Metal Transport across Biomembranes: Emerging Models for a Distinct Chemistry*

PubMed Central

Argüello, José M.; Raimunda, Daniel; González-Guerrero, Manuel

2012-01-01

Transition metals are essential components of important biomolecules, and their homeostasis is central to many life processes. Transmembrane transporters are key elements controlling the distribution of metals in various compartments. However, due to their chemical properties, transition elements require transporters with different structural-functional characteristics from those of alkali and alkali earth ions. Emerging structural information and functional studies have revealed distinctive features of metal transport. Among these are the relevance of multifaceted events involving metal transfer among participating proteins, the importance of coordination geometry at transmembrane transport sites, and the presence of the largely irreversible steps associated with vectorial transport. Here, we discuss how these characteristics shape novel transition metal ion transport models. PMID:22389499

Metal transport across biomembranes: emerging models for a distinct chemistry.

PubMed

Argüello, José M; Raimunda, Daniel; González-Guerrero, Manuel

2012-04-20

Transition metals are essential components of important biomolecules, and their homeostasis is central to many life processes. Transmembrane transporters are key elements controlling the distribution of metals in various compartments. However, due to their chemical properties, transition elements require transporters with different structural-functional characteristics from those of alkali and alkali earth ions. Emerging structural information and functional studies have revealed distinctive features of metal transport. Among these are the relevance of multifaceted events involving metal transfer among participating proteins, the importance of coordination geometry at transmembrane transport sites, and the presence of the largely irreversible steps associated with vectorial transport. Here, we discuss how these characteristics shape novel transition metal ion transport models.

Os isotopes in SNC meteorites and their implications to the early evolution of Mars and Earth

NASA Technical Reports Server (NTRS)

Jagoutz, E.; Luck, J. M.; Othman, D. Ben; Wanke, H.

1993-01-01

A new development on the measurement of the Os isotopic composition by mass spectrometry using negative ions opened a new field of applications. The Re-Os systematic provides time information on the differentiation of the nobel metals. The nobel metals are strongly partitioned into metal and sulphide phases, but also the generation of silicate melts might fractionate the Re-Os system. Compared to the other isotopic systems which are mainly dating the fractionation of the alkalis and alkali-earth elements, the Re-Os system is expected to disclose entirely new information about the geochemistry. Especially the differentiation and early evolution of the planets such as the formation of the core will be elucidated with this method.

Geochemical aspects of some Japanese lavas.

NASA Technical Reports Server (NTRS)

Philpotts, J. A.; Martin, W.; Schnetzler, C. C.

1971-01-01

K, Rb, Sr, Ba and rare-earth concentrations in some Japanese lavas have been determined by mass-spectrometric stable-isotope dilution. The samples fall into three rare-earth groups corresponding to tholeiitic, high alumina and alkali basalts. Japanese tholeiites have trace element characteristics similar to those of oceanic ridge tholeiites except for distinctly higher relative concentrations of Ba. Japanese lavas may result from various degrees of partial fusion of amphibole eclogite.

Petrology of the Western Highland Province: Ancient crust formation at the Apollo 14 site

NASA Astrophysics Data System (ADS)

Shervais, John W.; McGee, James J.

1999-03-01

Plutonic rocks found at the Apollo 14 site comprise four lithologic suites: the magnesian suite, the alkali suite, evolved lithologies, and the ferroan anorthosite suite (FAN). Rocks of the magnesian suite include troctolite, anorthosite, norite, dunite, and harzburgite; they are characterized by plagioclase ~An95 and mafic minerals with mg#s 82-92. Alkali suite rocks and evolved rocks generally have plagioclase ~An90 to ~An40, and mafic minerals with mg#s 82-40. Lithologies include anorthosite, norite, quartz monzodiorite, granite, and felsite. Ferroan anorthosites have plagioclase ~An96 and mafic minerals with mg#s 45-70. Whole rock geochemical data show that most magnesian suite samples and all alkali anorthosites are cumulates with little or no trapped liquid component. Norites may contain significant trapped liquid component, and some alkali norites may represent cumulate-enriched, near-liquid compositions, similar to KREEP basalt 15386. Evolved lithologies include evolved partial cumulates related to alkali suite fractionation (quartz monzodiorite), immiscible melts derived from these evolved magmas (granites), and impact melts of preexisting granite (felsite). Plots of whole rock mg# versus whole rock Ca/(Ca+Na+K) show a distinct gap between rocks of the magnesian suite and rocks of the alkali suite, suggesting either distinct parent magmas or distinct physical processes of formation. Chondrite-normalized rare earth element (REE) patterns show that rocks of both the magnesian suite and alkali suite have similar ranges, despite the large difference in major element chemistry. Current models for the origin of the magnesian suite call for a komatiitic parent magma derived from early magma ocean cumulates; these melts must assimilate plagiophile elements to form troctolites at low pressures and must assimilate a highly enriched KREEP component so that the resulting mixture has REE concentrations similar to high-K KREEP. There are as yet no plausible scenarios that can explain these unusual requirements. We propose that partial melting of a primitive lunar interior and buffering of these melts by ultramagnesian early magma ocean cumulates provides a more reasonable pathway to form magnesian troctolites. Alkali anorthosites and norites formed by crystallization of a parent magma with major element compositions similar to KREEP basalt 15386. If the parent magma of the alkali suite and evolved rocks is related to the magnesian suite, then that magma must have evolved through combined assimilation-fractional crystallization processes to form the alkali suite cumulates.

Partitioning of Large-ion Lithophile Elements Between Aqueous Fluids and Melts: Role of Saline Fluids in Sub-arc Mantle

NASA Astrophysics Data System (ADS)

Kawamoto, T.; Mibe, K.

2014-12-01

Chemical fractionation of slab-derived supercritical fluids can play an important role in elemental transfer from subducting slab to the mantle wedge and arc magmatism [1]. Recent findings of saline fluids from sub-arc mantle peridotite indicate that aqueous fluids in mantle wedge can contain 3.7 wt% NaCl in Ichinomageta, Northeast Japan arc [2] to 5.1 wt% NaCl in Pinatubo, Luzon arc [3]. It is, therefore, important to determine the effect of Cl on the trace element partitioning between aqueous fluids and melts. Synchrotron radiation X-ray fluorescence (XRF) analysis is conducted to know Rb, Sr, and Pb partitioning between aqueous fluids and melts [4]. There is a positive correlation between partition coefficients and pressure, as well as salinity. Two slab-derived components, melt and fluid components, are suggested to explain trace element characteristics of arc-basalts in the Mariana arc [5]. The fluid component is characterized by enrichment of alkali and alkali earth elements. Such features can be explained if the fluid component is a saline fluid, because alkali earth elements and Pb are much less mobile with Cl-free fluids than Cl-rich fluids [4]. We suggest that slab-derived components have compositional features consistent with a saline fluid and a melt, which can be formed through a separation of a slab-derived supercritical fluid [1]. Slab derived supercritical fluids contain Cl, and aqueous fluids inherit much of the Cl and some of the large-ion lithophile elements. [1] Kawamoto et al. 2012, Separation of supercritical slab-fluids to form aqueous fluid and melt components in subduction zone magmatism. PNAS, pnas.org/content/109/46/18695 [2] Kumagai et al. Evolution of carbon dioxide bearing saline fluids in the mantle wedge beneath the Northeast Japan arc, CMP [3] Kawamoto et al. 2013, Mantle wedge infiltrated with saline fluids from dehydration and decarbonation of subducting slab. PNAS, pnas.org/content/110/24/9663 [4] Kawamoto et al. 2014, Large ion lithophile elements delivered by saline fluids to the sub-arc mantle, EPS, earth-planets-space.com/content/66/1/61 [5] Pearce et al. 2005, Geochemical mapping of the Mariana arc-basin system: Implications for the nature and distribution of subduction components. G-cubed, onlinelibrary.wiley.com/doi/10.1029/2004GC000895/full

Structural and Crystal Chemical Properties of Alkali Rare-earth Double Phosphates

DOE PAGES

Farmer, James Matthew; Boatner, Lynn A.; Chakoumakos, Bryan C.; ...

2016-01-01

When appropriately activated, alkali rare-earth double phosphates of the form: M 3RE(PO 4) 2 (where M denotes an alkali metal and RE represents either a rare-earth element or Y or Sc) are of interest for use as inorganic scintillators for radiation detection at relatively long optical emission wavelengths. These compounds exhibit layered crystal structures whose symmetry properties depend on the relative sizes of the rare-earth and alkali-metal cations. Single-crystal X-ray and powder neutron diffraction methods were used here to refine the structures of the series of rare-earth double phosphate compounds: K 3RE(PO 4) 2 with RE = Lu, Er, Ho,more » Dy, Gd, Nd, Ce, plus Y and Sc - as well as the compounds: A 3Lu(PO 4) 2, with A = Rb, and Cs. The double phosphate K 3Lu(PO 4) 2 was reported and structurally refined previously. This material had a hexagonal unit cell at room temperature with the Lu ion six-fold coordinated with oxygen atoms of the surrounding phosphate groups. Additionally two lower-temperature phases were observed for K 3Lu(PO 4) 2. The first phase transition to a monoclinic P21/m phase occurred at ~230 K, and the Lu ion retained its six-fold coordination. The second K 3Lu(PO 4) 2 phase transition occurred at ~130 K. The P21/m space group symmetry was retained, however, one of the phosphate groups rotated to increase the oxygen coordination number of Lu from six to seven. This structure then became isostructural with the room-temperature form of the compound K 3Yb(PO 4) 2 reported here that also exhibits an additional high-temperature phase which occurs at T = 120 °C with a transformation to hexagonal P-3 space group symmetry and a Yb-ion coordination number reduction from seven to six. This latter result was confirmed using EXAFS. The single-crystal growth methods structural systematics, and thermal expansion properties of the present series of alkali rare-earth double phosphates, as determined by X-ray and neutron diffraction methods, are treated here.« less

Structural and Crystal Chemical Properties of Alkali Rare-earth Double Phosphates

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

Farmer, James Matthew; Boatner, Lynn A.; Chakoumakos, Bryan C.

When appropriately activated, alkali rare-earth double phosphates of the form: M 3RE(PO 4) 2 (where M denotes an alkali metal and RE represents either a rare-earth element or Y or Sc) are of interest for use as inorganic scintillators for radiation detection at relatively long optical emission wavelengths. These compounds exhibit layered crystal structures whose symmetry properties depend on the relative sizes of the rare-earth and alkali-metal cations. Single-crystal X-ray and powder neutron diffraction methods were used here to refine the structures of the series of rare-earth double phosphate compounds: K 3RE(PO 4) 2 with RE = Lu, Er, Ho,more » Dy, Gd, Nd, Ce, plus Y and Sc - as well as the compounds: A 3Lu(PO 4) 2, with A = Rb, and Cs. The double phosphate K 3Lu(PO 4) 2 was reported and structurally refined previously. This material had a hexagonal unit cell at room temperature with the Lu ion six-fold coordinated with oxygen atoms of the surrounding phosphate groups. Additionally two lower-temperature phases were observed for K 3Lu(PO 4) 2. The first phase transition to a monoclinic P21/m phase occurred at ~230 K, and the Lu ion retained its six-fold coordination. The second K 3Lu(PO 4) 2 phase transition occurred at ~130 K. The P21/m space group symmetry was retained, however, one of the phosphate groups rotated to increase the oxygen coordination number of Lu from six to seven. This structure then became isostructural with the room-temperature form of the compound K 3Yb(PO 4) 2 reported here that also exhibits an additional high-temperature phase which occurs at T = 120 °C with a transformation to hexagonal P-3 space group symmetry and a Yb-ion coordination number reduction from seven to six. This latter result was confirmed using EXAFS. The single-crystal growth methods structural systematics, and thermal expansion properties of the present series of alkali rare-earth double phosphates, as determined by X-ray and neutron diffraction methods, are treated here.« less

Understanding the Role of a nano Ce Additive in the Size Distribution and Organic Composition of Diesel Emissions

EPA Science Inventory

A number of alkali, alkaline earth, transition, and metalloid elements are known to act as fuel catalysts to limit the formation of soot precursors or promote its oxidation. These have been used with varying success on a variety of stationary and mobile combustion sources. Iron...

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.

Hydrothermal carbonization of rice husk for fuel upgrading

NASA Astrophysics Data System (ADS)

Suteerawattananonda, N.; Kongkaew, N.; Patumsawad, S.

2018-01-01

The biomass is popularly used as renewable energy. In Thailand rice is the most consume agricultural products. Agricultural residues from rice husk can be an energy resource. However, alkali and alkali earth materials (AAEMs) in biomass ash are the causes of corrosion and erosion problem in the heat exchanger equipment, while the acidity of ash affects the slagging agglomeration problem. Reduction of alkali and alkali earth materials can minimize the problem. In order to challenge the reduction of alkali and alkali earth materials in biomass ash, hydrothermal carbonization process was selected. Thai rice husk was used as sample to compare the result of treatment. The rice husk was heated under the condition of different temperature ranged from 180°C to 250°C, at operate pressure ranges from 12 bar to 42 bar with residence holding reaction time 1 hour. The results of proximate analysis show that the percentage by mass of fixed carbon are increased 2 times, but volatile matter is decreased by 40% and ash content is decreased by 11% due to the increment of temperature. Meanwhile, the X-Ray fluorescence (XRF) analysis results show the decreasing of alkali and alkali earth materials are reduced.

Understanding the Role of a nano Ce Additive in the Size Distribution and Organic Composition of the Particulate Phase of Diesel Emissions

EPA Science Inventory

A number of alkali, alkaline earth, transition, and metalloid elements are known to act as fuel catalysts to limit the formation of soot precursors or promote its oxidation. These have been used with varying success on a variety of stationary and mobile combustion sources. Iron...

Carbonatite magmatism in northeast India

NASA Astrophysics Data System (ADS)

Kumar, D.; Mamallan, R.; Dwivedy, K. K.

The Shillong Plateau of northeast India is identified as an alkaline province in view of the development of several carbonatite complexes e.g. the Sung Valley (Jaintia Hills), Jasra (Karbi-Anglong), Samchampi and Barpung (Mikir Hills) and lamprophyre dyke swarms (Swangkre, Garo-Khasi Hills). On the basis of limited KAr data, magmatic activity appears to have taken place over a protracted period, ranging from the Late Jurassic to the Early Cretaceous. The carbonatite complexes of the Shillong Plateau share several common traits: they are emplaced along rift zones, either within Archaean gneisses or Proterozoic metasediments and granites, and exhibit enrichment in the light rare-earth elements, U, Th, Nb, Zr, Ti, K and Na. The enrichment in incompatible trace elements can best be accounted for if the parental magmas were of alkali basaltic type (e.g. mela-nephelinite or carbonate-rich alkali picrite).

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.

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.

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.

Space processing of chalcogenide glasses

NASA Technical Reports Server (NTRS)

Larsen, D. C.; Ali, M. A.

1975-01-01

Chalcogenide glasses are discussed as good infrared transmitters, possessing the strength, corrosion resistance, and scale-up potential necessary for large 10.6-micron windows. The disadvantage of earth-produced chalcogenide glasses is shown to be an infrared absorption coefficient which is unacceptably high relative to alkali halides. This coefficient is traced to optical nonhomogeneities resulting from environmental and container contamination. Space processing is considered as a means of improving the infrared transmission quality of chalcogenides and of eliminating the following problems: optical inhomogeneities caused by thermal currents and density fluctuation in the l-g earth environment; contamination from the earth-melting crucible by oxygen and other elements deleterious to infrared transmission; and, heterogeneous nucleation at the earth-melting crucible-glass interface.

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.

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

Temperature dependent mobility measurements of alkali earth ions in superfluid helium

NASA Astrophysics Data System (ADS)

Putlitz, Gisbert Zu; Baumann, I.; Foerste, M.; Jungmann, K.; Riediger, O.; Tabbert, B.; Wiebe, J.; Zühlke, C.

1998-05-01

Mobility measurements of impurity ions in superfluid helium are reported. Alkali earth ions were produced with a laser sputtering technique and were drawn inside the liquid by an electric field. The experiments were carried out in the temperature region from 1.27 up to 1.66 K. The temperature dependence of the mobility of Be^+-ions (measured here for the first time) differs from that of the other alkali earth ions Mg^+, Ca^+, Sr^+ and Ba^+, but behaves similar to that of He^+ (M. Foerste, H. Günther, O. Riediger, J. Wiebe, G. zu Putlitz, Z. Phys. B) 104, 317 (1997). Theories of Atkins (A. Atkins, Phys. Rev.) 116, 1339 (1959) and Cole (M.W. Cole, R.A. Bachmann Phys. Rev. B) 15, 1388 (1977) predict a different defect structure for He^+ and the alkali earth ions: the helium ion is assumed to form a snowball like structure whereas for the alkali earth ions a bubble structure is assumed. If the temperature dependence is a characteristic feature for the different structures, then it seems likely that the Be^+ ion builds a snowball like structure.

Ab initio study of the alkali and alkaline-earth monohydroxides

NASA Technical Reports Server (NTRS)

Bauschlicher, C. W., Jr.; Langhoff, S. R.; Partridge, H.

1986-01-01

A systematic study of the structures and dissociation energies of all the alkali and alkaline-earth monohydroxides is conducted. A theoretical model for determining accurate dissociation energies of ionic molecules is discussed. The obtained theoretical structures and dissociation energies of the alkali and alkaline-earth monohydroxides, respectively, are compared with experimental data. It is found that the theoretical studies of the bending potentials of BeOH, MgOH, and CaOH reveal the different admixture of covalent character in these systems. The BeOH molecule with the largest degree of covalent character is found to be bent (theta equals 147 deg). The MgOH is also linear. The theoretical dissociation energies for the alkali and akaline-earth hydroxides are thought to be accurate to 0.1 eV.

The petrogenesis of L-6 chondrites - Insights from the chemistry of minerals

NASA Technical Reports Server (NTRS)

Curtis, D. B.; Schmitt, R. A.

1979-01-01

Measurements of the major, minor and trace element abundances of the major minerals of the L-6 chondrites Alfianello, Colby (WI) and Leedey are used to investigate the formation mechanisms of L-6 chondrites. Electron microprobe analysis was performed on individual grains of each mineral, and separated minerals were analyzed by instrumental and radiochemical neutron activation analysis. The compositions of the three meteorites are observed to be generally uniform, however different abundances and distributions of rare earth elements and Co and Ni indicate that the meteorites have different petrogenetic histories. Alkali element distributions are found to be incompatible with internal equilibration of a closed system.

Chemical durability of alkali-borosilicate glasses studied by analytical SEM, IBA, isotopic-tracing and SIMS

NASA Astrophysics Data System (ADS)

Trocellier, P.; Djanarthany, S.; Chêne, J.; Haddi, A.; Brass, A. M.; Poissonnet, S.; Farges, F.

2005-10-01

Simple and complex alkali-borosilicate glasses were submitted to aqueous corrosion at room temperature, 60 and 90 °C in solutions with pH ranging between 0 and 12. Analytical scanning electron microscopy (SEM), ion beam analysis (IBA) techniques, isotopic tracing and secondary ion mass-depth profiling (SIMS) have been used to investigate the variations of the surface composition of glass. In acidic medium, the glass surface is generally covered by a thick hydrated silica layer, mobile elements like Li, Na and B and transition elements (Fe, Zr, Mo, etc.) are strongly depleted. Near pH 7, relative enrichments of aluminium, iron and rare earths are shown together with strong Li, Na and B depletions. In basic medium, the glass surface exhibits relative enrichments of the major part of transition metals (from Cr to U) whereas mobile elements seem to be kept close to their nominal concentration level at the glass surface and Si is severely impoverished. Hydrogen incorporated at the glass surface after leaching is much more immobile in neutral and basic media than in acid medium.

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.

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.

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K-Fr) and alkaline earth (Ca-Ra) elements

NASA Astrophysics Data System (ADS)

Hill, J. Grant; Peterson, Kirk A.

2017-12-01

New correlation consistent basis sets based on pseudopotential (PP) Hamiltonians have been developed from double- to quintuple-zeta quality for the late alkali (K-Fr) and alkaline earth (Ca-Ra) metals. These are accompanied by new all-electron basis sets of double- to quadruple-zeta quality that have been contracted for use with both Douglas-Kroll-Hess (DKH) and eXact 2-Component (X2C) scalar relativistic Hamiltonians. Sets for valence correlation (ms), cc-pVnZ-PP and cc-pVnZ-(DK,DK3/X2C), in addition to outer-core correlation [valence + (m-1)sp], cc-p(w)CVnZ-PP and cc-pwCVnZ-(DK,DK3/X2C), are reported. The -PP sets have been developed for use with small-core PPs [I. S. Lim et al., J. Chem. Phys. 122, 104103 (2005) and I. S. Lim et al., J. Chem. Phys. 124, 034107 (2006)], while the all-electron sets utilized second-order DKH Hamiltonians for 4s and 5s elements and third-order DKH for 6s and 7s. The accuracy of the basis sets is assessed through benchmark calculations at the coupled-cluster level of theory for both atomic and molecular properties. Not surprisingly, it is found that outer-core correlation is vital for accurate calculation of the thermodynamic and spectroscopic properties of diatomic molecules containing these elements.

Electric dipole moments and chemical bonding of diatomic alkali-alkaline earth molecules.

PubMed

Pototschnig, Johann V; Hauser, Andreas W; Ernst, Wolfgang E

2016-02-17

We investigate the properties of alkali-alkaline earth diatomic molecules in the lowest Σ(+) states of the doublet and quartet multiplicity by ab initio calculations. In all sixteen cases studied, the permanent electric dipole moment points in opposite directions for the two spin states. This peculiarity can be explained by molecular orbital theory. We further discuss dissociation energies and bond distances. We analyze trends and provide an empirically motivated model for the prediction of the permanent electric dipole moment for combinations of alkali and alkaline earth atoms not studied in this work.

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.

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.

Geology of the Mahd Adh Dhahab District, Kingdom of Saudi Arabia

USGS Publications Warehouse

Afifi, A.M.

1990-01-01

Major-element data show that the Mahd Group was produced from separate basaltic and dacitic-rhyolitic magmas that overlapped without mixing. The alkalis and alkaline-earth elements were particularly mobile during metamorphism (which caused widespread albitization of feldspars) and also during hydrothermal alteration (which added secondary microcline). This mobility adversely affected rubidium-strontium whole-rock systematics, which makes whole-rock isochron dates obtained from these rocks questionable. The new geological data presented here are combined with the geochronologic data of Calvez and Kemp (1982) to re-interpret the geologic history of this area.

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.

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.

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.

Alkali (Li, K and Na) and alkali-earth (Be, Ca and Mg) adatoms on SiC single layer

NASA Astrophysics Data System (ADS)

Baierle, Rogério J.; Rupp, Caroline J.; Anversa, Jonas

2018-03-01

First-principles calculations within the density functional theory (DFT) have been addressed to study the energetic stability, and electronic properties of alkali and alkali-earth atoms adsorbed on a silicon carbide (SiC) single layer. We observe that all atoms are most stable (higher binding energy) on the top of a Si atom, which moves out of the plane (in the opposite direction to the adsorbed atom). Alkali atoms adsorbed give raise to two spin unpaired electronic levels inside the band gap leading the SiC single layer to exhibit n-type semiconductor properties. For alkaline atoms adsorbed there is a deep occupied spin paired electronic level inside the band gap. These finding suggest that the adsorption of alkaline and alkali-earth atoms on SiC layer is a powerful feature to functionalize two dimensional SiC structures, which can be used to produce new electronic, magnetic and optical devices as well for hydrogen and oxygen evolution reaction (HER and OER, respectively). Furthermore, we observe that the adsorption of H2 is ruled by dispersive forces (van der Waals interactions) while the O2 molecule is strongly adsorbed on the functionalized system.

Chelating resin immobilizing carboxymethylated polyethyleneimine for selective solid-phase extraction of trace elements: Effect of the molecular weight of polyethyleneimine and its carboxymethylation rate.

PubMed

Kagaya, Shigehiro; Kajiwara, Takehiro; Gemmei-Ide, Makoto; Kamichatani, Waka; Inoue, Yoshinori

2016-01-15

The effect of the molecular weight of polyethyleneimine (PEI), defined as a compound having two or more ethyleneamine units, and of its carboxymethylation rate (CM/N), represented by the ratio of ion-exchange capacity to the amount of N on the resin, on the selective solid-phase extraction ability of the chelating resin immobilizing carboxymethylated (CM) PEI was investigated. The chelating resins (24 types) were prepared by immobilization of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, PEI300 (MW=ca. 300), and PEI600 (MW=ca. 600) on methacrylate resins, followed by carboxymethylation with various amounts of sodium monochloroacetate. When resins with approximately the same CM/N ratio (0.242-0.271) were used, the recovery of Cd, Co, Cu, Fe, Ni, Pb, Ti, Zn, and alkaline earth elements increased with increasing the molecular weight of PEIs under acidic and weakly acidic conditions; however, the extraction behavior of Mo and V was only slightly affected. This was probably due to the increase in N content of the resin, resulting in an increase in carboxylic acid groups; the difference in the molecular weight of PEIs immobilized on the resin exerts an insignificant influence on the selective extraction ability. The CM/N ratio considerably affected the extraction behavior for various elements. Under acidic and neutral conditions, the recovery of Cd, Co, Cu, Fe, Ni, Pb, Ti, and Zn increased with increasing CM/N values. However, under these conditions, the recovery of alkaline earth elements was considerably low when a resin with low CM/N ratio was used. This is presumably attributed to the different stability constants of the complexes of these elements with aminocarboxylic acids and amines, and to the electrostatic repulsion between the elements and the protonated amino groups in the CM-PEI. The recovery of Mo and V decreased or varied with increasing CM/N values, suggesting that the extraction of these elements occurred mainly by the anion-exchange reaction. For the separation and preconcentration of trace elements in samples containing large amounts of alkali and alkaline earth elements, the CM-PEI600 resin with CM/N=0.131 (Cu(II) extraction capacity, 0.37mmol g(-)(1)) was found to be the most suitable because it scarcely extracts alkali and alkaline earth elements under acidic and neutral conditions. This resin proved to be convenient for separating and preconcentrating Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in the certified reference materials (EnviroMAT EU-L-1 wastewater and ES-L-1 ground water) and commercially available table salt. Copyright © 2015 Elsevier B.V. All rights reserved.

Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

ERIC Educational Resources Information Center

Dietrich, Bernard

1985-01-01

Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

PROCESS OF RECOVERING ALKALI METALS

DOEpatents

Wolkoff, J.

1961-08-15

A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

Recent advances in rare earth doped alkali-alkaline earth borates for solid state lighting applications

NASA Astrophysics Data System (ADS)

Verma, Shefali; Verma, Kartikey; Kumar, Deepak; Chaudhary, Babulal; Som, Sudipta; Sharma, Vishal; Kumar, Vijay; Swart, Hendrik C.

2018-04-01

As a novel class of inorganic phosphor, the alkali-alkaline earth borate phosphors have gained huge attention due to their charming applications in solid-state lighting (SSL) and display devices. The current research drive shows that phosphors based on the alkali-alkaline earth borates have transformed the science and technology due to their high transparency over a broad spectral range, their flexibility in structure and durability for mechanical and high-laser applications. Recent advances in various aspects of rare-earth (RE) doped borate based phosphors and their utilizations in SSL and light emitting diodes are summarized in this review article. Moreover, the present status and upcoming scenario of RE-doped borate phosphors were reviewed in general along with the proper credential from the existing literature. It is believed that this review is a sole compilation of crucial information about the RE-doped borate phosphors in a single platform.

Theoretical study of the alkali and alkaline-earth monosulfides

NASA Technical Reports Server (NTRS)

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

1988-01-01

Ab initio calculations have been used to obtain accurate spectroscopic constants for the X2Pi and A2Sigma(+) states of the alkali sulfides and the X1Sigma(+), a3Pi, and A1Pi states of the alkaline-earth sulfides. In contrast to the alkali oxides, the alkali sulfides are found to have X2Pi ground states, due to the larger electrostatic interaction. Dissociation energies of 3.27 eV for BeS, 2.32 eV for MgS, 3.29 eV for CaS, and 3.41 eV for SrS have been obtained for the X1Sigma(+) states of the alkaline-earth sulfides, in good agreement with experimental results. Core correlation is shown to increase the Te values for the a3Pi and A1Pi states of MgS, CaS, and SrS.

Rare earth elements recycling from waste phosphor by dual hydrochloric acid dissolution.

PubMed

Liu, Hu; Zhang, Shengen; Pan, Dean; Tian, Jianjun; Yang, Min; Wu, Maolin; Volinsky, Alex A

2014-05-15

This paper is a comparative study of recycling rare earth elements from waste phosphor, which focuses on the leaching rate and the technical principle. The traditional and dual dissolution by hydrochloric acid (DHA) methods were compared. The method of dual dissolution by hydrochloric acid has been developed. The Red rare earth phosphor (Y0.95Eu0.05)2O3 in waste phosphor is dissolved during the first step of acid leaching, while the Green phosphor (Ce0.67Tb0.33MgAl11O19) and the Blue phosphor (Ba0.9Eu0.1MgAl10O17) mixed with caustic soda are obtained by alkali sintering. The excess caustic soda and NaAlO2 are removed by washing. The insoluble matter is leached by the hydrochloric acid, followed by solvent extraction and precipitation (the DHA method). In comparison, the total leaching rate of the rare earth elements was 94.6% by DHA, which is much higher than 42.08% achieved by the traditional method. The leaching rate of Y, Eu, Ce and Tb reached 94.6%, 99.05%, 71.45%, and 76.22%, respectively. DHA can decrease the consumption of chemicals and energy. The suggested DHA method is feasible for industrial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

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.

Effects of various additives on sintering of aluminum nitride

NASA Technical Reports Server (NTRS)

Komeya, K.; Inoue, H.; Tsuge, A.

1982-01-01

Effects of thirty additives on sintering A/N were investigated. The addition of alkali earth oxides and rare earth oxides gave fully densified aluminum nitride. This is due to the formation of nitrogen-containing aluminate liquid in the system aluminum nitride-alkali earth oxides or rare earth oxides. Microstructural studies of the sintered specimens with the above two types of additives suggested that the densification was due to the liquid phase sintering. Additions of silicon compounds resulted in poor densification by the formation of highly refractory compounds such as A/N polytypes.

Magmatic-hydrothermal fluid interaction and mineralization in alkali-syenite nodules from the Breccia Museo pyroclastic deposit, Naples, Italy: Chapter 7 in Volcanism in the Campania Plain — Vesuvius, Campi Flegrei and Ignimbrites

USGS Publications Warehouse

Fedele, Luca; Tarzia, Maurizio; Belkin, Harvey E.; De Vivo, Benedetto; Lima, Annamaria; Lowenstern, Jacob

2007-01-01

The Breccia Museo, a pyroclastic flow that crops out in the Campi Flegrei volcanic complex (Naples, Italy), contains alkali-syenite (trachyte) nodules with enrichment in Cl and incompatible elements (e.g., U, Zr, Th, and rare-earth elements). Zircon was dated at ≈52 ka, by U-Th isotope systematics using a SHRIMP. Scanning electron microscope and electron microprobe analysis of the constituent phases have documented the mineralogical and textural evolution of the nodules of feldspar and mafic accumulations on the magma chamber margins. Detailed electron microprobe data are given for alkali and plagioclase feldspar, salite to ferrosalite clinopyroxene, pargasite, ferrogargasite, magnesio-hastingsite hornblende amphibole, biotite mica, Cl-rich scapolite, and a member (probable davyne-type) of the cancrinite group. Detailed whole rock, major and minor element data are also presented for selected nodules. A wide variety of common and uncommon accessory minerals were identified such as zircon, baddeleyite, zirconolite, pollucite, sodalite, titanite, monazite, cheralite, apatite, titanomagnetite and its alteration products, scheelite, ferberite, uraninite/thorianite, uranpyrochlore, thorite, pyrite, chalcopyrite, and galena. Scanning electron microscope analysis of opened fluid inclusions identified halite, sylvite, anhydrite, tungstates, carbonates, silicates, sulfides, and phosphates; most are probably daughter minerals. Microthermometric determinations on secondary fluid inclusions hosted by alkali feldspar define a temperature regime dominated by hypersaline aqueous fluids. Fluid-inclusion temperature data and mineral-pair geothermometers for coexisting feldspars and hornblende and plagioclase were used to construct a pressure-temperature scenario for the development and evolution of the nodules. We have compared the environment of porphyry copper formation and the petrogenetic environment constructed for the studied nodules. The suite of ore minerals observed in the nodules supports a potential for mineralization, which is similar to that observed in the alkaline volcanic systems of southern Italy (Pantelleria, Pontine Archipelago, Mt. Somma-Vesuvius).

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.

Energetics of alkali and alkaline earth ion-exchanged zeolite A

DOE PAGES

Sun, Hui; Wu, Di; Liu, Kefeng; ...

2016-06-30

Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential ( Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO 2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A)more » to –48.02 ± 1.85 kJ/mol per TO 2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO 2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

Surface disposal of produced waters in western and southwestern Pennsylvania: potential for accumulation of alkali-earth elements in sediments

USGS Publications Warehouse

Skalak, Katherine J.; Engle, Mark A.; Rowan, Elisabeth L.; Jolly, Glenn D.; Conko, Kathryn M.; Benthem, Adam J.; Kraemer, Thomas F.

2014-01-01

Waters co-produced with hydrocarbons in the Appalachian Basin are of notably poor quality (concentrations of total dissolved solids (TDS) and total radium up to and exceeding 300,000 mg/L and 10,000 pCi/L, respectively). Since 2008, a rapid increase in Marcellus Shale gas production has led to a commensurate rise in associated wastewater while generation of produced water from conventional oil and gas activities has continued. In this study, we assess whether disposal practices from treatment of produced waters from both shale gas and conventional operations in Pennsylvania could result in the accumulation of associated alkali earth elements. The results from our 5 study sites indicate that there was no increase in concentrations of total Ra (Ra-226) and extractable Ba, Ca, Na, or Sr in fluvial sediments downstream of the discharge outfalls (p > 0.05) of publicly owned treatment works (POTWs) and centralized waste treatment facilities (CWTs). However, the use of road spreading of brines from conventional oil and gas wells for deicing resulted in accumulation of Ra-226 (1.2 ×), and extractable Sr (3.0 ×), Ca (5.3 ×), and Na (6.2 ×) in soil and sediment proximal to roads (p < 0.05). Although this study is an important initial assessment of the impacts of these disposal practices, more work is needed to consider the environmental consequences of produced waters management.

Separation of thorium (IV) from lanthanide concentrate (LC) and water leach purification (WLP) residue

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

AL-Areqi, Wadeeah M.; Majid, Amran Ab.; Sarmani, Sukiman

Thorium (IV) content in industrial residue produced from rare earth elements production industry is one of the challenges to Malaysian environment. Separation of thorium from the lanthanide concentrate (LC) and Water Leach Purification (WLP) residue from rare earth elements production plant is described. Both materials have been tested by sulphuric acid and alkaline digestions. Th concentrations in LC and WLP were determined to be 1289.7 ± 129 and 1952.9±17.6 ppm respectively. The results of separation show that the recovery of Th separation from rare earth in LC after concentrated sulphuric acid dissolution and reduction of acidity to precipitate Th wasmore » found 1.76-1.20% whereas Th recovery from WLP was less than 4% after concentrated acids and alkali digestion processes. Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) was used to determine Th concentrations in aqueous phase during separation stages. This study indicated that thorium maybe exists in refractory and insoluble form which is difficult to separate by these processes and stays in WLP residue as naturally occurring radioactive material (NORM)« less

Method of treating waste water

DOEpatents

Deininger, James P.; Chatfield, Linda K.

1995-01-01

A process of treating water to remove metal ion contaminants contained therein, said metal ion contaminants selected from the group consisting of metals in Groups 8, 1b, 2b, 4a, 5a, or 6a of the periodic table, lanthanide metals, and actinide metals including transuranic element metals, by adjusting the pH of a metal ion contaminant-containing water source to within the range of about 6.5 to about 14.0, admixing the water source with a mixture of an alkali or alkaline earth ferrate and a water soluble salt, e.g., a zirconium salt, in an amount sufficient to form a precipitate within the water source, the amount the mixture of ferrate and water soluble salt effective to reduce the metal ion contaminant concentration in the water source, permitting the precipitate in the admixture to separate and thereby yield a supernatant liquid having a reduced metal ion contaminant concentration, and separating the supernatant liquid having the reduced metal ion contaminant concentration from the admixture is provided. A composition of matter including an alkali or alkaline earth ferrate and a water soluble salt, e.g., a zirconium salt, is also provided.

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.

Crystal-chemistry of alteration products of vitrified wastes: Implications on the retention of polluting elements

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

Sterpenich, Jerome

2008-07-01

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO{sub 4} . nH{sub 2}O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes themore » altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.« less

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.

Genetic interpretations of elemental and chemical differences in a soil chronosequence, California

USGS Publications Warehouse

Harden, J.W.

1988-01-01

Soils developed on fluvial terraces in central California have similar parent materials, climatic settings, vegetation cover and slopes but range in age from 40,000 to 3,000,000 years. The soils have chemical compositions that change systematically with increasing age. Such chemical differentiation is most likely the result of long-term weathering and mineralogical transformations that occurred since deposition of terrace fills and stabilization of the geomorphic surfaces. The changes in composition with time closely mimic other studies on mineral weathering, in which alkali and alkali-earth elements are lost more rapidly than transitional elements. The relative rates of element loss were determined by changes in element ratios over time. Net losses and gains of elements in different size fractions were monitored by their concentrations relative to Zr, the most stable constituent. Both sand and finer size fractions have lost considerable amounts of Ca, Mg, Na and K. Aluminum appears to have been lost from the sand fraction and gained in the fine fraction over a 3-million-year-time-span. Although there is no evidence for losses of Fe and Ti from sands, there is a net influx of Fe and Ti into finer fractions, probably gained from undetectable yet significant weathering of sand grains. Etching of sand grains, clay mineralogy, and microprobe analyses also indicate that the soils have undergone these chemical transformations during their formation. Mineralogical analyses also mimic other studies on mineral weathering, in which the pyroxenes weather more rapidly than hornblende, which weathers more rapidly than sphene or zircon. ?? 1988.

In-place alkalic lavas recovered from Hilina Bench off-shore Kilauea, Hawaii: significance in reconstructing ancient Kilauea history

NASA Astrophysics Data System (ADS)

Kimura, J.; Sisson, T. W.; Coombs, M.; Lipman, P. W.

2002-12-01

Lava samples recovered from off-shore Hawaii Island, using remote and manned submersibles during JAMSTEC cruises in 1998, 1999, and 2001, were analyzed for major and trace elements. On the scarp below the Hilina bench (~ 3000 m bmsl), clasts of alkali and transitional basalt were recovered from debris-flow breccias, but tholeiite basalt of modern Kilauea type is absent (Sisson et al., 2002). In 2001 (dive K508), a succession of in-place pillow lavas of alkali basalt was found for the first time on the slope above the Hilina bench, along a well-exposed a rib. These in-place samples of alklic material in relative shallow water depths provide a critical link between modern-day and ancestral Kilauea. The rib is part of ancient Kilauea volcano that has remained in place, while the Hilina Bench contains slide/slump material from Kilauea (Lipman et al., 2002). At the same water depths but ~15 km to the southwest, Dive K207 sampled a series of alkali basalt breccia clasts that are compositionally similar to the in-place lavas of K208. In contrast, a dive on Papa'u Seamount (K509), located at the upper southwest margin of the bench, traversed massive breccias of subaerially erupted tholeiitic basalt. The breccias are compositionally similar to Mauna Loa lavas, and must be ancient landslide material from this volcano. Geochemical characteristics of transitional basalts from the slope above the Hilina bench are related to historical Kilauea tholeiites in major and trace elements. Alkali basalts from both the lower flank of the Hilina bench and the upper rib are more Ti rich than the transitional basalts, with elevated light-rare-earth and large-ion-lithophile elements. Various binary plots between highly incompatible trace element pairs define confined straight lines, including historical Kilauea tholeiite, the transitional basalts, and the Hilina alkalic pillows, suggesting a common mantle source with different degrees of partial melting. However, chemistry of these basalts differ from the more alkalic basanite and nephelinite lava clasts from the lower flank (Sisson et al., 2002). The highly alkaline lavas would have derived from different mantle sources, perhaps from perimeters of the Hawaiian mantle plume, whereas alkali, transitional, and tholeiitic basalts are from more central parts of the plume. The in-place alkalic pillow basalts provides new insights on earlier growth history and changes in states of basalt sources during the magmatic evolution of Kilauea, which is still in progress.

Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH−

PubMed Central

2017-01-01

We have performed a systematic ab initio study on alkali and alkaline earth hydroxide neutral (MOH) and anionic (MOH−) species where M = Li, Na, K, Rb, Cs or Be, Mg, Ca, Sr, Ba. The CCSD(T) method with extended basis sets and Dirac-Fock relativistic effective core potentials for the heavier atoms has been used to study their equilibrium geometries, interaction energies, electron affinities, electric dipole moment, and potential energy surfaces. All neutral and anionic species exhibit a linear shape with the exception of BeOH, BeOH−, and MgOH−, for which the equilibrium structure is found to be bent. Our analysis shows that the alkaline earth hydroxide anions are valence-bound whereas the alkali hydroxide anions are dipole bound. In the context of sympathetic cooling of OH− by collision with ultracold alkali and alkaline earth atoms, we investigate the 2D MOH− potential energy surfaces and the associative detachment reaction M + OH→− MOH + e−, which is the only energetically allowed reactive channel in the cold regime. We discuss the implication for the sympathetic cooling of OH− and conclude that Li and K are the best candidates for an ultracold buffer gas. PMID:28527437

Surface Tension of Liquid Alkali, Alkaline, and Main Group Metals: Theoretical Treatment and Relationship Investigations

NASA Astrophysics Data System (ADS)

Aqra, Fathi; Ayyad, Ahmed

2011-09-01

An improved theoretical method for calculating the surface tension of liquid metals is proposed. A recently derived equation that allows an accurate estimate of surface tension to be made for the large number of elements, based on statistical thermodynamics, is used for a means of calculating reliable values for the surface tension of pure liquid alkali, alkaline earth, and main group metals at the melting point, In order to increase the validity of the model, the surface tension of liquid lithium was calculated in the temperature range 454 K to 1300 K (181 °C to 1027 °C), where the calculated surface tension values follow a straight line behavior given by γ = 441 - 0.15 (T-Tm) (mJ m-2). The calculated surface excess entropy of liquid Li (- dγ/ dT) was found to be 0.15 mJ m-2 K-1, which agrees well with the reported experimental value (0.147 mJ/m2 K). Moreover, the relations of the calculated surface tension of alkali metals to atomic radius, heat of fusion, and specific heat capacity are described. The results are in excellent agreement with the existing experimental data.

Formation and evolution of a metasomatized lithospheric root at the motionless Antarctic plate: the case of East Island, Crozet Archipelago (Indian Ocean)

NASA Astrophysics Data System (ADS)

Meyzen, Christine; Marzoli, Andrea; Bellieni, Giuliano; Levresse, Gilles

2016-04-01

Sitting atop the nearly stagnant Antarctic plate (ca. 6.46 mm/yr), the Crozet archipelago midway between Madagascar and Antarctica constitutes a region of unusually shallow (1543-1756 m below sea level) and thickened oceanic crust (10-16.5 km), high geoid height, and deep low-velocity zone, which may reflect the surface expression of a mantle plume. Here, we present new major and trace element data for Quaternary sub-aerial alkali basalts from East Island, the easterly and oldest island (ca. 9 Ma) of the Crozet archipelago. Crystallization at uppermost mantle depth and phenocryst accumulation have strongly affected their parental magma compositions. Their trace element patterns show a large negative K anomaly relative to Ta-La, moderate depletions in Rb and Ba with respect to Th-U, and heavy rare earth element (HREE) depletions relative to light REE. These characteristics allow limits to be placed upon the composition and mineralogy of their mantle source. The average trace element spectrum of East Island basalts can be matched by melting of about 2 % of a garnet-phlogopite-bearing peridotite source. The stability field of phlogopite restricts melting depth to lithospheric levels. The modelled source composition requires a multistage evolution, where the mantle has been depleted by melt extraction before having been metasomatized by alkali-rich plume melts. The depleted mantle component may be sourced by residual mantle plume remnants stagnated at the melting locus due to a weak lateral flow velocity inside the melting regime, whose accumulation progressively edifies a depleted lithospheric root above the plume core. Low-degree alkali-rich melts are likely derived from the plume source. Such a mantle source evolution may be general to both terrestrial and extraterrestrial environments where the lateral component velocity of the mantle flow field is extremely slow.

Lead isotope relations in oceanic Ridge basalts from the Juan de Fuca-Gorda Ridge area N.E. Pacific Ocean

USGS Publications Warehouse

Church, S.E.; Tatsumoto, M.

1975-01-01

Lead isotopic analyses of a suite of basaltic rocks from the Juan de Fuca-Gorda Ridge and nearby seamounts confirm an isotopically heterogeneous mantle known since 1966. The process of mixing during partial melting of a heterogeneous mantle necessarily produces linear data arrays that can be interpreted as secondary isochrons. Moreover, the position of the entire lead isotope array, with respect to the geochron, requires that U/Pb and Th/Pb values are progressively increased over the age of the earth. Partial melting theory also dictates analogous behavior for the other incompatible trace elements. This process explains not only the LIL element character of MOR basalts, but also duplicates the spread of radiogenic lead data collected from alkali-rich oceanic basalts. This dynamic, open-system model of lead isotopic and chemical evolution of the mantle is believed to be the direct result of tectonic flow and convective overturn within the mantle and is compatible with geophysical models of a dynamic earth. ?? 1975 Springer-Verlag.

Volatile Loss from the Proto-Lunar Disk

NASA Astrophysics Data System (ADS)

Albarede, F.

2016-12-01

Exchange of volatile elements between the Moon and Earth depends on the intrinsic volatility of each element in a H-free tenuous gas, gravitational escape, and the mean free path of elements. The H2 pressure in the gas formed by the giant impact is far too low to allow hydrodynamic entrainment of other species. A condition for gravitational escape is, therefore, that thermal velocity exceeds escape velocity at the base of the exosphere where collisions between atoms cease. Away from the Earth, the vertical pull of the disk is only a small fraction of the radial pull of the Earth, which is strong enough to keep all the elements but H and He in terrestrial orbits, and the disk exosphere is thick. The proportion of gas orbiting above the exosphere is small, its temperature has been strongly reduced by adiabatic expansion, and therefore escape of lunar volatiles to Earth should be very limited. Whether elements have been lost by escape from the Moon to Earth nevertheless can be tested by comparing the relative abundances of elements with very similar chemistry and intrinsic volatility, but with very different atomic masses. Standard sequences of mineral condensation from the Solar Nebula and T50 are irrelevant to the proto-lunar disk. Condensation temperatures in the Solar Nebula are known to vary wildly with PH2, and the PH2 of the Solar Nebula is largely insensitive to the condensation of solid mineral phases, such as those forming the mantle and core of planets. Lunar accretion follows an opposite scenario, with an early and dramatic pressure drop due to metal and silicate condensation, which is the rationale behind the intrinsic volatility scale of Albarede et al. (2015). It is observed that, despite a broad mass range, the degree of depletion in the Moon relative to the Earth or CIs is similar for chemical kins, such as the groups of alkali elements (Li, Na, K, Rb, Cs), halogens (F, Cl, Br, I), or Zn and Cd. This observation argues against massive escape of volatile elements from the Moon to Earth and against massive lunar devolatilization. It is therefore suggested that, in agreement with the mineralogy of most lunar samples, volatile depletion of the Moon is inherited from the impactor rather than a result of the impact itself. Albarède, F., E. Albalat, and C.-T. A. Lee (2015), MAPS 50(4), 568-577.

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.

Implications for metal and volatile cycles from the pH of subduction zone fluids

NASA Astrophysics Data System (ADS)

Galvez, Matthieu E.; Connolly, James A. D.; Manning, Craig E.

2016-11-01

The chemistry of aqueous fluids controls the transport and exchange—the cycles—of metals and volatile elements on Earth. Subduction zones, where oceanic plates sink into the Earth’s interior, are the most important geodynamic setting for this fluid-mediated chemical exchange. Characterizing the ionic speciation and pH of fluids equilibrated with rocks at subduction zone conditions has long been a major challenge in Earth science. Here we report thermodynamic predictions of fluid-rock equilibria that tie together models of the thermal structure, mineralogy and fluid speciation of subduction zones. We find that the pH of fluids in subducted crustal lithologies is confined to a mildly alkaline range, modulated by rock volatile and chlorine contents. Cold subduction typical of the Phanerozoic eon favours the preservation of oxidized carbon in subducting slabs. In contrast, the pH of mantle wedge fluids is very sensitive to minor variations in rock composition. These variations may be caused by intramantle differentiation, or by infiltration of fluids enriched in alkali components extracted from the subducted crust. The sensitivity of pH to soluble elements in low abundance in the host rocks, such as carbon, alkali metals and halogens, illustrates a feedback between the chemistry of the Earth’s atmosphere-ocean system and the speciation of subduction zone fluids via the composition of the seawater-altered oceanic lithosphere. Our findings provide a perspective on the controlling reactions that have coupled metal and volatile cycles in subduction zones for more than 3 billion years7.

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

Gordon, John Howard; Alvare, Javier

Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution andmore » may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.« less

Monitoring of photoluminescence decay by alkali and alkaline earth metal cations using a photoluminescent bolaamphiphile self-assembly as an optical probe.

PubMed

Kim, Sunhyung; Kwak, Jinyoung; Lee, Sang-Yup

2014-05-01

Photoluminescence (PL) decay induced by the displacement of an ionic fluorescence component, Tb(3+), with alkali and alkaline earth metal cations was investigated using photoluminescent spherical self-assemblies as optical probes. The photoluminescent spherical self-assembly was prepared by the self-organization of a tyrosine-containing bolaamphiphile molecule with a photosensitizer and Tb(3+) ion. The lanthanide ion, Tb(3+), electrically bound to the carboxyl group of the bolaamphiphile molecule, was displaced by alkali and alkaline earth metal cations that had stronger electrophilicity. The PL of the self-assembly decayed remarkably due to the substitution of lanthanide ions with alkali and alkaline earth metal cations. The PL decay showed a positive correlation with cation concentration and was sensitive to the cation valency. Generally, the PL decay was enhanced by the electrophilicity of the cations. However, Ca(2+) showed greater PL decay than Mg(2+) because Ca(2+) could create various complexes with the carboxyl groups of the bolaamphiphile molecule. Microscopic and spectroscopic investigations were conducted to study the photon energy transfer and displacement of Tb(3+) by the cation exchange. This study demonstrated that the PL decay by the displacement of the ionic fluorescent compound was applied to the detection of various cations in aqueous media and is applicable to the development of future optical sensors. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Charkin, Dmitri O.; Black, Cameron; Downie, Lewis J.

Two new rare-earth – alkali – tellurium oxide halides were synthesized by a salt flux technique and characterized by single-crystal X-ray diffraction. The structures of the new compounds Cs{sub 7}Sm{sub 11}[TeO{sub 3}]{sub 12}Cl{sub 16} (I) and Rb{sub 7}Nd{sub 11}[TeO{sub 3}]{sub 12}Br{sub 16} (II) (both tetragonal, space group I4/mcm) correspond to the sequence of [MLn{sub 11}(TeO{sub 3}){sub 12}] and [M{sub 6}X{sub 16}] layers and bear very strong similarities to those of known selenite analogs. We discuss the trends in similarities and differences in compositions and structural details between the Se and Te compounds; more members of the family are predicted. -more » Graphical abstract: Two new rare-earth – alkali – tellurium oxide halides were predicted and synthesized. - Highlights: • Two new rare-earth – alkali – tellurium oxide halides were synthesized. • They adopt slab structure of rare earth-tellurium-oxygen and CsCl-like slabs. • The Br-based CsCl-like slabs have been observed first in this layered family.« less

Petrogenesis of ore-bearing porphyry in non-subduction setting: a case study of the Eocene potassic intrusions in the western Yangtze Block

NASA Astrophysics Data System (ADS)

Liu, Zheng; Liao, Shi-Yong; Zhou, Qing; Zhang, Xin

2018-05-01

In the western Yangtze Block, abundant Eocene ( 38-34 Ma) potassic adakite-like intrusions and associated porphyry copper deposits are exposed in non-subduction setting, including Machangjing, Beiya, Binchuan, Habo and Tongchang intrusions. All these ore-bearing porphyries share many geochemical characteristics of adakite such as depletion in heavy rare earth elements (HREEs), enrichment in Sr and Ba, absence of negative Eu anomalies, high SiO2, Al2O3, Sr/Y, La/Yb and low Y, Yb contents. They also exhibit affinities of potassic rocks, e.g., alkali-rich, high K2O/Na2O ratios and enrichment in light rare earth elements (LREEs) and large ion lithophile elements (LILEs). Their Sr-Nd isotopic ratios are similar to coeval shoshonitic lamprophyres. Geochemical data indicate that they were probably produced by partial melting of newly underplated potassic rocks sourced from a modified and enriched lithospheric mantle. These underplated rocks have elevated oxygen fugacity, water and copper contents, with high metallogenic potential. We propose that all the studied potassic rocks were emplaced in a post-collisional setting, associated with the local removal of lithospheric mantle.

Magmatic evolution and controls on rare metal-enrichment of the Strange Lake A-type peralkaline granitic pluton, Québec-Labrador

NASA Astrophysics Data System (ADS)

Siegel, Karin; Vasyukova, Olga V.; Williams-Jones, Anthony E.

2018-05-01

Although it is well known that A-type granites are enriched in the rare earth elements (REE) and other high field strength elements (HFSE), the magmatic processes that concentrate these elements are still poorly understood. The 1.24 Ga Strange Lake pluton in northern Québec-Labrador provides an extraordinary example of hyper-enrichment in the REE, Zr, and Nb in a peralkaline A-type granite. The pluton consists of two hypersolvus granite units (southern and northern) and a transsolvus granite, all of which contain perthitic alkali feldspar as the earliest major mineral; the transsolvus granite also contains separate albite and microcline crystals. Arfvedsonite, a sodic amphibole, occurs exclusively as phenocrysts in the transsolvus granite, whereas in the hypersolvus granite it is present as a late, interstitial phase. The primary HFSE minerals are zircon, monazite-(Ce), gagarinite-(Ce) and the pyrochlore group minerals. Magma evolution was monitored by the alumina content in the bulk rock, which decreases from the southern to the northern hypersolvus granite and is lowest in the transsolvus granite. Alkalinity indices and bulk Si, Fe, Rb, REE, Zr, Nb concentrations show the opposite trend. Alkali feldspar compositions mirror the trend shown by the bulk rock, i.e., decreasing Al contents are accompanied by increasing Si, Fe3+, REE, Zr and Nb contents. The major driving forces for the evolution of the hypersolvus magma prior to emplacement were the early separation of a fluoride melt from the silicate melt and the crystallization of alkali feldspar and HFSE-rich phases (zircon, monazite-(Ce), pyrochlore group). An alkali feldspar-rich crystal-mush containing LREE-fluoride melt droplets was emplaced as the least evolved southern hypersolvus granite. Massive fractionation of alkali feldspar led to a sharp increase in ƒH2O and F- activity in the magma chamber that triggered the crystallization of arfvedsonite and was followed by emplacement of the northern hypersolvus granite, which contained a higher proportion of LREE-fluoride melt droplets. Further evolution in the magma chamber led to a transition from a miaskitic to an agpaitic composition. The transsolvus granite was intruded in the form of a low viscosity crystal mush of alkali feldspar, quartz, arfvedsonite (after appreciable crystallization of arfvedsonite) and LREE-fluoride melt droplets. Upon emplacement, arfvedsonite (and gagarinite-(Ce)) crystals segregated as cumulates in response to a combination of flow differentiation and gravity settling. The immiscible fluoride melt accumulated in a volatile-rich residual silicate magma, which migrated to the top of the pluton where it formed the F-REE-rich cores of highly mineralized pegmatites.

Characterization of ash melting behaviour at high temperatures under conditions simulating combustible solid waste gasification.

PubMed

Niu, Miaomiao; Dong, Qing; Huang, Yaji; Jin, Baosheng; Wang, Hongyan; Gu, Haiming

2018-05-01

To achieve high-temperature gasification-melting of combustible solid waste, ash melting behaviour under conditions simulating high-temperature gasification were studied. Raw ash (RA) and gasified ash (GA) were prepared respectively by waste ashing and fluidized bed gasification. Results of microstructure and composition of the two-ash indicated that GA showed a more porous structure and higher content of alkali and alkali earth metals among metallic elements. Higher temperature promoted GA melting and could reach a complete flowing state at about 1250°C. The order of melting rate of GA under different atmospheres was reducing condition > inert condition > oxidizing condition, which might be related to different existing forms of iron during melting and different flux content with atmosphere. Compared to RA, GA showed lower melting activity at the same condition due to the existence of an unconverted carbon and hollow structure. The melting temperature for sufficient melting and separation of GA should be at least 1250°C in this work.

Effects of pH on frog gustatory responses to chloride salts of alkali-metal and alkali-earth-metal.

PubMed

Kumai, T; Nomura, H

1980-01-01

The pH effects on frog gustatory responses to alkali-metal and alkali-earth-metal chloride salts were examined using single fungi-form papilla preparations. Responses to 0.1-0.5 M NaCl were clearly dependent upon the pH of the stimulating solutions. The responses increased as the pH decreased from 6.5 to 4.5 and were almost completely suppressed at pH's above 6.5. There was no significant difference in the pH dependency of the response among alkali-metal chlorides. HCl solutions elicited only a poor response under conditions in which the water response was suppressed by the simultaneous presence of a low NaCl concentration. Responses to alkali-earth-metal chlorides varied in their pH dependency. Response to CaCl2 was slightly affected by pH changes from 4.5 to 9.0, response to SrCl2 was considerably suppressed in the alkaline region, and responses to BaCl2 and MgCl2 were strongly suppressed at pH's above 6.5. BeCl2 solutions showed less marked stimulating effects over the pH range tested. The differences in pH dependency described above suggest the existence of two kinds of receptor sites, one being pH-insensitive sites responsible for the calcium response and the other pH-sensitive sites responsible for the sodium response. A cross-adaptation test appeared to support this possibility. Assuming that the pH effect mentioned is related to changes in the state of ionization of the receptor molecule, the pKa of the ionizable group responsible for the sodium response was determined to be approximately 5.5.

METHOD AND APPARATUS FOR EFFECTING THERMAL BONDS

DOEpatents

Monson, H.O.; Jaross, R.A.

1961-10-17

A device is described for completing the alkali metal bend between a fael element and its jacket. It consists of a heater and electo1nagic surrounding the fael element so tbat while it is heated a rotating magnetic field will agirate the alkali metal and work out void spaces. (AEC)

SilMush: A procedure for modeling of the geochemical evolution of silicic magmas and granitic rocks

NASA Astrophysics Data System (ADS)

Hertogen, Jan; Mareels, Joyce

2016-07-01

A boundary layer crystallization modeling program is presented that specifically addresses the chemical fractionation in silicic magma systems and the solidification of plutonic bodies. The model is a Langmuir (1989) type approach and does not invoke crystal settling in high-viscosity silicic melts. The primary aim is to model a granitic rock as a congealed crystal-liquid mush, and to integrate major element and trace element modeling. The procedure allows for some exploratory investigation of the exsolution of H2O-fluids and of the fluid/melt partitioning of trace elements. The procedure is implemented as a collection of subroutines for the MS Excel spreadsheet environment and is coded in the Visual Basic for Applications (VBA) language. To increase the flexibility of the modeling, the procedure is based on discrete numeric process simulation rather than on solution of continuous differential equations. The program is applied to a study of the geochemical variation within and among three granitic units (Senones, Natzwiller, Kagenfels) from the Variscan Northern Vosges Massif, France. The three units cover the compositional range from monzogranite, over syenogranite to alkali-feldspar granite. An extensive set of new major element and trace element data is presented. Special attention is paid to the essential role of accessory minerals in the fractionation of the Rare Earth Elements. The crystallization model is able to reproduce the essential major and trace element variation trends in the data sets of the three separate granitic plutons. The Kagenfels alkali-feldspar leucogranite couples very limited variation in major element composition to a considerable and complex variation of trace elements. The modeling results can serve as a guide for the reconstruction of the emplacement sequence of petrographically distinct units. Although the modeling procedure essentially deals with geochemical fractionation within a single pluton, the modeling results bring up a number of questions about the petrogenetic relationships among parental magmas of nearly coeval granitic units emplaced in close proximity.

Spill-Resistant Alkali-Metal-Vapor Dispenser

NASA Technical Reports Server (NTRS)

Klipstein, William

2005-01-01

A spill-resistant vessel has been developed for dispensing an alkali-metal vapor. Vapors of alkali metals (most commonly, cesium or rubidium, both of which melt at temperatures slightly above room temperature) are needed for atomic frequency standards, experiments in spectroscopy, and experiments in laser cooling. Although the present spill-resistant alkali-metal dispenser was originally intended for use in the low-gravity environment of outer space, it can also be used in normal Earth gravitation: indeed, its utility as a vapor source was confirmed by use of cesium in a ground apparatus. The vessel is made of copper. It consists of an assembly of cylinders and flanges, shown in the figure. The uppermost cylinder is a fill tube. Initially, the vessel is evacuated, the alkali metal charge is distilled into the bottom of the vessel, and then the fill tube is pinched closed to form a vacuum seal. The innermost cylinder serves as the outlet for the vapor, yet prevents spilling by protruding above the surface of the alkali metal, no matter which way or how far the vessel is tilted. In the event (unlikely in normal Earth gravitation) that any drops of molten alkali metal have been shaken loose by vibration and are floating freely, a mesh cap on top of the inner cylinder prevents the drops from drifting out with the vapor. Liquid containment of the equivalent of 1.2 grams of cesium was confirmed for all orientations with rubbing alcohol in one of the prototypes later used with cesium.

Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO2 glasses.

PubMed

Sato, K; Hatta, T

2015-03-07

Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO2 glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

Positron Annihilation in Insulating Materials

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

Asoka-Kumar, P; Sterne, PA

2002-10-18

We describe positron results from a wide range of insulating materials. We have completed positron experiments on a range of zeolite-y samples, KDP crystals, alkali halides and laser damaged SiO{sub 2}. Present theoretical understanding of positron behavior in insulators is incomplete and our combined theoretical and experimental approach is aimed at developing a predictive understanding of positrons and positronium annihilation characteristics in insulators. Results from alkali halides and alkaline-earth halides show that positrons annihilate with only the halide ions, with no apparent contribution from the alkali or alkaline-earth cations. This contradicts the results of our existing theory for metals, whichmore » predicts roughly equal annihilation contributions from cation and anion. We also present result obtained using Munich positron microprobe on laser damaged SiO{sub 2} samples.« less

Electron- and Photon-stimulated Desorption of Alkali Atoms from Lunar Sample and a Model Mineral Surface

NASA Technical Reports Server (NTRS)

Yakshinskiy, B. V.; Madey, T. E.

2003-01-01

We report recent results on an investigation of source mechanisms for the origin of alkali atoms in the tenuous planetary atmospheres, with focus on non-thermal processes (photon stimulated desorption (PSD), electron stimulated desorption (ESD), and ion sputtering). Whereas alkaline earth oxides (MgO, CaO) are far more abundant in lunar samples than alkali oxides (Na2O, K2O), the atmosphere of the Moon contains easily measurable concentrations of Na and K, while Ca and Mg are undetected there; traces of Ca have recently been seen in the Moon's atmosphere (10-3 of Na). The experiments have included ESD, PSD and ion sputtering of alkali atoms from model mineral surface (amorphous SiO2) and from a lunar basalt sample obtained from NASA. The comparison is made between ESD and PSD efficiency of monovalent alkalis (Na, K) and divalent alkaline earths (Ba, Ca).The ultrahigh vacuum measurement scheme for ESD and PSD of Na atoms includes a highly sensitive alkali metal detector based on surface ionization, and a time-of-flight technique. For PSD measurements, a mercury arc light source (filtered and chopped) is used. We find that bombardment of the alkali covered surfaces by ultraviolet photons or by low energy electrons (E>4 eV) causes desorption of hot alkali atoms. This results are consistent with the model developed to explain our previous measurements of sodium desorption from a silica surface and from water ice: electron- or photon-induced charge transfer from the substrate to the ionic adsorbate causes formation of a neutral alkali atom in a repulsive configuration, from which desorption occurs. The two-electron charge transfer to cause desorption of divalent alkaline eath ions is a less likely process.The data support the suggestion that PSD by UV solar photons is a dominant source process for alkalis in the tenuous lunar atmosphere.

Interactions of Hydrazine and of Hydrazine Derivatives with Soil Constituents and with Soils

DTIC Science & Technology

1984-08-23

vigorously. After flocs which formed on addition of alkali had redissolved a homogeneous dark red solution (pH 2.0) was obtained. This solution was allowed to...collected fractions of the eluate. Scintillation techniques (Smedley, 1978), atomic absorption and radioisotopic labelling techniques (Hartmann, 1981), and...but significantly less exothermic in the cases of the alkali -earth than the alkali metals. The heat of hydration of the divalent cations is greater than

Recovery of protactinium from molten fluoride nuclear fuel compositions

DOEpatents

Baes, C.F. Jr.; Bamberger, C.; Ross, R.G.

1973-12-25

A method is provided for separating protactinium from a molten fluonlde salt composition consisting essentially of at least one alkali and alkaline earth metal fluoride and at least one soluble fluoride of uranium or thorium which comprises oxidizing the protactinium in said composition to the + 5 oxidation state and contacting said composition with an oxide selected from the group consisting of an alkali metal oxide, an alkaline earth oxide, thorium oxide, and uranium oxide, and thereafter isolating the resultant insoluble protactinium oxide product from said composition. (Official Gazette)

Corrosion resistant positive electrode for high-temperature, secondary electrochemical cell

DOEpatents

Otto, Neil C.; Warner, Barry T.; Smaga, John A.; Battles, James E.

1983-01-01

The corrosion rate of low carbon steel within a positive electrode of a high-temperature, secondary electrochemical cell that includes FeS as active material is substantially reduced by incorporating therein finely divided iron powder in stoichiometric excess to the amount required to form FeS in the fully charged electrode. The cell typically includes an alkali metal or alkaline earth metal as negative electrode active material and a molten metal halide salt as electrolyte. The excess iron permits use of inexpensive carbon steel alloys that are substantially free of the costly corrosion resistant elements chromium, nickel and molybdenum while avoiding shorten cell life resulting from high corrosion rates.

Corrosion resistant positive electrode for high-temperature, secondary electrochemical cell

DOEpatents

Otto, N.C.; Warner, B.T.; Smaga, J.A.; Battles, J.E.

1982-07-07

The corrosion rate of low carbon steel within a positive electrode of a high-temperature, secondary electrochemical cell that includes FeS as active material is substantially reduced by incorporating therein finely divided iron powder in stoichiometric excess to the amount required to form FeS in the fully charged electrode. The cell typically includes an alkali metal or alkaline earth metal as negative electrode active material and a molten metal halide salt as electrolyte. The excess iron permits use of inexpensive carbon steel alloys that are substantially free of the costly corrosion resistant elements chromium, nickel and molybdenum while avoiding shorten cell life resulting from high corrosion rates.

Minor elements incorporation control by ionic radius and growth rate on a stalagmite from the Chauvet Cave (SE-France)

NASA Astrophysics Data System (ADS)

Bourdin, C.; Douville, E.; Genty, D.

2009-12-01

A multi-elemental study focusing on earth-alkalis (Mg, Ca, Sr and Ba), uranium and rare-earth elements (REE) in the calcite of a stalagmite from the Chauvet Cave (SE of France) has been achieved by ICP-MS. The Chau-stm6 stalagmite which grew from 33 to 11.5 ky had already been dated and the published d13C and d18O profile is used as a paleoclimatic benchmark. Ba and Sr profiles show an abrupt concentration increase at the beginning of the last deglaciation whereas U and Mg feature a decreasing trend. REY (REE+yttrium) concentrations decrease markedly during early deglaciation (between 15 and 14.5 ky). The transition corresponds to a change from a slow to a fast growth rate. These variations can be explained by the crystallographic control of ionic radii of the minor elements: incorporation of small ions compared to Ca such as U, Mg, heavy REE are favoured during slow growth period (i.e. glacial) whereas large ions such as Ba, Sr and light REE are preferentially precipitated during fast growth period (i.e. Bolling-Allerod). This crystallographic effect seems to be dominant here because the soil above the cave is sparse. And may not have played a major role on the opposite to the water-limestone interaction.

Geochemistry of Archean shales from the Pilbara Supergroup, Western Australia

NASA Astrophysics Data System (ADS)

McLennan, Scott M.; Taylor, S. R.; Eriksson, K. A.

1983-07-01

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group ( ca. 3.4 Ae) and shales from the Whim Creek Group ( ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition. Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ( La N/Yb N ≥ 7.5 ) and no or very slight Eu depletion ( Eu/Eu ∗ = 0.82 - 0.99 ). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.

Enamel for high-temperature superalloys

NASA Technical Reports Server (NTRS)

Levin, H.; Lent, W. E.

1977-01-01

Desired optical and high temperature enamel properties are obtained with glasses prepared from the system Li2O-ZrO2-nSiO2. Molar compositions range from n=4 to n=1.3, to which are added minor amounts in varying combinations of alumina, alkali fluorides, boric oxide, alkali oxides, and akaline earth oxides.

Phosphates behaviours in conversion of FP chlorides

NASA Astrophysics Data System (ADS)

Amamoto, I.; Kofuji, H.; Myochin, M.; Takasaki, Y.; Terai, T.

2009-06-01

The spent electrolyte of the pyroprocessing by metal electrorefining method should be considered for recycling after removal of fission products (FP) such as, alkali metals (AL), alkaline earth metals (ALE), and/or rare earth elements (REE), to reduce the volume of high-level radioactive waste. Among the various methods suggested for this purpose is precipitation by converting FP from chlorides to phosphates. Authors have been carrying out the theoretical analysis and experiment showing the behaviours of phosphate precipitates so as to estimate the feasibility of this method. From acquired results, it was found that AL except lithium and ALE are unlikely to form phosphate precipitates. However their conversion behaviours including REE were compatible with the theoretical analysis; in the case of LaPO 4 as one of the REE precipitates, submicron-size particles could be observed while that of Li 3PO 4 was larger; the precipitates were apt to grow larger at higher temperature; etc.

Comparative Analysis of Processes for Recovery of Rare Earths from Bauxite Residue

NASA Astrophysics Data System (ADS)

Borra, Chenna Rao; Blanpain, Bart; Pontikes, Yiannis; Binnemans, Koen; Van Gerven, Tom

2016-11-01

Environmental concerns and lack of space suggest that the management of bauxite residue needs to be re-adressed. The utilization of the residue has thus become a topic high on the agenda for both academia and industry, yet, up to date, it is only rarely used. Nonetheless, recovery of rare earth elements (REEs) with or without other metals from bauxite residue, and utilization of the left-over residue in other applications like building materials may be a viable alternative to storage. Hence, different processes developed by the authors for recovery of REEs and other metals from bauxite residue were compared. In this study, preliminary energy and cost analyses were carried out to assess the feasibility of the processes. These analyses show that the combination of alkali roasting-smelting-quenching-leaching is a promising process for the treatment of bauxite residue and that it is justified to study this process at a pilot scale.

The role of hydrothermal processes in concentrating high-field strength elements in the Strange Lake peralkaline complex, northeastern Canada

NASA Astrophysics Data System (ADS)

Salvi, Stefano; Williams-Jones, Anthony E.

1996-06-01

The middle-Proterozoic peralkaline pluton at Strange Lake, Quebec/Labrador, comprises hypersolvus to subsolvus phases which are unusually enriched in Zr, Y, REEs, Nb, Be, and F, as exotic alkali and alkaline-earth silicate minerals. The highest concentrations of these elements are in subsolvus granite, which underwent intense low temperature (≤200°C) hydrothermal alteration involving hematization and the replacement of alkali high-field strength element (HFSE) minerals by calcic equivalents. This alteration is interpreted to have been caused by meteoric or formational waters. High temperature (≥ 350°C) alteration, attributed to orthomagmatic fluids, is evident in other parts of the subsolvus granite by the replacement of arfvedsonite by aegirine. Comparisons of the chemical compositions of fresh and altered rocks indicate that rocks subjected to high temperature alteration were chemically unaffected, except for depletion in Zr, Y, and HREEs. These elements were appreciably enriched in rocks that underwent low temperature alteration. Other elements affected by low temperature alteration include Ca and Mg, which were added and Na, which was removed. Available data on HFSE speciation in aqueous fluids and the chemistry of the pluton, suggest that the HFSEs were transported as fluoride complexes. If this was the case, the low temperature fluid could not have been responsible for HFSE transport, because the high concentration of Ca and low solubility of fluorite would have buffered F - activity to levels too low to permit significant complexation. We propose that HFSE mineralization and accompanying alteration were the result of mixing, in the apical parts of the pluton, of a F-rich, essentially Ca-free orthomagmatic fluid containing significant concentrations of HFSEs, with an externally derived meteoric-dominated fluid, enriched in Ca as a result of interaction with calc-silicate gneisses and gabbros. According to this interpretation, the latter fluid was responsible for the exchange of Ca for alkalis, mainly Na, in HFSE-rich minerals and, by sharply reducing F - activity in the mixed fluid through fluorite precipitation and/or increasing pH, destabilised the HFSE-fluoride complexes, causing deposition of HFSE-bearing minerals. An important implication of this study is that major HFSE enrichment may be restricted to those rare cases where F-rich, Ca-free, metal leaching environments and Ca-rich depositional environments are juxtaposed.

PLUTONIUM ELECTROREFINING CELLS

DOEpatents

Mullins, L.J. Jr.; Leary, J.A.; Bjorklund, C.W.; Maraman, W.J.

1963-07-16

Electrorefining cells for obtaining 99.98% plutonium are described. The cells consist of an impure liquid plutonium anode, a molten PuCl/sub 3/-- alkali or alkaline earth metal chloanode, a molten PuCl/sub 3/-alkali or alkaline earth metal chloride electrolyte, and a nonreactive cathode, all being contained in nonreactive ceramic containers which separate anode from cathode by a short distance and define a gap for the collection of the purified liquid plutonium deposited on the cathode. Important features of these cells are the addition of stirrer blades on the anode lead and a large cathode surface to insure a low current density. (AEC)

Theoretical dissociation energies for the alkali and alkaline-earth monofluorides and monochlorides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.

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

Apps, John A.; Wilkin, Richard T.

This report contains a series of tables summarizing the thermodynamic properties of aqueous carbonate complexes and solid carbonate phases of the following elements: arsenic (As), barium (Ba), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), mercury (Hg), nickel (Ni) thallium (Tl), uranium (U) and zinc (Zn). Most of these elements are potentially hazardous as defined by extant primary drinking water standards of the United States Environmental Protection Agency (EPA). The remainder are not considered hazardous, but are either listed by EPA under secondary standards, or because they can adversely affect drinking water quality. Additionalmore » tables are included giving the thermodynamic properties for carbonates of the alkali metal and alkali earth elements, sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), and strontium (Sr), because of their value in developing correlative models to estimate the thermodynamic properties of carbonate minerals for which no such data currently exist. The purpose in creating the tables in this report is to provide future investigators with a convenient source for selecting and tracing the sources of thermodynamic data of the above listed elements for use in modeling their geochemical behavior in “underground sources of drinking water” (USDW). The incentive for doing so lies with a heightened concern over the potential consequences of the proposed capture and storage of carbon dioxide (CO2) generated by fossil fuel fired power plants in deep subsurface reservoirs. If CO2 were to leak from such reservoirs, it could migrate upward and contaminate USDWs with undesirable, but undetermined, consequences to water quality. The EPA, Office of Research and Development, through an Interagency Agreement with the U.S. Department of Energy at the Lawrence Berkeley National Laboratory, funded the preparation of this report.« less

Theoretical study of the diatomic alkali and alkaline-earth oxides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Theoretical dissociation energies for the ground states of the alkali and alkaline earth oxides are presented that are believed to be accurate to 0.1 eV. The 2 Pi - 2 Sigma + separations for the alkali oxides are found to be more sensitive to basis set than to electron correlation. Predicted 2 Pi ground states for LiO and NaO and 2 Sigma + ground states for RbO and CsO are found to be in agreement with previous theoretical and experimental work. For KO, a 2 Sigma + state is found at both the numerical Hartree-Fock (NHF) level and at the singles plus doubles configuration interaction level using a Slater basis set that is within 0.02 eV of the NHF limit. It is found that an accurate balanced treatment of the two states requires correlating the electrons on both the metal and oxide ion.

Theoretical study of the BeLi, BeNa, MgLi, MgNa, and AlBe molecules and their negative ions

NASA Technical Reports Server (NTRS)

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

1992-01-01

The alkaline earth-alkali diatomics are found to have weak bonds, because the diffuse alkali valence s orbitals cannot form a bond of sufficient strength to pay the promotion energy of the alkaline-earth atoms. This leads to van der Waals bonding in the neutrals as well as the negative ions. In fact, the negative ions have larger binding energies than the neutrals as a result of the much larger polarizability of the negative ion. The binding energy of AlBe is significantly larger than the Be-alkali molecules, due to a covalent contribution to the bonding. The binding energy in AlBe(-) is considerably larger than AlBe; the binding energy of the X 3Sigma(-) state of AlBe(-) is computed to be 1.36 eV, as compared with 0.57 eV for the X 2Pi state of AlBe.

Article Including Environmental Barrier Coating System

NASA Technical Reports Server (NTRS)

Lee, Kang N. (Inventor)

2015-01-01

An enhanced environmental barrier coating for a silicon containing substrate. The enhanced barrier coating may include a bond coat doped with at least one of an alkali metal oxide and an alkali earth metal oxide. The enhanced barrier coating may include a composite mullite bond coat including BSAS and another distinct second phase oxide applied over said surface.

Alkali trace elements in Gale crater, Mars, with ChemCam: Calibration update and geological implications

NASA Astrophysics Data System (ADS)

Payré, V.; Fabre, C.; Cousin, A.; Sautter, V.; Wiens, R. C.; Forni, O.; Gasnault, O.; Mangold, N.; Meslin, P.-Y.; Lasue, J.; Ollila, A.; Rapin, W.; Maurice, S.; Nachon, M.; Le Deit, L.; Lanza, N.; Clegg, S.

2017-03-01

The Chemistry Camera (ChemCam) instrument onboard Curiosity can detect minor and trace elements such as lithium, strontium, rubidium, and barium. Their abundances can provide some insights about Mars' magmatic history and sedimentary processes. We focus on developing new quantitative models for these elements by using a new laboratory database (more than 400 samples) that displays diverse compositions that are more relevant for Gale crater than the previous ChemCam database. These models are based on univariate calibration curves. For each element, the best model is selected depending on the results obtained by using the ChemCam calibration targets onboard Curiosity. New quantifications of Li, Sr, Rb, and Ba in Gale samples have been obtained for the first 1000 Martian days. Comparing these data in alkaline and magnesian rocks with the felsic and mafic clasts from the Martian meteorite NWA7533—from approximately the same geologic period—we observe a similar behavior: Sr, Rb, and Ba are more concentrated in soluble- and incompatible-element-rich mineral phases (Si, Al, and alkali-rich). Correlations between these trace elements and potassium in materials analyzed by ChemCam reveal a strong affinity with K-bearing phases such as feldspars, K-phyllosilicates, and potentially micas in igneous and sedimentary rocks. However, lithium is found in comparable abundances in alkali-rich and magnesium-rich Gale rocks. This very soluble element can be associated with both alkali and Mg-Fe phases such as pyroxene and feldspar. These observations of Li, Sr, Rb, and Ba mineralogical associations highlight their substitution with potassium and their incompatibility in magmatic melts.

Niobium-bearing arsenides and germanides from elemental mixtures not involving niobium: a new twist to an old problem in solid-state synthesis.

PubMed

Baranets, Sviatoslav; He, Hua; Bobev, Svilen

2018-05-01

Three isostructural transition-metal arsenides and germanides, namely niobium nickel arsenide, Nb 0.92(1) NiAs, niobium cobalt arsenide, NbCoAs, and niobium nickel germanide, NbNiGe, were obtained as inadvertent side products of high-temperature reactions in sealed niobium containers. In addition to reporting for the very first time the structures of the title compounds, refined from single-crystal X-ray diffraction data, this article also serves as a reminder that niobium containers may not be suitable for the synthesis of ternary arsenides and germanides by traditional high-temperature reactions. Synthetic work involving alkali or alkaline-earth metals, transition or early post-transition metals, and elements from groups 14 or 15 under such conditions may yield Nb-containing products, which at times could be the major products of such reactions.

The solvated electron battery

NASA Astrophysics Data System (ADS)

Bennett, J.; Harney, D.; Mitchell, T.

A novel ambient temperture secondary battery using sodium and sulfur dissolved in liquid ammonia is being developed at ELTECH Systems corpooration. The key element of the system is the solvated electron electrode, a metallic liquid which is formed by ammonia and a number of alkali and alkaline earth metals. These solutions are excellent ionic and electronic conductors and have been shown to contain 'free' solvated electrons as the anionic species in solution. Sulfur was chosen as the cathodic reactant because of its high solubility in ammonia, and also because of the high solubiity and good conductivity of the polysulfide reaction products. Development efforts have thus far concentrated on basic electrochemical measurements and establishment of system feasibility.

Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

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

Srinivas, G., E-mail: srinu123g@gmail.com; Ramesh, B.; Shareefuddin, Md.

2016-05-06

The mixed alkali and alkaline earth oxide borate glass with the composition xK{sub 2}O - (25-x) Li{sub 2}O-12.5BaO-12.5MgO-50B{sub 2}O{sub 3} (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α{sub 0}2-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α{sub 0}2-), and (Λ) increases with increasing of K{sub 2}O content and electronicmore » polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K{sub 2}O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).« less

Alkali activated slag mortars provide high resistance to chloride-induced corrosion of steel

NASA Astrophysics Data System (ADS)

Criado, Maria; Provis, John L.

2018-06-01

The pore solutions of alkali-activated slag cements and Portland-based cements are very different in terms of their chemical and redox characteristics, particularly due to the high alkalinity and high sulfide content of alkali-activated slag cement. Therefore, differences in corrosion mechanisms of steel elements embedded in these cements could be expected, with important implications for the durability of reinforced concrete elements. This study assesses the corrosion behaviour of steel embedded in alkali-activated blast furnace slag (BFS) mortars exposed to alkaline solution, alkaline chloride-rich solution, water, and standard laboratory conditions, using electrochemical techniques. White Portland cement (WPC) mortars and blended cement mortars (white Portland cement and blast furnace slag) were also tested for comparative purposes. The steel elements embedded in immersed alkali-activated slag mortars presented very negative redox potentials and high apparent corrosion current values; the presence of sulfide reduced the redox potential, and the oxidation of the reduced sulfur-containing species within the cement itself gave an electrochemical signal that classical electrochemical tests for reinforced concrete durability would interpret as being due to steel corrosion processes. However, the actual observed resistance to chloride-induced corrosion was very high, as measured by extraction and characterisation of the steel at the end of a 9-month exposure period, whereas the steel embedded in white Portland cement mortars was significantly damaged under the same conditions.

METHOD AND APPARATUS FOR EXAMINING FUEL ELEMENTS FOR LEAKAGE

DOEpatents

Smith, R.R.; Echo, M.W.; Doe, C.B.

1963-12-31

A process and a device for the continuous monitoring of fuel elements while in use in a liquid-metal-cooled, argonblanketed nuclear reactor are presented. A fraction of the argon gas is withdrawn, contacted with a negative electrical charge for attraction of any alkali metal formed from argon by neutron reaction, and recycled into the reactor. The electrical charge is introduced into water, and the water is examined for radioactive alkali metals. (AEC)

Alkali trace elements in Gale crater, Mars, with ChemCam: Calibration update and geological implications

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

Payre, Valerie; Fabre, Cecile; Cousin, Agnes

The Chemistry Camera (ChemCam) instrument onboard Curiosity can detect minor and trace elements such as lithium, strontium, rubidium, and barium. Their abundances can provide some insights about Mars' magmatic history and sedimentary processes. We focus on developing new quantitative models for these elements by using a new laboratory database (more than 400 samples) that displays diverse compositions that are more relevant for Gale crater than the previous ChemCam database. These models are based on univariate calibration curves. For each element, the best model is selected depending on the results obtained by using the ChemCam calibration targets onboard Curiosity. New quantificationsmore » of Li, Sr, Rb, and Ba in Gale samples have been obtained for the first 1000 Martian days. Comparing these data in alkaline and magnesian rocks with the felsic and mafic clasts from the Martian meteorite NWA7533—from approximately the same geologic period—we observe a similar behavior: Sr, Rb, and Ba are more concentrated in soluble- and incompatible-element-rich mineral phases (Si, Al, and alkali-rich). Correlations between these trace elements and potassium in materials analyzed by ChemCam reveal a strong affinity with K-bearing phases such as feldspars, K-phyllosilicates, and potentially micas in igneous and sedimentary rocks. However, lithium is found in comparable abundances in alkali-rich and magnesium-rich Gale rocks. This very soluble element can be associated with both alkali and Mg-Fe phases such as pyroxene and feldspar. Here, these observations of Li, Sr, Rb, and Ba mineralogical associations highlight their substitution with potassium and their incompatibility in magmatic melts.« less

Alkali trace elements in Gale crater, Mars, with ChemCam: Calibration update and geological implications

DOE PAGES

Payre, Valerie; Fabre, Cecile; Cousin, Agnes; ...

2017-03-20

The Chemistry Camera (ChemCam) instrument onboard Curiosity can detect minor and trace elements such as lithium, strontium, rubidium, and barium. Their abundances can provide some insights about Mars' magmatic history and sedimentary processes. We focus on developing new quantitative models for these elements by using a new laboratory database (more than 400 samples) that displays diverse compositions that are more relevant for Gale crater than the previous ChemCam database. These models are based on univariate calibration curves. For each element, the best model is selected depending on the results obtained by using the ChemCam calibration targets onboard Curiosity. New quantificationsmore » of Li, Sr, Rb, and Ba in Gale samples have been obtained for the first 1000 Martian days. Comparing these data in alkaline and magnesian rocks with the felsic and mafic clasts from the Martian meteorite NWA7533—from approximately the same geologic period—we observe a similar behavior: Sr, Rb, and Ba are more concentrated in soluble- and incompatible-element-rich mineral phases (Si, Al, and alkali-rich). Correlations between these trace elements and potassium in materials analyzed by ChemCam reveal a strong affinity with K-bearing phases such as feldspars, K-phyllosilicates, and potentially micas in igneous and sedimentary rocks. However, lithium is found in comparable abundances in alkali-rich and magnesium-rich Gale rocks. This very soluble element can be associated with both alkali and Mg-Fe phases such as pyroxene and feldspar. Here, these observations of Li, Sr, Rb, and Ba mineralogical associations highlight their substitution with potassium and their incompatibility in magmatic melts.« less

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)

Theoretical study of mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes.

PubMed

Groen, Cornelis Petrus; Oskam, Ad; Kovács, Attila

2003-02-10

The structure, bonding, and vibrational properties of the mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes have been studied using the MP2 method in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. From the three characteristic structures, possessing 1- (C(3)(v)), 2- (C(2)(v)), or 3-fold coordination (C(3)(v)) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are stable isomers with close dissociation energies. In general, for the complexes existing of lighter alkali metals and halogens, the bidentate structure corresponds to the global minimum of the potential energy surface, while the heavier analogues favor the tridentate structure. At experimentally relevant temperatures (T > 800 K), however, the isomerization entropy leads to a domination of the bidentate structures over the tridentate forms for all complexes. An important effect of the size of the alkali metal is manifested in the larger stabilities of the K and Cs complexes. The natural atomic charges are in agreement with strong electrostatic interactions in the title complexes. The marginal covalent contributions show a slight increasing trend in the heavier analogues. The calculated vibrational data indicate that infrared spectroscopy may be an effective tool for experimental investigation and characterization of MLaX(4) molecules.

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon. (1) Weathering reactions in the volcanics

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

Banfield, J.F.; Veblen, D.R.; Jones, B.F.

1991-10-01

Abert Lake in south-central Oregon provides a site suitable for the study of sequential weathering and diagenetic events. In this first of two papers, transmission electron microscopy was used to characterize the igneous mineralogy, subsolidus alteration assemblage, and the structural and chemical aspects of silicate weathering reactions that occur in the volcanic rocks that outcrop around the lake. Olivine and pyroxene replacement occurred topotactically, whereas feldspar and glass alteration produced randomly oriented smectite in channels and cavities. The tetrahedral, octahedral, and interlayer compositions of the weathering products, largely dioctahedral smectites, varied with primary mineral composition, rock type, and as themore » result of addition of elements released from adjacent reaction sites. The variability within and between the smectite assemblages highlights the microenvironmental diversity, fluctuating redox conditions, and variable solution chemistry associated with mineral weathering reactions in the surficial environment. Late-stage exhalative and aqueous alteration of the volcanics redistributed many components and formed a variety of alkali and alkali-earth carbonate, chloride, sulfate, and fluoride minerals in vugs and cracks. Overall, substantial Mg, Si, Na, Ca, and K are released by weathering reactions that include the almost complete destruction of the Mg-smectite that initially replaced olivine. The leaching of these elements from the volcanics provides an important source of these constituents in the lake water. The nature of subsequent diagenetic reactions resulting from the interaction between the materials transported to the lake and the solution will be described in part.« less

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

Bonamici, Chloë E.; Kinman, William S.; Fournelle, John H.

Reprocessed earth material is a glassy nuclear fallout debris from near-surface nuclear tests. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. Our study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclearmore » test (“trinitite”) and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. Furthermore, the volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.« less

Geochemical associations between fluorite mineralization and A-type shoshonitic magmatism in the Keban-Elazig area, East Anatolia, Turkey

NASA Astrophysics Data System (ADS)

Akgul, Bunyamin

2015-11-01

Keban fluorite mineralizations are closely related Coniacian-Campanian subvolcanics intruded into Permian-Triassic Keban metamorphites; this event caused pyrometasomatic, porphyry, and vein-type Pb-Zn-Ag, Cu, W, and Pb-Zn-Ag-Mo-F mineralizations. These rocks are syenitic and syenomonzonitic in composition and have high Al2O3, alkali (Na2O + K2O), FeO*/MgO, Zr, Nb, Ta, Ga, Rb, Y, and rare earth element (REE) contents. They are A-type, metaluminous, and all fall in the shoshonitic series field in K2O vs SiO2 and Th/Yb vs Ta/Yb diagrams. The trace element contents and discriminations indicate that the Keban syenitoids were derived from lithospheric mantle metasomatized by oceanic-crust/sediment fluids. The metal and halogen contents of the Keban mineralizations apparently originated from metasomatized mantle and were transported to the crust by syenitoid magmas. Clear resemblances in chondrite-normalized REE patterns, LREE-HREE partionation, and high LILE contents of the magmatics and fluorites indicate a close kinship between the syenitoids and fluorite mineralizations. The HFSE contents of the fluorites are lower than those of the magmatics, as HFSEs are not soluble in aqueous fluids. The fluorites are products of early-phase alkali magmatism (LREE > HREE). The high contents of Rb, Sr, and Ba of fluorites are inherited from the magma, which also has very high contents of these elements. In Sc-∑REE, (La/Yb)n-(Eu/Eu*)n and (Tb/La)n-(Tb/Ca)n diagrams, Keban fluorites fall into distinct areas from Akcakisla-Akdagmadeni and Celikhan-Adiyaman fluorites.

The timing of alkali metasomatism in paleosols

NASA Technical Reports Server (NTRS)

MacFarlane, A. W.; Holland, H. D.

1991-01-01

We have measured the concentrations of rubidium and strontium and 87Sr/86Sr values of whole-rock samples from three paleosols of different ages. The oldest of the three weathering horizons, the 2,760 Ma Mt. Roe #1 paleosol in the Fortescue Group of Western Australia, experienced addition of Rb, and probably Sr, at 2,168 +/- 10 Ma. The intermediate paleosol, developed on the Hekpoort Basalt in South Africa, is estimated to have formed at 2,200 Ma, and yields a Rb-Sr isochron age of 1,925 +/- 32 Ma. The youngest of the three paleosols, developed on the Ongeluk basalt in Griqualand West, South Africa ca. 1,900 Ma, yielded a Rb-Sr age of 1,257 +/- 11 Ma. The Rb-Sr systematics of all three paleosols were reset during post-weathering metasomatism related to local or regional thermal disturbances. The Rb-Sr systematics of the paleosols were not subsequently disturbed. The near-complete removal of the alkali and alkaline earth elements from these paleosols during weathering made them particularly susceptible to resetting of their Rb-Sr systematics. Paleosols of this type are therefore sensitive indicators of the timing of thermal disturbances.

Element Mass Balance in Soils : the Mount Cameroon Case

NASA Astrophysics Data System (ADS)

Dia, A.; Chauvel, C.; Bulourde, M.

2002-12-01

Mount Cameroon is an active volcano located in Central Africa. Its location in a tropical climate area leads to abundant vegetation and intense weathering conditions that favor rapid alteration. Soils develop rapidly on the flanks of the volcano. We measured major and trace element contents as well as Pb, Nd and Sr isotopic compositions in three soil sections developed on basaltic tuffaceous units. Each section comprises 2-3 units, the upper portions of which are altered to soil (Andepts). The starting material is pyroclastic alkali basalt characterized by marked enrichment in trace elements. To determine the element flux during soil formation, two corrections have to be performed: (1) the parental rock composition has to be determined and (2) addition of Saharan dust as evidenced by [1] has to be corrected for. The starting rock composition is constrained using the Al/Fe vs C.I.A. relationship and the uppermost part of each soil is corrected for its eolian dust contribution (*10%). The budget for each element can then be estimated in the soils. Calculations are performed relative to an `immobile' element whose concentration is assumed to be unchanged during soil formation. We chose Th as a reference because its behavior during magmatic processes is similar to those of U, Rb, Ba, Cs and K which are known to be mobile during weathering processes. Results of the element budget calculations show that: alkali and alkaline earth elements are leached out of the soils (~ 50%). Silica losses (~ 30%) are also clear in all samples. For the other elements, systematic differences exist between bottom and top parts of each soil. The uppermost levels display significant changes Ni, U, Pb, P, Ni and Co contents. These mobilities are most probably related to hydrolysis of primary magmatic minerals triggered by the biological activity. Since the three studied sections correspond to the superposition of several soils where new tephra cover an older soil to be the basis of the formation of a new and younger soil, the element mass balance depends both on the paleoclimate conditions that prevailed during exposure to surface conditions, and on the duration of the exposure to air before the soil was covered by a new eruption. [1] Chauvel C., Dia A and Bulourde M., GCA, Vol 66, 14A, p A132, 2002.

Electron Spectroscopy for Chemical Analysis (ESCA) study of atmospheric particles

NASA Technical Reports Server (NTRS)

Dillard, J. G.; Seals, R. D.; Wightman, J. P.

1979-01-01

The results of analyses by ESCA (Electron Spectroscopy for Chemical Analysis) on several Nuclepore filters which were exposed during air pollution studies are presented along with correlative measurements by Neutron Activation Analysis and Scanning Electron Microscopy. Samples were exposed during air pollution studies at Norfolk, Virginia and the NASA Kennedy Space Center (KSC). It was demonstrated that with the ESCA technique it was possible to identify the chemical (bonding) state of elements contained in the atmospheric particulate matter collected on Nuclepore filters. Sulfur, nitrogen, mercury, chlorine, alkali, and alkaline earth metal species were identified in the Norfolk samples. ESCA binding energy data for aluminum indicated that three chemically different types of aluminum are present in the launch and background samples from NASA-KSC.

Highly alkaline lavas in a Proterozoic rift zone: Implications for Precambrian mantle metasomatic processes

NASA Astrophysics Data System (ADS)

Gaonac'h, H.; Ludden, J. N.; Picard, C.; Francis, D.

1992-03-01

An occurrence of Proterozoic nephelinite and basanite lavas and pyroclastic rocks and associated phonolites indicates that the processes that generate modern alkaline magmas in intraplate settings were operative in the Early Proterozoic. These lavas occur near the top of a 1.9 Ga continental-margin sequence in the Cape Smith fold and thrust belt of northern Quebec. The lavas are classified as nephelinites, basanites, and phonolites on the basis of high field strength and rare earth element contents, although large ion lithophile elements, including alkalis, appear to have been strongly depleted by greenschist facies metamorphism and alteration. Certain major elements define trends consistent with low-pressure fractionation dominated by clinopyroxene, which is the only mafic phenocryst present in the lavas. The mafic and felsic lavas have identical 143Nd/144Nd ratios, consistent with consanguinity and a lack of contamination by older crust of the Superior province. Values for ɛNd (1.96 Ga) of +2 represent an enriched mantle source relative to +4 to +5 for the contemporaneous mid-oceanic-ridge basalt reservoir.

Uptake of trace elements and radionuclides from uranium mill tailings by four-wing saltbush (Atriplex canescens) and alkali sacaton (Sporobolus airoides). [Radium 226; Uranium; Molybdenum; Selenium; Vanadium; Astatine

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

Dreesen, D.R.; Marple, M.L.

1979-01-01

A greenhouse experiment was performed to determine the uptake of trace elements and radionuclides from uranium mill tailings by native plant species. Four-wing saltbush and alkali sacaton were grown in alkaline tailings covered with soil and in soil alone as controls. The tailings material was highly enriched in Ra-226, Mo, U, Se, V, and As compared with three local soils. The shrub grown in tailings had elevated concentrations of Mo, Se, Ra-226, U, As, and Na compared with the controls. Alkali sacaton contained high concentrations of Mo, Se, Ra-226, and Ni when grown on tailings. Molybdenum and selenium concentrations inmore » plants grown in tailings are above levels reported to be toxic to grazing animals. These results indicate that the bioavailability of Mo and Se in alkaline environments makes these elements among the most hazardous contaminants present in uranium mill wastes.« less

Nanominerals and potentially hazardous elements from coal cleaning rejects of abandoned mines: Environmental impact and risk assessment.

PubMed

Fdez-Ortiz de Vallejuelo, Silvia; Gredilla, Ainara; da Boit, Kátia; Teixeira, Elba C; Sampaio, Carlos H; Madariaga, Juan Manuel; Silva, Luis F O

2017-02-01

Soils around coal mining are important reservoir of hazardous elements (HEs), nanominerals, and ultrafine compounds. This research reports and discusses the soil concentrations of HEs (As, Cd, Cr, Cu, Ni, Pb, and Zn) in coal residues of abandoned mines. To assess differences regarding environmental impact and risk assessment between coal abandoned mines from the Santa Catarina state, eighteen coal cleaning rejects with different mineralogical and chemical composition, from eight abandoned mines were collected. Nanominerals and ultra-fine minerals from mining-contaminated areas were analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscope (HR-TEM), providing new information on the mineralogy and nano-mineralogy of these coal residues. The total contents of 57 elements (HEs, alkali metals, and rare earth elements) were analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The calculation of NWACs (Normalized Average Weighted Concentration), together with the chemometric analysis by Principal component analysis (PCA) confirmed the variability of the samples regarding their city and their mine of origin. Moreover, the results confirmed the existence of hotspots in mines near urban areas. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electronic structure of semiconducting alkali-metal silicides and germanides

NASA Astrophysics Data System (ADS)

Tegze, M.; Hafner, J.

1989-11-01

We present self-consistent linearized-muffin-tin-orbital calculations of the electronic structure of three alkali-metal germanides and silicides (KGe, NaGe, and NaSi). Like the alkali-metal-lead compounds investigated in our earlier work [M. Tegze and J. Hafner, Phys. Rev. B 39, 8263 (1989)] the Ge and Si compounds of the alkali metals form complex structures based on the packing of tetrahedral Ge4 and Si4 clusters. Our calculations show that all three compounds are narrow-gap semiconductors. The width of the energy gap depends on two main factors: the ratio of the intracluster to the intercluster interactions between the group-IV elements (which increases from Pb to Si) and the strength of the interactions between the alkali-metal atoms (which varies with the size ratio).

Review of the geochemistry and metallogeny of approximately 1.4 Ga granitoid intrusions of the conterminous United States

USGS Publications Warehouse

du Bray, Edward A.; Holm-Denoma, Christopher S.; Lund, Karen; Premo, Wayne R.

2018-03-27

The conterminous United States hosts numerous volumetrically significant and geographically dispersed granitoid intrusions that range in age from 1.50 to 1.32 billion years before present (Ga). Although previously referred to as A-type granites, most are better described as ferroan granites. These granitoid intrusions are distributed in the northern and central Rocky Mountains, the Southwest, the northern midcontinent, and a swath largely buried beneath Phanerozoic cover across the Great Plains and into the southern midcontinent. These intrusions, with ages that are bimodally distributed between about 1.455–1.405 Ga and 1.405–1.320 Ga, are dispersed nonsystematically with respect to age across their spatial extents. Globally, although A-type or ferroan granites are genetically associated with rare-metal deposits, most U.S. 1.4 Ga granitoid intrusions do not contain significant deposits. Exceptions are the light rare-earth element deposit at Mountain Pass, California, and the iron oxide-apatite and iron oxide-copper-gold deposits in southeast Missouri.Most of the U.S. 1.4 Ga granitoid intrusions are composed of hornblende ± biotite or biotite ± muscovite monzogranite, commonly with prominent alkali feldspar megacrysts; however, modal compositions vary widely. These intrusions include six of the eight commonly identified subtypes of ferroan granite: alkali-calcic and calc-alkalic peraluminous subtypes; alkalic, alkali-calcic, and calc-alkalic metaluminous subtypes; and the alkalic peralkaline subtype. The U.S. 1.4 Ga granitoid intrusions also include variants of these subtypes that have weakly magnesian compositions. Extreme large-ion lithophile element enrichments typical of ferroan granites elsewhere are absent among these intrusions. Chondrite-normalized rare-earth element patterns for these intrusions have modest negative slopes and moderately developed negative europium anomalies. Their radiogenic isotopic compositions are consistent with mixing involving primitive, mantle-derived components and evolved, crust-derived components.Each compositional subtype can be ascribed to a relatively unique petrogenetic history. The numerically dominant ferroan, peraluminous granites probably represent low-degree, relatively high-pressure partial melting of preexisting, crust-derived, intermediate-composition granitoids. The moderately numerous, weakly magnesian, peraluminous granites probably reflect similar partial melting but at a higher degree and in a lower pressure environment. In contrast, the ferroan but metaluminous granites may be the result of extensive differentiation of tholeiitic basalt. Finally, the peralkaline igneous rocks at Mountain Pass have compositions potentially derived by differentiation of alkali basalt. The varying alkalic character of each subtype probably reflects polybaric petrogenesis and the corresponding effect of diverse mineral stabilities on ultimate melt compositions. Mantle-derived mafic magma and variably assimilated partial melts of mainly juvenile Paleoproterozoic crustal components are required to generate the relatively low initial strontium (87Sr/86Sr) and distinctive neodymium isotope compositions characteristic of the U.S. 1.4 Ga granitoid intrusions. The characteristics of these intrusions are consistent with crustal melting in an extensional/decompressional, intracratonic setting that was triggered by mantle upwelling and emplacement of tholeiitic basaltic magma at or near the base of the crust. Composite magmas, formed by mingling and mixing mantle components with partial melts of Paleoproterozoic crust, produced variably homogenized storage reservoirs that continued polybaric evolution as intrusions lodged at various crustal depths.

Molecular Dynamics Study of Crystalline Swelling of Montmorillonite as Affected by Interlayer Cation Hydration

NASA Astrophysics Data System (ADS)

Li, Hongliang; Song, Shaoxian; Dong, Xianshu; Min, Fanfei; Zhao, Yunliang; Peng, Chenliang; Nahmad, Yuri

2018-04-01

Swelling of montmorillonite (Mt) is an important factor for many industrial applications. In this study, crystalline swelling of alkali-metal- and alkaline-earth-metal-Mt has been studied through energy optimization and molecular dynamics simulations using the clay force field by Materials Studio 8.0. The delamination and exfoliation of Mt are primarily realized by crystalline swelling caused by the enhanced interlayer cation hydration. The initial position of the interlayer cations and water molecules is the dominated factor for the accuracy of the Mt simulations. Crystalline swelling can be carried out in alkali-metal-Mt and Mg-Mt but with difficulty in Ca-Mt, Sr-Mt and Ba-Mt. The crystalline swelling capacity values are in the order Na-Mt > K-Mt > Cs-Mt > Mg-Mt. This order of crystalline swelling of Mt in the same group can be attributed to the differences between the interlayer cation hydration strengths. In addition, the differences in the crystalline swelling between the alkali-metal-Mt and alkaline-earth-metal-Mt can be primarily attributed to the valence of the interlayer cations.

Electrolyte salts for power sources

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

Doddapaneni, Narayan; Ingersoll, David

Electrolyte salts for power sources comprising salts of phenyl polysulfonic acids and phenyl polyphosphonic acids. The preferred salts are alkali and alkaline earth metal salts, most preferably lithium salts.

Geochemical insights into the lithology of mantle sources for Cenozoic alkali basalts in West Qinling, China

NASA Astrophysics Data System (ADS)

Dai, Li-Qun; Zheng, Fei; Zhao, Zi-Fu; Zheng, Yong-Fei

2018-03-01

Although alkali basalts are common in oceanic islands and continental rifts, the lithology of their mantle sources is still controversial. While the peridotite is usually viewed as a common source lithology, there are increasing studies suggesting significant contributions from ultramafic metasomatites such as carbonated peridotite, pyroxenite and hornblendite to the origin of alkali basalts. The present study indicates that carbonated peridotite plus hornblendite would have served as the mantle sources of Cenozoic alkali basalts from the West Qinling orogen in China. The target basalts show low SiO2 contents of 36.9 to 40.8 wt% and highly variable Na2O + K2O contents from 0.86 to 4.77 wt%, but high CaO contents of 12.5 to 16.3 wt% and CaO/Al2O3 ratios of 1.42 to 2.19. They are highly enriched in the majority of incompatible trace elements, but depleted in Rb, K, Pb, Zr, Hf, and Ti. Furthermore, they exhibit high (La/Yb)N, Zr/Hf, Ce/Pb and Nb/Ta ratios, but low Ti/Eu and Hf/Sm ratios. Generally, with increasing (La/Yb)N and CaO/Al2O3 ratios, their Ti/Eu and Hf/Sm ratios decrease whereas their Zr/Hf, Ce/Pb and Nb/Ta ratios increase. These major and trace element features are similar to those of carbonatites and hornblendite-derived melts to some extent, but significantly different from those of mid-ocean ridge basalts (MORB). This suggests that the alkali basalts would be originated from metasomatic mantle sources. A comparison of the major-trace elements in the alkali basalts with those of some representative mantle-derived melts indicates that the source lithology of alkali basalts is a kind of ultramafic metasomatites that are composed of carbonated peridotite and hornblendite. Such metasomatites would be generated by reaction of the depleted MORB mantle peridotite with hydrous, carbonate-bearing felsic melts derived from partial melting of the subducted Paleotethyan oceanic crust. Therefore, the melt-peridotite reaction at the slab-mantle interface in the Paleotethyan subduction channel plays the key role in transferring the geochemical signatures from the subducted Paleotethyan oceanic crust to the alkali basalts in the fossil convergent plate margin.

Catalytically active Au-O(OH) x- species stabilized by alkali ions on zeolites and mesoporous oxides

DOE PAGES

Yang, Ming; Li, Sha; Wang, Yuan; ...

2014-11-27

Here we report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH) x-(Na or K) ensembles. This single-site gold species is active for the low-temperature (<200°C) water-gas shift (WGS) reaction. Unexpectedly, gold is thus similar to platinum in creating –O linkages with more than eight alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports, apparently all sharing a common, similarly structured gold activemore » site. This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel-processing reactions.« less

Alkali-earth metal bridges formed in biofilm matrices regulate the uptake of fluoroquinolone antibiotics and protect against bacterial apoptosis.

PubMed

Kang, Fuxing; Wang, Qian; Shou, Weijun; Collins, Chris D; Gao, Yanzheng

2017-01-01

Bacterially extracellular biofilms play a critical role in relieving toxicity of fluoroquinolone antibiotic (FQA) pollutants, yet it is unclear whether antibiotic attack may be defused by a bacterial one-two punch strategy associated with metal-reinforced detoxification efficiency. Our findings help to assign functions to specific structural features of biofilms, as they strongly imply a molecularly regulated mechanism by which freely accessed alkali-earth metals in natural waters affect the cellular uptake of FQAs at the water-biofilm interface. Specifically, formation of alkali-earth-metal (Ca 2+ or Mg 2+ ) bridge between modeling ciprofloxacin and biofilms of Escherichia coli regulates the trans-biofilm transport rate of FQAs towards cells (135-nm-thick biofilm). As the addition of Ca 2+ and Mg 2+ (0-3.5 mmol/L, CIP: 1.25 μmol/L), the transport rates were reduced to 52.4% and 63.0%, respectively. Computational chemistry analysis further demonstrated a deprotonated carboxyl in the tryptophan residues of biofilms acted as a major bridge site, of which one side is a metal and the other is a metal girder jointly connected to the carboxyl and carbonyl of a FQA. The bacterial growth rate depends on the bridging energy at anchoring site, which underlines the environmental importance of metal bridge formed in biofilm matrices in bacterially antibiotic resistance. Copyright © 2016 Elsevier Ltd. All rights reserved.

Method and composition for testing for the presence of an alkali metal

DOEpatents

Guon, Jerold

1981-01-01

A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

Alkali elemental and potassium isotopic compositions of Semarkona chondrules

USGS Publications Warehouse

Alexander, C.M. O'D.; Grossman, J.N.

2005-01-01

We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX-mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh-type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX-mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX-mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled. ?? The Meteoritical Society, 2005.

The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

NASA Astrophysics Data System (ADS)

Amelina, Anna; Grinberg, Evgenii

A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used for producing of thin coats on ceramics and metallic surfaces.

The History and Use of Our Earth's Chemical Elements: A Reference Guide (by Robert E. Krebs)

NASA Astrophysics Data System (ADS)

Bracken, Reviewed By Jeffrey D.

1999-04-01

Greenwood Press: Westport, CT, 1998. 282 pp + 25 pp glossary + 37 pp index. 15.9 x 24.1 cm. ISBN 0-313-30123-9. $39.95. This book is an excellent resource for chemical educators at the high school and college levels. The format of the text is consistent and the writing style is clear and concise, making it ideally suited for student use also. The first three chapters serve to introduce the reader to a brief history of chemistry, early models of the atom, and the development of the periodic table. Names of the contributing scientists are mentioned whenever necessary, but the overall purpose of these introductory chapters is simply to lay a foundation for the subsequent seven chapters. A complete glossary of important scientific terms mentioned in the text should allow beginning students to use this book without feeling overwhelmed. Each entry for the 112 elements contains the following information: elemental symbol, atomic number, period, common valence, atomic weight, natural state, common isotopes, properties, characteristics, abundance, natural sources, history, common uses and compounds, and safety hazards. This information is well organized, with clear headings and separate sections making the book extremely user-friendly. Readers can easily obtain the information they desire without having to skim the full entry for a chosen element. One very nice feature of this book is that the elements entries are arranged by their locations in the periodic table. For example, chapter 4 contains the alkali metals and alkaline earth metals. This organizational scheme allows one to quickly see the patterns and trends within groups of elements. This format is significantly better than arranging the elements in alphabetical order, which places the entry for sodium far removed from the entries for lithium and potassium. I would highly recommend this book to high school teachers and college chemistry professors. It is well written and is an excellent source of information for both students and educators.

Characterization of flux-grown Trace-element-doped titanite using the high-mass-resolution ion microprobe (SHRIMP-RG)

USGS Publications Warehouse

Mazdab, F.K.

2009-01-01

Crystals of titanite can be readily grown under ambient pressure from a mixture of CaO, TiO2 and SiO2 in the presence of molten sodium tetraborate. The crystals produced are euhedral and prismatic, lustrous and transparent, and up to 5 mm in length. Titanite obtained by this method contains approximately 4300 ppm Na and 220 ppm B contributed from the flux. In addition to dopant-free material, titanite containing trace alkali and alkaline earth metals (K, Sr, Ba), transition metals (Sc, Cr, Ni, Y, Zr, Nb, Hf and Ta), rare-earth elements (REE), actinides (Th, U) and p-block elements (F, S, Cl, Ge, Sn and Pb) have been prepared using the same procedure. Back-scattered electron (BSE) imaging accompanied by ion-microprobe (SHRIMP-RG) analysis confirms significant incorporation of selected trace-elements at structural sites. Regardless of some zonation, the large size of the crystals and broad regions of chemical homogeneity make these crystals useful as experimental starting material, and as matrix-matched trace-element standards for a variety of microbeam analytical techniques where amorphous titanite glass, heterogeneous natural titanite or a non-titanite standard may be less than satisfactory. Trace-element-doped synthetic crystals can also provide a convenient proxy for a better understanding of trace-element incorporation in natural titanite. Comparisons with igneous, authigenic and high-temperature metasomatic titanite are examined. The use of high-mass-resolution SIMS also demonstrates the analytical challenges inherent to any in situ mass-spectrometry-based analysis of titanite, owing to the production of difficult-to-resolve molecular interferences. These interferences are dominated by Ca-Ca, Ca-Ti and Ti-Ti dimers that are significant in the mass range of 80-100, affecting all isotopes of Sr and Zr, as well as 89Y and 93Nb. Methods do exist for the evaluation of interferences by these dimers and of polyatomic interferences on the LREE.

A geochemical approach to constraining the formation of glassy fallout debris from nuclear tests

DOE PAGES

Bonamici, Chloë E.; Kinman, William S.; Fournelle, John H.; ...

2016-12-15

Reprocessed earth material is a glassy nuclear fallout debris from near-surface nuclear tests. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. Our study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclearmore » test (“trinitite”) and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. Furthermore, the volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.« less

A geochemical approach to constraining the formation of glassy fallout debris from nuclear tests

NASA Astrophysics Data System (ADS)

Bonamici, Chloë E.; Kinman, William S.; Fournelle, John H.; Zimmer, Mindy M.; Pollington, Anthony D.; Rector, Kirk D.

2017-01-01

Glassy nuclear fallout debris from near-surface nuclear tests is fundamentally reprocessed earth material. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. This study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclear test ("trinitite") and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. The volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.

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.

Depolarizing collisions with hydrogen: Neutral and singly ionized alkaline earths

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

Manso Sainz, Rafael; Ramos, Andrés Asensio; Bueno, Javier Trujillo

2014-06-20

Depolarizing collisions are elastic or quasielastic collisions that equalize the populations and destroy the coherence between the magnetic sublevels of atomic levels. In astrophysical plasmas, the main depolarizing collider is neutral hydrogen. We consider depolarizing rates on the lowest levels of neutral and singly ionized alkali earths Mg I, Sr I, Ba I, Mg II, Ca II, and Ba II, due to collisions with H°. We compute ab initio potential curves of the atom-H° system and solve the quantum mechanical dynamics. From the scattering amplitudes, we calculate the depolarizing rates for Maxwellian distributions of colliders at temperatures T ≤ 10,000more » K. A comparative analysis of our results and previous calculations in the literature is completed. We discuss the effect of these rates on the formation of scattering polarization patterns of resonant lines of alkali earths in the solar atmosphere, and their effect on Hanle effect diagnostics of solar magnetic fields.« less

Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

PubMed

Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

2017-06-01

We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

Measurement of Total Site Mercury Emissions from a Chlor-Alkali Plant Using Ultraviolet Differential Optical Absorption Spectroscopy and Cell Room Roof-Vent Monitoring

EPA Science Inventory

Mercury-cell chlor-alkali plants can emit significant quantities of fugitive elemental mercury vapor to the air as part of production operations and maintenance activities. In the fall of 2006, the U.S. Environmental Protection Agency (EPA) conducted a measurement project at a ch...

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.

Production of chlorine from chloride salts

DOEpatents

Rohrmann, Charles A.

1981-01-01

A process for converting chloride salts and sulfuric acid to sulfate salts and elemental chlorine is disclosed. A chloride salt and sulfuric acid are combined in a furnace where they react to produce a sulfate salt and hydrogen chloride. Hydrogen chloride from the furnace contacts a molten salt mixture containing an oxygen compound of vanadium, an alkali metal sulfate and an alkali metal pyrosulfate to recover elemental chlorine. In the absence of an oxygen-bearing gas during the contacting, the vanadium is reduced, but is regenerated to its active higher valence state by separately contacting the molten salt mixture with an oxygen-bearing gas.

REE enrichment due to fenitization of Devonian granites, Rodeo de Los Molles, Central Argentina

NASA Astrophysics Data System (ADS)

Lorenz, M.; Altenberger, U.; Trumbull, R. B.; Lira, R.; Lopez De Luchi, M. G.; Viñas, N.

2017-12-01

The Rodeo de Los Molles rare earth element (REE) mineralization is characterized by an uncommon REE-bearing assemblage located within a fenitized biotite-monzogranite. The fenitization is found in a NNE-SSW trending, possibly fault related elliptical body in the northern margin of the Devonian Las Chacras-Piedras Coloradas Batholith, San Luis province, Central Argentina. The fenite was produced by the metasomatic addition of K and Na, as well as the loss of Ca and Sr, leading to the transformation of monzogranite to (quartz) alkali-feldspar syenite composition. Whole-rock geochemistry revealed a local enrichment in light rare earth elements within the fenitized zone. Drill-core samples from a mineral exploration campaign (Lira et al., 1999) and new surface samples are the basis for the present investigation, which aims to decipher the fluid evolution and REE-mineralization. REE-bearing minerals are located in irregularly patches and nodules ranging from a few millimeters to more than one meter in diameter. The REE-rich assemblage comprises an intergrowth of primary britholite (Ce,Ca)5(SiO4, PO4)3(OH,F), allanite and apatite with aegirine-augite, titanite, fluorite, bastnaesite and, quartz as well as complex thorium-rich accessory minerals. In more intensely altered areas clinochlore, spherolitic quartz, calcite, kaolinite, hematite and phlogopite also occur. Britholite is an extraordinary mineral belonging to the apatite group, usually described as an accessory mineral. Aside from being one of only three localites in the world where it occurs in ore quantities, Rodeo de Los Molles further contains atypical huge aggregates of the rare mineral. In general, britholite is thought to form by late-magmatic crystallization or alteration of primary minerals in alkali-rich granites (Uher et al., 2015). Its origin as an abundant phase in the Rodeo de Los Molles mineralization is one focus of this study. Lira, R., Barbieri, M., Ripley, E.M., Viñas, N.A. (1999) Actas II South American Symposium on Isotope Geology, p.219-222. Uher, P., Ondrejka, M., Bačík, P., Broska, I., & Konečný, P. (2015) Lithos, 236, p.212-225.

Where else might be life in the Solar system?

NASA Astrophysics Data System (ADS)

Vidmachenko, A. P.; Steklov, A. F.

2017-05-01

We know that there is life on Earth. But some bacteria live in nearly boiling liquid of an extinct volcano, which is saturated by acids, alkalis and salts in various combinations. The main problem of the modern theory of the origin of life is the emergence from the initial chaotic mixture of chemical elements and simple compounds of polymer systems that can to organize themselves, and their subsequent evolution. The main forms of life on Earth are organisms of cellular structure. Exceptions are viruses, that are non-cellular life forms. If we find somewhere life in the Solar system, most likely, it will be microscopic cells. The most likely candidates for this honorable role are: Jupiter's moon Io, Jupiter's moon Europa, Saturn's moons Titan and Enceladus, Neptune's satellite Triton; on the surface of Pluto also found two cryovolcanoes, spacecraft "Dawn" discovered the vast reserves of water on dwarf planet Ceres; also, on its surface was found a large cryovolcano. The most likely candidate for the presence of life is Mars. These bodies are possible objects in the Solar system, where one can search for life of different forms.

Trace element studies of silicate-rich inclusions in the Guin (UNGR) and Kodaikanal (IIE) iron meteorites

NASA Astrophysics Data System (ADS)

Kurat, Gero; Zinner, Ernst; Varela, Maria Eugenia

2007-08-01

A devitrified glass inclusion from the Guin (UNGR) iron consists of cryptocrystalline feldspars, pyroxenes, and silica and is rich in SiO2, Al2O3, and Na2O. It contains a rutile grain and is in contact with a large Cl apatite. The latter is very rich in rare earth elements (REEs) (˜80 × CI), which display a flat abundance pattern, except for Eu and Yb, which are underabundant. The devitrified glass is very poor in REEs (<0.1 × CI), except for Eu and Yb, which have positive abundance anomalies. Devitrified glass and Cl apatite are out of chemical equilibrium and their complementary REE patterns indicate a genesis via condensation under reducing conditions. Inclusion 1 in the Kodaikanal (IIE) iron consists of glass only, whereas inclusion 2 consists of clinopyroxene, which is partly overgrown by low-Ca pyroxene, and apatite embedded in devitrified glass. All minerals are euhedral or have skeletal habits indicating crystallization from the liquid precursor of the glass. Pyroxenes and the apatite are rich in trace elements, indicating crystallization from a liquid that had 10-50 × CI abundances of REEs and refractory lithophile elements (RLEs). The co-existing glass is poor in REEs (˜0.1-1 × CI) and, consequently, a liquid of such chemical composition cannot have crystallized the phenocrysts. Glasses have variable chemical compositions but are rich in SiO2, Al2O3, Na2O, and K2O as well as in HFSEs, Be, B, and Rb. The REE abundance patterns are mostly flat, except for the glass-only inclusion, which has heavy rare earth elements (HREEs) > light rare earth elements (LREEs) and deficits in Eu and Yb—an ultrarefractory pattern. The genetic models suggested so far cannot explain what is observed and, consequently, we offer a new model for silicate inclusion formation in IIE and related irons. Nebular processes and a relationship with E meteorites (Guin) or Ca-Al-rich inclusions (CAIs) (Kodaikanal) are indicated. A sequence of condensation (CaS, TiN or refractory pyroxene-rich liquids) and vapor-solid elemental exchange can be identified that took place beginning under reducing and ending at oxidizing conditions (phosphate, rutile formation, alkali and Fe2+ metasomatism, metasomatic loss of REEs from glass).

Boson peak of alkali and alkaline earth silicate glasses: influence of the nature and size of the network-modifying cation.

PubMed

Richet, Nicolas F

2012-01-21

The influence of the size of the alkaline earth cation on the boson peak of binary metasilicate glasses, MSiO(3) (M = Mg, Ca, Sr, Ba), has been investigated from vibrational densities of states determined by inversion of low-temperature heat capacities. As given both by C(p)/T(3) and g(ω)/ω(2), the intensity of the boson peak undergoes a 7-fold increase from Mg to Ba, whereas its temperature and frequency correlatively decrease from 18 to 10 K and from 100 to 20 cm(-1), respectively. The boson peak results from a combination of librations of SiO(4) tetrahedra and localized vibrations of network-modifying cations with non-bridging oxygens whose contribution increases markedly with the ionic radius of the alkaline earth. As a function of ionic radii, the intensity for Sr and Ba varies in the same way as previously found for alkali metasilicate glasses. The localized vibrations involving alkali and heavy alkaline earth cations appear to be insensitive to the overall glass structure. Although the new data are coherent with an almost linear relationship between the temperature of the boson peak and transverse sound velocity, pure SiO(2) and SiO(2)-rich glasses make marked exceptions to this trend because of the weak transverse character of SiO(4) librations. Finally, the universality of the calorimetric boson peak is again borne out because all data for silicate glasses collapse on the same master curve when plotted in a reduced form (C(P)∕/T(3))/(C(P)/T(3))(b) vs. T/T(b). © 2012 American Institute of Physics

Differentiation of the matter of the moon

NASA Technical Reports Server (NTRS)

Vinogradov, A. P.

1977-01-01

The following facts were uncovered in comparing the basaltic surface rocks of the moon with terrestrial tholeiitic basalts and ordinary chondrites: (1) there is an excess of the so-called refractory chemical elements, including the group of truly refractory elements, the rare earths, U, and Th, in comparison with their content in primitive terrestrial basalts and chondrites; (2) the so-called siderophilic elements have lower contents in the lunar surface rocks than in terrestrial rocks; (3) the low alkali content (Na, K, Rb) in lunar rocks is established; (4) there is a low content of H2O and the ordinary gases CO2, halides, etc.; (5) the low content of metals with high vapor pressure, (In, Tl, etc.) has been established. It is proposed that U and Th were carried from the internal areas to the peripheral rocks of the moon during magmatic activity, i.e., up to 3 billion years ago. This redistribution of U and Th lead to their concentration in surface layers of the moon, and the heat which they generated was lost into surrounding space. The conclusion is then reached that in order to understand processes on the moon, the chondritic model cannot be used.

Ab Initio Predictions of K, He and Ar Partitioning Between Silicate Melt and Liquid Iron Under High Pressure

NASA Astrophysics Data System (ADS)

Xiong, Z.; Tsuchiya, T.

2017-12-01

Element partitioning is an important property in recording geochemical processes during the core-mantle differentiation. However, experimental measurements of element partitioning coefficients under extreme temperature and pressure condition are still challenging. Theoretical modeling is also not easy, because it requires estimation of high temperature Gibbs free energy, which is not directly accessible by the standard molecular dynamics method. We recently developed an original technique to simulate Gibbs free energy based on the thermodynamics integration method[1]. We apply it to element partitioning of geochemical intriguing trace elements between molten silicate and liquid iron such as potassium, helium and argon as starting examples. Radiogenic potassium in the core can provide energy for Earth's magnetic field, convection in the mantle and outer core[2]. However, its partitioning behavior between silicate and iron remains unclear under high pressure[3,4]. Our calculations suggest that a clear positive temperature dependence of the partitioning coefficient but an insignificant pressure effect. Unlike sulfur and silicon, oxygen dissolved in the metals considerably enhances potassium solubility. Calculated electronic structures reveal alkali-metallic feature of potassium in liquid iron, favoring oxygen with strong electron affinity. Our results suggest that 40K could serve as a potential radiogenic heat source in the outer core if oxygen is the major light element therein.­­ We now further extend our technique to partitioning behaviors of other elements, helium and argon, to get insides into the `helium paradox' and `missing argon' problems. References [1] T. Taniuchi, and T. Tsuchiya, Phys.Rev.B. In press [2] B.A. Buffett, H.E. Huppert, J.R. Lister, and A.W. Woods, Geophys.Res.Lett. 29 (1996) 7989-8006. [3] V.R. Murthy, W. Westrenen, and Y. Fei, Nature. 426 (2003) 163-165. [4] A. Corgne, S.Keshav, Y. Fei, and W.F. McDonough, Earth.Planet.Sci.Lett. 256 (2007) 567-576

NMR parameters in alkali, alkaline earth and rare earth fluorides from first principle calculations.

PubMed

Sadoc, Aymeric; Body, Monique; Legein, Christophe; Biswal, Mamata; Fayon, Franck; Rocquefelte, Xavier; Boucher, Florent

2011-11-07

(19)F isotropic chemical shifts for alkali, alkaline earth and rare earth of column 3 basic fluorides are measured and the corresponding isotropic chemical shieldings are calculated using the GIPAW method. When using the PBE exchange-correlation functional for the treatment of the cationic localized empty orbitals of Ca(2+), Sc(3+) (3d) and La(3+) (4f), a correction is needed to accurately calculate (19)F chemical shieldings. We show that the correlation between experimental isotropic chemical shifts and calculated isotropic chemical shieldings established for the studied compounds allows us to predict (19)F NMR spectra of crystalline compounds with a relatively good accuracy. In addition, we experimentally determine the quadrupolar parameters of (25)Mg in MgF(2) and calculate the electric field gradients of (25)Mg in MgF(2) and (139)La in LaF(3) using both PAW and LAPW methods. The orientation of the EFG components in the crystallographic frame, provided by DFT calculations, is analysed in terms of electron densities. It is shown that consideration of the quadrupolar charge deformation is essential for the analysis of slightly distorted environments or highly irregular polyhedra. This journal is © the Owner Societies 2011

Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

NASA Technical Reports Server (NTRS)

Yokoyama, T.; Misawa, K.; Okano, O.; Shih, C.-Y.; Nyquist, L. E.; Simo, J. I.; Tappa, M. J.; Yoneda, S.

2012-01-01

Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

PubMed

Yin, Jun; Hu, Ying; Yoon, Juyoung

2015-07-21

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

Geochemistry of continental subduction-zone fluids

NASA Astrophysics Data System (ADS)

Zheng, Yong-Fei; Hermann, Joerg

2014-12-01

The composition of continental subduction-zone fluids varies dramatically from dilute aqueous solutions at subsolidus conditions to hydrous silicate melts at supersolidus conditions, with variable concentrations of fluid-mobile incompatible trace elements. At ultrahigh-pressure (UHP) metamorphic conditions, supercritical fluids may occur with variable compositions. The water component of these fluids primarily derives from structural hydroxyl and molecular water in hydrous and nominally anhydrous minerals at UHP conditions. While the breakdown of hydrous minerals is the predominant water source for fluid activity in the subduction factory, water released from nominally anhydrous minerals provides an additional water source. These different sources of water may accumulate to induce partial melting of UHP metamorphic rocks on and above their wet solidii. Silica is the dominant solute in the deep fluids, followed by aluminum and alkalis. Trace element abundances are low in metamorphic fluids at subsolidus conditions, but become significantly elevated in anatectic melts at supersolidus conditions. The compositions of dissolved and residual minerals are a function of pressure-temperature and whole-rock composition, which exert a strong control on the trace element signature of liberated fluids. The trace element patterns of migmatic leucosomes in UHP rocks and multiphase solid inclusions in UHP minerals exhibit strong enrichment of large ion lithophile elements (LILE) and moderate enrichment of light rare earth elements (LREE) but depletion of high field strength elements (HFSE) and heavy rare earth elements (HREE), demonstrating their crystallization from anatectic melts of crustal protoliths. Interaction of the anatectic melts with the mantle wedge peridotite leads to modal metasomatism with the generation of new mineral phases as well as cryptic metasomatism that is only manifested by the enrichment of fluid-mobile incompatible trace elements in orogenic peridotites. Partial melting of the metasomatic mantle domains gives rise to a variety of mafic igneous rocks in collisional orogens and their adjacent active continental margins. The study of such metasomatic processes and products is of great importance to understanding of the mass transfer at the slab-mantle interface in subduction channels. Therefore, the property and behavior of subduction-zone fluids are a key for understanding of the crust-mantle interaction at convergent plate margins.

Method for uniformly distributing carbon flakes in a positive electrode, the electrode made thereby and compositions

DOEpatents

Mrazek, Franklin C.; Smaga, John A.; Battles, James E.

1983-01-01

A positive electrode for a secondary electrochemical cell wherein an electrically conductive current collector is in electrical contact with a particulate mixture of gray cast iron and an alkali metal sulfide and an electrolyte including alkali metal halides or alkaline earth metal halides. Also present may be a transition metal sulfide and graphite flakes from the conversion of gray cast iron to iron sulfide. Also disclosed is a method of distributing carbon flakes in a cell wherein there is formed an electrochemical cell of a positive electrode structure of the type described and a suitable electrolyte and a second electrode containing a material capable of alloying with alkali metal ions. The cell is connected to a source of electrical potential to electrochemically convert gray cast iron to an iron sulfide and uniformly to distribute carbon flakes formerly in the gray cast iron throughout the positive electrode while forming an alkali metal alloy in the negative electrode. Also disclosed are compositions useful in preparing positive electrodes.

Mineralized aplite—pegmatite at Jabal Sa'id, Hijaz region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Hackett, Damien

The Jabal Sa'id aplite—pegmatite, located at 23°49'03″N, 40°56'30″E, is part of the Jabal Hadb ash Sharar granite complex and resulted from emplacement of a residual volatile-rich fraction of alkali granite magma dominantly above a chilled carapace. Mineralization is layered, with four peak grades in layers 20-25 m wide, one of which may represent a mineral resource with greater potential than the aplite—pegmatite as a whole. The grades of all elements, except Zr, increase towards the upper part of the body. Chemical composition is extremely variable. Major-oxide data confirm previously determined geochemical characteristics and genetic relationships that suggested this body is an apogranite. However, the abundant new data also show that differences between the aplite—pegmatite and cognate alkali microgranite are not as great as previously reported, except for Na 2O which is extremely depleted in the apogranite. REE data support suggested genetic relationships and indicate that feldspar fractionation was important during crystallization. They also show that the content of HREE is comparatively constant throughout the aplite—pegmatite, and that variations in total REE content are caused by variations in the content of LREE. Bastnaesite and synchysite-(Y) are the principal rare-earth-element minerals, and are accompanied by monazite and synchesite; pyrochlore and thorite are also important ore minerals. Other elements concentrated in the aplite—pegmatite, such as Ta, Sn and U, occur only in solid solution in these minerals. The grain size of the ore minerals is commonly in the range 0.02-0.2 mm, and the grain size of gangue minerals, quartz, microcline and lesser amounts of aegirine and arfvedsonite, is typically in the range 1.0-4.0 mm. The ore minerals occur typically along gangue mineral boundaries. Zoning within the body permits calculation of high- and low-grade reserves which correspond to the upper and lower part of the apogranite.

The Effects of Various Amendments on Trace Element Stabilization in Acidic, Neutral, and Alkali Soil with Similar Pollution Index

PubMed Central

Kim, Min-Suk; Min, Hyun-Gi; Lee, Sang-Hwan; Kim, Jeong-Gyu

2016-01-01

Many studies have examined the application of soil amendments, including pH change-induced immobilizers, adsorbents, and organic materials, for soil remediation. This study evaluated the effects of various amendments on trace element stabilization and phytotoxicity, depending on the initial soil pH in acid, neutral, and alkali conditions. As in all types of soils, Fe and Ca were well stabilized on adsorption sites. There was an effect from pH control or adsorption mechanisms on the stabilization of cationic trace elements from inorganic amendments in acidic and neutral soil. Furthermore, acid mine drainage sludge has shown great potential for stabilizing most trace elements. In a phytotoxicity test, the ratio of the bioavailable fraction to the pseudo-total fraction significantly affected the uptake of trace elements by bok choy. While inorganic amendments efficiently decreased the bioavailability of trace elements, significant effects from organic amendments were not noticeable due to the short-term cultivation period. Therefore, the application of organic amendments for stabilizing trace elements in agricultural soil requires further study. PMID:27835687

The Effects of Various Amendments on Trace Element Stabilization in Acidic, Neutral, and Alkali Soil with Similar Pollution Index.

PubMed

Kim, Min-Suk; Min, Hyun-Gi; Lee, Sang-Hwan; Kim, Jeong-Gyu

2016-01-01

Many studies have examined the application of soil amendments, including pH change-induced immobilizers, adsorbents, and organic materials, for soil remediation. This study evaluated the effects of various amendments on trace element stabilization and phytotoxicity, depending on the initial soil pH in acid, neutral, and alkali conditions. As in all types of soils, Fe and Ca were well stabilized on adsorption sites. There was an effect from pH control or adsorption mechanisms on the stabilization of cationic trace elements from inorganic amendments in acidic and neutral soil. Furthermore, acid mine drainage sludge has shown great potential for stabilizing most trace elements. In a phytotoxicity test, the ratio of the bioavailable fraction to the pseudo-total fraction significantly affected the uptake of trace elements by bok choy. While inorganic amendments efficiently decreased the bioavailability of trace elements, significant effects from organic amendments were not noticeable due to the short-term cultivation period. Therefore, the application of organic amendments for stabilizing trace elements in agricultural soil requires further study.

Charge transfer in ultracold gases via Feshbach resonances

NASA Astrophysics Data System (ADS)

Gacesa, Marko; Côté, Robin

2017-06-01

We investigate the prospects of using magnetic Feshbach resonance to control charge exchange in ultracold collisions of heteroisotopic combinations of atoms and ions of the same element. The proposed treatment, readily applicable to alkali or alkaline-earth metals, is illustrated on cold collisions of +9Be and 10Be. Feshbach resonances are characterized by quantum scattering calculations in a coupled-channel formalism that includes non-Born-Oppenheimer terms originating from the nuclear kinetic operator. Near a resonance predicted at 322 G, we find the charge exchange rate coefficient to rise from practically zero to values greater than 10-12cm3 /s. Our results suggest controllable charge exchange processes between different isotopes of suitable atom-ion pairs, with potential applications to quantum systems engineered to study charge diffusion in trapped cold atom-ion mixtures and emulate many-body physics.

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)

Treatment of organic waste

DOEpatents

Grantham, LeRoy F.

1979-01-01

An organic waste containing at least one element selected from the group consisting of strontium, cesium, iodine and ruthenium is treated to achieve a substantial reduction in the volume of the waste and provide for fixation of the selected element in an inert salt. The method of treatment comprises introducing the organic waste and a source of oxygen into a molten salt bath maintained at an elevated temperature to produce solid and gaseous reaction products. The gaseous reaction products comprise carbon dioxide and water vapor, and the solid reaction products comprise the inorganic ash constituents of the organic waste and the selected element which is retained in the molten salt. The molten salt bath comprises one or more alkali metal carbonates, and may optionally include from 1 to about 25 wt.% of an alkali metal sulfate.

Solvent- and catalyst-free mechanochemical synthesis of alkali metal monohydrides

DOE PAGES

Hlova, Ihor Z.; Castle, Andra; Goldston, Jennifer F.; ...

2016-07-06

Alkali metal monohydrides, AH (A = Li–Cs) have been synthesized in quantitative yields at room temperature by reactive milling of alkali metals in the presence of hydrogen gas at 200 bar or less. The mechanochemical approach reported here eliminates problems associated with the malleability of alkali metals — especially Li, Na, and K — and promotes effective solid–gas reactions, ensuring their completion. This is achieved by incorporating a certain volume fraction of the corresponding hydride powder as a process control agent, which allows continuous and efficient milling primarily by coating the surface of metal particles, effectively blocking cold welding. Formationmore » of high-purity crystalline monohydrides has been confirmed by powder X-ray diffraction, solid-state NMR spectroscopy, and volumetric analyses of reactively desorbed H 2 from as-milled samples. The proposed synthesis method is scalable and particularly effective for extremely air-sensitive materials, such as alkali and alkaline earth metal hydrides. Furthermore, the technique may also be favorable for production in continuous reactors operating at room temperature, thereby reducing the total processing time, energy consumption and, hence, the cost of production of these hydrides or their derivatives and composites.« less

Ion-Exchange Interdiffusion Model with Potential Application to Long-Term Nuclear Waste Glass Performance

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

Neeway, James Joseph; Kerisit, Sebastien N.; Liu, Jia

2016-05-05

Abstract: Ion exchange is an integral mechanism influencing the corrosion of glasses. Due to the formation of alteration layers in aqueous conditions, it is difficult to conclusively deconvolute the process of ion exchange from other processes, principally dissolution of the glass matrix. Therefore, we have developed a method to isolate alkali diffusion that involves contacting glass coupons with a solution of 6LiCl dissolved in functionally inert dimethyl sulfoxide. We employ the method at temperatures ranging from 25 to 150 °C with various glass formulations. Glass compositions include simulant nuclear waste glasses, such as SON68 and the international simple glass (ISG),more » glasses in which the nature of the alkali element was varied, and glasses that contained more than one alkali element. An interdiffusion model based on Fick’s second law was developed and applied to all experiments to extract diffusion coefficients. The model expands established models of interdiffusion to the case where multiple types of alkali sites are present in the glass. Activation energies for alkali ion exchange were calculated and the results are in agreement with those obtained in glass strengthening experiments but are nearly five times higher than values reported for diffusion-controlled processes in nuclear waste glass corrosion experiments. A discussion of the root causes for this apparent discrepancy is provided. The interdiffusion model derived from laboratory experiments is expected to be useful for modeling glass corrosion in a geological repository when the silicon concentration is high.« less

[Determination of multi-element contents in gypsum by ICP-AES].

PubMed

Guo, Zhong-bao; Bai, Yong-zhi; Cui, Jin-hua; Mei, Yi-fei; Ma, Zhen-zhu

2014-08-01

The content of multi-element in gypsum was determined by ICP-AES. The sample was pretreated by acid-soluble method or alkali-fusion method. Acid-soluble method is suitable for the determination of CaO, SOs, Al2O3, Fe2O3, MgO, K2O, Na2O, TiO2, P2O5, MnO, SrO and BaO. Alkali-fusion method is suitable for the determination of CaO, SO3, SiO2, Al2O3, Fe2O3, MgO, TiO2, P2O5, MnO, SrO, BaO and B2O3. Different series standard solutions were prepared considering the properties and content of elements and solution matrix. The limit of detection and quantification were confirmed for each element under their best analysis spectral lines. The recoveries of the two pretreatment methods were from 93% to 110%, besides that for TiO2 was 81%-87% as pretreated by acid-soluble method. All RSDs (n=6) of tests were from 0.70%-3.42%. The accuracies of CaO and SO3 with ICP-AES method were less than the chemical analysis method. The determination of CaO and SO3 with ICP-AES method is only suitable for the case of low accuracy requirement. The results showed that the method can be used for the determination of multi-element contents in gypsum, with simple operation, fast analysis and reliable results. Total elements can be analysed with both acid-soluble method and alkali-fusion method.

Study of 3-Ethylamino-but-2-enoic acid phenylamide as a new ligand for preconcentration of lanthanides from aqueous media by liquid-liquid extraction prior to ICP-MS analysis.

PubMed

Varbanova, Evelina K; Angelov, Plamen A; Stefanova, Violeta M

2016-11-01

In the present work the potential of a new ligand 3-Ethylamino-but-2-enoic acid phenylamide (representing the class of enaminones) for selective preconcentration of lanthanides (La, Ce, Eu, Gd and Er) from aqueous medium is examined. Liquid-liquid extraction parameters, such as pH of the water phase, type and volume of organic solvent, quantity of ligand and reaction time are optimized on model solutions. Recovery of lanthanides by re-extraction with nitric acid makes the LLE procedure compatible with Inductively Coupled Plasma Mass Spectrometry. Spectral and non-spectral interferences are studied. Two isotopes per element are measured (with exception of La) for dynamic evaluation of the potential risk of spectral interference in variable real samples. The selectivity of complex formation reaction towards concomitant alkali and alkali-earth elements eliminates the interferences from sample matrix. Subjecting the standards to the optimized extraction procedure in combination with Re as internal standard is recommended as calibration strategy. The accuracy of developed method is approved by analysis of CRM Bush branches and leaves (NCS DC 73348) and recovery of spiked water and plant samples. The method's limits of detection for both studied objects are in the ranges from 0.2 ((158)Gd) to 3.7 ((139)La) ngl(-1) and 0.02 ((158)Gd) to 0.37((139)La) ngg(-1) for waters and plants respectively. The studied compound is an effective new ligand for preconcentration/separation of lanthanides from aqueous medium by LLE and subsequent determination by ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Chlorine in solid fuels fired in pulverized fuel boilers sources, forms, reactions, and consequences: a literature review

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

David A. Tillman; Dao Duong; Bruce Miller

2009-07-15

Chlorine is a significant source of corrosion and deposition, both from coal and from biomass, and in PF boilers. This investigation was designed to highlight the potential for corrosion risks associated with once-through units and advanced cycles. The research took the form of a detailed literature investigation to evaluate chlorine in solid fuels: coals of various ranks and origins, biomass fuels of a variety of types, petroleum cokes, and blends of the above. The investigation focused upon an extensive literature review of documents dating back to 1991. The focus is strictly corrosion and deposition. To address the deposition and corrosionmore » issues, this review evaluates the following considerations: concentrations of chlorine in available solid fuels including various coals and biomass fuels, forms of chlorine in those fuels, and reactions - including reactivities - of chlorine in such fuels. The assessment includes consideration of alkali metals and alkali earth elements as they react with, and to, the chlorine and other elements (e.g., sulfur) in the fuel and in the gaseous products of combustion. The assessment also includes other factors of combustion: for example, combustion conditions including excess O{sub 2} and combustion temperatures. It also considers analyses conducted at all levels: theoretical calculations, bench scale laboratory data and experiments, pilot plant experiments, and full scale plant experience. Case studies and plant surveys form a significant consideration in this review. The result of this investigation focuses upon the concentrations of chlorine acceptable in coals burned exclusively, in coals burned with biomass, and in biomass cofired with coal. Values are posited based upon type of fuel and combustion technology. Values are also posited based upon both first principles and field experience. 86 refs., 8 figs., 7 tabs.« less

Microwave hydrothermal synthesis and characterization of rare-earth stannate nanoparticles

NASA Astrophysics Data System (ADS)

Huang, Shuang; Xu, Hua-lan; Zhong, Sheng-liang; Wang, Lei

2017-07-01

Rare-earth stannate (Ln2Sn2O7 (Ln = Y, La-Lu)) nanocrystals with an average diameter of 50 nm were prepared through a facile microwave hydrothermal method at 200°C within 60 min. The products were well characterized. The effect of reaction parameters such as temperature, reaction time, pH value, and alkali source on the preparation was investigated. The results revealed that the pH value plays an important role in the formation process of gadolinium stannate (Gd2Sn2O7) nanoparticles. By contrast, the alkali source had no effect on the phase composition or morphology of the final product. Uniform and sphere-like nanoparticles with an average size of approximately 50 nm were obtained at the pH value of 11.5. A possible formation mechanism was briefly proposed. Gd2Sn2O7:Eu3+ nanoparticles displayed strong orange-red emission. Magnetic measurements revealed that Gd2Sn2O7 nanoparticles were paramagnetic. The other rare-earth stannate Ln2Sn2O7 (Ln = Y, La-Lu) nanocrystals were prepared by similar approaches.

Investigation of non-uniformity and inclusions in 6LiInSe2 utilizing laser induced breakdown spectroscopy (LIBS)

NASA Astrophysics Data System (ADS)

Wiggins, Brenden; Tupitsyn, Eugene; Bhattacharya, Pijush; Rowe, Emmanuel; Lukosi, Eric; Chvala, Ondrej; Burger, Arnold; Stowe, Ashley

2013-09-01

Impurity analysis and compositional distribution studies have been conducted on a crystal of LiInSe2, a compound semiconductor which recently has been shown to respond to ionizing radiation. IR microscopy and laser induced breakdown spectroscopy (LIBS) revealed the presence of inclusions within the crystal lattice. These precipitates were revealed to be alkali and alkaline earth elemental impurities with non-uniform spatial distribution in the crystal. LIBS compositional maps correlate the presence of these impurities with visual color differences in the crystal as well as a significant shift of the band gap. Further, LIBS revealed variation in the ratio of I-III-VI2 elemental constituents throughout the crystal. Analysis of compositional variation and impurities will aid in discerning optimal synthesis and crystal growth parameters to maximize the mobility-lifetime product and charge collection efficiency in the LiInSe2 crystal. Preliminary charge trapping calculations have also been conducted with the Monte Carlo N-particle eXtended (MCNPx) package indicating preferential trapping of holes during irradiation with thermal neutrons.

Modeling the Time-dependent Changes in Electrical Conductivity of Basaltic Melts With Redox State

NASA Astrophysics Data System (ADS)

Pommier, A.; Gaillard, F.; Pichavant, M.

2008-12-01

The electrical conductivity σ is an efficient probe of mass transfer processes within silicate melts and magmas. Little attention has been given to the influence of redox state (fO2) on the melts conductivity. We present an experimental setup allowing electrical conductivity measurements for basaltic melts under variable fO2. We demonstrate a significant dependence of σ with fO2, allowing to characterize in situ the mechanisms and kinetics of redox changes in the melt. Experiments were conducted on basalts from Pu'u 'O'o, Hawaii, and Mt.Vesuvius, Italy. Measurements were performed cylindrical glass samples (OD: 6mm, ID: 1mm, L: 8mm) using an impedance spectrometer. Experiments were conducted in a 1atm vertical furnace, from 1200°C to 1400°C. Variable gas atmosphere (air, CO2 or CO-CO2 gas mixtures) were used, imposing ΔNNO from -1 to +7. Electrical conductivities were determined for the two melts at constant fO2, different T (constant fO2) and constant T, different fO2 (variable fO2) obtained by changing the gas composition. Isothermal reduction and oxidation cycles were performed. Glasses quenched from different T and fO2 conditions were analyzed by electron microprobe, the FeO concentration was determined by wet chemistry. In constant fO2 experiments, a small but detectable effect of fO2 on σ is evidenced. At 1300°C, the difference in the Kilauea sample conductivity between reduced (ΔNNO=-1) and oxidized (ΔNNO=+7) fO2 is <1(ohm.m)-1, the sample being more conductive when reduced. The temperature dependence of σ was fitted using Arrhenian equations, the activation energy Ea being 100kJ/mol. Sodium was identified as the main charge carrier in the melts. The fO2-effect on σ can thus be attributed to the influence of the Fe2+/Fe3+ ratio on sodium mobility. The fO2-dependence of σ was included in the model of Pommier et al.(2008), allowing the conductivity of natural melts to be calculated as a function of T, P, H2O, and fO2. Variable fO2 experiments confirmed the increase in σ when reducing the melt. At 1200°C, for both reduction-oxidation cycles, a stable value of σ following a change in fO2 is reached in 15hours, while 2hours are needed at 1400°C. The real-time changes in σ of basaltic melts following fO2 step changes were monitored. The time-dependent changes in σ are interpreted in terms of kinetics processes due to redox reequilibration between melt and gas. The evolution of σ with time can be fitted using a diffusion-limited process for reduction in CO-CO2 gas mixtures and oxidation in air. However, a reaction at the gas-melt interface probably rate limits oxidation in CO2. Reduction and oxidation rates are similar and increase with T. Oxidation-reduction rates calculated from the analysis of the conductivity evolution with time range from 10-9 to 10-8m2/s for the T range 1200-1400°C. These reaction rates are in agreement with typical alkali diffusion coefficients in basaltic melts. However, the high value of Ea (230kJ/mol) calculated from the T dependence of the oxidation-reduction rates agrees with the Ea for alkali-Earth elements. Furthermore, microprobe analyses document the existence of alkali-Earth cation fluxes during oxidations and reductions. Such cation migration probably occurs to charge-balance electron fluxes in the melt, in agreement with the study of Cooper et al. (1996). Our results suggest that the migration of alkali and alkali-Earth elements rate-limits the redox state changes in basaltic melts, and that redox mechanisms are not restricted to oxygen chemical diffusion. A discussion of chemical vs tracer oxygen diffusion studies is proposed.

RECOVERY OF URANIUM AND THORIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Calkins, G.D.

1958-06-10

>A process is described for the recovery of uranium and thorium from monazite sand, which is frequently processed by treating it with a hot sodium hydroxide solution whereby a precipitate forms consisting mainly of oxides or hydroxides of the rare earths, thorium and uranium. The precipitate is dissolved in mineral acid, and the acid solution is then neutralized to a pH value of between 5.2 and 6.2 whereby both the uranium and thorium precipitate as the hydroxides, while substantially all the rare earth metal values present remain in the solution. The uranium and thoriunn can then be separated by dissolving the precipitate in a solution containing a mixture of alkali carbonate and alkali bicarbonate: and contacting the carbonate solution with a strong-base anion exchange resin whereby the uranium values are adsorbed on the resin while the thorium remains in solution.

Bonding of Alkali-Alkaline Earth Molecules in the Lowest Σ^+ States of Doublet and Quartet Multiplicity

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Hauser, Andreas W.; Ernst, Wolfgang E.

2016-06-01

n the present study the ground state as well as the lowest ^4Σ^+ state were determined for 16 AK-AKE molecules. Multireference configuration interaction calculations were carried out in order to understand the bonding of diatomic alkali-alkaline earth (AK-AKE) molecules. The correlations between molecular properties (disociation energy, bond distances, electric dipole moment) and atomic properties (electronegativity, polarizability) will be discussed. A correlation between the dissociation energy and the dipole moment of the lowest ^4Σ^+ state was observed, while the dipole moment of the lowest ^2Σ^+ state does not show such a simple dependency. In this case an empirical relation could be established. The class of AK-AKE molecules was selected for this investigation due to their possible applications in ultracold molecular physics. J. V. Pototschnig, A. W. Hauser and W. E. Ernst, Phys. Chem. Chem. Phys., 2016,18, 5964-5973

Structural Information Inference from Lanthanoid Complexing Systems: Photoluminescence Studies on Isolated Ions

NASA Astrophysics Data System (ADS)

Greisch, Jean Francois; Harding, Michael E.; Chmela, Jiri; Klopper, Willem M.; Schooss, Detlef; Kappes, Manfred M.

2016-06-01

The application of lanthanoid complexes ranges from photovoltaics and light-emitting diodes to quantum memories and biological assays. Rationalization of their design requires a thorough understanding of intramolecular processes such as energy transfer, charge transfer, and non-radiative decay involving their subunits. Characterization of the excited states of such complexes considerably benefits from mass spectrometric methods since the associated optical transitions and processes are strongly affected by stoichiometry, symmetry, and overall charge state. We report herein spectroscopic measurements on ensembles of ions trapped in the gas phase and soft-landed in neon matrices. Their interpretation is considerably facilitated by direct comparison with computations. The combination of energy- and time-resolved measurements on isolated species with density functional as well as ligand-field and Franck-Condon computations enables us to infer structural as well as dynamical information about the species studied. The approach is first illustrated for sets of model lanthanoid complexes whose structure and electronic properties are systematically varied via the substitution of one component (lanthanoid or alkali,alkali-earth ion): (i) systematic dependence of ligand-centered phosphorescence on the lanthanoid(III) promotion energy and its impact on sensitization, and (ii) structural changes induced by the substitution of alkali or alkali-earth ions in relation with structures inferred using ion mobility spectroscopy. The temperature dependence of sensitization is briefly discussed. The focus is then shifted to measurements involving europium complexes with doxycycline an antibiotic of the tetracycline family. Besides discussing the complexes' structural and electronic features, we report on their use to monitor enzymatic processes involving hydrogen peroxide or biologically relevant molecules such as adenosine triphosphate (ATP).

Alkalis in Coal and Coal Cleaning Products / Alkalia W Węglu I Productach Jego Wzbogacania

NASA Astrophysics Data System (ADS)

Bytnar, Krzysztof; Burmistrz, Piotr

2013-09-01

In the coking process, the prevailing part of the alkalis contained in the coal charge goes to coke. The content of alkalis in coal (and also in coke) is determined mainly by the content of two elements: sodium and potasium. The presence of these elements in coal is connected with their occurrence in the mineral matter and moisture of coal. In the mineral matter and moisture of the coals used for the coke production determinable the content of sodium is 26.6 up to 62. per cent, whereas that of potassium is 37.1 up to 73.4 per cent of the total content of alkalis. Major carriers of alkalis are clay minerals. Occasionally alkalis are found in micas and feldspars. The fraction of alkalis contained in the moisture of the coal used for the production of coke in the total amount of alkalis contained there is 17.8 up to 62.0 per cent. The presence of sodium and potassium in the coal moisture is strictly connected with the presence of the chloride ions. The analysis of the water drained during process of the water-extracting from the flotoconcentrate showed that the Na to K mass ratio in the coal moisture is 20:1. Increased amount of the alkalis in the coal blends results in increased content of the alkalis in coke. This leads to the increase of the reactivity (CRI index), and to the decrease of strength (CSR index) determined with the Nippon Steel Co. method. W procesie koksowania przeważająca część zawartych we wsadzie węglowym alkaliów przechodzi do koksu. Zawartość alkaliów w węglu, a co za tym idzie i w koksie determinowana jest głównie zawartością dwóch pierwiastków: sodu i potasu. Obecność tych pierwiastków w węglu wiąże się z występowaniem ich w substancji mineralnej i wilgoci węgla. W substancji mineralnej oraz wilgoci węgli stosowanych do produkcji koksu, oznaczona zawartość sodu wynosi od 26.6 do 62.9%, a zawartość potasu od 37.1 do 73.4% alkaliów ogółem. Głównymi nośnikami alkaliów w substancji mineralnej są minerały ilaste, sporadycznie też miki oraz skalenie. Udział alkaliów zawartych w wilgoci węgli stosowanych do produkcji koksu w ogólnej ilości zawartych w nim alkaliów wynosi dla badanych węgli od 17.8 do 62.0%. Obecność sodu i potasu w wilgoci węgla związana jest wyłącznie z obecnością w niej jonów chlorkowych. Wyniki analizy wody odprowadzanej z procesu wirowania flotokoncentratu wskazują, że stosunek masowy Na do K w wilgoci węgla wynosi 20:1. Wzrost zawartość wilgoci w koksie będący wynikiem ich zwiększonej ilości w mieszance węglowej prowadzi do wzrostu reaktywności (wskaźnik CRI) oraz spadku wytrzymałości (wskaźnik CSR) oznaczonych metoda Nippon Steel Co.

Alkali Metal Heat Pipe Life Issues

NASA Technical Reports Server (NTRS)

Reid, Robert S.

2004-01-01

One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

A study of physical and optical absorption spectra of VO2+ ions in potassium and sodium oxide borate glasses

NASA Astrophysics Data System (ADS)

Srinivas, G.; Ramesh, B.; Kumar, J. Siva; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

2016-05-01

Spectroscopic and physical properties of V2O5 doped mixed alkali borate glasses are investigated. Borate glasses containing fixed concentrations of alkaline earth oxides (MgO and BaO) and alkali oxides (K2O and Na2O) were changes and are prepared by melt quenching technique. The values of ri, rp, Rm, αm molar volume and Λth increase and oxygen packing density, density and dopant ion concentration decrease with increasing of K2O content. As a result there shall be an increase in the disorder of the glass network. The optical band gap energies, Urbach energy, boron-boron separation,refractive index, dielectric constant, electronic polarizability and reflection loss values are varies nonlinearly with the K2O content which manifests the mixed alkali effect.

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.

Role of tectonomagmatic processes for surface environmental changes and evolution of biosphere on terrestrial planets: Evidence for evolution of the life on the Earth

NASA Astrophysics Data System (ADS)

Sharkov, Evgenii; Bogina, Maria

It is known that ecological systems on the Earth in the Middle Paleoproterozoic was experienced fundamental change, which finally led to the appearance of multicellular organisms. Though life has been already existed in the Paleoarchean (Harris et al., 2009 and references herein), the multicellular organisms appeared only in the middle Paleoproterozoic about 1.6 Ga ago. It was preceded by fundamental change of tectononagmatic processes at period from 2.35 to 2.0 Ga, when early Precambrian high-Mg magmas, derived from depleted mantle, were gradually changed by geochemical-enriched Fe-Ti picrites and basalts, similar to Phanerozoic within-plate magmas. A drastic change of the tectonic pattern occurred at ca. 2 Ga when plate-tectonics changed plume-tectonics of the early Precambrian. Since that time tectonomagmatic processes irretrievably changed over the whole Earth and gradually change of ancient continental crust for secondary oceanic (basaltic) crust has occurred. New type of magmatic melts, appeared in the Middle Paleoproterozoic, was characterized by elevated and high contents of Fe, Ti, Cu, P, Mn, alkalis, LREE, and other incompatible elements (Zr, Ba, Sr, U, Th, F, etc.). A large-scale influx of alkalis in the World Ocean presumably neutralized its water, making it more suitable for the life, while input of Fe-group metals, P, and other trace elements, which are required for metabolism and fermentation, rapidly expanded the possibility for the development of bio-sphere. This caused a rapid evolution of organic life, especially photosynthesizing cyanobacteria and, subsequently, the emergence of oxidizing atmosphere, marked by formation of cupriferous red beds at all Precambrian shields and generation of first hydrocarbon deposits (Melezhik et al., 2005). A drop in atmospheric CO2 presumably suppressed the greenhouse effect, while significant intensification of relief ruggedness caused by wide development of plate tectonics after 2 Ga resulted in the change of atmospheric circulation. All these processes finally led to the global glaciations. The latters commenced earlier, in the Paleoproterozoic, simultaneously with first manifestations of Fe-Ti basaltic magmatism, which came into force only in the middle Paleoproterozoic. Thus, a fundamental change in tectonomagmatic activity acted as the trigger for environmental changes and biospheric evolution, supplying a qualitatively new material on the Earth's surface. Data available on Venus and Mars suggest that their tectonomagmatic evolution also occurred at the close scenario. Two major types of morphostructures, which are vast plains, composed by young basaltic flows, and older lightweight uplifted segments with a complicated topography (tesseras on the Venus and earths (terras) on the Mars), can evidence about two-stage evolution of these planets. Presence of drainage systems on Mars and valles on Venus assumes existence of liquid water on early stages of their development. Like on the Earth, red beds and global glacials appeared on the Mars at the middle stage of it's evolu-tion, and may be at this period ancient microorganisms existed on Mars (McKay et al., 1996). Powerful eruptions of gigantic volcanoes of Tharsis and Elysium, probably, led to fall of tem-perature and disappearance of liquid water on Mars. In contrast to Mars, on Venus appeared speeded up greenhouse effect, which also led to dry and very hot surface. So, development of tectonomagmatic processes was favourable for the biosphere evolution only on the Earth.

PREPARATION OF PURE METAL FROM THEIR COMPOUNDS

DOEpatents

Slatin, H.L.

1961-08-01

S>A method is described for the preparation of uranium from U/sub 3/O/ sub 6/ by electrolytic deposition at the cathode from an alkali and/or alkaline earth fused salt bath such as fused strontium potassium chloride. (AEC)

A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

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

Wang, Jin-Hua; Tang, Gui-Mei, E-mail: meiguit@163.com; Qin, Ting-Xiao

2014-11-15

Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11more » nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one-dimensional structures have been observed. • The properties of second harmonic generation and ferroelectricity for complex 2.« less

Geochemistry, mineralogy, and petrology of boninitic and komatiitic rocks on the mercurian surface: Insights into the mercurian mantle

NASA Astrophysics Data System (ADS)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Nittler, Larry R.; Peplowski, Patrick N.; Weider, Shoshana Z.; Frank, Elizabeth A.; McCoy, Timothy J.

2017-03-01

Orbital data from the MESSENGER mission to Mercury have facilitated a new view of the planet's structure, chemical makeup, and diverse surface, and have confirmed Mercury's status as a geochemical endmember among the terrestrial planets. In this work, the most recent results from MESSENGER's X-Ray Spectrometer, Gamma-Ray Spectrometer, and Neutron Spectrometer have been used to identify nine distinct geochemical regions on Mercury. Using a variation on the classical CIPW normative mineralogy calculation, elemental composition data is used to constrain the potential mineralogy of Mercury's surface; the calculated silicate mineralogy is dominated by plagioclase, pyroxene (both orthopyroxene and clinopyroxene), and olivine, with lesser amounts of quartz. The range in surface compositions indicate that the rocks on the surface of Mercury are diverse and vary from komatiitic to boninitic. The high abundance of alkalis on Mercury's surface results in several of the nine regions being classified as alkali-rich komatiites and/or boninites. In addition, Mercury's surface terranes span a wide range of SiO2 values that encompass crustal compositions that are more silica-rich than geochemical terranes on the Moon, Mars, and Vesta, but the range is similar to that of Earth. Although the composition of Mercury's surface appears to be chemically evolved, the high SiO2 content is a primitive feature and a direct result of the planet's low oxygen fugacity.

Combustion of Biosolids in a Bubbling Fluidized Bed, Part 1: Main Ash-Forming Elements and Ash Distribution with a Focus on Phosphorus.

PubMed

Skoglund, Nils; Grimm, Alejandro; Ohman, Marcus; Boström, Dan

2014-02-20

This is the first in a series of three papers describing combustion of biosolids in a 5-kW bubbling fluidized bed, the ash chemistry, and possible application of the ash produced as a fertilizing agent. This part of the study aims to clarify whether the distribution of main ash forming elements from biosolids can be changed by modifying the fuel matrix, the crystalline compounds of which can be identified in the raw materials and what role the total composition may play for which compounds are formed during combustion. The biosolids were subjected to low-temperature ashing to investigate which crystalline compounds that were present in the raw materials. Combustion experiments of two different types of biosolids were conducted in a 5-kW benchscale bubbling fluidized bed at two different bed temperatures and with two different additives. The additives were chosen to investigate whether the addition of alkali (K 2 CO 3 ) and alkaline-earth metal (CaCO 3 ) would affect the speciation of phosphorus, so the molar ratios targeted in modified fuels were P:K = 1:1 and P:K:Ca = 1:1:1, respectively. After combustion the ash fractions were collected, the ash distribution was determined and the ash fractions were analyzed with regards to elemental composition (ICP-AES and SEM-EDS) and part of the bed ash was also analyzed qualitatively using XRD. There was no evidence of zeolites in the unmodified fuels, based on low-temperature ashing. During combustion, the biosolid pellets formed large bed ash particles, ash pellets, which contained most of the total ash content (54%-95% (w/w)). This ash fraction contained most of the phosphorus found in the ash and the only phosphate that was identified was a whitlockite, Ca 9 (K,Mg,Fe)(PO 4 ) 7 , for all fuels and fuel mixtures. With the addition of potassium, cristobalite (SiO 2 ) could no longer be identified via X-ray diffraction (XRD) in the bed ash particles and leucite (KAlSi 2 O 6 ) was formed. Most of the alkaline-earth metals calcium and magnesium were also found in the bed ash. Both the formation of aluminum-containing alkali silicates and inclusion of calcium and magnesium in bed ash could assist in preventing bed agglomeration during co-combustion of biosolids with other renewable fuels in a full-scale bubbling fluidized bed.

Combustion of Biosolids in a Bubbling Fluidized Bed, Part 1: Main Ash-Forming Elements and Ash Distribution with a Focus on Phosphorus

PubMed Central

2014-01-01

This is the first in a series of three papers describing combustion of biosolids in a 5-kW bubbling fluidized bed, the ash chemistry, and possible application of the ash produced as a fertilizing agent. This part of the study aims to clarify whether the distribution of main ash forming elements from biosolids can be changed by modifying the fuel matrix, the crystalline compounds of which can be identified in the raw materials and what role the total composition may play for which compounds are formed during combustion. The biosolids were subjected to low-temperature ashing to investigate which crystalline compounds that were present in the raw materials. Combustion experiments of two different types of biosolids were conducted in a 5-kW benchscale bubbling fluidized bed at two different bed temperatures and with two different additives. The additives were chosen to investigate whether the addition of alkali (K2CO3) and alkaline-earth metal (CaCO3) would affect the speciation of phosphorus, so the molar ratios targeted in modified fuels were P:K = 1:1 and P:K:Ca = 1:1:1, respectively. After combustion the ash fractions were collected, the ash distribution was determined and the ash fractions were analyzed with regards to elemental composition (ICP-AES and SEM-EDS) and part of the bed ash was also analyzed qualitatively using XRD. There was no evidence of zeolites in the unmodified fuels, based on low-temperature ashing. During combustion, the biosolid pellets formed large bed ash particles, ash pellets, which contained most of the total ash content (54%–95% (w/w)). This ash fraction contained most of the phosphorus found in the ash and the only phosphate that was identified was a whitlockite, Ca9(K,Mg,Fe)(PO4)7, for all fuels and fuel mixtures. With the addition of potassium, cristobalite (SiO2) could no longer be identified via X-ray diffraction (XRD) in the bed ash particles and leucite (KAlSi2O6) was formed. Most of the alkaline-earth metals calcium and magnesium were also found in the bed ash. Both the formation of aluminum-containing alkali silicates and inclusion of calcium and magnesium in bed ash could assist in preventing bed agglomeration during co-combustion of biosolids with other renewable fuels in a full-scale bubbling fluidized bed. PMID:24678140

Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se2 solar cells on glass substrate

NASA Astrophysics Data System (ADS)

Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo; Tayagaki, Takeshi; Guthrey, Harvey; Shibata, Hajime; Matsubara, Koji; Niki, Shigeru

2018-03-01

The precise control of alkali-metal concentrations in Cu(In,Ga)Se2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance from the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.

Selection and preparation of activated carbon for fuel gas storage

DOEpatents

Schwarz, James A.; Noh, Joong S.; Agarwal, Rajiv K.

1990-10-02

Increasing the surface acidity of active carbons can lead to an increase in capacity for hydrogen adsorption. Increasing the surface basicity can facilitate methane adsorption. The treatment of carbons is most effective when the carbon source material is selected to have a low ash content i.e., below about 3%, and where the ash consists predominantly of alkali metals alkali earth, with only minimal amounts of transition metals and silicon. The carbon is washed in water or acid and then oxidized, e.g. in a stream of oxygen and an inert gas at an elevated temperature.

Molten salts in Nuclear Reactors (Bibliography); LES SELS FONDUS DANS LES REACTEURS NUCLEAIRES (BIBLIOGRAPHIE)

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

Dirian, J.; Saint-James, R.

1959-01-01

A collection is presented of references dealing with the physicochemical studies of fused salts, in partictular the alkali and alkali earth halides. Numerous binary, ternary and quaternary systems of these halides with those of uranium and thoriuna are examined, and the physical properties, density, viscosity, and vapor pressure going from the halides to the mixtures are also considered. References relating to the corrosion of materials by these salts are included and the treatment of the salts with a view to recovery after irradiation in a nuclear reactor is discussed. (auth)

Experimental Constraints on Alkali Volatilization during Chondrule Formation: Implications for Early Solar System Heterogeneity

NASA Astrophysics Data System (ADS)

Ustunisik, G. K.; Ebel, D. S.; Nekvasil, H.

2014-12-01

The chemical variability of chondrule volatile element contents provide a wealth of information on the processes that shaped the early solar system and its compositional heterogeneity. An essential observation is that chondrule melts contain very low alkalies and other volatile elements (e.g., Cl). The reason for this depletion is the combined effects of cooling rates (10 to 1000K/h), the small size of chondrules, and their high melting temperatures (~1700 to 2100 K) resulting in extensive loss of volatiles at canonical pressures (e.g., 10-4bar). However, we observe some chondrules with significant concentrations of volatiles (Na, Cl), that differ markedly from chondrules dominated by refractory elements. Could such heterogeneity arise from loss of alkalis and Cl to a gas phase that itself later condenses, thereby yielding variations in volatile enrichments in chondrules? Does Cl enhance volatility of the alkalis to varying extents? Experiments on Cl-bearing and Cl-free melts of equivalent composition for 10 min, 4 h, and 6 h reveal systematic effects of Cl on alkali volatility. Cl-bearing melts lose 48% of initial Na2O, 66% of K2O, 96% of Cl within the first 10 minutes of degassing. Then the amount of alkali loss decreases due to the absence of Cl. Cl-free melts loses only 15% of initial Na2O and 33% K2O. After 4 hours, melts lose 1/3 of initial Na2O and 1/2 of K2O. For both systems, Na2O is more compatible in the melt relative to K2O. Therefore, the vapor given off has a K/Na ratio higher than the melt through time in spite of the much higher initial Na abundance in the melt. Enhanced vaporization of alkalis from Cl-bearing melt suggests that Na and K evaporate more readily as volatile chlorides than as monatomic gases. Cl-free initial melts with normative plagioclase of An50Ab44Or6 evolved into slightly normal zoned ones (An49Ab50Or1) while Cl-bearing initial melts normative to albitic plagioclase (An46Ab50Or4) evolved to reverse zoned ones (An54Ab45Or1). The vapor phase over Cl-bearing chondrule melts may have a bimodal character over time. The heteregeneous volatile contents of chondrules may result from quenching of melt droplets at different stages of repeated heating, chondrule fragment recycling, and recondensation of exsolved volatiles.

Characterization of the extent of Mercury Contamination in the Androscoggin River from a former Chlor-alkali Facility, Berlin, New Hampshire

NASA Astrophysics Data System (ADS)

Chalmers, A.; Marvin-Dipasquale, M. C.; Rosiu, C.; Luce, D.; Coles, J.; Zimmerman, M.; Smith, T.

2010-12-01

From the late 1800s to the 1960s a chlor-alkali plant was used to produce chlorine gas for the papermaking industry in Berlin, New Hampshire. During operation of the chlor-alkali facility, elemental mercury (Hg) was released to the environment, contaminating soils and the underlying fractured rock. Investigations have revealed that elemental Hg continues to seep through bedrock fractures into the adjacent Androscoggin River. This study evaluates the extent and transformation of Hg contamination in the Androscoggin River by comparing a reference site 17 kilometers above the former chlor-alkali facility to 5 sites ranging from 1 to 16 km downstream from the facility. Total and methyl Hg (THg and MeHg, respectively), among other analytes, were characterized in surface water, pore water, sediment and biological tissue samples at each site. Bed sediment was also assessed for bio-available (tin-reducible) inorganic Hg (II) and microbial MeHg production potential rates. Acid extractable ferrous iron, crystalline and amorphous (poorly crystalline) ferric iron, total reduced sulfur, particle size, and organic content in bed sediment was analyzed to help explain spatial differences in MeHg production rates and bio-available Hg (II) among sites. The information provided by this study will help evaluate the extent of Hg contamination in the Androscoggin River, will improve our understanding of the controls on MeHg production in the Androscoggin River system, and will be used by the U.S. Environmental Protection Agency to support remediation of the chlor-alkali facility site.

Method for uniformly distributing carbon flakes in a positive electrode, the electrode made thereby and compositions. [Patent application

DOEpatents

Mrazek, F.C.; Smaga, J.A.; Battles, J.E.

1981-01-19

A positive electrode for a secondary electrochemical cell is described wherein an electrically conductive current collector is in electrical contact with a particulate mixture of gray cast iron and an alkali metal sulfide and an electrolyte including alkali metal halides or alkaline earth metal halides. Also present may be a transition metal sulfide and graphite flakes from the conversion of gray cast iron to iron sulfide. Also disclosed is a method of distributing carbon flakes in a cell wherein there is formed an electrochemical cell of a positive electrode structure of the type described and a suitable electrolyte and a second electrode containing a material capable of alloying with alkali metal ions. The cell is connected to a source of electrical potential to electrochemically convert gray cast iron to an iron sulfide and uniformly to distribute carbon flakes formerly in the gray cast iron throughout the positive electrode while forming an alkali metal alloy in the negative electrode. Also disclosed are compositions useful in preparing positive electrodes.

Distribution and leaching characteristics of trace elements in ashes as a function of different waste fuels and incineration technologies.

PubMed

Saqib, Naeem; Bäckström, Mattias

2015-10-01

Impact of waste fuels (virgin/waste wood, mixed biofuel (peat, bark, wood chips) industrial, household, mixed waste fuel) and incineration technologies on partitioning and leaching behavior of trace elements has been investigated. Study included 4 grate fired and 9 fluidized boilers. Results showed that mixed waste incineration mostly caused increased transfer of trace elements to fly ash; particularly Pb/Zn. Waste wood incineration showed higher transfer of Cr, As and Zn to fly ash as compared to virgin wood. The possible reasons could be high input of trace element in waste fuel/change in volatilization behavior due to addition of certain waste fractions. The concentration of Cd and Zn increased in fly ash with incineration temperature. Total concentration in ashes decreased in order of Zn>Cu>Pb>Cr>Sb>As>Mo. The concentration levels of trace elements were mostly higher in fluidized boilers fly ashes as compared to grate boilers (especially for biofuel incineration). It might be attributed to high combustion efficiency due to pre-treatment of waste in fluidized boilers. Leaching results indicated that water soluble forms of elements in ashes were low with few exceptions. Concentration levels in ash and ash matrix properties (association of elements on ash particles) are crucial parameters affecting leaching. Leached amounts of Pb, Zn and Cr in >50% of fly ashes exceeded regulatory limit for disposal. 87% of chlorine in fly ashes washed out with water at the liquid to solid ratio 10 indicating excessive presence of alkali metal chlorides/alkaline earths. Copyright © 2015. Published by Elsevier B.V.

Mobility and fluxes of major, minor and trace metals during basalt weathering and groundwater transport at Mt. Etna volcano (Sicily)

NASA Astrophysics Data System (ADS)

Aiuppa, Alessandro; Allard, Patrick; D'Alessandro, Walter; Michel, Agnes; Parello, Francesco; Treuil, Michel; Valenza, Mariano

2000-06-01

The concentrations and fluxes of major, minor and trace metals were determined in 53 samples of groundwaters from around Mt Etna, in order to evaluate the conditions and extent of alkali basalt weathering by waters enriched in magma-derived CO 2 and the contribution of aqueous transport to the overall metal discharge of the volcano. We show that gaseous input of magmatic volatile metals into the Etnean aquifer is small or negligible, being limited by cooling of the rising fluids. Basalt leaching by weakly acidic, CO 2-charged water is the overwhelming source of metals and appears to be more extensive in two sectors of the S-SW (Paternò) and E (Zafferana) volcano flanks, where out flowing groundwaters are the richest in metals and bicarbonate of magmatic origin. Thermodynamic modeling of the results allows to evaluate the relative mobility and chemical speciation of various elements during their partitioning between solid and liquid phases through the weathering process. The facts that rock-forming minerals and groundmass dissolve at different rates and secondary minerals are formed are taken into account. At Mt. Etna, poorly mobile elements (Al, Th, Fe) are preferentially retained in the solid residue of weathering, while alkalis, alkaline earth and oxo-anion-forming elements (As, Se, Sb, Mo) are more mobile and released to the aqueous system. Transition metals display an intermediate behavior and are strongly dependent on either the redox conditions (Mn, Cr, V) or solid surface-related processes (V, Zn, Cu). The fluxes of metals discharged by the volcanic aquifer of Etna range from 7.0 × 10 -3 t/a (Th) to 7.3 × 10 4 t/a (Na). They are comparable in magnitude to the summit crater plume emissions for a series of elements (Na, K, Ca, Mg, U, V, Li) with lithophile affinity, but are minor for volatile elements. Basalt weathering at Mt Etna also consumes about 2.1 × 10 5 t/a of magma-derived carbon dioxide, equivalent to ca. 7% of contemporaneous crater plume emissions. The considerable transport of some metals in Etna's aquifer reflects a particularly high chemical erosion rate, evaluated at 2.3∗10 5 t/a, enhanced by the initial acidity of magmatic CO 2-rich groundwater.

Zirconium and hafnium fractionation in differentiation of alkali carbonatite magmatic systems

NASA Astrophysics Data System (ADS)

Kogarko, L. N.

2016-05-01

Zirconium and hafnium are valuable strategic metals which are in high demand in industry. The Zr and Hf contents are elevated in the final products of magmatic differentiation of alkali carbonatite rocks in the Polar Siberia region (Guli Complex) and Ukraine (Chernigov Massif). Early pyroxene fractionation led to an increase in the Zr/Hf ratio in the evolution of the ultramafic-alkali magmatic system due to a higher distribution coefficient of Hf in pyroxene with respect to Zr. The Rayleigh equation was used to calculate a quantitative model of variation in the Zr/Hf ratio in the development of the Guli magmatic system. Alkali carbonatite rocks originated from rare element-rich mantle reservoirs, in particular, the metasomatized mantle. Carbonated mantle xenoliths are characterized by a high Zr/Hf ratio due to clinopyroxene development during metasomatic replacement of orthopyroxene by carbonate fluid melt.

Thermodynamics of Liquid Alkali Metals and Their Binary Alloys

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Patel, Minal H.; Gajjar, P. N.; Jani, A. R.

2009-07-01

The theoretical investigation of thermodynamic properties like internal energy, entropy, Helmholtz free energy, heat of mixing (ΔE) and entropy of mixing (ΔS) of liquid alkali metals and their binary alloys are reported in the present paper. The effect of concentration on the thermodynamic properties of Ac1Bc2 alloy of the alkali-alkali elements is investigated and reported for the first time using our well established local pseudopotential. To investigate influence of exchange and correlation effects, we have used five different local field correction functions viz; Hartree(H), Taylor(T), Ichimaru and Utsumi(IU), Farid et al. (F) and Sarkar et al. (S). The increase of concentration C2, increases the internal energy and Helmholtz free energy of liquid alloy Ac1Bc2. The behavior of present computation is not showing any abnormality in the outcome and hence confirms the applicability of our model potential in explaining the thermodynamics of liquid binary alloys.

Synthesizing new types of ultrathin 2D metal oxide nanosheets via half-successive ion layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Gao, Linjie; Li, Yaguang; Xiao, Mu; Wang, Shufang; Fu, Guangsheng; Wang, Lianzhou

2017-06-01

Two-dimensional (2D) metal oxide nanosheets have demonstrated their great potential in a broad range of applications. The existing synthesis strategies are mainly preparing 2D nanosheets from layered and specific transition metal oxides. How to prepare the other types of metal oxides as ultrathin 2D nanosheets remains unsolved, especially for metal oxides containing alkali, alkaline earth metal, and multiple metal elements. Herein, we developed a half-successive ion layer adsorption and reaction (SILAR) method, which could synthesize those types of metal oxides as ultrathin 2D nanosheets. The synthesized 2D metal oxides nanosheets are within 1 nm level thickness and 500 m2 · g-1 level surface area. This method allows us to develop many new types of ultrathin 2D metal oxides nanosheets that have never been prepared before.

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.

Line Lists for LiF and LiCl in the X^{1}Σ^{+} State

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Bernath, Peter F.

2017-06-01

Alkali-containing molecules are expected to be present in the atmospheres of exoplanets such as rocky super-Earths as well as in cool dwarf stars. Line lists for LiF and LiCl in their X^{1}Σ^{+} ground states have been calculated using LeRoy's LEVEL program. The potential energy functions, including the effects of the breakdown of the Born-Oppenheimer approximation, are obtained by direct fitting the experimental infrared vibration-rotation and microwave pure rotation data with extended Morse oscillator potentials using LeRoy's dPotFit program. The transition dipole matrix elements and line intensities were obtained with LEVEL using a dipole moment function from a high level ab initio calculation. Phil. Trans. R. Soc. A 372, 20130087 (2014) Astrophys. J. 519, 793 (1999) J. Quant. Spectrosc. Radiat. Transfer 186, 167 (2017) J. Quant. Spectrosc. Radiat. Transfer 186, 179 (2017)

Positron Annihilation Studies of High-Tc Superconductors

NASA Astrophysics Data System (ADS)

Peter, M.; Manuel, A. A.

1989-01-01

First we present the principles involved in the study of the two-photon momentum distribution: The method requires deconvolution of the positron wavefunction and the estimation of matrix elements effects. Single crystal samples must be of sufficient quality to avoid positron trapping (tested by positron lifetime measurements). In ordinary metals (alkalis, transition- and rare earth metals and compounds) two-photon momentum distribution studies have given results in close agreement with relevant band structure calculations. Discrepancies have been successfully described as enhancement effects due to correlations. In the superconducting oxides, measurements are more difficult because there are fewer conduction electrons and more trapping. Correlation effects of a different nature are expected to be important and might render the band picture inappropriate. Two-photon momentum distribution measurements have now been made by several groups, but have been interpreted in different ways. We relate the current state of affairs, and our present interpretation, to the latest available results.

Synergistic combination of biomass torrefaction and co-gasification: Reactivity studies.

PubMed

Zhang, Yan; Geng, Ping; Liu, Rui

2017-12-01

Two typical biomass feedstocks obtained from woody wastes and agricultural residues were torrefied or mildly pyrolized in a fixed-bed reactor. Effects of the torrefaction conditions on product distributions, compositional and energetic properties of the solid products, char gasification reactivity, and co-gasification behavior between coal and torrefied solids were systematically investigated. Torrefaction pretreatment produced high quality bio-solids with not only increased energy density, but also concentrated alkali and alkaline earth metals (AAEM). As a consequence of greater retention of catalytic elements in the solid products, the chars derived from torrefied biomass exhibited a faster conversion than those derived from raw biomass during CO 2 gasification. Furthermore, co-gasification of coal/torrefied biomass blends exhibited stronger synergy compared to the coal/raw biomass blends. The results and insights provided by this study filled a gap in understanding synergy during co-gasification of coal and torrefied biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multiple enrichment of the Carpathian-Pannonian mantle: Pb-Sr-Nd isotope and trace element constraints

NASA Astrophysics Data System (ADS)

Rosenbaum, Jeffrey M.; Wilson, Marjorie; Downes, Hilary

1997-07-01

Pb isotope compositions of acid-leached clinopyroxene and amphibole mineral separates from spinel peridotite mantle xenoliths entrained in Tertiary-Quaternary alkali basalts from the Carpathian-Pannonian Region of eastern Europe provide important constraints on the processes of metasomatic enrichment of the mantle lithosphere in an extensional tectonic setting associated with recent subduction. Principal component analysis of Pb-Sr-Nd isotope and rare earth element compositions of the pyroxenes is used to identify the geochemical characteristics of the original lithospheric mantle protolith and a spectrum of infiltrating metasomatic agents including subduction-related aqueous fluids and silicate melts derived from a subduction-modified mantle wedge which contains a St. Helena-type (HIMU) plume component. The mantle protolith is highly depleted relative to mid-ocean ridge basalt-source mantle with Pb-Nd-Sr isotope compositions consistent with an ancient depletion event. Silicate melt infiltration into the protolith accounts for the primary variance in the Pb-Sr-Nd isotope compositions of the xenoliths and has locally generated metasomatic amphibole. Infiltration of aqueous fluids has introduced radiogenic Pb and Sr without significantly perturbing the rare earth element signature of the protolith. The Pb isotope compositions of the fluid-modified xenoliths suggest that they reacted with aqueous fluids released from a subduction zone which had equilibrated with sediment derived from an ancient basement terrain. We propose a model for mantle lithosphere evolution consistent with available textural and geochemical data for the xenolith population. The Pb-Sr-Nd isotope compositions of both alkaline mafic magmas and rare, subduction-related, calc-alkaline basaltic andesites from the region provide important constraints for the nature of the asthenospheric mantle wedge and confirm the presence of a HIMU plume component. These silicate melts contribute to the metasomatism of the mantle lithosphere rather than being derived therefrom.

High temperature alkali corrosion of ceramics in coal gas: Final report

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

Pickrell, G.R.; Sun, T.; Brown, J.J. Jr.

1994-12-31

There are several ceramic materials which are currently being considered for use as structural elements in coal combustion and coal conversion systems because of their thermal and mechanical properties. These include alumina (refractories, membranes, heat engines); silicon carbide and silicon nitride (turbine engines, internal combustion engines, heat exchangers, particulate filters); zirconia (internal combustion engines, turbine engines, refractories); and mullite and cordierite (particulate filters, refractories, heat exchangers). High temperature alkali corrosion has been known to cause premature failure of ceramic components used in advanced high temperature coal combustion systems such as coal gasification and clean-up, coal fired gas turbines, and highmore » efficiency heat engines. The objective of this research is to systematically evaluate the alkali corrosion resistance of the most commonly used structural ceramics including silicon carbide, silicon nitride, cordierite, mullite, alumina, aluminum titanate, and zirconia. The study consists of identification of the alkali reaction products and determination of the kinetics of the alkali reactions as a function of temperature and time. 145 refs., 29 figs., 12 tabs.« less

Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

NASA Astrophysics Data System (ADS)

Hummelshøj, J. S.; Landis, D. D.; Voss, J.; Jiang, T.; Tekin, A.; Bork, N.; Dułak, M.; Mortensen, J. J.; Adamska, L.; Andersin, J.; Baran, J. D.; Barmparis, G. D.; Bell, F.; Bezanilla, A. L.; Bjork, J.; Björketun, M. E.; Bleken, F.; Buchter, F.; Bürkle, M.; Burton, P. D.; Buus, B. B.; Calborean, A.; Calle-Vallejo, F.; Casolo, S.; Chandler, B. D.; Chi, D. H.; Czekaj, I.; Datta, S.; Datye, A.; DeLaRiva, A.; Despoja, V.; Dobrin, S.; Engelund, M.; Ferrighi, L.; Frondelius, P.; Fu, Q.; Fuentes, A.; Fürst, J.; García-Fuente, A.; Gavnholt, J.; Goeke, R.; Gudmundsdottir, S.; Hammond, K. D.; Hansen, H. A.; Hibbitts, D.; Hobi, E.; Howalt, J. G.; Hruby, S. L.; Huth, A.; Isaeva, L.; Jelic, J.; Jensen, I. J. T.; Kacprzak, K. A.; Kelkkanen, A.; Kelsey, D.; Kesanakurthi, D. S.; Kleis, J.; Klüpfel, P. J.; Konstantinov, I.; Korytar, R.; Koskinen, P.; Krishna, C.; Kunkes, E.; Larsen, A. H.; Lastra, J. M. G.; Lin, H.; Lopez-Acevedo, O.; Mantega, M.; Martínez, J. I.; Mesa, I. N.; Mowbray, D. J.; Mýrdal, J. S. G.; Natanzon, Y.; Nistor, A.; Olsen, T.; Park, H.; Pedroza, L. S.; Petzold, V.; Plaisance, C.; Rasmussen, J. A.; Ren, H.; Rizzi, M.; Ronco, A. S.; Rostgaard, C.; Saadi, S.; Salguero, L. A.; Santos, E. J. G.; Schoenhalz, A. L.; Shen, J.; Smedemand, M.; Stausholm-Møller, O. J.; Stibius, M.; Strange, M.; Su, H. B.; Temel, B.; Toftelund, A.; Tripkovic, V.; Vanin, M.; Viswanathan, V.; Vojvodic, A.; Wang, S.; Wellendorff, J.; Thygesen, K. S.; Rossmeisl, J.; Bligaard, T.; Jacobsen, K. W.; Nørskov, J. K.; Vegge, T.

2009-07-01

We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition metal atom (M2) plus two to five (BH4)- groups, i.e., M1M2(BH4)2-5, using a number of model structures with trigonal, tetrahedral, octahedral, and free coordination of the metal borohydride complexes. Of the over 700 investigated structures, about 20 were predicted to form potentially stable alloys with promising decomposition energies. The M1(Al/Mn/Fe)(BH4)4, (Li/Na)Zn(BH4)3, and (Na/K)(Ni/Co)(BH4)3 alloys are found to be the most promising, followed by selected M1(Nb/Rh)(BH4)4 alloys.

Substantial enhancement in intrinsic coercivity on M-type strontium hexaferrite through the increase in magneto-crystalline anisotropy by co-doping of group-V and alkali elements

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

Ahn, Kyunghan, E-mail: kyunghan.ahn@samsung.com; Ryu, Byungki; Korolev, Dmitry

2013-12-09

The effect of d{sup 1} impurity doping in Sr-hexaferrite (SrM) on the magnetic anisotropy is investigated. First-principles calculations revealed that group-V elements (V, Nb) are stabilized with co-doping of alkali elements. Na{sup 1+}/K{sup 1+} doping at Sr{sup 2+}-site is found to be critical to form the d{sup 1} impurities at Fe-site. Experimentally, Na–V doped SrM shows the intrinsic coercivity of ∼5.4 kOe, which is ∼300% enhancement compared to undoped SrM and comparable value to La–Co co-doped SrM. Finally, the spin-orbit coupling from non-vanishing angular momentum of d{sup 1} impurity in SrM should be a main factor for such a substantialmore » improvement of intrinsic coercivity.« less

The interaction between cations and anionic groups inducing SHG enhancement in a series of apatite-like crystals: A first-principles study

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

Jing, Qun; University of Chinese Academy of Sciences, Beijing 100049; Department of Physics, School of Science, Shihezi University, Shihezi 832000

2014-11-15

It is an interesting topic to reveal the origin of the SHG intensity enhancement after substitution from alkali and alkali-earth metal atoms to cadmium in a series of apatite-like borates KSr{sub 4}(BO{sub 3}){sub 3}, Ca{sub 5}(BO{sub 3}){sub 3}F, Cd{sub 5}(BO{sub 3}){sub 3}F. Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the electronic structure, the optical properties and the contribution of respective ion and ion groups have been investigated. Second harmonic generation (SHG) responses are mainly attributed to BO{sub 3} groups with π conjugated configuration and their alignment framework. The contributions of A site are more important inmore » CaBOF and CdBOF compounds than in KSrBO. It is also demonstrated that the strong covalent interactions between the boron–oxygen groups and the cadmium atoms contribute the enhancement of SHG responses after substitution from alkali and alkali-earth metal atoms. - graphical abstract: Combined with the first-principles method, SHG-density method and real-space atom-cutting method, the enhancement of SHG response are attributed to the interaction between cadmium and BO{sub 3} groups. - Highlights: • SHG response on a series of apatite-like borates was studied by a SHG-density method. • SHG responses are mainly attributed to BO{sub 3} groups and their alignment framework. • The contributions of A site are more important in CaBOF and CdBOF than in KSrBO. • Covalent interaction between BO and Cd is responsible for SHG of CdBOF.« less

METAL SURFACE TREATMENT

DOEpatents

Eubank, L.D.

1958-08-12

Improved flux baths are described for use in conjunction with hot dipped coatings for uranium. The flux bath consists of molten alkali metal, or alkaline earth metal halides. One preferred embodiment comprises a bath containing molten KCl, NaCl, and LiCl in proportions approximating the triple eutectic.

Petrogenesis of Pliocene Alkaline Volcanic Rocks from Southeastern Styrian Basin, Austria

NASA Astrophysics Data System (ADS)

Ali, Sh.; Ntaflos, Th.

2009-04-01

Petrogenesis of Pliocene Alkaline Volcanic Rocks from Southeastern Styrian Basin, Austria Sh. Ali and Th. Ntaflos Dept. of Lithospheric Research, University of Vienna, Austria Neogene volcanism in the Alpine Pannonian Transition Zone occurred in a complex geodynamic setting. It can be subdivided into a syn-extentional phase that comprises Middle Miocene dominantly potassic, intermediate to acidic volcanism and a post-extensional phase, which is characterized by eruption of alkaline basaltic magmas during the Pliocene to Quartenary in the Styrian Basin. These alkaline basaltic magmas occur as small eruptive centers dominating the geomorphology of the southeastern part of the Styrian Basin. The eruptive centers along the SE Styrian Basin from North to South are: Oberpullendorf, Pauliberg, Steinberg, Strandenerkogel, Waltrafelsen and Klöch. The suite collected volcanic rocks comprise alkali basalts, basanites and nephelinites. Pauliberg: consists of alkali basalts that exhibit a narrow range of SiO2 (44.66-47.70 wt %) and wide range of MgO (8.52-13.19-wt %), are enriched in TiO2 (3.74-4.18 wt %). They are enriched in incompatible trace elements such as Zr (317-483 ppm), Nb (72.4-138 ppm) and Y (30.7-42 ppm). They have Nb/La ratio of 1.89 (average) and Cen/Ybn=15.22-23.11. Oberpullendorf: it also consists of alkali basalts with higher SiO2 (50.39 wt %) and lower TiO2 (2.80 wt %) if compared with the Pauliberg suite. Incompatible trace elements are lower than in Pauliberg; Zr =217 ppm, Nb=49.8 ppm, Y=23.6 ppm and Nb/La=1.93. The Oberpullendorf alkalibasalts are relative to Pauliberg lavas more depleted in LREE (Cen/Ybn=12.78). Steinberg: it consists of basanites with SiO2=44.49-46.85 wt %, MgO=6.30-9.13-wt %, and TiO2 =2.09-2.26 wt %. They are enriched in incompatible trace elements such as Zr (250-333 ppm), Nb (94-130 ppm), Y (24.7-31.9 ppm) and Nb/La=1.59 (average). The Cen/Ybn ratio varies between 18.17 and 22.83 indicating relative steep REE chondrite normalized patterns. Strandenerkogel: it consists of nephelinites with narrow compositional ranges; SiO2 =40.99-42.44 wt %, MgO=6.63-6.92 wt % and TiO2=2.03-2.07 wt %. They are enriched in incompatible trace elements such as Zr (362-382 ppm), Nb (139-153 ppm) and Y (39.5-40.7 ppm). They have Nb/La ratio of 1.20 and are strongly enriched in LREE (Cen/Ybn=25.04-28.11). Waltrafelsen: there are like in Strandenerkogel and have SiO2=42.42 wt %, MgO=6.55 wt %, and TiO2=2.01 wt %. The incompatible trace elements such as Zr (362 ppm), Nb (145 ppm) and Y (38.3 ppm) are similar to that of Stranerkogel. They have Nb/La ratio of 1.27 and are strongly enriched in LREE (Cen/Ybn=24.92). Klöch: it consists of basanites with similar to Steinberg composition (SiO2=45.34-46.60 wt %, MgO=8.98-10.11 wt %, and TiO2= 2.28-2.37 wt %. Incompatible trace elements such as Zr (252-273 ppm), Nb (94.2-101 ppm) and Y (24.4-27.2 ppm) are high. They have Nb/La ratio of 1.71 (average). Their REE abundances compared to Steinberg are slightly lower (Cen/Ybn=18.19-20.17). The Nb/La ratio of all the studied rock varieties is greater than one indicates an OIB-like asthenospheric mantle source for the basaltic magma. All the studied rock varieties except alkali basalts of Pauliberg have Tbn/Ybn ratios which are comparable to those of the alkali basalts of Hawaii ((Tbn/Ybn range from 1.89 to 2.45); the Hawaiian basalts are considered to have been derived from a garnet-lherzolite mantle source (Frey et al. 1991; McKenzie & O'Nions, 1991). The chondrite normalized HREE abundances indicate the presence of garnet as a residual phase in the melt source region as can be inferred from the Dy/Yb ratio (average 2.93) which is greater than that of chondritic Dy/Yb ratio (1.57) All the studied rock varieties display alkaline affinity and negative K-anomaly. The negative K-anomaly suggests either a source character, (e.g. frozen HIMU-like veins or pockets in the depleted lherzolite)? or it is consistent with the presence of a K-bearing hydrous phase in the residual mantle. References FREY, F. A., GARCIA, M. O., WISE, W. S., KENNEDY, A., GURRIET, P. & ALBAREDE, F. 1991. The evolution of Mauna Kea volcano, Hawaii: Petrogenesis of tholeiitic and alkali basalts. Journal of Geophysical Research 96, 14347-75. MCKENZIE, D. P. & O'NIONS, R. K. 1991. Partial melting distributions from inversion of rare earth element concentrations. Journal of Petrology 32, 1021-91.

Crystallization conditions and controls on trace element residence in the main minerals from the Pedra Branca Syenite, Brazil: An electron microprobe and LA-ICPMS study

NASA Astrophysics Data System (ADS)

Carvalho, Bruna Borges; Janasi, Valdecir de Assis

2012-11-01

Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite ± hornblende + ilmenite ± magnetite + titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of ~ 1060-1090 °C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 kbar. Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilmss. In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts ~ 50% of whole-rock Sr and ~ 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2 +) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization.

Recent Advances on Sodium-Oxygen Batteries: A Chemical Perspective.

PubMed

Yadegari, Hossein; Sun, Xueliang

2018-06-19

Releasing greenhouse gases into the atmosphere because of widespread use of fossil fuels by humankind has resulted in raising the earth's temperature during the past few decades. Known as global warming, increasing the earth's temperature may in turn endanger civilization on the earth by starting a cycle of environmental changes including climate change and sea level rise. Therefore, replacing fossil fuels with more sustainable energy resources has been considered as one of the main strategies to tackle the global warming crisis. In this regard, energy saving devices are required to store the energy from sustainable resources like wind and solar when they are available and deliver them on demand. Moreover, developing plug-in electric vehicles (PEVs) as an alternative for internal combustion engines has been extensively pursued, since a major sector of fossil fuels is used for transportation purposes. However, currently available battery systems fail to meet the required demands for energy storage. Alkali metal-O 2 battery systems demonstrate a promising prospect as a high-energy density solution regarding the increasing demand of mankind for energy storage. Combining a metallic negative electrode with a breathing oxygen electrode, a metal-O 2 cell can be considered as a half battery/half fuel cell system. The negative electrode in the metal-O 2 cells operates a conversion reaction rather than intercalation mechanism, which eliminates the need for a host lattice. In addition, the positive electrode material (O 2 ) comes from the ambient air and hence is not stored in the battery. Therefore, the resultant battery systems exhibit the highest theoretical energy density, which is comparable to that of gasoline. Accordingly, an unprecedented amount of research activity was directed toward alkali metal-O 2 batteries in the past decade in response to the need for high-energy storage technology in electric transportation. This extensive research surge has resulted in a rapid expansion of our knowledge about alkali metal-O 2 batteries. The present Account summarizes the most recent findings over the underlying chemistry of all components in Na-O 2 cells as one of the most efficient members of alkali metal-O 2 family.

Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

PubMed

Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2017-10-05

We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se 2 solar cells on glass substrate

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

Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo

The precise control of alkali-metal concentrations in Cu(In,Ga)Se 2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance frommore » the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.« less

Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se 2 solar cells on glass substrate

DOE PAGES

Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo; ...

2018-03-07

The precise control of alkali-metal concentrations in Cu(In,Ga)Se 2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance frommore » the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.« less

Distribution and grain-size partitioning of metals in bovfom sediments of an experimentally acidified Wisconsin lake

USGS Publications Warehouse

Elder, John F.

2007-01-01

A study of concentrations and distribution of major and trace elements in surficial bottom sediments of Little Rock Lake in northern Wisconsin included examination of spatial variation and grain-size effects. No significant differences with respect to metal distribution in sediments were observed between the two basins of the lake, despite the experimental acidification of one of the basins from pH 6.1 to 4.6. The concentrations of most elements in the lake sediments were generally similar to soil concentrations in the area and were well below sediment quality criteria. Two exceptions were lead and zinc, whose concentrations in July 1990 exceeded the criteria of 50 μg/g and 100 μg/g, respectively, in both littoral and pelagic sediments. Concentrations of some elements, particularly Cu, Pb, and Zn, increased along transects from nearshore to midlake, following a similar gradient of sedimentary organic carbon. In contrast, Mn, Fe, and alkali/alkaline-earth elements were at maximum concentrations in nearshore sediments. These elements are less likely to partition to organic particles, and their distribution is more dependent on mineralogical composition, grain size, and other factors. Element concentrations varied among different sediment grain-size fractions, although a simple inverse relation to grain size was not observed. Fe, Mn, Pb, and Zn were more concentrated in a grain-size range 20–60 tm than in either the very fine or the coarse fractions, possibly because of the aggregation of smaller particles cemented together by organic and Fe/Mn hydrous-oxide coatings.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-24

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Recovery of UO[sub 2]/PuO[sub 2] in IFR electrorefining process

DOEpatents

Tomczuk, Z.; Miller, W.E.

1994-10-18

A process is described for converting PuO[sub 2] and UO[sub 2] present in an electrorefiner to the chlorides, by contacting the PuO[sub 2] and UO[sub 2] with Li metal in the presence of an alkali metal chloride salt substantially free of rare earth and actinide chlorides for a time and at a temperature sufficient to convert the UO[sub 2] and PuO[sub 2] to metals while converting Li metal to Li[sub 2]O. Li[sub 2]O is removed either by reducing with rare earth metals or by providing an oxygen electrode for transporting O[sub 2] out of the electrorefiner and a cathode, and thereafter applying an emf to the electrorefiner electrodes sufficient to cause the Li[sub 2]O to disassociate to O[sub 2] and Li metal but insufficient to decompose the alkali metal chloride salt. The U and Pu and excess lithium are then converted to chlorides by reaction with CdCl[sub 2].

Recovery of UO.sub.2 /Pu O.sub.2 in IFR electrorefining process

DOEpatents

Tomczuk, Zygmunt; Miller, William E.

1994-01-01

A process for converting PuO.sub.2 and UO.sub.2 present in an electrorefiner to the chlorides, by contacting the PuO.sub.2 and UO.sub.2 with Li metal in the presence of an alkali metal chloride salt substantially free of rare earth and actinide chlorides for a time and at a temperature sufficient to convert the UO.sub.2 and PuO.sub.2 to metals while converting Li metal to Li.sub.2 O. Li.sub.2 O is removed either by reducing with rare earth metals or by providing an oxygen electrode for transporting O.sub.2 out of the electrorefiner and a cathode, and thereafter applying an emf to the electrorefiner electrodes sufficient to cause the Li.sub.2 O to disassociate to O.sub.2 and Li metal but insufficient to decompose the alkali metal chloride salt. The U and Pu and excess lithium are then converted to chlorides by reaction with CdCl.sub.2.

UV-active plasmons in alkali and alkaline-earth intercalated graphene

NASA Astrophysics Data System (ADS)

Despoja, V.; Marušić, L.

2018-05-01

The interband π and π +σ plasmons in pristine graphene and the Dirac plasmon in doped graphene are not applicable, since they are broad or weak, and weakly couple to an external longitudinal or electromagnetic probe. Therefore, the ab initio density functional theory is used to demonstrate that the chemical doping of the graphene by the alkali or alkaline-earth atoms dramatically changes the poor graphene excitation spectrum in the ultraviolet frequency range (4-10 eV). Four prominent modes are detected. Two of them are the intralayer plasmons with square-root dispersion, characteristic of the two-dimensional modes. The remaining two are the interlayer plasmons, very strong in the long-wavelength limit but damped for larger wave vectors. The optical absorption calculations show that the interlayer plasmons are both optically active, which makes these materials suitable for small-organic-molecule sensing. This is particularly intriguing because the optically active two-dimensional plasmons have not been detected in other materials.

Hydrogen and syngas production by catalytic gasification of algal biomass (Cladophora glomerata L.) using alkali and alkaline-earth metals compounds.

PubMed

Ebadi, Abdol Ghaffar; Hisoriev, Hikmat; Zarnegar, Mohammad; Ahmadi, Hamed

2018-01-02

The steam gasification of algal biomass (Cladophora glomerata L.) in presence of alkali and alkaline-earth metal compounds catalysts was studied to enhance the yield of syngas and reduce its tar content through cracking and reforming of condensable fractions. The commercial catalysts used include NaOH, KHCO 3 , Na 3 PO 4 and MgO. The gasification runs carried out with a research scale, biomass gasification unit, show that the NaOH has a strong potential for production of hydrogen, along with the added advantages of char converting and tar destruction, allowing enhancement of produced syngas caloric value. When the temperature increased from 700°C to 900°C, the tar content in the gas sharply decreased, while the hydrogen yield increased. Increasing steam/biomass ratio significantly increased hydrogen yield and tar destruction; however, the particle size in the range of 0.5-2.5 mm played a minor role in the process.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1993-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

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

Capillary electrochromatography of inorganic cations in open tubular columns with a controllable capacity multilayered stationary phase architecture.

PubMed

Kubán, Pavel; Kubán, Petr; Kubán, Vlastimil; Hauser, Peter C; Bocek, Petr

2008-05-09

In this paper capillary electrochromatography of alkali and alkaline-earth metal cations in open tubular capillary columns is described. Capillary columns are prepared by coating fused silica capillaries of 75 microm I.D. with poly(butadiene-maleic acid) copolymer (PBMA) in multiple layers. Thermally initiated radical polymerization is used to crosslink the stationary phase. Capillary columns with different number of stationary phase layers can be prepared and allow for the adjustment of separation selectivity in the electrochromatographic mode. Fast and sensitive separations of common inorganic cations are achieved in less than 6 min in a 60 cm capillary column with on-column capacitively coupled contactless conductivity detector. Limits of detection (S/N=3) for the determination of alkali and alkaline-earth metal cations range from 0.3 to 2.5 microM and repeatability is better than 0.5, 4.5 and 6.1% for migration times, peak heights and peak areas, respectively.

PROCESSING OF URANIUM-METAL-CONTAINING FUEL ELEMENTS

DOEpatents

Moore, R.H.

1962-10-01

A process is given for recovering uranium from neutronbombarded uranium- aluminum alloys. The alloy is dissolved in an aluminum halide--alkali metal halide mixture in which the halide is a mixture of chloride and bromide, the aluminum halide is present in about stoichiometric quantity as to uranium and fission products and the alkali metal halide in a predominant quantity; the uranium- and electropositive fission-products-containing salt phase is separated from the electronegative-containing metal phase; more aluminum halide is added to the salt phase to obtain equimolarity as to the alkali metal halide; adding an excess of aluminum metal whereby uranium metal is formed and alloyed with the excess aluminum; and separating the uranium-aluminum alloy from the fission- productscontaining salt phase. (AEC)

Electronic structure of clathrates Bax@AlySi46-y ; thermoelectric devices

NASA Astrophysics Data System (ADS)

Eguchi, Haruki; Nagano, Takatoshi; Takenaka, Hiroyuki; Tsumuraya, Kazuo

2002-03-01

Clathrates have received much attention as a candidate of high performance thermoelectric devices. This is because they have a) low thermal conductivity due to rattle effect of the alkali or heavy alkali-earth metals such as Ba atoms in the cages of clusters of the clathrates, and b) adjustablity of the Fermi levels through replacement of frame Si atoms with acceptor Al atoms and addition of the cage atoms as donors. We present the dispersion curves with LDA and GGA approximations for the exchange correlation of electrons using the planewave based pseudopotential methods and predict the electronic properties of the clathrates.

SOx/NOx sorbent and process of use

DOEpatents

Ziebarth, M.S.; Hager, M.J.; Beeckman, J.W.; Plecha, S.

1993-01-19

An alumina sorbent capable of adsorbing NOx and SOx from waste gases and being regenerated by heating above 600 C. is made by incorporating an alumina stabilizing agent into the sorbent. A preferred method is to add the stabilizer when the alumina is precipitated. The precipitated powder is formed subsequently into a slurry, milled and dripped to form the stabilizing spheroidal alumina particles. These particles are impregnated with an alkali metal or alkaline earth metal to form the stabilized sorbent. Alumina stabilizers include one or more of silica, lanthana, other rare earths, titania, zirconia and alkaline earths.

SOX/NOX sorbent and process of use

DOEpatents

Ziebarth, M.S.; Hager, M.J.; Beeckman, J.W.; Plecha, S.

1995-05-09

An alumina sorbent capable of adsorbing NOx and SOx from waste gases and being regenerated by heating above 600 C is made by incorporating an alumina stabilizing agent into the sorbent. A preferred method is to add the stabilizer when the alumina is precipitated. The precipitated powder is formed subsequently into a slurry, milled and dripped to form the stabilized spheroidal alumina particles. These particles are impregnated with an alkali metal or alkaline earth metal to form the stabilized sorbent. Alumina stabilizers include one or more of silica, lanthana, other rare earths, titania, zirconia and alkaline earths. 3 figs.

SOX/NOX sorbent and process of use

DOEpatents

Ziebarth, Michael S.; Hager, Michael J.; Beeckman, Jean W.; Plecha, Stanislaw

1995-01-01

An alumina sorbent capable of adsorbing NOx and SOx from waste gases and being regenerated by heating above 600.degree. C. is made by incorporating an alumina stabilizing agent into the sorbent. A preferred method is to add the stabilizer when the alumina is precipitated. The precipitated powder is formed subsequently into a slurry, milled and dripped to form the stabilized spheroidal alumina particles. These particles are impregnated with an alkali metal or alkaline earth metal to form the stabilized sorbent. Alumina stabilizers include one or more of silica, lanthana, other rare earths, titania, zirconia and alkaline earths.

SOx/NOx sorbent and process of use

DOEpatents

Ziebarth, Michael S.; Hager, Michael J.; Beeckman, Jean W.; Plecha, Stanislaw

1993-01-19

An alumina sorbent capable of adsorbing NOx and SOx from waste gases and being regenerated by heating above 600.degree. C. is made by incorporating an alumina stabilizing agent into the sorbent. A preferred method is to add the stabilizer when the alumina is precipitated. The precipitated powder is formed subsequently into a slurry, milled and dripped to form the stabilizing spheroidal alumina particles. These particles are impregnated with an alkali metal or alkaline earth metal to form the stabilized sorbent. Alumina stabilizers include one or more of silica, lanthana, other rare earths, titania, zirconia and alkaline earths.

Research on the properties and interactions of simple atomic and ionic systems

NASA Technical Reports Server (NTRS)

Novick, R.

1972-01-01

Simple ionic systems were studied, such as metastable autoionizing states of the negative He ion, two-photon decay spectrum of metastable He ion, optical excitation with low energy ions, and lifetime measurements of singly ionized Li and metastable He ion. Simple atomic systems were also investigated. Metastable autoionizing atomic energy levels in alkali elements were included, along with lifetime measurements of Cr-53, group 2A isotopes, and alkali metal atoms using level crossing and optical double resonance spectroscopy.

Beryl pegmatite at Jabal Tarban, southern Najd region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Jackson, Norman J.

Beryl pegmatite near Jabal Tarban forms a carapace on a small stock of alkali-feldspar microgranite. Geological, petrographic and geochemical features indicate a genetic relationship between pegmatite and microgranite. Crystallization of quartz and alkali feldspar from a low-Ca granitic magma resulted in formation of a residuum enriched in rare elements. Silica separated from this residuum to form a pegmatitic carapace over the stock; the remainder crystallized as the fine-grained albite-rich groundmass of the microgranite.

Non-Adiabatic Atomic Transitions: Computational Cross Section Calculations of Alkali Metal-Noble Gas Collisions

DTIC Science & Technology

2011-09-01

there a one time transfer of prob- ability between Coriolis coupled states. One possible way to answer this question would be to literally create and... time -dependent numerical algorithm was developed using FORTRAN 90 to predict S-Matrix elements for alkali metal - noble gas (MNg) collisions. The...committee and the physics department for their time and effort to see me through the completion of my doctorate degree. Charlton D. Lewis, II v Table of

Model potentials for main group elements Li through Rn

NASA Astrophysics Data System (ADS)

Sakai, Yoshiko; Miyoshi, Eisaku; Klobukowski, Mariusz; Huzinaga, Sigeru

1997-05-01

Model potential (MP) parameters and valence basis sets were systematically determined for the main group elements Li through Rn. For alkali and alkaline-earth metal atoms, the outermost core (n-1)p electrons were treated explicitly together with the ns valence electrons. For the remaining atoms, only the valence ns and np electrons were treated explicitly. The major relativistic effects at the level of Cowan and Griffin's quasi-relativistic Hartree-Fock method (QRHF) were incorporated in the MPs for all atoms heavier than Kr. The valence orbitals thus obtained have inner nodal structure. The reliability of the MP method was tested in calculations for X-, X, and X+ (X=Br, I, and At) at the SCF level and the results were compared with the corresponding values given by the numerical HF (or QRHF) calculations. Calculations that include electron correlation were done for X-, X, and X+ (X=Cl and Br) at the SDCI level and for As2 at the CASSCF and MRSDCI levels. These results were compared with those of all-electron (AE) calculations using the well-tempered basis sets. Close agreement between the MP and AE results was obtained at all levels of the treatment.

Origin of Transitions between Metallic and Insulating States in Simple Metals

DOE PAGES

Naumov, Ivan I.; Hemley, Russell J.

2015-04-17

Unifying principles that underlie recently discovered transitions between metallic and insulating states in elemental solids under pressure are developed. Using group theory arguments and first principles calculations, we show that the electronic properties of the phases involved in these transitions are controlled by symmetry principles not previously recognized. The valence bands in these systems are described by simple and composite band representations constructed from localized Wannier functions centered on points unoccupied by atoms, and which are not necessarily all symmetrical. The character of the Wannier functions is closely related to the degree of s-p(-d) hybridization and reflects multi-center chemical bondingmore » in these insulating states. The conditions under which an insulating state is allowed for structures having an integer number of atoms per primitive unit cell as well as re-entrant (i.e., metal-insulator-metal) transition sequences are detailed, resulting in predictions of novel behavior such as phases having three-dimensional Dirac-like points. The general principles developed are tested and applied to the alkali and alkaline earth metals, including elements where high-pressure insulating phases have been identified or reported (e.g., Li, Na, and Ca).« less

A hybrid composite dike suite from the northern Arabian Nubian Shield, southwest Jordan: Implications for magma mixing and partial melting of granite by mafic magma

NASA Astrophysics Data System (ADS)

Jarrar, Ghaleb H.; Yaseen, Najel; Theye, Thomas

2013-03-01

The Arabian Nubian Shield is an exemplary juvenile continental crust of Neoproterozoic age (1000-542 Ma). The post-collisional rift-related stage (~ 610 to 542 Ma) of its formation is characterized among others by the intrusion of several generations of simple and composite dikes. This study documents a suite of hybrid composite dikes and a natural example of partial melting of granite by a mafic magma from the northernmost extremity of Arabian Nubian Shield in southwest Jordan. The petrogenesis of this suite is discussed on the basis of field, petrographic, geochemical, and Rb/Sr isotopic data. These dikes give spectacular examples of the interaction between basaltic magma and the granitic basement. This interaction ranges from brecciation, partial melting of the host alkali feldspar granite to complete assimilation of the granitic material. Field structures range from intrusive breccia (angular partially melted granitic fragments in a mafic groundmass) to the formation of hybrid composite dikes that are up to 14 m in thickness. The rims of these dikes are trachyandesite (latite) with alkali feldspar ovoids (up to 1 cm in diameter); while the central cores are trachydacite to dacite and again with alkali feldspar ovoids and xenoliths from the dike rims. The granitic xenoliths in the intrusive breccia have been subjected to at least 33% partial melting. A seven-point Rb/Sr isochron from one of these composite dikes yields an age of 561 ± 33 Ma and an initial 87Sr/86Sr ratio of 0.70326 ± 0.0003 (2σ) and MSWD of 0.62. Geochemical modeling using major, trace, rare earth elements and isotopes suggests the generation of the hybrid composite dike suite through the assimilation of 30% to 60% granitic crustal material by a basaltic magma, while the latter was undergoing fractional crystallization at different levels in the continental crust.

Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

PubMed

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2016-08-01

Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in [4]- and [6]-coordination, Na(+) in [4]- and [6]-coordination. For alkali-metal and alkaline-earth-metal ions, there is a positive correlation between cation coordination number and the grand mean incident bond-valence sum at the central cation, the values varying from 0.84 v.u. for ([5])K(+) to 1.06 v.u. for ([8])Li(+), and from 1.76 v.u. for ([7])Ba(2+) to 2.10 v.u. for ([12])Sr(2+). Bond-valence arguments suggest coordination numbers higher than [12] for K(+), Rb(+), Cs(+) and Ba(2+).

Timing and composition of continental volcanism at Harrat Hutaymah, western Saudi Arabia

USGS Publications Warehouse

Duncan, Robert A.; Kent, Adam J R; Thornber, Carl; Schliedler, Tyler D; Al-Amri, Abdullah M

2016-01-01

Harrat Hutaymah is an alkali basalt volcanic field in north-central Saudi Arabia, at the eastern margin of a large Neogene continental, intraplate magmatic province. Lava flow, tephra and spatter cone compositions in the field include alkali olivine basalts and basanites. These compositions contrast with the predominantly tholeiitic, fissure-fed basalts found along the eastern margin of the Red Sea. The Hutaymah lava flows were erupted through Proterozoic arc-associated plutonic and meta-sedimentary rocks of the Arabian shield, and commonly contain a range of sub-continental lithospheric xenoliths, although the lavas themselves show little indication of crustal contamination. Previous radiometric dating of this volcanic field (a single published K–Ar age; 1.8 Ma) is suspiciously old given the field measurement of normal magnetic polarity only (i.e. Brunhes interval, ≤ 780 Ka). We report new age determinations on 14 lava flows by the 40Ar–39Ar laser step heating method, all younger than ~ 850 Ka, to better constrain the time frame of volcanism, and major, trace and rare earth element compositions to describe the chemical variation of volcanic activity at Harrat Hutaymah. Crystal fractionation was dominated by olivine ± clinopyroxene at a range of upper mantle and crustal pressures. Rapid ascent and eruption of magma is indicated by the array of lower crustal and lithospheric xenoliths observed in lava flows and tephra. Modeling suggests 1–7% melting of an enriched asthenospheric mantle source occurred beneath Harrat Hutaymah under a relatively thick lithospheric cap (60–80 km).

Timing and composition of continental volcanism at Harrat Hutaymah, western Saudi Arabia

NASA Astrophysics Data System (ADS)

Duncan, Robert A.; Kent, Adam J. R.; Thornber, Carl R.; Schlieder, Tyler D.; Al-Amri, Abdullah M.

2016-03-01

Harrat Hutaymah is an alkali basalt volcanic field in north-central Saudi Arabia, at the eastern margin of a large Neogene continental, intraplate magmatic province. Lava flow, tephra and spatter cone compositions in the field include alkali olivine basalts and basanites. These compositions contrast with the predominantly tholeiitic, fissure-fed basalts found along the eastern margin of the Red Sea. The Hutaymah lava flows were erupted through Proterozoic arc-associated plutonic and meta-sedimentary rocks of the Arabian shield, and commonly contain a range of sub-continental lithospheric xenoliths, although the lavas themselves show little indication of crustal contamination. Previous radiometric dating of this volcanic field (a single published K-Ar age; 1.8 Ma) is suspiciously old given the field measurement of normal magnetic polarity only (i.e. Brunhes interval, ≤ 780 Ka). We report new age determinations on 14 lava flows by the 40Ar-39Ar laser step heating method, all younger than ~ 850 Ka, to better constrain the time frame of volcanism, and major, trace and rare earth element compositions to describe the chemical variation of volcanic activity at Harrat Hutaymah. Crystal fractionation was dominated by olivine ± clinopyroxene at a range of upper mantle and crustal pressures. Rapid ascent and eruption of magma is indicated by the array of lower crustal and lithospheric xenoliths observed in lava flows and tephra. Modeling suggests 1-7% melting of an enriched asthenospheric mantle source occurred beneath Harrat Hutaymah under a relatively thick lithospheric cap (60-80 km).

Elemental mercury contamination survey in a chlor-alkali plant by the use of transplanted Spanish moss, Tillandsia usneoides (L.).

PubMed

Calasans, C F; Malm, O

1997-12-22

Atmospheric Hg0 contamination and the potential risk of occupational exposure were evaluated in a chlor-alkali facility by the use of transplanted Tillandsia usneoides. This plant species was selected since it presents some features that makes it useful for air monitoring purposes. After short-term exposure (15 days), control plants showed a mean concentration of 0.2 microgram Hg.g-1 whereas Hg values in transplants ranged from 1 to 10,400 micrograms.g-1. This latter value was observed near an elemental Hg spillage. Even after exposure to toxic conditions plant metabolism was still operative, allowing the transplant technique to be employed to assess both Hg taken up through the stomata and Hg associated with particles deposited on the biomonitor.

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

Proceedings of the Air Force Geophysics Laboratory Workshop on the Earth’s Radiation Belts: 26-27 January 1981.

DTIC Science & Technology

1981-10-21

characteristics of five types of magnetometers flown on spacecraft. These are: (1) search coils, (2) fluxgates , (3)proton precession, (4) alkali vapor and... Fluxgate magnetometers are most useful for measuring the dc magnetic field of the earth as well as its low frequency (:s 100 Hz) fluctuations...Characteristics of fluxgates are discussed in detail in the paragraphs immediately following. The last three types of magnetometers provide very high resolution

K-Ca Dating of Alkali-Rich Fragments in the Y-74442 and Bhola LL-Chondritic Breccias

NASA Technical Reports Server (NTRS)

Yokoyama, T; Misawa, K.; Okano, O; Shih, C. -Y.; Nyquist, L. E.; Simon, J. I.; Tappa, M. J.; Yoneda, S.

2013-01-01

Alkali-rich igneous fragments in the brecciated LL-chondrites, Krahenberg (LL5) [1], Bhola (LL3-6) [2], Siena (LL5) [3] and Yamato (Y)-74442 (LL4) [4-6], show characteristic fractionation patterns of alkali and alkaline elements [7]. The alkali-rich fragments in Krahenberg, Bhola and Y-74442 are very similar in mineralogy and petrography, suggesting that they could have come from related precursor materials [6]. Recently we reported Rb-Sr isotopic systematics of alkali-rich igneous rock fragments in Y-74442: nine fragments from Y-74442 yield the Rb-Sr age of 4429 plus or minus 54 Ma (2 sigma) for lambda(Rb-87) = 0.01402 Ga(exp -1) [8] with the initial ratio of Sr-87/Sr-86 = 0.7144 plus or minus 0.0094 (2 sigma) [9]. The Rb-Sr age of the alkali-rich fragments of Y-74442 is younger than the primary Rb-Sr age of 4541 plus or minus 14 Ma for LL-chondrite whole-rock samples [10], implying that they formed after accumulation of LL-chondrite parental bodies, although enrichment may have happened earlier. Marshall and DePaolo [11,12] demonstrated that the K-40 - Ca-40 decay system could be an important chronometer as well as a useful radiogenic tracer for studies of terrestrial rocks. Shih et al. [13,14] and more recently Simon et al. [15] determined K-Ca ages of lunar granitic rocks, and showed the application of the K-Ca chronometer for K-rich planetary materials. Since alkali-rich fragments in the LL-chondritic breccias are highly enriched in K, we can expect enhancements of radiogenic Ca-40. Here, we report preliminary results of K-Ca isotopic systematics of alkali-rich fragments in the LL-chondritic breccias, Y-74442 and Bhola.

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

Mineral resource of the month: rare earth elements

USGS Publications Warehouse

,

2011-01-01

The article provides information on rare earth elements, which are group of 17 natural metallic elements. The rare earth elements are scandium, yttrium and lanthanides and classified into light rare earth elements (LREE) and heavy rate earth elements (HREE). The principal ores of the rare earth elements are identified. An overview of China's production of 97 percent of the rare earths in the world is provided. Commercial applications of rare earths are described.

The Use of an Air-Natural Gas Flame in Atomic Absorption.

ERIC Educational Resources Information Center

Melucci, Robert C.

1983-01-01

Points out that excellent results are obtained using an air-natural gas flame in atomic absorption experiments rather than using an air-acetylene flame. Good results are obtained for alkali metals, copper, cadmium, and zinc but not for the alkaline earths since they form refractory oxides. (Author/JN)

PROCESS OF PRODUCING ACTINIDE METALS

DOEpatents

Magel, T.T.

1959-07-14

The preparation of actinide metals in workable, coherent form is described. In general, the objects of the invention are achieved by heating a mixture of an oxide and a halide of an actinide metal such as uranium with an alkali metal on alkaline earth metal reducing agent in the presence of iodine.

Analyzing Solutions High in Total Dissolved Solids for Rare Earth Elements (REEs) Using Cation Exchange and Online Pre-Concentration with the seaFAST2 Unit; NETL-TRS-7-2017; NETL Technical Report Series; U.S. Department of Energy, National Energy Technology Laboratory: Albany, OR, 2017; p 32

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

Yang, J.; Torres, M.; Verba, C.

The accurate quantification of the rare earth element (REE) dissolved concentrations in natural waters are often inhibited by their low abundances in relation to other dissolved constituents such as alkali, alkaline earth elements, and dissolved solids. The high abundance of these constituents can suppress the overall analytical signal as well as create isobaric interferences on the REEs during analysis. Waters associated with natural gas operations on black shale plays are characterized by high salinities and high total dissolved solids (TDS) contents >150,000 mg/L. Methods used to isolate and quantify dissolved REEs in seawater were adapted in order to develop themore » capability of analyzing REEs in waters that are high in TDS. First, a synthetic fluid based on geochemical modelling of natural brine formation fluids was created within the Marcellus black shale with a TDS loading of 153,000 mg/L. To this solution, 1,000 ng/mL of REE standards was added based on preliminary analyses of experimental fluids reacted at high pressure and temperature with Marcellus black shale. These synthetic fluids were then run at three different dilution levels of 10, 100, and 1,000–fold dilutions through cation exchange columns using AG50-X8 exchange resin from Eichrom Industries. The eluent from the cation columns were then sent through a seaFAST2 unit directly connected to an inductively coupled plasma mass spectrometer (ICP-MS) to analyze the REEs. Percent recoveries of the REEs ranged from 80–110% and fell within error for the external reference standard used and no signal suppression or isobaric interferences on the REEs were observed. These results demonstrate that a combined use of cation exchange columns and seaFAST2 instrumentation are effective in accurately quantifying the dissolved REEs in fluids that are >150,000 mg/L in TDS and have Ba:Eu ratios in excess of 380,000.« less

Low-δ13C carbonates in the Miocene basalt of the northern margin of the North China Craton: Implications for deep carbon recycling

NASA Astrophysics Data System (ADS)

Zhang, Huiting; Liu, Yongsheng; Hu, Zhaochu; Zong, Keqing; Chen, Haihong; Chen, Chunfei

2017-08-01

Three types of carbonates have been found in the Miocene basalt in the Dongbahao area (Inner Mongolia), including wide veins and veinlets of carbonate in basalt and carbonates in peridotite xenoliths. Except for the dolomitic zonation in the basalt, all of the carbonates are calcite. Despite their different appearances, they share almost identical geochemical characteristics of low LILE (low large ion lithophile element), HFSE (high field strength element), and REE (rare earth elements) contents (ΣREE = 0.51-137 ppm); negative Ce anomalies; and low Ce/Pb ratios (0.51-74.5). Moreover, they show high δ18OSMOW values (20.95-22.61‰) and 87Sr/86Sr ratios (0.7087 ± 0.0003 (1σ, n = 17)). These characteristics indicate a sedimentary precursor for these carbonates. However, the occurrence and petrographic characteristics imply an igneous origin for the carbonates rather than a hypergene process. Further, the trace element compositions of the silicate melt and carbonate melt in the calcite-dolomite-silicate zonations fall on the same variation lines in the plots of Y-Ho, La-Yb, Li-Pb and Ba-Cu. It is suggested that these melts could have evolved from one magma system or could have been equilibrated. Given the partition coefficients of REEs and alkali elements (Cs, Rb, and K) between the carbonate melt and silicate melt, it can be inferred that these melts could have been formed from a primary H2O-Si-bearing Mg-Ca-carbonate melt by an immiscibility process at 1-3 GPa. Considering the southward subduction of the Paleo-Asian ocean along the northern margin of the North China Craton (NCC), these carbonate melts could have been derived from the melting of subducted sedimentary carbonate rocks. Interestingly, these carbonates have quite depleted carbon isotopic compositions (δ13CPDB = -8.23‰ to -11.76‰) but moderate δ18OSMOW values, implying coupled H2O-CO2 degassing during subduction and/or recycling to the Earth's surface. Low-δ13CPBD carbonates appearing at the global scale may suggest an underestimated path of CO2 emission back to the atmosphere.

OSL studies of alkali fluoroperovskite single crystals for radiation dosimetry

NASA Astrophysics Data System (ADS)

Daniel, D. Joseph; Raja, A.; Madhusoodanan, U.; Annalakshmi, O.; Ramasamy, P.

2016-08-01

This paper presents a preliminary investigation of the optically stimulated luminescence (OSL) of alkali fluoroperovskite single crystals for radiation dosimetry. The perovskite-like KMgF3, NaMgF3 and LiBaF3 polycrystalline compounds doped with rare earths (Eu2+ and Ce3+) were synthesized by standard solid state reaction technique. Phase purity of the synthesized compounds was analyzed by powder X-ray diffraction technique. Single crystals of these compounds have been grown from melt by using vertical Bridgman-Stockbarger method. The Linearly Modulated OSL and Continuous Wave OSL measurements were performed in these alkali fluorides using blue light stimulation. Thermal bleaching experiments have shown that OSL signals originate from traps which are unstable near 200 °C, thus proving the suitability of the signals for dosimetric purposes. Optical bleaching measurements were also performed for these fluoride samples. OSL dose response was studied as a function of dose which was found to increase with beta dose.

A study of physical and optical absorption spectra of VO{sup 2+} ions in potassium and sodium oxide borate glasses

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

Srinivas, G., E-mail: srinu123g@gmail.com; Ramesh, B.; Kumar, J. Siva

2016-05-23

Spectroscopic and physical properties of V{sub 2}O{sub 5} doped mixed alkali borate glasses are investigated. Borate glasses containing fixed concentrations of alkaline earth oxides (MgO and BaO) and alkali oxides (K{sub 2}O and Na{sub 2}O) were changes and are prepared by melt quenching technique. The values of r{sub i}, r{sub p}, R{sub m}, α{sub m} molar volume and Λ{sub th} increase and oxygen packing density, density and dopant ion concentration decrease with increasing of K{sub 2}O content. As a result there shall be an increase in the disorder of the glass network. The optical band gap energies, Urbach energy, boron-boronmore » separation,refractive index, dielectric constant, electronic polarizability and reflection loss values are varies nonlinearly with the K{sub 2}O content which manifests the mixed alkali effect.« less

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, O.H.; Curtis, P.G.

1992-03-31

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof. 1 figure.

Mercury emissions during cofiring of sub-bituminous coal and biomass (chicken waste, wood, coffee residue, and tobacco stalk) in a laboratory-scale fluidized bed combustor

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

Yan Cao; Hongcang Zhou; Junjie Fan

Four types of biomass (chicken waste, wood pellets, coffee residue, and tobacco stalks) were cofired at 30 wt % with a U.S. sub-bituminous coal (Powder River Basin Coal) in a laboratory-scale fluidized bed combustor. A cyclone, followed by a quartz filter, was used for fly ash removal during tests. The temperatures of the cyclone and filter were controlled at 250 and 150{sup o}C, respectively. Mercury speciation and emissions during cofiring were investigated using a semicontinuous mercury monitor, which was certified using ASTM standard Ontario Hydra Method. Test results indicated mercury emissions were strongly correlative to the gaseous chlorine concentrations, butmore » not necessarily correlative to the chlorine contents in cofiring fuels. Mercury emissions could be reduced by 35% during firing of sub-bituminous coal using only a quartz filter. Cofiring high-chlorine fuel, such as chicken waste (Cl = 22340 wppm), could largely reduce mercury emissions by over 80%. When low-chlorine biomass, such as wood pellets (Cl = 132 wppm) and coffee residue (Cl = 134 wppm), is cofired, mercury emissions could only be reduced by about 50%. Cofiring tobacco stalks with higher chlorine content (Cl = 4237 wppm) did not significantly reduce mercury emissions. Gaseous speciated mercury in flue gas after a quartz filter indicated the occurrence of about 50% of total gaseous mercury to be the elemental mercury for cofiring chicken waste, but occurrence of above 90% of the elemental mercury for all other cases. Both the higher content of alkali metal oxides or alkali earth metal oxides in tested biomass and the occurrence of temperatures lower than 650{sup o}C in the upper part of the fluidized bed combustor seemed to be responsible for the reduction of gaseous chlorine and, consequently, limited mercury emissions reduction during cofiring. 36 refs., 3 figs. 1 tab.« less

Sox/Nox Sorbent And Process Of Use

DOEpatents

Ziebarth, Michael S.; Hager, Michael J.; Beeckman, Jean W.; Plecha, Stanislaw

1995-06-27

An alumina sorbent capable of adsorbing NOx and SOx from waste gases and being regenerated by heating above 650.degree. C. is made by incorporating an alumina stabilizing agent into the sorbent. A preferred method is to add the stabilizer when the alumina is precipitated. The precipitated powder is formed subsequently into a slurry, milled and spray dried to form the stabilized spheroidal alumina particles having a particle size of less than 500 microns. These particles are impregnated with an alkali metal or alkaline earth metal to form the stabilized sorbent. Alumina stabilizers include one or more of silica, lanthana, other rare earths, titania, zirconia and alkaline earths.

Sox/Nox Sorbent And Process Of Use

DOEpatents

Ziebarth, Michael S.; Hager, Michael J.; Beeckman, Jean W.; Plecha, Stanislaw

1996-12-17

An alumina sorbent capable of adsorbing NOx and SOx from waste gases and being regenerated by heating above 650.degree. C. is made by incorporating an alumina stabilizing agent into the sorbent. A preferred method is to add the stabilizer when the alumina is precipitated. The precipitated powder is formed subsequently into a slurry, milled and spray dried to form the stabilized spheroidal alumina particles having a particle size of less than 500 microns. These particles are impregnated with an alkali metal or alkaline earth metal to form the stabilized sorbent. Alumina stabilizers include one or more of silica, lanthana, other rare earths, titania, zirconia and alkaline earths.

METHOD OF SEPARATING TETRAVALENT PLUTONIUM VALUES FROM CERIUM SUB-GROUP RARE EARTH VALUES

DOEpatents

Duffield, R.B.; Stoughton, R.W.

1959-02-01

A method is presented for separating plutonium from the cerium sub-group of rare earths when both are present in an aqueous solution. The method consists in adding an excess of alkali metal carbonate to the solution, which causes the formation of a soluble plutonium carbonate precipitate and at the same time forms an insoluble cerium-group rare earth carbonate. The pH value must be adjusted to bctween 5.5 and 7.5, and prior to the precipitation step the plutonium must be reduced to the tetravalent state since only tetravalent plutonium will form the soluble carbonate complex.

Control of wavepacket dynamics in mixed alkali metal clusters by optimally shaped fs pulses

NASA Astrophysics Data System (ADS)

Bartelt, A.; Minemoto, S.; Lupulescu, C.; Vajda, Š.; Wöste, L.

We have performed adaptive feedback optimization of phase-shaped femtosecond laser pulses to control the wavepacket dynamics of small mixed alkali-metal clusters. An optimization algorithm based on Evolutionary Strategies was used to maximize the ion intensities. The optimized pulses for NaK and Na2K converged to pulse trains consisting of numerous peaks. The timing of the elements of the pulse trains corresponds to integer and half integer numbers of the vibrational periods of the molecules, reflecting the wavepacket dynamics in their excited states.

40 CFR 721.4740 - Alkali metal nitrites.

Code of Federal Regulations, 2010 CFR

2010-07-01

... periodic classification of chemical elements) lithium, sodium, potassium, rubidium, cesium, and francium... defined in 40 CFR 721.3) containing amines. (b) [Reserved] [58 FR 27944, May 12, 1993, as amended at 58 FR...

40 CFR 721.4740 - Alkali metal nitrites.

Code of Federal Regulations, 2011 CFR

2011-07-01

... periodic classification of chemical elements) lithium, sodium, potassium, rubidium, cesium, and francium... defined in 40 CFR 721.3) containing amines. (b) [Reserved] [58 FR 27944, May 12, 1993, as amended at 58 FR...

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

DOE PAGES

Aston, John E.; Thompson, David N.; Westover, Tyler L.

2016-08-30

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greatermore » yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.« less

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

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

Aston, John E.; Thompson, David N.; Westover, Tyler L.

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greatermore » yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.« less

Methods for treating hydrocarbon recovery operations and industrial waters

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

Thompson, N.E.S.; Asperger, R.G.

1989-05-02

This patent describes a method for consisting adding to the emulsion an effective demulsifying amount of a composition comprising a compound containing: an alkane triyl group of 1 to 30 carbon atoms; an alkylene group of 1 to 30 carbon atoms; and an alkali or alkaline earth metal group or an ammonium group.

Production of aluminum metal by electrolysis of aluminum sulfide

DOEpatents

Minh, N.Q.; Loutfy, R.O.; Yao, N.P.

1982-04-01

Metallic aluminum may be produced by the electrolysis of Al/sub 2/S/sub 3/ at 700 to 800/sup 0/C in a chloride melt composed of one or more alkali metal chlorides, and one or more alkaline earth metal chlorides and/or aluminum chloride to provide improved operating characteristics of the process.

PRODUCTION OF METALS

DOEpatents

Spedding, F.H.; Wilhelm, H.A.; Keller, W.H.

1961-09-19

A process is described producing metallic thorium, titanium, zirconium, or hafnium from the fluoride. In the process, the fluoride is reduced with alkali or alkaline earth metal and a booster compound (e.g. iodine or a decomposable oxysalt) in a sealed bomb at superatmospheric pressure and a temperature above the melting point of the metal to be produced.

Hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, Robert G.; Stephens, Howard P.

1990-01-01

A catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchange with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Catalytic coal liquefaction process

DOEpatents

Garg, D.; Sunder, S.

1986-12-02

An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids. 1 fig.

Catalytic coal liquefaction process

DOEpatents

Garg, Diwakar; Sunder, Swaminathan

1986-01-01

An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids.

Production of aluminum metal by electrolysis of aluminum sulfide

DOEpatents

Minh, Nguyen Q.; Loutfy, Raouf O.; Yao, Neng-Ping

1984-01-01

Production of metallic aluminum by the electrolysis of Al.sub.2 S.sub.3 at 700.degree.-800.degree. C. in a chloride melt composed of one or more alkali metal chlorides, and one or more alkaline earth metal chlorides and/or aluminum chloride to provide improved operating characteristics of the process.

Superconducting critical fields of alkali and alkaline-earth intercalates of MoS2

NASA Technical Reports Server (NTRS)

Woollam, J. A.; Somoano, R. B.

1976-01-01

Results are reported for measurements of the critical-field anisotropy and temperature dependence of group-VIB semiconductor MoS2 intercalated with the alkali and alkaline-earth metals Na, K, Rb, Cs, and Sr. The temperature dependences are compared with present theories on the relation between critical field and transition temperature in the clean and dirty limits over the reduced-temperature range from 1 to 0.1. The critical-field anisotropy data are compared with predictions based on coupled-layers and thin-film ('independent-layers') models. It is found that the critical-field boundaries are steep in all cases, that the fields are greater than theoretical predictions at low temperatures, and that an unusual positive curvature in the temperature dependence appears which may be related to the high anisotropy of the layer structure. The results show that materials with the largest ionic intercalate atom diameters and hexagonal structures (K, Rb, and Cs compounds) have the highest critical temperatures, critical fields, and critical-boundary slopes; the critical fields of these materials are observed to exceed the paramagnetic limiting fields.

The long-range non-additive three-body dispersion interactions for the rare gases, alkali, and alkaline-earth atoms

NASA Astrophysics Data System (ADS)

Tang, Li-Yan; Yan, Zong-Chao; Shi, Ting-Yun; Babb, James F.; Mitroy, J.

2012-03-01

The long-range non-additive three-body dispersion interaction coefficients Z111, Z112, Z113, and Z122 are computed for many atomic combinations using standard expressions. The atoms considered include hydrogen, the rare gases, the alkali atoms (up to Rb), and the alkaline-earth atoms (up to Sr). The term Z111 arising from three mutual dipole interactions is known as the Axilrod-Teller-Muto coefficient or the DDD (dipole-dipole-dipole) coefficient. Similarly, the terms Z112, Z113, and Z122 arise from the mutual combinations of dipole (1), quadrupole (2), and octupole (3) interactions between atoms and they are sometimes known, respectively, as dipole-dipole-quadrupole, dipole-dipole-octupole, and dipole-quadrupole-quadrupole coefficients. Results for the four Z coefficients are given for the homonuclear trimers, for the trimers involving two like-rare-gas atoms, and for the trimers with all combinations of the H, He, and Li atoms. An exhaustive compilation of all coefficients between all possible atomic combinations is presented as supplementary data.

Recovery of UO{sub 2}/PuO{sub 2} in IFR electrorefining process

DOEpatents

Tomczuk, Z.; Miller, W.E.

1992-01-01

This invention is comprised of a process for converting PuO{sub 2} and U0{sub 2} present in an electrorefiner to the chlorides, by contacting the PuO{sub 2} and U0{sub 2} with Li metal in the presence of an alkali metal chloride salt substantially free of rare earth and actinide chlorides for a time and at a temperature sufficient to convert the U0{sub 2} and PuO{sub 2} to metals while converting Li metal to Li{sub 2}O. Li{sub 2}O is removed either by reducing with rare earth metals or by providing an oxygen electrode for transporting 0{sub 2} out of the electrorefiner and a cathode, and thereafter applying an emf to the electrorefiner electrodes sufficient to cause the Li{sub 2}O to disassociate to 0{sub 2} and Li metal but insufficient to decompose the alkali metal chloride salt. The U and Pu and excess lithium are then converted to chlorides by reaction with CdCl{sub 2}.

Synthesis of substantially monodispersed colloids

NASA Technical Reports Server (NTRS)

Stoeva, Savka (Inventor); Klabunde, Kenneth J. (Inventor); Sorensen, Christopher (Inventor)

2003-01-01

A method of forming ligated nanoparticles of the formula Y(Z).sub.x where Y is a nanoparticle selected from the group consisting of elemental metals having atomic numbers ranging from 21-34, 39-52, 57-83 and 89-102, all inclusive, the halides, oxides and sulfides of such metals, and the alkali metal and alkaline earth metal halides, and Z represents ligand moieties such as the alkyl thiols. In the method, a first colloidal dispersion is formed made up of nanoparticles solvated in a molar excess of a first solvent (preferably a ketone such as acetone), a second solvent different than the first solvent (preferably an organic aryl solvent such as toluene) and a quantity of ligand moieties; the first solvent is then removed under vacuum and the ligand moieties ligate to the nanoparticles to give a second colloidal dispersion of the ligated nanoparticles solvated in the second solvent. If substantially monodispersed nanoparticles are desired, the second dispersion is subjected to a digestive ripening process. Upon drying, the ligated nanoparticles may form a three-dimensional superlattice structure.

Electrochemical cell having cylindrical electrode elements

DOEpatents

Nelson, Paul A.; Shimotake, Hiroshi

1982-01-01

A secondary, high temperature electrochemical cell especially adapted for lithium alloy negative electrodes, transition metal chalcogenide positive electrodes and alkali metal halide or alkaline earth metal halide electrolyte is disclosed. The cell is held within an elongated cylindrical container in which one of the active materials is filled around the outside surfaces of a plurality of perforate tubular current collectors along the length of the container. Each of the current collector tubes contain a concentric tubular layer of electrically insulative ceramic as an interelectrode separator. The active material of opposite polarity in elongated pin shape is positioned longitudinally within the separator layer. A second electrically conductive tube with perforate walls can be swagged or otherwise bonded to the outer surface of the pin as a current collector and the electrically insulative ceramic layer can be coated or otherwise layered onto the outer surface of this second current collector. Alternatively, the central pin electrode can include an axial core as a current collector.

Hexaacetato calix(6)arene as the novel extractant for palladium.

PubMed

Mathew, V J; Khopkar, S M

1997-10-01

A novel method is proposed for the solvent extraction of palladium. A superamolecular compound, hexaacetato calix(6)arene in low concentration in toluene quantitatively extracts microgram concentration of palladium at pH 7.5. It can be stripped from the organic phase with 2 M nitric acid and determined spectrophotometrically as its stannous chloride complex at 635 nm. The probable composition of the extracted species is Pd(HR)(2)Cl. As low as 1x10(-3) M of extractant is adequate for quantitative extraction. Toluene was the best diluent. With nitric and perchloric acid (1.5-3 M) the stripping was complete. Palladium was separated in large ratios from alkali and alkaline earths (1:50). The main group elements were tolerated in higher ratios (1:25), but ions like zinc, cadmium, iron, nickel, platinium, thorium, vanadium and molydenum were tolerated at low concentrations (1:1). The ions showing strong interference were copper, chromium. The relative standard deviation is +/-1.1%.

RECOVERY OF THORIUM AND URANIUM VALUES FROM AQUEOUS SOLUTIONS

DOEpatents

Calkins, G.D.

1958-02-18

This patent deals with the separation and recovery of uranium from monazite sand. After initial treatment of the sand with sodium hydroxide, a precipitate is obtuined which contains the uranium, thorium, rare earths and some phosphorus. This precipitate is then dissolved in nitric acid. The bulk of the rare earths are removed from thls soiution by adding aa excess of alkali carbonate, causing precipitation of the rare earths together with part of the thorium present. The solution still contains a considerable amount of thorium, some rare earths, and practically all of the uranium originally present. Thorium and rare earth values are readily precipitated from such solution, and the uranium values thus isolated, by the addition of an excess hydrogen peroxide. The pH value of the solution is preferably adjusted to at least 9 prior to the addition of the peroxide.

Magnetic Nanofluid Rare Earth Element Extraction Process Report, Techno Economic Analysis, and Results for Geothermal Fluids

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

Pete McGrail

This GDR submission is an interim technical report and raw data files from the first year of testing on functionalized nanoparticles for rare earth element extraction from geothermal fluids. The report contains Rare Earth Element uptake results (percent removal, mg Rare Earth Element/gram of sorbent, distribution coefficient) for the elements of Neodymium, Europium, Yttrium, Dysprosium, and Cesium. A detailed techno economic analysis is also presented in the report for a scaled up geothermal rare earth element extraction process. All rare earth element uptake testing was done on simulated geothermal brines with one rare earth element in each brine. The raremore » earth element uptake testing was conducted at room temperature.« less

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1982

1982-01-01

Presents background information, laboratory procedures, classroom materials/activities, and experiments for chemistry. Topics include superheavy elements, polarizing power and chemistry of alkali metals, particulate carbon from combustion, tips for the chemistry laboratory, interesting/colorful experiments, behavior of bismuth (III) iodine, and…

Trace element and isotope geochemistry of geothermal fluids, East Rift Zone, Kilauea, Hawaii

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

West, H.B.; Delanoy, G.A.; Thomas, D.M.

1992-01-01

A research program has been undertaken in an effort to better characterize the composition and the precipitation characteristic of the geothermal fluids produced by the HGP-A geothermal well located on the Kilauea East Rift Zone on the Island of Hawaii. The results of these studies have shown that the chemical composition of the fluids changed over the production life of the well and that the fluids produced were the result of mixing of at least two, and possibly three, source fluids. These source fluids were recognized as: a sea water composition modified by high temperature water-rock reactions; meteoric recharge; andmore » a hydrothermal fluid that had been equilibrated with high temperature reservoir rocks and magmatic volatiles. Although the major alkali and halide elements show clearly increasing trends with time, only a few of the trace transition metals show a similar trend. The rare earth elements, were typically found at low concentrations and appeared to be highly variable with time. Studies of the precipitation characteristics of silica showed that amorphous silica deposition rates were highly sensitive to fluid pH and that increases in fluid pH above about 8.5 could flocculate more than 80% of the suspended colloidal silica in excess of its solubility. Addition of transition metal salts were also found to enhance the recovery fractions of silica from solution. The amorphous silica precipitate was also found to strongly scavenge the alkaline earth and transition metal ions naturally present in the brines; mild acid treatments were shown to be capable of removing substantial fractions of the scavenged metals from the silica flocs yielding a moderately pure gelatinous by-product. Further work on the silica precipitation process is recommended to improve our ability to control silica scaling from high temperature geothermal fluids or to recover a marketable silica by-product from these fluids prior to reinjection.« less

Trace element and isotope geochemistry of geothermal fluids, East Rift Zone, Kilauea, Hawaii

NASA Astrophysics Data System (ADS)

West, H. B.; Delanoy, G. A.; Thomas, D. M.; Gerlach, D. C.; Chen, B.; Takahashi, P.; Thomas, D. M.

1992-03-01

A research program has been undertaken in an effort to better characterize the composition and the precipitation characteristic of the geothermal fluids produced by the HGP-A geothermal well located on the Kilauea East Rift Zone on the island of Hawaii. The results of these studies have shown that the chemical composition of the fluids changed over the production life of the well and that the fluids produced were the result of the mixing of at least two, and possibly three, source fluids. These source fluids were recognized as a sea water composition modified by high temperature water-rock reactions; meteoric recharge; and a hydrothermal fluid that had been equilibriated with high temperature reservoir rocks and magmatic volatiles. Although the major alkali and halide elements show clearly increasing trends with time, only a few of the trace transition metals show a similar trend. The rare earth elements were typically found at low concentrations and appeared to be highly variable with time. Studies of the precipitation characteristics of silica showed that amorphous silica deposition rates were highly sensitive to fluid pH and that increases in fluid pH above about 8.5 could flocculate more than 80 percent of the suspended colloidal silica in excess of its solubility. Addition of transition metal salts were also found to enhance the recovery fractions of silica from solution. The amorphous silica precipitate was also found to strongly scavenge the alkaline earth and transition metal ions naturally present in the brines; mild acid treatments were shown to be capable of removing substantial fractions of the scavenged metals from the silica flocs, yielding a moderately pure gelatinous by-product. Further work on the silica precipitation process is recommended to improve our ability to control silica scaling from high temperature geothermal fluids or to recover a marketable silica by-product from these fluids prior to reinjection.

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.

Rare earth elements: end use and recyclability

USGS Publications Warehouse

Goonan, Thomas G.

2011-01-01

Rare earth elements are used in mature markets (such as catalysts, glassmaking, lighting, and metallurgy), which account for 59 percent of the total worldwide consumption of rare earth elements, and in newer, high-growth markets (such as battery alloys, ceramics, and permanent magnets), which account for 41 percent of the total worldwide consumption of rare earth elements. In mature market segments, lanthanum and cerium constitute about 80 percent of rare earth elements used, and in new market segments, dysprosium, neodymium, and praseodymium account for about 85 percent of rare earth elements used. Regardless of the end use, rare earth elements are not recycled in large quantities, but could be if recycling became mandated or very high prices of rare earth elements made recycling feasible.

Apollo 16 Evolved Lithology Sodic Ferrogabbro

NASA Technical Reports Server (NTRS)

Zeigler, Ryan; Jolliff, B. L.; Korotev, R. L.

2014-01-01

Evolved lunar igneous lithologies, often referred to as the alkali suite, are a minor but important component of the lunar crust. These evolved samples are incompatible-element rich samples, and are, not surprisingly, most common in the Apollo sites in (or near) the incompatible-element rich region of the Moon known as the Procellarum KREEP Terrane (PKT). The most commonly occurring lithologies are granites (A12, A14, A15, A17), monzogabbro (A14, A15), alkali anorthosites (A12, A14), and KREEP basalts (A15, A17). The Feldspathic Highlands Terrane is not entirely devoid of evolved lithologies, and rare clasts of alkali gabbronorite and sodic ferrogabbro (SFG) have been identified in Apollo 16 station 11 breccias 67915 and 67016. Curiously, nearly all pristine evolved lithologies have been found as small clasts or soil particles, exceptions being KREEP basalts 15382/6 and granitic sample 12013 (which is itself a breccia). Here we reexamine the petrography and geochemistry of two SFG-like particles found in a survey of Apollo 16 2-4 mm particles from the Cayley Plains 62283,7-15 and 62243,10-3 (hereafter 7-15 and 10-3 respectively). We will compare these to previously reported SFG samples, including recent analyses on the type specimen of SFG from lunar breccia 67915.

Rapid separation of beryllium and lanthanide derivatives by capillary gas chromatography

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

Harvey, Scott D.; Lucke, Richard B.; Douglas, Matt

2012-09-04

Previous studies describe derivatization of metal ions followed by analysis using gas chromatography, usually on packed columns. In many of these studies, stable and volatile derivatives were formed using fluorinated β-diketonate reagents. This paper extends previous work by investigating separations of the derivatives on small-diameter capillary gas chromatography columns and exploring on-fiber, solid-phase microextraction derivatization techniques for beryllium. The β-diketonate used for these studies was 1,1,1,2,2,6,6,7,7,7-decafluoro-3,5-heptanedione. Derivatization of lanthanides also required addition of a neutral donor, dibutyl sulfoxide, in addition to 1,1,1,2,2,6,6,7,7,7-decafluoro-3,5-heptanedione. Unoptimized separations on a 100-μm i.d. capillary column proved capable of rapid separations (within 15 min) of lanthanidemore » derivatives that are adjacent to one another in the periodic table. Full-scan mass spectra were obtained from derivatives containing 5 ng of each lanthanide. Studies also developed a simple on-fiber solid-phase microextraction derivatization of beryllium. Beryllium could be analyzed in the presence of other alkali earth elements (Ba(II) and Sr(II)) without interference. Finally, extension of the general approach was demonstrated for several additional elements (i.e. Cu(II), Cr(III), and Ga(III)).« less

Systematic Studies on Anharmonicity of Rattling Phonons in Type I Clathrates by Low Temperature Heat Capacity Measurements

NASA Astrophysics Data System (ADS)

Tanigaki, Katsumi; Wu, Jiazhen; Tanabe, Yoichi; Heguri, Satoshi; Shiimotani, Hidekazu; Tohoku University Collaboration

2014-03-01

Clathrates are featured by cage-like polyhedral hosts mainly composed of the IVth group elements of Si, Ge, or Sn and alkali metal or alkaline-earth metal elements can be accommodated inside as a guest atom. One of the most intriguing issues in clathrates is their outstanding high thermoelectric performances thanks to the low thermal conductivity. Being irrespective of good electric conductivity σ, the guest atom motions provide a low-energy lying less-dispersive phonons and can greatly suppress thermal conductivity κ. This makes clathrates close to the concept of ``phonon glass electron crystal: PGEC'' and useful in thermoelectric materials from the viewpoint of the figure of merit. In the present study, we show that the local phonon anharmonicity indicated by the tunneling-term of the endohedral atoms (αT) and the itinerant-electron term (γeT), both of which show T-linear dependences in specific heat Cp, can successfully be separated by employing single crystals with various carrier concentrations in a wide range of temperture experimennts. The factors affecting on the phonon anharmonicity as well as the strength of electron-phonon interactions will be discussed based on our recent experiments. The research was financially supported by Ministry of Education, Science, Sports and Culture, Grant in Aid for Science, and Technology of Japan.

Comparison of Elemental Mercury Oxidation Across Vanadium and Cerium Based Catalysts in Coal Combustion Flue Gas: Catalytic Performances and Particulate Matter Effects.

PubMed

Wan, Qi; Yao, Qiang; Duan, Lei; Li, Xinghua; Zhang, Lei; Hao, Jiming

2018-03-06

This paper discussed the field test results of mercury oxidation activities over vanadium and cerium based catalysts in both coal-fired circulating fluidized bed boiler (CFBB) and chain grate boiler (CGB) flue gases. The characterizations of the catalysts and effects of flue gas components, specifically the particulate matter (PM) species, were also discussed. The catalytic performance results indicated that both catalysts exhibited mercury oxidation preference in CGB flue gas rather than in CFBB flue gas. Flue gas component studies before and after dust removal equipment implied that the mercury oxidation was well related to PM, together with gaseous components such as NO, SO 2 , and NH 3 . Further investigations demonstrated a negative PM concentration-induced effect on the mercury oxidation activity in the flue gases before the dust removal, which was attributed to the surface coverage by the large amount of PM. In addition, the PM concentrations in the flue gases after the dust removal failed in determining the mercury oxidation efficiency, wherein the presence of different chemical species in PM, such as elemental carbon (EC), organic carbon (OC) and alkali (earth) metals (Na, Mg, K, and Ca) in the flue gases dominated the catalytic oxidation of mercury.

Rare Earth Elements | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

- Mineral Resources main content Rare Earth Elements Rare earth elements and the supply and demand of these deposits containing rare earth elements to meet the perceived future demand. High prices for rare earth earth element occurrences in the DGGS publications catalog. Department of Natural Resources, Division of

REGENERATION OF FISSION-PRODUCT-CONTAINING MAGNESIUM-THORIUM ALLOYS

DOEpatents

Chiotti, P.

1964-02-01

A process of regenerating a magnesium-thorium alloy contaminated with fission products, protactinium, and uranium is presented. A molten mixture of KCl--LiCl-MgCl/sub 2/ is added to the molten alloy whereby the alkali, alkaline parth, and rare earth fission products (including yttrium) and some of the thorium and uranium are chlorinated and

Improved hydrous oxide ion-exchange compound catalysts

DOEpatents

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

1986-04-09

Disclosed is a catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchanged with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Two stage sorption of sulfur compounds

DOEpatents

Moore, William E.

1992-01-01

A two stage method for reducing the sulfur content of exhaust gases is disclosed. Alkali- or alkaline-earth-based sorbent is totally or partially vaporized and introduced into a sulfur-containing gas stream. The activated sorbent can be introduced in the reaction zone or the exhaust gases of a combustor or a gasifier. High efficiencies of sulfur removal can be achieved.

Radiation creation of cation defects in alkali halide crystals: Review and today's concept (Review Article)

NASA Astrophysics Data System (ADS)

Lushchik, A.; Lushchik, Ch.; Vasil'chenko, E.; Popov, A. I.

2018-04-01

Irradiation of alkali halide crystals creates pairs of Frenkel defects both in anion and cation sublattices. However, the particular nonimpact creation mechanisms (related to the decay of different electronic excitations) of cation Frenkel pairs are still unclear. At helium temperatures, there is yet no direct evidences of the creation of stable (long-lived) elemental cation defects. On the other hand, a number of complex structural defects containing cation vacancies and/or interstitials, were detected after irradiation of alkali halides at higher temperatures. Besides already proved mechanism related to the association of H and VK centers into trihalide molecules, the following possibilities of cation interstitial-vacancy pair creation are analyzed as well: (i) a direct decay of cation or anion excitons, (ii) the transformation of anion Frenkel pairs, formed at the decay of anion excitons or e-h recombination, into cation ones.

Fractionation and physicochemical characterization of lignin from waste jute bags: Effect of process parameters on yield and thermal degradation.

PubMed

Ahuja, Dheeraj; Kaushik, Anupama; Chauhan, Ghanshyam S

2017-04-01

In this work lignin was extracted from waste jute bags using soda cooking method and effect of varying alkali concentration and pH on yield, purity, structure and thermal degradation of lignin were studied. The Lignin yield, chemical composition and purity were assessed using TAPPI method and UV-vis spectroscopy. Yield and purity of lignin ranged from 27 to 58% and 50-94%, respectively for all the samples and was maximum for 8% alkali concentration and at pH 2 giving higher thermal stability. Chemical structure, thermal stability and elementary analysis of lignin were studied using FTIR, H NMR, thermo gravimetric analysis (TGA) and Elemental analyzer. FTIR and H NMR results showed that core structure of lignin starts breaking beyond 10% alkali concentration. S/G ratio shows the dominance of Syringyl unit over guaiacyl unit. Copyright © 2017 Elsevier B.V. All rights reserved.

Submarine alkalic through tholeiitic shield-stage development of Kīlauea volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Sisson, Thomas W.; Lipman, Peter W.; Naka, Jiro

The submarine Hilina region exposes a succession of magma compositions spanning the juvenile "Lō'ihi" through tholeiitic shield stages of Kīlauea volcano. Early products, preserved as glass grains and clasts in volcaniclastic rocks of the 3000 m deep Hilina bench, include nephelinite, basanite, phonotephrite, hawaiite, alkali basalt, transitional basalt, and rare alkali-poor Mauna Loa-like tholeiite. Transitional basalt pillow lavas overlie the volcaniclastic section and record an early phase of subsequent subalkaline magmatism. Rare degassed tholeiitic pillow lava and talus above the volcaniclastic section are products of subaerial shield volcanism. Major and trace element variations of clasts and pillow lavas point to a factor of 2-2.5 increase in degree of melting from juvenile alkalic to modern tholeiitic Kīlauea. Progressive changes in element ratios that distinguish Hawaiian shield volcanoes, without commensurate changes in elements fractionated by partial melting, also signal increased contributions from Mauna Loa-type source regions as Kīlauea matured from its juvenile alkalic to its tholeiitic shield stage. Ancestral Kīlauea basanites and nephelinites were not primitive magmas but might have evolved from plume-derived alkali picritic parents by lithospheric-level crystallization differentiation, or solidification and remelting, involving pyroxene and garnet, similar to the subcrustal differentiation origin of hawaiites [Frey et al., 1990]. Low magmatic productivity early in Kīlauea's history sustained a poorly integrated trans-lithospheric conduit system in which magmas stalled and differentiated, producing evolved hawaiites, nephelinites, and basanites. This contrasts with shield-stage Kīlauea where high magmatic productivity flushes the conduit system and delivers primitive magmas to shallow levels.

Oxidation of hydrogen halides to elemental halogens

DOEpatents

Rohrmann, Charles A.; Fullam, Harold T.

1985-01-01

A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

Atmospheric Deposition of Mercury

EPA Science Inventory

With the advent of the industrial era, the amount of mercury entering the global environment increased dramatically. Releases of mercury in its elemental form from gold mines and chlor-alkali plants, as sulfides such as mercaptans and agricultural chemicals, and as volatile emiss...

Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

NASA Astrophysics Data System (ADS)

Ke, Haochen; van der Linde, Christian; Lisy, James M.

2014-06-01

Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

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

PubMed

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

2015-09-01

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

Origin of dioritic magma and its contribution to porphyry Cu-Au mineralization at Pulang in the Yidun arc, eastern Tibet

NASA Astrophysics Data System (ADS)

Cao, Kang; Yang, Zhi-Ming; Xu, Ji-Feng; Fu, Bin; Li, Wei-Kai; Sun, Mao-Yu

2018-04-01

The giant Pulang porphyry Cu-Au deposit in the Yidun arc, eastern Tibet, formed due to westward subduction of the Garze-Litang oceanic plate in the Late Triassic. The deposit is hosted in an intrusive complex comprising primarily coarse-grained quartz diorite and cored quartz monzonite. Here, we investigate a suite of simultaneous (216.6 ± 1.9 Ma) diorite porphyries within the complex. The diorite porphyries are geochemically similar to mafic magmatic enclaves (MME) hosted in coarse-grained quartz diorite, and both are characterized by low SiO2 (59.4-63.0 wt%) and high total alkali (Na2O + K2O = 7.0-9.2 wt%), K2O (3.5-6.4 wt%), MgO (3.2-5.5 wt%), and compatible trace element (e.g., Cr = 72-149 ppm) concentrations. They are enriched in large-ion lithophile and light rare earth elements (LILE and LREE, respectively), but depleted in high field-strength and heavy rare earth elements (HFSE and HREE, respectively), and yield variably high (La/Yb)N ratios (17-126, average 65) with weak to negligible Eu anomalies. Furthermore, they yield low (87Sr/86Sr)i ratios (0.7054-0.7067), weakly negative εNd(t) (-2.8 to -0.8) values, and variable zircon εHf(t) (-5.4 to +0.8) and δ18O (6.0‰-6.7‰) values. These geochemical features indicate that the diorite porphyry and MME formed through crustal assimilation of a magma produced during low-degree partial melting of metasomatized phlogopite-rich subcontinental lithospheric mantle. In contrast, the coarse-grained quartz diorite and quartz monzonite have relatively high concentrations of SiO2 (61.1-65.3 wt%), K2O (4.1-5.4 wt%), and total alkali (Na2O + K2O = 7.1-8.1 wt%), and low concentrations of MgO (generally <3.0 wt%) and compatible trace elements (e.g., Cr = 38-61 ppm). They yield high Sr/Y ratios (50-63) that indicate an adakitic affinity, and are enriched in LILE, depleted in HFSE, and yield lower (La/Yb)N values (13-20, average 17) than the diorite porphyry and MME. They yield low (87Sr/86Sr)i ratios (0.7046-0.7066), negative εNd(t) (-3.3 to -1.7) values, and zircon εHf(t) and δ18O values of -2.9 to -0.1 and 5.7‰-6.5‰, respectively, suggesting that they represent high-K calc-alkaline to shoshonitic adakitic magmas that were sourced from subduction-modified juvenile lower crust. Observations of the newly identified diorite porphyry and previously reported MME suggest that input of such dioritic magma into the upper crustal porphyry magma chamber would have contributed not only the necessary metals (e.g., Cu and Au), sulfur, but also H2O to the system, thus aiding in the generation of the giant Pulang porphyry Cu-Au deposit.

Sign Changes in the Electric Dipole Moment of Excited States in Rubidium-Alkaline Earth Diatomic Molecules

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

2015-06-01

In a recent series of combined experimental and theoretical studies we investigated the ground state and several excited states of the Rb-alkaline earth molecules RbSr and RbCa. The group of alkali-alkaline earth (AK-AKE) molecules has drawn attention for applications in ultracold molecular physics and the measurement of fundamental constants due to their large permanent electric and magnetic dipole moments in the ground state. These properties should allow for an easy manipulation of the molecules and simulations of spin models in optical lattices. In our studies we found that the permanent electric dipole moment points in different directions for certain electronically excited states, and changes the sign in some cases as a function of bond length. We summarize our results, give possible causes for the measured trends in terms of molecular orbital theory and extrapolate the tendencies to other combinations of AK and AKE - elements. F. Lackner, G. Krois, T. Buchsteiner, J. V. Pototschnig, and W. E. Ernst, Phys. Rev. Lett., 2014, 113, 153001; G. Krois, F. Lackner, J. V. Pototschnig, T. Buchsteiner, and W. E. Ernst, Phys. Chem. Chem. Phys., 2014, 16, 22373; J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Chem. Phys., 2014, 141, 234309 J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Mol. Spectrosc., in Press (2015), doi:10.1016/j.jms.2015.01.006 M. Kajita, G. Gopakumar, M. Abe, and M. Hada, J. Mol. Spectrosc., 2014, 300, 99-107 A. Micheli, G. K. Brennen, and P. Zoller, Nature Physics, 2006, 2, 341-347

Silicate-catalyzed chemical grouting compositions

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

Not Available

1972-09-28

Chemical grouting compositions for stabilizing earth, sand, and other porous particulate formations or agglomerates of solids are described. The composition for producing a chemically grouting structure consists of an aqueous base solution of: (1) vegetative polyphenolic material consisting of condensed type tannins, and an aqueous catalyst solution of (2) a water-soluble alkali metal silicate. The polyphenolic material is present in an amount from 5% to 40% based on the weight of the base solution, and the water- soluble alkali metal silicate is present in an amount to provide from 1% to 15% SiOD2U in the silicate compound based on themore » weight of the polyphenolic material. These grouting compositions are completely safe to operating personnel and to surrounding environment, since the potassium or sodium silicate catalysts are nontoxic. (15 claims)« less

Excimer Emission from Alkali Diatomic and Alkaline-Earth-Noble-Gas Molecules

DTIC Science & Technology

1989-10-01

line at 792 nm is also shown as a solid line for 1.18 ami . respectively. The oven temperature and buffer gas comparison. The oven contained pure sodium...Hasselbrink, and G. Hillrichs. Chem. Phys. Lett. 30J. Huennekens, H. J. Park, T. Colbert , and S. C. McClain. 112,441 (1984). Phys. Rev. A 35, 2892 (1987). 15R

Inorganic rechargeable non-aqueous cell

DOEpatents

Bowden, William L.; Dey, Arabinda N.

1985-05-07

A totally inorganic non-aqueous rechargeable cell having an alkali or alkaline earth metal anode such as of lithium, a sulfur dioxide containing electrolyte and a discharging metal halide cathode, such as of CuCl.sub.2, CuBr.sub.2 and the like with said metal halide being substantially totally insoluble in SO.sub.2 and admixed with a conductive carbon material.

SEPARATION OF PROTACTINIUM FROM MOLTEN SALT REACTOR FUEL COMPOSITIONS

DOEpatents

Shaffer, J.H.; Strain, J.E.; Cuneo, D.R.; Kelly, M.J.

1963-11-12

A method for selectively precipitating protactinium from a neutron- irradiated fused fluoride salt composition comprising at least one metal fluoride selected from the group consisting of an alkali metal fluoride and an alkaline earth metal fluoride containing dissolved thorium-232 values is presented. An inorganic metal oxide corresponding to any of the metal fluorides of the composition is also added. (AEC)

Hydrogen storage property of alkali and alkaline-earth metal atoms decorated C24 fullerene: A DFT study

NASA Astrophysics Data System (ADS)

Zhang, Yafei; Cheng, Xinlu

2018-04-01

The hydrogen storage behavior of alkali and alkaline-earth metal (AM = Li, Na, K, Mg, Ca) atoms decorated C24 fullerene was investigated by using density functional theory (DFT) study. Our results indicate that the AM atoms prefer to adsorb atop the center of tetragon of C24 fullerene with the largest binding energy than other possible adsorption sites. Moreover, the hydrogen storage gravimetric density of 24H2/6Li/C24, 24H2/6Na/C24 and 36H2/6Ca/C24 configurations reaches up to 12.7 wt%, 10.1 wt% and 12 wt%, higher than the year 2020 target from the US department of energy (DOE). Also, the average adsorption energies of H2 molecules of the 24H2/6Li/C24, 24H2/6Na/C24 and 36H2/6Ca/C24 configurations are -0.198 eV/H2, -0.164 eV/H2 and -0.138 eV/H2, locate the desirable range under the physical adsorption at near ambient conditions. These findings will have important implications on designing new hydrogen storage materials in the future.

Trends in water monomer adsorption and dissociation on flat insulating surfaces.

PubMed

Hu, Xiao Liang; Carrasco, Javier; Klimeš, Jiří; Michaelides, Angelos

2011-07-21

The interaction of water with solid surfaces is key to a wide variety of industrial and natural processes. However, the basic principles that dictate how stable and in which state (intact or dissociated) water will be on a given surface are not fully understood. Towards this end, we have used density functional theory to examine water monomer adsorption on the (001) surfaces of a broad range of alkaline earth oxides, alkaline earth sulfides, alkali fluorides, and alkali chlorides. Some interesting general conclusions are arrived at: (i) on all the surfaces considered only a few specific adsorption structures are favoured; (ii) water becomes more stable upon descending the oxide and fluoride series but does not vary much upon going down the chloride and sulfide series; (iii) water is stabilised both by an increase in the lattice constant, which facilitates hydrogen bonding to the substrate, and by the flexibility of the substrate. These are also factors that favour water dissociation. We hope that this study is of some value in better understanding the surface science of water in general, and in assisting in the interpretation and design of future experiments. This journal is © the Owner Societies 2011

Quantum defect theory for the orbital Feshbach resonance

NASA Astrophysics Data System (ADS)

Cheng, Yanting; Zhang, Ren; Zhang, Peng

2017-01-01

In the ultracold gases of alkali-earth-metal-like atoms, a new type of Feshbach resonance, i.e., the orbital Feshbach resonance (OFR), has been proposed and experimentally observed in ultracold 173Yb atoms [R. Zhang et al., Phys. Rev. Lett. 115, 135301 (2015), 10.1103/PhysRevLett.115.135301]. When the OFR of the 173Yb atoms occurs, the energy gap between the open and closed channels is smaller by two orders of magnitude than the van der Waals energy. As a result, quantitative accurate results for the low-energy two-body problems can be obtained via multichannel quantum defect theory (MQDT), which is based on the exact solution of the Schrödinger equation with the van der Waals potential. In this paper we use MQDT to calculate the two-atom scattering length, effective range, and binding energy of two-body bound states for the systems with OFR. With these results we further study the clock-transition spectrum for the two-body bound states, which can be used to experimentally measure the binding energy. Our results are helpful for the quantitative theoretical and experimental research for the ultracold gases of alkali-earth-metal-like atoms with OFR.

Vibronic transitions in the alkali-metal (Li, Na, K, Rb) - alkaline-earth-metal (Ca, Sr) series: A systematic analysis of de-excitation mechanisms based on the graphical mapping of Frank-Condon integrals

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Meyer, Ralf; Hauser, Andreas W.; Ernst, Wolfgang E.

2017-02-01

Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

USGS Publications Warehouse

Sorensen, Sorena S.; Grossman, J.N.

1989-01-01

The abundance, P-T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600??C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high-T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of "average" island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H2O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. "Exotic" LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by "subduction-zone metasomatism," although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments. ?? 1989.

Health risk assessment of rare earth elements in cereals from mining area in Shandong, China.

PubMed

Zhuang, Maoqiang; Wang, Liansen; Wu, Guangjian; Wang, Kebo; Jiang, Xiaofeng; Liu, Taibin; Xiao, Peirui; Yu, Lianlong; Jiang, Ying; Song, Jian; Zhang, Junli; Zhou, Jingyang; Zhao, Jinshan; Chu, Zunhua

2017-08-29

To investigate the concentrations of rare earth elements in cereals and assess human health risk through cereal consumption, a total of 327 cereal samples were collected from rare earth mining area and control area in Shandong, China. The contents of 14 rare earth elements were determined by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The medians of total rare earth elements in cereals from mining and control areas were 74.22 μg/kg and 47.83 μg/kg, respectively, and the difference was statistically significant (P < 0.05). The wheat had the highest rare earth elements concentrations (109.39 μg/kg and 77.96 μg/kg for mining and control areas, respectively) and maize had the lowest rare earth elements concentrations (42.88 μg/kg and 30.25 μg/kg for mining and control areas, respectively). The rare earth elements distribution patterns for both areas were characterized by enrichment of light rare earth elements. The health risk assessment demonstrated that the estimated daily intakes of rare earth elements through cereal consumption were considerably lower than the acceptable daily intake (70 μg/kg bw). The damage to adults can be neglected, but more attention should be paid to the effects of continuous exposure to rare earth elements on children.

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.

Synthesis and characterization of magnetic solids featuring 3d-4f heterometallic oxides comprised of spin chains and 3d-6p noncentrosymmetric oxides templated by acentric salt units

NASA Astrophysics Data System (ADS)

West, Jennings Palmer

The studies and syntheses presented in this dissertation were primarily aimed at exploring new magnetic solids comprised of special framework oxides with novel magnetic properties. Low-dimensional magnetic behavior has been of great interest, especially pertaining to molecular solids having single magnetic domains where slow relaxation and quantum properties of magnetization are evident. In attempts to mimic molecular magnets and achieve reduced dimensionality of, in this case 3d-4f magnetic sublattices, diamagnetic oxyanions, XOmn-, and A-site cations (A = alkali and alkaline-earth metals) were used as nonmagnetic spacers in hopes of disrupting or confining magnetic interactions in certain dimensions. The general system type explored throughout these studies was of the form: A-R-M-X-O, where A = alkali and alkaline-earth metals, R = Bi3+ or lanthanide metals (4f), M = first row transition metals (3d), and X = P, As, or Ge. The scope of this research consisted of, first, finding new low-dimensional magnetic systems of the A-R-M-X-O type through exploratory molten-salt synthetic approaches, and upon characterizing these new systems, attempts were made to chemically modify these materials in order to understand and gain insight into how the structures of these materials dictate properties through structure and property correlations. Due to the refractory nature and low solubility of the covalent metal oxides, namely the lanthanide and transition metal oxides, excess amounts of eutectic halide flux mixtures (alkali and alkaline-earth halides) were employed to assist the reaction and promote crystal growth. One can think of these halide fluxes as a high-temperature solvent, in the molten state, that helps speed up the otherwise slow diffusion processes typically associated with traditional solid state synthetic approaches via unconventional dissolution (decomposition) and reprecipitation processes. Also advantageous in using alkali and alkaline-earth metal halides as solvent media is the fact that the salt itself or the alkali/alkaline-earth oxides formed in situ can be incorporated in phase formations. Both of the aforementioned cases, if incorporated, lead to an additional and different type of nonmagnetic spacer for the formation of low-dimensional 3d-4 f extended solids. It is believed that these nonmagnetic, ionic spacers are more disruptive to magnetic super-super-exchange in comparison to the nonmagnetic oxyanionic spacers, and should assist further in achieving truly confined magnetic sublattices. In the studies presented, the overall highlight considering structure and property correlations will be most exemplified through the comparison of two different pseudo-one-dimensional (1D), 3d-4 f arsenate systems (Chapters 3 and 4) where it is observed that further spacing of the 3d-4f sublattices leads to interesting low-dimensional magnetic behavior. In addition, an extension of one of these pseudo-1D, 3d-4f systems (Chapter 5) will highlight the intriguing properties resulting from the study of a family of compounds whereby a double aliovalent substitution has been performed with respect to the parent family. This particular system features a solid solution series where charge disorder exists, and in terms of magnetic properties, there are unique variations in comparison to the parent family. And finally, in relation to heterometallic system types, a new noncentrosymmetric phosphate family containing mixed 3d-6p (where 3 d = Mn, Fe; 6p = Bi3+) will be discussed (Chapter 6). As will be mentioned, new 3d-6p systems were explored originally for host materials where lanthanides could be substituted. Independent of lanthanide substitutions that are yet to be proven, the combination of both bulk acentricity and magnetically active ions makes systems of this type worthy of study due to multiferroic potentials aimed toward the coupling of polarization and magnetization.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

Depletions of siderophile elements in mantles have placed constraints on the conditions on core segregation and differentiation in bodies such as Earth, Earth's Moon, Mars, and asteroid 4 Vesta. Among the siderophile elements there are a sub-set that are also volatile (volatile siderophile elements or VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd), and thus can help to constrain the origin of volatile elements in these bodies, and in particular the Earth and Moon. One of the fundamental observations of the geochemistry of the Moon is the overall depletion of volatile elements relative to the Earth, but a satisfactory explanation has remained elusive. Hypotheses for Earth include addition during accretion and core formation and mobilized into the metallic core, multiple stage origin, or addition after the core formed. Any explanation for volatile elements in the Earth's mantle must also be linked to an explanation of these elements in the lunar mantle. New metal-silicate partitioning data will be applied to the origin of volatile elements in both the Earth and Moon, and will evaluate theories for exogenous versus endogenous origin of volatile elements.

Laboratory Studies of Alkali Components in Tenuous Planetary Atmospheres

NASA Astrophysics Data System (ADS)

Yakshinskiy, B. V.

2004-05-01

We report on studies performed at the Laboratory for Surface Modification of Rutgers University and focused on the origin of alkali vapors (Na, K) in the tenuous atmospheres of the planet Mercury, the Moon, and Jupiter's icy satellite Europa [1, 2]; we also address the question why alkaline-earth metals (Mg, Ca) are less abundant in the atmospheres. A variety of ultrahigh-vacuum surface science techniques are used, including X-ray Photoelectron Spectroscopy (XPS), Low-Energy Ion Scattering (LEIS), Thermal Programmed Desorption (TPD), Electron- and Photon-Stimulated Desorption (ESD and PSD), Surface Ionization (SI). Measurements have been made on different samples, including the model mineral binary oxide SiO2 that simulates lunar silicates, and a lunar sample obtained from NASA. Desorption induced by electronic excitations (mainly PSD) rather than by thermal processes is found to be the dominant source process on the lunar surface. The flux at the lunar surface of ultraviolet photons from the Sun is adequate to insure that PSD of sodium contributes substantially to the Moon's atmosphere. A model based on irradiation-induced charge-transfer is proposed to explain the desorption process. There is a strong temperature-dependence of Na ESD and PSD signals from a lunar sample, under conditions where the Na surface coverage is constant and thermal desorption is negligible [3]. On Mercury solar heating of the surface is high enough that thermal desorption will also be a potential source of atmospheric sodium. Ion bombardment of the lunar sample causes both the sputtering of alkali atoms into vacuum and implantation into the sample bulk. In the future we outline the use a novel method, Nuclear Resonance Profiling (NRP) to study the diffusion of alkalis through model minerals, ices, and lunar samples; these measurements would provide additional information to understand the replenishment of Na at the surface of the Moon, Mercury and Europa. We also describe a new detector that we will use to search for desorption of alkaline-earth atoms. [1] T.E. Madey, R.E. Johnson, T.M. Orlando, Surf. Sci. 500 (2002) 838. [2] B.V. Yakshinskiy, T.E. Madey, Surf. Sci. 528 (2003) 54. [3] B.V. Yakshinskiy, T.E. Madey, Icarus 168 (2004) 53.

Carbonatite and alkaline intrusion-related rare earth element deposits–A deposit model

USGS Publications Warehouse

Verplanck, Philip L.; Van Gosen, Bradley S.

2011-01-01

The rare earth elements are not as rare in nature as their name implies, but economic deposits with these elements are not common and few deposits have been large producers. In the past 25 years, demand for rare earth elements has increased dramatically because of their wide and diverse use in high-technology applications. Yet, presently the global production and supply of rare earth elements come from only a few sources. China produces more than 95 percent of the world's supply of rare earth elements. Because of China's decision to restrict exports of these elements, the price of rare earth elements has increased and industrial countries are concerned about supply shortages. As a result, understanding the distribution and origin of rare earth elements deposits, and identifying and quantifying our nation's rare earth elements resources have become priorities. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. The general mineral deposit model summarized here is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Carbonatite and alkaline intrusion-related REE deposits are discussed together because of their spatial association, common enrichment in incompatible elements, and similarities in genesis. A wide variety of commodities have been exploited from carbonatites and alkaline igneous rocks, such as rare earth elements, niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other enrichments include manganese, strontium, tantalum, thorium, vanadium, and uranium.

Modeling of Thermochemical Behavior in an Industrial-Scale Rotary Hearth Furnace for Metallurgical Dust Recycling

NASA Astrophysics Data System (ADS)

Wu, Yu-Liang; Jiang, Ze-Yi; Zhang, Xin-Xin; Xue, Qing-Guo; Yu, Ai-Bing; Shen, Yan-Song

2017-10-01

Metallurgical dusts can be recycled through direct reduction in rotary hearth furnaces (RHFs) via addition into carbon-based composite pellets. While iron in the dust is recycled, several heavy and alkali metal elements harmful for blast furnace operation, including Zn, Pb, K, and Na, can also be separated and then recycled. However, there is a lack of understanding on thermochemical behavior related to direct reduction in an industrial-scale RHF, especially removal behavior of Zn, Pb, K, and Na, leading to technical issues in industrial practice. In this work, an integrated model of the direct reduction process in an industrial-scale RHF is described. The integrated model includes three mathematical submodels and one physical model, specifically, a three-dimensional (3-D) CFD model of gas flow and heat transfer in an RHF chamber, a one-dimensional (1-D) CFD model of direct reduction inside a pellet, an energy/mass equilibrium model, and a reduction physical experiment using a Si-Mo furnace. The model is validated by comparing the simulation results with measurements in terms of furnace temperature, furnace pressure, and pellet indexes. The model is then used for describing in-furnace phenomena and pellet behavior in terms of heat transfer, direct reduction, and removal of a range of heavy and alkali metal elements under industrial-scale RHF conditions. The results show that the furnace temperature in the preheating section should be kept at a higher level in an industrial-scale RHF compared with that in a pilot-scale RHF. The removal rates of heavy and alkali metal elements inside the composite pellet are all faster than iron metallization, specifically in the order of Pb, Zn, K, and Na.

Atmospheric mercury incorporation in soils of an area impacted by a chlor-alkali plant (Grenoble, France): contribution of canopy uptake.

PubMed

Guédron, Stéphane; Grangeon, Sylvain; Jouravel, Glorianne; Charlet, Laurent; Sarret, Géraldine

2013-02-15

This study focused on the fluxes of mercury (Hg) and mechanisms of incorporation into soils surrounding a chlor-alkali plant suspected to have emitted up to ~600 kg Hg year(-1) for decades into the atmosphere. Comparison of vertical Hg soil profiles with As, Cu, Ni and Zn (which were not emitted by the plant) support Hg enrichment in surface horizons due to atmospheric Hg inputs from the chlor-alkali plant. Based on chemical extractions and elemental correlations, Hg was found to be weakly leachable and bio-available for plants, and most probably strongly bound to organic matter. In contrast, other trace elements were probably associated with phyllosilicates, iron oxides or with primary minerals. Hg stocks in the surface horizon of a forested soil (1255 mg Hg m(-3)) were two-fold higher than in an agricultural soil (636 mg Hg m(-3)) at a similar distance to the plant. The difference was attributed to the interception of atmospheric Hg by the canopy (most likely gaseous elemental Hg and reactive gaseous Hg) and subsequent litterfall incorporation. Some differences in the ability to trap atmospheric Hg were observed between tree species. The characterization of the litter showed an increasing Hg concentration in the plant material proportional to their degradation stage. In agricultural soils, very low Hg concentrations found in corn leaves and grains suggested a limited uptake via both the foliar and root pathways. Thus, the short-term risk of Hg transfer to agricultural crops and higher levels of the trophic chain appeared limited. A possible risk which remains to be evaluated is the possible transfer of Hg-rich particles from the forest topsoil to downstream aquatic ecosystems during rain and snowmelt events. Copyright © 2012 Elsevier B.V. All rights reserved.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

PubMed

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Enhancement of lipase catalyzed-fatty acid methyl esters production from waste activated bleaching earth by nullification of lipase inhibitors.

PubMed

Dwiarti, Lies; Ali, Ehsan; Park, Enoch Y

2010-01-01

This study sought to identify inhibitory factors of lipase catalyzed-fatty acid methyl esters (FAME) production from waste activated bleaching earth (wABE). During the vegetable oil refinery process, activated bleaching earth (ABE) is used for removing the impure compounds, but adsorbs vegetable oil up to 35-40% as on a weight basis, and then the wABE is discarded as waste material. The impurities were extracted from the wABE with methanol and evaluated by infra-red (IR) spectroscopy, which revealed that some were chlorophyll-plant pigments. The chlorophylls inhibited the lipase during FAME conversion from wABE. The inhibition by a mixture of chlorophyll a and b was found to be competitive. The inhibition of the enzymatic hydrolysis of waste vegetable oil contained in wABE by chlorophyll a alone was competitive, while the inhibition by chlorophyll b alone was non-competitive. Furthermore, the addition of a small amount of alkali nullified this inhibitory effect and accelerated the FAME production rate. When 0.9% KOH (w/w wABE) was added to the transesterification reaction with only 0.05% lipase (w/w wABE), the maximum FAME production rate improved 120-fold, as compared to that without the addition of KOH. The alkali-combined lipase significantly enhanced the FAME production rate from wABE, in spite of the presence of the plant pigments, and even when a lower amount of lipase was used as a catalyst.

A Thermodynamic Approach for Modeling H2O-CO2 Solubility in Alkali-rich Mafic Magmas at Mid-crustal Pressures

NASA Astrophysics Data System (ADS)

Allison, C. M.; Roggensack, K.; Clarke, A. B.

2017-12-01

Volatile solubility in magmas is dependent on several factors, including composition and pressure. Mafic (basaltic) magmas with high concentrations of alkali elements (Na and K) are capable of dissolving larger quantities of H2O and CO2 than low-alkali basalt. The exsolution of abundant gases dissolved in alkali-rich mafic magmas can contribute to large explosive eruptions. Existing volatile solubility models for alkali-rich mafic magmas are well calibrated below 200 MPa, but at greater pressures the experimental data is sparse. To allow for accurate interpretation of mafic magmatic systems at higher pressures, we conducted a set of mixed H2O-CO2 volatile solubility experiments between 400 and 600 MPa at 1200 °C in six mafic compositions with variable alkali contents. Compositions include magmas from volcanoes in Italy, Antarctica, and Arizona. Results from our experiments indicate that existing volatile solubility models for alkali-rich mafic magmas, if extrapolated beyond their calibrated range, over-predict CO2 solubility at mid-crustal pressures. Physically, these results suggest that volatile exsolution can occur at deeper levels than what can be resolved from the lower-pressure experimental data. Existing thermodynamic models used to calculate volatile solubility at different pressures require two experimentally derived parameters. These parameters represent the partial molar volume of the condensed volatile species in the melt and its equilibrium constant, both calculated at a standard temperature and pressure. We derived these parameters for each studied composition and the corresponding thermodynamic model shows good agreement with the CO2 solubility data of the experiments. A general alkali basalt solubility model was also constructed by establishing a relationship between magma composition and the thermodynamic parameters. We utilize cation fractions from our six compositions along with four compositions from the experimental literature in a linear regression to generate this compositional relationship. Our revised general model provides a new framework to interpret volcanic data, yielding greater depths for melt inclusion entrapment than previously calculated using other models, and it can be applied to mafic magma compositions for which no experimental data is available.

Calculation of Collisional Cross Sections for the 2P3/2 - 2P1/2 Transition in Alkali-Noble Gas Systems

DTIC Science & Technology

2010-03-01

matrix elements. From scattering matrix elements for several different effective potential values and using the Method of Partial Waves[7], the...scattering matrix elements. Through the Method of Par- tial Waves[7], the procedure was repeated for several different effective potentials. The...section calculations. It is important to note that lmax may differ for σel and σi→f . This method may only be used if both σi→f and σel have

Distribution, movement, and evolution of the volatile elements in the lunar regolith

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.

1975-01-01

The abundances and distributions of carbon, nitrogen, and sulfur in lunar soils are reviewed. Carbon and nitrogen have a predominantly extra-lunar origin in lunar soils and breccias, while sulfur is mostly indigeneous to the moon. The lunar processes which effect the movement, distribution, and evolution of carbon, nitrogen, and sulfur, along with the volatile alkali elements sodium, potassium, and rubidium during regolith processes are discussed. Possible mechanisms which may result in the addition to or loss from the moon of these volatile elements are considered.

Angrites: A Volatile-rich Variety of Asteroidal Basalt (Except for Alkalis and Gallium!)

NASA Astrophysics Data System (ADS)

Warren, P. H.; Kallemeyn, G. W.

1995-09-01

Angrites are commonly viewed as extremely volatile-depleted, and a related notion is that they formed by differentiation of a very CAI-rich material [e.g., 1]. Partial melting experiments reportedly reproduce the bulk compositions (although not fassaite-rich mineralogy) of angrites with Allende as starting material [2], but highly CAI-rich parent materials are difficult to reconcile with isotopic and REE data [3,4]. Mittlefehldt and Lindstrom [5] inferred from the low Na/Al ratios of angrites that outgassing, and thus primordial magmatism, was more intense on their parent body than on the eucrite parent asteroid. Of seven elements that (a) have been adequately determined in angrites, and (b) are far more volatile (solar-nebula 50% condensation T [6] = 690-430 K) than the alkalis (1000-910 K), four are enriched, and none is significantly depleted, in average angrite compared to average eucrite or low-Ti mare basalt (Figure). Gallium, which is of intermediate volatility (830 K), is depleted to roughly the same extent as Na and K. Results for A881371 [3] are incomplete (Zn, 6 micrograms/g, is near INAA detection limit), but even based only on AdoR and the two LEW angrites, this pattern seems firmly established. Apparent gas cavities in A881371 [7] also suggest that volatiles are far from uniformly depleted. The only elements known to be depleted, as volatiles, by clearly significant factors in angrites versus eucrites or lunar basalts, are alkalis plus gallium. Besides being moderately volatile, a noteworthy characteristic shared among Ga and alkalis (and not shared with elements such as Br, Se, and Zn) is that these elements probably tend to partition into crustal feldspar during gross differentiation of small (low-pressure) bodies. If gallium + alkalis were depleted by a single process starting from "normal" chondritic material, that process would seem to require selective exposure of a feldspar-enriched region (i.e., crust) to extremely high temperature. Igneous crystallization of the angrites occurred when the solar system was still extremely young, and apparently <=2 Ma after the volatile-depletion process [4]. The data of [4] eliminate 26Al as a potential heat source for magmatism. The angrite volatile pattern may be the product of heating by an intense, short-lived heat source that melted and partially vaporized the crust of an asteroid(s) (not necessarily the final angrite asteroid), without much affecting the deep interior(s), which later (through mixing and/or magmatism) replenished the angritic materials in most volatiles, but not alkalis and Ga. Exogenic heating, as in the often-conjectured (but hard to test) hypothesis that a major early heat source was enhanced solar luminosity (as in FU-Orionis cycles), would seem to be required. LEW 87051 and A881371 are rich in compositionally diverse olivine xenocrysts, and A881371 contains a possible FeS xenocryst [7]. These, and the angrites' great siderophile diversity [3], tend to suggest that magmatism and intensely disruptive cratering (with mixing of precursor materials) were contemporaneous. This scenario is admittedly speculative, but the volatile-depletion pattern is difficult to rationalize with any other model. References: [1] Prinz M. and Weisberg M. (1995) Antarct. Meteorites, XX, 207-210. [2] Jurewicz A. et al. (1993) GCA, 57, 2123-2139. [3] Warren P. et al. (1995) Antarct. Meteorites, XX, 261-264. [4] Lugmair G. and Galer S. 1992) GCA, 56, 1673-1694. [5] Mittlefehldt D. and Lindstrom M. (1990) GCA, 54, 3209-3218. [6] Wasson J. (1985) Meteorites. [7] Warren P. and Davis A. (1995) Antarct. Meteorites, XX, 257-260.

Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury.

PubMed

Tang, Hongjian; Duan, Yufeng; Zhu, Chun; Cai, Tianyi; Li, Chunfeng; Cai, Liang

2017-10-01

Alkali metal-based sorbents are potential for oxidized mercury (Hg 2+ ) selective adsorption but show hardly effect to elemental mercury (Hg 0 ) in flue gas. Density functional theory (DFT) was employed to investigate the Hg 0 and HgCl 2 adsorption mechanism over alkali metal-based sorbents, including calcium oxide (CaO), magnesium oxide (MgO), potassium chloride (KCl) and sodium chloride (NaCl). Hg 0 was found to weakly interact with CaO (001), MgO (001), KCl (001) and NaCl (001) surfaces while HgCl 2 was effectively adsorbed on top-O and top-Cl sites. Charge transfer and bond population were calculated to discuss the covalency and ionicity of HgCl 2 bonding with the adsorption sites. The partial density of states (PDOS) analysis manifests that HgCl 2 strongly interacts with surface sites through the orbital hybridizations between Hg and top O or Cl. Frontier molecular orbital (FMO) energy and Mulliken electronegativity are introduced as the quantitative criteria to evaluate the reactivity of mercury species and alkali metal-based sorbents. HgCl 2 is identified as a Lewis acid and more reactive than Hg 0 . The Lewis basicity of the four alkali metal-based sorbents is predicted as the increasing order: NaCl < MgO < KCl < CaO, in consistence with the trend of HgCl 2 adsorption energies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Host-rock controlled epigenetic, hydrothermal metasomatic origin of the Bayan Obo REEFe-Nb ore deposit, Inner Mongolia, P.R.C.

USGS Publications Warehouse

Chao, E.C.T.; Back, J.M.; Minkin, J.A.; Yinchen, R.

1992-01-01

Bayan Obo, a complex rare earth element (REE)FeNb ore deposit, located in Inner Mongolia, P.R.C. is the world's largest known REE deposit. The deposit is chiefly in a marble unit (H8), but extends into an overlying unit of black shale, slate and schist unit (H9), both of which are in the upper part of the Middle Proterozoic Bayan Obo Group. Based on sedimentary structures, the presence of detrital quartz and algal fossil remains, and the 16-km long geographic extent, the H8 marble is a sedimentary deposit, and not a carbonatite of magmatic origin, as proposed by some previous investigators. The unit was weakly regionally metamorphosed (most probably the lower part of the green schist facies) into marble and quartzite prior to mineralization. Tectonically, the deposit is located on the northern flank of the Sino-Korean craton. Many hypotheses have been proposed for the origin of the Bayan Obo deposit; the studies reported here support an epigenetic, hydrothermal, metasomatic origin. Such an origin is supported by field and laboratory textural evidence; 232Th/208Pb internal isochron mineral ages of selected monazite and bastnaesite samples; 40Ar/39Ar incremental heating minimum mineral ages of selected alkali amphiboles; chemical compositions of different generations of both REE ore minerals and alkali amphiboles; and evidence of host-rock influence on the various types of Bayan Obo ores. The internal isochron ages of the REE minerals indicate Caledonian ages for various episodes of REE and Fe mineralization. No evidence was found to indicate a genetic relation between the extensive biotite granitic rocks of Hercynian age in the mine region and the Bayan Obo are deposit, as suggested by previous workers. ?? 1992.

A discussion on the tectonic implications of Ediacaran late- to post-orogenic A-type granite in the northeastern Arabian Shield, Saudi Arabia

NASA Astrophysics Data System (ADS)

Robinson, F. A.; Bonin, B.; Pease, V.; Anderson, J. L.

2017-03-01

The transition from late-orogenic to post-orogenic magmatism following major orogenic episodes such as the Neoproterozoic to Cambrian East African Orogen (EAO) is an important, yet not well-understood geological event marking the cessation of subduction-controlled magmatism between buoyant lithospheric fragments. Forming the northern part of the EAO in the Arabian-Nubian Shield are three granitic suites that successively intruded the same northeastern area and post-date the 640 Ma major orogenic episode: (1) 620-600 Ma alkali feldspar (hypersolvous) granite with alkaline/ferroan/A-type geochemistry, (2) 599 Ma granite cumulates (some garnet-bearing) with calc-alkaline/magnesian affinities, and (3) 584-566 Ma alkali feldspar (hypersolvous) granite (aegirine-bearing) with a distinctive peralkaline/ferroan/A-type signature. Combining whole-rock geochemistry from the southern and northern Arabian Shield, suites 1 and 2 are suggested to be products of late-orogenic slab tear/rollback inducing asthenospheric mantle injection and lower crustal melting/fractionation toward A-type/ferroan geochemistry. Suite 3, however, is suggested to be produced by post-orogenic lithospheric delamination, which replaced the older mantle with new asthenospheric (rare earth element-enriched) mantle that ultimately becomes the thermal boundary layer of the new lithosphere. Major shear zones, such as the 620-540 Ma Najd Fault System (NFS), are some of the last tectonic events recorded across the Arabian Shield. Data presented here suggest that the NFS is directly related to the late-orogenic (620-600 Ma) slab tear/rollback in the northeastern Shield as it met with opposing subduction polarity in the southern Shield. Furthermore, this study infers that east and west Gondwana amalgamation interacted with opposing convergence reflected by the NFS.

Squeezing clathrate cages to host trivalent rare-earth guests

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

Wang, Jian; He, Yuping; Mordvinova, Natalia E.

Strike difference of the trivalent rare-earth cations from their alkali and alkaline-earth peers is in the presence of localized 4f-electrons and strong spin-orbit coupling. Placing trivalent rare-earth cations inside the fullerene molecules or in between the blocks of itinerant magnetic intermetallics gave rise to plethora of fascinating properties and materials. A long-time missing but hardly desired piece is the semiconducting or metallic compound where rare-earth cations are situated inside the oversized polyhedral cages of three-dimensional framework. In this work we present a synthesis of such compounds, rare-earth containing clathrates Ba 8-xR xCu 16P 30. The unambiguous proofs of their compositionmore » and crystal structure were achieved by a combination of synchrotron powder diffraction, time-of-flight neutron powder diffraction, scanning-transmission electron microscopy, and electron energy-loss spectroscopy. Our quantum-mechanical calculations and experimental characterizations show that the incorporation of the rare-earth cations significantly enhances the hole mobility and concentration which results in the drastic increase in the thermoelectric performance.« less

Volatile element chemistry in the solar nebula - Na, K, F, Cl, Br, and P

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Lewis, J. S.

1980-01-01

The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.

Petrographic and geochemical characterization of the granitic rocks of the Araguainha impact crater, Brazil

NASA Astrophysics Data System (ADS)

Silva, Dailto; Lana, Cristiano; Souza Filho, Carlos Roberto

2016-03-01

Petrographic and geochemical data obtained on the Araguainha impact crater (Goiás/Mato Grosso States, Brazil) indicate the existence of several molten products that originated during impact-induced congruent melting of an alkali-granite exposed in the inner part of the central uplift of the structure. Although previous studies have described these melts to some extent, there is no detailed discussion on the petrographic and geochemical variability in the granite and its impactogenic derivatives, and therefore, little is known about the geochemical behavior and mobility of trace elements during its fusion in the central part of the Araguainha crater. This paper demonstrates that the preserved granitoid exposed in the core of the structure is a magnesium-rich granite, similar to postcollisional, A-type granites, also found in terrains outside the Araguainha crater, in the Brasília orogenic belt. The molten products are texturally distinct and different from the original rock, but have very similar geochemical composition, making it difficult to separate these lithotypes based on concentrations of major and minor elements. This also applies for trace and rare earth elements (REE), thus indicating a high degree of homogenization during impact-induced congruent melting under high pressure and postshock temperature conditions. Petrographic observations, along with geochemical data, indicate that melting occurs selectively, where some of the elements are transported with the melt. Simultaneously, there is an effective dissolution of the rock (granite), which leads to entrainment of the most resistant solid phases (intact or partially molten minerals) into the melt. Minerals more resistant to melting, such as quartz and oxides, contribute substantially to a chemical balance between the preserved granite and the fusion products generated during the meteoritic impact.

Electron core ionization in compressed alkali metal cesium

NASA Astrophysics Data System (ADS)

Degtyareva, V. F.

2018-01-01

Elements of groups I and II in the periodic table have valence electrons of s-type and are usually considered as simple metals. Crystal structures of these elements at ambient pressure are close-packed and high-symmetry of bcc and fcc-types, defined by electrostatic (Madelung) energy. Diverse structures were found under high pressure with decrease of the coordination number, packing fraction and symmetry. Formation of complex structures can be understood within the model of Fermi sphere-Brillouin zone interactions and supported by Hume-Rothery arguments. With the volume decrease there is a gain of band structure energy accompanied by a formation of many-faced Brillouin zone polyhedra. Under compression to less than a half of the initial volume the interatomic distances become close to or smaller than the ionic radius which should lead to the electron core ionization. At strong compression it is necessary to assume that for alkali metals the valence electron band overlaps with the upper core electrons, which increases the valence electron count under compression.

Internal structure of cesium-bearing radioactive microparticles released from Fukushima nuclear power plant

PubMed Central

Yamaguchi, Noriko; Mitome, Masanori; Kotone, Akiyama-Hasegawa; Asano, Maki; Adachi, Kouji; Kogure, Toshihiro

2016-01-01

Microparticles containing substantial amounts of radiocesium collected from the ground in Fukushima were investigated mainly by transmission electron microscopy (TEM) and X-ray microanalysis with scanning TEM (STEM). Particles of around 2 μm in diameter are basically silicate glass containing Fe and Zn as transition metals, Cs, Rb and K as alkali ions, and Sn as substantial elements. These elements are homogeneously distributed in the glass except Cs which has a concentration gradient, increasing from center to surface. Nano-sized crystallites such as copper- zinc- and molybdenum sulfide, and silver telluride were found inside the microparticles, which probably resulted from the segregation of the silicate and sulfide (telluride) during molten-stage. An alkali-depleted layer of ca. 0.2 μm thick exists at the outer side of the particle collected from cedar leaves 8 months after the nuclear accident, suggesting gradual leaching of radiocesium from the microparticles in the natural environment. PMID:26838055

ELECTROLYTIC PROCESS FOR PRODUCING METALS

DOEpatents

Kopelman, B.; Holden, R.B.

1961-06-01

A method is described for reducing beryllium halides to beryllium. The beryllfum halide fs placed in an eutectic mixture of alkali halides and alkaline earth halides. The constituents of this eutectic bath are so chosen that it has a melting point less than the boiling point of mercury, which acts as a cathode for the system. The beryllium metal is then deposited in the mercury upon electrolysis.

Catalytic asymmetric nitro-Mannich reactions with a Yb/K heterobimetallic catalyst.

PubMed

Nitabaru, Tatsuya; Kumagai, Naoya; Shibasaki, Masakatsu

2010-03-04

A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines.

Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalysts

DOEpatents

Wingfield, Jr., Robert C.; Braslaw, Jacob; Gealer, Roy L.

1985-01-01

The invention relates to a process for improving the pyrolytic conversion of waste selected from rubber and plastic to low molecular weight olefinic materials by employing basis salt catalysts in the waste mixture. The salts comprise alkali or alkaline earth compounds, particularly sodium carbonate, in an amount of greater than about 1 weight percent based on the waste feed.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

Nuclear fuel cycle waste stream immobilization with cermets for improved thermal properties and waste consolidation

NASA Astrophysics Data System (ADS)

Ortega, Luis H.; Kaminski, Michael D.; Zeng, Zuotao; Cunnane, James

2013-07-01

In the pursuit of methods to improve nuclear waste form thermal properties and combine potential nuclear fuel cycle wastes, a bronze alloy was combined with an alkali, alkaline earth metal bearing ceramic to form a cermet. The alloy was prepared from copper and tin (10 mass%) powders. Pre-sintered ceramic consisting of cesium, strontium, barium and rubidium alumino-silicates was mixed with unalloyed bronze precursor powders and cold pressed to 300 × 103 kPa, then sintered at 600 °C and 800 °C under hydrogen. Cermets were also prepared that incorporated molybdenum, which has a limited solubility in glass, under similar conditions. The cermet thermal conductivities were seven times that of the ceramic alone. These improved thermal properties can reduce thermal gradients within the waste forms thus lowering internal temperature gradients and thermal stresses, allowing for larger waste forms and higher waste loadings. These benefits can reduce the total number of waste packages necessary to immobilize a given amount of high level waste and immobilize troublesome elements.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

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

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Bulk, rare earth and other trace elements in Apollo 14 and 15 and Luna 16 samples

NASA Technical Reports Server (NTRS)

Laul, J. C.; Wakita, H.; Showalter, D. L.; Boynton, W. V.; Schmitt, R. A.

1971-01-01

The chemical abundances were measured by instrumental and radiochemical neutron activation analysis in a variety of lunar specimens. Apollo 14 soils are characterized by significant enrichments of Al2O3, Na2O and K2O and depletions of TiO2, FeO, MnO and Cr2O3 relative to Apollo 11 and to most of Apollo 12 soils. The uniform abundances in 14230 core tube soils and three other Apollo 14 soils indicate that the regolith is uniform to at least 22 cm depth and within approximately 200 m from the lunar module. Two Luna 16 breccias are similar in composition to Luna 16 soils. Four Apollo 15 soils (LM, STA 4, 9, and 9a) have variable compositions. Interelement correlations between MnO-FeO, Sc-FeO, V-Cr2O3 and K2O-Hf negate the hypothesis that howardite achondrites may be primitive lunar matter, argue against the fission hypothesis for the origin of the moon, and precludes any selective large scale volatilization of alkalies during lunar magmatic events.

Method for making polysilsesquioxanes and organohydridosilanes

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

Loy, Douglas A.; Rahimian, Kamyar

2001-01-01

A method for disproportionation of an oligohydridosiloxane to produce a polysilsesquioxane compound and an organohydridosilane compound when contacted with a basic catalyst. The basic catalyst can be a tetraalkylammonium hydroxide, an alkali metal hydroxide, and an alkali earth hydroxide. These basic catalysts are generally dissolved in an organic solvent for delivery. The hydroxide catalysts are attractive because many readily decompose by heating above 150.degree. C., thus being easily removed from the final materials. The oligohydridosiloxane is contacted with the basic catalyst under conditions effective to catalytically convert the oligohydridosiloxane into a polysilsesquioxane compound and an organohydridosilane compound. The reaction canmore » occur in either an inert or oxidative atmosphere and can occur without heating, at room temperature. Both polysilsesquioxane foams and gels of the formula (RSiO.sub.1.5).sub.n can be produced.« less

Destabilized and catalyzed borohydride for reversible hydrogen storage

DOEpatents

Mohtadi, Rana F [Northville, MI; Nakamura, Kenji [Toyota, JP; Au, Ming [Martinez, GA; Zidan, Ragaiy [Alken, SC

2012-01-31

A process of forming a hydrogen storage material, including the steps of: providing a first material of the formula M(BH.sub.4).sub.X, where M is an alkali metal or an alkali earth metal, providing a second material selected from M(AlH.sub.4).sub.x, a mixture of M(AlH.sub.4).sub.x and MCl.sub.x, a mixture of MCl.sub.x and Al, a mixture of MCl.sub.x and AlH.sub.3, a mixture of MH.sub.x and Al, Al, and AlH.sub.3. The first and second materials are combined at an elevated temperature and at an elevated hydrogen pressure for a time period forming a third material having a lower hydrogen release temperature than the first material and a higher hydrogen gravimetric density than the second material.

Thermoluminescence (TL) dosimeter of dysprosium doped strontium borate glass for different glass modifiers (Na, Li, Ca) subjected from 1 to 9 Gy doses

NASA Astrophysics Data System (ADS)

Hamzah, S. A.; Saeed, M. A.; Wagiran, H.; Hashim, I. H.

2017-10-01

This article reports TL response for different glass modifier and doping concentration. Alkali oxides (Na2O and Li2O) and alkali earth oxide (CaO) will be used as a glass modifier for strontium borate based glass. The samples were prepared by melt quenching technique. Dy2O3 concentrations ranging from 0.00 to 0.70 mol% and exposure doses of 1 to 9 Gy will be varied. All glass samples exhibit the prominent peak temperature positioned at 186 oC to 232 oC. From all the samples, one of the samples shows an excellent linearity dose response, higher TL and show good reproducibility after 5 cycles exposure which is sodium strontium borate doped with 0.1 mol% Dy2O3 (optimum concentration).

Igneous rocks of the East Pacific Rise

USGS Publications Warehouse

Engel, A.E.J.; Engel, C.G.

1964-01-01

The apical parts of large volcanoes along the East Pacific Rise (islands and seamounts) are encrusted with rocks of the alkali volcanic suite (alkali basalt, andesine- and oligoclase-andesite, and trachyte). In contrast, the more submerged parts of the Rise are largely composed of a tholeiitic basalt which has low concentrations of K, P, U, Th, Pb, and Ti. This tholeiitic basalt is either the predominant or the only magma generated in the earth's mantle under oceanic ridges and rises. It is at least 1000-fold more abundant than the alkali suite, which is probably derived from tholeiitic basalt by magmatic differentiation in and immediately below the larger volcanoes. Distinction of oceanic tholeiites from almost all continental tholeiites is possible on the simple basis of total potassium content, with the discontinuity at 0.3 to 0.5 percent K2O by weight. Oceanic tholeiites also are readily distinguished from some 19 out of 20 basalts of oceanic islands and seamount cappings by having less than 0.3 percent K2O by weight and more than 48 percent SiO2. Deep drilling into oceanic volcanoes should, however, core basalts transitional between the oceanic tholeiites and the presumed derivative alkali basalts.The composition of the oceanic tholeiites suggests that the mantle under the East Pacific Rise contains less than 0.10 percent potassium oxide by weight; 0.1 part per million of uranium and 0.4 part of thorium; a potassium:rubidium ratio of about 1200 and a potassium: uranium ratio of about 104.

The Charge-Balancing Role of Calcium and Alkali Ions in Per-Alkaline Aluminosilicate Glasses.

PubMed

Thomsen, René M; Skibsted, Jørgen; Yue, Yuanzheng

2018-03-29

The structural arrangement of alkali-modified calcium aluminosilicate glasses has implications for important properties of these glasses in a wide range of industrial applications. The roles of sodium and potassium and their competition with calcium as network modifiers in peralkaline aluminosilicate glasses have been investigated by 27 Al and 29 Si MAS NMR spectroscopy. The 29 Si MAS NMR spectra are simulated using two models for distributing Al in the silicate glass network. One model assumes a hierarchical, quasi-heterogeneous aluminosilicate network, whereas the other is based on differences in relative lattice energies between Si-O-Si, Al-O-Al, and Si-O-Al linkages. A systematic divergence between these simulations and the experimental 29 Si NMR spectra is observed as a function of the sodium content exceeding that required for stoichiometric charge-balancing of the negatively charged AlO 4 tetrahedra. Similar correlations between simulations and experimental 29 Si NMR spectra cannot be made for the excess calcium content. Moreover, systematic variations in the 27 Al isotropic chemical shifts and the second-order quadrupole effect parameters, derived from the 27 Al MAS NMR spectra, are reported as a function of the SiO 2 content. These observations strongly suggest that alkali ions preferentially charge-balance AlO 4 3- as compared to alkaline earth (calcium) ions. In contrast, calcium dominates over the alkali ions in the formation of nonbridging oxygens associated with the SiO 4 tetrahedra.

A novel coumarin Schiff-base as a Ni(II) ion colorimetric sensor

NASA Astrophysics Data System (ADS)

Wang, Lingyun; Ye, Decheng; Cao, Derong

2012-05-01

A novel coumarin Schiff base compound (L) prepared from 7-diethylaminocoumarin-3-aldehyde and 3-amino-7-hydroxycoumarin was synthesized and evaluated as a chemoselective Ni2+ sensor. Addition of Ni2+ to CH3CN solution of L resulted in a rapid color change from yellow to red together with a large red shift from 465 to 516 nm. Moreover, other common alkali-, alkaline earth-, transition- and rare earth metal ions induced no or minimal spectral changes. Experimental results indicated that L could be used as a potential Ni2+ colorimetric and naked-eye chemosensor in CH3CN solution.

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.

Genesis of iron-apatite ores in Posht-e-Badam Block (Central Iran) using REE geochemistry

NASA Astrophysics Data System (ADS)

Mokhtari, Mir Ali Asghar; Zadeh, Ghader Hossein; Emami, Mohamad Hashem

2013-06-01

Rare earth elements in apatites of different ore types show characteristic patterns which are related to different modes of formation of the ores. Most of the apatite-bearing iron ores are associated with alkaline magmas with LREE/HREE fractionation varying from moderate to steep. Iron-apatite deposits in Posht-e-Badam Block (Central Iran) have a high concentration of REE (more than 1000 ppm up to 2.5%), and show a strong LREE/HREE ratio with a pronounced negative Eu anomaly. This REE pattern is typical of magmatic apatite and quiet distinct from sedimentary apatites (phosphorites) which have a low REE contents and Ce negative anomalies. On the other hand, they are comparable to the REE patterns of apatites in Kiruna-type iron ores in different parts of the world. The REE patterns of apatites, iron-apatite ores and iron ores are similar and only have different REE contents. This similarity indicates a genetic relation for these rocks. Most of the iron-apatite deposits in Central Iran have similar REE patterns too, which in turn show a genetic relation for all of these deposits. This similarity indicates a similar origin and processes in their genesis. There are some small intrusions around some of the iron-apatite deposits that are petrographically identified as syenite and gabbro. These intrusions also have REE patterns similar to that of iron-apatite ores. This demonstrates a genetic relation between these intrusions and iron-apatite ores. The REE patterns of apatites in different deposits of Posht-e-Badam Block iron-apatite ores show an affinity to alkaline to sub-alkaline magmas and rifting environment. The alkaline host rocks of Central Iran iron-apatite ores are clearly related to an extensional setting where rifting was important (SSE-NNW fault lines). A probable source for this large scale ore forming processes is relatively low partial melting of mantle rocks. The ores have originated by magmatic differentiation as a late phase in the volcanic cycle forming sub-surface injections or surface flows. These ores have formed during magmatism as immiscible liquids (silicate and Fe-P-rich magmatic liquids) which separated from strongly differentiated magmas aided by a large volatile and alkali element content. Separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits. We proposed that the separation of an iron oxide melt and the ensuing hydrothermal processes dominated by alkali metasomatism were both involved to different degrees in the formation of Posht-e-Badam Block iron-apatite deposits.

Nuclear reactivity control using laser induced polarization

DOEpatents

Bowman, Charles D.

1991-01-01

A control element for reactivity control of a fission source provides an atomic density of .sup.3 He in a control volume which is effective to control criticality as the .sup.3 He is spin-polarized. Spin-polarization of the .sup.3 He affects the cross section of the control volume for fission neutrons and hence, the reactivity. An irradiation source is directed within the .sup.3 He for spin-polarizing the .sup.3 He. An alkali-metal vapor may be included with the .sup.3 He where a laser spin-polarizes the alkali-metal atoms which in turn, spin-couple with .sup.3 He to spin-polarize the .sup.3 He atoms.

Nuclear reactivity control using laser induced polarization

DOEpatents

Bowman, Charles D.

1990-01-01

A control element for reactivity control of a fission source provides an atomic density of .sup.3 He in a control volume which is effective to control criticality as the .sup.3 He is spin-polarized. Spin-polarization of the .sup.3 He affects the cross section of the control volume for fission neturons and hence, the reactivity. An irradiation source is directed within the .sup.3 He for spin-polarizing the .sup.3 He. An alkali-metal vapor may be included with the .sup.3 He where a laser spin-polarizes the alkali-metal atoms which in turn, spin-couple with .sup.3 He to spin-polarize the .sup.3 He atoms.

Alkaline igneous rocks of Magnet Cove, Arkansas: Mineralogy and geochemistry of syenites

USGS Publications Warehouse

Flohr, M.J.K.; Ross, M.

1990-01-01

Syenites from the Magnet Cove alkaline igneous complex form a diverse mineralogical and geochemical suite. Compositional zoning in primary and late-stage minerals indicates complex, multi-stage crystallization and replacement histories. Residual magmatic fluids, rich in F, Cl, CO2 and H2O, reacted with primary minerals to form complex intergrowths of minerals such as rinkite, fluorite, V-bearing magnetite, F-bearing garnet and aegirine. Abundant sodalite and natrolite formed in pegmatitic segregations within nepheline syenite where Cl- and Na-rich fluids were trapped. During autometasomatism compatible elements such as Mn, Ti, V and Zr were redistributed on a local scale and concentrated in late-stage minerals. Early crystallization of apatite and perovskite controlled the compatible behavior of P and Ti, respectively. The formation of melanite garnet also affected the behaviour of Ti, as well as Zr, Hf and the heavy rare-earth elements. Pseudoleucite syenite and garnet-nepheline syenite differentiated along separate trends, but the two groups are related to the same parental magma by early fractionation of leucite, the presumed precursor of intergrowths of K-feldspar and nepheline. The Diamond Jo nepheline syenite group defines a different differentiation trend. Sphene-nepheline syenite, alkali syenite and several miscellaneous nepheline syenites do not consistently plot with the other syenite groups or each other on element and oxide variation diagrams, indicating that they were derived from still other parental syenite magmas. Mineral assemblages indicate that relatively high f{hook};O2, at or above the fayalite-magnetite-quartz buffer, prevailed throughout the crystallization history of the syenites. ?? 1990.

Cosmochemical Estimates of Mantle Composition

NASA Astrophysics Data System (ADS)

Palme, H.; O'Neill, H. St. C.

2003-12-01

In 1794 the German physicist Chladni published a small book in which he suggested the extraterrestrial origin of meteorites. The response was skepticism and disbelief. Only after additional witnessed falls of meteorites did scientists begin to consider Chladni's hypothesis seriously. The first chemical analyses of meteorites were published by the English chemist Howard in 1802, and shortly afterwards by Klaproth, a professor of chemistry in Berlin. These early investigations led to the important conclusion that meteorites contained the same elements that were known from analyses of terrestrial rocks. By the year 1850, 18 elements had been identified in meteorites: carbon, oxygen, sodium, magnesium, aluminum, silicon, phosphorous, sulfur, potassium, calcium, titanium, chromium, manganese, iron, cobalt, nickel, copper, and tin (Burke, 1986). A popular hypothesis, which arose after the discovery of the first asteroid Ceres on January 1, 1801 by Piazzi, held that meteorites came from a single disrupted planet between Mars and Jupiter. In 1847 the French geologist Boisse (1810-1896) proposed an elaborate model that attempted to account for all known types of meteorites from a single planet. He envisioned a planet with layers in sequence of decreasing densities from the center to the surface. The core of the planet consisted of metallic iron surrounded by a mixed iron-olivine zone. The region overlying the core contained material similar to stony meteorites with ferromagnesian silicates and disseminated grains of metal gradually extending into shallower layers with aluminous silicates and less iron. The uppermost layer consisted of metal-free stony meteorites, i.e., eucrites or meteoritic basalts. About 20 years later, Daubrée (1814-1896) carried out experiments by melting and cooling meteorites. On the basis of his results, he came to similar conclusions as Boisse, namely that meteorites come from a single, differentiated planet with a metal core, a silicate mantle, and a crust. Both Daubrée and Boisse also expected that the Earth was composed of a similar sequence of concentric layers (see Burke, 1986; Marvin, 1996).At the beginning of the twentieth century Harkins at the University of Chicago thought that meteorites would provide a better estimate for the bulk composition of the Earth than the terrestrial rocks collected at the surface as we have only access to the "mere skin" of the Earth. Harkins made an attempt to reconstruct the composition of the hypothetical meteorite planet by compiling compositional data for 125 stony and 318 iron meteorites, and mixing the two components in ratios based on the observed falls of stones and irons. The results confirmed his prediction that elements with even atomic numbers are more abundant and therefore more stable than those with odd atomic numbers and he concluded that the elemental abundances in the bulk meteorite planet are determined by nucleosynthetic processes. For his meteorite planet Harkins calculated Mg/Si, Al/Si, and Fe/Si atomic ratios of 0.86, 0.079, and 0.83, very closely resembling corresponding ratios of the average solar system based on presently known element abundances in the Sun and in CI-meteorites (see Burke, 1986).If the Earth were similar compositionally to the meteorite planet, it should have a similarly high iron content, which requires that the major fraction of iron is concentrated in the interior of the Earth. The presence of a central metallic core to the Earth was suggested by Wiechert in 1897. The existence of the core was firmly established using the study of seismic wave propagation by Oldham in 1906 with the outer boundary of the core accurately located at a depth of 2,900km by Beno Gutenberg in 1913. In 1926 the fluidity of the outer core was finally accepted. The high density of the core and the high abundance of iron and nickel in meteorites led very early to the suggestion that iron and nickel are the dominant elements in the Earth's core (Brush, 1980; see Chapter 2.15).Goldschmidt (1922) introduced his zoned Earth model. Seven years later he published details ( Goldschmidt, 1929). Goldschmidt thought that the Earth was initially completely molten and separated on cooling into three immiscible liquids, leading on solidification to the final configuration of a core of FeNi which was overlain by a sulfide liquid, covered by an outer shell of silicates. Outgassing during melting and crystallization produced the atmosphere. During differentiation elements would partition into the various layers according to their geochemical character. Goldschmidt distinguished four groups of elements: siderophile elements preferring the metal phase, chalcophile elements preferentially partitioning into sulfide, lithophile elements remaining in the silicate shell, and atmophile elements concentrating into the atmosphere. The geochemical character of each element was derived from its abundance in the corresponding phases of meteorites.At about the same time astronomers began to extract compositional data from absorption line spectroscopy of the solar photosphere, and in a review article, Russell (1941) concluded: "The average composition of meteorites differs from that of the earth's crust significantly, but not very greatly. Iron and magnesium are more abundant and nickel and sulfur rise from subordinate positions to places in the list of the first ten. Silicon, aluminum, and the alkali metals, especially potassium, lose what the others gain." And Russell continued: "The composition of the earth as a whole is probably much more similar to the meteorites than that of its `crust&'." Russell concludes this paragraph by a statement on the composition of the core: "The known properties of the central core are entirely consistent with the assumption that it is composed of molten iron - though not enough to prove it. The generally accepted belief that it is composed of nickel-iron is based on the ubiquitous appearance of this alloy in metallic meteorites," and, we should add, also on the abundances of iron and nickel in the Sun.Despite the vast amount of additional chemical data on terrestrial and meteoritic samples and despite significant improvements in the accuracy of solar abundances, the basic picture as outlined by Russell has not changed. In the following sections we will demonstrate the validity of Russell's assumption and describe some refinements in the estimate of the composition of the Earth and the relationship to meteorites and the Sun.

Accumulation of rare earth elements by siderophore-forming Arthrobacter luteolus isolated from rare earth environment of Chavara, India.

PubMed

Emmanuel, E S Challaraj; Ananthi, T; Anandkumar, B; Maruthamuthu, S

2012-03-01

In this study, Arthrobacter luteolus, isolated from rare earth environment of Chavara (Quilon district, Kerala, India), were found to produce catechol-type siderophores. The bacterial strain accumulated rare earth elements such as samarium and scandium. The siderophores may play a role in the accumulation of rare earth elements. Catecholate siderophore and low-molecular-weight organic acids were found to be present in experiments with Arthrobacter luteolus. The influence of siderophore on the accumulation of rare earth elements by bacteria has been extensively discussed.

Google Earth locations of USA and seafloor hydrothermal vents with associated rare earth element data

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

Andrew Fowler

Google Earth .kmz files that contain the locations of geothermal wells and thermal springs in the USA, and seafloor hydrothermal vents that have associated rare earth element data. The file does not contain the actual data, the actual data is available through the GDR website in two tier 3 data sets entitled "Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge (MOR) Hydrothermal Vents" and "Rare earth element content of thermal fluids from Surprise Valley, California"

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.

Composition and method to remove asbestos

DOEpatents

Block, J.

1998-05-19

A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed. The composition comprises water, at least about 30% by weight of an inorganic acid, and from about 0.1 to about 4% by weight of a tetrafluoroborate of ammonia, an alkali metal or an alkaline earth metal. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition also is disclosed.

Composition and method to remove asbestos

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

Block, J.

A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed. The composition comprises water, at least about 30% by weight of an inorganic acid, and from about 0.1 to about 4% by weight of a hexafluorosilicate of ammonia, an alkali metal or an alkaline earth metal. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition also is disclosed.

Composition and method to remove asbestos

DOEpatents

Block, J.

1998-05-19

A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed. The composition comprises water, at least about 30% by weight of an inorganic acid, and from about 0.1 to about 4% by weight of a hexafluorosilicate of ammonia, an alkali metal or an alkaline earth metal. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition also is disclosed.

Composition and method to remove asbestos

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

Block, J.

A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed. The composition comprises water, at least about 30% by weight of an inorganic acid, and from about 0.1 to about 4% by weight of a tetrafluoroborate of ammonia, an alkali metal or an alkaline earth metal. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition also is disclosed.

METHOD FOR THE REDUCTION OF URANIUM COMPOUNDS

DOEpatents

Cooke, W.H.; Crawford, J.W.C.

1959-05-12

An improved technique of preparing massive metallic uranium by the reaction at elevated temperature between an excess of alkali in alkaline earth metal and a uranium halide, such ss uranium tetrafluoride is presented. The improvement comprises employing a reducing atmosphere of hydrogen or the like, such as coal gas, in the vessel during the reduction stage and then replacing the reducing atmosphere with argon gas prior to cooling to ambient temperature.

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

PRODUCTION OF TRIFLUOROACETIC ACID

DOEpatents

Haworth, W.N.; Stacey, M.

1949-07-19

A method is given for the production of improved yields of trifluoroacetic acid. The compound is prepared by oxidizing m-aminobenzotrifluoride with an alkali metal or alkaline earth metal permanganate at a temperature in the range of 80 deg C to 100 deg C while dissolved ln a mixture of water with glacial acetic acid and/or trifluoroacetic acid. Preferably a mixture of water and trifluoroacetic acid ls used as the solvent.

ELECTROCHEMICAL DECONTAMINATION AND RECOVERY OF URANIUM VALUES

DOEpatents

McLaren, J.A.; Goode, J.H.

1958-05-13

An electrochemical process is described for separating uranium from fission products. The method comprises subjecting the mass of uranium to anodic dissolution in an electrolytic cell containing aqueous alkali bicarbonate solution as its electrolyte, thereby promoting a settling from the solution of a solid sludge from about the electrodes and separating the resulting electrolyte solution containing the anodically dissolved uranium from the sludge which contains the rare earth fission products.

"Leaching or not leaching": an alternative approach to antimicrobial materials via copolymers containing crown ethers as active groups.

PubMed

De Rosa, M; Vigliotta, G; Soriente, A; Capaccio, V; Gorrasi, G; Adami, R; Reverchon, E; Mella, M; Izzo, L

2017-03-28

In this work, new copolymers containing either MMA and 18C6 crown-ether pendants, or PEG, MMA and 18C6 crown-ether pendants were synthesized to test the idea that sequestering structural alkali-earth ions from the bacterial outer membrane (OM) may lead to bacterial death. The copolymers were obtained either via uncontrolled radical polymerization or ATRP; the latter approached allowed us to produce not only linear copolymers but also branched Y-like structures. After checking for the capability of complexing magnesium and calcium ions, the antimicrobial activity of all copolymers was tested placing their casted plaques in contact with pure water E. coli suspensions. All plaques adsorbed alkali-earth ions and killed bacteria, albeit with different antimicrobial efficiencies. Differences in the latter characteristic were attributed to different plaque roughness. The role of the 18C6 crown-ether pendants was elucidated by pre-saturating plaques with Mg/Ca ions, the marked reduction in antimicrobial efficiency indicating that losing the latter from OM due to surface complexation does play an important role in killing bacteria at short (<5 h) contact times. At longer times, the mode of action is instead related to the poly-cationic nature acquired by the plaques due to ion sequestering.

Determination of amines used in the oil and gas industry (upstream section) by ion chromatography.

PubMed

Kadnar, R

1999-07-30

During production and purification of crude oil and natural gas several different amines are used as chemicals or operating materials, e.g. film forming long chain amines as corrosion inhibitors, steam volatile amines for pH correction and corrosion protection, alkanolamines as absorbents in sour gas treatment plants, etc. For analytical checks, e.g. determination of corrosion inhibitor concentration in produced media, classical chemical methods are used predominantly, because most of them can be performed in small field laboratories. Some amines, especially the small molecular aliphatic and heterocyclic amines can also be determined by ion chromatography. In our laboratory two types of separation columns (IonPac CS10 and CS12A) were available for ion chromatographic separation. The analysis of the amines in low-salt-containing water, soft water or steam condensate can be performed without problems. The presence of alkali and/or alkaline earth ions in the sample can lead to coelution with these ions, to poor peak resolution or enhanced analysis times, depending on the chromatographic conditions. This work shows some examples of ion chromatography applications for the determination of low-molecular-mass ethanolamines, morpholine and piperazine and discusses the possible interferences and troubles caused by alkali and alkaline earth ions in the matrix.

Alkali and alkaline earth metallic (AAEM) species leaching and Cu(II) sorption by biochar.

PubMed

Li, Mi; Lou, Zhenjun; Wang, Yang; Liu, Qiang; Zhang, Yaping; Zhou, Jizhi; Qian, Guangren

2015-01-01

Alkali and alkaline earth metallic (AAEM) species water leaching and Cu(II) sorption by biochar prepared from two invasive plants, Spartina alterniflora (SA) and water hyacinth (WH), were explored in this work. Significant amounts of Na and K can be released (maximum leaching for Na 59.0 mg g(-1) and K 79.9 mg g(-1)) from SA and WH biochar when they are exposed to contact with water. Cu(II) removal by biochar is highly related with pyrolysis temperature and environmental pH with 600-700 °C and pH of 6 showing best performance (29.4 and 28.2 mg g(-1) for SA and WH biochar). Cu(II) sorption exerts negligible influence on Na/K/Mg leaching but clearly promotes the release of Ca. Biochars from these two plant species provide multiple benefits, including nutrient release (K), heavy metal immobilization as well as promoting the aggregation of soil particles (Ca) for soil amelioration. AAEM and Cu(II) equilibrium concentrations in sorption were analyzed by positive matrix factorization (PMF) to examine the factors underlying the leaching and sorption behavior of biochar. The identified factors can provide insightful understanding on experimental phenomena. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermophysical and Electronic Properties Information Analysis Center (TEPIAC): A Continuing Systematic Program on Tables of Thermophysical and Electronic Properties of Materials.

DTIC Science & Technology

1977-02-01

oxides and their mixtures, arsenides, borides, bromides , carbides , chlorides , fluoride s, nitride s, phosphides, silicides , sulfides , tellurides...ivity of alkali elements (lithium , sodium , potassium , rubi- dium , ces ium , and francium) and contains recomme nded reference values generated

ORGANIZATION II, NOVA SCIENCE UNIT 3.

ERIC Educational Resources Information Center

Broward County Schools, Fort Lauderdale, FL.

THE ORGANIZATION OF THE NATURE OF SCIENCE IS EMPHASIZED THROUGH A FOCUS ON CHEMICAL REACTIONS. SIMILARITIES OF THE REACTIONS OF THE HALOGENS WITH THE ALKALI METALS OF LITHIUM, SODIUM, POTASSIUM, AND HYDROGEN ARE INTRODUCED TO THE STUDENT. STUDENTS ARE INTRODUCED TO THE PERIODIC TABLE OF ELEMENTS WHICH EMPHASIZES THE ORGANIZATION OF CHEMICAL…

Industrial Location Research Studies: Reports 9-16.

ERIC Educational Resources Information Center

Fantus Co., Inc., New York, NY.

Eight studies identify, examine, and evaluate significant elements of industry-location decisions as they relate directly or indirectly to public investment policies and activities that may be considered as economic growth stimulants for the Appalachian region. Examined in the document are the chlor-alkali industry; the manufacturing of trucks,…

Alkali-Activated Geopolymers: A Literature Review

DTIC Science & Technology

2010-07-01

Typical Fly Ash Composition (%) [32] .................................................................................... 15 3. Typical Geopolymer ... geopolymer matrix. Fly ash composition is generally measured and evaluated by the percentage of existing elements present in the by-product...pozzolan bear great significance to the strength potential of a given geopolymer specimen. Table 2. Typical Fly Ash Composition (%) [32

[Rare earth elements content in farmland soils and crops of the surrounding copper mining and smelting plant in Jiangxi province and evaluation of its ecological risk].

PubMed

Jin, Shu-Lan; Huang, Yi-Zong; Wang, Fei; Xu, Feng; Wang, Xiao-Ling; Gao, Zhu; Hu, Ying; Qiao Min; Li, Jin; Xiang, Meng

2015-03-01

Rare earth elements content in farmland soils and crops of the surrounding copper mining and smelting plant in Jiangxi province was studied. The results showed that copper mining and smelting could increase the content of rare earth elements in soils and crops. Rare earth elements content in farmland soils of the surrounding Yinshan Lead Zinc Copper Mine and Guixi Smelting Plant varied from 112.42 to 397.02 mg x kg(-1) and 48.81 to 250.06 mg x kg(-1), and the average content was 254.84 mg x kg(-1) and 144.21 mg x kg(-1), respectively. The average contents of rare earth elements in soils in these two areas were 1.21 times and 0.68 times of the background value in Jiangxi province, 1.36 times and 0.77 times of the domestic background value, 3.59 times and 2.03 times of the control samples, respectively. Rare earth elements content in 10 crops of the surrounding Guixi Smelting Plant varied from 0.35 to 2.87 mg x kg(-1). The contents of rare earth elements in the leaves of crops were higher than those in stem and root. The contents of rare earth elements in Tomato, lettuce leaves and radish leaves were respectively 2.87 mg x kg(-1), 1.58 mg x kg(-1) and 0.80 mg x kg(-1), which were well above the hygienic standard limit of rare earth elements in vegetables and fruits (0.70 mg x kg(-1)). According to the health risk assessment method recommended by America Environmental Protection Bureau (USEPA), we found that the residents' lifelong average daily intake of rare earth elements was 17.72 mg x (kg x d)(-1), lower than the critical value of rare earth elements damage to human health. The results suggested that people must pay attention to the impact of rare earth elements on the surrounding environment when they mine and smelt copper ore in Jiangxi.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Degassing of metals and metalloids from erupting seamount and mid-ocean ridge volcanoes: Observations and predictions

NASA Astrophysics Data System (ADS)

Rubin, Ken

1997-09-01

Recently, it has been reported that the element polonium degasses from mid-ocean ridge and seamount volcanoes during eruptions. Published and new observations on other volatile metal and metalloid elements can also be interpreted as indicating significant degassing of magmatic vapors during submarine eruptions. This process potentially plays an important role in the net transfer of chemical elements from erupting volcanoes to seawater in addition to that arising from sea floor hydrothermal systems. In this paper, a framework is constructed for predicting and assessing semiquantitatively the potential magnitude and chemical fingerprints in the water column of metal and metalloid degassing using (1) predictions from a summary of element volatilities during mafic subaerial volcanism worldwide and (2) limited data from submarine volcanic effusives. The latter include analyses of polonium and trace metals in near-volcano water masses sampled following a submarine eruption at Loihi seamount, Hawaii (1000 m bsl) in 1996. The element volatility predictions and observations show good agreement, considering the limited dataset. Some of the highest volatility main group and transition element enrichments in seawater over Loihi are predicted by the degassing mass transfer model I present. When expanded to cover all submarine volcanic activity, it is predicted that exit fluxes of these elements are up to 10 2-10 3 greater by degassing than by normal MOR hydrothermalism. In contrast, MOR exit fluxes of low volatility alkali and alkaline earth elements are likely 10 2-10 6 greater from hydrothermal inputs. Degassing inputs to the ocean are probably highly episodic, occurring almost entirely during eruptions; these are times of enhanced and abnormal hydrothermalism as well. Although major hydrothermal and degassing events may not be chemically recognizable in real water masses as wholly distinct entities, it is nevertheless possible to predict to what extent each process flavors the effluents of the other. Degassing at mid-ocean ridges may explain a variety of observations previously ascribed to complexities occurring during hydrothermal venting and/or fluid ascent in the buoyant hydrothermal plumes above ridges.

Concentrations and health risk assessment of rare earth elements in vegetables from mining area in Shandong, China.

PubMed

Zhuang, Maoqiang; Zhao, Jinshan; Li, Suyun; Liu, Danru; Wang, Kebo; Xiao, Peirui; Yu, Lianlong; Jiang, Ying; Song, Jian; Zhou, Jingyang; Wang, Liansen; Chu, Zunhua

2017-02-01

To investigate the concentrations of rare earth elements in vegetables and assess human health risk through vegetable consumption, a total of 301 vegetable samples were collected from mining area and control area in Shandong, China. The contents of 14 rare earth elements were determined by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The total rare earth elements in vegetables from mining and control areas were 94.08 μg kg -1 and 38.67 μg kg -1 , respectively, and the difference was statistically significant (p < 0.05). The leaf vegetable had the highest rare earth elements concentration (984.24 μg kg -1 and 81.24 μg kg -1 for mining and control areas, respectively) and gourd vegetable had the lowest rare earth elements concentration (37.34 μg kg -1 and 24.63 μg kg -1 for mining and control areas, respectively). For both areas, the rare earth elements concentration in vegetables declined in the order of leaf vegetable > taproot vegetable > alliaceous vegetable > gourd vegetable. The rare earth elements distribution patterns for both areas were characterized by enrichment of light rare earth elements. The health risk assessment demonstrated that the estimated daily intakes (0.69 μg kg -1 d -1 and 0.28 μg kg -1 d -1 for mining and control areas, respectively) of rare earth elements through vegetable consumption were significantly lower than the acceptable daily intake (70 μg kg -1 d -1 ). The damage to adults can be neglected, but more attention should be paid to the effects of continuous exposure to low levels of rare earth elements on children. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biogeochemistry of the rare-earth elements with particular reference to hickory trees

USGS Publications Warehouse

Robinson, W.O.; Bastron, H.; Murata, K.J.

1958-01-01

Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally in terms of the relative abundance of the cerium group and the yttrium group, except for the element cerium. The large fluctuations in the proportion of cerium [Ce/(La + Nd) atomic ratios of 0.16 to 0.86] correlate with oxidation-reduction conditions in the soil profile. The substitution of dilute H2SO3 for dilute HC1 in the determination of available rare-earth elements brings about a large increase in the proportion of cerium that is extracted from an oxygenated subsoil. These relationships strongly suggest that quadrivalent cerium is present in oxygenated subsoil and is less available to plants than the other rare-earth elements that do not undergo such a change in valence. A few parts per billion of rare-earth elements have been detected in two samples of ground water. ?? 1958.

Theoretical dissociation energies for ionic molecules

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

Chloride, bromide and iodide scintillators with europium

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

Zhuravleva, Mariya; Yang, Kan

A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has beenmore » studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.« less

Flame Atomic Absorption Spectrometric Determination of Gold After Solid-Phase Extraction of Its 2-Aminobenzothiazole Complex on Diaion SP-207.

PubMed

Unsal, Yunus Emre; Tuzen, Mustafa; Soylak, Mustafa

2016-01-01

An SPE of Au (III) on a 2-aminobenzothiazole-coated Diaion SP 207-column system has been developed. The parameters, including pH of solution, amount of 2-aminobenzothiazole, eluent type, sample volume, and flow rates, were examined. The effects of alkali, alkali earth, and some metals were also studied. The recovery values at optimal conditions and detection limits for Au (III) were found as >95% and 3.8 μg L(-1), respectively. The factor of preconcentration was 250. The RSD value was <5%. The capacity of adsorption for the resin was 10.4 mg g(-1). The accuracy of the method was evaluated by the use of CDN-GS-3D gold-certified reference material. The proposed procedure for the determination of gold was applied to water, mine, soil, and anodic slime samples.

Theoretical study of metal noble-gas positive ions

NASA Technical Reports Server (NTRS)

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

1989-01-01

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

The Not-So-Rare Earths.

ERIC Educational Resources Information Center

Muecke, Gunter K.; Moller, Peter

1988-01-01

Describes the characteristics of rare earth elements. Details the physical chemistry of rare earths. Reviews the history of rare earth chemistry and mineralogy. Discusses the mineralogy and crystallography of the formation of rare earth laden minerals found in the earth's crust. Characterizes the geologic history of rare earth elements. (CW)

The elements of the Earth's magnetism and their secular changes between 1550 and 1915

NASA Technical Reports Server (NTRS)

Fritsche, H.

1983-01-01

The results of an investigation about the magnetic agents outside the Earth's surface as well as the Earth's magnetic elements for the epochs 1550, 1900, 1915 are presented. The secular changes of the Earth's magnetic elements during the time interval 1550 - 1900 are also included.

Sedimentary carbonate-hosted giant Bayan Obo REE-Fe-Nb ore deposit of Inner Mongolia, China; a cornerstone example for giant polymetallic ore deposits of hydrothermal origin

USGS Publications Warehouse

Chao, E.C.T.; Back, J.M.; Minkin, J.A.; Tatsumoto, M.; Junwen, Wang; Conrad, J.E.; McKee, E.H.; Zonglin, Hou; Qingrun, Meng; Shengguang, Huang

1997-01-01

Detailed, integrative field and laboratory studies of the textures, structures, chemical characteristics, and isotopically determined ages and signatures of mineralization of the Bayan Obo deposit provided evidence for the origin and characteristics favorable for its formation and parameters necessary for defining giant polymetallic deposits of hydrothermal origin. Bayan Obo is an epigenetic, metasomatic, hydrothermal rare earth element (REE)-Fe-Nb ore deposit that is hosted in the metasedimentary H8 dolostone marble of the Middle Proterozoic Bayan Obo Group. The metasedimentary sequence was deposited on the northern continental slope of the North China craton. The mine area is about 100 km south of the suture marking Caledonian subduction of the Mongolian oceanic plate from the north beneath the North China craton. The mineralogy of the deposit is very complex, consisting of more than 120 different minerals, some of which are epigenetic minerals introduced by hydrothermal solutions, and some of which are primary and secondary metamorphic minerals. The major REE minerals are monazite and bastnaesite, whereas magnetite and hematite are the dominant Fe-ore minerals, and columbite is the most abundant Nb mineral. Dolomite, alkali amphibole, fluorite, barite, aegirine augite, apatite, phlogopite, albite, and microcline are the most widespread gangue minerals. Three general types of ores occur at Bayan Obo: disseminated, banded, and massive ores. Broad zoning of these ore types occurs in the Main and East Orebodies. Disseminated ores are in the outermost zone, banded ores are in the intermediate zone, and massive ores are in the cores of the orebodies. On the basis of field relations, host rocks, textures, structures, and mineral assemblages, many varieties of these three types of ores have been recognized and mapped. Isotopic dating of monazite, bastnaesite, aeschynite, and metamorphic and metasomatic alkali amphiboles associated with the deposit provides constraints on the ages of mineralization and the history of the deposit. Textural relations, differences in chemical composition, and 232Th/208Pb internal isochron ages of monazite and bastnaesite samples indicate that many episodes of REE mineralization occurred at Bayan Obo, ranging from about 555 Ma to about 398 Ma. Initial 208Pb/204Pb ratios suggest different sources of REE's for different generations of REE minerals. Relative ages of Fe mineralization were deduced from textural relationships of Fe minerals with other, dated mineral phases in the deposit. Most Nb mineralization was in the area of the West Orebodies and resulted in disseminated ore. Aeschynite, an early stage of Nb mineralization (438+-25.1 Ma), occurs with huanghoite and alkali amphiboles in veins. The 40Ar/39Ar ages of amphiboles, as well as petrographic textures, were used to distinguish three periods of regional metamorphism in the Bayan Obo mine area: (1) Late Proterozoic, about 890 Ma, which recrystallized H8 carbonate to marble and crystallized lineated alkali amphiboles along foliation planes in the marble; (2) Caledonian, about 425-395 Ma, which resulted in metamorphic and metasomatic-metamorphic alkali amphiboles; and (3) Hercynian, about 300 Ma, based on biotite 40Ar/39Ar analyses from biotite schist and folded banded ores. The 40Ar/39Ar ages of metasomatic alkali amphiboles also place time constraints on the hydrothermal history of the ore deposit. Metasomatic amphiboles represent periods of intense hydrothermal activity, which began as early as 1.26 Ga; that date is based on the age of amphibole from a vein that crosscuts the H6 quartzite that underlies the H8 dolostone marble. Although much of the metasomatic amphibole formed during periods that overlapped the peak period of REE mineralization of banded ores, REE and alkali amphibole phases generally occur in different mineral assemblages or are of very different ages in the same assemblage and, therefore, may have been derived from

Roles and Transport of Sodium and Potassium in Plants.

PubMed

Nieves-Cordones, Manuel; Al Shiblawi, Fouad Razzaq; Sentenac, Hervé

2016-01-01

The two alkali cations Na(+) and K(+) have similar relative abundances in the earth crust but display very different distributions in the biosphere. In all living organisms, K(+) is the major inorganic cation in the cytoplasm, where its concentration (ca. 0.1 M) is usually several times higher than that of Na(+). Accumulation of Na(+) at high concentrations in the cytoplasm results in deleterious effects on cell metabolism, e.g., on photosynthetic activity in plants. Thus, Na(+) is compartmentalized outside the cytoplasm. In plants, it can be accumulated at high concentrations in vacuoles, where it is used as osmoticum. Na(+) is not an essential element in most plants, except in some halophytes. On the other hand, it can be a beneficial element, by replacing K(+) as vacuolar osmoticum for instance. In contrast, K(+) is an essential element. It is involved in electrical neutralization of inorganic and organic anions and macromolecules, pH homeostasis, control of membrane electrical potential, and the regulation of cell osmotic pressure. Through the latter function in plants, it plays a role in turgor-driven cell and organ movements. It is also involved in the activation of enzymes, protein synthesis, cell metabolism, and photosynthesis. Thus, plant growth requires large quantities of K(+) ions that are taken up by roots from the soil solution, and then distributed throughout the plant. The availability of K(+) ions in the soil solution, slowly released by soil particles and clays, is often limiting for optimal growth in most natural ecosystems. In contrast, due to natural salinity or irrigation with poor quality water, detrimental Na(+) concentrations, toxic for all crop species, are present in many soils, representing 6 % to 10 % of the earth's land area. Three families of ion channels (Shaker, TPK/KCO, and TPC) and 3 families of transporters (HAK, HKT, and CPA) have been identified so far as contributing to K(+) and Na(+) transport across the plasmalemma and internal membranes, with high or low ionic selectivity. In the model plant Arabidopsis thaliana, these families gather at least 70 members. Coordination of the activities of these systems, at the cell and whole plant levels, ensures plant K(+) nutrition, use of Na(+) as a beneficial element, and adaptation to saline conditions.

Real World of Industrial Chemistry: Technology of the Rare Earths.

ERIC Educational Resources Information Center

Kremers, Howard E.

1985-01-01

The 17 rare earth elements account for one-fifth of the 83 naturally occurring elements and collectively rank as the 22nd most abundant "element." Properties of these elements (including their chemical similarity), their extraction from the earth, and their uses are discussed. (JN)

Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

DOEpatents

Rohrmann, Charles A.

1978-01-01

A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

[Physiological effects of rare earth elements and their application in traditional Chinese medicine].

PubMed

Zhou, Jie; Guo, Lanping; Xiao, Wenjuan; Geng, Yanling; Wang, Xiao; Shi, Xin'gang; Dan, Staerk

2012-08-01

The process in the studies on physiological effects of rare earth elements in plants and their action mechanisms were summarized in the aspects of seed germination, photosynthesis, mineral metabolism and stress resistance. And the applications of rare earth elements in traditional Chinese medicine (TCM) in recent years were also overviewed, which will provide reference for further development and application of rare earth elements in TCM.

Geochemical stratigraphy of lava flows sampled by the Hawaii Scientific Drilling Project

NASA Astrophysics Data System (ADS)

Rhodes, J. M.

1996-05-01

Geochemical discriminants are used to place the boundary between Mauna Loa flows and underlying Mauna Kea flows at a depth of about 280 m. At a given MgO content the Mauna Kea flows are lower in SiO2 and total iron and higher in total alkali, TiO2, and incompatible elements than the Mauna Loa lavas. The uppermost Mauna Kea lavas (280 to 340 m) contain alkali basalts interlayered with tholeiites and correlate with the postshield Hamakua Volcanics. In addition to total alkalis, the alkali basalts have higher TiO2, P2O5, Sr, Ba, Ce, La, Zr, Nb, Y, and V relative to the tholeiites and lower Zr/Nb and Sr/Nb ratios. Some of the alkali basalts are extensively differentiated. Below 340 m all the flows are tholeiitic, with compositions broadly similar to the few "fresh" subaerial shield-building Mauna Kea tholeiites studied to date. High-MgO lavas are unusually abundant, although there is a wide range (7-28%) in MgO content reflecting olivine control. FeO/MgO relationships are used to infer parental picritic magmas with about 15 wt % MgO. Lavas with more MgO than this have accumulated olivine. The Mauna Loa lavas have compositional trends that are controlled by olivine crystallization and accumulation. They compare closely with trends for historical (1843-1984) flows, tending toward the depleted end of the spectrum. They are, though, much more MgO-rich (9-30%) than is typical for most historical and young (<30 ka) prehistoric lavas. The unusual abundance of high-MgO and picritic lavas is attributed to the likelihood that only large-volume, hot, mobile flows will reach Hilo Bay from the northeast rift zone. FeO/MgO relationships are used to infer parental picritic magmas with about 17 wt % MgO. Again, lavas with more MgO than this have accumulated olivine. Systematic changes in incompatible element ratios are used to argue that the magma supply rate has diminished over time. On the other hand, the relatively constant Zr/Nb and Sr/Nb ratios that compare closely with historical and young (<30 kyr) prehistoric flows are used to argue that the source components for these lavas in the Hawaiian plume have remained relatively uniform over the last 100 kyr.

Quasiclassical calculations of blackbody-radiation-induced depopulation rates and effective lifetimes of Rydberg nS, nP, and nD alkali-metal atoms with n{<=}80

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

Beterov, I. I.; Ryabtsev, I. I.; Tretyakov, D. B.

2009-05-15

Rates of depopulation by blackbody radiation (BBR) and effective lifetimes of alkali-metal nS, nP, and nD Rydberg states have been calculated in a wide range of principal quantum numbers n{<=}80 at the ambient temperatures of 77, 300, and 600 K. Quasiclassical formulas were used to calculate the radial matrix elements of the dipole transitions from Rydberg states. Good agreement of our numerical results with the available theoretical and experimental data has been found. We have also obtained simple analytical formulas for estimates of effective lifetimes and BBR-induced depopulation rates, which well agree with the numerical data.

Matrix-isolation and comparative far-IR investigation of free linear [Cl3]- and a series of alkali trichlorides.

PubMed

Redeker, F A; Beckers, H; Riedel, S

2017-11-30

Here we discuss the reaction products of laser ablated alkali chlorides and elemental chlorine. Salt ablation using this technique combined with matrix-isolation spectroscopy allows for the formation and characterization of novel anionic species. The laser ablation of solid MCl with M = Cs, Rb, and K in the presence of Cl 2 produced free [Cl 3 ] - ions which were isolated in solid noble-gas matrices. For M = Cs, Rb, K, and Na, the ion pairs M + [Cl 3 ] - are the main reaction products. Trends in the formation and bonding of these trichloride anions will be discussed. In contrast to the trifluoride analogues, the isolated ion pairs M + [Cl 3 ] - feature a systematic distortion due to metal coordination.

Rare Earth Element Concentration of Wyoming Thermal Waters Update

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

Quillinan, Scott; Nye, Charles; Neupane, Hari

Updated version of data generated from rare earth element investigation of produced waters. These data represent major, minor, trace, isotopes, and rare earth element concentrations in geologic formations and water associated with oil and gas production.

Composition and method to remove asbestos

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

Block, Jacob

A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed, wherein the composition comprises water, at least about 30% by weight of an inorganic acid, and from about 0.1 to about 4% by weight of a tetrafluoroborate of ammonia, an alkali metal or an alkaline earth metal. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition also is disclosed.

Composition and method to remove asbestos

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

Block, Jacob

A composition for transforming a chrysotile asbestos-containing material into a non-asbestos material is disclosed, wherein the composition comprises water, at least about 30% by weight of an inorganic acid, and from about 0.1 to about 4% by weight of a hexafluorosilicate of ammonia, an alkali metal or an alkaline earth metal. A method of transforming the asbestos-containing material into a non-asbestos material using the present composition also is disclosed.

Enhanced catalyst stability for cyclic co methanation operations

DOEpatents

Risch, Alan P.; Rabo, Jule A.

1983-01-01

Carbon monoxide-containing gas streams are passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. The active carbon is thereafter reacted with steam or hydrogen to form methane. Enhanced catalyst stability for long term, cyclic operation is obtained by the incorporation of an alkali or alkaline earth dopant in a silica binding agent added to the catalyst-support additive composition.

Gas magnetometer

DOEpatents

Walker, Thad Gilbert; Lancor, Brian Robert; Wyllie, Robert

2016-05-03

Measurement of a precessional rate of a gas, such as an alkali gas, in a magnetic field is made by promoting a non-uniform precession of the gas in which substantially no net magnetic field affects the gas during a majority of the precession cycle. This allows sensitive gases that would be subject to spin-exchange collision de-phasing to be effectively used for extremely sensitive measurements in the presence of an environmental magnetic field such as the Earth's magnetic field.

SEPARATION OF METAL VALUES FROM NUCLEAR REACTOR

DOEpatents

Campbell, D.O.; Cathers, G.I.

1962-06-19

A method is given for separating beryllium fluoride and an alkali metal fluoride from a mixture containing same and rare earth fluorides. The method comprises contacting said mixture with a liquid hydrogen fluoride solvent containing no more than about 30 per cent water by weight and saturated with a fluoride salt characterized by its solubility in anhydrous hydrogen fluoride for a period of time sufficient to dissolve said beryllium fluoride in said solvent. (AEC)

Demonstration/Validation of the Snap Sampler Passive Groundwater Sampling Device at the Former McClellan Air Force Base

DTIC Science & Technology

2011-02-01

and Development Center Fe Iron gpd Gallons per Day HDPE High Density Polyethylene Hg Mercury ICP Inductively Coupled Plasma ICP/MS...Inductively Coupled Plasma Mass Spectrometry IROD Interim Record of Decision ITRC Interstate Technology and Regulatory Council K Potassium Kow...alkaline earth metals, alkali metals, and a metalloid, were sampled. This particular demonstration took place at the McClellan Air Force Base (AFB) in

Characterization and quantification of biochar alkalinity.

PubMed

Fidel, Rivka B; Laird, David A; Thompson, Michael L; Lawrinenko, Michael

2017-01-01

Lack of knowledge regarding the nature of biochar alkalis has hindered understanding of pH-sensitive biochar-soil interactions. Here we investigate the nature of biochar alkalinity and present a cohesive suite of methods for its quantification. Biochars produced from cellulose, corn stover and wood feedstocks had significant low-pK a organic structural (0.03-0.34 meq g -1 ), other organic (0-0.92 meq g -1 ), carbonate (0.02-1.5 meq g -1 ), and other inorganic (0-0.26 meq g -1 ) alkalinities. All four categories of biochar alkalinity contributed to total biochar alkalinity and are therefore relevant to pH-sensitive soil processes. Total biochar alkalinity was strongly correlated with base cation concentration, but biochar alkalinity was not a simple function of elemental composition, soluble ash, fixed carbon, or volatile matter content. More research is needed to characterize soluble biochar alkalis other than carbonates and to establish predictive relationships among biochar production parameters and the composition of biochar alkalis. Copyright © 2016 Elsevier Ltd. All rights reserved.

2nd International Symposium on Fundamental Aspects of Rare-earth Elements Mining and Separation and Modern Materials Engineering (REES-2015)

NASA Astrophysics Data System (ADS)

Tavadyan, Levon, Prof; Sachkov, Viktor, Prof; Godymchuk, Anna, Dr.; Bogdan, Anna

2016-01-01

The 2nd International Symposium «Fundamental Aspects of Rare-earth Elements Mining and Separation and Modern Materials Engineering» (REES2015) was jointly organized by Tomsk State University (Russia), National Academy of Science (Armenia), Shenyang Polytechnic University (China), Moscow Institute of Physics and Engineering (Russia), Siberian Physical-technical Institute (Russia), and Tomsk Polytechnic University (Russia) in September, 7-15, 2015, Belokuriha, Russia. The Symposium provided a high quality of presentations and gathered engineers, scientists, academicians, and young researchers working in the field of rare and rare earth elements mining, modification, separation, elaboration and application, in order to facilitate aggregation and sharing interests and results for a better collaboration and activity visibility. The goal of the REES2015 was to bring researchers and practitioners together to share the latest knowledge on rare and rare earth elements technologies. The Symposium was aimed at presenting new trends in rare and rare earth elements mining, research and separation and recent achievements in advanced materials elaboration and developments for different purposes, as well as strengthening the already existing contacts between manufactures, highly-qualified specialists and young scientists. The topics of the REES2015 were: (1) Problems of extraction and separation of rare and rare earth elements; (2) Methods and approaches to the separation and isolation of rare and rare earth elements with ultra-high purity; (3) Industrial technologies of production and separation of rare and rare earth elements; (4) Economic aspects in technology of rare and rare earth elements; and (5) Rare and rare earth based materials (application in metallurgy, catalysis, medicine, optoelectronics, etc.). We want to thank the Organizing Committee, the Universities and Sponsors supporting the Symposium, and everyone who contributed to the organization of the event and to publication of this proceeding.

Petrogenesis of Tertiary continental intra-plate lavas between Siebengebirge and Westerwald, Germany: Constraints from trace element systematics and Nd, Sr and Pb isotopes

NASA Astrophysics Data System (ADS)

Schubert, S.; Jung, S.; Pfänder, J. A.; Hauff, F.; Garbe-Schönberg, D.

2015-10-01

New 39Ar/40Ar ages and major- and trace-element and radiogenic isotope data are presented for basanites and alkali basalts from the transition area between the Westerwald and Siebengebirge volcanic fields (Germany) that belongs to the Central European Volcanic Province (CEVP). The 39Ar/40Ar ages indicate ages of c. 24 and c. 5 Ma which are fully compatible with previous K/Ar ages indicating that the evolution of this volcanic field belongs to the Westerwald area (28-22 Ma and 5 Ma) rather than to the Siebengebirge area (26-23 Ma). Based on the occurrence of > 30 isolated volcanic plugs with a simple igneous history, this volcanic field can be viewed as a monogenetic volcanic field. Compositions of some basanites are primitive, whereas others and the alkali basalts show decreasing Cr and Ni contents and CaO/Al2O3 ratios. However, increasing TiO2, Al2O3 and incompatible elements (Sr, Zr, Y, Hf, Ta) concentrations with decreasing MgO indicating fractionation of mainly olivine with minor amounts of clinopyroxene and spinel can be noticed. Rare earth element systematics suggest that most of the alkaline rocks are generated by different degrees of melting (5%-10%) of a garnet-bearing peridotite containing some residual amphibole. Negative anomalies of Rb and K in primitive mantle-normalized diagrams and a lack of Ba/Rb fractionation suggest that amphibole was the major OH-bearing mineral phase in the mantle. The alkaline rocks have a restricted range in 87Sr/86Sr and 143Nd/144Nd ratios ranging from 0.7033 to 0.7044 and from 0.51275 to 0.51285, respectively. Lead isotope compositions (206Pb/204Pb: 19.21-19.65; 207Pb/204Pb: 15.62-15.67; 208Pb/204Pb: 39.10-39.46) of the alkaline rocks are within the range of most OIB in which the higher values approach the composition of the European Asthenospheric Reservoir (EAR). The correlation between Sr and Nd isotopes and trace element constraints (Ce/Pb; Nb/U) indicates that for some samples interaction with crustal rocks during fractionation has occurred. Miocene intraplate basaltic volcanism in the area probably occurred as a result of minor "baby plume" activity. Each volcanic plug records evidence of a specific stage of fractionation with or without assimilation; however, in summary the lavas plot on a single fractionation path. This implies that during evolution of the volcanic field initial melting took place in the asthenosphere or at the lithosphere-asthenosphere interface. The melts moved through the lithospheric mantle and stagnated at crustal levels, however the observed fractionation paths suggest that they were fed from a single reservoir. This model, which involves small-scale plume impact followed by asthenosphere-lithosphere interaction together with minor crustal contamination, should also be applicable to other intra-continental rift-related areas.

Structure, age, and ore potential of the Burpala rare-metal alkaline massif, northern Baikal region

NASA Astrophysics Data System (ADS)

Vladykin, N. V.; Sotnikova, I. A.; Kotov, A. B.; Yarmolyuk, V. V.; Sal'nikova, E. B.; Yakovleva, S. Z.

2014-07-01

The Burpala alkaline massif is a unique geological object. More than 50 Zr, Nb, Ti, Th, Be, and REE minerals have been identified in rare-metal syenite of this massif. Their contents often reach tens of percent, and concentrations of rare elements in rocks are as high as 3.6% REE, 4% Zr, 0.5% Y, 0.5% Nb, 0.5% Th, and 0.1% U. Geological and geochemical data show that all rocks in the Burpala massif are derivatives of alkaline magma initially enriched in rare elements. These rocks vary in composition from shonkinite, melanocratic syenite, nepheline and alkali syenites to alaskite and alkali granite. The extreme products of magma fractionation are rare-metal pegmatites, apatite-fluorite rocks, and carbonatites. The primary melts were related to the enriched EM-2 mantle source. The U-Pb zircon ages of pulaskite (main intrusive phase) and rare-metal syenite (vein phase) are estimated at 294 ± 1 and 283 ± 8 Ma, respectively. The massif was formed as a result of impact of the mantle plume on the active continental margin of the Siberian paleocontinent.

Microbial Carbonic Anhydrases in Biomimetic Carbon Sequestration for Mitigating Global Warming: Prospects and Perspectives

PubMed Central

Bose, Himadri; Satyanarayana, Tulasi

2017-01-01

All the leading cities in the world are slowly becoming inhospitable for human life with global warming playing havoc with the living conditions. Biomineralization of carbon dioxide using carbonic anhydrase (CA) is one of the most economical methods for mitigating global warming. The burning of fossil fuels results in the emission of large quantities of flue gas. The temperature of flue gas is quite high. Alkaline conditions are necessary for CaCO3 precipitation in the mineralization process. In order to use CAs for biomimetic carbon sequestration, thermo-alkali-stable CAs are, therefore, essential. CAs must be stable in the presence of various flue gas contaminants too. The extreme environments on earth harbor a variety of polyextremophilic microbes that are rich sources of thermo-alkali-stable CAs. CAs are the fastest among the known enzymes, which are of six basic types with no apparent sequence homology, thus represent an elegant example of convergent evolution. The current review focuses on the utility of thermo-alkali-stable CAs in biomineralization based strategies. A variety of roles that CAs play in various living organisms, the use of CA inhibitors as drug targets and strategies for overproduction of CAs to meet the demand are also briefly discussed. PMID:28890712

The formation environment of potassic-chloro-hastingsite in the nakhlites MIL 03346 and pairs and NWA 5790: Insights from terrestrial chloro-amphibole

NASA Astrophysics Data System (ADS)

Giesting, Paul A.; Filiberto, Justin

2016-11-01

Potassic-chloro-hastingsite has been found in melt inclusions in MIL 03346, its paired stones, and NWA 5790. It is some of the most chlorine-rich amphibole ever analyzed. In this article, we evaluate what crystal chemistry, terrestrial analogs, and experiments have shown about how chlorine-dominant amphibole (chloro-amphibole) forms and apply these insights to the nakhlites. Chloro-amphibole is rare, with about a dozen identified localities on Earth. It is always rich in potassium and iron and poor in titanium. In terrestrial settings, its presence has been interpreted to result from medium to high-grade alteration (>400 °C) of a protolith by an alkali and/or iron chloride-rich aqueous fluid. Ferrous chloride fluids exsolved from mafic magmas can cause such alteration, as can crustal fluids that have reacted with rock and lost H2O in preference to chloride, resulting in concentrated alkali chloride fluids. In the case of the nakhlites, an aqueous alkali-ferrous chloride fluid was exsolved from the parental melt as it crystallized. This aqueous chloride fluid itself likely unmixed into chloride-dominant and water-dominant fluids. Chloride-dominant fluid was trapped in some melt inclusions and reacted with the silicate contents of the inclusion to form potassic-chloro-hastingsite.

Microbial Carbonic Anhydrases in Biomimetic Carbon Sequestration for Mitigating Global Warming: Prospects and Perspectives.

PubMed

Bose, Himadri; Satyanarayana, Tulasi

2017-01-01

All the leading cities in the world are slowly becoming inhospitable for human life with global warming playing havoc with the living conditions. Biomineralization of carbon dioxide using carbonic anhydrase (CA) is one of the most economical methods for mitigating global warming. The burning of fossil fuels results in the emission of large quantities of flue gas. The temperature of flue gas is quite high. Alkaline conditions are necessary for CaCO 3 precipitation in the mineralization process. In order to use CAs for biomimetic carbon sequestration, thermo-alkali-stable CAs are, therefore, essential. CAs must be stable in the presence of various flue gas contaminants too. The extreme environments on earth harbor a variety of polyextremophilic microbes that are rich sources of thermo-alkali-stable CAs. CAs are the fastest among the known enzymes, which are of six basic types with no apparent sequence homology, thus represent an elegant example of convergent evolution. The current review focuses on the utility of thermo-alkali-stable CAs in biomineralization based strategies. A variety of roles that CAs play in various living organisms, the use of CA inhibitors as drug targets and strategies for overproduction of CAs to meet the demand are also briefly discussed.

Two main and a new type rare earth elements in Mg alloys: A review

NASA Astrophysics Data System (ADS)

Kong, Linghang

2017-09-01

Magnesium (Mg) alloys stand for the lightest structure engineering materials. Moreover, the strengthening of Mg alloys in ductility, toughness and corrosion predominates their wide applications. With adding rare earth elements in Mg, the mechanical properties will be improved remarkably, especially their plasticity and strength. A brief overview of the addition of rare earth elements for Mg alloys is shown. The basic mechanisms of strengthening Mg alloys with rare earth elements are reviewed, including the solid solution strengthening, grain refinement and long period stacking ordered (LPSO) phase. Furthermore, the available rare earth elements are summarized by type, chemical or physical effects and other unique properties. Finally, some challenge problems that the research is facing and future expectations of ra-re-earth Mg alloys are stated and discussed.

Theory of long-range interactions for Rydberg states attached to hyperfine-split cores

NASA Astrophysics Data System (ADS)

Robicheaux, F.; Booth, D. W.; Saffman, M.

2018-02-01

The theory is developed for one- and two-atom interactions when the atom has a Rydberg electron attached to a hyperfine-split core state. This situation is relevant for some of the rare-earth and alkaline-earth atoms that have been proposed for experiments on Rydberg-Rydberg interactions. For the rare-earth atoms, the core electrons can have a very substantial total angular momentum J and a nonzero nuclear spin I . In the alkaline-earth atoms there is a single (s ) core electron whose spin can couple to a nonzero nuclear spin for odd isotopes. The resulting hyperfine splitting of the core state can lead to substantial mixing between the Rydberg series attached to different thresholds. Compared to the unperturbed Rydberg series of the alkali-metal atoms, the series perturbations and near degeneracies from the different parity states could lead to qualitatively different behavior for single-atom Rydberg properties (polarizability, Zeeman mixing and splitting, etc.) as well as Rydberg-Rydberg interactions (C5 and C6 matrices).

Leaching behavior of rare earth elements in Fort Union lignite coals of North America

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

Laudal, Daniel A.; Benson, Steven A.; Addleman, Raymond Shane

Rare earth elements are crucial materials in an incredible array of consumer goods, energy system components and military defense applications. However, the global production and entire value chain for rare earth elements is dominated by China, with the U.S. currently 100% import reliant for these critical materials. Traditional mineral ores including those previously mined in the U.S., however, have several challenges. Chief among these is that the content of the most critical and valuable of the rare earths are deficient, making mining uneconomical. Further, the supply of these most critical rare earths is nearly 100% produced in China from amore » single resource that is only projected to last another 10 to 20 years. The U.S. currently considers the rare earths market an issue of national security. It is imperative that alternative domestic sources of rare earths be identified and methods developed to produce them. Recently, coal and coal byproducts have been identified as one of these promising alternative resources. This paper details the results of a study on characterization of North Dakota lignite and lignite-related feedstocks as an assessment of their feasibility for rare earth element recovery. The abundance, distribution and modes of occurrence of the rare earth elements in the samples collected were determined in this initial study to inform the selection of appropriate extraction and concentration methods to recover the rare earth elements. Materials investigated include the lignite coals, clay-rich sediments associated with the coal seams, and materials associated with a lignite beneficiation system and power plant. The results show that high rare earth element levels exist both in lignite coals and associated sediments. The form of the rare earth elements in the clay materials is primarily as ultra-fine mineral grains. In the lignite coals, approximately 80-95% of the rare earths content is organically associated, primarily as coordination complexes.« less

A miniaturized capacitively coupled plasma microtorch optical emission spectrometer and a Rh coiled-filament as small-sized electrothermal vaporization device for simultaneous determination of volatile elements from liquid microsamples: spectral and analytical characterization.

PubMed

Frentiu, Tiberiu; Darvasi, Eugen; Butaciu, Sinziana; Ponta, Michaela; Petreus, Dorin; Mihaltan, Alin I; Frentiu, Maria

2014-11-01

A low power and low argon consumption (13.56 MHz, 15 W, 150 ml min(-1)) capacitively coupled plasma microtorch interfaced with a low-resolution microspectrometer and a small-sized electrothermal vaporization Rh coiled-filament as liquid microsample introduction device into the plasma was investigated for the simultaneous determination of several volatile elements of interest for environment. Constructive details, spectral and analytical characteristics, and optimum operating conditions of the laboratory equipment for the simultaneous determination of Ag, Cd, Cu, Pb and Zn requiring low vaporization power are provided. The method involves drying of 10 μl sample at 100°C, vaporization at 1500°C and emission measurement by capture of 20 successive spectral episodes each at an integration time of 500 ms. Experiments showed that emission of elements and plasma background were disturbed by the presence of complex matrix and hot Ar flow transporting the microsample into plasma. The emission spectrum of elements is simple, dominated by the resonance lines. The analytical system provided detection limits in the ng ml(-1) range: 0.5(Ag); 1.5(Cd); 5.6(Cu); 20(Pb) and 3(Zn) and absolute detection limits of the order of pg: 5(Ag); 15(Cd); 56(Cu); 200(Pb) and 30(Zn). It was demonstrated the utility and capability of the miniaturized analytical system in the simultaneous determination of elements in soil and water sediment using the standard addition method to compensate for the non-spectral effects of alkali and earth alkaline elements. The analysis of eight certified reference materials exhibited reliable results with recovery in the range of 95-108% and precision of 0.5-9.0% for the five examined elements. The proposed miniaturized analytical system is attractive due to the simple construction of the electrothermal vaporization device and microtorch, low costs associated to plasma generation, high analytical sensitivity and easy-to-run for simultaneous multielemental analysis of liquid microsamples. Copyright © 2014. Published by Elsevier B.V.

ARC: An open-source library for calculating properties of alkali Rydberg atoms

NASA Astrophysics Data System (ADS)

Šibalić, N.; Pritchard, J. D.; Adams, C. S.; Weatherill, K. J.

2017-11-01

We present an object-oriented Python library for the computation of properties of highly-excited Rydberg states of alkali atoms. These include single-body effects such as dipole matrix elements, excited-state lifetimes (radiative and black-body limited) and Stark maps of atoms in external electric fields, as well as two-atom interaction potentials accounting for dipole and quadrupole coupling effects valid at both long and short range for arbitrary placement of the atomic dipoles. The package is cross-referenced to precise measurements of atomic energy levels and features extensive documentation to facilitate rapid upgrade or expansion by users. This library has direct application in the field of quantum information and quantum optics which exploit the strong Rydberg dipolar interactions for two-qubit gates, robust atom-light interfaces and simulating quantum many-body physics, as well as the field of metrology using Rydberg atoms as precise microwave electrometers. Program Files doi:http://dx.doi.org/10.17632/hm5n8w628c.1 Licensing provisions: BSD-3-Clause Programming language: Python 2.7 or 3.5, with C extension External Routines: NumPy [1], SciPy [1], Matplotlib [2] Nature of problem: Calculating atomic properties of alkali atoms including lifetimes, energies, Stark shifts and dipole-dipole interaction strengths using matrix elements evaluated from radial wavefunctions. Solution method: Numerical integration of radial Schrödinger equation to obtain atomic wavefunctions, which are then used to evaluate dipole matrix elements. Properties are calculated using second order perturbation theory or exact diagonalisation of the interaction Hamiltonian, yielding results valid even at large external fields or small interatomic separation. Restrictions: External electric field fixed to be parallel to quantisation axis. Supplementary material: Detailed documentation (.html), and Jupyter notebook with examples and benchmarking runs (.html and .ipynb). [1] T.E. Oliphant, Comput. Sci. Eng. 9, 10 (2007). http://www.scipy.org/. [2] J.D. Hunter, Comput. Sci. Eng. 9, 90 (2007). http://matplotlib.org/.

Effect of Alkali-Acid-Heat Chemical Surface Treatment on Electron Beam Melted Porous Titanium and Its Apatite Forming Ability

PubMed Central

Bsat, Suzan; Amin Yavari, Saber; Munsch, Maximilian; Valstar, Edward R.; Zadpoor, Amir A.

2015-01-01

Advanced additive manufacturing techniques such as electron beam melting (EBM), can produce highly porous structures that resemble the mechanical properties and structure of native bone. However, for orthopaedic applications, such as joint prostheses or bone substitution, the surface must also be bio-functionalized to promote bone growth. In the current work, EBM porous Ti6Al4V alloy was exposed to an alkali acid heat (AlAcH) treatment to bio-functionalize the surface of the porous structure. Various molar concentrations (3, 5, 10M) and immersion times (6, 24 h) of the alkali treatment were used to determine optimal parameters. The apatite forming ability of the samples was evaluated using simulated body fluid (SBF) immersion testing. The micro-topography and surface chemistry of AlAcH treated samples were evaluated before and after SBF testing using scanning electron microscopy and energy dispersive X-ray spectroscopy. The AlAcH treatment successfully modified the topographical and chemical characteristics of EBM porous titanium surface creating nano-topographical features ranging from 200–300 nm in size with a titania layer ideal for apatite formation. After 1 and 3 week immersion in SBF, there was no Ca or P present on the surface of as manufactured porous titanium while both elements were present on all AlAcH treated samples except those exposed to 3M, 6 h alkali treatment. An increase in molar concentration and/or immersion time of alkali treatment resulted in an increase in the number of nano-topographical features per unit area as well as the amount of titania on the surface. PMID:28788021

Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

2012-01-01

Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

Effect of Alkali-Acid-Heat Chemical Surface Treatment on Electron Beam Melted Porous Titanium and Its Apatite Forming Ability.

PubMed

Bsat, Suzan; Yavari, Saber Amin; Munsch, Maximilian; Valstar, Edward R; Zadpoor, Amir A

2015-04-08

Advanced additive manufacturing techniques such as electron beam melting (EBM), can produce highly porous structures that resemble the mechanical properties and structure of native bone. However, for orthopaedic applications, such as joint prostheses or bone substitution, the surface must also be bio-functionalized to promote bone growth. In the current work, EBM porous Ti6Al4V alloy was exposed to an alkali acid heat (AlAcH) treatment to bio-functionalize the surface of the porous structure. Various molar concentrations (3, 5, 10M) and immersion times (6, 24 h) of the alkali treatment were used to determine optimal parameters. The apatite forming ability of the samples was evaluated using simulated body fluid (SBF) immersion testing. The micro-topography and surface chemistry of AlAcH treated samples were evaluated before and after SBF testing using scanning electron microscopy and energy dispersive X-ray spectroscopy. The AlAcH treatment successfully modified the topographical and chemical characteristics of EBM porous titanium surface creating nano-topographical features ranging from 200-300 nm in size with a titania layer ideal for apatite formation. After 1 and 3 week immersion in SBF, there was no Ca or P present on the surface of as manufactured porous titanium while both elements were present on all AlAcH treated samples except those exposed to 3M, 6 h alkali treatment. An increase in molar concentration and/or immersion time of alkali treatment resulted in an increase in the number of nano-topographical features per unit area as well as the amount of titania on the surface.

[Application of ICP-MS to Detect Rare Earth Elements in Three Economic Macroalgaes in China].

PubMed

Zhao, Yan-fang; Shang, De-rong; Zhai, Yu-xiu; Ning, Jin-song; Ding, Hai-yan; Sheng, Xiao-feng

2015-11-01

In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha.

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

USGS Publications Warehouse

Birdwell, Justin E.

2012-01-01

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, μg g-1) than are typical of material in the upper crust (approximately 170 μg g-1) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 μg g-1). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Deep-sea mud in the Pacific Ocean as a potential resource for rare-earth elements

NASA Astrophysics Data System (ADS)

Kato, Yasuhiro; Fujinaga, Koichiro; Nakamura, Kentaro; Takaya, Yutaro; Kitamura, Kenichi; Ohta, Junichiro; Toda, Ryuichi; Nakashima, Takuya; Iwamori, Hikaru

2011-08-01

World demand for rare-earth elements and the metal yttrium--which are crucial for novel electronic equipment and green-energy technologies--is increasing rapidly. Several types of seafloor sediment harbour high concentrations of these elements. However, seafloor sediments have not been regarded as a rare-earth element and yttrium resource, because data on the spatial distribution of these deposits are insufficient. Here, we report measurements of the elemental composition of over 2,000 seafloor sediments, sampled at depth intervals of around one metre, at 78 sites that cover a large part of the Pacific Ocean. We show that deep-sea mud contains high concentrations of rare-earth elements and yttrium at numerous sites throughout the eastern South and central North Pacific. We estimate that an area of just one square kilometre, surrounding one of the sampling sites, could provide one-fifth of the current annual world consumption of these elements. Uptake of rare-earth elements and yttrium by mineral phases such as hydrothermal iron-oxyhydroxides and phillipsite seems to be responsible for their high concentration. We show that rare-earth elements and yttrium are readily recovered from the mud by simple acid leaching, and suggest that deep-sea mud constitutes a highly promising huge resource for these elements.

Felsic plutonism in the Al Amar—Idsas area, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Le Bel, L.; Laval, M.

A tonalite—trondhjemite suite, calc-alkalic plutons and alkali-feldspar granites dated 670 and 580 Ma, intrude thick volcano-sedimentary rocks of the Al Amar group E of the Al Amar fault and the Abt schist W of the fault. The tonalite—trondhjemite suite (group I) is characterized by low Rb (50 ppm) and Sr (100-400 ppm) and by weakly fractionated rare-earth patterns (La/Yb Nca 2-3) with a weak negative Eu anomaly. Calc-alkalic plutons (group II) are richer in Rb (50-150 ppm), contain variable Sr (50-1000 ppm), and have strongly fractionated rare-earth patterns (La/Yb Nca 6-22) with no Eu anomaly. Alkali-feldspar granite (group III) is characterized by high Rb (150-200 ppm) and shows fractionated rare-earth patterns (La/Yb Nca 6-18) with a well-developed Eu anomaly. Group III includes 'specialized granites' with high Rb (300-400 ppm) and Sn (28-66 ppm), and rare-earth patterns showing a distinctive 'sea gull' profile with a very strong Eu anomaly (Eu*/Eu = 20). Oxygen isotope geochemistry suggests that group I rocks (¯x δ18O ca 7.0) were mantle-derived, and that group II and III rocks intruding the Al Amar group ( δ18O ca 7.9 and 8.8 respectively) were derived by remelting of group I, whereas those intruding Abt schist ( δ18O ca 8.7 and 10.8 respectively) were partially derived by anatexis of the Afif block. Magmatogenesis reflects an island-arc development. Rocks of group I represent the initial subduction phase. Syn- to late-tectonic plutons of group II intruded the arc east of the Al Amar fault and the accretionary prism (Abt schist) to the west, which was in collision with the older Afif block. Post-tectonic group III rocks were emplaced in an already cratonized area.

[Influence of cations on the laser Raman spectra of silicate glasses].

PubMed

Xiong, Yi; Zhao, Hong-xia; Gan, Fu-xi

2012-04-01

Na2O(K2O)-CaO(MgO)-SiO2, Na2O(K2O)-Al2O3-SiO2, Na2O(K2O)-B2O3-SiO2, Na2O(K2O)-PbO-SiO2 and PbO-BaO-SiO2 glass systems were investigated using laser Raman spectroscopic technique. The modification of short-range structure of glass caused by network modifier cations will influence Raman signature. Alkali and alkali-earth ions can weaken the bridging oxygen bond, thus lower the frequency of Si-O(b)-Si anti-symmetric stretching vibration. When coordina ted by oxygen ions, B3+ can form [BO4] tetrahedron and enter the silicon-oxygen network, but this effect had little impact on the frequency of Raman peaks located in the high-frequency region. Al3+ can also be coordinated by oxygen ions to form [AlO4] tetrahedron. [AlO4] will increase the disorder degree of network while entering network. Ba2+ can increase the density of electron cloud along the Si-O(nb) bond when it bonds with non-bridging oxygen, which will lead to a higher peak intensity of O-Si-O stretching vibration. The Raman peaks of alkli- and alkali-earth silicate glasses are mainly distributed in the region of 400 - 1 200 cm(-1), while in the spectrum of Na2O(K2O)-PbO-SiO2 glass system a 131 cm(-1) peak existed. The authors assigned it to the Pb-O symmetric stretching vibration. Some of the samples were produced in the laboratory according to the average compositions of ancient glasses, so this research is very significant to discriminating ancient silicate glasses of different systems by Laser Raman spectroscopic technique.

Characterization of environmentally-friendly alkali activated slag cements and ancient building materials

NASA Astrophysics Data System (ADS)

Sakulich, Aaron Richard

Alternative cement technologies are an area of increasing interest due to growing environmental concerns and the relatively large carbon footprint of the cement industry. Many new cements have been developed, but one of the most promising is that made from granulated, ground blast furnace slag activated by a high-pH solution. Another is related to the discovery that some of the pyramid limestone blocks may have been cast using a combination of diatomaceous earth activated by lime which provides the high pH needed to dissolve the diatomaceous earth and bind the limestone aggregate together. The emphasis of this thesis is not on the latter---which was explored elsewhere---but on the results supplying further evidence that some of the pyramid blocks were indeed reconstituted limestone. The goal of this work is to chemically and mechanically characterize both alkali-activated slag cements as well as a number of historic materials, which may be ancient analogues to cement. Alkali activated slag cements were produced with a number of additives; concretes were made with the addition of a fine limestone aggregate. These materials were characterized mechanically and by XRD, FTIR, SEM, and TGA. Samples from several Egyptian pyramids, an 'ancient floor' in Colorado, and the 'Bosnian Pyramids' were investigated. In the cements, it has been unequivocally shown that C-S-H, the same binding phase that is produced in ordinary portland cement, has been produced, as well as a variety of mineral side products. Significant recarbonation occurs during the first 20 months, but only for the Na2CO3-activated formulae. Radiocarbon dating proves that the 'Bosnian Pyramids' and 'ancient floors' are not made from any type of recarbonated lime; however, Egyptian pyramid limestones were finite, thus suggesting that they are of a synthetic nature. XRD and FTIR results were inconclusive, while TGA results indicate the limestones are identical to naturally occurring limestones, and SEM/EDS analysis shows the presence of a Si-rich species.

Rare Earth Element Partition Coefficients from Enstatite/Melt Synthesis Experiments

NASA Technical Reports Server (NTRS)

Schwandt, Craig S.; McKay, Gordon A.

1997-01-01

Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.

Effect of the addition of low rare earth elements (lanthanum, neodymium, cerium) on the biodegradation and biocompatibility of magnesium.

PubMed

Willbold, Elmar; Gu, Xuenan; Albert, Devon; Kalla, Katharina; Bobe, Katharina; Brauneis, Maria; Janning, Carla; Nellesen, Jens; Czayka, Wolfgang; Tillmann, Wolfgang; Zheng, Yufeng; Witte, Frank

2015-01-01

Rare earth elements are promising alloying element candidates for magnesium alloys used as biodegradable devices in biomedical applications. Rare earth elements have significant effects on the high temperature strength as well as the creep resistance of alloys and they improve magnesium corrosion resistance. We focused on lanthanum, neodymium and cerium to produce magnesium alloys with commonly used rare earth element concentrations. We showed that low concentrations of rare earth elements do not promote bone growth inside a 750 μm broad area around the implant. However, increased bone growth was observed at a greater distance from the degrading alloys. Clinically and histologically, the alloys and their corrosion products caused no systematic or local cytotoxicological effects. Using microtomography and in vitro experiments, we could show that the magnesium-rare earth element alloys showed low corrosion rates, both in in vitro and in vivo. The lanthanum- and cerium-containing alloys degraded at comparable rates, whereas the neodymium-containing alloy showed the lowest corrosion rates. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Eocene melting of Precambrian lithospheric mantle: Analcime-bearing volcanic rocks from the Challis-Kamloops belt of south central British Columbia

NASA Astrophysics Data System (ADS)

Dostal, J.; Breitsprecher, K.; Church, B. N.; Thorkelson, D.; Hamilton, T. S.

2003-08-01

Potassic silica-undersaturated mafic volcanic rocks form a minor portion of the predominantly calc-alkaline Eocene Challis-Kamloops volcanic belt, which extends from the northwestern United States into central British Columbia (Canada). Their major occurrence is in the Penticton Group in south central British Columbia, where they reach a thickness of up to 500 m and form the northwestern edge of the Montana alkaline province. These analcime-bearing rocks (˜53-52 Ma old) are typically rhomb porphyries of ternary feldspar (An 28Ab 52Or 20). Additional phenocryst phases include clinopyroxene, analcime, phlogopite and rare olivine. The rocks are characterized by high total alkalis, particularly K 2O (>4.5 wt%) as well as by a distinct enrichment of large-ion lithophile elements versus heavy rare-earth elements and high-field-strength elements. They have unusual isotopic compositions compared to most other rocks of the Challis-Kamloops belt, particularly high negative ɛNd values and elevated but relatively uniform initial 87Sr/ 86Sr ratios (˜0.7065). The potassic silica-undersaturated rocks overlie Precambrian crust and lithosphere and were at least in part derived from ancient metasomatized subcontinental mantle lithosphere, which was modified in a Precambrian subduction setting. The alkaline rocks of the Challis-Kamloops belt are related to a slab-window environment. In particular, they were formed above the southern edge of the Kula plate adjacent to the Kula-Farallon slab window, whereas the Montana alkaline province situated well to the southeast was formed directly above the Kula-Farallon slab window. Upwelling of the hotter asthenospheric mantle may have been the thermal trigger necessary to induce melting of fertile and metasomatized lithospheric mantle.

Geochemical characterization of the siliciclastic rocks of Chitravati Group, Cuddapah Supergroup: Implications for provenance and depositional environment

NASA Astrophysics Data System (ADS)

Somasekhar, V.; Ramanaiah, S.; Sarma, D. Srinivasa

2018-06-01

Petrological and geochemical studies have been carried out on Pulivendla and Gandikota Quartzite from Chitravati Group of Cuddapah Supergroup to decipher the provenance and depositional environment. Both the units are texturally mature with sub-rounded to well-rounded and moderately to well-sorted grains. Majority of the framework grains are quartz, in the form of monocrystalline quartz, followed by feldspars (K-feldspar and plagioclase), mica, rock fragments, heavy minerals, with minor proportion of the matrix and cement. Based on major element geochemical classification diagram, Pulivendla Quartzite is considered as quartz-arenite and arkose to sub-arkose, whereas Gandikota Quartzite falls in the field of lith-arenite and arkose to sub-arkose. Weathering indices like CIA, PIA, CIW, ICV, Th/U ratio and A-CN-K ternary diagram suggest moderate to intense chemical weathering of the source rocks of these quartzites. Whole rock geochemistry of quartzites indicate that they are primarily from the first-cycle sediments, along with some minor recycled components. Also their sources were mostly intermediate-felsic igneous rocks of Archean age. The tectonic discrimination plots, Th-Sc-Zr/10 of both these formations reflect active to passive continental margin setting. Chondrite-normalized rare earth element (REE) patterns, and various trace element ratios like Cr/Th, Th/Co, La/Sc and Th/Cr indicate dominantly felsic source with minor contribution from mafic source. Th/Sc ratios of Pulivendla and Gandikota Quartzite are in close proximity with average values of 2.83, 3.45 respectively, which is higher than AUCC (Th/Sc=0.97), demonstrating that the contributions from more alkali source rocks than those that contributed to AUCC.

Differing responses of zircon, chevkinite-(Ce), monazite-(Ce) and fergusonite-(Y) to hydrothermal alteration: Evidence from the Keivy alkaline province, Kola Peninsula, Russia

NASA Astrophysics Data System (ADS)

Macdonald, Ray; Bagiński, Bogusław; Zozulya, Dmitry

2017-09-01

A quartzolite from the Rova occurrence, Keivy alkali granite province, Kola Peninsula, Russia, is used to examine the differing responses of certain rare-metal minerals during interaction with hydrothermal fluids. The minerals are two silicates [chevkinite-(Ce) and zircon], a phosphate [monazite-(Ce)] and an oxide [fergusonite-(Y)]. Textural evidence is taken to show that the dominant alteration mechanism was interface-coupled dissolution-reprecipitation. Zircon was the most pervasively altered, possibly by broadening of cleavage planes or fractures; the other minerals were altered mainly on their rims and along cracks. The importance of cracks in promoting fluid access is stressed. The compositional effects of the alteration of each phase are documented. The hydrothermal fluids carried few ligands capable of transporting significant amounts of rare-earth elements (REE), high field strength elements (HFSE) and actinides; alteration is inferred to have been promoted by mildly alkaline, Ca-bearing fluids. Expansion cracks emanating from fergusonite-(Y) are filled with unidentified material containing up to 35 wt% UO2 and 25 wt% REE2O3, indicating late-stage, short-distance mobility of these elements. Electron microprobe chemical dating of monazite yielded an age of 1665 ± 22 Ma, much younger than the formation age of the Keivy province (2.65-2.67 Ga) but comparable to that of the Svecofennian metamorphic event which affected the area (1.9-1.7 Ga) or during fluid-thermal activation of the region during rapakivi granite magmatism (1.66-1.56 Ga). Dates for altered monazite range from 2592 ± 244 Ma to 773 ± 88 Ma and reflect disturbance of the U-Th-Pb system during alteration.

Solubility of some alkali and alkaline earth chlorides in water at moderate temperatures

USGS Publications Warehouse

Clynne, M.A.; Potter, R.W.

1979-01-01

Solubilities for the binary systems, salt-H2O, of the chlorides of lithium, rubidium, cesium, magnesium, calcium, strontium, and barium from near 0??C to the saturated boiling point are reported. The experimental data and coefficients of an equation for a smoothed curve describing each system are listed in the tables. The data are improvements on those previously reported in the literature, having a precision on the average of ??0.09%.

Influence of crude oil cracking on distribution of hydrocarbons in the Earth's interior (experimental data)

NASA Astrophysics Data System (ADS)

Balitsky, V. S.; Balitskaya, L. V.; Penteley, S. V.; Novikova, M. A.

2012-02-01

The compositions and phase conditions of water-hydrocarbon fluids in synthetic quartz inclusions were studied by the methods of microthermometry, local IR spectroscopy, and gas-liquid chromatography. Synthetic quartz was grown in near-neutral fluoride, low-alkali bicarbonate, and alkali carbonate solutions with crude oil and its major fractions. The crystals with fluid inclusions were grown under thermal gradient conditions at relatively low temperatures (240-280°C) and pressures (6-45 MPa). After the study, the inclusions of grown crystals were subject to thermal processing in autoclaves at 350-380°C and 80-125 MPa. As a result, the initial water-hydrocarbon inclusions underwent significant changes. Hydrocarbon gases, largely methane and residual solid bitumens, appeared in their composition; the gasoline-kerosene fraction content increased substantially in liquid hydrocarbons (HCs). These changes are caused, first of all, by crude oil cracking, which is manifested already at 330°C and attains its maximum activity at 350-500°C (pressure of saturated vapor and higher). In natural conditions with increase in depths and, thus, the thermobaric parameters, this process is inevitable. According to the obtained experimental data, this very phenomenon and the existence of real thermal and baric gradients in the Earth's interior provide for the formation of vertical zoning in the distribution of hydrocarbon deposits of different types.

Pma1 is an alkali/alkaline earth metal cation ATPase that preferentially transports Na(+) and K(+) across the Mycobacterium smegmatis plasma membrane.

PubMed

Ayala-Torres, Carlos; Novoa-Aponte, Lorena; Soto, Carlos Y

2015-07-01

Mycobacterium smegmatis Pma1 is the orthologue of M. tuberculosis P-type ATPase cation transporter CtpF, which is activated under stress conditions, such as hypoxia, starvation and response to antituberculous and toxic substances. The function of Pma1 in the mycobacterial processes across the plasma membrane has not been characterised. In this work, bioinformatic analyses revealed that Pma1 likely contains potential sites for, Na(+), K(+) and Ca(2+) binding and transport. Accordingly, RT-qPCR experiments showed that M. smegmatis pma1 transcription is stimulated by sub-lethal doses of Na(+), K(+) and Ca(2+); in addition, the ATPase activity of plasma membrane vesicles in recombinant Pma1-expressing M. smegmatis cells is stimulated by treatment with these cations. In contrast, M. smegmatis cells homologously expressing Pma1 displayed tolerance to high doses of Na(+) and K(+) but not to Ca(2+) ions. Consistently, the recombinant protein Km embedded in plasma membrane demonstrated that Ca(2+) has more affinity for Pma1 than Na(+) and K(+) ions; furthermore, the estimation of Vmax/Km suggests that Na(+) and K(+) ions are more efficiently translocated than Ca(2+). Thus, these results strongly suggest that Pma1 is a promiscuous alkali/alkaline earth cation ATPase that preferentially transports Na(+) and/or K(+) across the mycobacterial plasma membrane. Copyright © 2015 Elsevier GmbH. All rights reserved.

Removal of arsenic compounds from petroliferous liquids

DOEpatents

Fish, R.H.

1984-04-06

The present invention in one aspect comprises a process for removing arsenic from petroliferous-derived liquids by contacting said liquid with a divinylbenzene-crosslinked polystyrene polymer (i.e. PS-DVB) having catechol ligands anchored to said polymer, said contacting being at an elevated temperature. In another aspect, the invention is a process for regenerating spent catecholated polystyrene polymer by removal of the arsenic bound to it from contacting petroliferous liquid in accordance with the aspect described above which regenerating process comprises: (a) treating said spent catecholated polystyrene polymer with an aqueous solution of at least one member selected from the group consisting of carbonates and bicarbonates of ammonium, alkali metals, and alkaline earth metals, said solution having a pH between about 8 and 10, and said treating being at a temperature in the range of about 20/sup 0/ to 100/sup 0/C; (b) separating the solids and liquids from each other. In a preferred embodiment the regeneration treatment is in two steps wherein step: (a) is carried out with an aqueous alcoholic carbonate solution which includes at least one lower alkyl alcohol, and, steps (c) and (d) are added. Steps (c) and (d) comprise: (c) treating the solids with an aqueous alcoholic solution of at least one ammonium, alkali or alkaline earth metal bicarbonate at a temperature in the range of about 20 to 100/sup 0/C; and (d) separating the solids from the liquids.

Microwave-assisted rapid synthesis and characterization of CaF₂ particles-filled cellulose nanocomposites in ionic liquid.

PubMed

Deng, Fu; Fu, Lian-Hua; Ma, Ming-Guo

2015-05-05

In this article, we try to compound cellulose/alkali earth metal fluorides (MF2, M=Ca, Mg, Sr, Ba) nanocomposites via microwave-assisted ionic liquid method, wherein cellulose/CaF2 and cellulose/MgF2 were successfully synthesized through this method while cellulose/SrF2 and cellulose/BaF2 could not be synthesized. We focused on the synthesis of cellulose/CaF2 and investigated the influences of the different time and different temperature for the synthesis of cellulose/CaF2 nanocomposites. The influence of different heating methods such as oil-bath heating method was also studied. Ionic liquid ([Bmim][BF4]) was used for dissolving microcrystalline cellulose and providing the source of fluoride ionic and the alkali earth metal nitrate (Ca(NO3)2, Mg(NO3)2, Sr(NO3)2, and Ba(NO3)2) was used as the reaction initiator. They were investigated by X-ray powder diffraction (XRD), Fourier transform infrared spectrometry (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TG), derivative thermogravimetric (DTG), and energy-dispersive X-ray spectra (EDS). The different heating modes have influence on the morphology and property. The different temperature and heating time also have a certain influence on the morphology and crystallinity of calcium fluoride. Copyright © 2014 Elsevier Ltd. All rights reserved.

Binding in alkali and alkaline-earth tetrahydroborates: Special position of magnesium tetrahydroborate

NASA Astrophysics Data System (ADS)

Łodziana, Zbigniew; van Setten, Michiel J.

2010-01-01

Compounds of light elements and hydrogen are currently extensively studied due to their potential application in the field of hydrogen or energy storage. A number of new interesting tetrahydroborates that are especially promising due to their very high gravimetric hydrogen content were recently reported. However, the determination and understanding of their complex crystalline structures has created considerable debate. Metal tetrahydroborates, in general, form a large variety of structures ranging from simple for NaBH4 to very complex for Mg(BH4)2 . Despite the extensive discussion in the literature no clear explanation has been offered for this variety so far. In this paper we analyze the structural and electronic properties of a broad range of metal tetrahydroborates and reveal the factors that determine their structure: ionic bonding, the orientation of the BH4 groups, and the coordination number of the metal cation. We show, in a simple way, that the charge transfer in the metal tetrahydroborates rationally explains the structural diversity of these compounds. Being ionic systems, the metal tetrahydroborates fall into the classification of Linus Pauling. By using the ionic radius for the BH4 group as determined in this paper, this allows for structural predictions for new and mixed compounds.

Comparative evaluation of anaerobic digestion for sewage sludge and various organic wastes with simple modeling.

PubMed

Hidaka, Taira; Wang, Feng; Tsumori, Jun

2015-09-01

Anaerobic co-digestion of sewage sludge and other organic wastes, such as kitchen garbage, food waste, and agricultural waste, at a wastewater treatment plant (WWTP) is a promising method for both energy and material recovery. Substrate characteristics and the anaerobic digestion performance of sewage sludge and various organic wastes were compared using experiments and modeling. Co-digestion improved the value of digested sewage sludge as a fertilizer. The relationship between total and soluble elemental concentrations was correlated with the periodic table: most Na and K (alkali metals) were soluble, and around 20-40% of Mg and around 10-20% of Ca (alkaline earth metals) were soluble. The ratio of biodegradable chemical oxygen demand of organic wastes was 65-90%. The methane conversion ratio and methane production rate under mesophilic conditions were evaluated using a simplified mathematical model. There was reasonably close agreement between the model simulations and the experimental results in terms of methane production and nitrogen concentration. These results provide valuable information and indicate that the model can be used as a pre-evaluation tool to facilitate the introduction of co-digestion at WWTPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Water contents of clinopyroxenes from sub-arc mantle peridotites

USGS Publications Warehouse

Turner, Michael; Turner, Simon; Blatter, Dawnika; Maury, Rene; Perfit, Michael; Yogodzinski, Gene

2017-01-01

One poorly constrained reservoir of the Earth's water budget is that of clinopyroxene in metasomatised, mantle peridotites. This study presents reconnaissance Sensitive High-Resolution, Ion Microprobe–Stable Isotope (SHRIMP–SI) determinations of the H2O contents of (dominantly) clinopyroxenes in rare mantle xenoliths from four different subduction zones, i.e. Mexico, Kamchatka, Philippines, and New Britain (Tabar-Feni island chain) as well as one intra-plate setting (western Victoria). All of the sub-arc xenoliths have been metasomatised and carry strong arc trace element signatures. Average measured H2O contents of the pyroxenes range from 70 ppm to 510 ppm whereas calculated bulk H2O contents range from 88 ppm to 3 737 ppm if the variable presence of amphibole is taken into account. In contrast, the intra-plate, continental mantle xenolith from western Victoria has higher water contents (3 447 ppm) but was metasomatised by alkali and/or carbonatitic melts and does not carry a subduction-related signature. Material similar to the sub-arc peridotites can either be accreted to the base of the lithosphere or potentially be transported by convection deeper into the mantle where it will lose water due to amphibole breakdown.

Sulfur in Earth's Mantle and Its Behavior During Core Formation

NASA Technical Reports Server (NTRS)

Chabot, Nancy L.; Righter,Kevin

2006-01-01

The density of Earth's outer core requires that about 5-10% of the outer core be composed of elements lighter than Fe-Ni; proposed choices for the "light element" component of Earth's core include H, C, O, Si, S, and combinations of these elements [e.g. 1]. Though samples of Earth's core are not available, mantle samples contain elemental signatures left behind from the formation of Earth's core. The abundances of siderophile (metal-loving) elements in Earth's mantle have been used to gain insight into the early accretion and differentiation history of Earth, the process by which the core and mantle formed, and the composition of the core [e.g. 2-4]. Similarly, the abundance of potential light elements in Earth's mantle could also provide constraints on Earth's evolution and core composition. The S abundance in Earth's mantle is 250 ( 50) ppm [5]. It has been suggested that 250 ppm S is too high to be due to equilibrium core formation in a high pressure, high temperature magma ocean on early Earth and that the addition of S to the mantle from the subsequent accretion of a late veneer is consequently required [6]. However, this earlier work of Li and Agee [6] did not parameterize the metalsilicate partitioning behavior of S as a function of thermodynamic variables, limiting the different pressure and temperature conditions during core formation that could be explored. Here, the question of explaining the mantle abundance of S is revisited, through parameterizing existing metal-silicate partitioning data for S and applying the parameterization to core formation in Earth.

Use of municipal solid waste incineration bottom ashes in alkali-activated materials, ceramics and granular applications: A review.

PubMed

Silva, R V; de Brito, J; Lynn, C J; Dhir, R K

2017-10-01

This paper presents a literature review on the incorporation of municipal solid waste incinerated bottom ash as raw material in several markets, other than those where it is conventionally used, such as geotechnical applications and road pavement construction. The main findings of an ample selection of experimental investigations on the use of the bottom ash as precursor of alkali-activated materials, as an adsorbent material for the removal of hazardous elements from wastewater and landfill gases, as soil replacement in agricultural activities, as partial or complete substitute of raw materials for the manufacture of ceramic-based products, as landfill cover and as biogas production enhancer, were gathered, collated and analysed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ab initio perspective on the Mollwo-Ivey relation for F centers in alkali halides

NASA Astrophysics Data System (ADS)

Tiwald, Paul; Karsai, Ferenc; Laskowski, Robert; Gräfe, Stefanie; Blaha, Peter; Burgdörfer, Joachim; Wirtz, Ludger

2015-10-01

We revisit the well-known Mollwo-Ivey relation that describes the "universal" dependence of the absorption energies of F-type color centers on the lattice constant a of alkali-halide crystals, Eabs∝a-n. We perform both state-of-the-art ab initio quantum chemistry and post-DFT calculations of F-center absorption spectra. By "tuning" independently the lattice constant and the atomic species we show that the scaling with the lattice constant alone (keeping the elements fixed) would yield n =2 in agreement with the "particle-in-the-box" model. Keeping the lattice constant fixed and changing the atomic species enables us to quantify the ion-size effects which are shown to be responsible for the exponent n ≈1.8 .

How PNNL Extracts Rare Earth Elements from Geothermal Brine

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

None

2016-07-12

By looking at a problem at a nanoscale level, PNNL researchers are developing an economic way to extract valuable rare earth elements from geothermal fluids. This novel approach may help meet the high demand for rare earth elements that are used in many clean energy technologies.

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.

Extra-terrestrial igneous granites and related rocks: A review of their occurrence and petrogenesis

NASA Astrophysics Data System (ADS)

Bonin, Bernard

2012-11-01

The telluric planets and the asteroid belt display the same internal structure with a metallic inner core and a silicate outer shell. Experimental data and petrological evidence in silicate systems show that granite can be produced by extreme igneous differentiation through various types of igneous processes. On Moon, 4.4-3.9 Ga granite clasts display dry mineral assemblages. They correspond to at least 8 discrete intrusive events. Large K/Ca enrichment and low REE abundances in granite relative to KREEP are consistent with silicate liquid immiscibility, a process observed in melt inclusions within olivine of lunar basalts and in lunar meteorites. Steep-sided domes identified by remote sensing can represent intrusive or extrusive felsic formations. On Mars, black-and-white rhythmic layers observed on the Tharsis rise along the flanks of the peripheral scarps of the Tharsis Montes giant volcanoes suggest the possible eruption of felsic pyroclastites. Though no true granites were found so far in the Martian SNC meteorites, felsic glasses and mesostases were identified and a component close to terrestrial continental (granitic) crust is inferred from trace element and isotope systematics. Venus has suffered extensive volcanic resurfacing, whereas folded and faulted areas resemble terrestrial continents. Near large shield volcanoes, with dominant basaltic compositions, steep-sided domes have been interpreted as non-degassed silicic extrusions. The hypothesis of a granitic component is "tantalising". Extra-terrestrial granite is frequently found as clasts and mesostases in asteroidal meteorites. Porphyritic textures, with alkali feldspar crystals up to several centimetres in size, were observed in silicate enclaves within iron meteorites. In the chondrite clan, polymict breccias can contain granitic clasts, whose provenance is debated. One clast from the Adzhi-Bogdo meteorite yields a 4.53 ± 0.03 Ga Pb-Pb age, making it the oldest known granite in the solar system. The vast majority of granitic materials recognised so far in the extra-terrestrial record are characterised by ferroan A-type compositions, characterised by high to very high K2O and medium CaO contents, sodic varieties being exceedingly rare. Textural evidence of graphic quartz-alkali feldspar intergrowths within crystallised products suggests that they are igneous in origin and crystallised quickly from a liquid. In water-depleted to water-free environments, fluorine and chlorine can play significant roles, as their effects on liquidus temperatures and crystallising assemblages are nearly identical to those of water. The distribution of alkalis and alkaline earths cannot be related only to extensive crystal fractionation, but is likely induced by supplementary silicate liquid immiscibility. Medium-temperature silicate liquid immiscibility is well known as a mode of differentiation in experimental petrology studies at very low pressures on systems dominated by Fe, Ti, K, and P as major elements. The ultimate question is, therefore, not whether granite (s.l.) occurs in any given planetary body, but if sufficient volumes of granitic materials could have been produced to constitute stable continental nuclei.

Unirradiated testing of the demonstration-scale ceramic waste form at ANL-West

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

Goff, K.M.; Simpson, M.F.; Bateman, K.J.

1997-12-01

The ceramic waste form is being developed by Argonne National Laboratory (ANL) as part of the demonstration of the electrometallurgical treatment of spent nuclear fuel for disposal. The alkali, alkaline earth, halide, and rare earth fission products are stabilized in zeolite, which is combined with glass and processed in a hot isostatic press (HIP) to form a ceramic composite. The transuranics, including plutonium, are also stabilized in this high-level waste. Most of the laboratory-scale development work is performed in the Chemical Technology Division of ANL in Illinois. At ANL-West in Idaho, this technology is being demonstrated on an engineering scalemore » before implementation with irradiated materials in a remote environment.« less

Innovative Approaches to Remote Sensing in NASA's Earth System Science Pathfinder (ESSP) Program

NASA Technical Reports Server (NTRS)

Peri, Frank; Volz, Stephen

2013-01-01

NASA's Earth Venture class (EV) of mission are competitively selected, Principal Investigator (PI) led, relatively low cost and narrowly focused in scientific scope. Investigations address a full spectrum of earth science objectives, including studies of the atmosphere, oceans, land surface, polar ice regions, and solid Earth. EV has three program elements: EV-Suborbital (EVS) are suborbital/airborne investigations; EV-Mission (EVM) element comprises small complete spaceborne missions; and EV-Instrument (EVI) element develops spaceborne instruments for flight as missions-of-opportunity (MoO). To ensure the success of EV, the management approach of each element is tailored according to the specific needs of the element.

Opportunities for Small Satellites in NASA's Earth System Science Pathfinder (ESSP) Program

NASA Technical Reports Server (NTRS)

Peri, Frank; Law, Richard C.; Wells, James E.

2014-01-01

NASA's Earth Venture class (EV) of missions are competitively selected, Principal Investigator (PI) led, relatively low cost and narrowly focused in scientific scope. Investigations address a full spectrum of earth science objectives, including studies of the atmosphere, oceans, land surface, polar ice regions, and solid Earth. EV has three program elements: EV-Suborbital (EVS) are suborbital/airborne investigations; EV-Mission (EVM) element comprises small complete spaceborne missions; and EV-Instrument (EVI) element develops spaceborne instruments for flight as Missions-of-Opportunity (MoO). To ensure the success of EV, frequent opportunities for selecting missions has been established in NASA's Earth Science budget. This paper will describe those opportunities and how the management approach of each element is tailored according to the specific needs of the element.

Determination of thorium and of rare earth elements in cerium earth minerals and ores

USGS Publications Warehouse

Carron, M.K.; Skinner, D.L.; Stevens, R.E.

1955-01-01

The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

Geochemistry of ultramafic xenoliths from Kapfenstein, Austria: evidence for a variety of upper mantle processes

NASA Astrophysics Data System (ADS)

Kurat, G.; Palme, H.; Spettel, B.; Baddenhausen, Hildegard; Hofmeister, H.; Palme, Christl; Wänke, H.

1980-01-01

Major, minor, and trace element contents have been determined in seven ultramafic xenoliths, the host basanite, and some mineral separates from xenoliths from Kapfenstein, Austria. Most of the xenoliths represent residues after extraction of different amounts of basaltic liquid. Within the sequence Iherzolite to harzburgite contents of Al, Ca, Ti, Na, Sc, V, Cr and the HREE decrease systematically with increasing Mg/Fe and decreasing Yb/Sc. Although all samples are depleted in highly incompatible elements, the less depleted end of our suite very closely approaches the chondritic Yb/Sc ratio and consequently the primitive upper mantle composition. Chromium behaved as a non-refractory element. Consequently it should have higher abundances in basalts than observed, suggesting that most basalts experienced Cr fractionation by chromite separation during ascent. Several processes have been active in addition to partial melting within the upper mantle beneath Kapfenstein: (1) a hornblendite has been identified as wet alkali-basaltic mobilisate; (2) an amphibole Iherzolite is the product of alkali-basalt metasomatism of a common depleted Iherzolite; (3) two amphibole Iherzolites contain evidence for rather pure water metasomatism of normal depleted Iherzolites; (4) a garnet-spinel websterite was a tholeiitic liquid trapped within the upper mantle and which suffered a subsequent partial melting event (partial remobilization of a mobilisate). (5) Abundances of highly incompatible elements are generally very irregular, indicating contamination of upper mantle rocks by percolating liquids (in the mantle). Weathering is an important source of contamination: e.g. U mobilization by percolating groundwater. Contamination of the xenoliths by the host basanite liquid can only amount to approximately 5.5 × 10 -4 parts. Distributions of minor and trace elements between different minerals apparently reflect equilibrium and vary with equilibration temperature.

Spirit Discovers New Class of Igneous Rocks

NASA Technical Reports Server (NTRS)

2006-01-01

During the past two-and-a-half years of traversing the central part of Gusev Crater, NASA's Mars Exploration Rover Spirit has analyzed the brushed and ground-into surfaces of multiple rocks using the alpha particle X-ray spectrometer, which measures the abundance of major chemical elements. In the process, Spirit has documented the first example of a particular kind of volcanic region on Mars known as an alkaline igneous province. The word alkaline refers to the abundance of sodium and potassium, two major rock-forming elements from the alkali metals on the left-hand side of the periodic table.

All of the relatively unaltered rocks -- those least changed by wind, water, freezing, or other weathering agents -- examined by Spirit have been igneous, meaning that they crystallized from molten magmas. One way geologists classify igneous rocks is by looking at the amount of potassium and sodium relative to the amount of silica, the most abundant rock-forming mineral on Earth. In the case of volcanic rocks, the amount of silica present gives scientists clues to the kind of volcanism that occurred, while the amounts of potassium and sodium provide clues about the history of the rock. Rocks with more silica tend to erupt explosively. Higher contents of potassium and sodium, as seen in alkaline rocks like those at Gusev, may indicate partial melting of magma at higher pressure, that is, deeper in the Martian mantle. The abundance of potassium and sodium determines the kinds of minerals that make up igneous rocks. If igneous rocks have enough silica, potassium and sodium always bond with the silica to form certain minerals.

The Gusev rocks define a new chemical category not previously seen on Mars, as shown in this diagram plotting alkalis versus silica, compiled by University of Tennessee geologist Harry McSween. The abbreviations 'Na2O' and 'K2O' refer to oxides of sodium and potassium. The abbreviation 'SiO2' refers to silica. The abbreviation 'wt. %' indicates that the numbers tell what percentage of the total weight of each rock is silica (on the horizontal scale) and what percentage is oxides of sodium and potassium (on the vertical scale). The thin lines separate volcanic rock types identified on Earth by different scientific names such as foidite and picrobasalt. Various classes of Gusev rocks (see box in upper right) all plot either on or to the left of the green lines, which define 'alkaline' and 'subalkaline' categories (subalkaline rocks have more silica than alkaline rocks).

Members of the rover team have named different classes of rocks after specimens examined by Spirit that represent their overall character. During the rover's travels, Spirit discovered that Adirondack-class rocks littered the Gusev plains; that Backstay, Irvine, and Wishstone-class rocks occurred as loose blocks on the northwest slope of 'Husband Hill'; and that outcrops of Algonquin-class rocks protruded in several places on the southeast face.

These rocks have less silica than all previously analyzed Mars samples, which are subalkaline. The previously analyzed Mars samples include Martian meteorites found on Earth and rocks analyzed by the Mars Pathfinder rover in 1997. Gusev is the first documented example of an alkaline igneous province on Mars.

Increasing the endurance of electrodes of heating salt tanks

NASA Astrophysics Data System (ADS)

Kulikov, A. I.

1997-05-01

Electrodes used for heating, melting, and sustaining the requisite temperature regime in salt tanks for heat treatment of metals and alloys operate under severe conditions (heating to 1300°C, aggressive medium of the melts of salts of alkali and alkali-earth metals). This causes early failure of the electrodes, and the heat treatment unit is stopped for repair. For example, the design service life of electrodes for SVS 2.3/13I tanks is two months, but as a rule it does not exceed one month of continuous operation. The replacement of conventional low-carbon electrode steel (for example, of grade 10) by a more expensive heat- and corrosion-resistant steel has not proved effective but rather increased the cost of the electrodes and hence the cost of the produced parts. In this connection, it is interesting to get acquainted with works devoted to increasing the service life of salt-tank electrodes for heat treatment shops of machine-building and tool plants. The present paper describes such an attempt.

Chloride, bromide and iodide scintillators with europium doping

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

Zhuravleva, Mariya; Yang, Kan

A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has beenmore » studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.« less

Ash chemistry and sintering

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

Skrifvars, B.J.; Backman, R.; Hupa, Mikko

1996-12-31

The thermal behavior of a fuel ash is one important factor to consider when fireside slagging and fouling problems in steam boilers are addressed. It is well known that different types of chemical reactions and melts in deposits play an important role in the build-up of problematic fireside deposits. Low viscous melts occur in steam boilers mainly when salt mixtures are present in the ash. Such are Merent mixtures of alkali and earth alkali sulfates, chlorides and carbonates. These mixtures do not melt at a certain temperature but form a melt in a temperature range which in some cases maymore » be several hundreds of degrees. The amount of melt is crucial for the deposit build-up. For some boilers it has been found that roughly 10 - 20 weight-% melt in an ash mixture would be enough to cause extensive deposit formation, while 60 - 80 weight-% melt would already cause the ash to be so wet it would flow down a vertical tube and not cause any further deposit growth.« less

Advance concepts for the conversion of syngas liquids. Quarterly report {number_sign}5, October 30, 1995--January 31, 1996

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

Szostak, R.; Ingram, C.

Research efforts for the report period have been focused on the characterization of catalyst samples, mainly by ion exchange and spectroscopic techniques. Other activities included the preparation of more variants of the MeAPO-36 family containing various types and amounts of metals in their frameworks. Characterization of these samples by X-ray diffraction analysis was delayed due to malfunction of the Diffractometer since October of 1995. The instrument was back in working condition only since the ending of January and XRD analysis has resumed since then. Efforts from the research group were also concentrated on the preparation of manuscripts for publication. Workmore » in progress includes: synthesis of MnAPO5 and MgAPO5; synthesis of CoAPO5; chemical analysis; preliminary investigation of ion exchange capacities of zeolites; uptake kinetics on the Na-exchanged MnAPO5 and MgAPO5 with alkali and alkali earth metals.« less

Strong Turbulence in Alkali Halide Negative Ion Plasmas

NASA Astrophysics Data System (ADS)

Sheehan, Daniel

1999-11-01

Negative ion plasmas (NIPs) are charge-neutral plasmas in which the negative charge is dominated by negative ions rather than electrons. They are found in laser discharges, combustion products, semiconductor manufacturing processes, stellar atmospheres, pulsar magnetospheres, and the Earth's ionosphere, both naturally and man-made. They often display signatures of strong turbulence^1. Development of a novel, compact, unmagnetized alkali halide (MX) NIP source will be discussed, it incorporating a ohmically-heated incandescent (2500K) tantulum solenoid (3cm dia, 15 cm long) with heat shields. The solenoid ionizes the MX vapor and confines contaminant electrons, allowing a very dry (electron-free) source. Plasma densities of 10^10 cm-3 and positive to negative ion mass ratios of 1 <= fracm_+m- <= 20 are achievable. The source will allow tests of strong turbulence theory^2. 1 Sheehan, D.P., et al., Phys. Fluids B5, 1593 (1993). 2 Tsytovich, V. and Wharton, C.W., Comm. Plasma Phys. Cont. Fusion 4, 91 (1978).

Theoretical study on the ground state of the polar alkali-metal-barium molecules: Potential energy curve and permanent dipole moment

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

Gou, Dezhi; Kuang, Xiaoyu, E-mail: scu-kuang@163.com; Gao, Yufeng

2015-01-21

In this paper, we systematically investigate the electronic structure for the {sup 2}Σ{sup +} ground state of the polar alkali-metal-alkaline-earth-metal molecules BaAlk (Alk = Li, Na, K, Rb, and Cs). Potential energy curves and permanent dipole moments (PDMs) are determined using power quantum chemistry complete active space self-consistent field and multi-reference configuration interaction methods. Basic spectroscopic constants are derived from ro-vibrational bound state calculation. From the calculations, it is shown that BaK, BaRb, and BaCs molecules have moderate values of PDM at the equilibrium bond distance (BaK:1.62 D, BaRb:3.32 D, and BaCs:4.02 D). Besides, the equilibrium bond length (4.93 Åmore » and 5.19 Å) and dissociation energy (0.1825 eV and 0.1817 eV) for the BaRb and BaCs are also obtained.« less

Alkali Metal CO2 Sorbents and the Resulting Metal Carbonates: Potential for Process Intensification of Sorption-Enhanced Steam Reforming.

PubMed

Memon, Muhammad Zaki; Zhao, Xiao; Sikarwar, Vineet Singh; Vuppaladadiyam, Arun K; Milne, Steven J; Brown, Andy P; Li, Jinhui; Zhao, Ming

2017-01-03

Sorption-enhanced steam reforming (SESR) is an energy and cost efficient approach to produce hydrogen with high purity. SESR makes it economically feasible to use a wide range of feedstocks for hydrogen production such as methane, ethanol, and biomass. Selection of catalysts and sorbents plays a vital role in SESR. This article reviews the recent research aimed at process intensification by the integration of catalysis and chemisorption functions into a single material. Alkali metal ceramic powders, including Li 2 ZrO 3 , Li 4 SiO 4 and Na 2 ZrO 3 display characteristics suitable for capturing CO 2 at low concentrations (<15% CO 2 ) and high temperatures (>500 °C), and thus are applicable to precombustion technologies such as SESR, as well as postcombustion capture of CO 2 from flue gases. This paper reviews the progress made in improving the operational performance of alkali metal ceramics under conditions that simulate power plant and SESR operation, by adopting new methods of sorbent synthesis and doping with additional elements. The paper also discusses the role of carbonates formed after in situ CO 2 chemisorption during a steam reforming process in respect of catalysts for tar cracking.

Coated phosphors, methods of making them, and articles comprising the same

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

Lyons, Robert Joseph

Compositions comprising a phosphor and a compound having the formula R.sub.1R.sub.2M, wherein R.sub.1 is a substituted or unsubstituted alkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, alkoxyl, acyl heterocycle, haloalkyl, oxaalkyl, or silyl; R.sub.2 is a sulfate, sulfonate, or carboxylate and M is an alkali metal or an alkaline earth metal are provided. Phosphors coated with the compound, methods of making the coated phosphors and articles comprising the compositions are provided.

Carbon fuel particles used in direct carbon conversion fuel cells

DOEpatents

Cooper, John F.; Cherepy, Nerine

2012-10-09

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Carbon Fuel Particles Used in Direct Carbon Conversion Fuel Cells

DOEpatents

Cooper, John F.; Cherepy, Nerine

2008-10-21

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Carbon fuel particles used in direct carbon conversion fuel cells

DOEpatents

Cooper, John F [Oakland, CA; Cherepy, Nerine [Oakland, CA

2011-08-16

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Carbon fuel particles used in direct carbon conversion fuel cells

DOEpatents

Cooper, John F [Oakland, CA; Cherepy, Nerine [Oakland, CA

2012-01-24

A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

Process for making structure for a MCFC

DOEpatents

Pasco, Wayne D.; Arendt, Ronald H.

1986-01-01

A process of making a porous carbonate-containing structure for use in a molten carbonate fuel cell, wherein a suitable porous structure is prepared having disposed therein a metal salt selected from the alkali metals and the alkaline earth metals or mixtures thereof with at least a portion of the salt being a monobasic organic acid salt. The monobasic acid salt is converted to the carbonate in situ by heating in the presence of oxygen. Both electrode and electrolyte structures can be prepared. Formic acid is preferred.

An Overview of Hydrogen Generation and Storage for Low-Temperature PEM Fuel Cells

DTIC Science & Technology

1999-11-01

environment. Otherwise, the wt % of stored hydrogen is attractive; e.g., LiH is 25 percent. Thermal stability of pure alkali and alkaline earth- metal ...nanofibers can be prepared by metal -catalyzed decomposition (at 450 to 750 °C) of carbon-containing gases to possess a cross-sectional area between 30 to ...respect to the face of the metal particle. Separation distance between layers depends on the type of catalyst, gas, and reaction conditions used

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.

Volcanism on the fossil Galapagos Rise spreading centre, SE Pacific

NASA Astrophysics Data System (ADS)

Haase, K. M.; Stroncik, N. A.

2002-12-01

A part of the fossil spreading centre of the Galapagos Rise at 10° S, 95° W in the SE Pacific Ocean was mapped and sampled. This spreading centre was active for about 12 Ma and was abandoned about 6.5 Ma ago when the spreading rate of the East Pacific Rise (EPR) increased. The aim of this study is to understand the tectonic and petrological implications of the ridge jump for the spreading centre and to gain insights into the processes in its melting column. Bathymetric swath mapping of a part of the Galapagos Rise revealed an elongated structure with a NNE-SSW strike direction which is bounded by a large fracture zone in the north. The mapped area can be divided into three segments, each of about 50 km length. The northernmost segment consists of an ~4400 m deep rift which shows similarities to a slow-spreading centre, e.g. the Mid-Atlantic Ridge. The southern two segments are volcanic ridges with numerous volcanic flank cones which reach water depths up to 490 m. This volcanic ridge is interpreted as the continuation of the fossil spreading axis. While the northernmost segment is magmatically starved, the volcanic ridges of the southern two segments apparently formed after cessation of spreading. The rock samples from the rift flanks in the north are incompatible element-depleted (K/Ti 0.08-0.28) and plagioclase-phyric basalts resembling typical mid-ocean ridge basalts (MORB). In contrast, the lavas from the two volcanic ridge segments in the south are highly vesicular incompatible element-enriched alkali basalts with K/Ti of 0.65-1.4. The depleted rift basalts have Sr isotope ratios below 0.7027 while the alkali basalts from the ridge range between 0.7029 and 0.7031. The rift basalts have significantly lower sodium contents than the alkali basalts and thus the southern lavas are probably derived by smaller degrees of partial melting. The relatively low Si contents of the alkali basalts also indicates formation deeper in the melting column than the northern MORB-like samples. The mantle source of the alkali basalts is similar to the enriched source of off-axis seamounts along the EPR. Our preliminary data suggest that the northernmost segment formed by tectonic processes during a final slow-spreading phase of the Galapagos Rise while the southern two segments erupted alkaline lavas probably after spreading stopped.

A novel approach for acid mine drainage pollution biomonitoring using rare earth elements bioaccumulated in the freshwater clam Corbicula fluminea.

PubMed

Bonnail, Estefanía; Pérez-López, Rafael; Sarmiento, Aguasanta M; Nieto, José Miguel; DelValls, T Ángel

2017-09-15

Lanthanide series have been used as a record of the water-rock interaction and work as a tool for identifying impacts of acid mine drainage (lixiviate residue derived from sulphide oxidation). The application of North-American Shale Composite-normalized rare earth elements patterns to these minority elements allows determining the origin of the contamination. In the current study, geochemical patterns were applied to rare earth elements bioaccumulated in the soft tissue of the freshwater clam Corbicula fluminea after exposure to different acid mine drainage contaminated environments. Results show significant bioaccumulation of rare earth elements in soft tissue of the clam after 14 days of exposure to acid mine drainage contaminated sediment (ΣREE=1.3-8μg/gdw). Furthermore, it was possible to biomonitor different degrees of contamination based on rare earth elements in tissue. The pattern of this type of contamination describes a particular curve characterized by an enrichment in the middle rare earth elements; a homologous pattern (E MREE =0.90) has also been observed when applied NASC normalization in clam tissues. Results of lanthanides found in clams were contrasted with the paucity of toxicity studies, determining risk caused by light rare earth elements in the Odiel River close to the Estuary. The current study purposes the use of clam as an innovative "bio-tool" for the biogeochemical monitoring of pollution inputs that determines the acid mine drainage networks affection. Copyright © 2017 Elsevier B.V. All rights reserved.

The New Element Americium (Atomic Number 95)

DOE R&D Accomplishments Database

Seaborg, G.T.; James, R.A.; Morgan, L.O.

1948-01-01

Several isotopes of the new element 95 have been produced and their radiations characterized. The chemical properties of this tripositive element are similar to those of the typical tripositive lanthanide rare-earth elements. Element 95 is different from the latter in the degree and rate of formation of certain compounds of the complex ion type, which makes possible the separation of element 95 from the lanthanide rare-earths. The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series.

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.

Protected Nuclear Fuel Element

DOEpatents

Kittel, J. H.; Schumar, J. F.

1962-12-01

A stainless steel-clad actinide metal fuel rod for use in fast reactors is reported. In order to prevert cladding failures due to alloy formation between the actinide metal and the stainless steel, a mesh-like sleeve of expanded metal is interposed between them, the sleeve metal being of niobium, tantalum, molybdenum, tungsten, zirconium, or vanadium. Liquid alkali metal is added as a heat transfer agent. (AEC)

40 CFR Table 7 to Subpart IIIii of... - Required Elements of Washdown Plans

Code of Federal Regulations, 2012 CFR

2012-07-01

... baskets 6. Hydrogen system piping 7. Basement floor of cell rooms 8. Tanks 9. Pillars and beams in cell... Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII, Table 7 Table 7 to Subpart IIIII of Part 63... following as part of your plan . . . 1. Center aisles of cell rooms A description of the manner of washdown...

40 CFR Table 7 to Subpart IIIii of... - Required Elements of Washdown Plans

Code of Federal Regulations, 2011 CFR

2011-07-01

... baskets 6. Hydrogen system piping 7. Basement floor of cell rooms 8. Tanks 9. Pillars and beams in cell... Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII, Table 7 Table 7 to Subpart IIIII of Part 63... following as part of your plan . . . 1. Center aisles of cell rooms A description of the manner of washdown...

ENVIRONMENTAL PERFORMANCE AND COSTS ASSOCIATED WITH THE TREATMENT AND DISPOSAL OF ELEMENTAL MERCURY IN A MONOFILL

EPA Science Inventory

It has been predicted that there will be a worldwide glut of mercury. The magnitude and timing depends on when the chlor-alkali industry switches from Hg cell technology. Mercury cell plants typically have a working life of 40 to 60 years and no U.S. plant has been built since ab...

40 CFR Table 7 to Subpart IIIii of... - Required Elements of Washdown Plans

Code of Federal Regulations, 2010 CFR

2010-07-01

... Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII, Table 7 Table 7 to Subpart IIIII of Part 63... following as part of your plan . . . 1. Center aisles of cell rooms A description of the manner of washdown... baskets 6. Hydrogen system piping 7. Basement floor of cell rooms 8. Tanks 9. Pillars and beams in cell...

40 CFR Table 7 to Subpart IIIii of... - Required Elements of Washdown Plans

Code of Federal Regulations, 2013 CFR

2013-07-01

... Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII, Table 7 Table 7 to Subpart IIIII of Part 63... following as part of your plan . . . 1. Center aisles of cell rooms A description of the manner of washdown... baskets 6. Hydrogen system piping 7. Basement floor of cell rooms 8. Tanks 9. Pillars and beams in cell...

40 CFR Table 7 to Subpart IIIii of... - Required Elements of Washdown Plans

Code of Federal Regulations, 2014 CFR

2014-07-01

... Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII, Table 7 Table 7 to Subpart IIIII of Part 63... following as part of your plan . . . 1. Center aisles of cell rooms A description of the manner of washdown... baskets 6. Hydrogen system piping 7. Basement floor of cell rooms 8. Tanks 9. Pillars and beams in cell...

Structural and electronic properties of the alkali metal incommensurate phases

NASA Astrophysics Data System (ADS)

Woolman, Gavin; Naden Robinson, Victor; Marqués, Miriam; Loa, Ingo; Ackland, Graeme J.; Hermann, Andreas

2018-05-01

Under pressure, the alkali elements sodium, potassium, and rubidium adopt nonperiodic structures based on two incommensurate interpenetrating lattices. While all elements form the same "host" lattice, their "guest" lattices are all distinct. The physical mechanism that stabilizes these phases is not known, and detailed calculations are challenging due to the incommensurability of the lattices. Using a series of commensurate approximant structures, we tackle this issue using density functional theory calculations. In Na and K, the calculations prove accurate enough to reproduce not only the stability of the host-guest phases, but also the complicated pressure dependence of the host-guest ratio and the two guest-lattice transitions. We find Rb-IV to be metastable at all pressures, and suggest it is a high-temperature phase. The electronic structure of these materials is unique: they exhibit two distinct, coexisting types of electride behavior, with both fully localized pseudoanions and electrons localized in 1D wells in the host lattice, leading to low conductivity. While all phases feature pseudogaps in the electronic density of states, the perturbative free-electron picture applies to Na, but not to K and Rb, due to significant d -orbital population in the latter.

A high-pyrite semianthracite of Late Permian age in the Songzao Coalfield, southwestern China: Mineralogical and geochemical relations with underlying mafic tuffs

USGS Publications Warehouse

Dai, S.; Wang, X.; Chen, W.; Li, D.; Chou, C.-L.; Zhou, Y.; Zhu, Chen; Li, H.; Zhu, Xudong; Xing, Y.; Zhang, W.; Zou, J.

2010-01-01

The No. 12 Coal (Late Permian) in the Songzao Coalfield, Chongqing, southwestern China, is characteristically high in pyrite and some trace elements. It is uniquely deposited directly above mafic tuff beds. Samples of coal and tuffs have been studied for their mineralogy and geochemistry using inductively coupled plasma-mass spectrometry, X-ray fluorescence, plasma low-temperature ashing plus powder X-ray diffraction, and scanning electron microscopy equipped with energy-dispersive X-ray analysis.The results show that the minerals of the No. 12 Coal are mainly composed of pyrite, clay minerals (kaolinite, chamosite, and illite), ankerite, calcite, and trace amounts of quartz and boehmite. Kaolinite and boehmite were mainly derived from sediment source region of mafic tuffs. Chamosite was formed by the reaction of kaolinite with Fe-Mg-rich fluids during early diagenesis. The high pyrite (Sp,d=8.83%) in the coal was related to marine transgression over peat deposits and abundant Fe derived from the underlying mafic tuff bed. Ankerite and calcite were precipitated from epigenetic fluids.Chemical compositions of incompatible elements indicate that the tuffs were derived from enriched mantle and the source magmas had an alkali-basalt character. Compared to other coals from the Songzao Coalfield and common Chinese coals, the No. 12 Coal has a lower SiO2/Al2O3 (1.13) but a higher Al2O3/Na2O (80.1) value and is significantly enriched in trace elements including Sc (13.5??g/g), V (121??g/g), Cr (33.6??g/g), Co (27.2??g/g), Ni (83.5??g/g), Cu (48.5??g/g), Ga (17.3??g/g), Y (68.3??g/g), Zr (444??g/g), Nb (23.8??g/g), and REE (392??g/g on average). Above mineralogical compositions, as well as similar ratios of selected elements (e.g., SiO2/Al2O3 and Al2O3/Na2O) and similar distribution patterns of incompatible elements (e.g., the mantle-normalized diagram for incompatible elements and chondrite-normalized diagram for rare earth elements) of coal and tuff, indicated that enriched trace elements above were largely derived from mafic tuffs, in addition to a minor amount from the Kandian Oldland. ?? 2010 Elsevier B.V.

Experimental evidence for a phase transition in magnesium oxide at exoplanet pressures

DOE PAGES

Coppari, F.; Smith, R. F.; Eggert, J. H.; ...

2013-09-22

Here, magnesium oxide, an important component of the Earth’s mantle, has been extensively studied in the pressure and temperature range found within the Earth. However,much less is known about its behavior under conditions appropriate for newly-discovered super-Earth planets, where pressures can exceed 1000 GPa (10 Mbar). It is widely believed that MgO will follow the rocksalt (B1) to cesium chloride (B2) transformation pathway commonly found for many alkali halides, alkaline earth oxides and various other ionic compounds. Static compression experiments have determined the structure of MgO to 250 GPa but have been unable to reach pressures necessary to induce themore » predicted transformation, resulting in large uncertainties regarding its properties under conditions relevant to super-Earths and other large planets. Here we report new dynamic x-ray diffraction measurements of ramp-compressed MgO to 900 GPa.We report evidence for the B2 phase beginning near 600 GPa, remaining stable on further compression to 900 GPa, the highest pressure diffraction data ever collected.« less

The elemental abundances (with uncertainties) of the most Earth-like planet

NASA Astrophysics Data System (ADS)

Wang, Haiyang S.; Lineweaver, Charles H.; Ireland, Trevor R.

2018-01-01

To first order, the Earth as well as other rocky planets in the Solar System and rocky exoplanets orbiting other stars, are refractory pieces of the stellar nebula out of which they formed. To estimate the chemical composition of rocky exoplanets based on their stellar hosts' elemental abundances, we need a better understanding of the devolatilization that produced the Earth. To quantify the chemical relationships between the Earth, the Sun and other bodies in the Solar System, the elemental abundances of the bulk Earth are required. The key to comparing Earth's composition with those of other objects is to have a determination of the bulk composition with an appropriate estimate of uncertainties. Here we present concordance estimates (with uncertainties) of the elemental abundances of the bulk Earth, which can be used in such studies. First we compile, combine and renormalize a large set of heterogeneous literature values of the primitive mantle (PM) and of the core. We then integrate standard radial density profiles of the Earth and renormalize them to the current best estimate for the mass of the Earth. Using estimates of the uncertainties in i) the density profiles, ii) the core-mantle boundary and iii) the inner core boundary, we employ standard error propagation to obtain a core mass fraction of 32.5 ± 0.3 wt%. Our bulk Earth abundances are the weighted sum of our concordance core abundances and concordance PM abundances. Unlike previous efforts, the uncertainty on the core mass fraction is propagated to the uncertainties on the bulk Earth elemental abundances. Our concordance estimates for the abundances of Mg, Sn, Br, B, Cd and Be are significantly lower than previous estimates of the bulk Earth. Our concordance estimates for the abundances of Na, K, Cl, Zn, Sr, F, Ga, Rb, Nb, Gd, Ta, He, Ar, and Kr are significantly higher. The uncertainties on our elemental abundances usefully calibrate the unresolved discrepancies between standard Earth models under various geochemical and geophysical assumptions.

Non-noble metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution

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

Song, Jun-Ling, E-mail: s070054@e.ntu.edu.sg; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002; Zhang, Jian-Han

2016-05-15

We reported the synthesis and crystal structures of alkali metal and alkali-earth metal phosphite, namely, CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} (1), and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} (2). Both compounds were prepared by hydrothermal reactions and feature unique new structures. They both exhibit 3D complicated frameworks based on VO{sub 6} octahedra which are connected by HPO{sub 3} tetrahedra via corner-sharing. Alkali or alkali earth metal cations are filled in the different channels of the frameworks. Topological analysis shows that the framework of CsV{sub 2}(H{sub 3}O) (HPO{sub 3}){sub 4} (1) is a new 3,3,3,4,5-connected network with the Schläfli symbol of {4.6"2}{submore » 2}{4"2.6"6.8"2}{6"3}{6"5.8}. The investigations of X-ray photoelectron spectroscopy (XPS) and magnetic measurement on CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} suggest a +3 oxidation state of the vanadium ions in compound 1. Photocatalytic performance was evaluated by photocatalytic H{sub 2} evolution and degradation of methylene blue, which shows that both compounds exhibit activity under visible-light irradiation. IR spectrum, UV–vis-NIR spectrum and thermogravimetric analysis (TGA) of compounds were also investigated. - Graphical abstract: Metal vanadium phosphites with broad absorption for photocatalytic hydrogen evolution and the degradation of methylene blue aqueous solution. - Highlights: • Two new vanadium phosphites, CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6}, are reported. • CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} feature complicated 3D framework structures with different channels. • CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} exhibit strong and broad absorptions in the visible and Near IR region. • Photocatalytic properties of CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} and Ba{sub 3}V{sub 2}(HPO{sub 3}){sub 6} are investigated. • The magnetic measurement of CsV{sub 2}(H{sub 3}O)(HPO{sub 3}){sub 4} was performed in the temperature range of 2–300 K.« less

[Analysis of X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry of Pangxidong Composite Granitoid Pluton and Its Implications for Magmatic Differentiation].

PubMed

Zeng, Chang-yu; Ding, Ru-xin; Li, Hong-zhong; Zhou, Yong-zhang; Niu, Jia; Zhang, Jie-tang

2015-11-01

Pangxidong composite granitoid pluton located in the southwestern margin of Yunkai massif. The metamorphic grade of this pluton increases from outside to inside, that is, banded-augen granitic gneisses, gneissoid granites and granites distribute in order from edge to core. X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry are conducted to study the geochemical characteristics of the three types of rocks. The result shows that all the three types of rocks are peraluminous rocks and their contents of main elements and rare earth elements change gradually. From granitic gneisses to granites, the contents of Al₂O₃, CaO, MgO, TiO₂, total rare earth elements and light rare earth elements increase, but the contents of SiO₂ and heavy rare earth elements decrease. It is suggested that the phylogenetic relationship exists between granitic gneisses, gneissoid granites and granites during the multi-stage tectonic evolution process. Furthermore, the remelting of metamorphosed supracrustal rocks in Yunkai massif is probably an important cause of granitoid rocks forming. The evolutionary mechanism is probably that SiO₂ and heavy rare earth elements were melt out from the protolith and gradually enriched upward, but Al₂O₃, CaO, MgO, TiO₂ and light rare earth elements enriched downward.

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

DOEpatents

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

Semiconductor sensor for optically measuring polarization rotation of optical wavefronts using rare earth iron garnets

DOEpatents

Duncan, Paul G.

2002-01-01

Described are the design of a rare earth iron garnet sensor element, optical methods of interrogating the sensor element, methods of coupling the optical sensor element to a waveguide, and an optical and electrical processing system for monitoring the polarization rotation of a linearly polarized wavefront undergoing external modulation due to magnetic field or electrical current fluctuation. The sensor element uses the Faraday effect, an intrinsic property of certain rare-earth iron garnet materials, to rotate the polarization state of light in the presence of a magnetic field. The sensor element may be coated with a thin-film mirror to effectively double the optical path length, providing twice the sensitivity for a given field strength or temperature change. A semiconductor sensor system using a rare earth iron garnet sensor element is described.

ChemCam Targeted Science at Gale Crater

NASA Astrophysics Data System (ADS)

Wiens, R. C.; Blaney, D. L.; Clark, B. C.; Bridges, N. T.; Clegg, S. M.; Maurice, S.; Newsom, H. E.; Vaniman, D. T.; Herkenhoff, K. E.; Ollila, A. M.; Gasnault, O.; Pinet, P. C.; Dromart, G.; Barraclough, B. L.; Lasue, J.

2011-12-01

The MSL rover, Curiosity, uses a novel remote-sensing instrument, ChemCam, which combines laser-induced breakdown spectroscopy (LIBS) with a high resolution remote micro-imager (RMI). ChemCam uses a focused, pulsed laser beam at targets up to 7 m away to excite a light-emitting plasma. Spectral analysis identifies elements present and provides rapid semi-quantitative analyses. Repeated laser pulses remove dust and weathering coatings from rock samples to depths >0.5 mm and ~0.4 mm in diameter. The RMI, with ~20x20 mrad field of view, provides a broad-band image with 100 μm resolution. LIBS yields abundances of H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, Cl, K, Ca, Ti, V, Cr, Fe, Ni, Zr, Rb, Sr, As, Ba, and Pb. Interference from atmospheric constituents raises the detection limits of C, N, and O (e.g., >2% wt for C). LIBS is very sensitive to alkali and alkali earth elements, with some detection limits to ~1 ppm at close range. Conversely, LIBS is insensitive to F, Cl, S, P, and N, with detection limits of several wt. %. Pointing accuracy is ~3 mrad, however relative pointing accuracy is better, so line scans and rasters will enable analyses of targeted features to ~1 mm. At Gale Crater, determination of elements not previously analyzed in-situ, i.e., H, Li, Rb, Sr, and Ba, along with other elements will constrain aqueous, hydrothermal and vapor geochemical transport processes. Initial analyses after landing will characterize air fall dust and weathering coatings on local rocks, and profile the soil and surfacial materials including bedforms to investigate compositional differences in near-surface layers. Targets within the landing ellipse include fan and inverted channel deposits derived from the crater rim, which may contain alteration minerals produced by impact hydrothermal processes. Enigmatic deposits with bright fracture fill could represent lake sediments modified by injection of deposits from groundwater. During the drive to the Gale mound, ChemCam will provide daily assays of soil composition and morphology, looking for changes en route. A scarp defining the boundary between low and high thermal inertia regions in the ellipse will be another target. Small craters may expose the stratigraphy of the fan. Near the mound ChemCam will study the transition from the fan to the basal unit of the mound to determine whether it contains lithified bedforms. What is the cementing material and what can we learn about the temperature history or depth of burial? At the mound, ChemCam will study chemostratigraphy, correlating elemental compositions against textural fabrics and cross-bedding geometries, and assessing the petrographic heterogeneity of sedimentary and/or diagenetic grains. ChemCam will also investigate questions such as: What are the hydration states of phyllosilicates and salts, including diurnal variability? What fraction of the material is phyllosilicates and how are they distributed? What characterizes the transition from phyllosilicates to sulfates? ChemCam will play a key role in unraveling the geologic history recorded in Gale Crater.

A new method for the determination of Gadolinium in ppq levels

NASA Astrophysics Data System (ADS)

Brünjes, Robert; Bichler, Andrea; Hofmann, Thilo

2015-04-01

The use of Gadolinium (Gd) complexes as a contrast agent in Magnetic Resonance Imaging (MRI) results in an enhanced Gd input in the aquatic environment. Gd-complexes are excreted by humans unmetabolized within 12h after application. Passing the sewage systems with almost no degradation taking place, they successively reach surface waters, which make Gd a capable tracer for surface water/groundwater (SW/GW) interactions. The natural background concentration of Gd and other rare earth elements (REE) occur at ultratrace levels [low ng/L]. Crust-normalized REE patterns show positive Gd-anomalies in surface water, groundwater, and recently also in tap water. The difference between the total concentration and its natural background concentration estimated by the REE pattern is the anthropogenic Gd. Not only densely populated areas are affected by the presence of anthropogenic Gd. Studies have shown that even in rural areas without MRI facilities, anthropogenic Gd can be detected, since people are sent home after treatment. However, low input concentrations and mixing with natural waters lead to a decrease of Gd concentration below the current limit of quantification (LOQ) [1-5ng/L]. Often anthropogenic Gd cannot be calculated, although it is present, because natural background concentration cannot be determined with current methods, in particular in areas with low waste water load (e.g. headwater catchments). A new method using an on-line preconcentration system "SeaFAST" (Elemental Scientific Inc., USA), in combination with a desolvation system "Apex Q" (Elemental Scientific Inc., USA) and a QQQ-ICP-MS instrument (Agilent Technologies, Japan) does lower the LOQ for REE by a factor of 10 to 20. The SeaFAST-system uses a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate specifically REE as they are exclusively trivalent while anions, alkali and alkaline earth cations are washed out. The Apex Q interface is also supposed to significantly lower oxide interferences. We also evaluate a pretreatment in order to degrade the complexes and reach high recoveries of anthropogenic Gd. Our method will provide a determination of REE in ppq-levels, that significantly improves the differentiation between naturally and anthropogenic Gd. This will allow the detection of less than 1% waste water in SW and GW and finally increase the areas where studies of anthropogenic Gd could be conducted. A first application of our method was conducted during a field study in November 2014.

Condensation and fractionation of rare earths in the solar nebula

NASA Technical Reports Server (NTRS)

Davis, A. M.; Grossman, L.

1979-01-01

The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

Membrane assisted solvent extraction for rare earth element recovery

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

Bhave, Ramesh R.; Kim, Daejin; Peterson, Eric S.

Systems and methods for the recovery of rare earth elements are provided. The systems and methods generally include membrane assisted solvent extraction using permeable hollow fibers having an immobilized organic phase within the pores of the hollow fibers. The permeable hollow fibers are generally in contact with an acidic aqueous feed on one side thereof and a strip solution on another side thereof. The systems and methods generally include the simultaneous extraction and stripping of rare earth elements as a continuous recovery process that is well suited for post-consumer products, end-of-life products, and other recovery sources of rare earth elements.

Rare earth elements in weathering profiles and sediments of Minnesota: Implications for provenance studies

USGS Publications Warehouse

Morey, G.B.; Setterholm, D.R.

1997-01-01

The relative abundance of rare earth elements in sediments has been suggested as a tool for determining their source rocks. This correlation requires that weathering, erosion, and sedimentation do not alter the REE abundances, or do so in a predictable manner. We find that the rare earth elements are mobilized and fractionated by weathering, and that sediments derived from the weathered materials can display modifications of the original pattern of rare earth elements of some due to grain-size sorting of the weathered material. However, the REE distribution pattern of the provenance terrane can be recognized in the sediments.

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

NASA Technical Reports Server (NTRS)

Righter, Kevin; Pando, K.; Danielson, L.; Nickodem, K.

2014-01-01

Depletions of volatile siderophile elements (VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd) in mantles of Earth and Moon, constrain the origin of volatile elements in these bodies, and the overall depletion of volatile elements in Moon relative to Earth. A satisfactory explanation has remained elusive [1,2]. We examine the depletions of VSE in Earth and Moon and quantify the amount of depletion due to core formation and volatility of potential building blocks. We calculate the composition of the Earth's PUM during continuous accretion scenarios with constant and variable fO2. Results suggest that the VSE can be explained by a rather simple scenario of continuous accretion leading to a high PT metal-silicate equilibrium scenario that establishes the siderophile element content of Earth's PUM near the end of accretion [3]. Core formation models for the Moon explain most VSE, but calculated contents of In, Sn, and Zn (all with Tc < 750 K) are all still too high after core formation, and must therefore require an additional process to explain the depletions in the lunar mantle. We discuss possible processes including magmatic degassing, evaporation, condensation, and vapor-liquid fractionation in the lunar disk.

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.

MaRGEE: Move and Rotate Google Earth Elements

NASA Astrophysics Data System (ADS)

Dordevic, Mladen M.; Whitmeyer, Steven J.

2015-12-01

Google Earth is recognized as a highly effective visualization tool for geospatial information. However, there remain serious limitations that have hindered its acceptance as a tool for research and education in the geosciences. One significant limitation is the inability to translate or rotate geometrical elements on the Google Earth virtual globe. Here we present a new JavaScript web application to "Move and Rotate Google Earth Elements" (MaRGEE). MaRGEE includes tools to simplify, translate, and rotate elements, add intermediate steps to a transposition, and batch process multiple transpositions. The transposition algorithm uses spherical geometry calculations, such as the haversine formula, to accurately reposition groups of points, paths, and polygons on the Google Earth globe without distortion. Due to the imminent deprecation of the Google Earth API and browser plugin, MaRGEE uses a Google Maps interface to facilitate and illustrate the transpositions. However, the inherent spatial distortions that result from the Google Maps Web Mercator projection are not apparent once the transposed elements are saved as a KML file and opened in Google Earth. Potential applications of the MaRGEE toolkit include tectonic reconstructions, the movements of glaciers or thrust sheets, and time-based animations of other large- and small-scale geologic processes.

IUPAC-NIST Solubility Data Series. 75. Nonmetals in Liquid Alkali Metals

NASA Astrophysics Data System (ADS)

Borgstedt, Hans Ulrich; Guminski, Cezary; Borgstedt, Hans Ulrich; Guminski, Cezary

2001-07-01

Liquid alkali metals have several physical properties which favor their use in a number of important applications. For example, their large liquidus temperature range and their excellent heat transfer properties are important for use as heat transfer media. They are used in large nuclear reactors in which hundreds of tons of sodium are circulating, and in small parts of engines for cooling of valves. Since these metals are among the most electropositive elements, several of them (Li, Na) can be used in high specific capacity and high energy density batteries at moderately elevated temperatures. The compatibility of metallic constructional materials which are used to contain the liquid metals is strongly influenced by nonmetals present in the liquids. The physical properties of the liquid metals are also influenced by dissolved substances. Several nonmetals dissolved in alkali metals are able to form ternary compounds with components of the constructional materials. Thus, corrosion and compatibility studies have been accompanied by extensive chemical work related to the solutions of non-metallic substances in liquid alkali metals. All available solubility data of nonmetallic elements and some of their compounds in the five liquid alkali metal solvents (Li, Na, K, Rb, and Cs) are collected and compiled. Original publications with reliable data and information on the methods used to generate them are reported in individual Compilations. When numerical data are not given in a publication, the data are often read out from figures and converted into numerical data by the compilers. The precision of this procedure is indicated in the Compilations under Estimated Error. Evaluated solubility data are tabulated at the end of the Critical Evaluations: if there is agreement of at least two independent studies within the experimental error, the solubility values are assigned to the "recommended" category. Values are assigned as "tentative," if only one reliable result was reported, or if the mean value of two or more reliable studies was outside the error limits. In the tabulation, three, two, or one significant figures are assigned for respective precisions that are better than ±1% and ±10% and worse than ±10%. If necessary, the solubilities are recalculated into mol %. The completeness of this investigation of the literature has been confirmed and extended by studying several reviews dealing with the solution chemistry of substances in the alkali metals. Solubility data are sometimes measured under parameters, which are not standard conditions of such measurements. Frequently measurements are performed under constrained pressure. The solubility of noble gases or other gases, which do not form compounds with the alkali metals, depends on the gas pressures. This dependency is documented in the data sheets. Schematic phase diagrams are presented in systems for which they assist the understanding of the data and the conclusions. They are based on the most recent state of knowledge and generally presented in the Critical Evaluations. Some solubility diagrams are shown in form of a log solubility versus reciprocal temperature function. These figures illustrate the larger scatter of data for systems in which interfering reactions cause unstable behavior of solutions. While several solutes are well defined substances, other systems need still additional studies to define the equilibrium solid state compound. One should realize that estimations of the stoichiometry and thermal stability of ternary compounds are experimentally difficult, and their results are often uncertain.

Alkali metal ion battery with bimetallic electrode

DOEpatents

Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

2015-04-07

Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

Selective liquid chromatographic separation of yttrium from heavier rare earth elements using acetic acid as a novel eluent.

PubMed

Kifle, Dejene; Wibetoe, Grethe

2013-09-13

One of the major difficulties in the rare earth elements separation is purification of yttrium from heavy rare earth elements. Thus, an HPLC method using acetic acid as novel eluent was explored for selective separation of yttrium form the heavy rare earth elements. When acetic acid is used as a mobile phase yttrium eluted with the lighter lanthanides. This is contrary to its relative position amongst heavier lanthanides when eluents commonly used for separation of rare earth elements were employed. The shift in elution position of yttrium with acetic acid as eluent may reflect a relatively lower stability constant of the yttrium-AcOH complex (in the same order as for the lighter lanthanides) compared to the corresponding AcOH complexes with heavy lanthanides, enabling selective separation of yttrium from the latter. The method was successfully used for selective separation of yttrium in mixed rare earth sample containing about 80% of yttrium and about 20% of heavy rare earth oxides. Thus, the use of AcOH as eluent is an effective approach for separating and determining the trace amounts of heavy rare earth elements in large amounts of yttrium matrix. Separation was performed on C18 column by running appropriate elution programs. The effluent from the column was monitored with diode array detector at absorbance wavelength of 658nm after post column derivatization with Arsenazo III. Copyright © 2013 Elsevier B.V. All rights reserved.

Cryptic microtextures and geological histories of K-rich alkali feldspars revealed by charge contrast imaging

NASA Astrophysics Data System (ADS)

Flude, Stephanie; Lee, Martin R.; Sherlock, Sarah C.; Kelley, Simon P.

2012-06-01

Charge contrast imaging in the scanning electron microscope can provide new insights into the scale and composition of alkali feldspar microtextures, and such information helps considerably with the interpretation of their geological histories and results of argon isotope thermochronological analyses. The effectiveness of this technique has been illustrated using potassium-rich alkali feldspars from the Dartmoor granite (UK). These feldspars contain strain-controlled lamellar crypto- and microperthites that are cross-cut by strain-free deuteric microperthites. The constituent albite- and orthoclase-rich phases of both microperthite generations can be readily distinguished by atomic number contrast imaging. The charge contrast results additionally show that sub-micrometre-sized albite `platelets' are commonplace between coarser exsolution lamellae and occur together to make cryptoperthites. Furthermore, charge contrast imaging reveals that the orthoclase-rich feldspar is an intergrowth of two phases, one that is featureless with uniform contrast and another that occurs as cross-cutting veins and grains with the {110} adularia habit. Transmission electron microscopy shows that the featureless feldspar is tweed orthoclase, whereas the veins and euhedral grains are composed of irregular microcline that has formed from orthoclase by `unzipping' during deuteric or hydrothermal alteration. The charge contrast imaging results are especially important in demonstrating that deuteric perthites are far more abundant in alkali feldspars than would be concluded from investigations using conventional microscopy techniques. The unexpected presence of such a high volume of replacement products has significant implications for understanding the origins and geological histories of crustal rocks and the use of alkali feldspars in geo- and thermochronology. Whilst the precise properties of feldspars that generate contrast remain unclear, the similarity between charge contrast images and corresponding cathodoluminescence images of deuteric microperthites indicates that trace element chemistry and possibly also elastic strain within the crystal play a major role.

40 CFR Table 5 to Subpart IIIii of... - Required Elements of Floor-Level Mercury Vapor Measurement and Cell Room Monitoring Plans

Code of Federal Regulations, 2010 CFR

2010-07-01

... Mercury Vapor Measurement and Cell Room Monitoring Plans 5 Table 5 to Subpart IIIII of Part 63 Protection... Hazardous Air Pollutants: Mercury Emissions From Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII... and Cell Room Monitoring Plans Your Floor-Level Mercury Vapor Measurement Plan required by § 63.8192(d...

40 CFR Table 5 to Subpart IIIii of... - Required Elements of Floor-Level Mercury Vapor Measurement and Cell Room Monitoring Plans

Code of Federal Regulations, 2013 CFR

2013-07-01

... Mercury Vapor Measurement and Cell Room Monitoring Plans 5 Table 5 to Subpart IIIII of Part 63 Protection... Hazardous Air Pollutants: Mercury Emissions From Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII... and Cell Room Monitoring Plans Your Floor-Level Mercury Vapor Measurement Plan required by § 63.8192(d...

40 CFR Table 5 to Subpart IIIii of... - Required Elements of Floor-Level Mercury Vapor Measurement and Cell Room Monitoring Plans

Code of Federal Regulations, 2012 CFR

2012-07-01

... Mercury Vapor Measurement and Cell Room Monitoring Plans 5 Table 5 to Subpart IIIII of Part 63 Protection... Hazardous Air Pollutants: Mercury Emissions From Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII... and Cell Room Monitoring Plans Your Floor-Level Mercury Vapor Measurement Plan required by § 63.8192(d...

40 CFR Table 5 to Subpart IIIii of... - Required Elements of Floor-Level Mercury Vapor Measurement and Cell Room Monitoring Plans

Code of Federal Regulations, 2014 CFR

2014-07-01

... Mercury Vapor Measurement and Cell Room Monitoring Plans 5 Table 5 to Subpart IIIII of Part 63 Protection... Hazardous Air Pollutants: Mercury Emissions From Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII... and Cell Room Monitoring Plans Your Floor-Level Mercury Vapor Measurement Plan required by § 63.8192(d...

40 CFR Table 5 to Subpart IIIii of... - Required Elements of Floor-Level Mercury Vapor Measurement and Cell Room Monitoring Plans

Code of Federal Regulations, 2011 CFR

2011-07-01

... Mercury Vapor Measurement and Cell Room Monitoring Plans 5 Table 5 to Subpart IIIII of Part 63 Protection... Hazardous Air Pollutants: Mercury Emissions From Mercury Cell Chlor-Alkali Plants Pt. 63, Subpt. IIIII... and Cell Room Monitoring Plans Your Floor-Level Mercury Vapor Measurement Plan required by § 63.8192(d...

Trace element distribution in peridotite xenoliths from Tok, SE Siberian craton: A record of pervasive, multi-stage metasomatism in shallow refractory mantle

NASA Astrophysics Data System (ADS)

Ionov, Dmitri A.; Chazot, Gilles; Chauvel, Catherine; Merlet, Claude; Bodinier, Jean-Louis

2006-03-01

Spinel peridotite xenoliths in alkali basalts at Tok, SE Siberian craton range from fertile lherzolites to harzburgites and wehrlites; olivine-rich (70-84%) rocks are dominant. REE patterns in the lherzolites range from nearly flat for fertile rocks (14-17% cpx) to LREE-enriched; the enrichments are positively correlated with modal olivine, consistent with high-permeability of olivine-rich rocks during melt percolation. Clinopyroxene in olivine-rich Tok peridotites typically has convex-upward trace element patterns (La/Nd PM < 1 and Nd/Yb PM ≫ 1), which we consider as evidence for equilibration with evolved silicate liquids (with higher REE and lower Ti contents than in host basalts). Whole-rock patterns of the olivine-rich xenoliths range from convex-upward to LREE-enriched (La/Nd PM > 1); the LREE-enrichments are positively correlated with phosphorus abundances and are mainly hosted by accessory phosphates and P-rich cryptocrystalline materials. In addition to apatite, some Tok xenoliths contain whitlockite (an anhydrous, halogen-poor and Na-Mg-rich phosphate), which is common in meteorites and lunar rocks, but has not been reported from any terrestrial mantle samples. Some olivine-rich peridotites have generations of clinopyroxene with distinct abundances of Na, LREE, Sr and Zr. The mineralogical and trace element data indicate that the lithospheric mantle section represented by the xenoliths experienced a large-scale metasomatic event produced by upward migration of mafic silicate melts followed by percolation of low- T, alkali-rich melts and fluids. Chromatographic fractionation and fractional crystallisation of the melts close to the percolation front produced strong LREE-enrichments, which are most common in the uppermost mantle and are related to carbonate- and P 2O 5-rich derivatives of the initial melt. Reversal and gradual retreat of the percolation front during thermal relaxation to ambient geotherm ("retrograde" metasomatism) caused local migration and entrapment of small-volume residual fluids and precipitation of volatile-rich accessory minerals. A distinct metasomatic episode, which mainly produced "anhydrous" late-stage interstitial materials was concomitant with the alkali basaltic magmatism, which brought the xenoliths to the surface.

RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

EPA Science Inventory

Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...