rocks are evolved subalkaline dacite and rhyolite; the mafic rocks are basalt to basaltic andesite. Granites and rhyolites display geochemical features typical of rocks produced by subduction. Rare earth element (REE) variations for the rhyolites are diagnostic of rocks affected by hydrothermal alteration and associated REE mineralization. The magnetite-rich rocks and REE-rich breccias show similar REE and mantle-normalized trace element patterns.Nd isotope compositions (age corrected) show that: (1) host rhyolites have ɛNd from 3.44 to 4.25 and TDM from 1.51 to 1.59 Ga; (2) magnetite ore and specular hematite rocks display ɛNd from 3.04 to 4.21 and TDM from 1.6 to 1.51 Ga, and ɛNd from 2.23 to 2.81, respectively; (3) REE-rich breccias have ɛNd from 3.04 to 4.11 and TDM from 1.6 to 1.51 Ga; and (4) mafic to intermediate-composition rocks range in ɛNd from 2.35 to 3.66 and in TDM from 1.66 to 1.56. The ɛNd values of the magnetite and specular hematite samples show that the REE mineralization is magmatic; no evidence exists for major overprinting by younger, crustal meteoric fluids, or by externally derived Nd. Host rocks, breccias, and magnetite ore shared a common origin from a similar source.Lead isotope ratios are diverse: (1) host rhyolite has 206Pb/204Pb from 24.261 to 50.091; (2) Pea Ridge and regional galenas have 206Pb/204Pb from 16.030 to 33.548; (3) REE-rich breccia, magnetite ore, and specular hematite rock are more radiogenic than galena; (4) REE-rich breccias have high 206Pb/204Pb (38.122–1277.61) compared to host rhyolites; and (5) REE-rich breccias are more radiogenic than magnetite ore and specular-hematite rock, having 206Pb/204Pb up to 230.65. Radiogenic 207Pb/206Pb age estimates suggest the following: (1) rhyolitic host rocks have ages of ~1.50 Ga, (2) magnetite ore is ~1.44 Ga, and (3) REE-rich breccias are ~1.48 Ga. These estimates are broadly consistent and genetically link the host rhyolite, REE-rich breccia, and magnetite ore as being contemporaneous.Alteration style and mineralogical or textural distinctions among the magnetite-rich rocks and REE-rich breccias do not correlate with different isotopic sources. In our model, magmatic fluids leached metals from the coeval felsic rocks (rhyolites), which provided the metal source reflected in the compositions of the REE-rich breccias and mineralized rocks. This model allows for the likelihood of contributions from other genetically related felsic and intermediate to more mafic rocks stored deeper in the crust. The deposit thus records an origin as a magmatic-hydrothermal system that was not affected by Nd and Pb remobilization processes, particularly if these processes also triggered mixing with externally sourced metal-bearing fluids. The Pea Ridge deposit was part of a single, widespread, homogeneous mixing system that produced a uniform isotopic composition, thus representing an excellent example of an igneous-dominated system that generated coeval magmatism and REE mineralization. Geochemical features suggest that components in the Pea Ridge deposit originated from sources in an orogenic margin. Basaltic magmatism produced by mantle decompression melting provided heat for extracting melts from the middle or lower crust. Continual addition of mafic magmas to the base of the subcontinental lithosphere, in a back-arc setting, remelted calc-alkaline rocks enriched in metals that were stored in the crust.The St. Francois Mountains terrane is adjacent to the regional TDM line (defined at a value of 1.55 Ga) that separates ~1600 Ma basement to the west, from younger basements to the east. Data for Pea Ridge straddle the TDM values proposed for the line. The Sm-Nd isotope system has been closed since formation of the deposit and the original igneous signatures have not been affected by cycles of alteration or superimposed mineralizing events. No evidence exists for externally derived Nd or Sm. The source region for metals within the Pea Ridge deposit had a moderate compositional variation and the REE-rich breccias and mineralized rocks are generally isotopically homogeneous. The Pea Ridge deposit thus constitutes a distinctive isotopic target for use as a model in identifying other mineralized systems that may share the same metal source in the St. Francois Mountains terrane and elsewhere in the eastern Granite-Rhyolite province.

Gaia Reveals a Metal-rich, in situ Component of the Local Stellar Halo

NASA Astrophysics Data System (ADS)

Bonaca, Ana; Conroy, Charlie; Wetzel, Andrew; Hopkins, Philip F.; Kereš, Dušan

2017-08-01

We use the first Gaia data release, combined with the RAVE and APOGEE spectroscopic surveys, to investigate the origin of halo stars within ≲ 3 kpc from the Sun. We identify halo stars kinematically as moving at a relative speed of at least 220 km s-1 with respect to the local standard of rest. These stars are generally less metal-rich than the disk, but surprisingly, half of our halo sample is comprised of stars with [{Fe}/{{H}}]> -1. The orbital directions of these metal-rich halo stars are preferentially aligned with the disk rotation, in sharp contrast with the intrinsically isotropic orbital distribution of the metal-poor halo stars. We find similar properties in the Latte cosmological zoom-in simulation of a Milky Way-like galaxy from the FIRE project. In Latte, metal-rich halo stars formed primarily inside of the solar circle, whereas lower-metallicity halo stars preferentially formed at larger distances (extending beyond the virial radius). This suggests that metal-rich halo stars in the solar neighborhood actually formed in situ within the Galactic disk, rather than having been accreted from satellite systems. These stars, currently on halo-like orbits, therefore have likely undergone substantial radial migration/heating.

THE EFFECT OF SECOND-GENERATION POPULATIONS ON THE INTEGRATED COLORS OF METAL-RICH GLOBULAR CLUSTERS IN EARLY-TYPE GALAXIES

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

Chung, Chul; Lee, Sang-Yoon; Yoon, Suk-Jin

2013-05-20

The mean color of globular clusters (GCs) in early-type galaxies is in general bluer than the integrated color of halo field stars in host galaxies. Metal-rich GCs often appear more associated with field stars than metal-poor GCs, yet show bluer colors than their host galaxy light. Motivated by the discovery of multiple stellar populations in Milky Way GCs, we present a new scenario in which the presence of second-generation (SG) stars in GCs is responsible for the color discrepancy between metal-rich GCs and field stars. The model assumes that the SG populations have an enhanced helium abundance as evidenced bymore » observations, and it gives a good explanation of the bluer optical colors of metal-rich GCs than field stars as well as strong Balmer lines and blue UV colors of metal-rich GCs. Ours may be complementary to the recent scenario suggesting the difference in stellar mass functions (MFs) as an origin for the GC-to-star color offset. A quantitative comparison is given between the SG and MF models.« less

Buffer layers for coated conductors

DOEpatents

Stan, Liliana [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM; Foltyn, Stephen R [Los Alamos, NM

2011-08-23

A composite structure is provided including a base substrate, an IBAD oriented material upon the base substrate, and a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the IBAD oriented material. Additionally, an article is provided including a base substrate, an IBAD oriented material upon the base substrate, a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the IBAD oriented material, and a thick film upon the cubic metal oxide material. Finally, a superconducting article is provided including a base substrate, an IBAD oriented material upon the base substrate, a cubic metal oxide material selected from the group consisting of rare earth zirconates and rare earth hafnates upon the IBAD oriented material, and an yttrium barium copper oxide material upon the cubic metal oxide material.

40 CFR 421.275 - Pretreatment standards for existing sources.

Code of Federal Regulations, 2012 CFR

2012-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... standards for existing sources. The mass of wastewater pollutants in primary rare earth metals process.... PSES for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for any 1...

40 CFR 421.275 - Pretreatment standards for existing sources.

Code of Federal Regulations, 2013 CFR

2013-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... standards for existing sources. The mass of wastewater pollutants in primary rare earth metals process.... PSES for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for any 1...

40 CFR 421.275 - Pretreatment standards for existing sources.

Code of Federal Regulations, 2014 CFR

2014-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... standards for existing sources. The mass of wastewater pollutants in primary rare earth metals process.... PSES for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for any 1...

40 CFR 421.275 - Pretreatment standards for existing sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... standards for existing sources. The mass of wastewater pollutants in primary rare earth metals process.... PSES for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for any 1...

40 CFR 421.275 - Pretreatment standards for existing sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... standards for existing sources. The mass of wastewater pollutants in primary rare earth metals process.... PSES for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for any 1...

AGB stars in Leo P and their use as metallicity probes

NASA Astrophysics Data System (ADS)

Lee, Chien-Hsiu

2016-09-01

Leo P is the most metal-poor yet star-forming galaxy in the local volume, and has the potential to serve as a local counterpart to interpret the properties of distant galaxies in the early universe. We present a comprehensive search of asymptotic giant branch (AGB) stars in Leo P using deep infrared imaging. AGB stars are the major dust contributors; the metal poor nature of Leo P can help to shed light on the dust formation process in very low-metallicity environments, similar to the early Universe. We select and classify oxygen-rich and carbon-rich candidate AGB stars using J - K versus K colour-magnitude diagram. To filter out contaminations from background galaxies, we exploit the high-resolution Hubble Space Telescope imaging and identify 9 oxygen-rich AGBs and 13 carbon-rich AGB stars in Leo P. We then use the ratio of carbon-rich and oxygen-rich AGB stars (C/M ratio) as an indicator of on-site metallicity and derive the global metallicity [Fe/H] = -1.8 dex for Leo P, in good agreement with previous studies using isochrone fitting. Follow-up observations of these Leo P AGB stars in the mid-infrared [e.g. Spitzer, James Webb Space Telescope (JWST)] will be invaluable to measure the dust formation rates using Spectral energy distribution (SED) fitting.

Transfer of rare earth elements from natural metalliferous (copper and cobalt rich) soils into plant shoot biomass of metallophytes from Katanga (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Pourret, Olivier; Lange, Bastien; Jitaru, Petru; Mahy, Grégory; Faucon, Michel-Pierre

2014-05-01

The geochemical behavior of rare earth elements (REE) is generally assessed for the characterization of the geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. REE behavior is investigated according to their concentrations normalized with respect to the upper continental crust. In this study, the geochemical fingerprint of REE in plant shoot biomass of an unique metallicolous flora (i.e., Crepidorhopalon tenuis and Anisopappus chinensis) was investigated. The plants originate from extremely copper and cobalt rich soils, deriving from Cu and Co outcrops in Katanga, Democratic Republic of Congo. Some of the species investigated in this study are able to accumulate high amounts of Cu and Co in shoot hence being considered as Cu and Co hyperaccumulators. Therefore, assessing the behavior of REE may lead to a better understanding of the mechanisms of metal accumulation by this flora. The data obtained in this study indicate that REE uptake by plants is not primarily controlled by their concentration and speciation in the soil as previously shown in the literature (Brioschi et al. 2013). Indeed, the REE patterns in shoots are relatively flat whereas soils patterns are Middle REE enriched. In addition, it is worth noting that Eu enrichments occur in aerial parts of the plants. These positive Eu anomalies suggest that Eu3 + can form stable organic complexes replacing Ca2 + in several biological processes as in xylem fluids associated with the general nutrient flux. Therefore, is is possible that the Eu mobility in these fluids is enhanced by its reductive speciation as Eu2 +. Eventually, the geochemical behavior of REE illustrates that metals accumulation in aerial parts of C. tenuis and A. chinensis is mainly driven by dissolved complexation. Brioschi, L., Steinmann, M., Lucot, E., Pierret, M., Stille, P., Prunier, J., Badot, P., 2013. Transfer of rare earth elements (REE) from natural soil to plant systems: implications for the environmental availability of anthropogenic REE. Plant and Soil, 366, 143-163.

Carbon dioxide capture process with regenerable sorbents

DOEpatents

Pennline, Henry W.; Hoffman, James S.

2002-05-14

A process to remove carbon dioxide from a gas stream using a cross-flow, or a moving-bed reactor. In the reactor the gas contacts an active material that is an alkali-metal compound, such as an alkali-metal carbonate, alkali-metal oxide, or alkali-metal hydroxide; or in the alternative, an alkaline-earth metal compound, such as an alkaline-earth metal carbonate, alkaline-earth metal oxide, or alkaline-earth metal hydroxide. The active material can be used by itself or supported on a substrate of carbon, alumina, silica, titania or aluminosilicate. When the active material is an alkali-metal compound, the carbon-dioxide reacts with the metal compound to generate bicarbonate. When the active material is an alkaline-earth metal, the carbon dioxide reacts with the metal compound to generate carbonate. Spent sorbent containing the bicarbonate or carbonate is moved to a second reactor where it is heated or treated with a reducing agent such as, natural gas, methane, carbon monoxide hydrogen, or a synthesis gas comprising of a combination of carbon monoxide and hydrogen. The heat or reducing agent releases carbon dioxide gas and regenerates the active material for use as the sorbent material in the first reactor. New sorbent may be added to the regenerated sorbent prior to subsequent passes in the carbon dioxide removal reactor.

The episodic influx of tin-rich cosmic dust particles during the last ice age

NASA Astrophysics Data System (ADS)

LaViolette, Paul A.

2015-12-01

This paper presents evidence of the first detection of interstellar dust in ice age polar ice. Neutron activation analysis (NAA) results are reported for 15 elements found in dust filtered from eight samples of Camp Century Greenland ice dating from 40 to 78 kyrs BP. High concentrations of Sn, Sb, Au, Ag, Ir, and Ni were found to be present in three out of these eight samples. One compositionally anomalous dust sample from an ice core depth of 1230.5 m (age ∼49 kyrs BP, near the beginning of D/O stadial No. 13) was found to contain tin with an average weight percent of 49% as determined by energy dispersive X-ray analysis (EDS). This sample was also found to contain high concentrations of Pb with an average weight abundance of 8.4% and matching the Sn:Pb ratio observed in interstellar spectra. Dust particles in this sample generally have a platy morphology and range from submicron size up to a size as large as 120 μm, a particle consisting almost entirely of SnO2 and being the largest monomineralic extraterrestrial dust particle so far discovered. One porous aggregate tin-bearing particle was found to contain nanometer sized chondrules indicating an extraterrestrial origin. The extraterrestrial origin for the tin is also indicated by the presence of isotopic anomalies in the 114Sn, 115Sn and 117Sn isotopes. Follow up isotopic measurements of this tin-rich dust need to be performed to improve confidence in the anomalies reported here. High abundances of the low melting point elements Ag, Au, and Sb are also present in this tin-rich sample along with elevated abundances of the siderophiles Ir, Ni, Fe, and Co, the latter being present in chondritic proportions and indicating that about 9% of the dust has a C1 chondrite component. Measurements indicate that about 97% of this dust is of extraterrestrial origin with a 3% residual being composed of terrestrial windblown dust. EDS analysis of another tin-rich Camp Century ice core dust sample dating to ∼130 kyrs BP was found to contain tin-rich particles with a similar platy morphology and to have Sn and Pb weight abundances averaging 39% and 7.5% respectively, again approximating the interstellar Sn:Pb ratio. The relative absence of cosmic microspheres and the unmelted appearance of the tin-rich particles in both of these samples suggests that these particles entered the Earth's atmosphere at low velocity, implicating a gradual accumulation of dust from a dispersed state in the near Earth space environment. The unusual enhancement of Sn and Pb could be explained if these dust particles were originally present in the solar system's interstellar environment in a superconducting native metal state and were preferentially concentrated through Meissner effect forces by the passage of cosmic ray driven hydromagnetic shocks which may also have transported them into the solar system. The 49 kyrs BP event is estimated to have lasted over 6 years and to have deposited dust onto the Earth at a rate 104-105 times higher than present rates. This had a significant cooling effect on climate and resulted in a transient 33 fold increase in snow accumulation. Future discovery of these events in ice cores at other locations should void any lingering thoughts that this heavy metal enhancement may be due to sample contamination.

A POSSIBLE CARBON-RICH INTERIOR IN SUPER-EARTH 55 Cancri e

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

Madhusudhan, Nikku; Lee, Kanani K. M.; Mousis, Olivier, E-mail: Nikku.Madhusudhan@yale.edu

Terrestrial planets in the solar system, such as the Earth, are oxygen-rich, with silicates and iron being the most common minerals in their interiors. However, the true chemical diversity of rocky planets orbiting other stars is yet unknown. Mass and radius measurements are used to constrain the interior compositions of super-Earths (exoplanets with masses of 1-10 M{sub Circled-Plus }), and are typically interpreted with planetary interior models that assume Earth-centric oxygen-rich compositions. Using such models, the super-Earth 55 Cancri e (mass 8 M{sub Circled-Plus }, radius 2 R{sub Circled-Plus }) has been suggested to bear an interior composition consisting ofmore » Fe, silicates, and an envelope ({approx}> 10% by mass) of supercritical water. We report that the mass and radius of 55 Cancri e can also be explained by a carbon-rich solid interior made of Fe, C, SiC, and/or silicates and without a volatile envelope. While the data allow Fe mass fractions of up to 40%, a wide range of C, SiC, and/or silicate mass fractions are possible. A carbon-rich 55 Cancri e is also plausible if its protoplanetary disk bore the same composition as its host star, which has been reported to be carbon-rich. However, more precise estimates of the stellar elemental abundances and observations of the planetary atmosphere are required to further constrain its interior composition. The possibility of a C-rich interior in 55 Cancri e opens a new regime of geochemistry and geophysics in extraterrestrial rocky planets, compared to terrestrial planets in the solar system.« less

Clouds Composition in Super-Earth Atmospheres: Chemical Equilibrium Calculations

NASA Astrophysics Data System (ADS)

Kempton, Eliza M.-R.; Mbarek, Rostom

2015-12-01

Attempts to determine the composition of super-Earth atmospheres have so far been plagued by the presence of clouds. Yet the theoretical framework to understand these clouds is still in its infancy. For the super-Earth archetype GJ 1214b, KCl, Na2S, and ZnS have been proposed as condensates that would form under the condition of chemical equilibrium, if the planet’s atmosphere has a bulk composition near solar. Condensation chemistry calculations have not been presented for a wider range of atmospheric bulk composition that is to be expected for super-Earth exoplanets. Here we provide a theoretical context for the formation of super-Earth clouds in atmospheres of varied composition by determining which condensates are likely to form, under the assumption of chemical equilibrium. We model super-Earth atmospheres assuming they are formed by degassing of volatiles from a solid planetary core of chondritic material. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350-3,000 K. Clouds should form along the temperature-pressure boundaries where the condensed species appear in our calculations. The super-Earth atmospheres that we study range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a diverse range of atmospheric composition that is appropriate for low-mass exoplanets. Some condensates appear across all of our models. However, the majority of condensed species appear only over specific ranges of H:O and C:O ratios. We find that for GJ 1214b, KCl is the primary cloud-forming condensate at solar composition, in agreement with previous work. However, for oxidizing atmospheres, where H:O is less than unity, K2SO4 clouds form instead. For carbon-rich atmospheres with super-solar C:O ratios, graphite clouds additionally appear. At higher temperatures, clouds are formed from a variety of materials including metals, metal oxides, and aluminosilicates.

Water inventories on Earth and Mars: Clues to atmosphere formation

NASA Technical Reports Server (NTRS)

Carr, M. H.

1992-01-01

Water is distributed differently on Earth and on Mars and the differences may have implications for the accretion of the two planets and the formation of their atmospheres. The Earth's mantle appears to contain at least several times the water content of the Martian mantle even accounting for differences in plate tectonics. One explanation is that the Earth's surface melted during accretion, as a result of development of a steam atmosphere, thereby allowing impact-devolitalized water at the surface to dissolve into the Earth's interior. In contrast, because of Mars' smaller size and greater distance from the Sun, the Martian surface may not have melted, so that the devolatilized water could not dissolve into the surface. A second possibility is suggested by the siderophile elements in the Earth's mantle, which indicates the Earth acquired a volatile-rich veneer after the core formed. Mars may have acquired a late volatile-rich veneer, but it did not get folded into the interior as with the Earth, but instead remained as a water rich veneer. This perception of Mars with a wet surface but dry interior is consistent with our knowledge of Mars' geologic history.

Can Nitrogen be a Candidate for the Fe-Core Formation?

NASA Astrophysics Data System (ADS)

Dobrzhinetskaya, L.; Wirth, R.; Yang, J.; Weber, P.; Hutcheon, I.; Green, H. W.

2008-12-01

Among the light elements that have been added to mineral physics experiments concerning the Fe-rich core of the Earth, nitrogen is less favorable. In general, this is because metal-nitrides are thought to be rare within Earth. However this may not be because they are rare, but because nitrogen is difficult to detect by conventional electron microprobe analysis unless one is specifically looking for it. Theoretically, metal-nitrides could be equally considered as potential candidates for the light element in the core, not only because nitrogen forms strong metallic bonds, but also because metal-nitrides are common constituents of many iron meteorites. Some Fe-nitrides are found to be stable at extreme pressures and temperatures corresponding to Earth's core in both diamond anvil cell and shock experiments (Adler and Williams, 2005; Sekine et al., 2007). We have discovered a metal-nitride phase, TiN (osbornite) within a mantle mineralogical assemblage, opening a new opportunity to understand the history of Earth's core formation. The TiN was found in the mantle section of an unmetamorphosed Tibetan ophiolite, a fragment of former mid-ocean spreading center, which now marks the tectonic boundary between Asia and India. The osbornite occurs as inclusions in coesite pseudomorphic after stishovite, in association with FeTi alloy, native Fe, TiO2 II, cubic BN and diamond included in Os-Ir alloy, all from a massive chromitite ore body enclosed within harzburgite (Yang et al., 2007; Dobrzhinetskaya et al., 2007). The chromite also exhibits coesite and diopside exsolution lamellae (Yamamoto et al., 2007) that might suggest the calcium-ferrite polymorph of chromite as a precursor decompressed during upwelling. Measurements of δ15N with a Cameca 50 NanoSIMS using the same Focused Ion Beam foils prepared and used for earlier TEM studies suggest that the Tibetan osbornite is characterized by negative δ15N (-10 ‰). The δ15N results from the Tibetan osbornite are somewhat more negative than the most commonly measured value for Earth's uppermost mantle (δ15N = -3 to -5 ‰), and they are clearly different from the δ15N of shallow reservoirs. The latter include atmosphere, ocean, and crust having values of delta δ15N -- 0 - +5 ‰ for the atmosphere and ocean and +5 - +12 ‰.) for the crustal rocks and sediments. We conclude that the Tibetan osbornite contains mantle N, perhaps from an old and/or deep mantle reservoir. Apropos of the suggestion of N in the core, we point out that most iron meteorites have extremely negative δ15N values of -60 ‰ or more, hence it is conceivable that part of the N signal in our materials comes from a leaky core.

An Operationally Simple Method for Separating the Rare-Earth Elements Neodymium and Dysprosium.

PubMed

Bogart, Justin A; Lippincott, Connor A; Carroll, Patrick J; Schelter, Eric J

2015-07-06

Rare-earth metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare earths. To incentivize recycling there is a clear need for simple methods for targeted separations of mixtures of rare-earth metal salts. Metal complexes of a tripodal nitroxide ligand [{(2-(t) BuNO)C6 H4 CH2 }3 N](3-) (TriNOx(3-) ), feature a size-sensitive aperture formed of its three η(2) -(N,O) ligand arms. Exposure of metal cations in the aperture induces a self-associative equilibrium comprising [M(TriNOx)thf]/ [M(TriNOx)]2 (M=rare-earth metal). Differences in the equilibrium constants (Keq ) for early and late metals enables simple Nd/Dy separations through leaching with a separation ratio SNd/Dy =359. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Salt transport extraction of transuranium elements from LWR fuel

DOEpatents

Pierce, R.D.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Miller, W.E.

1992-11-03

A process is described for separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl[sub 2] and a Cu--Mg alloy containing not less than about 25% by weight Mg at a temperature in the range of from about 750 C to about 850 C to precipitate uranium metal and some of the noble metal fission products leaving the Cu--Mg alloy having transuranium actinide metals and rare earth fission product metals and some of the noble metal fission products dissolved therein. The CaCl[sub 2] having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO[sub 2]. The Ca metal and CaCl[sub 2] is recycled to reduce additional oxide fuel. The Cu--Mg alloy having transuranium metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with a transport salt including MgCl[sub 2] to transfer Mg values from the transport salt to the Cu--Mg alloy while transuranium actinide and rare earth fission product metals transfer from the Cu--Mg alloy to the transport salt. Then the transport salt is mixed with a Mg--Zn alloy to transfer Mg values from the alloy to the transport salt while the transuranium actinide and rare earth fission product values dissolved in the salt are reduced and transferred to the Mg--Zn alloy. 2 figs.

Salt transport extraction of transuranium elements from lwr fuel

DOEpatents

Pierce, R. Dean; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a Cu--Mg alloy containing not less than about 25% by weight Mg at a temperature in the range of from about 750.degree. C. to about 850.degree. C. to precipitate uranium metal and some of the noble metal fission products leaving the Cu--Mg alloy having transuranium actinide metals and rare earth fission product metals and some of the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The Cu--Mg alloy having transuranium metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with a transport salt including Mg Cl.sub.2 to transfer Mg values from the transport salt to the Cu--Mg alloy while transuranium actinide and rare earth fission product metals transfer from the Cu--Mg alloy to the transport salt. Then the transport salt is mixed with a Mg--Zn alloy to transfer Mg values from the alloy to the transport salt while the transuranium actinide and rare earth fission product values dissolved in the salt are reduced and transferred to the Mg--Zn alloy.

Nanoparticulate-catalyzed oxygen transfer processes

DOEpatents

Hunt, Andrew T [Atlanta, GA; Breitkopf, Richard C [Dunwoody, GA

2009-12-01

Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

Unique Moon Formation Model: Two Impacts of Earth and After Moon's Birth

NASA Astrophysics Data System (ADS)

Miura, Y.

2018-04-01

The Moon rocks are mixed with two impact-processes of Earth's impact breccias and airless Moon's impact breccias; discussed voids-rich texture and crust-like composition. The present model might be explained as cave-rich interior on the airless-and waterless Moon.

THEORETICAL TRANSIT SPECTRA FOR GJ 1214b AND OTHER 'SUPER-EARTHS'

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

Howe, Alex R.; Burrows, Adam S., E-mail: arhowe@astro.princeton.edu, E-mail: burrows@astro.princeton.edu

2012-09-10

We present new calculations of transit spectra of super-Earths that allow for atmospheres with arbitrary proportions of common molecular species and haze. We test this method with generic spectra, reproducing the expected systematics and absorption features, then apply it to the nearby super-Earth GJ 1214b, which has produced conflicting observational data, leaving the questions of a hydrogen-rich versus hydrogen-poor atmosphere and the water content of the atmosphere ambiguous. We present representative transit spectra for a range of classes of atmosphere models for GJ 1214b. Our analysis supports a hydrogen-rich atmosphere with a cloud or haze layer, although a hydrogen-poor modelmore » with {approx}<10% water is not ruled out. Several classes of models are ruled out, however, including hydrogen-rich atmospheres with no haze, hydrogen-rich atmospheres with a haze of {approx}0.01 {mu}m tholin particles, and hydrogen-poor atmospheres with major sources of absorption other than water. We propose an observational test to distinguish hydrogen-rich from hydrogen-poor atmospheres. Finally, we provide a library of theoretical transit spectra for super-Earths with a broad range of parameters to facilitate future comparison with anticipated data.« less

The effects of nickel and sulphur on the core-mantle partitioning of oxygen in Earth and Mars

NASA Astrophysics Data System (ADS)

Tsuno, Kyusei; Frost, Daniel J.; Rubie, David C.

2011-03-01

Constraints on the partitioning of oxygen between silicates, oxides, and metallic liquids are important for determining the amount of oxygen that may have entered the cores of terrestrial planets and to identify likely reactions at the core-mantle boundary. Several previous studies have examined oxygen partitioning between liquid Fe metal and ferropericlase, however, the cores of terrestrial planets also contain nickel and most likely sulphur. We have performed experiments to examine the effects of both nickel and sulphur on the partitioning of oxygen between ferropericlase and liquid Fe alloy up to pressures of 24.5 GPa in the temperature range 2430-2750 K using a multianvil press. The results show that at a fixed oxygen fugacity the proportion of oxygen that partitions into liquid metal will decrease by approximately 1-2 mol% on the addition of 10-20 mol% nickel to the liquid. The addition of around 30 mol% sulphur will, on the other hand, increase the metal oxygen content by approximately 10 mol%. Experiments to examine the combined effects of both nickel and sulphur, show a decrease in the effect of nickel on oxygen partitioning as the sulphur content of the metal increases. We expand an existing thermodynamic model for the partitioning of oxygen at high pressures and temperatures to include the effects of nickel and sulphur by fitting these experimental data, with further constraints provided by existing phase equilibria studies at similar conditions in the Fe-S and Fe-O-S systems. Plausible terrestrial core sulphur contents have little effect on oxygen partitioning. When our model is extrapolated to conditions of the present day terrestrial core-mantle boundary, the presence of nickel is found to lower the oxygen content of the outer core that is in equilibrium with the expected mantle ferropericlase FeO content, by approximately 1 weight %, in comparison to nickel free calculations. In agreement with nickel-free experiments, this implies that the Earth's outer core is undersaturated in oxygen with respect to plausible mantle FeO contents, which will result in either the depletion of FeO from the base of the mantle or cause the development of an outer core layer that is enriched in oxygen. The oxygen content of the more sulphur-rich Martian core would be in the range 2-4 wt.% if it is in equilibrium with the FeO-rich Martian mantle.

Technological pretreatment of the synchysite non-oxidized ore

NASA Astrophysics Data System (ADS)

Munkhtsetseg, B.; Burmaa, G.

2013-06-01

Mongolia has rich deposits of rare, precious, and poly-metallic ores. Nowadays, it is important to research separation of rare earth elements oxides concentrates from the ores, analyze their unique physical chemical characteristics, and purified it. Our investigation on raw materials focuses on rare earth non-oxidized ores. Main mineral in this rock sample is Synchysite (LnCa(CO3)2F. We did technological and thermal pretreatment: direct sulphurization (H2SO4), sulphurization with subsequent roasting (800°C+H2SO4), sulphurization prior to roasting (H2SO4+650°C). Sulphurization method based on dissolution of rare earth mineral into sulfuric acid (93%) according to the reaction. The amount of rare earth element oxides is almost 10 times greater (29.16%) after direct sulphurization process, almost 8 times greater (21.14%) after sulphurization with subsequent roasting, and almost 20 times greater (44.62%) after sulphurization prior to roasting process. After those technological pretreatment raw material's micro elements Thorium and Uranium contents are reduced as follows: H2SO4>800°C+H2SO4>H2SO4+650°C. These results show that cerium group rare earth elements have very good solubility in water at +2°C temperature and decreasing micro elements content uranium and thorium good pretreatment condition is prior to roasting (H2SO4+650°C) of synchysite non-oxidized ore.

Molten metal containment vessel with rare earth oxysulfide protective coating thereon and method of making same

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

An improved molten metal containment vessel is disclosed in which wetting of the vessel's inner wall surfaces by molten metal is inhibited by coating at least the inner surfaces of the containment vessel with one or more rare earth oxysulfide or rare earth sulfide compounds to inhibit wetting and or adherence by the molten metal to the surfaces of the containment vessel.

Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

NASA Astrophysics Data System (ADS)

Takahashi, Yuriko

Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

Method For Improving The Oxidation Resistance Of Metal Substrates Coated With Thermal Barrier Coatings

DOEpatents

Thompson, Anthony Mark; Gray, Dennis Michael; Jackson, Melvin Robert

2003-05-13

A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described. A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described.

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Astrophysics Data System (ADS)

Westfall, Richard

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength and resist crack propagation.

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Technical Reports Server (NTRS)

Westfall, Richard

1991-01-01

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength and resist crack propagation.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

PubMed

Gärtner, Martin; Fischer, Reinald; Langer, Jens; Görls, Helmar; Walther, Dirk; Westerhausen, Matthias

2007-06-11

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

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

USDA-ARS?s Scientific Manuscript database

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...

Major- and minor-metal composition of three distinct solid material fractions associated with Juan de Fuca hydrothermal fluids (northeast Pacific), and calculation of dilution fluid samples

USGS Publications Warehouse

Hinkley, T.K.; Seeley, J.L.; Tatsumoto, M.

1988-01-01

Three distinct types of solid material are associated with each sample of the hydrothermal fluid that was collected from the vents of the Southern Juan de Fuca Ridge. The solid materials appear to be representative of deposits on ocean floors near mid-ocean ridges, and interpretation of the chemistry of the hydrothermal solutions requires understanding of them. Sr isotopic evidence indicates that at least two and probably all three of these solid materials were removed from the solution with which they are associated, by precipitation or adsorption. This occurred after the "pure" hydrothermal fluid was diluted and thoroughly mixed with ambient seawater. The three types of solid materials, are, respectively, a coarse Zn- and Fe-rich material with small amounts of Na and Ca; a finer material also rich in Zn and Fe, but with alkali and alkaline-earth metals; and a scum composed of Ba or Zn, with either considerable Fe or Si, and Sr. Mineral identification is uncertain because of uncertain anion composition. Only in the cases of Ba and Zn were metal masses greater in solid materials than in the associated fluids. For all other metals measured, masses in fluids dwarf those in solids. The fluids themselves contain greater concentrations of all metals measured, except Mg, than seawater. We discuss in detail the relative merits of two methods of determining the mixing proportions of "pure" hydrothermal solution and seawater in the fluids, one based on Sr isotopes, and another previously used method based on Mg concentrations. Comparison of solute concentrations in the several samples shows that degree of dilution of "pure" hydrothermal solutions by seawater, and amounts of original solutes that were removed from it as solid materials, are not related. There is no clear evidence that appreciable amounts of solid materials were not conserved (lost) either during or prior to sample collection. ?? 1988.

Enhanced pinning in mixed rare earth-123 films

DOEpatents

Driscoll, Judith L [Los Alamos, NM; Foltyn, Stephen R [Los Alamos, NM

2009-06-16

An superconductive article and method of forming such an article is disclosed, the article including a substrate and a layer of a rare earth barium cuprate film upon the substrate, the rare earth barium cuprate film including two or more rare earth metals capable of yielding a superconductive composition where ion size variance between the two or more rare earth metals is characterized as greater than zero and less than about 10.times.10.sup.-4, and the rare earth barium cuprate film including two or more rare earth metals is further characterized as having an enhanced critical current density in comparison to a standard YBa.sub.2Cu.sub.3O.sub.y composition under identical testing conditions.

When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

PubMed Central

Guino-o, Marites A.; Alexander, Jacob S.; McKee, Michael L.; Hope, Håkon; Englich, Ulrich B.

2014-01-01

The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline-earth-metal chemistry. PMID:19844925

Trophic transfer of trace metals from the polychaete worm Nereis diversicolor to the polychaete N. virens and the decapod crustacean Palaemonetes varians

USGS Publications Warehouse

Rainbow, P.S.; Poirier, L.; Smith, B.D.; Brix, K.V.; Luoma, S.N.

2006-01-01

Diet is an important exposure route for the uptake of trace metals by aquatic invertebrates, with trace metal trophic transfer depending on 2 stages - assimilation and subsequent accumulation by the predator. This study investigated the trophic transfer of trace metals from the sediment-dwelling polychaete worm Nereis diversicolor from metal-rich estuarine sediments in southwestern UK to 2 predators - another polychaete N. virens (Cu, Zn, Pb, Cd, Fe) and the decapod crustacean Palaemonetes varians (Cu, Zn, Pb, Cd, Fe, Ag, As, Mn). N. virens showed net accumulation of Cu, Zn, Pb and Cd from the prey; accumulation increased with increasing prey concentration, but a coefficient of trophic transfer decreased with increasing prey concentration, probably because a higher proportion of accumulated metal in the prey is bound in less trophically available (insoluble) detoxified forms. The trace metal accumulation patterns of P. varians apparently restricted significant net accumulation of metals from the diet of N. diversicolor to just Cd. There was significant mortality of the decapods fed on the diets of metal-rich worms. Metal-rich invertebrates that have accumulated metals from the rich historical store in the sediments of particular SW England estuaries can potentially pass these metals along food chains, with accumulation and total food chain transfer depending on the metal assimilation efficiencies and accumulation patterns of the animal at each trophic level. This trophic transfer may be significant enough to have ecotoxicological effects. ?? Inter-Research 2006.

Fundamental Physics

NASA Image and Video Library

2003-01-22

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Effect of H2O on metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe: Implications for the oxidation state of the Earth and Mars

NASA Astrophysics Data System (ADS)

Clesi, V.; Bouhifd, M. A.; Bolfan-Casanova, N.; Manthilake, G.; Fabbrizio, A.; Andrault, D.

2016-11-01

This study investigates the metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe during core mantle differentiation of terrestrial planets under hydrous conditions. For this, we equilibrated a molten hydrous CI chondrite model composition with various Fe-rich alloys in the system Fe-C-Ni-Co-Si-S in a multi-anvil over a range of P, T, fO2 and water content (5-20 GPa, 2073-2500 K, from 1 to 5 log units below the iron-wüstite (IW) buffer and for XH2O varying from 500 ppm to 1.5 wt%). By comparing the present experiments with the available data sets on dry systems, we observes that the effect of water on the partition coefficients of moderately siderophile elements is only moderate. For example, for iron we observed a decrease in the partition coefficient of Fe (Dmet/silFe) from 9.5 to 4.3, with increasing water content of the silicate melt, from 0 to 1.44 wt%, respectively. The evolution of metal-silicate partition coefficients of Ni, Co, V, Cr, Mn and Fe are modelled based on sets of empirical parameters. These empirical models are then used to refine the process of core segregation during accretion of Mars and the Earth. It appears that the likely presence of 3.5 wt% water on Mars during the core-mantle segregation could account for ∼74% of the FeO content of the Martian mantle. In contrast, water does not play such an important role for the Earth; only 4-6% of the FeO content of its mantle could be due to the water-induced Fe-oxidation, for a likely initial water concentration of 1.8 wt%. Thus, in order to reproduce the present-day FeO content of 8 wt% in the mantle, the Earth could initially have been accreted from a large fraction (between 85% and 90%) of reducing bodies (similar to EH chondrites), with 10-15% of the Earth's mass likely made of more oxidized components that introduced the major part of water and FeO to the Earth. This high proportion of enstatite chondrites in the original constitution of the Earth is consistent with the 17O,48Ca,50Ti,62Ni and 90Mo isotopic study by Dauphas et al. (2014). If we assume that the CI-chondrite was oxidized during accretion, its intrinsically high water content suggests a maximum initial water concentration in the range of 1.2-1.8 wt% for the Earth, and 2.5-3.5 wt% for Mars.

Catalysts Based on Earth-Abundant Metals for Visible Light-Driven Water Oxidation Reaction.

PubMed

Lin, Junqi; Han, Qing; Ding, Yong

2018-06-04

Exploration of water oxidation catalyst (WOC) with excellent performance is the key for the overall water splitting reaction, which is a feasible strategy to convert solar energy to chemical energy. Although some compounds composed of noble metals, mainly Ru and Ir, have been reported to catalyze water oxidation with high efficiency, catalysts based on low-cost and earth-abundant transition metals are essential for realizing economical and large-scale light-driven water splitting. Various WOCs containing earth-abundant metals (mainly Mn, Fe, Co, Ni, Cu) have been utilized for visible light-driven water oxidation in recent years. In this Personal Account, we summarize our recent developments in WOCs based on earth-abundant transition metals including polyoxometalates (POMs), metal oxides or bimetal oxides, and metal complexes containing multidentate ligand scaffolds for visible light-driven water oxidation reaction. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysis using hydrous metal oxide ion exchanges

DOEpatents

Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

1985-01-01

In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

Catalysis using hydrous metal oxide ion exchangers

DOEpatents

Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

1983-07-21

In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

Melting relations in the Fe-rich portion of the system FeFeS at 30 kb pressure

USGS Publications Warehouse

Brett, R.; Bell, P.M.

1969-01-01

The melting relations of FeFeS mixtures covering the composition range from Fe to Fe67S33 have been determined at 30 kb pressure. The phase relations are similar to those at low pressure. The eutectic has a composition of Fe72.9S27.1 and a temperature of 990??C. Solubility of S in Fe at elevated temperatures at 30 kb is of the same order of magnitude as at low pressure. Sulfur may have significantly lowered the melting point of iron in the upper mantle during the period of coalescence of metal prior to core formation in the primitive earth. ?? 1969.

Release of Nitrogen during Planetary Accretion Explains Missing Nitrogen in Earth's Mantle

NASA Astrophysics Data System (ADS)

Liu, J.; Dorfman, S.; Lv, M.; Li, J.; Kono, Y.

2017-12-01

Nitrogen and carbon are essential elements for life on Earth, and their relative abundances in planetary bodies (C/N ratios) are important for understanding planetary evolution and habitability1,2. However, the high C/N ratio in the bulk silicate Earth relative to CI chondrites and other volatile-rich chondrites is difficult to explain with partitioning behavior between silicate and metallic liquid or solubility in silicate melt, and has thus been a major unsolved problem in geochemistry1-5. Because core formation does not explain nitrogen depletion in the mantle, another process is required to match the observed BSE C/N ratio, such as devolatilization of metallic liquid. Previous studies have examined the Fe-C phase diagram extensively (e.g. ref. 6), but very limited melting data is available for the Fe-N system7. Here we examine melting relations for four Fe-N-C compositions with 1-7 wt% nitrogen up to 7 GPa and 2200 K in the Paris-Edinburgh press by a combination of in-situ X-ray radiography, X-ray diffraction and ex-situ electron microprobe techniques. In striking contrast to the Fe-C system, near-surface melting in all compositions in the Fe-N-C system entails release of nitrogen fluid and depletion of nitrogen from the liquid alloy. This could provide a pathway for nitrogen to escape the magma ocean in the accretion stage while carbon is retained. On the basis of our experimental results, we propose a new quantitative model of mantle nitrogen evolution during the core formation stage to explain the high BSE C/N ratios and resolve the paradox of missing mantle nitrogen1-5. Although nitrogen itself is not a greenhouse gas, the nitrogen released to the atmosphere from metallic melt early in Earth's history could amplify the greenhouse effect through collision-enhanced absorption8,9, which may help to explain warm surface temperatures during the Hadean and Archean eras on Earth when the solar luminosity was 25-30% lower than the present10. References1. Bergin et al., PNAS (2015). 2. Hirschmann, Am. Mineral. (2016). 3. Marty, EPSL (2012). 4. Halliday, GCA (2013). 5. Dalou et al., EPSL (2017). 6. Walker et al., Contrib. Mineral. Petrol. (2013). 7. Guillermet et al., Z. Metallkd. (1994). 8. Wordsworth et al., Science (2013). 9. Goldblatt et al. Nat. Geosci. (2009). 10. Gough. Sol. Phys. (1981)

Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

PubMed

Meshram, Pratima; Pandey, B D; Mankhand, T R

2016-05-01

Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

The redox state of the mantle during and just after core formation.

PubMed

Frost, D J; Mann, U; Asahara, Y; Rubie, D C

2008-11-28

Siderophile elements are depleted in the Earth's mantle, relative to chondritic meteorites, as a result of equilibration with core-forming Fe-rich metal. Measurements of metal-silicate partition coefficients show that mantle depletions of slightly siderophile elements (e.g. Cr, V) must have occurred at more reducing conditions than those inferred from the current mantle FeO content. This implies that the oxidation state (i.e. FeO content) of the mantle increased with time as accretion proceeded. The oxygen fugacity of the present-day upper mantle is several orders of magnitude higher than the level imposed by equilibrium with core-forming Fe metal. This results from an increase in the Fe2O3 content of the mantle that probably occurred in the first 1Ga of the Earth's history. Here we explore fractionation mechanisms that could have caused mantle FeO and Fe2O3 contents to increase while the oxidation state of accreting material remained constant (homogeneous accretion). Using measured metal-silicate partition coefficients for O and Si, we have modelled core-mantle equilibration in a magma ocean that became progressively deeper as accretion proceeded. The model indicates that the mantle would have become gradually oxidized as a result of Si entering the core. However, the increase in mantle FeO content and oxygen fugacity is limited by the fact that O also partitions into the core at high temperatures, which lowers the FeO content of the mantle. (Mg,Fe)(Al,Si)O3 perovskite, the dominant lower mantle mineral, has a strong affinity for Fe2O3 even in the presence of metallic Fe. As the upper mantle would have been poor in Fe2O3 during core formation, FeO would have disproportionated to produce Fe2O3 (in perovskite) and Fe metal. Loss of some disproportionated Fe metal to the core would have enriched the remaining mantle in Fe2O3 and, if the entire mantle was then homogenized, the oxygen fugacity of the upper mantle would have been raised to its present-day level.

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

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

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).

Carbon isotope fractionation between Fe-carbide and diamond; a light C isotope reservoir in the deep Earth and Core?

NASA Astrophysics Data System (ADS)

Mikhail, S.; Jones, A. P.; Hunt, S. A.; Guillermier, C.; Dobson, D. P.; Tomlinson, E.; Dan, H.; Milledge, H.; Franchi, I.; Wood, I.; Beard, A.; Verchovsky, S.

2010-12-01

The largest accessible reservoir for terrestrial carbon is the mantle; however the core may yield even more. Carbon is commonly proposed as the light element (or one of) to make up the observed density deficit in the earth’s metallic core (NAKAJIMA et al., 2009). The potential isotopic effects of carbon incorporation into the core have not yet been investigated. In-situ ion probe (nanoSIMS) mapping and imaging of carbon isotope variations across rare sub-mm-scale Fe-rich carbide inclusions in mantle diamond (from Jagersfontein, South Africa) show the carbide to be significantly depleted in 13C relative to their diamond host. Distinctive textures suggest metallic liquid precipitates similar in geometry to (giant) nitrogen platelets, controlled by the octahedral symmetry of diamond, which we interpret as syngenic formation. The difference in δ13C values between the two natural phases for diamond-Fe carbide, gives an isotopic fractionation factor (ΔC) which agrees well with HPHT multi-anvil experiments (5-9 GPa and >1400°C). Our measured ΔC between Fe-carbide and diamond may only have local significance, but the measured isotopic values represent characterization of the highest PT carbide known (i.e. > minimum depth of the diamond stability field ≈ 150 km). The direction and magnitude of ΔC agrees with observations of the ΔC between cohenite-graphite in iron meteorites (DEINES and WICKMAN, 1975) and both agree with HPHT experiments, thus suggesting that carbon in the deep Earth, and particularly in the core, may be similarly fractionated (i.e. depleted in the 13C). Since metallic liquid drained from the silicate mantle to form the core during the early Earth, we can use our values as a proxy to constrain evolution of deep carbon reservoirs such as the core and bulk silicate Earth. For example, we can test the suggestion of Grady et al (2004) that the upper mantle value of δ13C ≈ -5 ‰ may not be representative of the bulk Earth, since solar system meteorites (from Mars, Vesta and the Moon) suggest a preferred value of δ13C ≈ -20 +/- 4 ‰. If we adopt this particular model, not only could we explain fractionation between a bulk silicate Earth δ13C value of -5 ‰ from an initial δ13C value of -20 ‰, but we can constrain the relative proportion of carbon in the core/mantle by using simple isotopic mass balance. Such fractionation of carbon isotopes between HPT carbides (and/or metallic iron) within the lower mantle and core would be expected immediately from the time of core formation. Therefore, isotopically light carbon reservoirs may have been present deep in the Earth throughout its history, offering an alternative explanation for light carbon (eg in diamonds) which was not formed by, and/or predated subduction of oceanic crust and organic carbon. Deines, P. and Wickman, F. E., 1975. GCA; Grady, M. M. et al. 2004. Int Journal of Astrobiology; Nakajima, Y. et al. K.-i., 2009. Physics of the Earth and Planetary Interiors.

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

The toxicological geochemistry of Earth materials: An overview of processes and the interdisciplinary methods used to understand them

USGS Publications Warehouse

Plumlee, Geoffrey S.; Morman, Suzette A.; Ziegler, Thomas L.

2006-01-01

A broad spectrum of earth materials have been linked to, blamed for, and/or debated as sources for disease. In some cases, the links are clear. For example, excessive exposures to mineral dusts have long been recognized for their role in diseases such as: asbestosis, mesothelioma, and lung cancers (asbestos); silicosis and lung cancer (silica dusts); and coal-workers pneumoconiosis (coal dust). Lead poisoning, particularly in toddlers and young children, has been conclusively linked to involuntary ingestion of soils or other materials contaminated with lead-rich paint particles, leaded gasoline combustion byproducts, and some types of lead-rich mine wastes or smelter particulates. Waters with naturally elevated arsenic contents are common in many regions of the globe, and consumption of these waters has been documented as the source of arsenic-related diseases affecting thousands of people in south Asia and other regions. Exposure to dusts or soils containing pathogens has been documented as the cause of regionally common diseases such as valley fever (coccidioidomycosis) and much rarer diseases such as anthrax. Links between many other earth materials and specific diseases, although suspected, are less clear or are debated. For example, it has been suggested that geographic clusters of diseases such as leukemia are related to exposures to waters or atmospheric particulates containing organic or metal contaminants; however, for many clusters the exact causal relationships between disease and environmental exposure are difficult to prove conclusively. Even for many diseases in which the causal relationship is clear, such as in asbestosis and mesothelioma triggered by asbestos exposure, the minimum exposures needed to trigger disease, the influence of genetic factors, and the exact mechanisms of toxicity are still incompletely understood and are the focus of considerable debate within the public health community. Hence, understanding the health effects resulting from occupational and environmental exposures to a wide variety of earth materials remains a very active and fruitful area of research.

Gaia reveals a metal-rich in-situ component of the local stellar halo

NASA Astrophysics Data System (ADS)

Bonaca, Ana; Conroy, Charlie; Wetzel, Andrew; Hopkins, Philip; Keres, Dusan

2018-01-01

We use the first Gaia data release, combined with RAVE and APOGEE spectroscopic surveys, to investigate the origin of halo stars within ~3 kpc from the Sun. We identify halo stars kinematically, as moving with a relative speed of at least 220 km/s with respect to the local standard of rest. These stars are in general more metal-poor than the disk, but surprisingly, half of our halo sample is comprised of stars with [Fe/H]>-1. The orbital directions of these metal-rich halo stars are preferentially aligned with the disk rotation, in sharp contrast with the isotropic orbital distribution of the more metal-poor halo stars. We find similar properties in the Latte cosmological zoom-in simulation of a Milky Way-like galaxy from the FIRE project. In Latte, metal-rich halo stars formed primarily inside of the solar circle, while lower-metallicity halo stars preferentially formed at larger distances (extending beyond the virial radius). This suggests that metal-rich halo stars in the Solar neighborhood in fact formed in situ within the Galactic disk rather than having been accreted from satellite systems. These stars, currently on halo-like orbits, therefore have likely undergone substantial radial migration/heating.

Volcanic gas composition, metal dispersion and deposition during explosive volcanic eruptions on the Moon

NASA Astrophysics Data System (ADS)

Renggli, C. J.; King, P. L.; Henley, R. W.; Norman, M. D.

2017-06-01

The transport of metals in volcanic gases on the Moon differs greatly from their transport on the Earth because metal speciation depends largely on gas composition, temperature, pressure and oxidation state. We present a new thermochemical model for the major and trace element composition of lunar volcanic gas during pyroclastic eruptions of picritic magmas calculated at 200-1500 °C and over 10-9-103 bar. Using published volatile component concentrations in picritic lunar glasses, we have calculated the speciation of major elements (H, O, C, Cl, S and F) in the coexisting volcanic gas as the eruption proceeds. The most abundant gases are CO, H2, H2S, COS and S2, with a transition from predominantly triatomic gases to diatomic gases with increasing temperatures and decreasing pressures. Hydrogen occurs as H2, H2S, H2S2, HCl, and HF, with H2 making up 0.5-0.8 mol fractions of the total H. Water (H2O) concentrations are at trace levels, which implies that H-species other than H2O need to be considered in lunar melts and estimates of the bulk lunar composition. The Cl and S contents of the gas control metal chloride gas species, and sulfide gas and precipitated solid species. We calculate the speciation of trace metals (Zn, Ga, Cu, Pb, Ni, Fe) in the gas phase, and also the pressure and temperature conditions at which solids form from the gas. During initial stages of the eruption, elemental gases are the dominant metal species. As the gas loses heat, chloride and sulfide species become more abundant. Our chemical speciation model is applied to a lunar pyroclastic eruption model with isentropic gas decompression. The relative abundances of the deposited metal-bearing solids with distance from the vent are predicted for slow cooling rates (<5 °C/s). Close to a volcanic vent we predict native metals are deposited, whereas metal sulfides dominate with increasing distance from the vent. Finally, the lunar gas speciation model is compared with the speciation of a H2O-, CO2- and Cl-rich volcanic gas from Erta Ale volcano (Ethiopia) as an analogy for more oxidized planetary eruptions. In the terrestrial Cl-rich gas the metals are predominantly transported as chlorides, as opposed to metallic vapors and sulfides in the lunar gas. Due to the presence of Cl-species, metal transport is more efficient in the volcanic gas from Erta Ale compared to the Moon.

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Siderophile Element Partitioning between Sulfide- and Silicate melts.

NASA Astrophysics Data System (ADS)

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

2017-12-01

Different theories concerning the formation of the Earth are debated. Either Earth accreted mostly `dry' or volatile elements were delivered late after core formation was largely inactive [1, 2], or volatile rich material was accreted during the main stages of accretion and core formation [3, 4, 5]. The partitioning behavior of siderophile volatile elements (SVE; S, Se, Te, Tl, Ag, Au, Cd, Bi, Pb, Sn, Cu, Ge, and In) may provide first order constraints whether these element concentrations in Earth's mantle were established before or after core-mantle differentiation or perhaps during both periods by multi stage core formation [6]. A special interest is laid into chalcophile element behavior with respective to the possible formation and segregation of a hadean matte [7]. To examine the influence of sulfur on SVE partitioning between metal-silicate melts, we performed experiments simulating a magma ocean stage evolving from sulfur poor- (low fO2) to more oxidizing sulfur rich- (Fe, Ni)-S melts ( 20 wt% S) towards the end of accretion. We carried out partitioning experiments under various P-T-fO2 conditions with a Bristol type end loaded piston cylinder apparatus (<3 GPa) and a 1000 t walker-type multi-anvil press (3-20 GPa). Our results will be presented at the meeting. References: [1] Albarède F. (2009) Nature, 461, 1227-1233. [2] Ballhaus C. et al. (2013) EPSL, 362, 237-245. [3] Fischer-Gödde M. and Kleine T. (2017) Nature, 541, 525 527. [4] Wade J. and Wood B. J. (2005) EPSL, 236, 78-95. [5] Rubie D. et al. (2016) Science, 253, 1141-1144. [6] Rubie D. et al. (2011) EPSL, 301, 31-42. [7] O'Neill H. St. C. (1991) GCA, 55, 1159-1172.

Comment on "A hydrogen-rich early Earth atmosphere".

PubMed

Catling, David C

2006-01-06

Tian et al. (Reports, 13 May 2005, p. 1014) proposed a hydrogen-rich early atmosphere with slow hydrogen escape from a cold thermosphere. However, their model neglects the ultraviolet absorption of all gases other than H2. The model also neglects Earth's magnetic field, which affects the temperature and density of ions and promotes nonthermal escape of neutral hydrogen.

Numerical modelling of erosion and assimilation of sulfur-rich substrate by martian lava flows: Implications for the genesis of massive sulfide mineralization on Mars

NASA Astrophysics Data System (ADS)

Baumgartner, Raphael J.; Baratoux, David; Gaillard, Fabrice; Fiorentini, Marco L.

2017-11-01

Mantle-derived volcanic rocks on Mars display physical and chemical commonalities with mafic-ultramafic ferropicrite and komatiite volcanism on the Earth. Terrestrial komatiites are common hosts of massive sulfide mineralization enriched in siderophile-chalcophile precious metals (i.e., Ni, Cu, and the platinum-group elements). These deposits correspond to the batch segregation and accumulation of immiscible sulfide liquids as a consequence of mechanical/thermo-mechanical erosion and assimilation of sulfur-rich bedrock during the turbulent flow of high-temperature and low-viscosity komatiite lava flows. This study adopts this mineralization model and presents numerical simulations of erosion and assimilation of sulfide- and sulfate-rich sedimentary substrates during the dynamic emplacement of (channelled) mafic-ultramafic lava flows on Mars. For sedimentary substrates containing adequate sulfide proportions (e.g., 1 wt% S), our simulations suggest that sulfide supersaturation in low-temperature (< 1350 °C) flows could be attained at < 200 km distance, but may be postponed in high-temperature lavas flows (> 1400 °C). The precious-metals tenor in the derived immiscible sulfide liquids may be significantly upgraded as a result of their prolonged equilibration with large volumes of silicate melts along flow conduits. The influence of sulfate assimilation on sulfide supersaturation in martian lava flows is addressed by simulations of melt-gas equilibration in the Csbnd Hsbnd Osbnd S fluid system. However, prolonged sulfide segregation and deposit genesis by means of sulfate assimilation appears to be limited by lava oxidation and the release of sulfur-rich gas. The identification of massive sulfide endowments on Mars is not possible from remote sensing data. Yet the results of this study aid to define regions for the potential occurrence of such mineral systems, which may be the large canyon systems Noctis Labyrinthus and Valles Marineris, or the Hesperian channel systems of Mars' highlands (e.g., Kasei Valles), most of which have been periodically draped by mafic-ultramafic lavas.

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Resin catalysts and method of preparation

DOEpatents

Smith, Jr., Lawrence A.

1986-01-01

Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Resin catalysts and method of preparation

DOEpatents

Smith, L.A. Jr.

1986-12-16

Heat stabilized catalyst compositions are prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Distribution behavior of uranium, neptunium, rare-earth elements ( Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiClKCI eutectic salt and liquid cadmium or bismuth

NASA Astrophysics Data System (ADS)

Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

1995-12-01

Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCI eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Laminated rare earth structure and method of making

DOEpatents

Senor, David J [West Richland, WA; Johnson, Roger N [Richland, WA; Reid, Bruce D [Pasco, WA; Larson, Sandra [Richland, WA

2002-07-30

A laminated structure having two or more layers, wherein at least one layer is a metal substrate and at least one other layer is a coating comprising at least one rare earth element. For structures having more than two layers, the coating and metal substrate layers alternate. In one embodiment of the invention, the structure is a two-layer laminate having a rare earth coating electrospark deposited onto a metal substrate. In another embodiment of the invention, the structure is a three-layer laminate having the rare earth coating electrospark deposited onto a first metal substrate and the coating subsequently abonded to a second metal substrate. The bonding of the coating to the second metal substrate may be accomplished by hot pressing, hot rolling, high deformation rate processing, or combinations thereof. The laminated structure may be used in nuclear components where reactivity control or neutron absorption is desired and in non-nuclear applications such as magnetic and superconducting films.

Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

PubMed

Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

2015-08-18

The search for new catalysts for more efficient, selective chemical transformations and for the synthesis of new functional materials has been a long-standing research subject in both academia and industry. To develop new generations of catalysts that are superior or complementary to the existing ones, exploring the potential of untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, and the lanthanides (La-Lu), constitute one important frontier in the periodic table. Rare-earth elements possess unique chemical and physical properties that are different from those of main-group and late-transition metals. The development of rare-earth-based catalysts by taking the advantage of these unique properties is of great interest and importance. The most stable oxidation state of rare-earth metals is 3+, which is difficult to change under many reaction conditions. The oxidative addition and reductive elimination processes often observed in catalytic cycles involving late transition metals are generally difficult in the case of rare-earth complexes. The 18-electron rule that is applicable to late-transition-metal complexes does not fit rare-earth complexes, whose structures are mainly governed by the sterics (rather than the electron numbers) of the ligands. In the lanthanide series (La-Lu), the ionic radius gradually decreases with increasing atomic number because of the influence of the 4f electrons, which show poor shielding of nuclear charge. Rare-earth metal ions generally show strong Lewis acidity and oxophilicity. Rare-earth metal alkyl and hydride species are highly reactive, showing both nucleophilicity and basicity. The combination of these features, such as the strong nucleophilicity and moderate basicity of the alkyl and hydride species and the high stability, strong Lewis acidity, and unsaturated C-C bond affinity of the 3+ metal ions, can make rare-earth metals unique candidates for the formation of excellent single-site catalysts. This Account is intended to give an overview of our recent studies on organo rare-earth catalysis, in particular the synthesis and application of half-sandwich rare-earth alkyl complexes bearing monocyclopentadienyl ligands for olefin polymerization, carbometalation, and hydroarylation. Treatment of half-sandwich rare-earth dialkyl complexes having the general formula CpMR2 with an equimolar amount of an appropriate borate compound such as [Ph3C][B(C6F5)4] can generate the corresponding cationic monoalkyl species, which serve as excellent single-site catalysts for the polymerization and copolymerization of a wide range of olefin monomers such as ethylene, 1-hexene, styrene, conjugated and nonconjugated dienes, and cyclic olefins. The cationic half-sandwich rare-earth alkyl complexes can also catalyze the regio- and stereoselective alkylative alumination of alkenes and alkynes through insertion of the unsaturated C-C bond into the metal-alkyl bond followed by transmetalation between the resulting new alkyl or alkenyl species and an alkylaluminum compound. Moreover, a combination of deprotonative C-H bond activation of appropriate organic compounds such as anisoles and pyridines by the rare-earth alkyl species and insertion of alkenes into the resulting new metal-carbon bond can lead to catalytic C-H bond alkylation of the organic substrates. Most of these transformations are unique to the rare-earth catalysts with selectivity and functional group tolerance different from those of late-transition-metal catalysts.

Metal concentrations in the tissues of the hydrothermal vent mussel Bathymodiolus: reflection of different metal sources.

PubMed

Koschinsky, Andrea; Kausch, Matteo; Borowski, Christian

2014-04-01

Hydrothermal vent mussels of the genus Bathymodiolus are ideally positioned for the use of recording hydrothermal fluxes at the hydrothermal vent sites they inhabit. Barium, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Pb, Sr, and U concentrations in tissue sections of Bathymodiolus mussels from several hydrothermal fields between 15°N and 9°S at the Mid-Atlantic Ridge were determined and compared to the surrounding fluids and solid substrates in the habitats. Elements generally enriched in hydrothermal fluids, such as Fe, Cu, Zn, Pb and Cd, were significantly enriched in the gills and digestive glands of the hydrothermal mussels. The rather small variability of Zn (and Mn) and positive correlation with K and earth alkaline metals may indicate a biological regulation of accumulation. Enrichments of Mo and U in many tissue samples indicate that particulate matter such as hydrothermal mineral particles from the plumes can play a more important role as a metal source than dissolved metals. Highest enrichments of Cu in mussels from the Golden Valley site indicate a relation to the ≥400 °C hot heavy-metal rich fluids emanating in the vicinity. In contrast, mussels from the low-temperature Lilliput field are affected by the Fe oxyhydroxide sediment of their habitat. In a comparison of two different sites within the Logatchev field metal distributions in the tissues reflected small-scale local variations in the metal content of the fluids and the particulate material. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

NASA Technical Reports Server (NTRS)

Burns, R. G.; Martinez, S. L.

1991-01-01

Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

Weather, knowledge base and life-style

NASA Astrophysics Data System (ADS)

Bohle, Martin

2015-04-01

Why to main-stream curiosity for earth-science topics, thus to appraise these topics as of public interest? Namely, to influence practices how humankind's activities intersect the geosphere. How to main-stream that curiosity for earth-science topics? Namely, by weaving diverse concerns into common threads drawing on a wide range of perspectives: be it beauty or particularity of ordinary or special phenomena, evaluating hazards for or from mundane environments, or connecting the scholarly investigation with concerns of citizens at large; applying for threading traditional or modern media, arts or story-telling. Three examples: First "weather"; weather is a topic of primordial interest for most people: weather impacts on humans lives, be it for settlement, for food, for mobility, for hunting, for fishing, or for battle. It is the single earth-science topic that went "prime-time" since in the early 1950-ties the broadcasting of weather forecasts started and meteorologists present their work to the public, daily. Second "knowledge base"; earth-sciences are a relevant for modern societies' economy and value setting: earth-sciences provide insights into the evolution of live-bearing planets, the functioning of Earth's systems and the impact of humankind's activities on biogeochemical systems on Earth. These insights bear on production of goods, living conditions and individual well-being. Third "life-style"; citizen's urban culture prejudice their experiential connections: earth-sciences related phenomena are witnessed rarely, even most weather phenomena. In the past, traditional rural communities mediated their rich experiences through earth-centric story-telling. In course of the global urbanisation process this culture has given place to society-centric story-telling. Only recently anthropogenic global change triggered discussions on geoengineering, hazard mitigation, demographics, which interwoven with arts, linguistics and cultural histories offer a rich narrative of humankind's intersections with the geosphere. To gain public's curiosity for earth-science topics, thus to gain attention of various social groups that all have access to a high density of information, digestible rich messages are needed: earth-science story-telling has to weaves earth-science topics into culturally rich narrations of multiple forms offering a wide range of perspectives to which people can connect.

Rare earth element scavenging in seawater

NASA Astrophysics Data System (ADS)

Byrne, Robert H.; Kim, Ki-Hyun

1990-10-01

Examinations of rare earth element (REE) adsorption in seawater, using a variety of surface-types, indicated that, for most surfaces, light rare earth elements (LREEs) are preferentially adsorbed compared to the heavy rare earths (HREEs). Exceptions to this behavior were observed only for silica phases (glass surfaces, acid-cleaned diatomaceous earth, and synthetic SiO 2). The affinity of the rare earths for surfaces can be strongly affected by thin organic coatings. Glass surfaces which acquired an organic coating through immersion in Tampa Bay exhibited adsorptive behavior typical of organic-rich, rather than glass, surfaces. Models of rare earth distributions between seawater and carboxylate-rich surfaces indicate that scavenging processes which involve such surfaces should exhibit a strong dependence on pH and carbonate complexation. Scavenging models involving carboxylate surfaces produce relative REE abundance patterns in good general agreement with observed shale-normalized REE abundances in seawater. Scavenging by carboxylate-rich surfaces should produce HREE enrichments in seawater relative to the LREEs and may produce enrichments of lanthanum relative to its immediate trivalent neighbors. Due to the origin of distribution coefficients as a difference between REE solution complexation (which increases strongly with atomic number) and surface complexation (which apparently also increases with atomic number) the relative solution abundance patterns of the REEs produced by scavenging reactions can be quite complex.

Extraterrestrial amino acids identified in metal-rich CH and CB carbonaceous chondrites from Antarctica

NASA Astrophysics Data System (ADS)

Burton, Aaron S.; Elsila, Jamie E.; Hein, Jason E.; Glavin, Daniel P.; Dworkin, Jason P.

2013-03-01

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondrites but are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal-rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment (PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675 (CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time-of-flight mass spectrometry and fluorescence, and gas chromatography isotope ratio mass spectrometry. The δ13C/12C ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (13-16 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.2-2 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of β-, γ-, and δ-amino acids compared to the corresponding α-amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.

Extraterrestrial Amino Acids Identified in Metal-Rich CH and CB Carbonaceous Chondrites from Antarctica

NASA Technical Reports Server (NTRS)

Burton, Aaron S.; Elsila, Jamie E.; Hein, Jason E.; Glavin, Daniel P.; Dworkin, Jason P.

2013-01-01

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondritesbut are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal-rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment(PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675(CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time-of-flight mass spectrometry and fluorescence, and gas chromatography isotope ratiomass spectrometry. The (delta D, delta C-13, delta N-15) ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (1316 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.22 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of beta-, gamma-, and delta-amino acids compared to the corresponding alpha-amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.

SEPARATION OF METAL SALTS BY ADSORPTION

DOEpatents

Gruen, D.M.

1959-01-20

It has been found that certain metal salts, particularly the halides of iron, cobalt, nickel, and the actinide metals, arc readily absorbed on aluminum oxide, while certain other salts, particularly rare earth metal halides, are not so absorbed. Use is made of this discovery to separate uranium from the rare earths. The metal salts are first dissolved in a molten mixture of alkali metal nitrates, e.g., the eutectic mixture of lithium nitrate and potassium nitrate, and then the molten salt solution is contacted with alumina, either by slurrying or by passing the salt solution through an absorption tower. The process is particularly valuable for the separation of actinides from lanthanum-group rare earths.

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a rare earth fluoride-bearing flux of CaF[sub 2], CaCl[sub 2] or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy. 3 figs.

Method for improving the oxidation-resistance of metal substrates coated with thermal barrier coatings

DOEpatents

Thompson, Anthony Mark; Gray, Dennis Michael; Jackson, Melvin Robert

2002-01-01

A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described.

Density functional theory (DFT) studies of hydrogen rich solids and boron carbide under extreme conditions

NASA Astrophysics Data System (ADS)

Shamp, Andrew James

Since the first prediction that compressed hydrogen would metallize in 1935 and the further prediction that the metallic allotrope would be a superconductor at high temperatures, metallic hydrogen has been termed the "holy grail" of high-pressure science. A tremendous amount of theoretical and experimental research has been carried out, with the ultimate goal of metallizing hydrogen via the application of external pressure. It has been previously proposed that doping hydrogen with another element can lower the pressure at which metallization occurs. A number of experimental and theoretical studies have investigated doping hydrogen by either a group XIII or XIV element. Experiments in diamond anvil cells have illustrated that it is indeed possible to synthesize hydrogen-rich phases under conditions of extreme pressures, and SiH4 (H2)2, GeH4(H2) n, and Xe(H2)n have been shown to behave as true compounds. The focus herein is on the theoretical exploration of hydrogen-rich phases with novel stoichiometries, which contain a dopant element up to pressures of 350 GPa. In particular, the alkali-metal and alkaline Earth metal polyhydrides (MHn where n > 1) have been considered. Within this thesis the XtalOpt evolutionary algorithm was employed in order to complete this work, and predict the most stable structures of cesium and beryllium polyhydrides under pressure. In addition, we explore the possibility of mixing excess hydrogen with an electronegative element, iodine and phosphorus. The phases found are examined via detailed first principles calculations. In addition, because of its outstanding hardness, thermodynamic stability, low density, electronic properties, thermal stability, and high melting point boron carbide has many uses: i.e. as a refractory material, in abrasive powders and ballistics, as a neutron radiation absorbent, and in electronic applications. However, little is known about the behavior of boron carbide when under the external stress of pressure. The shock compression of boron carbide has been widely studied for decades both experimentally and theoretically. Due to its low density and high shock strength boron carbide is a candidate for use in ballistic applications, such as armor. However, even with the 40 years of boron carbide shocks, its properties and response while in a shocked state have remained difficult to ascertain. A series of first-principles equation of state (EOS) calculations of B4 C that are in excellent agreement with existing Omega laser measurements have been conducted. Furthermore, in the P-T range to 1.5 TPa and 60,000 K the EOS has been extended. These results are relevant for ongoing and future experimental efforts at high-energy laser facilities such as the National Ignition Facility at Lawrence Livermore National Laboratory.

Preparation of catalysts via ion-exchangeable coatings on supports

DOEpatents

Dosch, R.G.; Stephens, H.P.

1986-04-09

Disclosed are: new catalytic compositions which comprise an inert support coated with a hydrous alkali metal, alkaline earth metal, or quaternary ammonium titanate, niobate, zirconate, or tantalate, in which the alkali or alkaline earth metal or quaternary ammonium cations have been exchanged for a catalytically effective quantity of a catalytically effective metal.

The Electronic Structures and Optical Properties of Alkaline-Earth Metals Doped Anatase TiO2: A Comparative Study of Screened Hybrid Functional and Generalized Gradient Approximation

PubMed Central

Ma, Jin-Gang; Zhang, Cai-Rong; Gong, Ji-Jun; Wu, You-Zhi; Kou, Sheng-Zhong; Yang, Hua; Chen, Yu-Hong; Liu, Zi-Jiang; Chen, Hong-Shan

2015-01-01

Alkaline-earth metallic dopant can improve the performance of anatase TiO2 in photocatalysis and solar cells. Aiming to understand doping mechanisms, the dopant formation energies, electronic structures, and optical properties for Be, Mg, Ca, Sr, and Ba doped anatase TiO2 are investigated by using density functional theory calculations with the HSE06 and PBE functionals. By combining our results with those of previous studies, the HSE06 functional provides a better description of electronic structures. The calculated formation energies indicate that the substitution of a lattice Ti with an AEM atom is energetically favorable under O-rich growth conditions. The electronic structures suggest that, AEM dopants shift the valence bands (VBs) to higher energy, and the dopant-state energies for the cases of Ca, Sr, and Ba are quite higher than Fermi levels, while the Be and Mg dopants result into the spin polarized gap states near the top of VBs. The components of VBs and dopant-states support that the AEM dopants are active in inter-band transitions with lower energy excitations. As to optical properties, Ca/Sr/Ba are more effective than Be/Mg to enhance absorbance in visible region, but the Be/Mg are superior to Ca/Sr/Ba for the absorbance improvement in near-IR region. PMID:28793520

The Electronic Structures and Optical Properties of Alkaline-Earth Metals Doped Anatase TiO2: A Comparative Study of Screened Hybrid Functional and Generalized Gradient Approximation.

PubMed

Ma, Jin-Gang; Zhang, Cai-Rong; Gong, Ji-Jun; Wu, You-Zhi; Kou, Sheng-Zhong; Yang, Hua; Chen, Yu-Hong; Liu, Zi-Jiang; Chen, Hong-Shan

2015-08-24

Alkaline-earth metallic dopant can improve the performance of anatase TiO2 in photocatalysis and solar cells. Aiming to understand doping mechanisms, the dopant formation energies, electronic structures, and optical properties for Be, Mg, Ca, Sr, and Ba doped anatase TiO2 are investigated by using density functional theory calculations with the HSE06 and PBE functionals. By combining our results with those of previous studies, the HSE06 functional provides a better description of electronic structures. The calculated formation energies indicate that the substitution of a lattice Ti with an AEM atom is energetically favorable under O-rich growth conditions. The electronic structures suggest that, AEM dopants shift the valence bands (VBs) to higher energy, and the dopant-state energies for the cases of Ca, Sr, and Ba are quite higher than Fermi levels, while the Be and Mg dopants result into the spin polarized gap states near the top of VBs. The components of VBs and dopant-states support that the AEM dopants are active in inter-band transitions with lower energy excitations. As to optical properties, Ca/Sr/Ba are more effective than Be/Mg to enhance absorbance in visible region, but the Be/Mg are superior to Ca/Sr/Ba for the absorbance improvement in near-IR region.

Clouds in Super-Earth Atmospheres: Chemical Equilibrium Calculations

NASA Astrophysics Data System (ADS)

Mbarek, Rostom; Kempton, Eliza M.-R.

2016-08-01

Recent studies have unequivocally proven the existence of clouds in super-Earth atmospheres. Here we provide a theoretical context for the formation of super-Earth clouds by determining which condensates are likely to form under the assumption of chemical equilibrium. We study super-Earth atmospheres of diverse bulk composition, which are assumed to form by outgassing from a solid core of chondritic material, following Schaefer & Fegley. The super-Earth atmospheres that we study arise from planetary cores made up of individual types of chondritic meteorites. They range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a range of atmospheric composition that is appropriate for low-mass exoplanets. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of formation for over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350-3000 K. Clouds should form along the temperature-pressure boundaries where the condensed species appear in our calculation. We find that the composition of condensate clouds depends strongly on both the H:O and C:O ratios. For the super-Earth archetype GJ 1214b, KCl and ZnS are the primary cloud-forming condensates at solar composition, in agreement with previous work. However, for oxidizing atmospheres, K2SO4 and ZnO condensates are favored instead, and for carbon-rich atmospheres with super-solar C:O ratios, graphite clouds appear. For even hotter planets, clouds form from a wide variety of rock-forming and metallic species.

Process for preparing higher oxides of the alkali and alkaline earth metals

NASA Technical Reports Server (NTRS)

Sadhukhan, P.; Bell, A. (Inventor)

1978-01-01

High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

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

Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin

In this work, we establish a definitive structural model for lithium- and manganese-rich transition metal oxides and demonstrate the effect of composition on their bulk as well as the surface structure.

Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

DOE PAGES

Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin; ...

2018-01-01

In this work, we establish a definitive structural model for lithium- and manganese-rich transition metal oxides and demonstrate the effect of composition on their bulk as well as the surface structure.

Deetherification process

DOEpatents

Smith, Jr., Lawrence A.

1985-01-01

Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Deetherification process

DOEpatents

Smith, L.A. Jr.

1985-11-05

Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isoolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

Environmental assessment and management of metal-rich wastes generated in acid mine drainage passive remediation systems.

PubMed

Macías, Francisco; Caraballo, Manuel A; Nieto, José Miguel

2012-08-30

As acid mine drainage (AMD) remediation is increasingly faced by governments and mining industries worldwide, the generation of metal-rich solid residues from the treatments plants is concomitantly raising. A proper environmental management of these metal-rich wastes requires a detailed characterization of the metal mobility as well as an assessment of this new residues stability. The European standard leaching test EN 12457-2, the US EPA TCLP test and the BCR sequential extraction procedure were selected to address the environmental assessment of dispersed alkaline substrate (DAS) residues generated in AMD passive treatment systems. Significant discrepancies were observed in the hazardousness classification of the residues according to the TCLP or EN 12457-2 test. Furthermore, the absence of some important metals (like Fe or Al) in the regulatory limits employed in both leaching tests severely restricts their applicability for metal-rich wastes. The results obtained in the BCR sequential extraction suggest an important influence of the landfill environmental conditions on the metals released from the wastes. To ensure a complete stability of the pollutants in the studied DAS-wastes the contact with water or any other leaching solutions must be avoided and a dry environment needs to be provided in the landfill disposal selected. Copyright © 2012 Elsevier B.V. All rights reserved.

Designing solid-liquid interphases for sodium batteries.

PubMed

Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin; Gunceler, Deniz; Zachman, Michael J; Tu, Zhengyuan; Shin, Jung Hwan; Nath, Pooja; Agrawal, Akanksha; Kourkoutis, Lena F; Arias, Tomas A; Archer, Lynden A

2017-10-12

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid-electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid-electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.

Statistical Constraints from Siderophile Elements on Earth's Accretion, Differentiation, and Initial Core Stratification

NASA Astrophysics Data System (ADS)

O'Rourke, J. G.; Stevenson, D. J.

2015-12-01

Abundances of siderophile elements in the primitive mantle constrain the conditions of Earth's core/mantle differentiation. Core growth occurred as Earth accreted from collisions between planetesimals and larger embryos of unknown original provenance, so geochemistry is directly related to the overall dynamics of Solar System formation. Recent studies claim that only certain conditions of equilibration (pressure, temperature, and oxygen fugacity) during core formation can reproduce the available data. Typical analyses, however, only consider the effects of varying a few out of tens of free parameters in continuous core formation models. Here we describe the Markov chain Monte Carlo method, which simultaneously incorporates the large uncertainties on Earth's composition and the parameterizations that describe elemental partitioning between metal and silicate. This Bayesian technique is vastly more computationally efficient than a simple grid search and is well suited to models of planetary accretion that involve a plethora of variables. In contrast to previous work, we find that analyses of siderophile elements alone cannot yield a unique scenario for Earth's accretion. Our models predict a wide range of possible light element contents for the core, encompassing all combinations permitted by seismology and mineral physics. Specifically, we are agnostic between silicon and oxygen as the dominant light element, and the addition of carbon or sulfur is also permissible but not well constrained. Redox conditions may have remained roughly constant during Earth's accretion or relatively oxygen-rich material could have been incorporated before reduced embryos. Pressures and temperatures of equilibration, likewise, may only increase slowly throughout accretion. Therefore, we do not necessarily expect a thick (>500 km), compositionally stratified layer that is stable against convection to develop at the top of the core of Earth (or, by analogy, Venus). A thinner stable layer might inhibit the initialization of the dynamo.

Process for converting light alkanes to higher hydrocarbons

DOEpatents

Noceti, Richard P.; Taylor, Charles E.

1988-01-01

A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

Recent Advances of Graphitic Carbon Nitride-Based Structures and Applications in Catalyst, Sensing, Imaging, and LEDs

NASA Astrophysics Data System (ADS)

Wang, Aiwu; Wang, Chundong; Fu, Li; Wong-Ng, Winnie; Lan, Yucheng

2017-10-01

The graphitic carbon nitride (g-C3N4) which is a two-dimensional conjugated polymer has drawn broad interdisciplinary attention as a low-cost, metal-free, and visible-light-responsive photocatalyst in the area of environmental remediation. The g-C3N4-based materials have excellent electronic band structures, electron-rich properties, basic surface functionalities, high physicochemical stabilities and are "earth-abundant." This review summarizes the latest progress related to the design and construction of g-C3N4-based materials and their applications including catalysis, sensing, imaging, and white-light-emitting diodes. An outlook on possible further developments in g-C3N4-based research for emerging properties and applications is also included.

Rare earth metal-containing ionic liquids

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

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Lipid biomarker production and preservation in acidic ecosystems: Relevance to early Earth and Mars

NASA Astrophysics Data System (ADS)

Jahnke, L. L.; Parenteau, M. N.; Harris, R.; Bristow, T.; Farmer, J. D.; Des Marais, D. J.

2013-12-01

Compared to relatively benign carbonate buffered marine environments, terrestrial Archean and Paleoproterozoic life was forced to cope with a broader range of pH values. In particular, acidic terrestrial ecosystems arose from the oxidation of reduced species in hydrothermal settings and crustal reservoirs of metal sulfides, creating acid sulfate conditions. While oxidation of reduced species is facilitated by reactions with molecular oxygen, acidic conditions also arose in Archean hydrothermal systems before the rise of oxygen (Van Kranendonk, 2006), expanding the range of time over which acidophiles could have existed on the early Earth. Acidic terrestrial habitats would have included acidic hydrothermal springs, acid sulfate soils, and possibly lakes and streams lacking substantial buffering capacity with sources of acidity in their catchments. Although acidic hot springs are considered extreme environments on Earth, robust and diverse microbial communities thrive in these habitats. Such acidophiles are found across all three domains of life and include both phototrophic and chemotrophic members. In this presentation, we examine hopanes and sterols that are characteristic of microbial communities living in acidic hydrothermal environments. Moreover we discuss taphonomic processes governing the capture and preservation of these biosignatures in acid environments. In particular, we discuss the production and early preservation of hopanoids and sterols in the following geological/mineralogical settings: 1) rapid entombment of microbes and organic matter by predominantly fine-grained silica; 2) rapid burial of organic matter by clay-rich, silica poor sediments; 3) and the survival of organics in iron oxide and sulfate rich sediments. We discovered and isolated an acid-tolerant purple non-sulfur anoxygenic phototroph from Lassen Volcanic National Park that synthesizes 3methyl-bacteriohopanepolyols. These compounds were previously thought to be exclusively made by methanotrophic and acetic acid bacteria. We also documented the production of unique patterns of abundance of C27, C28, and C29 sterols by the early diverging red and green algae Cyanidiales and Chlorella in the acidic outflow channel of Nymph Creek in Yellowstone National Park. Hydrothermal processes associated with volcanism are common features of ancient habitable environments on Earth and have been inferred for ancient Mars as well. Understanding the preservation of organics in modern acidic hydrothermal settings thus helps inform the detection of these compounds in the ancient sedimentary record on Earth, and perhaps Mars. Van Kranendonk MJ (2006) . Earth-Science Reviews 74, 197-240

Solidification Based Grain Refinement in Steels

DTIC Science & Technology

2010-07-20

methods which worked in the SVSU foundry. However, additions of NbO powder, FeTi, misch metal , and rare earth silicide were successful. Misch metal ...and rare earth silicide additions at the ladle are the most promising from an industrial stand point. The project group has begun preparing for the... metal and rare earth silicide additions have also reduced grain size and improved hardness. Instructions: You may use this MS Word file to submit the

Color-magnitude diagrams for six metal-rich, low-latitude globular clusters

NASA Technical Reports Server (NTRS)

Armandroff, Taft E.

1988-01-01

Colors and magnitudes for stars on CCD frames for six metal-rich, low-latitude, previously unstudied globular clusters and one well-studied, metal-rich cluster (47 Tuc) have been derived and color-magnitude diagrams have been constructed. The photometry for stars in 47 Tuc are in good agreement with previous studies, while the V magnitudes of the horizontal-branch stars in the six program clusters do not agree with estimates based on secondary methods. The distances to these clusters are different from prior estimates. Redding values are derived for each program cluster. The horizontal branches of the program clusters all appear to lie entirely redwards of the red edge of the instability strip, as is normal for their metallicities.

High Performance High Temperature Thermoelectric Composites with Metallic Inclusions

NASA Technical Reports Server (NTRS)

Firdosy, Samad A. (Inventor); Kaner, Richard B. (Inventor); Ma, James M. (Inventor); Fleurial, Jean-Pierre (Inventor); Star, Kurt (Inventor); Bux, Sabah K. (Inventor); Ravi, Vilupanur A. (Inventor)

2017-01-01

The present invention provides a composite thermoelectric material. The composite thermoelectric material can include a semiconductor material comprising a rare earth metal. The atomic percent of the rare earth metal in the semiconductor material can be at least about 20%. The composite thermoelectric material can further include a metal forming metallic inclusions distributed throughout the semiconductor material. The present invention also provides a method of forming this composite thermoelectric material.

Extraction of volatiles and metals from extraterrestrial materials

NASA Technical Reports Server (NTRS)

Lewis, J. S.

1992-01-01

Recent progress in defining the physical, orbital, and chemical properties of the Earth-crossing asteroid and comet population was integrated into an elaborate Monte Carlo model of the fluxes of bodies in the inner Solar System. This model is of use in projecting flight opportunities to as-yet undiscovered near-Earth objects and in assessing the impact hazard to life on Earth and the evolutionary consequences of impacts on the other terrestrial planets. Further progress was made in defining desirable transportation system architectures for the use of non-terrestrial volatiles and metals, including the delivery of propellants to near-Earth space for fueling of space exploration initiative (SEI) type expeditions, the construction and resupply of Solar Power Satellite constellations in various Earth orbits (including geosynchronous earth orbit (GEO) and Highly Eccentric Earth Orbit (HEEO)), and retrieval of He-3 for use as a clean fusion fuel on Earth. These studies suggest a greater future role for SERC in the exploration of space energy sources to meet Earth's 21st-century energy requirements. Laboratory studies of volatilization and deposition of ferrous metal alloys demonstrated deposition of strong iron films from carbonyl chemical vapor deposition (CVD), showing the crucial role of additive gases in governing the CVD process, and pointing the way to specific experiments on extraction and deposition of ferrous metals from nonterrestrial materials.

Sediment heavy metals and benthic diversities in Hun-Tai River, northeast of China.

PubMed

Qu, Xiaodong; Ren, Ze; Zhang, Min; Liu, Xiaobo; Peng, Wenqi

2017-04-01

In aquatic ecosystems, metal contamination in sediments has become a ubiquitous environmental problem, causing serious issues. Hun-Tai River, located in northeast of China, flows through an important heavy industry region and metropolitan area. This study examined the heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, Ni, and Zn) of sediments and diversities (taxa richness, Shannon diversity, and evenness) of benthic assemblages (benthic algae and macroinvertebrate) in Hun-Tai River. The results clearly described the spatial patterns of metal contamination in terms of geo-accumulation index and contamination factor, as well as the spatial patterns of benthic diversities in terms of taxa richness, Shannon index, and evenness by kriging interpolation. The sediments were largely contaminated by Cd, followed by Cu, Fe, Zn, Mn, and Ni. Cd and Zn had similar spatial patterns and similar sources. Cu, Fe, Mn, and Ni showed similar spatial patterns and similar sources. The surface sediments were unpolluted by Cr and Pb. The metal mines and the heavy industry in the major cities were the potential pollution sources. Benthic algae and macroinvertebrate responded similarly to the heterogeneous environment and metal contamination, with high taxa richness and Shannon index in middle-upper reaches of Hun-Tai River. Evenness showed complex spatial patterns. Under low contamination, both taxa richness, Shannon diversity, and evenness had a large variation range. However, under the moderate and high contamination, the taxa richness and Shannon diversity kept to a low level but the evenness had a high level. This study provided insights into the sediment heavy metal contamination in Hun-Tai River.

High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

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

Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.

2008-07-01

High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalizationmore » in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)« less

Origin of spinel-rich chondrules and inclusions in carbonaceous and ordinary chondrites

NASA Technical Reports Server (NTRS)

Kornacki, A. S.; Fegley, B., Jr.

1984-01-01

The evaluation of three models of the origin of spinel-rich chondrules and inclusions presented here includes new calculations of the major-element refractory mineral condensation sequence from a gas of solar composition over a wide pressure interval. Condensation calculations show that spinel-rich chondrules did not crystallize from metastable liquid condensates, and that spinel-rich inclusions are not aggregates of refractory nebular condensates. It is proposed that spinel-rich objects are fractionated distillation residues of small aggregates of primitive dust that lost Ca, Si-rich partial melts by evaporation, ablation, or splashing during collisions. This model also explains why spinel-rich chondrules and inclusions (1) are usually smaller than melilite-rich chondrules and inclusions; (2) often have highly fractionated trace-element compositions; and (3) usually do not contain Pt-metal nuggets even when they are more enriched in the Pt-group metals than nugget-bearing melilite-rich objects.

Movie of phase separation during physics of colloids in space experiment

NASA Technical Reports Server (NTRS)

2002-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area in the video is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Phase separation during the Experiment on Physics of Colloids in Space

NASA Technical Reports Server (NTRS)

2003-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Alkali Metal/Salt Thermal-Energy-Storage Systems

NASA Technical Reports Server (NTRS)

Phillips, Wayne W.; Stearns, John W.

1987-01-01

Proposed thermal-energy-storage system based on mixture of alkali metal and one of its halide salts; metal and salt form slurry of two immiscible melts. Use of slurry expected to prevent incrustations of solidified salts on heat-transfer surfaces that occur where salts alone used. Since incrustations impede heat transfer, system performance improved. In system, charging heat-exchanger surface immersed in lower liquid, rich in halide-salt, phase-charge material. Discharging heat exchanger surface immersed in upper liquid, rich in alkali metal.

Jupiter Analogs Orbit Stars with an Average Metallicity Close to That of the Sun

NASA Astrophysics Data System (ADS)

Buchhave, Lars A.; Bitsch, Bertram; Johansen, Anders; Latham, David W.; Bizzarro, Martin; Bieryla, Allyson; Kipping, David M.

2018-03-01

Jupiter played an important role in determining the structure and configuration of the Solar System. Whereas hot-Jupiter type exoplanets preferentially form around metal-rich stars, the conditions required for the formation of planets with masses, orbits, and eccentricities comparable to Jupiter (Jupiter analogs) are unknown. Using spectroscopic metallicities, we show that stars hosting Jupiter analogs have an average metallicity close to solar, in contrast to their hot-Jupiter and eccentric cool-Jupiter counterparts, which orbit stars with super-solar metallicities. Furthermore, the eccentricities of Jupiter analogs increase with host-star metallicity, suggesting that planet–planet scatterings producing highly eccentric cool Jupiters could be more common in metal-rich environments. To investigate a possible explanation for these metallicity trends, we compare the observations to numerical simulations, which indicate that metal-rich stars typically form multiple Jupiters, leading to planet–planet interactions and, hence, a prevalence of either eccentric cool Jupiters or hot Jupiters with circularized orbits. Although the samples are small and exhibit variations in their metallicities, suggesting that numerous processes other than metallicity affect the formation of planetary systems, the data in hand suggests that Jupiter analogs and terrestrial-sized planets form around stars with average metallicities close to solar, whereas high-metallicity systems preferentially host eccentric cool Jupiter or hot Jupiters, indicating that higher metallicity systems may not be favorable for the formation of planetary systems akin to the Solar System.

Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

PubMed

Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

2016-02-01

The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

40 CFR 421.274 - Standards of performance for new sources.

Code of Federal Regulations, 2012 CFR

2012-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... Scrubber. NSPS for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for... wet rare earth chlorides Hexachlorobenzene 0.042 0.042 Chromium (total) 1.544 0.626 Lead 1.168 0.542...

30 CFR 75.700-1 - Approved methods of grounding.

Code of Federal Regulations, 2012 CFR

2012-07-01

... a borehole casing having low resistance to earth; (b) A solid connection to metal waterlines having low resistance to earth; (c) A solid connection to a grounding conductor, other than the neutral... ensures that there is no difference in potential between such metallic enclosures and the earth. ...

40 CFR 421.274 - Standards of performance for new sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... Scrubber. NSPS for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for... wet rare earth chlorides Hexachlorobenzene 0.042 0.042 Chromium (total) 1.544 0.626 Lead 1.168 0.542...

30 CFR 75.700-1 - Approved methods of grounding.

Code of Federal Regulations, 2014 CFR

2014-07-01

... a borehole casing having low resistance to earth; (b) A solid connection to metal waterlines having low resistance to earth; (c) A solid connection to a grounding conductor, other than the neutral... ensures that there is no difference in potential between such metallic enclosures and the earth. ...

40 CFR 421.274 - Standards of performance for new sources.

Code of Federal Regulations, 2013 CFR

2013-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... Scrubber. NSPS for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for... wet rare earth chlorides Hexachlorobenzene 0.042 0.042 Chromium (total) 1.544 0.626 Lead 1.168 0.542...

40 CFR 421.274 - Standards of performance for new sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... Scrubber. NSPS for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for... wet rare earth chlorides Hexachlorobenzene 0.042 0.042 Chromium (total) 1.544 0.626 Lead 1.168 0.542...

40 CFR 421.274 - Standards of performance for new sources.

Code of Federal Regulations, 2014 CFR

2014-07-01

...) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth... Scrubber. NSPS for the Primary Rare Earth Metals Subcategory Pollutant or pollutant property Maximum for... wet rare earth chlorides Hexachlorobenzene 0.042 0.042 Chromium (total) 1.544 0.626 Lead 1.168 0.542...

Synthesis and structures of metal chalcogenide precursors

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

1990-01-01

The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

Chemical fractionation in the solar nebula

NASA Technical Reports Server (NTRS)

Grossman, L.

1977-01-01

The sequence of condensation of minerals from a cooling gas of solar composition has been calculated from thermodynamic data over the pressure range 0.001-0.00001 atm, assuming that complete chemical equilibrium is maintained. The results suggest that the Ca-Al-rich inclusions Allende and other carbonaceous chondrites are aggregates of the highest temperature condensates. Complete condensation of these elements is followed, 100 deg later, by the onset of the crystallization of nickel-iron, forsterite and enstatite. Transport of Ca-Al-rich refractory condensates from one part of the nebula to another before the condensation of these lower-temperature phases may have been responsible for the refractory element fractionations between the different classes of chondrites and possibly for the inferred refractory element enrichment of the Moon. The temperature gap between the condensation temperatures of nickel-iron and forsterite increases with increasing total pressure. Because pressure and temperature probably increased with decreasing heliocentric distance in the solar nebula, Mercury may have accreted from a condensate assemblage having a higher metal/silicate ratio than Venus or Earth which may, in turn, have formed from less oxidized material than Mars.

Serpentinization as a source of energy at the origin of life.

PubMed

Russell, M J; Hall, A J; Martin, W

2010-12-01

For life to have emerged from CO₂, rocks, and water on the early Earth, a sustained source of chemically transducible energy was essential. The serpentinization process is emerging as an increasingly likely source of that energy. Serpentinization of ultramafic crust would have continuously supplied hydrogen, methane, minor formate, and ammonia, as well as calcium and traces of acetate, molybdenum and tungsten, to off-ridge alkaline hydrothermal springs that interfaced with the metal-rich carbonic Hadean Ocean. Silica and bisulfide were also delivered to these springs where cherts and sulfides were intersected by the alkaline solutions. The proton and redox gradients so generated represent a rich source of naturally produced chemiosmotic energy, stemming from geochemistry that merely had to be tapped, rather than induced, by the earliest biochemical systems. Hydrothermal mounds accumulating at similar sites in today's oceans offer conceptual and experimental models for the chemistry germane to the emergence of life, although the ubiquity of microbial communities at such sites in addition to our oxygenated atmosphere preclude an exact analogy. Published 2010. This article is a US Government work and is in the public domain in the USA.

Some metal-graphite and metal-ceramic composites for use as high energy brake lining materials

NASA Technical Reports Server (NTRS)

Bill, R. C.

1974-01-01

Materials were studied as candidates for development as potential new aircraft brake lining materials. These families were (1) copper-graphite composites; (2) nickel-graphite composites; (3) copper - rare-earth-oxide (gadolinium oxide (Gd2O3) or lanthanum oxide (La2O3)) composites and copper - rare-earth-oxide (La2O3) - rare-earth-fluoride (lanthanum fluoride (LaF3)) composites; (4) nickel - rare-earth-oxide composites and nickel - rare-earth-oxide - rare-earth-fluoride composites. For comparison purposes, a currently used metal-ceramic composite was also studied. Results showed that the nickel-Gd2O3 and nickel-La2O3-LaF3 composites were comparable or superior in friction and wear performance to the currently used composite and therefore deserve to be considered for further development.

Relationships between waste physicochemical properties, microbial activity and vegetation at coal ash and sludge disposal sites.

PubMed

Woch, Marcin W; Radwańska, Magdalena; Stanek, Małgorzata; Łopata, Barbara; Stefanowicz, Anna M

2018-06-11

The aim of the study was to assess the relationships between vegetation, physicochemical and microbial properties of substrate at coal ash and sludge disposal sites. The study was performed on 32 plots classified into 7 categories: dried ash sedimentation ponds, dominated by a grass Calamagrostis epigejos (AH-Ce), with the admixture of Pinus sylvestris (AH-CePs) or Robinia pseudoacacia (AH-CeRp), dry ash landfill dominated by Betula pendula and Pinus sylvestris (AD-BpPs) or Salix viminalis (AD-Sv) and coal sludge pond with drier parts dominated by Tussilago farfara (CS-Tf) and the wetter ones by Cyperus flavescens (CS-Cf). Ash sites were covered with soil layer imported as a part of technical reclamation. Ash had relatively high concentrations of some alkali and alkaline earth metals, Mn and pH, while coal sludge had high water and C, S, P and K contents. Concentrations of heavy metals were lower than allowable limits in all substrate types. Microbial biomass and, particularly, enzymatic activity in ash and sludge were generally low. The only exception were CS-Tf plots characterized by the highest microbial biomass, presumably due to large deposits of organic matter that became available for aerobic microbial biomass when water level fell. The properties of ash and sludge adversely affected microbial biomass and enzymatic activity as indicated by significant negative correlations between the content of alkali/alkaline earth metals, heavy metals, and macronutrients with enzymatic activity and/or microbial biomass, as well as positive correlations of these parameters with metabolic quotient (qCO 2 ). Plant species richness and cover were relatively high, which may be partly associated with alleviating influence of soil covering the ash. The effect of the admixture of R. pseudoacacia or P. sylvestris to stands dominated by C. epigejos was smaller than expected. The former species increased NNH 4 , NNO 3 and arylsulfatase activity, while the latter reduced activity of the enzyme. Copyright © 2018 Elsevier B.V. All rights reserved.

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals... rare earths to about 94-99 percent. The balance of tha alloy includes traces of other elements and one...

Trace Metal Associations with Manganese-Rich Surface Coatings of Lead Service Lines

EPA Science Inventory

Analysis of lead service line samples from U. S. Environmental Protection Agency’s long-term research program to evaluate control and metal release from domestic drinking water service lines has revealed that Manganese-rich solids also contain Iron and sometimes Aluminum have fre...

Rare-Earth Metals and Their Applications in Aviation

DTIC Science & Technology

1984-08-01

metals are not as common as iron and steel which are visible everywhere, yet they are not unfamiliar to us. We often encounter them in everyday life...the flint of a lighter. It is an alloy of rare-earth metal and iron . It contains about 30% iron and the remainder is a composite rare-earth alloy...used to manufacture the detonators of bullets and shells as well as the pyrophoric alloys of firing devices. This type of alloy has a 49.5% content of

Identification of the typical metal particles among haze, fog, and clear episodes in the Beijing atmosphere.

PubMed

Hu, Yunjie; Lin, Jun; Zhang, Suanqin; Kong, Lingdong; Fu, Hongbo; Chen, Jianmin

2015-04-01

For a better understanding of metal particle morphology and behaviors in China, atmospheric aerosols were sampled in the summer of 2012 in Beijing. The single-particle analysis shows various metal-bearing speciations, dominated by oxides, sulfates and nitrates. A large fraction of particles is soluble. Sources of Fe-bearing particles are mainly steel industries and oil fuel combustion, whereas Zn- and Pb-bearing particles are primarily contributed by waste incineration, besides industrial combustion. Other trace metal particles play a minor rule, and may come from diverse origins. Mineral dust and anthropogenic source like vehicles and construction activities are of less importance to metal-rich particles. Statistics of 1173 analyzed particles show that Fe-rich particles (48.5%) dominate the metal particles, followed by Zn-rich particles (34.9%) and Pb-rich particles (15.6%). Compared with the abundances among clear, haze and fog conditions, a severe metal pollution is identified in haze and fog episodes. Particle composition and elemental correlation suggest that the haze episodes are affected by the biomass burning in the southern regions, and the fog episodes by the local emission with manifold particle speciation. Our results show the heterogeneous reaction accelerated in the fog and haze episodes indicated by more zinc nitrate or zinc sulfate instead of zinc oxide or carbonate. Such information is useful in improving our knowledge of fine airborne metal particles on their morphology, speciation, and solubility, all of which will help the government introduce certain control to alleviate metal pollution. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Stellar abundances and ages for metal-rich Milky Way globular clusters. Stellar parameters and elemental abundances for 9 HB stars in NGC 6352

NASA Astrophysics Data System (ADS)

Feltzing, S.; Primas, F.; Johnson, R. A.

2009-01-01

Context: Metal-rich globular clusters provide important tracers of the formation of our Galaxy. Moreover, and not less important, they are very important calibrators for the derivation of properties of extra-galactic metal-rich stellar populations. Nonetheless, only a few of the metal-rich globular clusters in the Milky Way have been studied using high-resolution stellar spectra to derive elemental abundances. Additionally, Rosenberg et al. identified a small group of metal-rich globular clusters that appeared to be about 2 billion years younger than the bulk of the Milky Way globular clusters. However, it is unclear if like is compared with like in this dataset as we do not know the enhancement of α-elements in the clusters and the amount of α-elements is well known to influence the derivation of ages for globular clusters. Aims: We derive elemental abundances for the metal-rich globular cluster NGC 6352 and we present our methods to be used in up-coming studies of other metal-rich globular clusters. Methods: We present a study of elemental abundances for α- and iron-peak elements for nine HB stars in the metal-rich globular cluster NGC 6352. The elemental abundances are based on high-resolution, high signal-to-noise spectra obtained with the UVES spectrograph on VLT. The elemental abundances have been derived using standard LTE calculations and stellar parameters have been derived from the spectra themselves by requiring ionizational as well as excitational equilibrium. Results: We find that NGC 6352 has [Fe/H] = -0.55, is enhanced in the α-elements to about +0.2 dex for Ca, Si, and Ti relative to Fe. For the iron-peak elements we find solar values. Based on the spectroscopically derived stellar parameters we find that an E(B-V) = 0.24 and (m-M) ≃ 14.05 better fits the data than the nominal values. An investigation of log gf-values for suitable Fe i lines lead us to the conclusion that the commonly used correction to the May et al. (1974) data should not be employed. Full Table [see full text] are also only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/493/913 Based on observations collected at the European Southern Observatory, Chile, ESO No. 69.B-0467.

Destabilized and catalyzed borohydride for reversible hydrogen storage

DOEpatents

Mohtadi, Rana F [Northville, MI; Zidan, Ragaiy [Aiken, SC; Gray, Joshua [Aiken, SC; Stowe, Ashley C [Knoxville, TN; Sivasubramanian, Premkumar [Aiken, SC

2012-02-28

A process of forming a hydrogen storage material, including the steps of: providing a borohydride material of the formula: M(BH.sub.4).sub.x where M is an alkali metal or an alkaline earth metal and 1.ltoreq.x.ltoreq.2; providing an alanate material of the formula: M.sub.1(AlH.sub.4).sub.x where M.sub.1 is an alkali metal or an alkaline earth metal and 1.ltoreq.x.ltoreq.2; providing a halide material of the formula: M.sub.2Hal.sub.x where M.sub.2 is an alkali metal, an alkaline earth metal or transition metal and Hal is a halide and 1.ltoreq.x.ltoreq.4; combining the borohydride, alanate and halide materials such that 5 to 50 molar percent from the borohydride material is present forming a reaction product material having a lower hydrogen release temperature than the alanate material.

Crystallographic phases in heavy rare earth metals under megabar pressures

NASA Astrophysics Data System (ADS)

Samudrala, G. K.; Vohra, Y. K.

2012-07-01

Experiments aimed at understanding the crystallographic phases of heavy rare earth metals were carried out in a diamond anvil cell at the Advanced Photon Source, Argonne National Laboratory. Heavy rare earth metals dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (Tm) were compressed to multi-megabar pressures. The rare earth crystal sequence hcp→Sm-type→dhcp→distorted-fcc (dfcc) is observed in all four elements. Upon further compression, a structural transformation to a monoclinic C2/m phase has been observed. We summarize the results from these experiments and present Rietveld structural refinements on high pressure phases for the specific case of dysprosium.

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.

Achievement of high coercivity in sintered R-Fe-B magnets based on misch-metal by dual alloy method

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

Niu, E, E-mail: niue@aphy.iphy.ac.cn; Wang, Zhen-Xi; Beijing Zhong Ke San Huan Research, No.10 Chuangxin Road, Changping District, Beijing 102200

2014-03-21

The R-Fe-B (R, rare earth) sintered magnets prepared with different ratio of alloys of MM-Fe-B (MM, misch-metal) and Nd-Fe-B by dual alloy method were investigated. As expected, the high ratio of MM-Fe-B alloy degrades the hard magnetic properties heavily with intrinsic coercivity lower than 5 kOe. When the atomic ratio MM/R ≤ 21.5% the magnetic properties can reach a practical level of B{sub r} ≥ 12.1 kGs, H{sub cj} ≥ 10.7 kOe, and (BH){sub max} ≥ 34.0 MGOe. And the effect of H{sub cj} enhancement by the grain boundary diffusion process is obvious when MM/R ≤ 21.5%. It is revealed that the decrement of intrinsic magnetic properties of R{sub 2}Fe{submore » 14}B matrix phase is not the main reason of the degradation of the magnets with high MM ratio. The change of deteriorated microstructure together with phase component plays fundamental roles in low H{sub cj}. In high MM ratio magnets, (a) after annealing, Ce atoms inside main phase are inclined to be segregated in the outer layer of the main phase grains; (b) there is no thin layer of Ce-rich phase as an analogue of Nd-rich phase to separate main phase grains; (c) excessive Ce tends to form CeFe{sub 2} grains.« less

METAL-POOR LITHIUM-RICH GIANTS IN THE RADIAL VELOCITY EXPERIMENT SURVEY

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

Ruchti, Gregory R.; Fulbright, Jon P.; Wyse, Rosemary F. G.

We report the discovery of eight lithium-rich field giants found in a high-resolution spectroscopic sample of over 700 metal-poor stars ([Fe/H] < -0.5) selected from the Radial Velocity Experiment survey. The majority of the Li-rich giants in our sample are very metal-poor ([Fe/H] {approx}< -1.9), and have a Li abundance (in the form of {sup 7}Li), A(Li) = log (n(Li)/n(H)) + 12, between 2.30 and 3.63, well above the typical upper red giant branch (RGB) limit, A(Li) < 0.5, while two stars, with A(Li) {approx} 1.7-1.8, show similar lithium abundances to normal giants at the same gravity. We further includedmore » two metal-poor, Li-rich globular cluster giants in our sample, namely the previously discovered M3-IV101 and newly discovered (in this work) M68-A96. This comprises the largest sample of metal-poor Li-rich giants to date. We performed a detailed abundance analysis of all stars, finding that the majority of our sample stars have elemental abundances similar to that of Li-normal halo giants. Although the evolutionary phase of each Li-rich giant cannot be definitively determined, the Li-rich phase is likely connected to extra mixing at the RGB bump or early asymptotic giant branch that triggers cool bottom processing in which the bottom of the outer convective envelope is connected to the H-burning shell in the star. The surface of a star becomes Li-enhanced as {sup 7}Be (which burns to {sup 7}Li) is transported to the stellar surface via the Cameron-Fowler mechanism. We discuss and discriminate among several models for the extra mixing that can cause Li production, given the detailed abundances of the Li-rich giants in our sample.« less

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

Selle, J E

Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussedmore » in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.« less

A review of the processes and lab-scale techniques for the treatment of spent rechargeable NiMH batteries

NASA Astrophysics Data System (ADS)

Innocenzi, Valentina; Ippolito, Nicolò Maria; De Michelis, Ida; Prisciandaro, Marina; Medici, Franco; Vegliò, Francesco

2017-09-01

The purpose of this work is to describe and review the current status of the recycling technologies of spent NiMH batteries. In the first part of the work, the structure and characterization of NiMH accumulators are introduced followed by the description of the main scientific studies and the industrial processes. Various recycling routes including physical, pyrometallurgical and hydrometallurgical ones are discussed. The hydrometallurgical methods for the recovery of base metals and rare earths are mainly developed on the laboratory and pilot scale. The operating industrial methods are pyrometallurgical ones and are efficient only on the recovery of certain components of spent batteries. In particular fraction rich in nickel and other materials are recovered; instead the rare earths are lost in the slag and must be further refined by hydrometallurgical process to recover them. Considering the actual legislation regarding the disposal of spent batteries and the preservation of raw materials issues, implementations on laboratory scale and plant optimization studies should be conducted in order to overcome the industrial problems of the scale up for the hydrometallurgical processes.

Properties of the solar nebula and the origin of the moon.

NASA Technical Reports Server (NTRS)

Cameron, A. G. W.

1973-01-01

The basic geochemical model of the structure of the moon proposed by Anderson, in which the moon is formed by differentiation of the calcium, aluminium, and titanium-rich inclusions in the Allende meteorite, is accepted, and the conditions for formation of this moon within the solar nebula models of Cameron and Pine are discussed. The basic material condenses while iron remains in the gaseous phase, which places the formation of the moon slightly inside the orbit of Mercury. Some condensed metallic iron is likely to enter the moon in this position, and since the moon is assembled at a very high temperature, it is likely to have been fully molten, so that the iron can remove the iridium from the silicate material and carry it down to form a small core. Interactions between the moon and Mercury lead to the present rather eccentric Mercury orbit and to a much more eccentric orbit for the moon, reaching past the orbit of the earth, establishing conditions which are necessary for capture of the moon by the earth.

A Density Functional Theory Study of Codoping Characteristics of Sulfur with Alkaline Earth in Delafossite CuAlO2

NASA Astrophysics Data System (ADS)

Liu, Qi-Jun; Qin, Han; Liu, Zheng-Tang

2016-04-01

The structural, electronic properties and formation energies of sulfur and alkaline earth codoped delafossite CuAlO2 have been investigated using the first-principles density functional theory calculations. Our results reveal that the volume of codoping systems increases with the increasing atomic radius of metal atoms. The formation energies under different growth conditions have been calculated, showing that the codoping systems are formed easily under O-rich growth conditions. Electronic band structures and density of states have been obtained. The decreased bandgaps, enhanced covalence and appearance of electron acceptors after codoping are all good for p-type conductivity. Supported by the National Natural Science Foundation of China under Grant Nos. 11347199, 51402244, and 11547311, the Specialized Research Fund for Doctoral Program of Higher Education of China under Grant No. 20130184120028, the Fundamental Research Fund for the Central Universities, China under Grant Nos. 2682014CX084, 2682014ZT30, and 2682014ZT31, and the fund of the State Key Laboratory of Solidification Processing in NWPU under Grant No. SKLSP201511

New Fission Fragment Distributions and r-Process Origin of the Rare-Earth Elements

NASA Astrophysics Data System (ADS)

Goriely, S.; Sida, J.-L.; Lemaître, J.-F.; Panebianco, S.; Dubray, N.; Hilaire, S.; Bauswein, A.; Janka, H.-T.

2013-12-01

Neutron star (NS) merger ejecta offer a viable site for the production of heavy r-process elements with nuclear mass numbers A≳140. The crucial role of fission recycling is responsible for the robustness of this site against many astrophysical uncertainties, but calculations sensitively depend on nuclear physics. In particular, the fission fragment yields determine the creation of 110≲A≲170 nuclei. Here, we apply a new scission-point model, called SPY, to derive the fission fragment distribution (FFD) of all relevant neutron-rich, fissioning nuclei. The model predicts a doubly asymmetric FFD in the abundant A≃278 mass region that is responsible for the final recycling of the fissioning material. Using ejecta conditions based on relativistic NS merger calculations, we show that this specific FFD leads to a production of the A≃165 rare-earth peak that is nicely compatible with the abundance patterns in the Sun and metal-poor stars. This new finding further strengthens the case of NS mergers as possible dominant origin of r nuclei with A≳140.

Condensation of refractory metals in asymptotic giant branch and other stellar environments

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

Schwander, D.; Berg, T.; Schönhense, G.

2014-09-20

The condensation of material from a gas of solar composition has been extensively studied, but less so condensation in the environment of evolved stars, which has been mainly restricted to major compounds and some specific element groups such as the Rare Earth elements. Also of interest, however, are refractory metals like Mo, Ru, Os, W, Ir, and Pt, which may condense to form refractory metal nuggets (RMNs) like the ones that have been found in association with presolar graphite. We have performed calculations describing the condensation of these elements in the outflows of s-process enriched AGB stars as well asmore » from gas enriched in r-process products. While in carbon-rich environments (C > O), the formation of carbides is expected to consume W, Mo, and V (Lodders and Fegley), the condensation sequence for the other refractory metals under these conditions does not significantly differ from the case of a cooling gas of solar composition. The composition in detail, however, is significantly different due to the completely different source composition. Condensation from an r-process enriched source differs less from the solar case. Elemental abundance ratios of the refractory metals can serve as a guide for finding candidate presolar grains among the RMNs in primitive meteorites—most of which have a solar system origin—for confirmation by isotopic analysis. We apply our calculations to the case of the four RMNs found by Croat et al., which may very well be presolar.« less

CLOUDS IN SUPER-EARTH ATMOSPHERES: CHEMICAL EQUILIBRIUM CALCULATIONS

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

Mbarek, Rostom; Kempton, Eliza M.-R., E-mail: mbarekro@grinnell.edu, E-mail: kemptone@grinnell.edu

Recent studies have unequivocally proven the existence of clouds in super-Earth atmospheres. Here we provide a theoretical context for the formation of super-Earth clouds by determining which condensates are likely to form under the assumption of chemical equilibrium. We study super-Earth atmospheres of diverse bulk composition, which are assumed to form by outgassing from a solid core of chondritic material, following Schaefer and Fegley. The super-Earth atmospheres that we study arise from planetary cores made up of individual types of chondritic meteorites. They range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solarmore » and super-solar, thereby spanning a range of atmospheric composition that is appropriate for low-mass exoplanets. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of formation for over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350–3000 K. Clouds should form along the temperature–pressure boundaries where the condensed species appear in our calculation. We find that the composition of condensate clouds depends strongly on both the H:O and C:O ratios. For the super-Earth archetype GJ 1214b, KCl and ZnS are the primary cloud-forming condensates at solar composition, in agreement with previous work. However, for oxidizing atmospheres, K{sub 2}SO{sub 4} and ZnO condensates are favored instead, and for carbon-rich atmospheres with super-solar C:O ratios, graphite clouds appear. For even hotter planets, clouds form from a wide variety of rock-forming and metallic species.« less

Fractionation of families of major, minor, and trace metals across the melt-vapor interface in volcanic exhalations

USGS Publications Warehouse

Hinkley, T.K.; Le Cloarec, M.-F.; Lambert, G.

1994-01-01

Chemical families of metals fractionate systematically as they pass from a silicate melt across the interface with the vapor phase and on into a cooled volcanic plume. We measured three groups of metals in a small suite of samples collected on filters from the plumes of Kilauea (Hawaii, USA), Etna (Sicily), and Merapi (Java) volcanoes. These were the major, minor, and trace metals of the alkali and alkaline earth families (K, Rb, Cs, Ca, Sr, Ba), a group of ordinarily rare metals (Cd, Cu, In, Pb, Tl) that are related by their chalcophile affinities, and the radon daughter nuclides 210Po, 210Bi, and 210Pb. The measurements show the range and some details of systematic melt-vapor fractionation within and between these groups of metals. In the plumes of all three volcanoes, the alkali metals are much more abundant than the alkaline earth metals. In the Kilauea plume, the alkali metals are at least six times more abundant than the alkaline earth metals, relative to abundances in the melt; at Etna, the factor is at least 300. Fractionations within each family are, commonly, also distinctive; in the Kilauea plume, in addition to the whole alkaline earth family being depleted, the heaviest metals of the family (Sr, Ba) are progressively more depleted than the light metal Ca. In plumes of fumaroles at Merapi, K/Cs ratios were approximately three orders of magnitude smaller than found in other earth materials. This may represent the largest observed enrichment of the "light ion lithophile" (LIL) metals. Changes in metal ratios were seen through the time of eruption in the plumes of Kilauea and Etna. This may reflect degree of degassing of volatiles, with which metals complex, from the magma bodies. At Kilauea, the changes in fractionation were seen over about three years; fractionation within the alkaline earth family increased, and that between the two families decreased, over that time. All of the ordinarily rare chalcophile metals measured are extremely abundant in volcanic plumes, and Cd and Tl are enriched relative to the others. Indium is much more abundant in the plume of the hotspot volcano Kilauea than in the Etna plume (probably non-hotspot in character). It may be a useful indicator of the tapping of deep mantle zones, or could aid in the interpretation of reports of Pt group metals in exhalations from hot spot volcanoes. Indium in old glacial ice strata could help assess magnitude and variability of exhalations from hotspot volcanoes in past time. Strong melt-vapor fractionation of the alkali and alkaline earth metals may only be observed in plumes during quiescent degassing of volcanoes; when large amounts of ash or spatter (undifferentiated lava) enter the plume, its alkali and alkaline earth metal composition may approach that of the melt. Ratios among the chalcophile metals may not be much changed by addition of ash, because their concentrations in melt are so small, and masses of them in any plume may remain dominated by transfer across the melt-vapor interface. Radon daughter nuclides give information about state of volcanic activity at time of sampling. The precisely known origins, ultratrace detectability, decay systematics, and wide variations in volatility of these species provide information about residence times, degassing and travel histories, and identities of melt bodies in volcanic systems. ?? 1994.

Creation of high-pinning microstructures in post production YBCO coated conductors

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

Welp, Ulrich; Miller, Dean J.; Kwok, Wai-Kwong

A method comprising irradiating a polycrystalline rare earth metal-alkaline earth metal-transition metal-oxide superconductor layer with protons having an energy of 1 to 6 MeV. The irradiating process produces an irradiated layer that comprises randomly dispersed defects with an average diameter in the range of 1-10 nm.

Toward a Deterministic Model of Planetary Formation. II. The Formation and Retention of Gas Giant Planets around Stars with a Range of Metallicities

NASA Astrophysics Data System (ADS)

Ida, Shigeru; Lin, D. N. C.

2004-11-01

The apparent dependence of detection frequency of extrasolar planets on the metallicity of their host stars is investigated with Monte Carlo simulations using a deterministic core-accretion planet formation model. According to this model, gas giants formed and acquired their mass Mp through planetesimal coagulation followed by the emergence of cores onto which gas is accreted. These protoplanets migrate and attain their asymptotic semimajor axis a through tidal interaction with their nascent disk. Based on the observed properties of protostellar disks, we generate an Mp-a distribution. Our results reproduce the observed lack of planets with intermediate mass Mp=10-100 M⊕ and a<~3 AU and with large mass Mp>~103 M⊕ and a<~0.2 AU. Based on the simulated Mp-a distributions, we also evaluate the metallicity dependence of the fraction of stars harboring planets that are detectable with current radial velocity surveys. If protostellar disks attain the same fraction of heavy elements as contained in their host stars, the detection probability around metal-rich stars would be greatly enhanced because protoplanetary cores formed in them can grow to several Earth masses prior to their depletion. These large masses are required for the cores to initiate rapid gas accretion and to transform into giant planets. The theoretically extrapolated metallicity dependence is consistent with the observations. This correlation does not arise naturally in the gravitational-instability scenario. We also suggest other metallicity dependences of the planet distributions that can be tested by ongoing observations.

The Electronic Structure and Optical Properties of Anatase TiO₂ with Rare Earth Metal Dopants from First-Principles Calculations.

PubMed

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-24

The electronic and optical properties of the rare earth metal atom-doped anatase TiO₂ have been investigated systematically via density functional theory calculations. The results show that TiO₂ doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron-hole recombination. This effect of band change originates from the 4 f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO₂ is tuned by the introduction of impurity atoms.

The Electronic Structure and Optical Properties of Anatase TiO2 with Rare Earth Metal Dopants from First-Principles Calculations

PubMed Central

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-01

The electronic and optical properties of the rare earth metal atom-doped anatase TiO2 have been investigated systematically via density functional theory calculations. The results show that TiO2 doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron–hole recombination. This effect of band change originates from the 4f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO2 is tuned by the introduction of impurity atoms. PMID:29364161

Identification of New Neutron-Rich Isotopes in the Rare-Earth Region Produced by 345 MeV/nucleon 238U

NASA Astrophysics Data System (ADS)

Fukuda, Naoki; Kubo, Toshiyuki; Kameda, Daisuke; Inabe, Naohito; Suzuki, Hiroshi; Shimizu, Yohei; Takeda, Hiroyuki; Kusaka, Kensuke; Yanagisawa, Yoshiyuki; Ohtake, Masao; Tanaka, Kanenobu; Yoshida, Koichi; Sato, Hiromi; Baba, Hidetada; Kurokawa, Meiko; Ohnishi, Tetsuya; Iwasa, Naohito; Chiba, Ayuko; Yamada, Taku; Ideguchi, Eiji; Go, Shintaro; Yokoyama, Rin; Fujii, Toshihiko; Nishibata, Hiroki; Ieki, Kazuo; Murai, Daichi; Momota, Sadao; Nishimura, Daiki; Sato, Yoshiteru; Hwang, Jongwon; Kim, Sunji; Tarasov, Oleg B.; Morrissey, David J.; Simpson, Gary

2018-01-01

A search for new isotopes in the neutron-rich rare-earth region has been carried out using a 345 MeV/nucleon 238U beam at the RIKEN Nishina Center RI Beam Factory. Fragments produced were analyzed and identified using the BigRIPS in-flight separator. We observed a total of 29 new neutron-rich isotopes: 153Ba, 154,155,156La, 156,157,158Ce, 156,157,158,159,160,161Pr, 162,163Nd, 164,165Pm, 166,167Sm, 169Eu, 171Gd, 173,174Tb, 175,176Dy, 177,178Ho, and 179,180Er.

Siderophile Element Partitioning between Cohenite and Liquid in Fe-Ni-S-C System and Implications for Geochemistry of Planetary Cores and Mantles

NASA Astrophysics Data System (ADS)

Buono, A. S.; Dasgupta, R.; Walker, D.

2011-12-01

Secular cooling of terrestrial planets is known to cause crystallization of a solid inner core from metallic liquid core. Fractionation of light and siderophile elements is important during such crystallization for evolution of outer core and possible core-mantle interaction. Thus far studies focused on a pure Fe inner core in simple binary systems but the effects of possible formation of a carbide inner core component on siderophile element partitioning in a multi-component system has yet to be looked at in detail. We investigated the effects of pressure and S content on partition coefficients (D) between cohenite and liquid in the Fe-Ni-S-C system. Multi-anvil experiments were performed at 3 and 6 GPa at 1150 °C, in an Fe-rich mix containing a constant C and Ni to which S contents of 0, 5, and 14 wt.% were added. All the mixes were doped with W, Re, Os, Pt, and Co. Samples were imaged and analyzed for Fe, Ni, S, and C using an EPMA. Fe, Ni, and trace elements were analyzed using a LA-ICP-MS. All the experiments produced cohenite and Fe-Ni-C±S liquid. Compared to solid-Fe/melt Ds [1-2], cohenite/melt Ds are lower for all elements except W. The light element (S+C) content of the liquid is the dominant controlling factor in siderophile element partitioning between cohenite and liquid as it is between crystalline Fe and liquid. In the cohenite-metallic melt experiments, D Ni decreases as S+C increases. Ni is excluded from the crystallizing solid if the solid is cohenite. We also find that in the Fe-Ni-S-C system, cohenite is stabilized to higher P than in the Fe-S-C system [3-5]. Similar to the Fe-metallic liquid systems the non-metal avoidance model [6] is applicable to the Fe3C-metallic liquid system studied here. Our study has implications for both the cores of smaller planets and the mantles of larger planets. If inner core forms a cohenite layer we would predict that depletions in the outer core will be less than they might be for Fe metal crystallization. For the mantle of the earth, which is thought to become Fe-Ni metal-saturated as shallow as 250 km, the sub-system Fe-Ni + C + S becomes relevant and Fe-Ni carbide rather than metallic Fe-Ni alloy may become the crystalline phase of interest. Our study implies that because the partition coefficients between cohenite and Fe-C-S melts are significantly lower than those between Fe-metal and S-rich liquid, in the presence of cohenite and Fe-C-S melt in the mantle, the mantle budget of Ni, Co, and Pt may be dominated by Fe-C-S liquid. W, Re, and Os will also be slightly enriched in C-rich Fe-Ni liquid over cohenite if the metal sub-system of interest is S-free. [1] Chabot et al., GCA 70, 1322-1335, 2006 [2] Chabot et al., GCA 72, 4146-4158, 2008 [3] Chabot et al., Meteorit. Planet. Sci. 42, 1735-1750, 2007 [4] Stewart et al., EPSL 284, 302-309, 2009 [5] Van Orman et al., EPSL 274, 250-257, 2008 [6] Jones, J.H., Malvin, D.J., Metall Mater Trans B 21, 697-706, 1990

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.

Secular distribution of highly metalliferous black shales corresponds with peaks in past atmosphere oxygenation

NASA Astrophysics Data System (ADS)

Johnson, Sean C.; Large, Ross R.; Coveney, Raymond M.; Kelley, Karen D.; Slack, John F.; Steadman, Jeffrey A.; Gregory, Daniel D.; Sack, Patrick J.; Meffre, Sebastien

2017-08-01

Highly metalliferous black shales (HMBS) are enriched in organic carbon and a suite of metals, including Ni, Se, Mo, Ag, Au, Zn, Cu, Pb, V, As, Sb, Se, P, Cr, and U ± PGE, compared to common black shales, and are distributed at particular times through Earth history. They constitute an important future source of metals. HMBS are relatively thin units within thicker packages of regionally extensive, continental margin or intra-continental marine shales that are rich in organic matter and bio-essential trace elements. Accumulation and preservation of black shales, and the metals contained within them, usually require low-oxygen or euxinic bottom waters. However, whole-rock redox proxies, particularly Mo, suggest that HMBS may have formed during periods of elevated atmosphere pO2. This interpretation is supported by high levels of nutrient trace elements within these rocks and secular patterns of Se and Se/Co ratios in sedimentary pyrite through Earth history, with peaks occurring in the middle Paleoproterozoic, Early Cambrian to Early Ordovician, Middle Devonian, Middle to late Carboniferous, Middle Permian, and Middle to Late Cretaceous, all corresponding with time periods of HMBS deposition. This counter-intuitive relationship of strongly anoxic to euxinic, localized seafloor conditions forming under an atmosphere of peak oxygen concentrations is proposed as key to the genesis of HMBS. The secular peaks and shoulders of enriched Se in sedimentary pyrite through time correlate with periods of tectonic plate collision, which resulted in high nutrient supply to the oceans and consequently maximum productivity accompanying severe drawdown into seafloor muds of C, S, P, and nutrient trace metals. The focused burial of C and S over extensive areas of the seafloor, during these anoxic to euxinic periods, likely resulted in an O2 increase in the atmosphere, causing short-lived peaks in pO2 that coincide with the deposition of HMBS. As metals become scarce, particularly Mo, Ni, Se, Ag, and U, the geological times of these narrow HMBS horizons will become a future focus for exploration.

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

Du, Mao -Hua; Singh, David J.; Zhang, Lijun

Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn 2O 3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn 2O 3 andmore » BaSn 2O 3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO 3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn 2O 3) to 3.15 (SrSn 2O 3) eV, and hole effective masses ranging from 0.87 (BaSn 2O 3) to above 6.0 (SrSn 2O 3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.« less

Stability and anisotropy of (FexNi1-x)2O under high pressure and implications in Earth's and super-Earths' core.

PubMed

Huang, Shengxuan; Wu, Xiang; Qin, Shan

2018-01-10

Oxygen is thought to be an important light element in Earth's core but the amount of oxygen in Earth's core remains elusive. In addition, iron-rich iron oxides are of great interest and significance in the field of geoscience and condensed matter physics. Here, static calculations based on density functional theory demonstrate that I4/mmm-Fe 2 O is dynamically and mechanically stable and becomes energetically favorable with respect to the assemblage of hcp-Fe and [Formula: see text]-FeO above 270 GPa, which indicates that I4/mmm-Fe 2 O can be a strong candidate phase for stable iron-rich iron oxides at high pressure, perhaps even at high temperature. The elasticity and anisotropy of I4/mmm-(Fe x Ni 1-x ) 2 O at high pressures are also determined. Based on these results, we have derived the upper limit of oxygen to be 4.3 wt% in Earth's lower outer core. On the other hand, I4/mmm-(Fe x Ni 1-x ) 2 O with high AV S is likely to exist in a super-Earth's or an ocean planet's solid core causing the locally seismic heterogeneity. Our results not only give some clues to explore and synthesize novel iron-rich iron oxides but also shed light on the fundamental information of oxygen in the planetary core.

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.

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Promoting effect of alkaline earth metal doping on catalytic activity of HC and NOx conversion over Pd-only three-way catalyst.

PubMed

Yang, Linyan; Lin, Siyu; Yang, Xue; Fang, Weimin; Zhou, Renxian

2014-08-30

The influence of alkaline earth metal (M=Mg, Ca, Sr and Ba) promoter on the structural/textural properties of Ce0.67Zr0.33O2 (designated as CZ) and the catalytic behavior of its supported Pd-only three-way catalyst (Pd/CZM) have been investigated. The results show that the modification with alkaline earth metal obviously improves the catalytic activity for hydrocarbon (HC) and nitrogen oxides (NOx) conversion, especially the introduction of Ba. Furthermore, the operation window of the promoted catalysts has also been widened. The doping of alkaline earth metal leads to the formation of more homogeneous Ce-Zr-M ternary solid solution with higher surface area and smaller crystallite size, and the corresponding Pd/CZM catalysts present improved reducibility of PdO species. The modification with Ca, Sr and Ba improves the thermal aging resistance, especially Ba. DRIFTS results reveal that the doping of alkaline earth metal enhances the oxygen and electron transfer ability and favors the dissociation of NO, which promotes the activation and storage capacity of the acidic atoms like NOx, and leads to enhanced catalytic activity performance. Copyright © 2014 Elsevier B.V. All rights reserved.

Natural Pyrrhotite as a Catalyst in Prebiotic Chemical Evolution

PubMed Central

López Ibáñez de Aldecoa, Alejandra; Velasco Roldán, Francisco; Menor-Salván, César

2013-01-01

The idea of an autotrophic organism as the first living being on Earth leads to the hypothesis of a protometabolic, complex chemical system. In one of the main hypotheses, the first metabolic systems emerged from the interaction between sulfide minerals and/or soluble iron-sulfide complexes and fluids rich in inorganic precursors, which are reduced and derived from crustal or mantle activity. Within this context, the possible catalytic role of pyrrhotite, one of the most abundant sulfide minerals, in biomimetic redox and carbon fixation reactions was studied. Our results showed that pyrrhotite, under simulated hydrothermal conditions, could catalyze the pyruvate synthesis from lactate and that a dynamic system formed by coupling iron metal and iron-sulfur species in an electrochemical cell could promote carbon fixation from thioacetate esters. PMID:25369819

Optimization of thermoelectric performance of SrSi2-based alloys via the modification in band structure and phonon-point-defect scattering

PubMed Central

Kuo, Yung-Kang; Ramachandran, Balakrishnan; Lue, Chin-Shan

2014-01-01

Thermoelectric properties of alkaline-earth-metal disilicides are strongly dependent on their electronic band structure in the vicinity of the Fermi level. In particular, the strontium disilicide, SrSi2 with a narrow band gap of about few tens of meV is composed of non-toxic, naturally abundant elements, and its thermoelectric properties are very sensitive to the substitution/alloying with third elements. In this article, we summarize the thermoelectric performance of substituted and Sr-deficient/Sr-rich SrSi2 alloys to realize the high thermoelectric figure-of-merit (ZT) for practical applications in the electronic and thermoelectric aspects, and also to explore the alternative routes to further improve its ZT value. PMID:25505784

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.

Structural stability of super duplex stainless weld metals and its dependence on tungsten and copper

NASA Astrophysics Data System (ADS)

Nilsson, J.-O.; Huhtala, T.; Jonsson, P.; Karlsson, L.; Wilson, A.

1996-08-01

Three different superduplex stainless weld metals have been produced using manual metal arc welding under identical welding conditions. The concentration of the alloying elements tungsten and copper corresponded to the concentrations in commercial superduplex stainless steels (SDSS). Aging experiments in the temperature range 700 °C to 1110 °C showed that the formation of intermetallic phase was enhanced in tungsten-rich weld metal and also dissolved at higher temperatures compared with tungsten-poor and tungsten-free weld metals. It could be inferred from time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams produced in the present investigation that the critical cooling rate to avoid 1 wt pct of intermetallic phase was 2 times faster for tungsten-rich weld metal. Microanalysis in combination with thermodynamic calculations showed that tungsten was accommodated in χ phase, thereby decreasing the free energy. Experimental evidence supports the view that the formation of intermetallic phase is enhanced in tungsten-rich weld metal, owing to easier nucleation of nonequilibrium χ phase compared with σ phase. The formation of secondary austenite (γ2) during welding was modeled using the thermodynamic computer program Thermo-Calc. Satisfactory agreement between theory and practice was obtained. Thermo-Calc was capable of predicting observed lower concentrations of chromium and nitrogen in γ2 compared with primary austenite. The volume fraction of γ2 was found to be significantly higher in tungsten-rich and tungsten + copper containing weld metal. The results could be explained by a higher driving force for precipitation of γ2 in these.

Metal-rich fluid inclusions provide new insights into unconformity-related U deposits (Athabasca Basin and Basement, Canada)

NASA Astrophysics Data System (ADS)

Richard, Antonin; Cathelineau, Michel; Boiron, Marie-Christine; Mercadier, Julien; Banks, David A.; Cuney, Michel

2016-02-01

The Paleoproterozoic Athabasca Basin (Canada) hosts numerous giant unconformity-related uranium deposits. The scope of this study is to establish the pressure, temperature, and composition (P-T-X conditions) of the brines that circulated at the base of the Athabasca Basin and in its crystalline basement before, during and after UO2 deposition. These brines are commonly sampled as fluid inclusions in quartz- and dolomite-cementing veins and breccias associated with alteration and U mineralization. Microthermometry and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data from five deposits (Rabbit Lake, P-Patch, Eagle Point, Millennium, and Shea Creek) complement previously published data for the McArthur River deposit. In all of the deposits investigated, fluid inclusion salinity is between 25 and 40 wt.% NaCl equiv., with compositions displaying a continuum between a "NaCl-rich brine" end-member (Cl > Na > Ca > Mg > K) and a "CaCl2-rich brine" end-member (Cl > Ca ≈ Mg > Na > K). The CaCl2-rich brine has the highest salinity and shows evidence for halite saturation at the time of trapping. The continuum of compositions between the NaCl-rich brine and the CaCl2-rich brine end-members combined with P-T reconstructions suggest anisothermal mixing of the two brines (NaCl-rich brine, 180 ± 30 °C and 800 ± 400 bars; CaCl2-rich brine, 120 ± 30 °C and 600 ± 300 bars) that occurred under fluctuating pressure conditions (hydrostatic to supra-hydrostatic). However, because the two brines were U bearing and therefore oxidized, brine mixing was probably not the driving force for UO2 deposition. Several scenarios are put forward to account for the Cl-Na-Ca-Mg-K composition of the brines, involving combinations of seawater evaporation, halite dissolution, mixing with a halite-dissolution brine, Mg/Ca exchange by dolomitization, Na/Ca exchange by albitization of plagioclase, Na/K exchange by albitization of K-feldspar, and Mg loss by Mg-rich alteration. Finally, the metal concentrations in the NaCl-rich and CaCl2-rich brines are among the highest recorded compared to present-day sedimentary formation waters and fluid inclusions from basin-hosted base metal deposits (up to 600 ppm U, 3000 ppm Mn, 4000 ppm Zn, 6000 ppm Cu, 8000 ppm Pb, and 10,000 ppm Fe). The CaCl2-rich brine carries up to one order of magnitude more metal than the NaCl-rich brine. Though the exact origin of major cations and metals of the two brines remains uncertain, their contrasting compositions indicate that the two brines had distinct flow paths and fluid-rock interactions. Large-scale circulation of the brines in the Athabasca Basin and Basement was therefore a key parameter for metal mobility (including U) and formation of unconformity-related U deposits.

Direct synthesis of calcium borohydride

DOEpatents

Ronnebro, Ewa Carin Ellinor [Dublin, CA; Majzoub, Eric H [Pleasanton, CA

2009-10-27

A method is disclosed for directly preparing an alkaline earth metal borohydride, i.e. Ca(BH.sub.4).sub.2, from the alkaline earth metal hydride and the alkaline earth metal boride. The borohydride thus prepared is doped with a small portion of a metal chloride catalyst compound, such as RuCl.sub.3, TiCl.sub.3, or a mixture of TiCl.sub.3 and palladium metal. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen at about 70 MPa while heating the mixture to about 400.degree. C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.

Thermophysical properties of liquid rare earth metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Patel, H. P.; Jani, A. R.

2013-06-01

The thermodynamical properties like long wavelength limit S(0), iso-thermal compressibility (χT), thermal expansion coefficient (αV), thermal pressure coefficient (γV), specific heat at constant volume (CV) and specific heat at constant pressure (CP) are calculated for liquid rare earth metals. Our newly constructed parameter free model potential is used to describe the electron ion interaction due to Sarkar et al (S) local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermophysical properties of liquid rare earth metals.

CONTROL ROD FOR A NUCLEAR REACTOR AND METHOD OF PREPARATION

DOEpatents

Hausner, H.H.

1958-12-30

BS>An improved control rod is presented for a nuclear reactor. This control rod is comprised of a rare earth metal oxide or rare earth metal carbide such as gadolinium oxide or gadolinium carbide, uniformly distributed in a metal matrix having a low cross sectional area of absorption for thermal neutrons, such as aluminum, beryllium, and zirconium.

Formation of Apollo 16 impactites and the composition of late accreted material: Constraints from Os isotopes, highly siderophile elements and sulfur abundances

NASA Astrophysics Data System (ADS)

Gleißner, Philipp; Becker, Harry

2017-03-01

Fe-Ni metal-schreibersite-troilite intergrowths in Apollo 16 impact melt rocks and new highly siderophile element (HSE) and S abundance data indicate that millimeter-scale closed-system fractional crystallization processes during cooling of impactor-derived metal melt droplets in impact-melts are the main reason for compositional variations and strong differences in abundances and ratios of HSE in multiple aliquots from Apollo 16 impact melt rocks. Element ratios obtained from linear regression of such data are therefore prone to error, but weighted averages take into account full element budgets in the samples and thus represent a more accurate estimate of their impactor contributions. Modeling of solid metal-liquid metal partitioning in the Fe-Ni-S-P system and HSE patterns in impactites from different landing sites suggest that bulk compositions of ancient lunar impactites should be representative of impact melt compositions and that large-scale fractionation of the HSE by in situ segregation of solid metal or sulfide liquid in impact melt sheets most likely did not occur. The compositional record of lunar impactites indicates accretion of variable amounts of chondritic and non-chondritic impactor material and the mixing of these components during remelting of earlier ejecta deposits. The non-chondritic composition appears most prominently in some Apollo 16 impactites and is characterized by suprachondritic HSE/Ir ratios which increase from refractory to moderately volatile HSE and exhibit a characteristic enrichment of Ru relative to Pt. Large-scale fractional crystallization of solid metal from sulfur and phosphorous rich metallic melt with high P/S in planetesimal or embryo cores is currently the most likely process that may have produced these compositions. Similar materials or processes may have contributed to the HSE signature of the bulk silicate Earth (BSE).

Synthesis, structure, and catalytic activity of novel trinuclear rare-earth metal amido complexes incorporating μ-η5:η1 bonding indolyl and μ3-oxo groups.

PubMed

Yang, Song; Zhu, Xiancui; Zhou, Shuangliu; Wang, Shaowu; Feng, Zhijun; Wei, Yun; Miao, Hui; Guo, Liping; Wang, Fenhua; Zhang, Guangchao; Gu, Xiaoxia; Mu, Xiaolong

2014-02-14

The reactions of different pyrrolyl-functionalized indoles with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) produced different kinds of rare-earth metal amido complexes. Reactions of N-((1H-pyrrol-2-yl)methylene)-2-(1H-indol-3-yl)ethanamine with rare-earth metal amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) in toluene or THF at temperatures of 75-80 °C afforded the novel trinuclear rare-earth metal amido complexes incorporating the indolyl ligand in μ-η(5):η(1) bonding modes and a μ3-O group, which is believed to originate from cleavage of the THF ring based on experimental results. Reactions of 2-(1H-indol-3-yl)-N-((1-methyl-1H-pyrrol-2-yl)methylene)ethanamine with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Dy) produced mononuclear ytterbium and dysprosium amides having the indolyl ligand in an η(1) bonding fashion. The results indicate that substituents not only have an influence on reactivity, but also have an influence on the bonding of the indolyl ligands with metals. The catalytic activities of the novel lanthanide amido complexes for the hydrophosphonylation of both aromatic and aliphatic aldehydes and ketones were explored. The results indicate that these complexes display a high catalytic activity for the C-P bond formation under mild conditions when using low catalyst loadings (0.1 mol% for aldehydes and ketones). Thus, it provides a potential way to prepare α-hydroxy phosphonates.

Aerodynamic Levitation Reactor Studies of Fluorine Reactions with Refractory Ceramics

DTIC Science & Technology

1981-05-01

Melting Points of Rare-Earth Metals and Rare-Earth Trifluorides . 14 3. Aerodynamic Lavitation Flow Reactor. 15 4 Lanthanutm-Boron-Carbon Ternary Phase...the least volatile fluorides (CaF , SrT and rare-earth trifluorides ) would yield a 10% increase in w* (initially O.O cam) in about 1 hour at 1300K...measurement, and are, therefore, somewhat uncertain. The melting points of the rare-earth metals and their trifluorides are illustrated in Fig. 2. The melting

Composition of the low seismic velocity E' layer at the top of Earth's core

NASA Astrophysics Data System (ADS)

Badro, J.; Brodholt, J. P.

2017-12-01

Evidence for a layer (E') at the top of the outer core has been available since the '90s and while different studies suggest slightly different velocity contrasts and thicknesses, the common observation is that the layer has lower velocities than the bulk outer core (PREM). Although there are no direct measurements on the density of this layer, dynamic stability requires it to be less dense than the bulk outer core under those same pressure and temperature conditions. Using ab initio simulations on Fe-Ni-S-C-O-Si liquids we constrain the origin and composition of the low-velocity layer E' at the top of Earth's outer core. We find that increasing the concentration of any light-element always increases velocity and so a low-velocity and low-density layer (for stability) cannot be made by simply increasing light element concentration. This rules out barodiffusion or upwards sedimentation of a light phase for its origin. However, exchanging elements can—depending on the elements exchanged—produce such a layer. We evaluate three possibilities. Firstly, crystallization of a light phase from a core containing more than one light element may make such a layer, but only if the crystalizing phase is very Fe-rich, which is at odds with available phase diagrams at CMB conditions. Secondly, the E' layer may result from incomplete mixing of an early Earth core with a late impactor, depending on the light element compositions of the impactor and Earth's core, but such a primordial stratification is neither supported by dynamical models of the core nor thermodynamic models of core merger after the giant impact. The last and most plausible scenario is core-mantle chemical interaction; using thermodynamic models for metal-silicate partitioning of silicon and oxygen at CMB conditions, we show that a reaction between the core and an FeO-rich basal magma ocean can enrich the core in oxygen while depleting it in silicon, in relative amounts that produce a light and slow layer consistent with seismological observations.

Combinatorial study of Ni-Ti-Pt ternary metal gate electrodes on HfO{sub 2} for the advanced gate stack

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

Chang, K.-S.; Green, M. L.; Suehle, J.

2006-10-02

The authors have fabricated combinatorial Ni-Ti-Pt ternary metal gate thin film libraries on HfO{sub 2} using magnetron co-sputtering to investigate flatband voltage shift ({delta}V{sub fb}), work function ({phi}{sub m}), and leakage current density (J{sub L}) variations. A more negative {delta}V{sub fb} is observed close to the Ti-rich corner than at the Ni- and Pt-rich corners, implying smaller {phi}{sub m} near the Ti-rich corners and higher {phi}{sub m} near the Ni- and Pt-rich corners. In addition, measured J{sub L} values can be explained consistently with the observed {phi}{sub m} variations. Combinatorial methodologies prove to be useful in surveying the large compositionalmore » space of ternary alloy metal gate electrode systems.« less

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

Wang Qiushi; Peng, Eric W.; Blakeslee, John P.

We study the azimuthal distribution of globular clusters (GCs) in early-type galaxies and compare them to their host galaxies using data from the ACS Virgo Cluster Survey. We find that in host galaxies with visible elongation ({epsilon} > 0.2) and intermediate to high luminosities (M{sub z} < -19), the GCs are preferentially aligned along the major axis of the stellar light. The red (metal-rich) GC subpopulations show strong alignment with the major axis of the host galaxy, which supports the notion that these GCs are associated with metal-rich field stars. The metal-rich GCs in lenticular galaxies show signs of beingmore » more strongly associated with disks rather than bulges. Surprisingly, we also find that the blue (metal-poor) GCs can also show the same correlation. If the metal-poor GCs are part of the early formation of the halo and built up through mergers, then our results support a picture where halo formation and merging occur anisotropically, and that the present-day major axis is an indicator of the preferred merging axis.« less

Method and system for the combination of non-thermal plasma and metal/metal oxide doped .gamma.-alumina catalysts for diesel engine exhaust aftertreatment system

DOEpatents

Aardahl, Christopher L [Richland, WA; Balmer-Miller, Mari Lou [West Richland, WA; Chanda, Ashok [Peoria, IL; Habeger, Craig F [West Richland, WA; Koshkarian, Kent A [Peoria, IL; Park, Paul W [Peoria, IL

2006-07-25

The present disclosure pertains to a system and method for treatment of oxygen rich exhaust and more specifically to a method and system that combines non-thermal plasma with a metal doped .gamma.-alumina catalyst. Current catalyst systems for the treatment of oxygen rich exhaust are capable of achieving only approximately 7 to 12% NO.sub.x reduction as a passive system and only 25 40% reduction when a supplemental hydrocarbon reductant is injected into the exhaust stream. It has been found that treatment of an oxygen rich exhaust initially with a non-thermal plasma and followed by subsequent treatment with a metal doped .gamma.-alumina prepared by the sol gel method is capable of increasing the NO.sub.x reduction to a level of approximately 90% in the absence of SO.sub.2 and 80% in the presence of 20 ppm of SO.sub.2. Especially useful metals have been found to be indium, gallium, and tin.

Asymmetric Catalysis with bis(hydroxyphenyl)diamides/rare-earth metal complexes.

PubMed

Kumagai, Naoya; Shibasaki, Masakatsu

2013-01-02

A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare-earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

We present gallium concentration (normalized to CI chondrites) in the mantle is at the same level as that of lithophile elements with similar volatility, implying that there must be little to no gallium in Earth's core. Metal-silicate partitioning experiments, however, have shown that gallium is a moderately siderophile element and should be therefore depleted in the mantle by core formation. Moreover, gallium concentrations in the mantle (4 ppm) are too high to be only brought by the late veneer; and neither pressure, nor temperature, nor silicate composition has a large enough effect on gallium partitioning to make it lithophile. Wemore » therefore systematically investigated the effect of core composition (light element content) on the partitioning of gallium by carrying out metal–silicate partitioning experiments in a piston–cylinder press at 2 GPa between 1673 K and 2073 K. Four light elements (Si, O, S, C) were considered, and their effect was found to be sufficiently strong to make gallium lithophile. The partitioning of gallium was then modeled and parameterized as a function of pressure, temperature, redox and core composition. A continuous core formation model was used to track the evolution of gallium partitioning during core formation, for various magma ocean depths, geotherms, core light element contents, and magma ocean composition (redox) during accretion. The only model for which the final gallium concentration in the silicate Earth matched the observed value is the one involving a light-element rich core equilibrating in a FeO-rich deep magma ocean (>1300 km) with a final pressure of at least 50 GPa. More specifically, the incorporation of S and C in the core provided successful models only for concentrations that lie far beyond their allowable cosmochemical or geophysical limits, whereas realistic O and Si amounts (less than 5 wt.%) in the core provided successful models for magma oceans deeper that 1300 km. In conclusion, these results offer a strong argument for an O- and Si-rich core, formed in a deep terrestrial magma ocean, along with oxidizing conditions.« less

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

Phelps, Tommy Joe; Moon, Ji Won; Roh, Yul

The behavior of metal ions leaching and precipitated mineral phases of metal-rich fly ash (FA) was examined in order to evaluate microbial impacts on carbon sequestration and metal immobilization. The leaching solutions consisted of aerobic deionized water (DW) and artificial eutrophic water (AEW) that was anaerobic, organic- and mineral-rich, and higher salinity as is typical of bottom water in eutrophic algae ponds. The Fe- and Ca-rich FAs were predominantly composed of quartz, mullite, portlandite, calcite, hannebachite, maghemite, and hematite. After 86 days, only Fe and Ca contents exhibited a decrease in leaching solutions while other major and trace elements showedmore » increasing or steady trends in preference to the type of FA and leaching solution. Ca-rich FA showed strong carbon sequestration efficiency ranging up to 32.3 g CO(2)/kg FA after 86 days, corresponding to almost 65% of biotic carbon sequestration potential under some conditions. Variations in the properties of FAs such as chemical compositions, mineral constituents as well as the type of leaching solution impacted CO(2) capture. Even though the relative amount of calcite increased sixfold in the AEW and the relative amount of mineral phase reached 37.3 wt% using Ca-rich FA for 86 days, chemical sequestration did not accomplish simultaneous precipitation and sequestration of several heavy metals.« less

Method for the preparation of metal colloids in inverse micelles and product preferred by the method

DOEpatents

Wilcoxon, Jess P.

1992-01-01

A method is provided for preparing catalytic elemental metal colloidal particles (e.g. gold, palladium, silver, rhodium, iridium, nickel, iron, platinum, molybdenum) or colloidal alloy particles (silver/iridium or platinum/gold). A homogeneous inverse micelle solution of a metal salt is first formed in a metal-salt solvent comprised of a surfactant (e.g. a nonionic or cationic surfactant) and an organic solvent. The size and number of inverse micelles is controlled by the proportions of the surfactant and the solvent. Then, the metal salt is reduced (by chemical reduction or by a pulsed or continuous wave UV laser) to colloidal particles of elemental metal. After their formation, the colloidal metal particles can be stabilized by reaction with materials that permanently add surface stabilizing groups to the surface of the colloidal metal particles. The sizes of the colloidal elemental metal particles and their size distribution is determined by the size and number of the inverse micelles. A second salt can be added with further reduction to form the colloidal alloy particles. After the colloidal elemental metal particles are formed, the homogeneous solution distributes to two phases, one phase rich in colloidal elemental metal particles and the other phase rich in surfactant. The colloidal elemental metal particles from one phase can be dried to form a powder useful as a catalyst. Surfactant can be recovered and recycled from the phase rich in surfactant.

Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

1992-01-01

Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

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

Dayal, Pratika; Cockell, Charles; Rice, Ken

The field of astrobiology has made huge strides in understanding the habitable zones around stars (stellar habitable zones) where life can begin, sustain its existence and evolve into complex forms. A few studies have extended this idea by modeling galactic-scale habitable zones (galactic habitable zones) for our Milky Way (MW) and specific elliptical galaxies. However, estimating the habitability for galaxies spanning a wide range of physical properties has so far remained an outstanding issue. Here, we present a “cosmobiological” framework that allows us to sift through the entire galaxy population in the local universe and answer the question, “Which typemore » of galaxy is most likely to host complex life in the cosmos?” Interestingly, the three key astrophysical criteria governing habitability (total mass in stars, total metal mass and ongoing star formation rate) are found to be intricately linked through the “fundamental metallicity relation” as shown by Sloan Digital Sky Survey observations of more than a hundred thousand galaxies in the local universe. Using this relation we show that metal-rich, shapeless giant elliptical galaxies at least twice as massive as the MW (with a tenth of its star formation rate) can potentially host ten thousand times as many habitable (Earth-like) planets, making them the most probable “cradles of life” in the universe.« less

Tempo of magma degassing and the genesis of porphyry copper deposits.

PubMed

Chelle-Michou, Cyril; Rottier, Bertrand; Caricchi, Luca; Simpson, Guy

2017-01-12

Porphyry deposits are copper-rich orebodies formed by precipitation of metal sulphides from hydrothermal fluids released from magmatic intrusions that cooled at depth within the Earth's crust. Finding new porphyry deposits is essential because they are our largest source of copper and they also contain other strategic metals including gold and molybdenum. However, the discovery of giant porphyry deposits is hindered by a lack of understanding of the factors governing their size. Here, we use thermal modelling and statistical simulations to quantify the tempo and the chemistry of fluids released from cooling magmatic systems. We confirm that typical arc magmas produce fluids similar in composition to those that form porphyry deposits and conclude that the volume and duration of magmatic activity exert a first order control on the endowment (total mass of deposited copper) of economic porphyry copper deposits. Therefore, initial magma enrichment in copper and sulphur, although adding to the metallogenic potential, is not necessary to form a giant deposit. Our results link the respective durations of magmatic and hydrothermal activity from well-known large to supergiant deposits to their metal endowment. This novel approach can readily be implemented as an additional exploration tool that can help assess the economic potential of magmatic-hydrothermal systems.

A metallicity recipe for rocky planets

NASA Astrophysics Data System (ADS)

Dawson, Rebekah I.; Chiang, Eugene; Lee, Eve J.

2015-10-01

Planets with sizes between those of Earth and Neptune divide into two populations: purely rocky bodies whose atmospheres contribute negligibly to their sizes, and larger gas-enveloped planets possessing voluminous and optically thick atmospheres. We show that whether a planet forms rocky or gas-enveloped depends on the solid surface density of its parent disc. Assembly times for rocky cores are sensitive to disc solid surface density. Lower surface densities spawn smaller planetary embryos; to assemble a core of given mass, smaller embryos require more mergers between bodies farther apart and therefore exponentially longer formation times. Gas accretion simulations yield a rule of thumb that a rocky core must be at least 2M⊕ before it can acquire a volumetrically significant atmosphere from its parent nebula. In discs of low solid surface density, cores of such mass appear only after the gas disc has dissipated, and so remain purely rocky. Higher surface density discs breed massive cores more quickly, within the gas disc lifetime, and so produce gas-enveloped planets. We test model predictions against observations, using planet radius as an observational proxy for gas-to-rock content and host star metallicity as a proxy for disc solid surface density. Theory can explain the observation that metal-rich stars host predominantly gas-enveloped planets.

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

NASA Astrophysics Data System (ADS)

Elderfield, H.; Hawkesworth, C. J.; Greaves, M. J.; Calvert, S. E.

1981-04-01

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. 143Nd /144Nd ratios in the nodules (˜0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.

Thermodynamic Considerations of Direct Oxygen Removal from Titanium by Utilizing the Deoxidation Capability of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Okabe, Toru H.; Zheng, Chenyi; Taninouchi, Yu-ki

2018-06-01

Oxygen removal from metallic Ti is extremely difficult and, currently, there is no commercial process for effectively deoxidizing Ti or its alloys. The oxygen concentration in Ti scraps is normally higher than that in virgin metals such as in Ti sponges produced by the Kroll process. When scraps are remelted with virgin metals for producing primary ingots of Ti or its alloys, the amount of scrap that can be used is limited owing to the accumulation of oxygen impurities. Future demands of an increase in Ti production and of mitigating environmental impacts require that the amount of scrap recycled as a feed material of Ti ingots should also increase. Therefore, it is important to develop methods for removing oxygen directly from Ti scraps. In this study, we evaluated the deoxidation limit for β-Ti using Y or light rare earth metals (La, Ce, Pr, or Nd) as a deoxidant. Thermodynamic considerations suggest that extra-low-oxygen Ti, with an oxygen concentration of 100 mass ppm or less can be obtained using a molten salt equilibrating with rare earth metals. The results presented herein also indicate that methods based on molten salt electrolysis for producing rare earth metals can be utilized for effectively and directly deoxidizing Ti scraps.

Comprehensive process for the recovery of value and critical materials from electronic waste

DOE PAGES

Diaz, Luis A.; Lister, Tedd E.; Parkman, Jacob A.; ...

2016-04-08

The development of technologies that contribute to the proper disposal and treatment of electronic waste is not just an environmental need, but an opportunity for the recovery and recycle of valuable metals and critical materials. Value elements in electronic waste include gold, palladium, silver, copper, nickel, and rare earth elements (RE). Here, we present the development of a process that enables efficient recycling of metals from scrap mobile electronics. An electro recycling (ER) process, based on the regeneration of Fe 3+ as a weak oxidizer, is studied for the selective recovery of base metals while leaving precious metals for separatemore » extraction at reduced chemical demand. A separate process recovers rare earth oxides from magnets in electronics. Furthermore, recovery and extraction efficiencies ca. 90 % were obtained for the extraction of base metals from the non-ferromagnetic fraction in the two different solution matrices tested (H 2SO 4, and HCl). The effect of the pre-extraction of base metals in the increase of precious metals extraction efficiency was verified. On the other hand, the extraction of rare earths from the ferromagnetic fraction, performed by means of anaerobic extraction in acid media, was assessed for the selective recovery of rare earths. We developed a comprehensive flow sheet to process electronic waste to value products.« less

Individual metal-bearing particles in a regional haze caused by firecracker and firework emissions.

PubMed

Li, Weijun; Shi, Zongbo; Yan, Chao; Yang, Lingxiao; Dong, Can; Wang, Wenxing

2013-01-15

Intensive firecracker/firework displays during Chinese New Year (CNY) release fine particles and gaseous pollutants into the atmosphere, which may lead to serious air pollution. We monitored ambient PM(2.5) and black carbon (BC) concentrations at a regional background site in the Yellow River Delta region during the CNY in 2011. Our monitoring data and MOUDI images showed that there was a haze event during the CNY. Daily average PM(2.5) concentration reached 183 μg m(-3) during the CNY, which was six times higher than that before and after the CNY. Similarly, the black carbon (BC) concentrations were elevated during the CNY. In order to confirm whether the firecracker/firework related emission is the main source of the haze particles, we further analyzed the morphology and chemical composition of individual airborne particles collected before, during and after the CNY by using transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy (TEM/EDS). We found that sulfate and organic-rich particles were dominant in the atmosphere before and after the CNY. In contrast, K-rich sulfates and other metal (e.g., Ba-rich, Al-rich, Mg-rich, and Fe-rich) particles were much more abundant than ammoniated sulfate particles during the CNY. These data suggest that it was the aerosol particles from the firecracker/firework emissions that induced the regional haze episode during the CNY. In individual organic and K-rich particles, we often found more than two types of nano-metal particles. These metal-bearing particles also contained abundant S but not Cl. In contrast, fresh metal-bearing particles from firecrackers generated in the laboratory contained abundant Cl with minor amounts of S. This indicates that the firecracker/firework emissions during the CNY significantly changed the atmospheric transformation pathway of SO(2) to sulfate. Copyright © 2012 Elsevier B.V. All rights reserved.

Board on Earth Sciences and Resources and its Activities

NASA Technical Reports Server (NTRS)

Schiffries, Craig M.

1997-01-01

The Board will provide oversight of the earth science and resource activities within the National Research Council, provide a review of research and public activities in the solid-earth sciences, and provide analyses and recommendations relevant to the supply, delivery, and associated impacts of and issues related to hydrocarbon, metallic, and non-metallic mineral resources. The Board will monitor the status of the earth sciences, assess the health of the disciplines, and identify research opportunities, and will respond to specific agency requests.

Did Life Emerge in Thermo-Acidic Conditions?

NASA Astrophysics Data System (ADS)

Holmes, D. S.

2017-12-01

There is widespread, but not unanimous, agreement that life emerged in hot conditions by exploiting redox and pH disequilibria found on early earth. Although there are several hypotheses to explain the postulated pH disequilibria, few of these consider that life evolved at very low pH (<4). Such environments are thought to be hostile to life and certainly a poor area to search for clues for the abiotic to biotic transition and the early evolution of energetic pathways. However, low pH environments offer some remarkable opportunities for early biological evolution. This presentation will evaluate the pros and cons of the hypothesis that the early evolution of life occurred in thermo-acidic conditions. Such environments are thought to have been abundant on early earth and were probably rich in hydrogen and soluble metals including iron and sulfur that could have served as sources and sinks of electrons. Extant thermo-acidophiles thrive in such conditions. Low pH environments are rich in protons that are the major drivers of energy conservation by coupling to phosphorylation in virtually all organisms on earth; this may be a "biochemical fossil" reflecting the use of protons (low pH) in primitive energy conservation. It has also been proposed that acidic conditions favored the evolution of an RNA world with expanded catalytic activities. On the other hand, the idea that life emerged in thermo-acidic conditions can be challenged because of the proposed difficulties of folding and stabilizing proteins simultaneously exposed to high temperature and low pH. In addition, although thermo-acidophiles root to the base of the phylogenetic tree of life, consistent with the proposition that they evolved early, yet there are problems of interpretation of their subsequent evolution that cloud this simplistic phylogenetic view. We propose solutions to these problems and hypothesize that life evolved in thermo-acidic conditions.

THE OPTICAL COLORS OF GIANT ELLIPTICAL GALAXIES AND THEIR METAL-RICH GLOBULAR CLUSTERS INDICATE A BOTTOM-HEAVY INITIAL MASS FUNCTION

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

Goudfrooij, Paul; Diederik Kruijssen, J. M., E-mail: goudfroo@stsci.edu, E-mail: kruijssen@mpa-garching.mpg.de

2013-01-10

We report a systematic and statistically significant offset between the optical (g - z or B - I) colors of seven massive elliptical galaxies and the mean colors of their associated massive metal-rich globular clusters (GCs) in the sense that the parent galaxies are redder by {approx}0.12-0.20 mag at a given galactocentric distance. However, spectroscopic indices in the blue indicate that the luminosity-weighted ages and metallicities of such galaxies are equal to that of their averaged massive metal-rich GCs at a given galactocentric distance, to within small uncertainties. The observed color differences between the red GC systems and their parentmore » galaxies cannot be explained by the presence of multiple stellar generations in massive metal-rich GCs, as the impact of the latter to the populations' integrated g - z or B - I colors is found to be negligible. However, we show that this paradox can be explained if the stellar initial mass function (IMF) in these massive elliptical galaxies was significantly steeper at subsolar masses than canonical IMFs derived from star counts in the solar neighborhood, with the GC colors having become bluer due to dynamical evolution, causing a significant flattening of the stellar MF of the average surviving GC.« less

Soil fertility and plant diversity enhance microbial performance in metal-polluted soils.

PubMed

Stefanowicz, Anna M; Kapusta, Paweł; Szarek-Łukaszewska, Grażyna; Grodzińska, Krystyna; Niklińska, Maria; Vogt, Rolf D

2012-11-15

This study examined the effects of soil physicochemical properties (including heavy metal pollution) and vegetation parameters on soil basal respiration, microbial biomass, and the activity and functional richness of culturable soil bacteria and fungi. In a zinc and lead mining area (S Poland), 49 sites were selected to represent all common plant communities and comprise the area's diverse soil types. Numerous variables describing habitat properties were reduced by PCA to 7 independent factors, mainly representing subsoil type (metal-rich mining waste vs. sand), soil fertility (exchangeable Ca, Mg and K, total C and N, organic C), plant species richness, phosphorus content, water-soluble heavy metals (Zn, Cd and Pb), clay content and plant functional diversity (based on graminoids, legumes and non-leguminous forbs). Multiple regression analysis including these factors explained much of the variation in most microbial parameters; in the case of microbial respiration and biomass, it was 86% and 71%, respectively. The activity of soil microbes was positively affected mainly by soil fertility and, apparently, by the presence of mining waste in the subsoil. The mining waste contained vast amounts of trace metals (total Zn, Cd and Pb), but it promoted microbial performance due to its inherently high content of macronutrients (total Ca, Mg, K and C). Plant species richness had a relatively strong positive effect on all microbial parameters, except for the fungal component. In contrast, plant functional diversity was practically negligible in its effect on microbes. Other explanatory variables had only a minor positive effect (clay content) or no significant influence (phosphorus content) on microbial communities. The main conclusion from this study is that high nutrient availability and plant species richness positively affected the soil microbes and that this apparently counteracted the toxic effects of metal contamination. Copyright © 2012 Elsevier B.V. All rights reserved.

Variable Stars In the Unusual, Metal-Rich Globular Cluster

NASA Technical Reports Server (NTRS)

Pritzl, Barton J.; Smith, Horace A.; Catelan, Marcio; Sweigart, Allen V.; Oegerle, William R. (Technical Monitor)

2002-01-01

We have undertaken a search for variable stars in the metal-rich globular cluster NGC 6388 using time-series BV photometry. Twenty-eight new variables were found in this survey, increasing the total number of variables found near NGC 6388 to approx. 57. A significant number of the variables are RR Lyrae (approx. 14), most of which are probable cluster members. The periods of the fundamental mode RR Lyrae are shown to be unusually long compared to metal-rich field stars. The existence of these long period RRab stars suggests that the horizontal branch of NGC 6388 is unusually bright. This implies that the metallicity-luminosity relationship for RR Lyrae stars is not universal if the RR Lyrae in NGC 6388 are indeed metal-rich. We consider the alternative possibility that the stars in NGC 6388 may span a range in [Fe/H]. Four candidate Population II Cepheids were also found. If they are members of the cluster, NGC 6388 would be the most metal-rich globular cluster to contain Population II Cepheids. The mean V magnitude of the RR Lyrae is found to be 16.85 +/- 0.05 resulting in a distance of 9.0 to 10.3 kpc, for a range of assumed values of (M(sub V)) for RR Lyrae. We determine the reddening of the cluster to be E(B - V) = 0.40 +/- 0.03 mag, with differential reddening across the face of the cluster. We discuss the difficulty in determining the Oosterhoff classification of NGC 6388 and NGC 6441 due to the unusual nature of their RR Lyrae, and address evolutionary constraints on a recent suggestion that they are of Oosterhoff type II.

Pal 12 - A metal-rich globular cluster in the outer halo

NASA Technical Reports Server (NTRS)

Cohen, J. G.; Frogel, J. A.; Persson, S. E.; Zinn, R.

1980-01-01

New optical and infrared observations of several stars in the distant globular cluster Pal 12 show that they have CO strengths and heavy element abundances only slightly less than in M 71, one of the more metal-rich globular clusters. Pal 12 thus has a metal abundance near the high end of the range over which globular clusters exist and lies in the outer galactic halo. Its red horizontal branch is not anomalous in view of the abundance that has been found.

Alaska's rare earth deposits and resource potential

USGS Publications Warehouse

Barker, James C.; Van Gosen, Bradley S.

2012-01-01

Alaska’s known mineral endowment includes some of the largest and highest grade deposits of various metals, including gold, copper and zinc. Recently, Alaska has also been active in the worldwide search for sources of rare earth elements (REE) to replace exports now being limitedby China. Driven by limited supply of the rare earths, combined with their increasing use in new ‘green’ energy, lighting, transportation, and many other technological applications, the rare earth metals neodymium, europium and, in particular, the heavy rare earth elements terbium, dysprosium and yttrium are forecast to soon be in critical short supply (U.S. Department of Energy, 2010).

Cross-Cutting Interoperability in an Earth Science Collaboratory

NASA Technical Reports Server (NTRS)

Lynnes, Christopher; Ramachandran, Rahul; Kuo, Kuo-Sen

2011-01-01

An Earth Science Collaboratory is: A rich data analysis environment with: (1) Access to a wide spectrum of Earth Science data, (3) A diverse set of science analysis services and tools, (4) A means to collaborate on data, tools and analysis, and (5)Supports sharing of data, tools, results and knowledge

Polar Misunderstandings: Earth's Dynamic Dynamo

ERIC Educational Resources Information Center

DiSpezio, Michael A.

2011-01-01

This article discusses the movement of Earth's north and south poles. The Earth's poles may be a bit more complex and dynamic than what many students and teachers believe. With better understanding, offer them up as a rich landscape for higher-level critical analysis and subject integration. Possible curriculum tie-ins include magnets, Earth…

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.

Correlations between age, kinematics, and chemistry as seen by the RAVE survey

NASA Astrophysics Data System (ADS)

Wojno, Jennifer; Kordopatis, Georges; Steinmetz, Matthias; McMillan, Paul; Binney, James; Famaey, Benoit; Monari, Giacomo; Minchev, Ivan; Wyse, Rosemary F. G.; Antoja, Teresa; Siebert, Arnaud; Carrillo, Ismael; Bland-Hawthorn, Joss; Grebel, Eva K.; Zwitter, Tomaž; Bienaymé, Olivier; Gibson, Brad; Kunder, Andrea; Munari, Ulisse; Navarro, Julio; Parker, Quentin; Reid, Warren; Seabroke, George

2018-07-01

We explore the connections between stellar age, chemistry, and kinematics across a Galactocentric distance of 7.5 < R(kpc) < 9.0, using a sample of ˜12 000 intermediate-mass (FGK) turn-off stars observed with the RAdial Velocity Experiment (RAVE) survey. The kinematics of this sample are determined using radial velocity measurements from RAVE, and parallax and proper motion measurements from the Tycho-Gaia Astrometric Solution (TGAS). In addition, ages for RAVE stars are determined using a Bayesian method, taking TGAS parallaxes as a prior. We divide our sample into young (0 < τ < 3 Gyr) and old (8 < τ < 13 Gyr) populations, and then consider different metallicity bins for each of these age groups. We find significant differences in kinematic trends of young and old, metal-poor and metal-rich, stellar populations. In particular, we find a strong metallicity dependence in the mean Galactocentric radial velocity as a function of radius (partial {V_R}/partial R) for young stars, with metal-rich stars having a much steeper gradient than metal-poor stars. For partial {V_{φ }}/partial R, young, metal-rich stars significantly lag the LSR with a slightly positive gradient, while metal-poor stars show a negative gradient above the LSR. We interpret these findings as correlations between metallicity and the relative contributions of the non-axisymmetries in the Galactic gravitational potential (the spiral arms and the bar) to perturb stellar orbits.

Correlations between age, kinematics, and chemistry as seen by the RAVE survey

NASA Astrophysics Data System (ADS)

Wojno, Jennifer; Kordopatis, Georges; Steinmetz, Matthias; McMillan, Paul; Binney, James; Famaey, Benoit; Monari, Giacomo; Minchev, Ivan; Wyse, Rosemary F. G.; Antoja, Teresa; Siebert, Arnaud; Carrillo, Ismael; Bland-Hawthorn, Joss; K Grebel, Eva; Zwitter, Tomaž; Bienaymé, Olivier; Gibson, Brad; Kunder, Andrea; Munari, Ulisse; Navarro, Julio; Parker, Quentin; Reid, Warren; Seabroke, George

2018-04-01

We explore the connections between stellar age, chemistry, and kinematics across a Galactocentric distance of 7.5 < R (kpc) < 9.0, using a sample of ˜12 000 intermediate-mass (FGK) turnoff stars observed with the RAdial Velocity Experiment (RAVE) survey. The kinematics of this sample are determined using radial velocity measurements from RAVE, and parallax and proper motion measurements from the Tycho-Gaia Astrometric Solution (TGAS). In addition, ages for RAVE stars are determined using a Bayesian method, taking TGAS parallaxes as a prior. We divide our sample into young (0 < τ < 3 Gyr) and old (8 < τ < 13 Gyr) populations, and then consider different metallicity bins for each of these age groups. We find significant differences in kinematic trends of young and old, metal-poor and metal-rich, stellar populations. In particular, we find a strong metallicity dependence in the mean Galactocentric radial velocity as a function of radius (∂VR/∂R) for young stars, with metal-rich stars having a much steeper gradient than metal-poor stars. For ∂Vϕ/∂R, young, metal-rich stars significantly lag the LSR with a slightly positive gradient, while metal-poor stars show a negative gradient above the LSR. We interpret these findings as correlations between metallicity and the relative contributions of the non-axisymmetries in the Galactic gravitational potential (the spiral arms and the bar) to perturb stellar orbits.

Windblown Sand in Ganges Chasma

NASA Image and Video Library

2017-04-25

Dark, windblown sand covers intricate sedimentary rock layers in this image captured by NASA's Mars Reconnaissance Orbiter (MRO) from Ganges Chasma, a canyon in the Valles Marineris system. These features are at once familiar and unusual to those familiar with Earth's beaches and deserts. Most sand dunes on Earth are made of silica-rich sand, giving them a light color; these Martian dunes owe their dark color to the iron and magnesium-rich sand found in the region. https://photojournal.jpl.nasa.gov/catalog/PIA21600

Theoretical Study of pKa Values for Trivalent Rare-Earth Metal Cations in Aqueous Solution.

PubMed

Yu, Donghai; Du, Ruobing; Xiao, Ji-Chang; Xu, Shengming; Rong, Chunying; Liu, Shubin

2018-01-18

Molecular acidity of trivalent rare-earth metal cations in aqueous solution is an important factor dedicated to the efficiency of their extraction and separation processes. In this work, the aqueous acidity of these metal ions has been quantitatively investigated using a few theoretical approaches. Our computational results expressed in terms of pK a values agree well with the tetrad effect of trivalent rare-earth ions extensively reported in the extraction and separation of these elements. Strong linear relationships have been observed between the acidity and quantum electronic descriptors such as the molecular electrostatic potential on the acidic nucleus and the sum of the valence natural atomic orbitals energies of the dissociating proton. Making use of the predicted pK a values, we have also predicted the major ionic forms of these species in the aqueous environment with different pH values, which can be employed to rationalize the behavior difference of different rare-earth metal cations during the extraction process. Our present results should provide needed insights not only for the qualitatively understanding about the extraction and separation between yttrium and lanthanide elements but also for the prediction of novel and more efficient rare-earth metal extractants in the future.

Collisions with ice-volatile objects: Geological implications

NASA Technical Reports Server (NTRS)

Wilde, P.; Quinby-Hunt, M. S.; Berry, W. B. N.

1988-01-01

The collision of the Earth with extra-terrestrial ice-volatile bodies is proposed as a mechanism to produce rapid changes in the geologic record. These bodies would be analogs of the ice satellites found for the Jovian planets and suspected for comets and certain low density bodies in the Asteroid belt. Five generic end-members are postulated: (1) water ice; (2) dry ice: carbon-carbon dioxide rich, (3) oceanic (chloride) ice; (4) sulfur-rich ice; (5) ammonia hydrate-rich ice; and (6) clathrate: methane-rich ice. Due to the volatile nature of these bodies, evidence for their impact with the Earth would be subtle and probably best reflected geochemically or in the fossil record. Actual boloids impacting the Earth may have a variable composition, generally some admixture with water ice. However for discussion purposes, only the effects of a dominant component will be treated. The general geological effects of such collisions, as a function of the dominant component would be: (1) rapid sea level rise unrelated to deglaciation, (2) decreased oceanic pH and rapid climatic warming or deglaciation; (3) increased paleosalinities; (4) increased acid rain; (5) increased oceanic pH and rapid carbonate deposition; and (6) rapid climatic warming or deglaciation.

How Low Can You Go? Maximum Constraints on Hydrogen Concentrations Prior to the Great Oxidation Event

NASA Technical Reports Server (NTRS)

Domagal-Goldman, Shawn

2014-01-01

Shaw postulates that Earth's early atmosphere was rich in reducing gases such as hydrogen, brought to Earth via impact events. This commentary seeks to place constraints on this idea through a very brief review of existing geological and geochemical upper limits on the reducing power of Earth's atmosphere prior to the rise of oxygen. While these constraints place tight limits on this idea for rocks younger than 3.8 Ga, few constraints exist prior to that time, due to a paucity of rocks of that age. The time prior to these constraints is also a time frame for which the proposal is most plausible, and for which it carries the greatest potential to explain other mysteries. Given this potential, several tests are suggested for the H2-rich early Earth hypothesis.

MAVEN-Measured Meteoritic Ions on Mars - Tracers of Lower Ionosphere Processes With and Without Analogues On Earth

NASA Astrophysics Data System (ADS)

Benna, M.; Grebowsky, J. M.; Collinson, G.; Plane, J. M. C.; Mitchell, D.; Srivastava, N.

2017-12-01

MAVEN observations of meteoritic metal ion populations during "deep dip" campaigns at Mars have revealed unique non-Earth like behavior that are not yet understood. These deep dip campaigns (6 so far) consisted each of more than a score of repeated orbits through the Martian molecular-ion-dominated lower ionosphere, whose terrestrial parallel (Earth's E-region) has been rather sparcely surveyed in situ by sounding rockets. In regions of weak Mars magnetic fields, MAVEN found ordered exponentially decreasing metal ion concentrations above the altitude of peak meteor ablation. Such an ordered trend has never been observed on Earth. Isolated anomalous high-altitude layers in the metal ion are also encountered, typically on deep dip campaigns in the southern hemisphere where large localized surface remanent magnetic fields prevail. The source of these anomalous layers is not yet evident, although the occurrences of some high-altitude metal ion enhancements were in regions with measured perturbed magnetic fields, indicative of localized electrical currents. Further investigation shows that those currents are also sometimes associated with superthermal/energetic electron bursts offering evidence that that impact ionization of neutral metal populations persisting at high altitudes are the source of metal ion enhancement - a rather difficult assumption to accept far above the ablation region where the metal neutrals are deposited. The relationship of the anomalous layers to the coincident electron populations as well as to the orientation of the magnetic fields which can play a role in the neutral wind generated ion convergences as on Earth is investigated.

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.

Metal mining and the environment

USGS Publications Warehouse

Hudson, Travis L.; Fox, Frederick D.; Plumlee, Geoffrey S.

1999-01-01

The booklet, Metal Mining and the Environment, and the colorful companion poster offer new tools for raising awareness and understanding of the impact and issues surrounding metal mining and the environment. The 64-page full-color booklet contains a copy of the poster which includes a student activity on the back. This booklet and poster can help you: illustrate the importance of our natural and environmental resources; provide a geoscience perspective on metal mining and the environment; improve Earth science literacy; and increase student understandings of Earth resources and systems.

Phase I. Lanthanum-based Start Materials for Hydride Batteries

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

Gschneidner, K. A.; Schmidt, F. A.; Frerichs, A. E.

The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La 1-xR x)(Ni 1-yM y)(Si z), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

A new carbon-rich phase (COPS) in Antarctic micrometeorites

NASA Technical Reports Server (NTRS)

Engrand, C.; Maurette, M.; Kurat, G.; Brandstatter, F.; Perreau, M.

1993-01-01

The contemporary flux of micrometeorites with sizes greater than 50 microns reaching the Earth's surface each year (about 20,000 tons/a) is much greater than the value of approximately 100 tons/a reported for conventional meteorites up to masses of approximately 10,000 tons. Moreover, on the average, Antarctic micrometeorites contain at least as much carbon as does Orgueil, the most C-rich meteorite. Micrometeorites are thus responsible for most of the carbon accreted by the Earth. In this paper we report SEM observations of a new C-rich 'dirty magnetite' phase observed as tiny inclusions in both melted and unmelted micrometeorites. This phase, which is enriched in C, O, P, S, Fe, frequently shows Ni contents in excess of 0.2 percent, strongly suggestive of an 'extraterrestrial' origin. We also discovered this 'COPS' phase in the fusion crust of Murchison. It appears likely that COPS is a product of meteoroid reprocessing during frictional heating in the Earth's atmosphere and/or its fast 'weathering' in the upper atmosphere. Upon 'catalyzed' hydrolysis this phase might have facilitated the functioning of micrometeorites as 'micro-chondritic-reactors' for the synthesis of prebiotic molecules on the early Earth.

Advanced Launch Vehicle Upper Stages Using Liquid Propulsion and Metallized Propellants

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan A.

1990-01-01

Metallized propellants are liquid propellants with a metal additive suspended in a gelled fuel or oxidizer. Typically, aluminum (Al) particles are the metal additive. These propellants provide increase in the density and/or the specific impulse of the propulsion system. Using metallized propellant for volume-and mass-constrained upper stages can deliver modest increases in performance for low earth orbit to geosynchronous earth orbit (LEO-GEO) and other earth orbital transfer missions. Metallized propellants, however, can enable very fast planetary missions with a single-stage upper stage system. Trade studies comparing metallized propellant stage performance with non-metallized upper stages and the Inertial Upper Stage (IUS) are presented. These upper stages are both one- and two-stage vehicles that provide the added energy to send payloads to altitudes and onto trajectories that are unattainable with only the launch vehicle. The stage designs are controlled by the volume and the mass constraints of the Space Transportation System (STS) and Space Transportation System-Cargo (STS-C) launch vehicles. The influences of the density and specific impulse increases enabled by metallized propellants are examined for a variety of different stage and propellant combinations.

Data gaps in anthropogenically driven local-scale species richness change studies across the Earth's terrestrial biomes.

PubMed

Murphy, Grace E P; Romanuk, Tamara N

2016-05-01

There have been numerous attempts to synthesize the results of local-scale biodiversity change studies, yet several geographic data gaps exist. These data gaps have hindered ecologist's ability to make strong conclusions about how local-scale species richness is changing around the globe. Research on four of the major drivers of global change is unevenly distributed across the Earth's biomes. Here, we use a dataset of 638 anthropogenically driven species richness change studies to identify where data gaps exist across the Earth's terrestrial biomes based on land area, future change in drivers, and the impact of drivers on biodiversity, and make recommendations for where future studies should focus their efforts. Across all drivers of change, the temperate broadleaf and mixed forests and the tropical moist broadleaf forests are the best studied. The biome-driver combinations we have identified as most critical in terms of where local-scale species richness change studies are lacking include the following: land-use change studies in tropical and temperate coniferous forests, species invasion and nutrient addition studies in the boreal forest, and warming studies in the boreal forest and tropics. Gaining more information on the local-scale effects of the specific human drivers of change in these biomes will allow for better predictions of how human activity impacts species richness around the globe.

Photochemistry in terrestrial exoplanet atmospheres. III. Photochemistry and thermochemistry in thick atmospheres on super Earths and mini Neptunes

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

Hu, Renyu; Seager, Sara, E-mail: hury@caltech.edu

Some super Earths and mini Neptunes will likely have thick atmospheres that are not H{sub 2}-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H{sub 2}-dominated atmospheres and non-H{sub 2}-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO{sub 2} rather than CH{sub 4} or CO in a H{sub 2}-depleted water-dominated thick atmospheremore » and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to the formation of unsaturated hydrocarbons (C{sub 2}H{sub 2} and C{sub 2}H{sub 4}). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b, we find that (1) C{sub 2}H{sub 2} features at 1.0 and 1.5 μm in transmission and C{sub 2}H{sub 2} and C{sub 2}H{sub 4} features at 9-14 μm in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of the nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.« less

30 CFR 77.701-2 - Approved methods of grounding metallic frames, casings, and other enclosures of electric...

Code of Federal Regulations, 2012 CFR

2012-07-01

... enclosures and the earth. (b) A method of grounding of metallic frames, casings, and other enclosures of... there is no difference in potential between such frames, casings, and other enclosures, and the earth. ...

Non-rare earth magnetic nanoparticles

DOEpatents

Carpenter, Everett E.; Huba, Zachary J.; Carroll, Kyler J.; Farghaly, Ahmed; Khanna, Shiv N.; Qian, Meichun; Bertino, Massimo

2017-09-26

Continuous flow synthetic methods are used to make single phase magnetic metal alloy nanoparticles that do not contain rare earth metals. Soft and hard magnets made from the magnetic nanoparticles are used for a variety of purposes, e.g. in electric motors, communication devices, etc.

Fate of Metals in Relation to Water and Sediment Properties in a Subtropical Lake in Central Himalaya, India.

PubMed

Inaotombi, Shaikhom; Gupta, Prem Kumar

2017-04-01

Lakes of Himalaya are one of the most fragile ecosystems on earth. Tourism and urban development in the upland region strongly affect its water resources. The high rate of sedimentation and organic matter deposition alters the ecological state of sediment bed, which indirectly influences on dynamics of metallic elements. We investigated spatial and temporal variations of water and sediment characteristic in Lake Sattal of Central Himalaya, India. Samples were collected seasonally from four sampling locations from January 2011 to December 2012. Pearson's correlation and Canonical correspondence analysis (CCAs) were applied to examine the dynamics and behaviors of heavy metals. Concentrations of elements were in the order of fluoride (Fl) > zinc (Zn) > copper (Cu) > iron (Fe) > manganese (Mn). Sand size fraction was higher in the littoral zone while clay particle was dominant in the profundal zone of the lake. Dissolved oxygen at sediment-water-interface (SWI) and water temperature were the major factors influencing the dynamics of metallic contents in the water column. Spatially, total organic matter (TOM) was higher in the deeper portion of the lake. Our study revealed that mobility of Fe is temperature-dependent, whereas speciation of Mn and Cu are primarily controlled by the suboxic condition of SWI in organic-rich site. Upland lakes are more vulnerable to anoxic condition and have severe implications on heavy metals speciation. Proper implementation of land use policies and management practices, including stormwater detention, can be integrated into resolving such problems.

K2-155: A Bright Metal-poor M Dwarf with Three Transiting Super-Earths

NASA Astrophysics Data System (ADS)

Hirano, Teruyuki; Dai, Fei; Livingston, John H.; Fujii, Yuka; Cochran, William D.; Endl, Michael; Gandolfi, Davide; Redfield, Seth; Winn, Joshua N.; Guenther, Eike W.; Prieto-Arranz, Jorge; Albrecht, Simon; Barragan, Oscar; Cabrera, Juan; Cauley, P. Wilson; Csizmadia, Szilard; Deeg, Hans; Eigmüller, Philipp; Erikson, Anders; Fridlund, Malcolm; Fukui, Akihiko; Grziwa, Sascha; Hatzes, Artie P.; Korth, Judith; Narita, Norio; Nespral, David; Niraula, Prajwal; Nowak, Grzegorz; Pätzold, Martin; Palle, Enric; Persson, Carina M.; Rauer, Heike; Ribas, Ignasi; Smith, Alexis M. S.; Van Eylen, Vincent

2018-03-01

We report on the discovery of three transiting super-Earths around K2-155 (EPIC 210897587), a relatively bright early M dwarf (V = 12.81 mag) observed during Campaign 13 of the NASA K2 mission. To characterize the system and validate the planet candidates, we conducted speckle imaging and high-dispersion optical spectroscopy, including radial velocity measurements. Based on the K2 light curve and the spectroscopic characterization of the host star, the planet sizes and orbital periods are {1.55}-0.17+0.20 {R}\\oplus and 6.34365 ± 0.00028 days for the inner planet; {1.95}-0.22+0.27 {R}\\oplus and 13.85402 ± 0.00088 days for the middle planet; and {1.64}-0.17+0.18 {R}\\oplus and 40.6835 ± 0.0031 days for the outer planet. The outer planet (K2-155d) is near the habitable zone, with an insolation 1.67 ± 0.38 times that of the Earth. The planet’s radius falls within the range between that of smaller rocky planets and larger gas-rich planets. To assess the habitability of this planet, we present a series of three-dimensional global climate simulations, assuming that K2-155d is tidally locked and has an Earth-like composition and atmosphere. We find that the planet can maintain a moderate surface temperature if the insolation proves to be smaller than ∼1.5 times that of the Earth. Doppler mass measurements, transit spectroscopy, and other follow-up observations should be rewarding, as K2-155 is one of the optically brightest M dwarfs known to harbor transiting planets.

The neodymium stable isotope composition of the silicate Earth and chondrites

NASA Astrophysics Data System (ADS)

McCoy-West, Alex J.; Millet, Marc-Alban; Burton, Kevin W.

2017-12-01

The non-chondritic neodymium (Nd) 142Nd/144Nd ratio of the silicate Earth potentially provides a key constraint on the accretion and early evolution of the Earth. Yet, it is debated whether this offset is due to the Earth being formed from material enriched in s-process Nd isotopes or results from an early differentiation process such as the segregation of a late sulfide matte during core formation, collisional erosion or a some combination of these processes. Neodymium stable isotopes are potentially sensitive to early sulfide segregation into Earth's core, a process that cannot be resolved using their radiogenic counterparts. This study presents the first comprehensive Nd stable isotope data for chondritic meteorites and terrestrial rocks. Stable Nd measurements were made using a double spike technique coupled with thermal ionisation mass spectrometry. All three of the major classes of chondritic meteorites, carbonaceous, enstatite and ordinary chondrites have broadly similar isotopic compositions allowing calculation of a chondritic mean of δ146/144Nd = -0.025 ± 0.025‰ (±2 s.d.; n = 39). Enstatite chondrites yield the most uniform stable isotope composition (Δ146/144Nd = 26 ppm), with considerably more variability observed within ordinary (Δ146/144Nd = 72 ppm) and carbonaceous meteorites (Δ146/144Nd = 143 ppm). Terrestrial weathering, nucleosynthetic variations and parent body thermal metamorphism appear to have little measurable effect on δ146/144Nd in chondrites. The small variations observed between ordinary chondrite groups most likely reflect inherited compositional differences between parent bodies, with the larger variations observed in carbonaceous chondrites being linked to varying modal proportions of calcium-aluminium rich inclusions. The terrestrial samples analysed here include rocks ranging from basaltic to rhyolitic in composition, MORB glasses and residual mantle lithologies. All of these terrestrial rocks possess a broadly similar Nd isotope composition giving an average composition for the bulk silicate Earth of δ146/144Nd = -0.022 ± 0.034‰ (n = 30). In the samples here magmatic differentiation appears to only have an effect on stable Nd in highly evolved magmas with heavier δ146/144Nd values observed in samples with >70 wt% SiO2. The average stable Nd isotope composition of chondrites and the bulk silicate Earth are indistinguishable at the 95% confidence level. However, mantle samples do possess variable stable Nd isotope compositions (Δ146/144Nd = 75 ppm) with an average δ 146 / 144Nd value of -0.008‰. If these heavier values represent the true composition of pristine mantle then it is not possible to completely rule out some role for core formation in accounting for some of the offset between the mantle and chondrites. Overall, these results indicate that the mismatch of 142Nd between the Earth and chondrites is best explained by a higher proportion of s-process Nd in the Earth, rather than partitioning into sulfide or S-rich metal in the core.

Assessing rare earth elements in quartz rich geological samples.

PubMed

Santoro, A; Thoss, V; Ribeiro Guevara, S; Urgast, D; Raab, A; Mastrolitti, S; Feldmann, J

2016-01-01

Sodium peroxide (Na2O2) fusion coupled to Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) measurements was used to rapidly screen quartz-rich geological samples for rare earth element (REE) content. The method accuracy was checked with a geological reference material and Instrumental Neutron Activation Analysis (INAA) measurements. The used mass-mode combinations presented accurate results (only exception being (157)Gd in He gas mode) with recovery of the geological reference material QLO-1 between 80% and 98% (lower values for Lu, Nd and Sm) and in general comparable to INAA measurements. Low limits of detection for all elements were achieved, generally below 10 pg g(-1), as well as measurement repeatability below 15%. Overall, the Na2O2/ICP-MS/MS method proved to be a suitable lab-based method to quickly and accurately screen rock samples originating from quartz-rich geological areas for rare earth element content; particularly useful if checking commercial viability. Copyright © 2015 Elsevier Ltd. All rights reserved.

RNA Oligomerization in Laboratory Analogues of Alkaline Hydrothermal Vent Systems.

PubMed

Burcar, Bradley T; Barge, Laura M; Trail, Dustin; Watson, E Bruce; Russell, Michael J; McGown, Linda B

2015-07-01

Discovering pathways leading to long-chain RNA formation under feasible prebiotic conditions is an essential step toward demonstrating the viability of the RNA World hypothesis. Intensive research efforts have provided evidence of RNA oligomerization by using circular ribonucleotides, imidazole-activated ribonucleotides with montmorillonite catalyst, and ribonucleotides in the presence of lipids. Additionally, mineral surfaces such as borates, apatite, and calcite have been shown to catalyze the formation of small organic compounds from inorganic precursors (Cleaves, 2008 ), pointing to possible geological sites for the origins of life. Indeed, the catalytic properties of these particular minerals provide compelling evidence for alkaline hydrothermal vents as a potential site for the origins of life since, at these vents, large metal-rich chimney structures can form that have been shown to be energetically favorable to diverse forms of life. Here, we test the ability of iron- and sulfur-rich chimneys to support RNA oligomerization reactions using imidazole-activated and non-activated ribonucleotides. The chimneys were synthesized in the laboratory in aqueous "ocean" solutions under conditions consistent with current understanding of early Earth. Effects of elemental composition, pH, inclusion of catalytic montmorillonite clay, doping of chimneys with small organic compounds, and in situ ribonucleotide activation on RNA polymerization were investigated. These experiments, under certain conditions, showed successful dimerization by using unmodified ribonucleotides, with the generation of RNA oligomers up to 4 units in length when imidazole-activated ribonucleotides were used instead. Elemental analysis of the chimney precipitates and the reaction solutions showed that most of the metal cations that were determined were preferentially partitioned into the chimneys.

Effect of silicon fertilizers on cadmium in rice (Oryza sativa) tissue at tillering stage.

PubMed

Ji, Xionghui; Liu, Saihua; Juan, Huang; Bocharnikova, Elena A; Matichenkov, Vladimir V

2017-04-01

Silicon has been found to enhance the plants' tolerance to heavy metal stress. In a field study, the effect of different types of Si-rich soil amendments (slag, ground slag, and diatomaceous earth) and fertilizers (activated slag, ground activated slag, and commercial Si fertilizer) on the distribution of soluble and insoluble forms of Cd in the rice plant organs grown on long-term cultivated paddy soil contaminated with Cd (central part of Hunan Province, China) was investigated. The soluble Si and Cd were tested in the apoplast and symplast of the roots, stems, and leaves of rice at a tillering stage. The Si-rich materials increased rice biomass by up to 15.5% and reduced the total leaf Cd by 8.5 to 21.9%. Commercial Si fertilizer was the most effective. Three main locations of the most active Si-Cd interactions were distinguished in the soil-plant system: soil, where monosilicic acid affords adsorption and fixation of the bioavailable Cd and root apoplast and apoplast above roots, where monosilicic acid can precipitate Cd. The transport of Cd to stems and leaves and the mobility of Cd in the soil depend on the content of monosilicic acid in the system.

Morphological changes of olivine grains reacted with amino acid solutions by impact process

NASA Astrophysics Data System (ADS)

Umeda, Yuhei; Takase, Atsushi; Fukunaga, Nao; Sekine, Toshimori; Kobayashi, Takamichi; Furukawa, Yoshihiro; Kakegawa, Takeshi

2017-03-01

Early oceans on Earth might have contained certain amounts of biomolecules such as amino acids, and they were subjected to meteorite impacts, especially during the late heavy bombardment. We performed shock recovery experiments by using a propellant gun in order to simulate shock reactions among olivine as a representative meteorite component, water and biomolecules in oceans in the process of marine meteorite impacts. In the present study, recovered solid samples were analyzed by using X-ray powder diffraction method, scanning electron microscopy, electron probe microanalysis, and transmission electron microscopy with energy-dispersive X-ray spectrometry. The analytical results on shocked products in the recovered sample showed (1) morphological changes of olivine to fiber- and bamboo shoot-like crystals, and to pulverized grains; and features of lumpy surfaces affected by hot water, (2) the formation of carbon-rich substances derived from amino acids, and (3) the incorporation of metals from container into samples. According to the present results, fine-grained olivine in meteorites might have morphologically changed and shock-induced chemical reactions might have been enhanced so that amino acids related to the origin of life may have transformed to carbon-rich substances by impacts.

SEPARATION OF PLUTONYL IONS

DOEpatents

Connick, R.E.; McVey, Wm.H.

1958-07-15

A process is described for separating plutonyl ions from the acetate ions with which they are associated in certaln carrier precipitation methods of concentrating plutonium. The method consists in adding alkaline earth metal ions and subsequently alkalizing the solution, causing formation of an alkaltne earth plutonate precipitate. Barium hydroxide is used in a preferred embodiment since it provides alkaline earth metal ion and alkalizes the solution in one step forming insoluble barium platonate.

Comments on stellar boundary cooling and the reality of supermetallicity

NASA Technical Reports Server (NTRS)

Deming, D.

1980-01-01

The paper discusses the 'super-metal-rich' (SMR) stars and reexamines Peterson's analysis of the SMR prototype mu Leo (1978) with regard to a postulated error in continuum error. Model atmospheres are used to compute theoretical equivalent widths and to explore the sensitivity of these widths to metallicity, temperature, surface gravity, and microturbulence. It is shown that Peterson's results are sensitive to continuum placement, and that her data does not indicate that the temperature gradient is steeper in mu Leo than in normal giants. It is concluded that the SMR stars are very metal rich and are also somewhat boundary cooled, possibly due to high metallicity.

Environmental geochemistry at Red Mountain, an unmined volcanogenic massive sulphide deposit in the Bonnifield district, Alaska Range, east-central Alaska

USGS Publications Warehouse

Eppinger, R.G.; Briggs, P.H.; Dusel-Bacon, C.; Giles, S.A.; Gough, L.P.; Hammarstrom, J.M.; Hubbard, B.E.

2007-01-01

The unmined, pyrite-rich Red Mountain (Dry Creek) deposit displays a remarkable environmental footprint of natural acid generation, high metal and exceedingly high rate earth element (REE) concentrations in surface waters. The volcanogenic massive sulphide deposit exhibits well-constrained examples of acid-generating, metal-leaching, metal-precipitation and self-mitigation (via co-precipitation, dilution and neutralization) processes that occur in an undisturbed natural setting, a rare occurrence in North America. Oxidative dissolution of pyrite and associated secondary reactions under near-surface oxidizing conditions are the primary causes for the acid generation and metal leaching. The deposit is hosted in Devonian to Mississippian felsic metavolcanic rocks of the Mystic Creek Member of the Totatlanika Schist. Water samples with the lowest pH (many below 3.5), highest specific conductance (commonly >2500 ??S/cm) and highest major- and trace-element concentrations are from springs and streams within the quartz-sericite-pyrite alteration zone. Aluminum, Cd, Co, Cu, Fe, Mn, Ni, Pb, Y, Zn and, particularly, the REEs are found in high concentrations, ranging across four orders of magnitude. Waters collected upstream from the alteration zone have near-neutral pH, lower specific conductance (370 to 830 ??S/cm), lower metal concentrations and measurable alkalinities. Water samples collected downstream of the alteration zone have pH and metal concentrations intermediate between these two extremes. Stream sediments are anomalous in Zn, Pb, S, Fe, Cu, As, Co, Sb and Cd relative to local and regional background abundances. Red Mountain Creek and its tributaries do not, and probably never have, supported significant aquatic life. ?? 2007 AAG/ Geological Society of London.

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.

Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

2016-11-01

Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

DOEpatents

Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

2015-02-10

Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

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

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

Polymer Nanocomposite Film with Metal Rich Surface Prepared by In Situ Single-Step Formation of Palladium Nanoparticles: An Interesting Way to Combine Specific Functional Properties.

PubMed

Thompson, David; Kranbuehl, David; Espuche, Eliane

2016-10-18

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.

Non-LTE line-blanketed model atmospheres of hot stars. 2: Hot, metal-rich white dwarfs

NASA Technical Reports Server (NTRS)

Lanz, T.; Hubeny, I.

1995-01-01

We present several model atmospheres for a typical hot metal-rich DA white dwarf, T(sub eff) = 60,000 K, log g = 7.5. We consider pure hydrogen models, as well as models with various abundances of two typical 'trace' elements-carbon and iron. We calculte a number of Local Thermodynamic Equilibrium (LTE) and non-LTE models, taking into account the effect of numerous lines of these elements on the atmospheric structure. We demostrate that while the non-LTE effects are notvery significant for pure hydrogen models, except for describing correctly the central emission in H-alpha they are essential for predicting correctly the ionization balance of metals, such as carbon and iron. Previously reported discrepancies in LTE abundances determinations using C III and C IV lines are easily explained by non-LTE effects. We show that if the iron abundance is larger than 10(exp -5), the iron line opacity has to be considered not only for the spectrum synthesis, but also in the model construction itself. For such metal abundances, non-LTE metal line-blanketed models are needed for detailed abundance studies of hot, metal-rich white dwarfs. We also discuss the predicted Extreme Ultraviolet (EUV) spectrum and show that it is very sensitive to metal abundances, as well as to non-LTE effects.

Migration-driven diversity of super-Earth compositions

NASA Astrophysics Data System (ADS)

Raymond, Sean N.; Boulet, Thibault; Izidoro, Andre; Esteves, Leandro; Bitsch, Bertram

2018-06-01

A leading model for the origin of super-Earths proposes that planetary embryos migrate inward and pile up on close-in orbits. As large embryos are thought to preferentially form beyond the snow line, this naively predicts that most super-Earths should be very water-rich. Here we show that the shortest-period planets formed in the migration model are often purely rocky. The inward migration of icy embryos through the terrestrial zone accelerates the growth of rocky planets via resonant shepherding. We illustrate this process with a simulation that provided a match to the Kepler-36 system of two planets on close orbits with very different densities. In the simulation, two super-Earths formed in a Kepler-36-like configuration; the inner planet was pure rock while the outer one was ice-rich. We conclude from a suite of simulations that the feeding zones of close-in super-Earths are likely to be broad and disconnected from their final orbital radii.

Improved method for preparing rare earth sesquichalcogenides

DOEpatents

Takeshita, T.; Beaudry, B.J.; Gschneidner, K.A. Jr.

1982-04-14

An improved method for the preparation of high purity rare earth sesquichalcogenides is described. The rare earth, as one or more pieces of the metal, is sealed under a vacuum with a stoichiometric amount of sulfur or selenium and a small amount of iodine into a quartz reaction vessel. The sealed vessel is then heated to above the vaporization temperature of the chalcogen and below the melting temperature of the rare earth metal and maintained until the product has been formed. The iodine is then vaporized off leaving a pure product. The rare earth sulfides and selenides thus formed are useful as semiconductors and as thermoelectric generators. 3 tables.

Millimeter wavelength rectenna development

NASA Technical Reports Server (NTRS)

Gallagher, James; Gouker, Mark

1989-01-01

Rectennas were studied with the intent of converting the Earth's (black body) radiation into dc power for satellites in earth orbit. Power densities; metal-oxide-metal diodes; antenna design configurations; fluid patterns; substrate mounted antennas; and directions for future work are outlined. This presentation is represented by viewgraphs only.

[Differential study of the bonding characterization of dental porcelain to Ni-Cr alloys].

PubMed

Wei, Fang; Zhan, De-song; Wang, Yan-yan

2008-10-01

To study the bonding capability when Ni-Cr porcelain alloy was added with Ti, compound rare earth metals and removed the element of Be. Ni-Cr-Ti porcelain alloys manufactured by Institute of Metal Research of Chinese Academy of Sciences were tested. The test alloys were divided into three groups according to whether containing Be and compound rare earth metals or not. And HI BOND Ni-Cr base-metal alloy was chosen as control. The metal-ceramic specimens were prepared for shear test, scanning electron microscope (SEM) and energy spectrum analysis. The shear bond strength of the four groups were analyzed. No significant difference were observed among them (P > 0.05). No crackle was found and they were contacted tightly between the porcelain and metal. The composition and contents of the four groups' interfaces were closed. The shear bond strength of the self-made Ni-Cr-Ti porcelain alloys all can satisfy the clinical requirements. Experimental groups containing Ti, compound rare earth metals and removing the element of Be can be used as better recommendation for clinical practice.

A stable lithium-rich surface structure for lithium-rich layered cathode materials

PubMed Central

Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

2016-01-01

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface. PMID:27886178

Magnetic Partitioning Nanofluid for Rare Earth Extraction from Geothermal Fluids

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

McGrail, Bernard P.; Thallapally, Praveen K.; Liu, Jian

Rare earth metals are critical materials in a wide variety of applications in generating and storing renewable energy and in designing more energy efficient devices. Extracting rare earth metals from geothermal brines is a very challenging problem due to the low concentrations of these elements and engineering challenges with traditional chemical separations methods involving packed sorbent beds or membranes that would impede large volumetric flow rates of geothermal fluids transitioning through the plant. We are demonstrating a simple and highly cost-effective nanofluid-based method for extracting rare earth metals from geothermal brines. Core-shell composite nanoparticles are produced that contain a magneticmore » iron oxide core surrounded by a shell made of silica or metal-organic framework (MOF) sorbent functionalized with chelating ligands selective for the rare earth elements. By introducing the nanoparticles at low concentration (≈0.05 wt%) into the geothermal brine after it passes through the plant heat exchanger, the brine is exposed to a very high concentration of chelating sites on the nanoparticles without need to pass through a large and costly traditional packed bed or membrane system where pressure drop and parasitic pumping power losses are significant issues. Instead, after a short residence time flowing with the brine, the particles are effectively separated out with an electromagnet and standard extraction methods are then applied to strip the rare earth metals from the nanoparticles, which are then recycled back to the geothermal plant. Recovery efficiency for the rare earths at ppm level has now been measured for both silica and MOF sorbents functionalized with a variety of chelating ligands. A detailed preliminary techno-economic performance analysis of extraction systems using both sorbents showed potential to generate a promising internal rate of return (IRR) up to 20%.« less

Cost-benefit analysis of copper recovery in remediation projects: A case study from Sweden.

PubMed

Volchko, Yevheniya; Norrman, Jenny; Rosén, Lars; Karlfeldt Fedje, Karin

2017-12-15

Contamination resulting from past industrial activity is a problem throughout the world and many sites are severely contaminated by metals. Advances in research in recent years have resulted in the development of technologies for recovering metal from metal-rich materials within the framework of remediation projects. Using cost-benefit analysis (CBA), and explicitly taking uncertainties into account, this paper evaluates the potential social profitability of copper recovery as part of four remediation alternatives at a Swedish site. One alternative involves delivery of copper-rich ash to a metal production company for refining. The other three alternatives involve metal leaching from materials and sale of the resulting metal sludge for its further processing at a metal production company using metallurgical methods. All the alternatives are evaluated relative to the conventional excavation and disposal method. Metal recovery from the ash, metal sludge sale, and disposal of the contaminated soil and the ash residue at the local landfill site, was found to be the best remediation alternative. However, given the present conditions, its economic potential is low relative to the conventional excavation and disposal method but higher than direct disposal of the copper-rich ash for refining. Volatile copper prices, the high cost of processing equipment, the highly uncertain cost of the metal leaching and washing process, coupled with the substantial project risks, contribute most to the uncertainties in the CBA results for the alternatives involving metal leaching prior to refining. However, investment in processing equipment within the framework of a long-term investment project, production of safe, reusable soil residue, and higher copper prices on the metal market, can make metal recovery technology socially profitable. Copyright © 2017 Elsevier B.V. All rights reserved.

Relations between benthic community structure and metals concentrations in aquatic macroinvertebrates: Clark Fork River, Montana

USGS Publications Warehouse

1995-01-01

We sampled macroinvertebrate communities at six sites on the upper Clark Fork River, Montana, to determine relations between macroinvertebrate community structure and metals in invertebrates and the best benthic community metrics to use for ranking sites based on the relative severity of the effects of metals. Concentrations (μg/g) of six metals in invertebrates were determined: Al (range = 591–4193), As (2.7–34.1), Cd (0.13–8.38), Cu (26–1382), Pb (0.54–67.1), and Zn (212–1665). Concentrations of As, Cd, Cu, Pb, and total metals were significantly correlated with at least one benthic metric. Copper (r = 0.88–0.94) and total metals (r = 0.90–0.97) provided the most highly significant correlations. Based on longitudinal site comparisons of metals in invertebrates, benthic community structure, and differences between proportionally scaled ranks, five benthic metrics provided the best indicators of relative impact: taxa richness, Ephemeroptera-Plecoptera-Trichoptera (EPT) richness, chironomid richness, percentage of the most dominant taxon, and density. The two sites with the highest accumulations of invertebrate metals also demonstrated the greatest relative degree of impact based on these parameters. The most meaningful combinations of metrics indicate that the benthic community at the most upstream site is being severely impacted by metals. Two sites demonstrated little or no negative impact, and three sites demonstrated low or moderate levels of negative impacts, which may be due to a combination of metals and other factors such as organic enrichment. We recommend that benthic community structure and metals in invertebrates collected from riffle habitats be used to determine relative impacts in metals-contaminated river systems, owing to their close relation to metal availability and transfer to higher trophic levels.

New Technologies and Strategies to Exploit Near Earth Asteroids for Breakthrough Space Development

NASA Astrophysics Data System (ADS)

Rather, John; Powell, James; Maise, George

2010-01-01

The past two decades have brought a profound expansion of knowledge of near earth objects (NEO). If creatively exploited, NEOs can significantly increase human safety while reducing costs of exploration and development of the moon, Mars and the solar system. Synergistically, the ability to defend the Earth from devastating impacts will become very effective. A spherical volume having a radius equivalent to the moon's orbit, 400,000 km, is visited every day by approximately ten NEOs having diameters of ~10 meters, while ~30 meter diameter encounters occur about once per month. Because these objects are usually very faint and only within detectable range for a few days, they require specialized equipment to discover them with high probability of detection and to enable accurate determination of orbital parameters. Survey systems are now being implemented that are cataloging many thousands of objects larger than 30 meters, but numerous advantages will result from extending the complete NEO census down to 10 meter diameters. The typical compositions of such NEOs will range from ~80% that are low density dust & rock ``rubble piles'' to perhaps 2% containing heavy metals-properties well known from meteorite samples. It is quite possible that there will also be some fragments of short period comets that are rich in water ice and other volatile components. In this paper we will propose a set of new technologies and strategies for exploiting NEO resources that can yield important space development breakthroughs at much lower costs than existing concepts. Solar powered ``Tugboats'' deployed at the space station can rendezvous with carefully selected NEOs and steer them into captured orbits in the lunar L4 & L5 regions. Robotic equipment will then modify them for a plethora of benefits. Notably, the problem of radiation shielding against the Van Allen belts, solar flares and cosmic rays will be solved. Free transportation from low earth orbit to the moon and beyond will be feasible via shielded habitats in elliptical orbits. Large, comfortable habitats for long duration trips to Mars and beyond can be built. Propulsion for orbital transfer and maneuvering of heavy payloads can be accomplished by solar energized ejection of NEO materials. Industries can be developed based upon reconditioning materials for use in space and recovery of heavy metals for use on Earth.

Burn-Resistant, Strong Metal-Matrix Composites

NASA Technical Reports Server (NTRS)

Stoltzfus, Joel M.; Tayal, Moti J.

2003-01-01

Ceramic particulate fillers increase the specific strengths and burn resistances of metals: This is the conclusion drawn by researchers at Johnson Space Center's White Sands Test Facility. The researchers had theorized that the inclusion of ceramic particles in metal tools and other metal objects used in oxygen-rich atmospheres (e.g., in hyperbaric chambers and spacecraft) could reduce the risk of fire and the consequent injury or death of personnel. In such atmospheres, metal objects act as ignition sources, creating fire hazards. However, not all metals are equally hazardous: some are more burn-resistant than others are. It was the researchers purpose to identify a burn-resistant, high-specific-strength ceramic-particle/metal-matrix composite that could be used in oxygen-rich atmospheres. The researchers studied several metals. Nickel and cobalt alloys exhibit high burn resistances and are dense. The researchers next turned to ceramics, which they knew do not act as ignition sources. Unlike metals, ceramics are naturally burn-resistant. Unfortunately, they also exhibit low fracture toughnesses.

Metal-rich or misclassified? The case of four RR Lyrae stars

NASA Astrophysics Data System (ADS)

Molnar, L.; Juhasz, A. L.; Plachy, E.; Szabo, R.

2016-06-01

We analysed the light curve of four, apparently extremely metal-rich fundamenta-mode RR Lyrae stars. We identified two stars, MT Tel and ASAS J091803-3022.6 as RRc (first-overtone) pulsators that were misclassified as RRab ones in the ASAS survey. In the case of the other two stars, V397 Gem and ASAS J075127-4136.3, we could not decide conclusively, as they are outliers in the period-Fourier-coefficient space from the loci of both classes, but their photometric metallicities also favour the RRc classification.

The Role of Near-Earth Asteroids in Long-Term Platinum Supply

NASA Astrophysics Data System (ADS)

Blair, B. R.

2000-01-01

High-grade platinum-group metal concentrations have been identified in an abundant class of near-Earth asteroids known as LL Chondrites. The potential existence of a high-value asteroid-derived mineral product is examined from an economic perspective to assess the possible impacts on long-term precious metal supply. It is hypothesized that extraterrestrial sources of platinum group metals will become available in the global marketplace in a 20-year time frame, based on current trends of growth in technology and increasing levels of human activities in near-Earth space. Current and projected trends in platinum supply and demand are cited from the relevant literature to provide an economic context and provide an example for evaluating the economic potential of future asteroid-derived precious and strategic metals.

Method for the recovery of uranium values from uranium tetrafluoride

DOEpatents

Kreuzmann, Alvin B.

1983-01-01

The invention is a novel method for the recovery of uranium from dry, particulate uranium tetrafluoride. In one aspect, the invention comprises reacting particulate uranium tetrafluoride and calcium oxide in the presence of gaseous oxygen to effect formation of the corresponding alkaline earth metal uranate and alkaline earth metal fluoride. The product uranate is highly soluble in various acidic solutions wherein the product fluoride is virtually insoluble therein. The product mixture of uranate and alkaline earth metal fluoride is contacted with a suitable acid to provide a uranium-containing solution, from which the uranium is recovered. The invention can achieve quantitative recovery of uranium in highly pure form.

Method for the recovery of uranium values from uranium tetrafluoride

DOEpatents

Kreuzmann, A.B.

1982-10-27

The invention is a novel method for the recovery of uranium from dry, particulate uranium tetrafluoride. In one aspect, the invention comprises reacting particulate uranium tetrafluoride and calcium oxide in the presence of gaseous oxygen to effect formation of the corresponding alkaline earth metal uranate and alkaline earth metal fluoride. The product uranate is highly soluble in various acidic solutions whereas the product fluoride is virtually insoluble therein. The product mixture of uranate and alkaline earth metal fluoride is contacted with a suitable acid to provide a uranium-containing solution, from which the uranium is recovered. The invention can achieve quantitative recovery of uranium in highly pure form.

Water Analysis.

ERIC Educational Resources Information Center

MacCarthy, Patrick; And Others

1989-01-01

Analytical methods are reviewed for: alkali and alkaline earth metals; transition metals; precious metals; group 12, 13, 14, and 15 metals, nonmetals; radionuclides; multiple metals; anions; gases; chromatography; mass spectroscopy; photometry; sampling; volatile compounds; surfactants; detergents; pesticides; herbicides; and fungicides. (MVL)

Blending Non-Group-3 Transition Metal and Rare-Earth Metal into a C80 Fullerene Cage with D5h Symmetry.

PubMed

Wei, Tao; Jin, Fei; Guan, Runnan; Huang, Jing; Chen, Muqing; Li, Qunxiang; Yang, Shangfeng

2018-02-11

Rare-earth metals have been mostly entrapped into fullerene cages to form endohedral clusterfullerenes, whereas non-Group-3 transition metals that can form clusterfullerenes are limited to titanium (Ti) and vanadium (V), and both are exclusively entrapped within an I h -C 80 cage. Non-Group-3 transition-metal-containing endohedral fullerenes based on a C 80 cage with D 5h symmetry, V x Sc 3-x N@D 5h -C 80 (x=1, 2), have now been synthesized, which exhibit two variable cluster compositions. The molecular structure of VSc 2 N@D 5h -C 80 was unambiguously determined by X-ray crystallography. According to a comparative study with the reported Ti- and V-containing clusterfullerenes based on a I h -C 80 cage and the analogous D 5h -C 80 -based metal nitride clusterfullerenes containing rare-earth metals only, the decisive role of the non-Group-3 transition metal on the formation of the corresponding D 5h -C 80 -based clusterfullerenes is unraveled. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Metal-organic framework materials based on icosahedral boranes and carboranes

DOEpatents

Mirkin, Chad A.; Hupp, Joseph T.; Farha, Omar K.; Spokoyny, Alexander M.; Mulfort, Karen L.

2010-11-02

Disclosed herein are metal-organic frameworks of metals and boron rich ligands, such as carboranes and icosahedral boranes. Methods of synthesizing and using these materials in gas uptake are disclosed.

Composite nanoparticles containing rare earth metal and methods of preparation thereof

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

Kandapallil, Binil Itty Ipe; Krishnan, Lakshmi; Johnson, Francis

The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.

Hydrogen Abundances in Metal Grains from the Hammadah Al Hamra (HaH) 237 Metal-rich Chondrite: A Test of the Nebular-Formation Theory

NASA Technical Reports Server (NTRS)

Lauretta, D. S.; Guan, Y.; Leshin, L. A.

2005-01-01

The Bencubbin-like (CB) chondrites are metal-rich, primitive meteorites [1,2]. Some of these chondrites (HaH 237, QUE 94411) contain compositionally zoned metal grains with near-chondritic bulk compositions. Thermodynamic modeling of the zoning patterns in these grains suggests that they were formed by condensation in a region of the solar nebula with enhanced dust/gas ratios and a total pressure of 10(exp -4) bars at temperatures between 1400 - 1500 K [3]. If these predictions are correct than the metal grains would have been exposed to abundant H2 gas, which comprises the bulk of nebular systems. Since Fe-based alloys can absorb significant quantities of H, metal grains formed in the solar nebula should contain measurable abundances of H.

Induction slag reduction process for purifying metals

DOEpatents

Traut, Davis E.; Fisher, II, George T.; Hansen, Dennis A.

1991-01-01

A continuous method is provided for purifying and recovering transition metals such as neodymium and zirconium that become reactive at temperatures above about 500.degree. C. that comprises the steps of contacting the metal ore with an appropriate fluorinating agent such as an alkaline earth metal fluosilicate to form a fluometallic compound, and reducing the fluometallic compound with a suitable alkaline earth or alkali metal compound under molten conditions, such as provided in an induction slag metal furnace. The method of the invention is advantageous in that it is simpler and less expensive than methods used previously to recover pure metals, and it may be employed with a wide range of transition metals that were reactive with enclosures used in the prior art methods and were hard to obtain in uncontaminated form.

Iridium, sulfur isotopes and rare earth elements in the Cretaceous-Tertiary boundary clay at Stevns Klint, Denmark

NASA Astrophysics Data System (ADS)

Schmitz, Birger; Andersson, Per; Dahl, Jeremy

1988-01-01

Microbial activity and redox-controlled precipitation have been of major importance in the process of metal accumulation in the strongly Ir-enriched Cretaceous-Tertiary (K-T) boundary clay, the Fish Clay, at Stevns Klint in Denmark. Two important findings support this view: 1) Kerogen, recovered by leaching the Fish Clay in HCl and HF, shows an Ir concentration of 1100 ppb; this represents about 50% of the Ir present in the bulk sample Fish Clay. Strong organometallic complexes is the most probable carrier phase for this fraction of Ir. Kerogen separated from the K-T boundary clay at Caravaca, Spain, similarly exhibits enhanced Ir concentrations. 2) Sulfur isotope analyses of metal-rich pyrite spherules, which occur in extreme abundance (about 10% by weight) in the basal Fish Clay, give a δ 34S value of -32%.. This very low value shows that sulfide formation by anaerobic bacteria was intensive in the Fish Clay during early diagenesis. Since the pyrite spherules are major carriers of elements such as Ni, Co, As, Sb and Zn, microbial activity may have played an important role for concentrating these elements. In the Fish Clay large amounts of rare earth elements have precipitated from sea water on fish scales. Analyses reveal that, compared with sea water, the Fish Clay is only about four times less enriched in sea-water derived lanthanides than in Ir. This shows that a sea-water origin is plausible for elements that are strongly enriched in the clay, but whose origin cannot be accounted for by a lithogenic precursor.

Iron chemistry at the service of life.

PubMed

Sánchez, Manu; Sabio, Laura; Gálvez, Natividad; Capdevila, Mercè; Dominguez-Vera, Jose M

2017-06-01

Iron is an essential element for almost all organisms on Earth. It is necessary for a number of crucial processes such as hemoglobin and myoglobin transport and storage of oxygen in mammals; electron transfer support in a variety of iron-sulfur protein or cytochrome reactions; and activation and catalysis of reactions of a wide range of substrate like alkanes, olefins, and alcohols. Living organisms adopted iron as the main metal to carry out all of these functions due to the rich coordination chemistry of its two main redox states, Fe 2+ and Fe 3+ , and because of its abundance in the Earth's crust and oceans. This paper presents an overview of the coordination chemistry of iron that makes it suitable for a large variety of functions within biological systems. Despite iron's chemical advantages, organisms were forced to manage with some drawbacks: Fe 3+ insolubility and the formation of toxic radicals, especially the hydroxyl radical. Iron chemistry within biology is an example of how organisms evolved by creating molecular machinery to overcome these difficulties and perform crucial processes with extraordinary elegance and efficiency. © 2017 IUBMB Life, 69(6):382-388, 2017. © 2017 International Union of Biochemistry and Molecular Biology.

U, Th, and K in planetary cores: Implications for volatile elements and heat production

NASA Astrophysics Data System (ADS)

Boujibar, A.; Habermann, M.; Righter, K.; Ross, D. K.; Righter, M.; Chidester, B.; Rapp, J. F.; Danielson, L. R.; Pando, K.; Andreasen, R.

2016-12-01

The accretion of terrestrial planets is known to be accompanied with volatile loss due to strong solar winds produced by the young Sun and due to energetic impacts. It was previously expected that Mercury, the innermost planet is depleted in volatile elements in comparison to other terrestrial planets. These predictions have been recently challenged by the MESSENGER mission to Mercury that detected relatively high K/U and K/Th ratios on Mercury's surface, suggesting a volatile content similar to Earth and Mars. However previous studies showed that Fe-rich metals can incorporate substantial U, Th and K under reducing conditions and with high sulfur contents, which are two conditions relevant to Mercury. In order to quantify the fractionation of these heat-producing elements during core segregation, we determined experimentally their partition coefficients (Dmet/sil) between metal and silicate at varying pressure, temperature, oxygen fugacity and sulfur content. Our data confirm that U, Th, and K become more siderophile with decreasing fO2 and increasing sulfur content, with a stronger effect for U and Th in comparison to K. Hence Mercury's core is likely to have incorporated more U and Th than K, resulting in the elevated K/U and K/Th ratios measured on the surface. The bulk concentrations of U, Th, and K in terrestrial planets (Mercury, Venus, Earth and Mars) are calculated based on geochemical constraints on core-mantle differentiation. Significant amounts of U, Th and K are partitioned into the cores of Mercury, Venus and Earth, but much less into Mars' core. The resulting bulk planet K/U and K/Th correlate with the heliocentric distance, which suggests an overall volatile depletion in the inner Solar System. These results have important implications for internal heat production. The role of impact erosion on the evolution of Th/U ratio will also be addressed.

Ferroelectric fluoride compositions and methods of making and using same

DOEpatents

Halasyamani, P Shiv; Chang, Hong-Young

2015-04-07

A method for synthesis of a ferroelectric material characterized by the general formula A.sub.xB.sub.yF.sub.z where A is an alkaline earth metal, B is transition metal or a main group metal, x and y each range from about 1 to about 5, and z ranges from about 1 to about 20 comprising contacting an alkaline earth metal fluoride, a difluorometal compound and a fluoroorganic acid in a medium to form a reaction mixture; and subjecting the reaction mixture to conditions suitable for hydrothermal crystal growth.

Ion exchange polymers and method for making

NASA Technical Reports Server (NTRS)

Philipp, Warren H. (Inventor); Street, Kenneth W., Jr. (Inventor)

1994-01-01

An ion exchange polymer comprised of an alkali metal or alkaline earth metal salt of a poly(carboxylic acid) in a poly(vinyl acetal) matrix is described. The polymer is made by treating a mixture made of poly(vinyl alcohol) and poly(acrylic acid) with a suitable aldehyde and an acid catalyst to cause acetalization with some cross-linking. The material is then subjected to an alkaline aqueous solution of an alkali metal salt or an alkali earth metal salt. All of the film forming and cross-linking steps can be carried out simultaneously, if desired.

Generation of copper rich metallic phases from waste printed circuit boards.

PubMed

Cayumil, R; Khanna, R; Ikram-Ul-Haq, M; Rajarao, R; Hill, A; Sahajwalla, V

2014-10-01

The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150°C under argon gas flowing at 1L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Signatures of bulge triaxiality from kinematics in Baade's window

NASA Astrophysics Data System (ADS)

Zhao, Hongsheng; Spergel, David N.; Rich, R. Michael

1994-12-01

We study a sample of 62 Baade's Window, (l,b) = (1, -4)deg, K giants that have published proper motions, radial velocity, and metallicity. Using R0 = 8 kpc, we construct the velocity ellipsoids, namely the 3x3 velocity dispersion tensors, for the metal rich stars ((Fe/H) greater than or equal to 0) and metal poor stars ((Fe/H) less than or equal to -0.2). After diagonalizing the tensor, we find a vertex deviation characteristic of a nonaxisymmetric system. Eigenvalues for the two velocity ellipsoids (sigma1, sigma2, sigma3) are (126, 89, 65) +/- 13 km/s for the metal rich sample and (154, 77, 83) +/- 25 km/s for the metal poor sample with their long axes pointing to two nearly perpendicular directions (lv, bv) = (-65 +/- 9 deg, +14 +/- 9 deg) and (lv, bv) = (25 +/- 14 deg, -11 +/- 14 deg), respectively. The vertex deviations of the velocity ellipsoids cannot be consistently explained by any oblate model. We are able to reject the hypothesis that the metal poor and metal rich populations are drawn from the same distribution at better than the 97% confidence level. We populate orbits in a realistic bar potential with a Gaussian velocity distribution, allowing us to simulate and interpret observations. We conclude that the data are consistent with a triaxial bulge pointing towards (l,b) with l less than 0 deg and b = 0 deg as suggested by earlier work on gas dynamics and the observed light distribution. We also predict that low latitude (absolute value of b less than or equal to 4 deg) bulge fields should show the vertex deviation more strongly and would therefore be the best locations for future proper motion studies. In the classification scheme of Athanassoula et al. (1983) the metal rich stars appear to occupy the B-family orbits which rotate in the prograde sense in the rest frame and have boxy shapes that are aligned with and supporting the bar. The metal poor stars in the sample lag behind the metal rich bulge and appear to occupy R-family orbits which rotate in the retrograde sense in the rest frame. They have nearly round loop shapes and are aligned perpendicularly to the bar, hence limit the triaxiality of the bar potential. The correlations between the metallicity and the orbit families can develop if the bulge forms dissipatively on a sufficiently long time scale. However, it is difficult to explain such correlations if most stars in the inner Galaxy form during the violent relaxation phase.

Milky Way globular cluster metallicity and low-mass X-ray binaries: the red giant influence

NASA Astrophysics Data System (ADS)

Vulic, N.; Barmby, P.; Gallagher, S. C.

2018-02-01

Galactic and extragalactic studies have shown that metal-rich globular clusters (GCs) are approximately three times more likely to host bright low-mass X-ray binaries (LMXBs) than metal-poor GCs. There is no satisfactory explanation for this metallicity effect. We tested the hypothesis that the number density of red giant branch (RGB) stars is larger in metal-rich GCs, and thus potentially the cause of the metallicity effect. Using Hubble Space Telescope photometry for 109 unique Milky Way GCs, we investigated whether RGB star density was correlated with GC metallicity. Isochrone fitting was used to calculate the number of RGB stars, which were normalized by the GC mass and fraction of observed GC luminosity, and determined density using the volume at the half-light radius (rh). The RGB star number density was weakly correlated with metallicity [Fe/H], giving Spearman and Kendall Rank test p-values of 0.000 16 and 0.000 21 and coefficients rs = 0.35 and τ = 0.24, respectively. This correlation may be biased by a possible dependence of rh on [Fe/H], although studies have shown that rh is correlated with Galactocentric distance and independent of [Fe/H]. The dynamical origin of the rh-metallicity correlation (tidal stripping) suggests that metal-rich GCs may have had more active dynamical histories, which would promote LMXB formation. No correlation between the RGB star number density and metallicity was found when using only the GCs that hosted quiescent LMXBs. A complete census of quiescent LMXBs in our Galaxy is needed to further probe the metallicity effect, which will be possible with the upcoming launch of eROSITA.

Mineralogy controls on reactive transport of Marcellus Shale waters.

PubMed

Cai, Zhang; Wen, Hang; Komarneni, Sridhar; Li, Li

2018-07-15

Produced or flowback waters from Marcellus Shale gas extraction (MSWs) typically are highly saline and contain chemicals including trace metals, which pose significant concerns on water quality. The natural attenuation of MSW chemicals in groundwater is poorly understood due to the complex interactions between aquifer minerals and MSWs, limiting our capabilities to monitor and predict. Here we combine flow-through experiments and process-based reactive transport modeling to understand mechanisms and quantify the retention of MSW chemicals in a quartz (Qtz) column, a calcite-rich (Cal) column, and a clay-rich (Vrm, vermiculite) column. These columns were used to represent sand, carbonate, and clay-rich aquifers. Results show that the types and extent of water-rock interactions differ significantly across columns. Although it is generally known that clay-rich media retard chemicals and that quartz media minimize water-rock interactions, results here have revealed insights that differ from previous thoughts. We found that the reaction mechanisms are much more complex than merely sorption and mineral precipitation. In clay rich media, trace metals participate in both ion exchange and mineral precipitation. In fact, the majority of metals (~50-90%) is retained in the solid via mineral precipitation, which is surprising because we typically expect the dominance of sorption in clay-rich aquifers. In the Cal column, trace metals are retained not only through precipitation but also solid solution partitioning, leading to a total of 75-99% retention. Even in the Qtz column, trace metals are retained at unexpectedly high percentages (~20-70%) due to precipitation. The reactive transport model developed here quantitatively differentiates the relative importance of individual processes, and bridges a limited number of experiments to a wide range of natural conditions. This is particularly useful where relatively limited knowledge and data prevent the prediction of complex rock-contaminant interactions and natural attenuation. Copyright © 2018 Elsevier B.V. All rights reserved.

XUV-exposed, non-hydrostatic hydrogen-rich upper atmospheres of terrestrial planets. Part I: atmospheric expansion and thermal escape.

PubMed

Erkaev, Nikolai V; Lammer, Helmut; Odert, Petra; Kulikov, Yuri N; Kislyakova, Kristina G; Khodachenko, Maxim L; Güdel, Manuel; Hanslmeier, Arnold; Biernat, Helfried

2013-11-01

The recently discovered low-density "super-Earths" Kepler-11b, Kepler-11f, Kepler-11d, Kepler-11e, and planets such as GJ 1214b represent the most likely known planets that are surrounded by dense H/He envelopes or contain deep H₂O oceans also surrounded by dense hydrogen envelopes. Although these super-Earths are orbiting relatively close to their host stars, they have not lost their captured nebula-based hydrogen-rich or degassed volatile-rich steam protoatmospheres. Thus, it is interesting to estimate the maximum possible amount of atmospheric hydrogen loss from a terrestrial planet orbiting within the habitable zone of late main sequence host stars. For studying the thermosphere structure and escape, we apply a 1-D hydrodynamic upper atmosphere model that solves the equations of mass, momentum, and energy conservation for a planet with the mass and size of Earth and for a super-Earth with a size of 2 R(Earth) and a mass of 10 M(Earth). We calculate volume heating rates by the stellar soft X-ray and extreme ultraviolet radiation (XUV) and expansion of the upper atmosphere, its temperature, density, and velocity structure and related thermal escape rates during the planet's lifetime. Moreover, we investigate under which conditions both planets enter the blow-off escape regime and may therefore experience loss rates that are close to the energy-limited escape. Finally, we discuss the results in the context of atmospheric evolution and implications for habitability of terrestrial planets in general.

Methylenediphosphonotetrathioate: synthesis, characterization, and chemical properties.

PubMed

Amir, Aviran; Sayer, Alon Haim; Ezra, Alon; Fischer, Bilha

2013-03-18

Metal chelators are potential therapeutic agents for treating diseases such as Wilson's and Alzheimer's where the pathology involves an excess of metal-ions (Cu(II) and Zn(II)/Cu(II)/Fe(II/III), respectively). In addition to the high affinity of the metal-ion to the chelators, metal selectivity of the chelators is essential to achieve the therapeutic goal, that is, the successful removal of excess of harmful metal-ions in a physiological extracellular medium rich in alkali and alkali earth metal-ions. For this purpose, we synthesized a novel chelator, methylenediphosphonotetrathioate (MDPT) which is the tetrathio analogue of methylenediphosphonic acid (MDP). MDPT was synthesized from bis-methylene(phosphonicdichloride) in a 3-step synthesis and a 31% overall yield. MDPT formed a stable complex with Zn(II) (log K = 10.84), which is 10(7) times more stable than the corresponding Ca(II) complex. Moreover, the MDPT-Zn(II) complex was 50-fold more stable than the MDP-Zn(II) complex. In addition, MDPT was found to inhibit the Cu(I)-catalyzed Fenton reaction (IC50 26 μM) 2.5 times more potently than a Fe(II)-catalyzed Fenton reaction, and 2.5 times more potently than EDTA (IC50 64 μM) in the Cu(I)/H2O2 system, as monitored by electron spin resonance (ESR). Furthermore, MDPT was found to be relatively stable in both acidic (pD 1.9, t(½) = 71.5 h) and basic media (pD 12.4, t(½) = 81 h) as monitored by (31)P/(1)H NMR. However, MDPT was not stable in air because of intramolecular oxidation and disulfide formation (33% oxidation after 27 h). In conclusion, MDPT was found to be a water-soluble chelator showing a clear preference to soft/borderline metal-ions and a remarkable selectivity to those metal-ions vs Ca(II) ions. The relative sensitivity of MDPT to oxidation may limit its use; however, the application of MDPT in acidic or basic media will increase its lifetime.

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.

Corrosion protection of steel in ammonia/water heat pumps

DOEpatents

Mansfeld, Florian B.; Sun, Zhaoli

2003-10-14

Corrosion of steel surfaces in a heat pump is inhibited by adding a rare earth metal salt to the heat pump's ammonia/water working fluid. In preferred embodiments, the rare earth metal salt includes cerium, and the steel surfaces are cerated to enhance the corrosion-inhibiting effects.

IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR CERIUM OXIDE (STABLE) AND COMPOUNDS

EPA Science Inventory

Cerium is a member of the lanthanoid series of rare earth metals. It is also the most abundant and most reactive of the rare earth metals. Cerium oxidizes at room temperature and forms a variety of salt compounds including oxides, hydroxides, sulfates and chlorides. Cerium is ...

The Effect of Alkaline Earth Metal on the Cesium Loading of Ionsiv(R) IE-910 and IE-911

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

Fondeur, F.F.

2001-01-16

This study investigated the effect of variances in alkaline earth metal concentrations on cesium loading of IONSIV(R) IE-911. The study focused on Savannah River Site (SRS) ''average'' solution with varying amounts of calcium, barium and magnesium.

New technology of extracting the amount of rare earth metals from the red mud

NASA Astrophysics Data System (ADS)

Martoyan, G. A.; Karamyan, G. G.; Vardan, G. A.

2016-01-01

The paper outlined the environmental and economic problems associated with red mud - the waste generated in processing of bauxite ore for aluminum production. The chemical analysis of red mud has identified a number of useful elements including rare earth metals. The electromembrane technology of red mud processing with extraction of valuable elements is described. A possible scheme of separation of these metals through electrolysis is also given.

Microscopic evaluation of trace metals in cloud droplets in an acid precipitation region.

PubMed

Li, Weijun; Wang, Yan; Collett, Jeffrey L; Chen, Jianmin; Zhang, Xiaoye; Wang, Zifa; Wang, Wenxing

2013-05-07

Mass concentrations of soluble trace metals and size, number, and mixing properties of nanometal particles in clouds determine their toxicity to ecosystems. Cloud water was found to be acidic, with a pH of 3.52, at Mt. Lu (elevation 1,165 m) in an acid precipitation region in South China. A combination of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Transmission Electron Microscopy (TEM) for the first time demonstrates that the soluble metal concentrations and solid metal particle number are surprisingly high in acid clouds at Mt. Lu, where daily concentrations of SO2, NO2, and PM10 are 18 μg m(-3), 7 μg m(-3), and 22 μg m(-3). The soluble metals in cloudwater with the highest concentrations were zinc (Zn, 200 μg L(-1)), iron (Fe, 88 μg L(-1)), and lead (Pb, 77 μg L(-1)). TEM reveals that 76% of cloud residues include metal particles that range from 50 nm to 1 μm diameter with a median diameter of 250 nm. Four major metal-associated particle types are Pb-rich (35%), fly ash (27%), Fe-rich (23%), and Zn-rich (15%). Elemental mapping shows that minor soluble metals are distributed within sulfates of cloud residues. Emissions of fine metal particles from large, nonferrous industries and coal-fired power plants with tall stacks were transported upward to this high elevation. Our results suggest that the abundant trace metals in clouds aggravate the impacts of acid clouds or associated precipitation on the ecosystem and human health.

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.

The Redox Dynamics of Iron in a Seasonally Waterlogged Forest Soil (Chaux Forest, Eastern France) Traced with Rare Earth Element Distribution Patterns

NASA Astrophysics Data System (ADS)

Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.

2014-12-01

The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.

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

Koepf, Matthieu; Bergkamp, Jesse J.; Teillout, Anne-Lucie

The association of different metals in stable, well-defined molecular assemblies remains a great challenge of supramolecular chemistry. In such constructs, the emergence of synergism, or cooperative effects between the different metal centers is particularly intriguing. These effects can lead to uncommon reactivity or remarkable physico-chemical properties that are not otherwise achievable. For example, the association of alkaline or alkaline-earth cations and transition metals is pivotal for the activity of several biomolecules and human-made catalysts that carry out fundamental redox transformations (water oxidation, nitrogen reduction, water–gas shift reaction, etc.). In many cases the precise nature of the interactions between the alkaline-earthmore » cations and the redox-active transition metals remains elusive due to the difficulty of building stable molecular heterometallic assemblies that associate transition metals and alkaline or alkaline-earth cations in a controlled way. In this work we present the rational design of porphyrin-based ligands possessing a second binding site for alkaline-earth cations above the porphyrin macrocycle primary complexation site. We demonstrate that by using a combination of crown ether and carboxylic acid substituents suitably positioned on the periphery of the porphyrin, bitopic ligands can be obtained. The binding of calcium, a typical alkaline-earth cation, by the newly prepared ligands has been studied in detail and we show that a moderately large binding constant can be achieved in protic media using ligands that possess some degree of structural flexibility. The formation of Zn–Ca assemblies discussed in this work is viewed as a stepping stone towards the assembly of well defined molecular transition metal-alkaline earth bimetallic centers using a versatile organic scaffold.« less

Equilibrium distribution of rare earth elements between molten KCl-LiCl eutectic salt and liquid cadmium

NASA Astrophysics Data System (ADS)

Sakata, Masahiro; Kurata, Masaki; Hijikata, Takatoshi; Inoue, Tadashi

1991-11-01

Distribution experiments for several rare earth elements (La, Ce, Pr, Nd and Y) between molten KCl-LiCl eutectic salt and liquid Cd were carried out at 450, 500 and 600°C. The material balance of rare earth elements after reaching the equilibrium and their distribution and chemical states in a Cd sample frozen after the experiment were examined. The results suggested the formation of solid intermetallic compounds at the lower concentrations of rare earth metals dissolved in liquid Cd than those solubilities measured in the binary alloy system. The distribution coefficients of rare earth elements between two phases (mole fraction in the Cd phase divided by mole fraction in the salt phase) were determined at each temperature. These distribution coefficients were explained satisfactorily by using the activity coefficients of chlorides and metals in salt and Cd. Both the activity coefficients of metal and chloride caused a much smaller distribution coefficient of Y relative to those of other elements.

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare-Earth-Metal Cyclo-P3 Complexes.

PubMed

Du, Shanshan; Yin, Jianhao; Chi, Yue; Xu, Ling; Zhang, Wen-Xiong

2017-12-11

The [3+1] fragmentation reaction of rare-earth metallacyclopentadienes 1 a-c with 0.5 equivalents of P 4 affords a series of rare-earth metal cyclo-P 3 complexes 2 a-c and a phospholyl anion 3. 2 a-c demonstrate an unusual η 3 coordination mode with one P-P bond featuring partial π-bonding character. 2 a-c are the first cyclo-P 3 complexes of rare-earth metals, and also the first organo-substituted polyphosphides in the category of Group 3 and f-block elements. Rare-earth metallacyclopentadienes play a dual role in the combination of aromatization and Diels-Alder reaction. Compounds 2 a-c can coordinate to one or two [W(CO) 5 ] units, yielding 4 a-c or 5 c, respectively. Furthermore, oxidation of 2 a with p-benzoquinone produces its corresponding phospholyllithium and regenerated P 4 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seeded Nanowire and Microwire Growth from Lithium Alloys.

PubMed

Han, Sang Yun; Boebinger, Matthew G; Kondekar, Neha P; Worthy, Trevor J; McDowell, Matthew T

2018-06-06

Although vapor-liquid-solid (VLS) growth of nanowires from alloy seed particles is common in various semiconductor systems, related wire growth in all-metal systems is rare. Here, we report the spontaneous growth of nano- and microwires from metal seed particles during the cooling of Li-rich bulk alloys containing Au, Ag, or In. The as-grown wires feature Au-, Ag-, or In-rich metal tips and LiOH shafts; the results indicate that the wires grow as Li metal and are converted to polycrystalline LiOH during and/or after growth due to exposure to H 2 O and O 2 . This new process is a simple way to create nanostructures, and the findings suggest that metal nanowire growth from alloy seeds is possible in a variety of systems.

Melt containment member

DOEpatents

Rieken, Joel R.; Heidloff, Andrew J.

2014-09-09

A tubular melt containment member for transient containment of molten metals and alloys, especially reactive metals and alloys, includes a melt-contacting layer or region that comprises an oxygen-deficient rare earth oxide material that is less reactive as compared to the counterpart stoichiometric rare earth oxide. The oxygen-deficient (sub-stoichiometric) rare earth oxide can comprise oxygen-deficient yttria represented by Y.sub.2O.sub.3-x wherein x is from 0.01 to 0.1. Use of the oxygen-deficient rare earth oxide as the melt-contacting layer or region material reduces reaction with the melt for a given melt temperature and melt contact time.

Chemical solution seed layer for rabits tapes

DOEpatents

Goyal, Amit; Paranthaman, Mariappan; Wee, Sung-Hun

2014-06-10

A method for making a superconducting article includes the steps of providing a biaxially textured substrate. A seed layer is then deposited. The seed layer includes a double perovskite of the formula A.sub.2B'B''O.sub.6, where A is rare earth or alkaline earth metal and B' and B'' are different rare earth or transition metal cations. A superconductor layer is grown epitaxially such that the superconductor layer is supported by the seed layer.

Novel condensation of Au-centered trigonal prisms in rare-earth-metal-rich tellurides: Er7Au2Te2 and Lu7Au2Te2.

PubMed

Gupta, Shalabh; Corbett, John D

2010-07-14

A new monoclinic structure occurs for Er(7)Au(2)Te(2) according to X-ray diffraction analysis of single crystals grown at 1200 degrees C: C2/m, Z = 4, a = 17.8310(9) A, b = 3.9819(5) A, c = 16.9089(9) A, beta = 104.361(4) degrees. The isostructural Lu(7)Au(2)Te(2) also exists according to X-ray powder pattern means, a = 17.536(4) A, b = 3.9719(4) A, c = 16.695(2) A, beta = 104.33(1) degrees. The structure contains zigzag chains of condensed, Au-centered tricapped trigonal prisms (TCTP) of Er along c that also share basal faces along b to generate puckered sheets. Further bi-face-capping Er atoms between these generate the three dimensional network along a, with tellurium in cavities outlined by augmented trigonal prismatic Er polyhedra. Bonding analysis via LMTO-DFT methods reveal very significant Er-Au bonding interactions, as quantified by their energy-weighted Hamilton overlap populations (-ICOHP), approximately 49% of the total for all interactions. These and similar Er-Te contributions sharply contrast with the small Er-Er population, only approximately 14% of the total in spite of the high proportion of Er-Er contacts. The strong polar bonding of Er to the electronegative Au and Te leaves Er relatively oxidized, with many of its 5d states falling above the Fermi level and empty. The contradiction with customary representations of structures that highlight rare-earth metal clusters is manifest. The large Er-Au Hamilton overlap population is in accord with the strong bonding between early and late transition metals first noted by Brewer in 1973. The relationship of this structure to the more distorted orthorhombic (Imm2) structure type of neighboring Dy(7)Ir(2)Te(2) is considered.

Empirical links between trace metal cycling and marine microbial ecology during a large perturbation to Earth's carbon cycle

NASA Astrophysics Data System (ADS)

Owens, Jeremy D.; Reinhard, Christopher T.; Rohrssen, Megan; Love, Gordon D.; Lyons, Timothy W.

2016-09-01

Understanding the global redox state of the oceans and its cause-and-effect relationship with periods of widespread organic-carbon deposition is vital to interpretations of Earth's climatic and biotic feedbacks during periods of expanded oceanic oxygen deficiency. Here, we present a compilation of new and published data from an organic-rich locality within the proto-North Atlantic Ocean during the Cenomanian-Turonian boundary event that shows a dramatic drawdown of redox-sensitive trace elements. Iron geochemistry independently suggests euxinic deposition (i.e., anoxic and sulfidic bottom waters) for the entire section, thus confirming its potential as an archive of global marine metal inventories. In particular, depleted molybdenum (Mo) and vanadium (V) concentrations effectively record the global expansion of euxinic and oxygen-deficient but non-sulfidic waters, respectively. The V drawdown precedes the OAE, fingerprinting an expansion of oxygen deficiency prior to an expansion of euxinia. Molybdenum drawdown, in contrast, is delayed with respect to V and coincides with the onset of OAE2. Parallel lipid biomarker analyses provide evidence for significant and progressive reorganization of marine microbial ecology during the OAE in this region of the proto-North Atlantic, with the smallest relative eukaryotic contributions to total primary production occurring during metal-depleted intervals. This relationship may be related to decreasing supplies of enzymatically important trace elements. Similarly, box modeling suggests that oceanic drawdown of Mo may have approached levels capable of affecting marine nitrogen fixation. Predictions of possible nitrogen stress on eukaryotic production, locally and globally, are consistent with the low observed levels of Mo and a rise in 2-methylhopane index values during the peak of the OAE. At the same time, the environmental challenge presented by low dissolved oxygen and euxinia coincides with increased turnover rates of radiolarian clades, calcareous nanofossils, and foraminifera, suggesting that the temporal patterns of anoxia/euxinia and associated nutrient limitation may have contributed to the fabric of OAE2-related turnover.

Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

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

Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun

2016-06-06

We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead tomore » spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.« less

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 1. Scandium Group (Sc, Y, La)

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

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

2014-03-15

This work presents an assessment of solubility data for rare earth metal fluorides (generally of trivalent metals and of CeF{sub 4}) in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal fluoride with a corresponding critical evaluation. Every such evaluation contains a collection of all solubility results in water, a selection of suggested solubility data, and a brief discussion of the multicomponent systems. Because the ternary systems were seldom studied more than once, no critical evaluations of such data were possible. Only simple fluorides (no complexes or binary salts) aremore » treated as the input substances in this report. The literature has been covered through the end of 2013.« less

Extraction of heavy metal (Ba, Sr) and high silica glass powder synthesis from waste CRT panel glasses by phase separation.

PubMed

Xing, Mingfei; Wang, Jingyu; Fu, Zegang; Zhang, Donghui; Wang, Yaping; Zhang, Zhiyuan

2018-04-05

In this study, a novel process for the extraction of heavy metal Ba and Sr from waste CRT panel glass and synchronous preparation of high silica glass powder was developed by glass phase separation. CRT panel glass was first remelted with B 2 O 3 under air atmosphere to produce alkali borosilicate glass. During the phase separation process, the glass separated into two interconnected phases which were B 2 O 3 -rich phase and SiO 2 -rich phase. Most of BaO, SrO and other metal oxides including Na 2 O, K 2 O, Al 2 O 3 and CaO were mainly concentrated in the B 2 O 3 -rich phase. The interconnected B 2 O 3 -rich phase can be completely leached out by 5mol/L HNO 3 at 90 ℃. The remaining SiO 2 -rich phase was porous glasses consisting almost entirely of silica. The maximum Ba and Sr removal rates were 98.84% and 99.38% and high silica glass powder (SiO 2 purity > 90 wt%) was obtained by setting the temperature, B 2 O 3 added amount and holding time at 1000-1100 ℃, 20-30% and 30 min, respectively. Thus this study developed an potential economical process for detoxification and reclamation of waste heavy metal glasses. Copyright © 2017 Elsevier B.V. All rights reserved.

Uncharged positive electrode composition

DOEpatents

Kaun, Thomas D.; Vissers, Donald R.; Shimotake, Hiroshi

1977-03-08

An uncharged positive-electrode composition contains particulate lithium sulfide, another alkali metal or alkaline earth metal compound other than sulfide, e.g., lithium carbide, and a transition metal powder. The composition along with a binder, such as electrolytic salt or a thermosetting resin is applied onto an electrically conductive substrate to form a plaque. The plaque is assembled as a positive electrode within an electrochemical cell opposite to a negative electrode containing a material such as aluminum or silicon for alloying with lithium. During charging, lithium alloy is formed within the negative electrode and transition metal sulfide such as iron sulfide is produced within the positive electrode. Excess negative electrode capacity over that from the transition metal sulfide is provided due to the electrochemical reaction of the other than sulfide alkali metal or alkaline earth metal compound.

Contribution of eukaryotic microbial communities to the formation of Fe-rich accretions in an extreme acidic environment

NASA Astrophysics Data System (ADS)

Rodrigues, L.; Valente, T.; Correia, A.; Alves, A.; Foing, B.; Davies, G. R.

2012-04-01

In the acid mine drainage of Valdarcas, northern Portugal, Fe-rich tubular and spherical macroaccretions are directly associated with the presence of eukaryotic microorganisms. This raises the question whether they are biogenically-derived or the result of an abiotic process mediated by microeukaryotic phototrophs. The drainage water at Valdarcas is characterized by very low pH values (pH<3.5), high metal solubility and presence of iron colloids. Mineralogical analysis (XRD and SEM) of the precipitates indicates a mixture of goethite, schwertmannite and jarosite. Euglenophyta and Chlorophyta acidophilic algal were previously identified in this site. The spatial distribution of Euglena mutabilis indicated that it has a preference to grow up on schwertmannite-rich precipitates. Field observations demonstrate the existence of oxygenated microenvironments created by algal activity suggesting that algae influence iron minerals precipitation, especially schwertmannite. The mineral-microorganism interactions are relevant to understanding this unique and extreme environment. Further investigations regarding the mineralogical and chemical characterization of these deposits, and the identification of microorganisms involved in the process could be helpful to enhance our knowledge of past Fe formations throughout Earth's primordial environment. It is expectable that this information will contribute to establish a framework for recognition of biosignatures on other planets and extraterrestrial bodies. In this study, results on the chemical and mineralogical composition of the structures are presented. The biological context is characterised based on observations made by optical microscopy complemented with molecular data on the microbial communities obtained by culture independent methods. The results are discussed within the context of two models: the studied Fe-rich stromatolites are microeukaryotic-mediated as described by previous workers from similar environments or are the consequence of inorganic precipitation of reduced iron species (Fe(III)) due to the oxygen generated by the photosynthesis?

Improved Heat-of-Fusion Energy Storage

NASA Technical Reports Server (NTRS)

Chen, K. H.; Manvi, R.

1982-01-01

Alkali metal/alkali-halide mixtures proposed for preventing solid buildup during energy recovery. When mixture melts (by absorption of heat of fusion), it forms two immiscible liquids. Salt-rich phase is heavier and has higher melting/recrysallization temperature; so during energy recovery salt crystallizes in this phase first. Since heat exchanger for energy recovery is in lighter metal-rich phase, solids do not form and there is no reduction of heat-recovery efficiency.

Disturbances to metal partitioning during toxicity testing of iron(II)-rich estuarine pore waters and whole sediments.

PubMed

Simpson, Stuart L; Batley, Graeme E

2003-02-01

Metal partitioning is altered when suboxic estuarine sediments containing Fe(II)-rich pore waters are disturbed during collection, preparation, and toxicity testing. Experiments with model Fe(II)-rich pore waters demonstrated the rates at which adsorptive losses of Cd, Cu, Ni, Mn, Pb, and Zn occur upon exposure to air. Experiments with Zn-contaminated estuarine sediments demonstrated large and often unpredictable changes to metal partitioning during sediment storage, removal of organisms, and homogenization before testing. Small modifications to conditions, such as aeration of overlying waters, caused large changes to the metal partitioning. Disturbances caused by sediment collection required many weeks for reestablishment of equilibrium. Bioturbation by benthic organisms led to oxidation of pore-water Fe(II) and lower Zn fluxes because of the formation of Fe hydroxide precipitates that adsorb pore-water Zn. For five weeks after the addition of organisms to sediments, Zn fluxes increased slowly as the organisms established themselves in the sediments, indicating that the establishment of equilibrium was not rapid. The results are discussed in terms of the dynamic nature of suboxic, Fe(II)-rich estuarine sediments, how organisms perturb their environment, and the importance of understanding chemistry in toxicity testing with whole sediments or pore water. Recommendations are provided for the handling of sediments for toxicity testing.

Molybdenite in calcium-aluminum-rich inclusions in the Allende meteorite

NASA Technical Reports Server (NTRS)

Fuchs, L. H.; Blander, M.

1977-01-01

The first observations of molybdenite in a meteorite have been made in two Ca-Al-rich inclusions in the Allende chondrite. The mineral occurs as single individuals completely enclosed in high Ni metal (62-64.5 wt. % Ni). The association with refractories is consistent with thermodynamic calculations which predict that Mo is a high temperature condensate even when nucleation constraints are imposed on the formation of a metal phase. Kinetic factors (including nucleation constraints) appear to have played an important role in the formation of molybdenite and the associated sulfides, magnetite and high nickel metal.

Metal-halide mixtures for latent heat energy storage

NASA Astrophysics Data System (ADS)

Chen, K.; Manvi, R.

Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

Metal-halide mixtures for latent heat energy storage

NASA Technical Reports Server (NTRS)

Chen, K.; Manvi, R.

1981-01-01

Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

Model of Silicon Refining During Tapping: Removal of Ca, Al, and Other Selected Element Groups

NASA Astrophysics Data System (ADS)

Olsen, Jan Erik; Kero, Ida T.; Engh, Thorvald A.; Tranell, Gabriella

2017-04-01

A mathematical model for industrial refining of silicon alloys has been developed for the so-called oxidative ladle refining process. It is a lumped (zero-dimensional) model, based on the mass balances of metal, slag, and gas in the ladle, developed to operate with relatively short computational times for the sake of industrial relevance. The model accounts for a semi-continuous process which includes both the tapping and post-tapping refining stages. It predicts the concentrations of Ca, Al, and trace elements, most notably the alkaline metals, alkaline earth metal, and rare earth metals. The predictive power of the model depends on the quality of the model coefficients, the kinetic coefficient, τ, and the equilibrium partition coefficient, L for a given element. A sensitivity analysis indicates that the model results are most sensitive to L. The model has been compared to industrial measurement data and found to be able to qualitatively, and to some extent quantitatively, predict the data. The model is very well suited for alkaline and alkaline earth metals which respond relatively fast to the refining process. The model is less well suited for elements such as the lanthanides and Al, which are refined more slowly. A major challenge for the prediction of the behavior of the rare earth metals is that reliable thermodynamic data for true equilibrium conditions relevant to the industrial process is not typically available in literature.

Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

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

Marking, Gregory Allen

1994-01-04

Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf 10Ta 3S 3 was found to crystallize in a new-structure type similar to the knownmore » gamma brasses. This structure is unique in that it is the only reported "stuffed" gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co 2Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.« less

The Meaning of "Magma"

NASA Astrophysics Data System (ADS)

Bartley, J. M.; Glazner, A. F.; Coleman, D. S.

2016-12-01

Magma is a fundamental constituent of the Earth, and its properties, origin, evolution, and significance bear on issues ranging from volcanic hazards to planetary evolution. Unfortunately, published usages indicate that the term "magma" means distinctly different things to different people and this can lead to miscommunication among Earth scientists and between scientists and the public. Erupting lava clearly is magma; the question is whether partially molten rock imaged at depth and too crystal-rich to flow should also be called magma. At crystal fractions > 50%, flow can only occur via crystal deformation and solution-reprecipitation. As the solid fraction increases to 90% or more, the material becomes a welded crystal framework with melt in dispersed pores and/or along grain boundaries. Seismic images commonly describe such volumes of a few % melt as magma, yet the rheological differences between melt-rich and melt-poor materials make it vital not to confuse a large rock volume that contains a small melt fraction with melt-rich material. To ensure this, we suggest that "magma" be reserved for melt-rich materials that undergo bulk fluid flow on timescales consonant with volcanic eruptions. Other terms should be used for more crystal-rich and largely immobile partially molten rock (e.g., "crystal mush," "rigid sponge"). The distinction is imprecise but useful. For the press, the public, and even earth scientists who do not study magmatic systems, "magma" conjures up flowing lava; reports of a large "magma" body that contains a few percent melt can engender the mistaken perception of a vast amount of eruptible magma. For researchers, physical processes like crystal settling are commonly invoked to account for features in plutonic rocks, but many such processes are only possible in melt-rich materials.

Is There a Metallicity Ceiling to Form Carbon Stars? - A Novel Technique Reveals a Scarcity of C-Stars in the Inner M31 Disk

NASA Technical Reports Server (NTRS)

Boyer, Martha L.; Girardi, L.; Marigo, P.; Williams, B. F.; Aringer, B.; Nowotny, W.; Rosenfield, P.; Dorman, C. E.; Guhathakurta, P.; Dalcanton, J. J.;

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.

Voltage Control of Rare-Earth Magnetic Moments at the Magnetic-Insulator-Metal Interface

NASA Astrophysics Data System (ADS)

Leon, Alejandro O.; Cahaya, Adam B.; Bauer, Gerrit E. W.

2018-01-01

The large spin-orbit interaction in the lanthanides implies a strong coupling between their internal charge and spin degrees of freedom. We formulate the coupling between the voltage and the local magnetic moments of rare-earth atoms with a partially filled 4 f shell at the interface between an insulator and a metal. The rare-earth-mediated torques allow the power-efficient control of spintronic devices by electric-field-induced ferromagnetic resonance and magnetization switching.

Energetic Ionic Liquids Based on Anionic Rare Earth Nitrate Complexes (Preprint)

DTIC Science & Technology

2008-07-10

a glass transition temperature (Tg) at -46 oC. However, it is only stable in dry air, and thus must be protected from water. At 75 oC, clear weight...involved highly toxic and corrosive chemicals, N2O4 and NOCl. Ligands which coordinate via oxygen atoms to a rare earth metal ion give rise to stable...complexes. Thus higher air and thermal stabilities may be obtained by introducing rare earth metal nitrates as main components of ionic liquids. We

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

Chadid, Merieme; Sneden, Christopher; Preston, George W., E-mail: chadid@unice.fr, E-mail: chris@verdi.as.utexas.edu, E-mail: gwp@obs.carnegiescience.edu

We investigate atmospheric properties of 35 stable RRab stars that possess the full ranges of period, light amplitude, and metal abundance found in Galactic RR Lyrae stars. Our results are derived from several thousand echelle spectra obtained over several years with the du Pont telescope of Las Campanas Observatory. Radial velocities of metal lines and the H α line were used to construct curves of radial velocity versus pulsation phase. From these we estimated radial velocity amplitudes for metal lines (formed near the photosphere) and H α Doppler cores (formed at small optical depths). We also measured H α emissionmore » fluxes when they appear during primary light rises. Spectra shifted to rest wavelengths, binned into small phase intervals, and co-added were used to perform model atmospheric and abundance analyses. The derived metallicities and those of some previous spectroscopic surveys were combined to produce a new calibration of the Layden abundance scale. We then divided our RRab sample into metal-rich (disk) and metal-poor (halo) groups at [Fe/H] = −1.0; the atmospheres of RRab families, so defined, differ with respect to (a) peak strength of H α emission flux, (b) H α radial velocity amplitude, (c) dynamical gravity, (d) stellar radius variation, (e) secondary acceleration during the photometric bump that precedes minimum light, and (f) duration of H α line-doubling. We also detected H α line-doubling during the “bump” in the metal-poor family, but not in the metal-rich one. Although all RRab probably are core helium-burning horizontal branch stars, the metal-rich group appears to be a species sui generis.« less

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.

Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution.

PubMed

Tajmir-Riahi, H A

1990-10-01

The interaction of L-ascorbic acid with alkaline earth metal ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type Mg(L-ascorbate)2.4H2O, Ca(L-ascorbate)2.2H2O, Sr(L-ascorbate)2.2H2O and Ba(L-ascorbate)2.2H2O were isolated and characterized by means of 13C NMR and FT-IR spectroscopy. Spectroscopic and other evidence suggested that in aqueous solution, the binding of the alkaline earth metal ions is through the O-3 atom of the ascorbate anion, while in the solid state the binding of the Mg(II) is different from those of the other alkaline earth metal ion salts. The Mg(II) ion binds to the O-3, O-1 atom of the two ascorbate anions and to two H2O molecules, while the eight-coordination around the Ca(II), Sr(II), and Ba(II) ions would be completed by the coordination of three acid anions, through O-5, O-6 of the first, O-3, O-5, O-6 of the second and O-1 of the third anion as well as to two H2O molecules. The structural properties of the alkaline earth metal-ascorbate salts are different in the solid and aqueous solution.

A Geological Model for the Evolution of Early Continents (Invited)

NASA Astrophysics Data System (ADS)

Rey, P. F.; Coltice, N.; Flament, N. E.; Thébaud, N.

2013-12-01

Geochemical probing of ancient sediments (REE in black shales, strontium composition of carbonates, oxygen isotopes in zircons...) suggests that continents were a late Archean addition at Earth's surface. Yet, geochemical probing of ancient basalts reveals that they were extracted from a mantle depleted of its crustal elements early in the Archean. Considerations on surface geology, the early Earth hypsometry and the rheology and density structure of Archean continents can help solve this paradox. Surface geology: The surface geology of Archean cratons is characterized by thick continental flood basalts (CFBs, including greenstones) emplaced on felsic crusts dominated by Trondhjemite-Tonalite-Granodiorite (TTG) granitoids. This simple geology is peculiar because i/ most CFBs were emplaced below sea level, ii/ after their emplacement, CFBs were deformed into relatively narrow, curviplanar belts (greenstone basins) wrapping around migmatitic TTG domes, and iii/ Archean greenstone belts are richly endowed with gold and other metals deposits. Flat Earth hypothesis: From considerations on early Earth continental geotherm and density structure, Rey and Coltice (2008) propose that, because of the increased ability of the lithosphere to flow laterally, orogenic processes in the Archean produced only subdued topography (

Seasonal change: a device built to show why and how it happens

NASA Astrophysics Data System (ADS)

Marques, J. B.; Rocha, P. S.; Couto da Silva, T. C.

2003-08-01

Most of people believe that the seasonal change is caused by the varying distance between the Earth and the Sun as the Earth moves on its orbit around the Sun. If the varying solar distance were the cause of change of seasons, both the northern and southern hemispheres of the Earth would have the same seasonal change at the same time. But what happens is that the hemispheres have opposites seasons : when it is summer in the north it is winter in the south; when it is spring in the north it is autumn in the south, and vice-versa. The greatest factor responsible for this occurrence is the 23.5º tilt of Earth's rotational axis relative to the perpendicular to its orbit, and the fact that the Earth's rotational axis maintains a constant direction as the Earth orbits the Sun. This causes a 23.5º tilt of the celestial equator relative to the plane which contains the Sun. Because of this, the Sun can be seen as high as 23.5º above the celestial equator and low as 23.5º below it at any hemisphere. In an attempt to demonstrate why different seasons occur during the time the Earth takes to go around the Sun, a witty and original device was built using low price material such as : sewing machine pulley, wood pulley, woodbasis, wood rod, metal rod, metal bearing, metal axis, leash, nylon wire, double copper wire, isopor ball, pen tube, interrupter, lamp, nipple, plug, crank. This allow teachers to reproduce the device with their students. The idea of building a device with this goal is not new. However, a simple device which keeps the rotational axis of a figurative Earth constant in direction as it moves around the representative Sun was not found out in astronomy teaching literature. This device allows this to occur because the pen tube (which acts as the Earth's rotational axis) remains free to spin around the metal axis, kept settled. The pen tube is connected by a leash to the metal rod settled on the wood basis. When the wood system rod + pulley is turned round through a crank, the representative Earth's rotational axis (pen tube), is kept free to spin around the metal axis, maintaining its initial configuration. It is worthwhile to notice that the metal rod and the pen tube must have the same thickness. That is necessary because after a full revolution the wood system rod + pulley and the pen tube must return to the same position to keep the representative Earth's rotational axis with its initial configuration. The teacher may also explain to the students that the Earth's rotational axis really changes its positions in a very smooth way, in a period of nearly 26,000 years. This time is much greater than the lifetime of a human being, but this motion is noticed since ancient time. The device works as a helpful instrument to a teacher in any introductory astronomy course.

High pressure phase transitions in the rare earth metal erbium to 151 GPa.

PubMed

Samudrala, Gopi K; Thomas, Sarah A; Montgomery, Jeffrey M; Vohra, Yogesh K

2011-08-10

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence hcp → Sm type → dhcp → distorted fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

High pressure phase transitions in the rare earth metal erbium to 151 GPa

NASA Astrophysics Data System (ADS)

Samudrala, Gopi K.; Thomas, Sarah A.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

2011-08-01

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence {hcp} \\to {Sm}~ {type} \\to {dhcp} \\to {distorted} fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

Concentration of precious metals during their recovery from electronic waste.

PubMed

Cayumil, R; Khanna, R; Rajarao, R; Mukherjee, P S; Sahajwalla, V

2016-11-01

The rapid growth of electronic devices, their subsequent obsolescence and disposal has resulted in electronic waste (e-waste) being one of the fastest increasing waste streams worldwide. The main component of e-waste is printed circuit boards (PCBs), which contain substantial quantities of precious metals in concentrations significantly higher than those typically found in corresponding ores. The high value and limited reserves of minerals containing these metals makes urban mining of precious metals very attractive. This article is focused on the concentration and recovery of precious metals during pyro-metallurgical recycling of waste PCBs. High temperature pyrolysis was carried out for ten minutes in a horizontal tube furnace in the temperature range 800-1350°C under Argon gas flowing at 1L/min. These temperatures were chosen to lie below and above the melting point (1084.87°C) of copper, the main metal in PCBs, to study the influence of its physical state on the recovery of precious metals. The heat treatment of waste PCBs resulted in two different types of solid products, namely a carbonaceous non-metallic fraction (NMFs) and metallic products, composed of copper rich foils and/or droplets and tin-lead rich droplets and some wires. Significant proportions of Ag, Au, Pd and Pt were found concentrated within two types of metallic phases, with very limited quantities retained by the NMFs. This process was successful in concentrating several precious metals such as Ag, Au, Pd and Pt in a small volume fraction, and reduced volumes for further processing/refinement by up to 75%. The amounts of secondary wastes produced were also minimised to a great extent. The generation of precious metals rich metallic phases demonstrates high temperature pyrolysis as a viable approach towards the recovery of precious metals from e-waste. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Na-O anticorrelation in horizontal branch stars. IV. M 22

NASA Astrophysics Data System (ADS)

Gratton, R. G.; Lucatello, S.; Sollima, A.; Carretta, E.; Bragaglia, A.; Momany, Y.; D'Orazi, V.; Cassisi, S.; Salaris, M.

2014-03-01

We obtained high-resolution spectra for 94 candidate stars belonging to the HB of M 22 with FLAMES. Previous works have indicated that this cluster has split subgiant (SGB) and red giant branches (RGB) and hosts two different stellar populations, differing in overall metal abundance and both exhibiting a Na-O anti-correlation. The HB stars we observed span a restricted temperature range (7800 < Teff < 11 000 K), where about 60% of the HB stars of M 22 are. Within our sample, we can distinguish three groups of stars segregated (though contiguous) in colours: Group 1 (49 stars) is metal-poor, N-normal, Na-poor, and O-rich: our abundances for this (cooler) group match those determined for the primordial group of RGB stars (a third of the total) from previous studies very well. Group 2 (23 stars) is still metal-poor, but it is N- and Na-rich, though only very mildly depleted in O. We can identify this intermediate group as the progeny of the metal-poor RGB stars that occupy an intermediate location along the Na-O anti-correlation and include about 10% of the RGB stars. The third group (20 stars) is metal-rich, Na-rich, and O-rich. This hotter group most likely corresponds to the most O-rich component of the previously found metal-rich RGB population (a quarter of the total). We did not observe any severely O-depleted stars and we think that the progeny of these stars falls on the hotter part of the HB. Furthermore, we found that the metal-rich population is also over-abundant in Sr, in agreement with results for corresponding RGB and SGB stars. However, we do not find any significant variation in the ratio between the sum of N and O abundances to Fe. We do not have C abundances for our stars. There is some evidence of an enhancement of He content for Groups 2 and 3 stars (Y = 0.338 ± 0.014 ± 0.05); the error bar due to systematics is large, but a consistent analysis of data for several GCs confirms that stars in these groups within M 22 are probably overabundant in He. We conclude that on the whole, our results agree with the proposition that chemical composition drives the location of stars along the HB of a GC. Furthermore, we found a number of fast rotators. They are concentrated in a restricted temperature range along the HB of M 22. Fast rotating stars might be slightly less massive and bluer than slowly rotating ones, but other interpretations are possible. Based on observations collected at ESO telescopes under programmes 087.D-0230 and 091.D-0151.Tables 3-6 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/563/A13

Sources of Extraterrestrial Rare Earth Elements:To the Moon and Beyond

NASA Astrophysics Data System (ADS)

McLeod, C. L.; Krekeler, M. P. S.

2017-08-01

The resource budget of Earth is limited. Rare-earth elements (REEs) are used across the world by society on a daily basis yet several of these elements have <2500 years of reserves left, based on current demand, mining operations, and technologies. With an increasing population, exploration of potential extraterrestrial REE resources is inevitable, with the Earth's Moon being a logical first target. Following lunar differentiation at 4.50-4.45 Ga, a late-stage (after 99% solidification) residual liquid enriched in Potassium (K), Rare-earth elements (REE), and Phosphorus (P), (or "KREEP") formed. Today, the KREEP-rich region underlies the Oceanus Procellarum and Imbrium Basin region on the lunar near-side (the Procellarum KREEP Terrain, PKT) and has been tentatively estimated at preserving 2.2 × 10^8 km^3 of KREEP-rich lithologies. The majority of lunar samples (Apollo, Luna, or meteoritic samples) contain REE-bearing minerals as trace phases, e.g., apatite and/or merrillite, with merrillite potentially contributing up to 3% of the PKT. Other lunar REE-bearing lunar phases include monazite, yittrobetafite (up to 94,500 ppm yttrium), and tranquillityite (up to 4.6 wt % yttrium, up to 0.25 wt % neodymium), however, lunar sample REE abundances are low compared to terrestrial ores. At present, there is no geological, mineralogical, or chemical evidence to support REEs being present on the Moon in concentrations that would permit their classification as ores. However, the PKT region has not yet been mapped at high resolution, and certainly has the potential to yield higher REE concentrations at local scales (<10s of kms). Future lunar exploration and mapping efforts may therefore reveal new REE deposits. Beyond the Moon, Mars and other extraterrestrial materials are host to REEs in apatite, chevkinite-perrierite, merrillite, whitlockite, and xenotime. These phases are relatively minor components of the meteorites studied to date, constituting <0.6% of the total sample. Nonetheless, they dominate a samples REE budget with their abundances typically 1-2 orders of magnitude enriched relative to their host rock. As with the Moon, though phases which host REEs have been identified, no extraterrestrial REE resource, or ore, has been identified yet. At present extraterrestrial materials are therefore not suitable REE-mining targets. However, they are host to other resources that will likely be fundamental to the future of space exploration and support the development of in situ resource utilization, for example: metals (Fe, Al, Mg, PGEs) and water.

A correlation between the heavy element content of transiting extrasolar planets and the metallicity of their parent stars

NASA Astrophysics Data System (ADS)

Guillot, T.; Santos, N. C.; Pont, F.; Iro, N.; Melo, C.; Ribas, I.

2006-07-01

Context.Nine extrasolar planets with masses between 110 and 430 M_⊕ are known to transit their star. The knowledge of their masses and radii allows an estimate of their composition, but uncertainties on equations of state, opacities and possible missing energy sources imply that only inaccurate constraints can be derived when considering each planet separately.Aims.We seek to better understand the composition of transiting extrasolar planets by considering them as an ensemble, and by comparing the obtained planetary properties to that of the parent stars.Methods.We use evolution models and constraints on the stellar ages to derive the mass of heavy elements present in the planets. Possible additional energy sources like tidal dissipation due to an inclined orbit or to downward kinetic energy transport are considered.Results.We show that the nine transiting planets discovered so far belong to a quite homogeneous ensemble that is characterized by a mass of heavy elements that is a relatively steep function of the stellar metallicity, from less than 20 earth masses of heavy elements around solar composition stars, to up to ~100 M_⊕ for three times the solar metallicity (the precise values being model-dependant). The correlation is still to be ascertained however. Statistical tests imply a worst-case 1/3 probability of a false positive.Conclusions.Together with the observed lack of giant planets in close orbits around metal-poor stars, these results appear to imply that heavy elements play a key role in the formation of close-in giant planets. The large masses of heavy elements inferred for planets orbiting metal rich stars was not anticipated by planet formation models and shows the need for alternative theories including migration and subsequent collection of planetesimals.

Origin of enormous trace metal enrichments in weathering mantles of Jurassic carbonates: evidence from Sr, Nd and Pb isotopes

NASA Astrophysics Data System (ADS)

Hissler, C.; Stille, P.; Juilleret, J.; Iffly, J.; Perrone, T.; Morvan, G.

2013-12-01

Weathering mantels are widespread worldwide and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved carbonate rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual content of associated trace elements in this type of weathering mantle. For instance, these enrichments can represent about five times the content of the underlying Bajocian to Oxfordian limestone/marl complexes, which have been relatively poorly studied compared to weathering mantle developed on magmatic bedrocks. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources (saprolite, Bajocian silty marls and limestones, atmospheric particles deposition...). Of special interest has also been the origin of trace metals and the processes causing their enrichments. Especially Rare Earth Element (REE) distribution patterns and Sr, Nd and Pb isotope ratios are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments shall help to identify mobile phases in the soil system. This may inform on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. Trace metal migration and enrichments were studied on a cambisol developing on an underlying Jurassic limestone. The base is strongly enriched among others in rare earth elements (ΣREE: 2640ppm) or redox-sensitive elements such as Fe (44 wt.%), V (920ppm), Cr (700ppm), Zn (550ppm), As (260ppm), Co (45ppm) and Cd (2.4ppm). The underlying limestone and marl show, compared to average world carbonates, enrichments in the same elements and trace element distribution patterns similar to the soil suggesting their close genetic relationship. Pb, Sr and Nd isotope data allow to identify three principal components in the soil: a silicate-rich phase at close to the surface, a strongly trace metal enriched component at the bottom of the soil profile and an anthropogenic, atmosphere- derived component detected in the soil leachates. The isotopic mixing curves defined by the soil samples point to the close genetic connection between upper and lowermost soil horizons. The Nd isotopic composition of the leachates of all soil horizons are in contrast to the untreated soil and residual soil samples very homogeneous suggesting that the leachable phases of the upper and lower soil horizons are genetically connected. The downward migration of the trace metals is stopped at this soil level due to the presence of important secondary calcite precipitations, smectite and Fe-oxide accumulations. Mass balance calculations indicate that the enrichment process goes along with a volume increase relative to the bottom soil horizons.

The CR (Renazzo-type) carbonaceous chondrite group and its implications

NASA Technical Reports Server (NTRS)

Weisberg, Michael K.; Prinz, Martin; Clayton, Robert N.; Mayeda, Toshiko K.

1993-01-01

A petrologic, geochemical, and oxygen isotropic study of the CR chondrites including Renazzo, Al Rais, El Djouf 001 and the paired Acfer meteorites, EET87770 and the paired samples, MAC87320, Y790112, Y793495, and Y791498 is presented. It is concluded that the CR group is characterized by abundant large multilayered, Fe, Ni metal-rich, type I chondrules; abundant matrix and dark inclusions; unique assemblages of serpentine and chlorite-rich phyllosilicates and Ca-carbonates; Ca-carbonate rims on chondrules; abundant Fe, Ni metal with a positive Ni vs. Co trend and a solar Ni:Co ratio; and amoeboid olivine aggregates with Mn-rich and Mn-poor forsterite.

Fabricated nanogap-rich plasmonic nanostructures through an optothermal surface bubble in a droplet.

PubMed

Karim, Farzia; Vasquez, Erick S; Zhao, Chenglong

2018-01-15

A rapid and cost-effective method for the fabrication of nanogap-rich structures is demonstrated in this Letter. The method utilizes the Marangoni convection around an optothermal surface bubble inside a liquid droplet with a nanoliter volume. The liquid droplet containing metallic nanoparticles reduces the sample consumption and confines the liquid flow. The optothermal surface bubble creates a strong convective flow that allows for the rapid deposition of the metallic nanoparticles to form nanogap-rich structures on any substrate under ambient conditions. This method will enable a broad range of applications such as biosensing, environmental analysis, and nonlinear optics.

A volatile-rich Earth's core inferred from melting temperature of core materials

NASA Astrophysics Data System (ADS)

Morard, G.; Andrault, D.; Antonangeli, D.; Nakajima, Y.; Auzende, A. L.; Boulard, E.; Clark, A. N.; Lord, O. T.; Cervera, S.; Siebert, J.; Garbarino, G.; Svitlyk, V.; Mezouar, M.

2016-12-01

Planetary cores are mainly constituted of iron and nickel, alloyed with lighter elements (Si, O, C, S or H). Understanding how these elements affect the physical and chemical properties of solid and liquid iron provides stringent constraints on the composition of the Earth's core. In particular, melting curves of iron alloys are key parameter to establish the temperature profile in the Earth's core, and to asses the potential occurrence of partial melting at the Core-Mantle Boundary. Core formation models based on metal-silicate equilibration suggest that Si and O are the major light element components1-4, while the abundance of other elements such as S, C and H is constrained by arguments based on their volatility during planetary accretion5,6. Each compositional model implies a specific thermal state for the core, due to the different effect that light elements have on the melting behaviour of Fe. We recently measured melting temperatures in Fe-C and Fe-O systems at high pressures, which complete the data sets available both for pure Fe7 and other binary alloys8. Compositional models with an O- and Si-rich outer core are suggested to be compatible with seismological constraints on density and sound velocity9. However, their crystallization temperatures of 3650-4050 K at the CMB pressure of 136 GPa are very close to, if not higher than the melting temperature of the silicate mantle and yet mantle melting above the CMB is not a ubiquitous feature. This observation requires significant amounts of volatile elements (S, C or H) in the outer core to further reduce the crystallisation temperature of the core alloy below that of the lower mantle. References 1. Wood, B. J., et al Nature 441, 825-833 (2006). 2. Siebert, J., et al Science 339, 1194-7 (2013). 3. Corgne, A., et al Earth Planet. Sc. Lett. 288, 108-114 (2009). 4. Fischer, R. a. et al. Geochim. Cosmochim. Acta 167, 177-194 (2015). 5. Dreibus, G. & Palme, H. Geochim. Cosmochim. Acta 60, 1125-1130 (1995). 6. McDonough, W. F. Treatise in Geochemistry 2, 547-568 (2003). 7. Anzellini, S., et al Science 340, 464-6 (2013). 8. Morard, G. et al. Phys. Chem. Miner. 38, 767-776 (2011). 9. Badro, J., et al Proc. Natl. Acad. Sci. U. S. A. 111, 7542-5 (2014).

One-process fabrication of metal hierarchical nanostructures with rich nanogaps for highly-sensitive surface-enhanced Raman scattering.

PubMed

Liu, Gui-qiang; Yu, Mei-dong; Liu, Zheng-qi; Liu, Xiao-shan; Huang, Shan; Pan, Ping-ping; Wang, Yan; Liu, Mu-lin; Gu, Gang

2015-05-08

One-process fabrication of highly active and reproducible surface-enhanced Raman scattering (SERS) substrates via ion beam deposition is reported. The fabricated metal-dielectric-metal (MDM) hierarchical nanostructure possesses rich nanogaps and a tunable resonant cavity. Raman scattering signals of analytes are dramatically strengthened due to the strong near-field coupling of localized surface plasmon resonances (LSPRs) and the strong interaction of LSPRs of metal NPs with surface plasmon polaritons (SPPs) on the underlying metal film by crossing over the dielectric spacer. The maximum Raman enhancement for the highest Raman peak at 1650 cm(-1) is 13.5 times greater than that of a single metal nanoparticle (NP) array. Moreover, the SERS activity can be efficiently tailored by varying the size and number of voids between adjacent metal NPs and the thickness of the dielectric spacer. These findings may broaden the scope of SERS applications of MDM hierarchical nanostructures in biomedical and analytical chemistry.

The Gaia-ESO Survey: Churning through the Milky Way

NASA Astrophysics Data System (ADS)

Hayden, M. R.; Recio-Blanco, A.; de Laverny, P.; Mikolaitis, S.; Guiglion, G.; Hill, V.; Gilmore, G.; Randich, S.; Bayo, A.; Bensby, T.; Bergemann, M.; Bragaglia, A.; Casey, A.; Costado, M.; Feltzing, S.; Franciosini, E.; Hourihane, A.; Jofre, P.; Koposov, S.; Kordopatis, G.; Lanzafame, A.; Lardo, C.; Lewis, J.; Lind, K.; Magrini, L.; Monaco, L.; Morbidelli, L.; Pancino, E.; Sacco, G.; Stonkute, E.; Worley, C. C.; Zwitter, T.

2018-01-01

Context. There have been conflicting results with respect to the extent that radial migration has played in the evolution of the Galaxy. Additionally, observations of the solar neighborhood have shown evidence of a merger in the past history of the Milky Way that drives enhanced radial migration. Aims: We attempt to determine the relative fraction of stars that have undergone significant radial migration by studying the orbital properties of metal-rich ([Fe/H] > 0.1) stars within 2 kpc of the Sun. We also aim to investigate the kinematic properties, such as velocity dispersion and orbital parameters, of stellar populations near the Sun as a function of [Mg/Fe] and [Fe/H], which could show evidence of a major merger in the past history of the Milky Way. Methods: We used a sample of more than 3000 stars selected from the fourth internal data release of the Gaia-ESO Survey. We used the stellar parameters from the Gaia-ESO Survey along with proper motions from PPMXL to determine distances, kinematics, and orbital properties for these stars to analyze the chemodynamic properties of stellar populations near the Sun. Results: Analyzing the kinematics of the most metal-rich stars ([Fe/H] > 0.1), we find that more than half have small eccentricities (e< 0.2) or are on nearly circular orbits. Slightly more than 20% of the metal-rich stars have perigalacticons Rp> 7 kpc. We find that the highest [Mg/Fe], metal-poor populations have lower vertical and radial velocity dispersions compared to lower [Mg/Fe] populations of similar metallicity by 10 km s-1. The median eccentricity increases linearly with [Mg/Fe] across all metallicities, while the perigalacticon decreases with increasing [Mg/Fe] for all metallicities. Finally, the most [Mg/Fe]-rich stars are found to have significant asymmetric drift and rotate more than 40 km s-1 slower than stars with lower [Mg/Fe] ratios. Conclusions: While our results cannot constrain how far stars have migrated, we propose that migration processes are likely to have played an important role in the evolution of the Milky Way, with metal-rich stars migrating from the inner disk toward to solar neighborhood and past mergers potentially driving enhanced migration of older stellar populations in the disk.

The Potential of Aluminium Metal Powder as a Fuel for Space Propulsion Systems

NASA Astrophysics Data System (ADS)

Ismail, A. M.; Osborne, B.; Welch, C. S.

Metal powder propulsion systems have been addressed intermittently since the Second World War, initially in the field of underwater propulsion where research in the application of propelling torpedoes continues until this day. During the post war era, researchers attempted to utilise metal powders as a fuel for ram jet applications in missiles. The 1960's and 1970's saw additional interest in the use of `pure powder' propellants, i.e. fluidised metal fuel and oxidiser, both in solid particulate form. Again the application was for employment in space-constrained missiles where the idea was to maximise the performance of high energy density powder propellants in order to enhance the missile's flight duration. Metal powder as possible fuel was investigated for in-situ resource utilisation propulsion systems post-1980's where the emphasis was on the use of gaseous oxygen or liquid oxygen combined with aluminium metal powder for use as a ``lunar soil propellant'' or carbon dioxide and magnesium metal powder as a ``Martian propellant''.Albeit aluminium metal powder propellants are lower in performance than cryogenic and Earth storable propellants, the former does have an advantage inasmuch that the propulsion system is generic, i.e. it can be powered with chemicals mined and processed on Earth, the Moon and Mars. Thus, due to the potential refuelling capability, the lower performing aluminium metal powder propellant would effectively possess a much higher change in velocity (V) for multiple missions than the cryogenic or Earth storable propellant which is only suitable for one planet or one mission scenario, respectively.One of the principal limitations of long duration human spaceflight beyond cis-lunar orbit is the lack of refuelling capabilities on distant planets resulting in the reliance on con- ventional non-cryogenic, propellants produced on Earth. If one could develop a reliable propulsion system operating on pro- pellants derived entirely of ingredients found on nearby plan- etary bodies, then not only could mission duration be extended, larger amounts of payload could be ferried to and from the destination and eventually the cost of transporting propellant ingredients from Earth could be reduced, if not eliminated.

Unique, Non-Earthlike, Meteoritic Ion Behavior in Upper Atmosphere of Mars

NASA Technical Reports Server (NTRS)

Grebowsky, J. M.; Benna, M.; Plane, J. M. C.; Collinson, G. A.; Mahaffy, P. R.; Jakosky, B. M.

2017-01-01

Abstract Interplanetary dust particles have long been expected to produce permanent ionospheric metal ion layers at Mars, as on Earth, but the two environments are so different that uncertainty existed as to whether terrestrial-established understanding would apply to Mars. The Mars Atmosphere and Volatile EvolutioN (MAVEN) mission made the first in situ detection of the continuous presence of Na+, Mg+, and Fe+ at Mars and indeed revealed non-Earthlike features/processes. There is no separation of the light Mg+ and the heavy Fe+ with increasing altitude as expected for gravity control. The metal ions are well-mixed with the neutral atmosphere at altitudes where no mixing process is expected. Isolated metal ion layers mimicking Earths sporadic E layers occur despite the lack of a strong magnetic field as required at Earth. Further, the metal ion distributions are coherent enough to always show atmospheric gravity wave signatures. All features and processes are unique to Mars.

Effects of Cations on Corrosion of Inconel 625 in Molten Chloride Salts

NASA Astrophysics Data System (ADS)

Zhu, Ming; Ma, Hongfang; Wang, Mingjing; Wang, Zhihua; Sharif, Adel

2016-04-01

Hot corrosion of Inconel 625 in sodium chloride, potassium chloride, magnesium chloride, calcium chloride and their mixtures with different compositions is conducted at 900°C to investigate the effects of cations in chloride salts on corrosion behavior of the alloy. XRD, SEM/EDS were used to analyze the compositions, phases, and morphologies of the corrosion products. The results showed that Inconel 625 suffers more severe corrosion in alkaline earth metal chloride molten salts than alkaline metal chloride molten salts. For corrosion in mixture salts, the corrosion rate increased with increasing alkaline earth metal chloride salt content in the mixture. Cations in the chloride molten salts mainly affect the thermal and chemical properties of the salts such as vapor pressure and hydroscopicities, which can affect the basicity of the molten salt. Corrosion of Inconel 625 in alkaline earth metal chloride salts is accelerated with increasing basicity.

The lunar core and the origin of the moon

NASA Astrophysics Data System (ADS)

Newsom, H. E.

1984-05-01

The results of recent analyses of concentrations of refractory siderophile elements molybdenum and rhenium in lunar rock samples suggest that most siderophile elements in lunar crustal rocks and mare basalts are significantly less concentrated than in the earth's mantle and much less than in chondrite meteorites. The depletion of siderophile elements in the samples implies the existence of a metal core, and the amount of metal in the core is directly related to the conditions under which segregation occurs. The consequences of the data are discussed in terms of three theoretical models of lunar evolution: a terrestrial origin model; a terrestrial origin model which takes metal segregation into account; and an independent origin model. It is shown that less metal is needed for a terrestrial origin because the earth's mantle was already partially depleted in siderophile elements due to the formation of the earth core.

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

PubMed Central

Nigl, Thomas P.; Smith, Nathan D.; Lichtenstein, Timothy; Gesualdi, Jarrod; Kumar, Kuldeep; Kim, Hojong

2017-01-01

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition. PMID:29155770

Coproduction of volatiles and metals from extraterrestrial materials

NASA Technical Reports Server (NTRS)

Lewis, John S.

1991-01-01

Two main efforts in support of the general goals of SERC/culpr are presented. Investigations of processes for the coproduction of metals from extra-terrestrial materials in conjunction with plausible schemes for oxygen extraction continue. The principal emphasis was on the extraction and purification of iron from the ilmenite reduction process for oxygen, from the cathode metal deposits made in the magma electrolysis process for oxygen, and from native ferrous metal alloys on the moon and asteroids. All work on the separation and purification of ferrous metals was focussed upon the gaseous carbonyl process, a scheme that involves only temperatures attainable by passive thermal control. The exploration of a variety of schemes was initiated, involving the use of several different propulsion options and both propulsive and aerobraking capture at earth, for return of extraterrestrial resources to earth orbits. In addition, the search for new opportunities in space resource utilization continues. Examples include the continuation of work underway on: (1) the feasibility of locating solar power satellites in highly eccentric earth orbit; (2) the energetics of extracting the potential clean fusion fuel He-3 from the atmosphere for return to earth; and (3) the utility of a nuclear steam rocket (using non-terrestrial water as the working fluid) for transportation in the inner solar system.

Contaminant Interferences with SIMS Analyses of Microparticle Impactor Residues on LDEF Surfaces

NASA Technical Reports Server (NTRS)

Simon, C. G.; Batchelor, D.; Griffis, D. P.; Hunter, J. L.; Misra, V.; Ricks, D. A.; Wortman, J. J.

1992-01-01

Elemental analyses of impactor residues on high purity surface exposed to the low earth orbit (LEO) environment for 5.8 years on Long Duration Exposure Facility (LDEF) has revealed several probable sources for microparticles at this altitude, including natural micrometeorites and manmade debris ranging from paint pigments to bits of stainless steel. A myriad of contamination interferences were identified and their effects on impactor debris identification mitigated during the course of this study. These interferences included pre-, post-, and in-flight deposited particulate surface contaminants, as well as indigenous heterogeneous material contaminants. Non-flight contaminants traced to human origins, including spittle and skin oils, contributed significant levels of alkali-rich carbonaceous interferences. A ubiquitous layer of in-flight deposited silicaceous contamination varied in thickness with location on LDEF and proximity to active electrical fields. In-flight deposited (low velocity) contaminants included urine droplets and bits of metal film from eroded thermal blankets.

An in-situ phosphorus source for the synthesis of Cu 3P and the subsequent conversion to Cu 3PS 4 nanoparticle clusters

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

Sheets, Erik J.; Stach, Eric A.; Yang, Wei -Chang

2015-09-20

The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I-V-VI chalcogenides including copper phosphide (Cu 3P) and copper thiophosphate (Cu 3PS 4). Herein, we report a one-pot, solution-based synthesis of Cu 3P nanocrystals utilizing an in-situ phosphorus source: phosphorus pentasulfide (P 2S 5) in trioctylphosphine (TOP). By injecting this phosphorus source into a copper solution in oleylamine (OLA), uniform and size controlled Cu 3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cumore » 3P nanocrystals with decomposing thiourea forms nanoscale Cu 3PS 4 particles having p-type conductivity and an effective optical band gap of 2.36 eV.« less

Cretaceous Footprints Found on Goddard Campus

NASA Image and Video Library

2017-12-08

Seen here we have started to encase the dinosaur footprints in what is known as a field jacket. A field jacket is much like a cast that a doctor would place on a broken arm or leg. Our field jacket consisted of many layers of burlap soaked in plaster-of-Paris into which we also laminate metal pipes to act like splints for additional support. Here Michael is working to remove the very hard sandstone layer below the iron-rich clay layer in which the prints were preserved. Photo taken on January 7, 2013. Credit: NASA/GSFC/Rebecca Roth NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

A PRELIMINARY JUPITER MODEL

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

Hubbard, W. B.; Militzer, B.

In anticipation of new observational results for Jupiter's axial moment of inertia and gravitational zonal harmonic coefficients from the forthcoming Juno orbiter, we present a number of preliminary Jupiter interior models. We combine results from ab initio computer simulations of hydrogen–helium mixtures, including immiscibility calculations, with a new nonperturbative calculation of Jupiter's zonal harmonic coefficients, to derive a self-consistent model for the planet's external gravity and moment of inertia. We assume helium rain modified the interior temperature and composition profiles. Our calculation predicts zonal harmonic values to which measurements can be compared. Although some models fit the observed (pre-Juno) second-more » and fourth-order zonal harmonics to within their error bars, our preferred reference model predicts a fourth-order zonal harmonic whose absolute value lies above the pre-Juno error bars. This model has a dense core of about 12 Earth masses and a hydrogen–helium-rich envelope with approximately three times solar metallicity.« less

A seismologically consistent compositional model of Earth’s core

PubMed Central

Badro, James; Côté, Alexander S.; Brodholt, John P.

2014-01-01

Earth’s core is less dense than iron, and therefore it must contain “light elements,” such as S, Si, O, or C. We use ab initio molecular dynamics to calculate the density and bulk sound velocity in liquid metal alloys at the pressure and temperature conditions of Earth's outer core. We compare the velocity and density for any composition in the (Fe–Ni, C, O, Si, S) system to radial seismological models and find a range of compositional models that fit the seismological data. We find no oxygen-free composition that fits the seismological data, and therefore our results indicate that oxygen is always required in the outer core. An oxygen-rich core is a strong indication of high-pressure and high-temperature conditions of core differentiation in a deep magma ocean with an FeO concentration (oxygen fugacity) higher than that of the present-day mantle. PMID:24821817

Comparison of the optical responses of O-poor and O-rich thermochromic VOX films during semiconductor-to-metal transition

NASA Astrophysics Data System (ADS)

Luo, Zhenfei; Wu, Zhiming; Wang, Tao; Xu, Xiangdong; Li, Weizhi; Li, Wei; Jiang, Yadong

2012-09-01

O-poor and O-rich thermochromic vanadium oxide (VOX) nanostructured thin films were prepared by applying reactive direct current magnetron sputtering and post-annealing in oxygen ambient. UV-visible spectrophotometer and spectroscopic ellipsometry were used to investigate the optical properties of films. It was found that, when the O-poor VOX thin film underwent semiconductor-to-metal transition, the values of optical conductivity and extinction coefficient in the visible region increased due to the existence of occupied band-gap states. This noticeable feature, however, was not observed for the O-rich film, which showed a similar optical behavior with the stoichiometric crystalline VO2 films reported in the literatures. Moreover, the O-poor VOX film exhibits consistent variations of transmission values in the visible/near-infrared region when it undergoes semiconductor-to-metal transition.

LAMOST telescope reveals that Neptunian cousins of hot Jupiters are mostly single offspring of stars that are rich in heavy elements.

PubMed

Dong, Subo; Xie, Ji-Wei; Zhou, Ji-Lin; Zheng, Zheng; Luo, Ali

2018-01-09

We discover a population of short-period, Neptune-size planets sharing key similarities with hot Jupiters: both populations are preferentially hosted by metal-rich stars, and both are preferentially found in Kepler systems with single-transiting planets. We use accurate Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) Data Release 4 (DR4) stellar parameters for main-sequence stars to study the distributions of short-period [Formula: see text] Kepler planets as a function of host star metallicity. The radius distribution of planets around metal-rich stars is more "puffed up" compared with that around metal-poor hosts. In two period-radius regimes, planets preferentially reside around metal-rich stars, while there are hardly any planets around metal-poor stars. One is the well-known hot Jupiters, and the other one is a population of Neptune-size planets ([Formula: see text]), dubbed "Hoptunes." Also like hot Jupiters, Hoptunes occur more frequently in systems with single-transiting planets although the fraction of Hoptunes occurring in multiples is larger than that of hot Jupiters. About [Formula: see text] of solar-type stars host Hoptunes, and the frequencies of Hoptunes and hot Jupiters increase with consistent trends as a function of [Fe/H]. In the planet radius distribution, hot Jupiters and Hoptunes are separated by a "valley" at approximately Saturn size (in the range of [Formula: see text]), and this "hot-Saturn valley" represents approximately an order-of-magnitude decrease in planet frequency compared with hot Jupiters and Hoptunes. The empirical "kinship" between Hoptunes and hot Jupiters suggests likely common processes (migration and/or formation) responsible for their existence.

LAMOST telescope reveals that Neptunian cousins of hot Jupiters are mostly single offspring of stars that are rich in heavy elements

NASA Astrophysics Data System (ADS)

Dong, Subo; Xie, Ji-Wei; Zhou, Ji-Lin; Zheng, Zheng; Luo, Ali

2018-01-01

We discover a population of short-period, Neptune-size planets sharing key similarities with hot Jupiters: both populations are preferentially hosted by metal-rich stars, and both are preferentially found in Kepler systems with single-transiting planets. We use accurate Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) Data Release 4 (DR4) stellar parameters for main-sequence stars to study the distributions of short-period 1d

Formation of Hydrocarbons in the Outflows from Red Giants

NASA Technical Reports Server (NTRS)

Roberge, Wayne; Kress, Monika; Tielens, Alexander G.

1995-01-01

The formation of hydrocarbons in the oxygen-rich outflows from red giants was studied. The existence of organic molecules in such outflows has been known for several years; however, their surprisingly high abundances has been a mystery since all of the carbon had been thought to be irretrievably locked up in CO, the most strongly bound molecule. CO is the first molecule to form from the atoms present in the star's extended atmosphere, and as strong stellar winds drive a cooling outflow, dust grains condense out. In oxygen-rich outflows, the dust is thought to be composed mainly of silicates and other metal oxides. Perhaps the noble metals can condense out in metallic form, in particular the relatively abundant transition metals iron and nickel. We proposed that perhaps the carbon reservoir held as CO can be accessed through a catalytic process involving the chemisorption of CO and H2 onto grains rich in metallic iron. CO and H2 are the two most abundant molecules in circumstellar outflows, and they both are known to dissociate on transition metal surfaces at elevated temperatures, freeing carbon to form organic molecules such as methane. We believe methane is a precursor molecule to the organics observed in oxygen-rich red giants. We have developed a nonequilibrium numerical model of a surface chemical (catalytic) process. Based on this model, we believe that methane can be formed under the conditions present in circumstellar outflows. Although the methane formation rates are exceptionally low under these conditions, over dynamical timescales, a significant amount of CO can be converted to methane and driven further out in the envelope, explaining the presence of organics there.

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Development of experimental facilities for processing metallic crystals in orbit

NASA Technical Reports Server (NTRS)

Duncan, Bill J.

1990-01-01

This paper discusses the evolution, current status, and planning for facilities to exploit the microgravity environment of earth orbit in applied metallic materials science. Space-Shuttle based facilities and some precursor flight programs are reviewed. Current facility development programs and planned Space Station furnace capabilities are described. The reduced gravity levels available in earth orbit allow the processing of metallic materials without the disturbing influence of gravitationally induced thermal convection, stratification due to density differences in sample components, or the effects of hydrostatic pressure.

Extraction of trivalent rare-earth metal nitrates by solutions of tributyl phosphate and diisooctylmethylphosphonate in kerosene

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

Pyartman, A.K.; Puzikov, E.A.; Kopyrin, A.A.

1995-01-01

Isotherms of extraction of trivalent rare-earth metal nitrates in the series lanthanum-lutetium, yttrium by 0.5-2.5 M solutions of tri-n-buty1 phosphate and diisooctyl methylphosphonate in kerosene at 298.15 K, pH 2 are presented. The influence of the ionic strength of aqueous phase and extractant concentration on the concentration extraction constants in the case of formation of metal(III) trisolvates in organic phase is given by equation.

An Investigation of Chitosan for Sorption of Radionuclides

DTIC Science & Technology

2012-06-05

heavy metals, uranium and other actinides , and the rare earths. Alkali and alkaline earth metals have received little attention due to their low...15]. The importance and role of metal hydrolysis on biomass sorption has also been addressed by Gadd and White, for the case of 14 actinides , which are...added to plastic screw-top vials (2 mL, 4 mL or 15 mL) containing a given mass of sorbent at room temperature (20◦C ± 2◦C) or at elevated temperature (37

The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2005-01-01

Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

The Stability of Hydrogen-Rich Atmospheres of Earth-Like Planets

NASA Technical Reports Server (NTRS)

Zahnle, Kevin

2016-01-01

Understanding hydrogen escape is essential to understanding the limits to habitability, both for liquid water where the Sun is bright, but also to assess the true potential of H2 as a greenhouse gas where the Sun is faint. Hydrogen-rich primary atmospheres of Earth-like planets can result either from gravitational capture of solar nebular gases (with helium), or from impact shock processing of a wide variety of volatile-rich planetesimals (typically accompanied by H2O, CO2, and under the right circumstances, CH4). Most studies of hydrogen escape from planets focus on determining how fast the hydrogen escapes. In general this requires solving hydro- dynamic equations that take into account the acceleration of hydrogen through a critical transonic point and an energy budget that should include radiative heating and cooling, thermal conduction, the work done in lifting the hydrogen against gravity, and the residual heat carried by the hydrogen as it leaves. But for planets from which hydrogen escape is modest or insignificant, the atmosphere can be approximated as hydrostatic, which is much simpler, and for which a relatively full-featured treatment of radiative cooling by embedded molecules, atoms, and ions such as CO2 and H3+ is straightforward. Previous work has overlooked the fact that the H2 molecule is extremely efficient at exciting non-LTE CO2 15 micron emission, and thus that radiative cooling can be markedly more efficient when H2 is abundant. We map out the region of phase space in which terrestrial planets keep hydrogen-rich atmospheres, which is what we actually want to know for habitability. We will use this framework to reassess Tian et al's hypothesis that H2-rich atmospheres may have been rather long-lived on Earth itself. Finally, we will address the empirical observation that rocky planets with thin or negligible atmospheres are rarely or never bigger than 1.6 Earth radii.

Distribution and geochemistry of selected trace elements in the Sacramento River near Keswick Reservoir

USGS Publications Warehouse

Antweiler, Ronald C.; Taylor, Howard E.; Alpers, Charles N.

2012-01-01

The effect of heavy metals from the Iron Mountain Mines (IMM) Superfund site on the upper Sacramento River is examined using data from water and bed sediment samples collected during 1996-97. Relative to surrounding waters, aluminum, cadmium, cobalt, copper, iron, lead, manganese, thallium, zinc and the rare-earth elements (REE) were all present in high concentrations in effluent from Spring Creek Reservoir (SCR), which enters into the Sacramento River in the Spring Creek Arm of Keswick Reservoir. SCR was constructed in part to regulate the flow of acidic, metal-rich waters draining the IMM Superfund site. Although virtually all of these metals exist in SCR in the dissolved form, upon entering Keswick Reservoir they at least partially converted via precipitation and/or adsorption to the particulate phase. In spite of this, few of the metals settled out; instead the vast majority was transported colloidally down the Sacramento River at least to Bend Bridge, 67. km from Keswick Dam.The geochemical influence of IMM on the upper Sacramento River was variable, chiefly dependent on the flow of Spring Creek. Although the average flow of the Sacramento River at Keswick Dam is 250m 3/s (cubic meters per second), even flows as low as 0.3m 3/s from Spring Creek were sufficient to account for more than 15% of the metals loading at Bend Bridge, and these proportions increased with increasing Spring Creek flow.The dissolved proportion of the total bioavailable load was dependent on the element but steadily decreased for all metals, from near 100% in Spring Creek to values (for some elements) of less than 1% at Bend Bridge; failure to account for the suspended sediment load in assessments of the effect of metals transport in the Sacramento River can result in estimates which are low by as much as a factor of 100. ?? 2012.

Distribution and geochemistry of selected trace elements in the Sacramento River near Keswick Reservoir

USGS Publications Warehouse

Antweiler, Ronald C.; Taylor, Howard E.; Alpers, Charles N.

2012-01-01

The effect of heavy metals from the Iron Mountain Mines (IMM) Superfund site on the upper Sacramento River is examined using data from water and bed sediment samples collected during 1996-97. Relative to surrounding waters, aluminum, cadmium, cobalt, copper, iron, lead, manganese, thallium, zinc and the rare-earth elements (REE) were all present in high concentrations in effluent from Spring Creek Reservoir (SCR), which enters into the Sacramento River in the Spring Creek Arm of Keswick Reservoir. SCR was constructed in part to regulate the flow of acidic, metal-rich waters draining the IMM Superfund site. Although virtually all of these metals exist in SCR in the dissolved form, upon entering Keswick Reservoir they at least partially converted via precipitation and/or adsorption to the particulate phase. In spite of this, few of the metals settled out; instead the vast majority was transported colloidally down the Sacramento River at least to Bend Bridge, 67 km from Keswick Dam. The geochemical influence of IMM on the upper Sacramento River was variable, chiefly dependent on the flow of Spring Creek. Although the average flow of the Sacramento River at Keswick Dam is 250 m3/s (cubic meters per second), even flows as low as 0.3 m3/s from Spring Creek were sufficient to account for more than 15% of the metals loading at Bend Bridge, and these proportions increased with increasing Spring Creek flow. The dissolved proportion of the total bioavailable load was dependent on the element but steadily decreased for all metals, from near 100% in Spring Creek to values (for some elements) of less than 1% at Bend Bridge; failure to account for the suspended sediment load in assessments of the effect of metals transport in the Sacramento River can result in estimates which are low by as much as a factor of 100.

Nanostructured high-energy cathode materials for advanced lithium batteries

NASA Astrophysics Data System (ADS)

Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo; Lee, Dong-Ju; Jung, Hun-Gi; Ren, Yang; Wang, Steve; Yoon, Chong Seung; Myung, Seung-Taek; Amine, Khalil

2012-11-01

Nickel-rich layered lithium transition-metal oxides, LiNi1-xMxO2 (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures. Here, we report a nickel-rich lithium transition-metal oxide with a very high capacity (215 mA h g-1), where the nickel concentration decreases linearly whereas the manganese concentration increases linearly from the centre to the outer layer of each particle. Using this nano-functional full-gradient approach, we are able to harness the high energy density of the nickel-rich core and the high thermal stability and long life of the manganese-rich outer layers. Moreover, the micrometre-size secondary particles of this cathode material are composed of aligned needle-like nanosize primary particles, resulting in a high rate capability. The experimental results suggest that this nano-functional full-gradient cathode material is promising for applications that require high energy, long calendar life and excellent abuse tolerance such as electric vehicles.

Nanostructured high-energy cathode materials for advanced lithium batteries.

PubMed

Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo; Lee, Dong-Ju; Jung, Hun-Gi; Ren, Yang; Wang, Steve; Yoon, Chong Seung; Myung, Seung-Taek; Amine, Khalil

2012-11-01

Nickel-rich layered lithium transition-metal oxides, LiNi(1-x)M(x)O(2) (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures. Here, we report a nickel-rich lithium transition-metal oxide with a very high capacity (215 mA h g(-1)), where the nickel concentration decreases linearly whereas the manganese concentration increases linearly from the centre to the outer layer of each particle. Using this nano-functional full-gradient approach, we are able to harness the high energy density of the nickel-rich core and the high thermal stability and long life of the manganese-rich outer layers. Moreover, the micrometre-size secondary particles of this cathode material are composed of aligned needle-like nanosize primary particles, resulting in a high rate capability. The experimental results suggest that this nano-functional full-gradient cathode material is promising for applications that require high energy, long calendar life and excellent abuse tolerance such as electric vehicles.

Large Engine Technology Program. Task 21: Rich Burn Liner for Near Term Experimental Evaluations

NASA Technical Reports Server (NTRS)

Hautman, D. J.; Padget, F. C.; Kwoka, D.; Siskind, K. S.; Lohmann, R. P.

2005-01-01

The objective of the task reported herein, which was conducted as part of the NASA sponsored Large Engine Technology program, was to define and evaluate a near-term rich-zone liner construction based on currently available materials and fabrication processes for a Rich-Quench-Lean combustor. This liner must be capable of operation at the temperatures and pressures of simulated HSCT flight conditions but only needs sufficient durability for limited duration testing in combustor rigs and demonstrator engines in the near future. This must be achieved at realistic cooling airflow rates since the approach must not compromise the emissions, performance, and operability of the test combustors, relative to the product engine goals. The effort was initiated with an analytical screening of three different liner construction concepts. These included a full cylinder metallic liner and one with multiple segments of monolithic ceramic, both of which incorporated convective cooling on the external surface using combustor airflow that bypassed the rich zone. The third approach was a metallic platelet construction with internal convective cooling. These three metal liner/jacket combinations were tested in a modified version of an existing Rich-Quench-Lean combustor rig to obtain data for heat transfer model refinement and durability verification.

History of Metal Veins in Acapulcoite-Lodranite Clan Meteorite GRA 95209

NASA Technical Reports Server (NTRS)

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

2006-01-01

Graves Nunataks (GRA) 95209 has been hailed as the missing link of core formation processes in the acapulcoitelodranite parent asteroid because of the presence of a complex cm-scale metal vein network. Because the apparent liquid temperature of the metal vein (approximately 1500 C) is higher than inferred for the metamorphic grade of the meteorite, questions regarding the vein s original composition, temperature, and mechanism of emplacement have arisen. We have determined trace siderophile element compositions of metals in veins and surrounding matrix in an effort to clarify matters. We analyzed metals in GRA 95209 in a portion of thick metal vein and adjacent metal-rich (30-40 modal%), sulfide poor (less than 1%) matrix by EPMA and LA-ICP-MS for major and trace siderophile elements using methods described by [3]. We also examined metals from a metal-poor (approximately 15 modal%) and relatively sulfide-rich (2-5 modal%) region of the sample. Kamacite is the dominant metal phase in all portions of the sample. In comparison to matrix metal, vein metal contains more schreibersite and less tetrataenite, and is less commonly associated with Fe,Mn,Mg-bearing phosphates and graphite. Vein kamacite contains higher Co, P, and Cr and lower Cu and Ge. These minor variations aside, all metal types in GRA 95209 are fairly homogeneous in terms of their levels of enrichment of compatible siderophile elements (e.g. Pt, Ir, Os) relative to incompatible siderophile elements (e.g. As, Pd, Au), consistent with the loss of metal-sulfide partial melt that characterizes much of the clan. Whatever compositional differences between matrix and vein metal that may have originally existed, they have since largely co-equilibrated to similar restitic trace element compositions. We agree with [2] that metal veins, in their present state, do not represent a liquid composition. The original vein liquid was much more S-rich and emplaced at correspondingly lower liquid temperatures. Much of the Fe,Ni component solidified in cm scale conduits while S-rich melts were expelled and continued to migrate by percolation. The higher troilite content in metal poor regions of the sample results mostly from trapping of a small portion of these melts. The troilite is not remnant primary sulfide. Strong depletions of W, Mo, and especially Ga (greater than 50%, greater than 60%, and greater than 90% depletion, respectively) in metals of the metalpoor GRA 95209 lithology are localized at scales of 10-100 micrometers in the vicinity of graphite spherules. These depletions must have occurred below the temperatures at which cm-scale equilibration occurred, and future work will seek to determine their cause.