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Sample records for alkaline earth isotopes

  1. Parity violating radiative emission of neutrino pair in heavy alkaline earth atoms of even isotopes

    CERN Document Server

    Yoshimura, M; Uetake, S

    2014-01-01

    Metastable excited states ${}^3P_2, {}^3P_0$ of heavy alkaline earth atoms of even isotopes are studied for parity violating (PV) effects in radiative emission of neutrino pair (RENP). PV terms arise from interference between two diagrams containing neutrino pair emission of valence spin current and nuclear electroweak charge density proportional to the number of neutrons in nucleus. This mechanism gives large PV effects, since it does not suffer from the suppression of 1/(electron mass) usually present for non-relativistic atomic electrons. A controllable magnetic field is crucial to identify RENP process by measuring PV observables. Results of PV asymmetries under the magnetic field reversal and the photon circular polarization reversal are presented for an example of Yb atom.

  2. Electromigration in molten salts and application to isotopic separation of alkaline and alkaline-earth elements; Electromigration en sels fondus et application a la separation des isotopes des elements alcalins et alcalino-terreux

    Energy Technology Data Exchange (ETDEWEB)

    Menes, F. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    The separation of the isotopes of the alkaline-earth elements has been studied using counter-current electromigration in molten bromides. The conditions under which the cathode operates as a bromine electrode for the highest possible currents have been examined. For the separation of calcium, it has been necessary to use a stable CaBr{sub 2} - (CaBr{sub 2} + KBr) 'chain'. In the case of barium and strontium, it was possible to employ the pure bromides. Enrichment factors of the order of 10 for {sup 48}Ca and of the order of 1.5 for the rare isotopes of barium and strontium have been obtained. In the case of magnesium the method is slightly more difficult to apply because of material loss due to the relatively high vapour pressure of the salt requiring the use of electrolyte chains, MgBr{sub 2} - CeBr{sub 3}. A study has been made that has led to a larger-scale application of the method. These are essentially the inhibition of reversible operation of the cathode by traces of water, limiting the intensity which can be tolerated; evacuation of the heat produced by the Joule effect, in the absence of which the separation efficiency is reduced by thermal gradients; corrosion of the materials by molten salts at high temperature. Several cells capable of treating a few kilograms of substance have been put into operation; none of these has lasted long enough to produce a satisfactory enrichment. The method is thus limited actually to yields of the order of a few grams. (author) [French] On a etudie la separation des isotopes des elements alcalino-terreux par electromigration a contre-courant en bromures fondus. On a etudie les conditions dans lesquelles la cathode fonctionne en electrode a brome pour des intensites les plus elevees possibles. Pour la separation du calcium, il a ete necessaire d'utiliser une chaine stable CaBr{sub 2} - (CaBr{sub 2} + KBr). Pour le baryum et le strontium, on a pu operer sur les bromures purs. On a obtenu des facteurs d

  3. Separation of stable isotopes of alkali and alkaline earth metals in chemical exchange systems with crown ethers

    International Nuclear Information System (INIS)

    Chemical isotope exchange in two-phase water - organic systems Men+ (water) - MeLn+ (org), where Me = Li, Ca, K, Mg; L = crown ethers with 5 to 6 oxygen atoms in macrocyclic ring; org = CHCl3, CH2Cl2 has been studied. The process of isotope separation has been realized by extraction chromatography. The chromatographic column contained a fixed aqueous phase. The organic solution of metal complex with crown ether was eluted through the column. On contact with the fixed aqueous phase in the course of chromatography, metal salt reextraction occurred and interphase isotope exchange between aqueous and organic phases resulted. Isotope separation factors in these systems were in the range of: 1.0032 - 1.020 (6Li/7Li), 1.0016 - 1.0038 (40Ca/44Ca), 1.0007 - 1.0011 (39K/41K), 1.0014 - 1.0044 (24Mg/26Mg). The theoretical model has been proposed to interpret the high separation factors in crown ether extraction systems. According to this model, the potential in such systems has a very flat bottom. This type of potential results in weakening the force field and decreasing of β-factor (i.e., (s/s')f) in spite of comparatively high energy of complexation. This model can interpret both high separation factors and their strong dependence on the type of crown ether. (author)

  4. Alkaline earth filled nickel skutterudite antimonide thermoelectrics

    Science.gov (United States)

    Singh, David Joseph

    2013-07-16

    A thermoelectric material including a body centered cubic filled skutterudite having the formula A.sub.xFe.sub.yNi.sub.zSb.sub.12, where A is an alkaline earth element, x is no more than approximately 1.0, and the sum of y and z is approximately equal to 4.0. The alkaline earth element includes guest atoms selected from the group consisting of Be, Mb, Ca, Sr, Ba, Ra and combinations thereof. The filled skutterudite is shown to have properties suitable for a wide variety of thermoelectric applications.

  5. Controlled charge exchange between alkaline earth metals and their ions

    Science.gov (United States)

    Gacesa, Marko; Côté, Robin

    2015-05-01

    We theoretically investigate the prospects of realizing controlled charge exchange via magnetic Feshbach resonances in cold and ultracold collisions of atoms and ions. In particular, we focus on near-resonant charge exchange in heteroisotopic combinations of alkaline earth metals, such as 9Be++10 Be9 Be+10Be+ , which exhibit favorable electronic and hyperfine structure. The quantum scattering calculations are performed for a range of initial states and experimentally attainable magnetic fields in standard coupled-channel Feshbach projection formalism, where higher-order corrections such as the mass-polarization term are explicitely included. In addition, we predict a number of magnetic Feshbach resonances for different heteronuclear isotopic combinations of the listed and related alkaline earth elements. Our results imply that near-resonant charge-exchange could be used to realize atom-ion quantum gates, as well as controlled charge transfer in optically trapped cold quantum gases. This work is partially supported by ARO.

  6. Alkaline and alkaline earth metal phosphate halides and phosphors

    Science.gov (United States)

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  7. Alkaline earth cation extraction from acid solution

    Science.gov (United States)

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  8. Recent advances in Rydberg physics using alkaline-earth atoms

    Science.gov (United States)

    Dunning, F. B.; Killian, T. C.; Yoshida, S.; Burgdörfer, J.

    2016-06-01

    In this brief review, the opportunities that the alkaline-earth elements offer for studying new aspects of Rydberg physics are discussed. For example, the bosonic alkaline-earth isotopes have zero nuclear spin which eliminates many of the complexities present in alkali Rydberg atoms, permitting simpler and more direct comparison between theory and experiment. The presence of two valence electrons allows the production of singlet and triplet Rydberg states that can exhibit a variety of attractive or repulsive interactions. The availability of weak intercombination lines is advantageous for laser cooling and for applications such as Rydberg dressing. Excitation of one electron to a Rydberg state leaves behind an optically active core ion allowing, for high-L states, the optical imaging of Rydberg atoms and their (spatial) manipulation using light scattering. The second valence electron offers the possibility of engineering long-lived doubly excited states such as planetary atoms. Recent advances in both theory and experiment are highlighted together with a number of possible directions for the future.

  9. Magic wavelengths in the alkaline earth ions

    CERN Document Server

    Kaur, Jasmeet; Arora, Bindiya; Sahoo, B K

    2015-01-01

    We present magic wavelengths for the $nS$ - $nP_{1/2,3/2}$ and $nS$ - $mD_{3/2,5/2}$ transitions, with the respective ground and first excited $D$ states principal quantum numbers $n$ and $m$, in the Mg$^+$, Ca$^+$, Sr$^+$ and Ba$^+$ alkaline earth ions for linearly polarized lights by plotting dynamic polarizatbilities of the $nS$, $nP_{1/2,3/2}$ and $mD_{3/2,5/2}$ states of the ions. These dynamic polarizabilities are evaluated by employing a relativistic all-order perturbative method and their accuracies are ratified by comparing their static values with the available high precision experimental or other theoretical results. Moreover, some of the magic wavelengths identified by us in Ca$^+$ concurs with the recent measurements reported in [{\\bf Phys. Rev. Lett. 114, 223001 (2015)}]. Knowledge of these magic wavelengths are propitious to carry out many proposed high precision measurements trapping the above ions in the electric fields with the corresponding frequencies.

  10. Mixed alkaline earth effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.;

    2013-01-01

    While the mixed alkali effect has received significant attention in the glass literature, the mixed alkaline earth effect has not been thoroughly studied. Here, we investigate the latter effect by partial substitution of magnesium for calcium in sodium aluminosilicate glasses. We use Raman and NMR...... spectroscopies to obtain insights into the structural and topological features of these glasses, and hence into the mixed alkaline earth effect. We demonstrate that the mixed alkaline earth effect manifests itself as a maximum in the amount of bonded tetrahedral units and as a minimum in liquid fragility index...

  11. Solubility of fluorides of alkaline earth metals and some rare earths in anhydrous trifluoroacetic acid

    International Nuclear Information System (INIS)

    Solubility of fluorides of alkaline earth and some rare earth metals in anhydrous trifluoroacetic acid is studied. For each type of fluoride solubility depends on the ionic radius of the cation. Solubility of fluorides of alkaline earth metals grows from magnesium to barium. All the fluorides in anhydrous trifluoroacetic acid form solvates. Solvates of strontium and scandium fluorides are shown to decompose at 110 and 150 deg C respectively

  12. Surface-treatment of Alkaline Earth Sulfides Based Phosphor

    Institute of Scientific and Technical Information of China (English)

    GUO Chong-feng; CHU Ben-li; XU Jian; SU Qiang

    2004-01-01

    A series of alkaline earth sulfides based phosphors Ca0.8Sr0.2S∶Eu2+, Tm3+ were covered with a layer of protective coating with alkaline earth fluorides by heating the mixture of phosphor and NH4HF2 at elevated temperatures. The coatings were characterized by means of XRD and SEM. The optical properties of the coated phosphors and the influences of the coating on their properties have been discussed extensively. The stabilities of the coated and uncoated phosphors have been compared.

  13. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

    Institute of Scientific and Technical Information of China (English)

    XUXin; ZHUTun

    2002-01-01

    Solvent extraction equiliria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester, di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent of the e/r value and hydration energy of the metal ions. The minor shift of the P→O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P→O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compunds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effects is explained by using IR spectra of the loaded organic phase.

  14. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Science.gov (United States)

    2010-07-01

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

  15. Defect structure of cubic solid solutions of alkaline earth and rare earth fluorides

    NARCIS (Netherlands)

    DenHartog, HW

    1996-01-01

    In this paper we will consider the disorder in some cubic solid solutions consisting of one of the alkaline earth fluorides and one of the rare earth fluorides. This is an attractive group of model materials, because these materials have a rather simple overall cubic structure. We will discuss the m

  16. Bose-Einstein condensation of alkaline earth atoms: ;{40}Ca.

    Science.gov (United States)

    Kraft, Sebastian; Vogt, Felix; Appel, Oliver; Riehle, Fritz; Sterr, Uwe

    2009-09-25

    We have achieved Bose-Einstein condensation of ;{40}Ca, the first for an alkaline earth element. The influence of elastic and inelastic collisions associated with the large ground-state s-wave scattering length of ;{40}Ca was measured. From these findings, an optimized loading and cooling scheme was developed that allowed us to condense about 2 x 10;{4} atoms after laser cooling in a two-stage magneto-optical trap and subsequent forced evaporation in a crossed dipole trap within less than 3 s. The condensation of an alkaline earth element opens novel opportunities for precision measurements on the narrow intercombination lines as well as investigations of molecular states at the ;{1}S-;{3}P asymptotes. PMID:19905493

  17. Modelling the crystallisation of alkaline earth boroaluminosilicate glass ceramics

    DEFF Research Database (Denmark)

    Svenson, Mouritz Nolsøe; Agersted, Karsten; Holm, Paul Martin

    2014-01-01

    To investigate the potential use of a thermochemical software package (FactSage 6.2), in the design of alkaline earth boroaluminosilicate glass ceramics, experimental and modelled results on four glass ceramics were compared. Initially large discrepancies were found. These are described and related...... for the topology of multicomponent melts, before accurate prediction of phase relations within boron-containing glass ceramics can be obtained....

  18. Long range interactions between alkali and alkaline-earth atoms

    CERN Document Server

    Jiang, Jun; Mitroy, J

    2013-01-01

    Dispersion coefficients between the alkali metal atoms (Li-Rb) and alkaline-earth metal atoms (Be-Sr) are evaluated using matrix elements computed from frozen core configuration interaction calculations. Besides dispersion coefficients with both atoms in their respective ground states, dispersion coefficients are also given for the case where one atom is in its ground state and the other atom is in a low lying excited state.

  19. Interaction of alkali and alkaline earth ions with Ochratoxin A

    Energy Technology Data Exchange (ETDEWEB)

    Poor, Miklos [Institute of Laboratory Medicine, University of Pecs, Pecs H-7624 (Hungary); Kunsagi-Mate, Sandor; Matisz, Gergely; Li, Yin; Czibulya, Zsuzsanna [Department of General and Physical Chemistry, University of Pecs, Pecs H-7624 (Hungary); Janos Szentagothai Research Center, Pecs H-7624 (Hungary); Peles-Lemli, Beata [Department of General and Physical Chemistry, University of Pecs, Pecs H-7624 (Hungary); Koszegi, Tamas, E-mail: koszegit@freemail.hu [Institute of Laboratory Medicine, University of Pecs, Pecs H-7624 (Hungary)

    2013-03-15

    The effect of alkali and alkaline earth ions on the chemical equilibrium of mono- and dianionic forms of the mycotoxin Ochratoxin A (OTA) and their bonding onto the surface of Bovine Serum Albumin (BSA) have been investigated by fluorescence spectroscopy and fluorescence polarization techniques. Our results show that alkali metal ions shift the chemical equilibrium towards formation of dianionic form of OTA. Furthermore, the alkaline earth ions can compete with BSA for binding to OTA when these ions are present in millimolar concentrations. Our data also highlight the possibility that the 'free' fraction of OTA (not bound onto the surface of albumin) or at least a part of it is present in cation-bound form in body fluids. These observations are supported by stability constants and quantum-chemical calculations. Among the studied alkaline metal ions magnesium showed the highest affinity towards OTA under physiological conditions. Further research is required to analyze the potential significance of Mg{sup 2+}-OTA complex in cellular uptake and/or elimination of the toxin in the human body. - Highlights: Black-Right-Pointing-Pointer Fluorescence spectroscopy reveals cation-Ochratoxin A (OTA) interactions. Black-Right-Pointing-Pointer Alkali ions shift the equilibrium of OTA to formation of a dianionic structure. Black-Right-Pointing-Pointer Alkaline earth ions directly bind to OTA in the order: Mg{sup 2+}, Ca{sup 2+}, Ba{sup 2+}. Black-Right-Pointing-Pointer Quantum chemical calculations and logK values support our experimental data.

  20. Stable isotope composition of Earth's large lakes

    Science.gov (United States)

    Jasechko, S.; Gibson, J. J.; YI, Y.; Birks, S. J.; Sharp, Z. D.

    2011-12-01

    Lakes cover about three percent of Earth's continental area. Large lakes can significantly influence lake shore and regional climates by increasing specific humidity during evaporation and by moderating air temperatures. Stable isotopes of oxygen and hydrogen can be used to quantify lake evaporation, providing a supplementary and often cost-advantageous alternative to conventional hydrologic approaches that require over lake monitoring. Further, stable isotopes in lake sediments are an established tool in paleolimnology; however, interpreting changes to a lake's past isotope composition requires a comprehensive understanding of contemporary controls. Here, δ18O and δ2H values of water in modern lakes exceeding roughly five hundred square kilometres are compiled (n > 35). Voluminous and seasonally mixed lakes - such as the North American Great Lakes - have the most homogenous stable isotope compositions, while perennially-stratified and shallow lakes show greater variability. A rudimentary stable isotope mass balance is used to assess evaporation fluxes from large lakes on Earth. The approach taken simultaneously constrains evaporation outputs for both oxygen and hydrogen stable isotopes by accounting for lake effects on the overlying atmosphere. Model development highlights important considerations such as isotopic stratification (Tanganyika), disequilibrium isotopic mass balances (Baikal), and non-steady hydrologic balances. Further, the isotope composition of Earth's continental surface water reservoir is calculated. This value - weighted to volume - is δ18O = -7.5±1.7 per mille relative to standard mean ocean water. The compiled data may be a useful tracer of continental evaporate in global atmospheric water cycle studies and could be coupled to climate models capable of incorporating oxygen-18 and deuterium tracers to improve or validate calculations of lake effects on regional water cycling.

  1. Bose-Einstein condensation of alkaline earth atoms: $^{40}${Ca}

    OpenAIRE

    Kraft, Sebastian; Vogt, Felix; Appel, Oliver; Riehle, Fritz; Sterr, Uwe

    2009-01-01

    We have achieved Bose-Einstein condensation of $^{40}$Ca, the first for an alkaline earth element. The influence of elastic and inelastic collisions associated with the large ground state s-wave scattering length of $^{40}$Ca was measured. From these findings, an optimized loading and cooling scheme was developed that allowed us to condense about $2 \\cdot 10^4$ atoms after laser cooling in a two-stage magneto-optical trap and subsequent forced evaporation in a crossed dipole trap within less ...

  2. Structural variations in layered alkaline earth metal cyclohexyl phosphonates

    Indian Academy of Sciences (India)

    Ramaswamy Murugavel; Nayanmoni Gogoi

    2009-06-01

    Two series of alkaline earth metal cyclohexyl phosphonates, M(C6H11PO3H)2(H2O) (M = Ca, Sr and Ba) (1–3) and M(C6H11PO3)(H2O) (M = Mg, Ca, Sr, and Ba) (4–7) have been synthesized under mild reaction conditions. All new compounds have been characterized using elemental analysis, IR, TGA and powder X-ray diffraction techniques. The molecular structure of compound 2 determined using single crystal X-ray diffraction technique reveals a layered polymeric structure.

  3. Quantum computing with alkaline-Earth-metal atoms.

    Science.gov (United States)

    Daley, Andrew J; Boyd, Martin M; Ye, Jun; Zoller, Peter

    2008-10-24

    We present a complete scheme for quantum information processing using the unique features of alkaline-earth-metal atoms. We show how two completely independent lattices can be formed for the 1S0 and 3P0 states, with one used as a storage lattice for qubits encoded on the nuclear spin, and the other as a transport lattice to move qubits and perform gate operations. We discuss how the 3P2 level can be used for addressing of individual qubits, and how collisional losses from metastable states can be used to perform gates via a lossy blockade mechanism.

  4. Study on rare earth/alkaline earth oxide-doped CeO2 solid electrolyte

    Institute of Scientific and Technical Information of China (English)

    YAN Kai; ZHEN Qiang; Song Xiwen

    2007-01-01

    Five types of rare earth/alkaline earth oxide-doped CeO2 superfine-powders were synthesized by a low-temperature combustion technique. The relevant solid electrolyte materials were also sintered by pressureless sintering at different temperatures. The results of X-ray diffraction and transmission electron microscopy showed that the grain size of the powders was approximately 20-30 nm, and rare earth/alkaline earth oxides were completely dissolved into ceria-based solid solution with fluorite structure. The electrical conductivities of the Sm2O3-CeO2 system were measured by the ac impedance technique in air at temperatures ranging from 513-900℃. The results indicated that the ionic conductivities of Sm0.20Ce0.8O1.875 solid electrolyte increase with increasing sintering temperature, and the relationship between the conductivities and measuring temperature obeys the Arrhenius equation. Then the Sm2O3-CeO2 material was further doped with other rare earth/alkaline earth oxide, and the conductivities improve with the effective index.

  5. Proposal for Laser Cooling of Alkaline Earth Monoalkoxide Free Radicals

    Science.gov (United States)

    Baum, Louis; Kozyryev, Ivan; Matsuda, Kyle; Doyle, John M.

    2016-05-01

    Cold samples of polyatomic molecules will open new avenues in physics, chemistry, and quantum science. Non-diagonal Franck-Condon factors, technically challenging wavelengths, and the lack of strong electronic transitions inhibit direct laser cooling of nonlinear molecules. We identify a scheme for optical cycling in certain molecules with six or more atoms. Replacing hydrogen in alcohols with an alkaline earth metal (M) leads to alkaline earth monoalkoxide free radicals (MOR), which have favorable properties for laser cooling. M-O bond is very ionic, so the metal orbitals are slightly affected by the nature of R on the ligand. Diagonal Franck-Condon factors, laser accessible transitions, and a small hyperfine structure make MOR molecules suitable for laser cooling. We explore a scheme for optical cycling on the A - X transition of SrOCH3 . Molecules lost to dark vibrational states will be repumped on the B - X transition. Extension to larger species is possible through expansion of the R group since transitions involve the promotion of the metal-centered nonbonding valence electron. We will detail our estimations of the Franck-Condon factors, simulations of the cooling process and describe progress towards the Doppler cooling of MOR polyatomics.

  6. Uptake of alkaline earth metals in Alcyonarian spicules (Octocorallia)

    Science.gov (United States)

    Taubner, I.; Böhm, F.; Eisenhauer, A.; Garbe-Schönberg, D.; Erez, J.

    2012-05-01

    Alcyonarian corals (Octocorallia) living in shallow tropical seas produce spicules of high-Mg calcite with ˜13 mol% MgCO3. We cultured the tropical alcyonarian coral Rhythisma fulvum in experiments varying temperature (19-32 °C) and pH (8.15-8.44). Alkalinity depletion caused by spicule formation systematically varied in the temperature experiments increasing from 19 to 29 °C. Spicules were investigated for their elemental ratios (Mg/Ca, Sr/Ca) using ICP-OES, δ44/40Ca using TIMS, as well as δ18O and δ13C by IRMS. Mg/Ca increased with temperature from 146 to 164 mmol/mol, in good agreement with the range observed for marine inorganic calcite. Mg/Ca increased by 1.0 ± 0.4 mmol/mol/°C, similar to the sensitivity of Miliolid foraminifera. The pH experiments revealed a linear relationship between Mg/Ca and carbonate ion concentration of +0.03 ± 0.02 mmol/mol/μMol. Sr/Ca ranges from 2.5 to 2.9 mmol/mol being in good agreement with other high-Mg calcites. Temperature and pH experiments showed linear dependencies of Sr/Ca matching inorganic calcite trends and pointing to a decoupling of crystal precipitation rate and calcification rate. Ca isotopes range between 0.7‰ and 0.9‰ in good agreement with aragonitic scleractinian corals and calcitic coccoliths. Presumably Ca isotopes are fractionated by a biological mechanism that may be independent of the skeletal mineralogy. We observe no temperature trend, but a significant decrease of δ44/40Ca with increasing pH. This inverse correlation may characterise biologically controlled intracellular calcification. Oxygen isotope ratios are higher than expected for isotopic equilibrium with a temperature sensitivity of -0.15 ± 0.03‰/°C. Carbon isotope ratios are significantly lower than expected for equilibrium and positively correlated with temperature with a slope of 0.20 ± 0.04‰/°C. Many of our observations on trace element incorporation in R. fulvum may be explained by inorganic processes during crystal

  7. Effect of rare earth oxides on the properties of bio-soluble alkaline earth silicate fibers

    Institute of Scientific and Technical Information of China (English)

    王玺堂; 刘浩; 王周福; 马妍

    2016-01-01

    Using natural mineral wollastonite, talc and quartz sands as raw materials, rare earth oxides (La2O3, Nd2O3 and Y2O3) as additives, the bio-soluble alkaline earth silicate fibers were prepared by melting and blowing process. The viscosity of the molten ma-terials, bio-solubility and crystallization behavior of the fiber were investigated. The results indicated that the fiber drawing tempera-ture range could be broadened since the slope of the temperature-viscosity curve decreased with adding rare earth oxide. The addition of rare earth oxide was beneficial to the increase of crystallization temperature by strengthening the network structure of the fiber. The existence of rare earth oxide in the fibers would reduce the solubility of the fibers, which still belonged to bio-soluble fibers.

  8. Deep optical trap for cold alkaline-Earth atoms.

    Science.gov (United States)

    Cruz, Luciano S; Sereno, Milena; Cruz, Flavio C

    2008-03-01

    We describe a setup for a deep optical dipole trap or lattice designed for holding atoms at temperatures of a few mK, such as alkaline-Earth atoms which have undergone only regular Doppler cooling. We use an external optical cavity to amplify 3.2 W from a commercial single-frequency laser at 532 nm to 523 W. Powers of a few kW, attainable with low-loss optics or higher input powers, allow larger trap volumes for improved atom transfer from magneto-optical traps. We analyze possibilities for cooling inside the deep trap, the induced Stark shifts for calcium, and a cancellation scheme for the intercombination clock transition using an auxiliary laser. PMID:18542375

  9. Tune-out wavelengths for the alkaline earth atoms

    CERN Document Server

    Cheng, Yongjun; Mitroy, Jim

    2013-01-01

    The lowest 3 tune-out wavelengths of the four alkaline-earth atoms, Be, Mg, Ca and Sr are determined from tabulations of matrix elements produced from large first principles calculations. The tune-out wavelengths are located near the wavelengths for $^3P^o_1$ and $^1P^o_1$ excitations. The measurement of the tune-out wavelengths could be used to establish a quantitative relationship between the oscillator strength of the transition leading to existence of the tune-out wavelength and the dynamic polarizability of the atom at the tune-out frequency. The longest tune-out wavelengths for Be, Mg, Ca, Sr, Ba and Yb are 454.9813 nm, 457.2372 nm, 657.446 nm, 689.200 nm, 788.875 nm and 553.00 nm respectively.

  10. Alkaline Earth Core Level Photoemission Spectroscopy of High-Temperature Superconductors

    Science.gov (United States)

    Vasquez, R.

    1993-01-01

    This paper examines photoemission measurements of the alkaline Earth core levels of high-temperature superconductors and related materials, models that seek to explain the large negative shifts observed relative to the corresponding alkaline Earth metals, and the effect of lattice site disorder on the core level spectra and the presence or absence of intrinsic surface peaks.

  11. Conversion of ethanol to propylene over HZSM-5 type zeolites containing alkaline earth metals

    OpenAIRE

    Goto, Daisuke; Harada, Yasumitsu; Furumoto, Yoshiyasu; Takahashi, Atsushi; Fujitani, Tadahiro; Oumi, Yasunori; Sadakane, Masahiro; Sano, Tsuneji

    2010-01-01

    Protonated ZSM-5 type zeolites containing alkaline earth metals (M-HZSM-5, M: alkaline earth metal) were prepared under various synthesis conditions and their catalytic performance in conversion of ethanol to light olefins was investigated in detail. Among M-HZSM-5, Sr-HZSM-5 exhibited an excellent performance.

  12. IGCC sulfur compounds abatement with earth alkaline sorbents

    Energy Technology Data Exchange (ETDEWEB)

    Ramon Alvarez-Rodriguez; Carmen Clemente-Jul [Universidad Politecnica de Madrid, Madrid (Spain). Escuela Tecnica Superior de Ingenieros de Minas

    2007-07-01

    In Integrated Gasification Combined Cycle (IGCC) process, in the reference plant built in Puertollano, Spain by Elcogas, a consortium formed by several utilities and engineering companies with a technology that is one of the most promising electricity generation options, both from the environmental and the efficiency point of view and that allows an efficient and environmentally friendly use of national coal, and also a refinery residue, petroleum coke, the high sulphur contents in coal and specially in petcoke, their presence in the feedstock, led to significant contents of gaseous sulphur compounds whose advanced removal has been the aim of this project. Different sorbents to reduce the presence of H{sub 2}S have been researched and between them the earth alkaline compounds, dolomite and calcite that react with H{sub 2}S to give calcium sulphide have been chosen due to their properties and low cost. The calcium sulphide is a reactive product because it reacts with water to regenerate the H{sub 2}S but it can be converted in calcium sulphate, inert product with diverse uses. This conversion to sulphate present some problems of possible lack of total conversion and different conditions to improve this conversion have been investigated. The tests have been carried out with dolomite and calcite and firstly the sulphuration of the same have been produced using a mixture of gases that simulates the IGCC gas and after their oxidation has been studied. The influence of the conditions of sulfurization and oxidation on the final conversion of calcium sulphide to sulphate as the presence of H{sub 2}O vapour, the variation in the composition of the gases, the temperature and the bed length have been evaluated. The solid products obtained have been characterized by X-ray diffraction and scanning electronic microscopy and chemical analysis to assess the evolution and progress of the reactions. 8 refs., 3 figs., 1 tab.

  13. THE TRANSFER OF ALKALINE EARTH-METAL ION AT W/NB INTERFACE FACILITATED BY JOSAMYCIN

    Institute of Scientific and Technical Information of China (English)

    范瑞溪; 狄俊伟

    1991-01-01

    This paper describes the invesligation of the transfer behaviour of the alkaline earth-metal cations across the water/nitrobenzene interface facilitated by josamycin in the nitrobenzene phase using semi-differential cyclic voltammetry .The peak height is directly proportional to the concentration of josaycin (nb) and to the potential scan rate.The complexes formed from alkaline earth-metal ions and josamycin at the w/nb interface are ML22+ ion.

  14. Spectroscopic characterization of manganese-doped alkaline earth lead zinc phosphate glasses

    Indian Academy of Sciences (India)

    S Sreehari Sastry; B Rupa Venkateswara Rao

    2015-04-01

    Alkaline earth lead zinc phosphate glasses doped with Mn(II) are characterized by spectroscopic techniques like X-ray diffraction (XRD), UV–visible, differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), Fourier transform infrared (FTIR) and Raman. Optical absorption spectrum exhibits four bands which are characteristic of Mn(II) in distorted octahedral site symmetry. The crystal field parameter Dq and Racah interelectronic-repulsion parameters and have been evaluated. All investigated samples exhibit EPR signals which are characteristic to the Mn2+ ions. The shapes of spectra are also changed with varying alkaline earth ions content. FTIR spectra show specific vibrations of phosphate units. The characteristic Raman bands of these glasses due to stretching and bending vibrations were identified and analysed by varying alkaline earth content. The intensity and frequency variations for the characteristic phosphate group vibrations have been correlated with the changes of the structural units present in these glasses. Depolymerization of the phosphate chains in all the glasses is observed with replacement of alkaline earth content by spectroscopic studies. This leads to a strong decrease of the average chain length and a small decrease of the average P–O–P bridging angle with replacement of alkaline earth content.

  15. The Assessment of Radioactive Body Burdens of the Alkaline Earths

    International Nuclear Information System (INIS)

    The difficulties in obtaining data on the metabolism of bone-seeking radioactive isotopes in man are widely appreciated, especially on the distribution of the isotope between different bones and the microscopic distribution within the same bone. If a full understanding of the metabolism in man is to be obtained, there is at present no alternative but to resort to the use of experimental animals. The calcium and strontium metabolism of the rabbit, which is the smallest animal to have similar skeletal structure to that of human bone, has been studied. The research was planned to include as many parameters as possible. These included specific activity measurements of plasma, urine and faeces, total retention in the skeleton as well as individual bones and in some cases soft tissue. In addition the microscopic distribution of the isotope was studied by quantitative autoradiographic techniques at different time intervals. The results have been considered in the light of various models proposed for the retention of bone-seeking isotopes in mammals and the limitations of each of these models have been assessed. Measurements have been made over sufficiently long time intervals compared with the life-span of the rabbit to enable predictions to be made about the long-term behaviour in man. The results indicate that none of the existing models is completely satisfactory but that a modification of the power function is the most useful. The importance of exchange, as well as resorption, for the removal of radioactive isotopes from the skeleton is well illustrated by the quantitative autoradiographic measurements. (author)

  16. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    Science.gov (United States)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  17. Mercury Isotopes in Earth and Environmental Sciences

    Science.gov (United States)

    Blum, Joel D.; Sherman, Laura S.; Johnson, Marcus W.

    2014-05-01

    Virtually all biotic, dark abiotic, and photochemical transformations of mercury (Hg) produce Hg isotope fractionation, which can be either mass dependent (MDF) or mass independent (MIF). The largest range in MDF is observed among geological materials and rainfall impacted by anthropogenic sources. The largest positive MIF of Hg isotopes (odd-mass excess) is caused by photochemical degradation of methylmercury in water. This signature is retained through the food web and measured in all freshwater and marine fish. The largest negative MIF of Hg isotopes (odd-mass deficit) is caused by photochemical reduction of inorganic Hg and has been observed in Arctic snow and plant foliage. Ratios of MDF to MIF and ratios of 199Hg MIF to 201Hg MIF are often diagnostic of biogeochemical reaction pathways. More than a decade of research demonstrates that Hg isotopes can be used to trace sources, biogeochemical cycling, and reactions involving Hg in the environment.

  18. Isotopes and the early evolution of the earth

    International Nuclear Information System (INIS)

    The observed isotopic ratios of lead, strontium, neodymium, helium, and argon contain information about the chemical abundances of selected parent and daughter elements in the outer parts of the Earth. By necessity, we observe these isotopic ratios at the Earth's surface, which is a small, highly evolved part of the Earth. The studies of such isotopic ratios permit inferences to be made about interactions between this crust and the upper mantle. Helium has been especially valuable for demonstrating that primordial materials are still being outgassed from the earth. Models based on the observed argon isotopic ratios have lead to contradictory conclusions about the existence of an early period of extensive outgassing of the Earth. Lead has been a particularly interesting element because the ratio of the parents, 235U/238U, was very different in the Earth's early history than it is now. Therefore there is the potential for determining constraints on the early history of the Earth. A number of recently published papers offering lead isotope interpretations that reflect on the Earth's early history are reviewed, with special reference to models that are based upon uni-directional and bi-directional exchange between a protocrust and a residual mantle. Geochemical parameters for uranium, thorium and lead can be inferred for two evolving systems, as well as rate constants for differentiation. The principal conclusions are that the differentiation process extended beyond the first quarter of the Earth's history, and that it is possible to reproduce exactly the apparent oceanic basalt isochron by a simple two-reservoir model. In particular, such a model can explain quantitatively the observed lead-207 deficiency in the oceanic basalts

  19. New Alkaline-Earth Polymeric Frameworks as green materials for sorption and heterogeneous catalysis

    OpenAIRE

    Platero Prats, Ana Eva

    2011-01-01

    Metal-Organic Frameworks (or MOFs) are porous organic-inorganic crystalline materials in which the metallic centers are joined through organic ligands via coordination bonds to give frameworks with different dimensionalities. The work presented in this thesis is focused on the obtaining of new MOFs using alkaline-earth elements as metal centers, which could represent a comparatively cheap, nontoxic and green alternative to conventional MOFs based on transition metals or rare-earth elements.Th...

  20. Depolarizing collisions with hydrogen: neutral and singly ionized alkaline earths

    CERN Document Server

    Sainz, Rafael Manso; Sanz-Sanz, Cristina; Aguado, Alfredo; Ramos, Andres Asensio; Bueno, Javier Trujillo

    2014-01-01

    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 alkaly-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 <10000 K. A comparative analysis of our results and previous calculations in the literature is done. 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.

  1. The alkali and alkaline earth metal doped ZnO nanotubes: DFT studies

    Science.gov (United States)

    Peyghan, Ali Ahmadi; Noei, Maziar

    2014-01-01

    Doping of several alkali and alkaline earth metals into sidewall of an armchair ZnO nanotube has been investigated by employing the density functional theory in terms of energetic, geometric, and electronic properties. It has been found that doping processes of the alkali and alkaline metals are endothermic and exothermic, respectively. Based on the results, contrary to the alkaline metal doping, the electronic properties of the tube are much more sensitive to alkali metal doping so that it is transformed from intrinsic semiconductor with HOMO-LUMO energy gap of 3.77 eV to an extrinsic semiconductor with the energy gap of ~1.11-1.95 eV. The doping of alkali and alkaline metals increases and decreases the work function of the tube, respectively, which may influence the electron emission from the tube surface.

  2. The alkali and alkaline earth metal doped ZnO nanotubes: DFT studies

    Energy Technology Data Exchange (ETDEWEB)

    Peyghan, Ali Ahmadi [Department of Chemistry, Faculty of Science, Central Tehran Branch, Islamic Azad University, Tehran (Iran, Islamic Republic of); Noei, Maziar, E-mail: noeimaziar@gmail.com [Department of Chemistry, Mahshahr Branch, Islamic Azad University, Mahshahr (Iran, Islamic Republic of)

    2014-01-01

    Doping of several alkali and alkaline earth metals into sidewall of an armchair ZnO nanotube has been investigated by employing the density functional theory in terms of energetic, geometric, and electronic properties. It has been found that doping processes of the alkali and alkaline metals are endothermic and exothermic, respectively. Based on the results, contrary to the alkaline metal doping, the electronic properties of the tube are much more sensitive to alkali metal doping so that it is transformed from intrinsic semiconductor with HOMO–LUMO energy gap of 3.77 eV to an extrinsic semiconductor with the energy gap of ∼1.11–1.95 eV. The doping of alkali and alkaline metals increases and decreases the work function of the tube, respectively, which may influence the electron emission from the tube surface.

  3. Desorption of acetone from alkaline-earth exchanged Y zeolite after propane selective oxidation

    NARCIS (Netherlands)

    Xu, Jiang; Mojet, B.L.; Ommen, van J.G.; Lefferts, L.

    2004-01-01

    The desorption of products from a series of alkaline-earth exchanged Y zeolites after room-temperature propane selective oxidation was investigated by in situ infrared and mass spectroscopy. The intermediate product, isopropylhydroperoxide (IHP), did not desorb during temperature-programmed-desorpti

  4. FORMATION (DECOMPOSITION) ENTHALPY CALCULATIONS FOR CRYSTAL LATTICES OF ALKALINE-EARTH FLUORIDES

    OpenAIRE

    Gruba, O.; Germanyuk, N.; Ryabukhin, A.

    2015-01-01

    A series of calculations of structural and thermochemical properties has been carried out for the alkaline-earth fluorides. The calculations have been carried out using the modified model of effective ionic radii and the model of enthalpy calculation for the crystal lattice. The results of the calculations are in accordance with the known experimental data within confidence intervals.

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

    Science.gov (United States)

    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,…

  6. Conformation Switching in Gas-Phase Complexes of Histidine with Alkaline Earth Ions

    NARCIS (Netherlands)

    Dunbar, R. C.; Hopkinson, A. C.; Oomens, J.; Siu, C. K.; Siu, K. W. M.; Steill, J. D.; Verkerk, U. H.; Zhao, J. F.

    2009-01-01

    Infrared multiple photon dissociation spectroscopy of gas-phase doubly charged alkaline earth complexes of histidine reveals a transition from dominance of the zwitterion (salt bridge, SB) conformation with Ba2+ to substantial presence of the canonical (charge-solvated, CS) conformation with Ca2+. T

  7. Infrared absorption of H- and D- in the alkaline-earth fluorides

    NARCIS (Netherlands)

    Jones, G. D.; Sung, J. J. Y.; Hume, T.; Ing, L. S.; Bradley, I. V.; Wells, J. P. R.

    2001-01-01

    A revisit is made to the infrared absorption spectra of H- and D- local modes in the alkaline-earth fluorides. New data on the intensity ratios of the various harmonic lines, observation of a fourth harmonic for H- in CaF2 and revised values for the anharmonic potential well constants are presented,

  8. Non-covalent (iso)guanosine-based ionophores for alkali(ne earth) cations

    NARCIS (Netherlands)

    Leeuwen, van Fijs W.B.; Davis, Jeffery T.; Verboom, Willem; Reinhoudt, David N.

    2006-01-01

    Different (iso)guanosine-based self-assembled ionophores give distinctly different results in extraction experiments with alkali(ne earth) cations. A lipophilic guanosine derivative gives good extraction results for K+, Rb+, Ca2+, Sr2+, and Ba2+ and in competition experiments it clearly favors the d

  9. Vibrational study of isolated 18-crown-6 ether complexes with alkaline-earth metal cations

    NARCIS (Netherlands)

    Gamez, F.; Hurtado, P.; Martinez-Haya, B.; G. Berden,; Oomens, J.

    2011-01-01

    Laser infrared multiple photon dissociation (IRMPD) spectroscopy has been employed to probe the C-O and C-C stretching vibrational modes of 18-crown-6 ether (18c6) complexes with alkaline-earth metals (Mg(2+), Ca(2+). Sr(2+) and Ba(2+)) stored in the cell of a Fourier Transform Ion Cyclotron Resonan

  10. Vibrational study of isolated 18-crown-6 ether complexes with alkaline-earth metal cations

    NARCIS (Netherlands)

    F. Gámez; P. Hurtado; B. Martínez-Haya; G. Berden; J. Oomens

    2011-01-01

    Laser infrared multiple photon dissociation (IRMPD) spectroscopy has been employed to probe the C-O and C-C stretching vibrational modes of 18-crown-6 ether (18c6) complexes with alkaline-earth metals (Mg2+, Ca2+, Sr2+ and Ba2+) stored in the cell of a Fourier Transform Ion Cyclotron Resonance mass

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

    Science.gov (United States)

    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.

  12. Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism.

    Science.gov (United States)

    Bellini, Clément; Dorcet, Vincent; Carpentier, Jean-François; Tobisch, Sven; Sarazin, Yann

    2016-03-18

    Alkaline-earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross-dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph3 SiH with pyrrolidine or tBuNH2 . Ae{E(SiMe3)2}2 ⋅(THF)x (E=N, CH; x=2-3) are more efficient than {N^N}Ae{E(SiMe3)2}⋅(THF)n (E=N, CH; n=1-2) complexes (where {N^N}(-) ={ArN(o-C6H4)C(H)=NAr}(-) with Ar=2,6-iPr2 -C6H3) bearing an iminoanilide ligand, and alkyl precatalysts are better than amido analogues. Turnover frequencies (TOFs) increase in the order Ca30 products) includes diamines and di(hydrosilane)s. Kinetic analysis of the Ba-promoted CDC of pyrrolidine and Ph3SiH shows that 1) the kinetic law is rate=k[Ba](1) [amine](0) [hydrosilane](1), 2) electron-withdrawing p-substituents on the arylhydrosilane improve the reaction rate and 3) a maximal kinetic isotopic effect (kSiH/kSiD =4.7) is seen for Ph3SiX (X=H, D). DFT calculations identified the prevailing mechanism; instead of an inaccessible σ-bond-breaking metathesis pathway, the CDC appears to follow a stepwise reaction path with N-Si bond-forming nucleophilic attack of the catalytically competent Ba pyrrolide onto the incoming silane, followed by rate limiting hydrogen-atom transfer to barium. The participation of a Ba silyl species is prevented energetically. The reactivity trend Cametal centre and decreasing Ae-Namide bond strength upon descending Group 2. PMID:26864122

  13. Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism.

    Science.gov (United States)

    Bellini, Clément; Dorcet, Vincent; Carpentier, Jean-François; Tobisch, Sven; Sarazin, Yann

    2016-03-18

    Alkaline-earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross-dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph3 SiH with pyrrolidine or tBuNH2 . Ae{E(SiMe3)2}2 ⋅(THF)x (E=N, CH; x=2-3) are more efficient than {N^N}Ae{E(SiMe3)2}⋅(THF)n (E=N, CH; n=1-2) complexes (where {N^N}(-) ={ArN(o-C6H4)C(H)=NAr}(-) with Ar=2,6-iPr2 -C6H3) bearing an iminoanilide ligand, and alkyl precatalysts are better than amido analogues. Turnover frequencies (TOFs) increase in the order Ca30 products) includes diamines and di(hydrosilane)s. Kinetic analysis of the Ba-promoted CDC of pyrrolidine and Ph3SiH shows that 1) the kinetic law is rate=k[Ba](1) [amine](0) [hydrosilane](1), 2) electron-withdrawing p-substituents on the arylhydrosilane improve the reaction rate and 3) a maximal kinetic isotopic effect (kSiH/kSiD =4.7) is seen for Ph3SiX (X=H, D). DFT calculations identified the prevailing mechanism; instead of an inaccessible σ-bond-breaking metathesis pathway, the CDC appears to follow a stepwise reaction path with N-Si bond-forming nucleophilic attack of the catalytically competent Ba pyrrolide onto the incoming silane, followed by rate limiting hydrogen-atom transfer to barium. The participation of a Ba silyl species is prevented energetically. The reactivity trend Cametal centre and decreasing Ae-Namide bond strength upon descending Group 2.

  14. Molecular dynamics of liquid alkaline-earth metals near the melting point

    Indian Academy of Sciences (India)

    J K Baria; A R Jani

    2010-10-01

    Results of the studies of the properties like binding energy, the pair distribution function (), the structure factor (), specific heat at constant volume, velocity autocorrelation function (VACF), radial distribution function, self-diffusion coefficient and coordination number of alkaline-earth metals (Be, Mg, Ca, Sr and Ba) near melting point using molecular dynamics (MD) simulation technique using a pseudopotential proposed by us are presented in this article. Good agreement with the experiment is achieved for the binding energy, pair distribution function and structure factor, and these results compare favourably with the results obtained by other such calculations, showing the transferability of the pseudopotential used from solid to liquid environment in the case of alkaline-earth metals.

  15. Effects of inherent alkali and alkaline earth metallic species on biomass pyrolysis at different temperatures.

    Science.gov (United States)

    Hu, Song; Jiang, Long; Wang, Yi; Su, Sheng; Sun, Lushi; Xu, Boyang; He, Limo; Xiang, Jun

    2015-09-01

    This work aimed to investigate effects of inherent alkali and alkaline earth metallic species (AAEMs) on biomass pyrolysis at different temperatures. The yield of CO, H2 and C2H4 was increased and that of CO2 was suppressed with increasing temperature. Increasing temperature could also promote depolymerization and aromatization reactions of active tars, forming heavier polycyclic aromatic hydrocarbons, leading to decrease of tar yields and species diversity. Diverse performance of inherent AAEMs at different temperatures significantly affected the distribution of pyrolysis products. The presence of inherent AAEMs promoted water-gas shift reaction, and enhanced the yield of H2 and CO2. Additionally, inherent AAEMs not only promoted breakage and decarboxylation/decarbonylation reaction of thermally labile hetero atoms of the tar but also enhanced thermal decomposing of heavier aromatics. Inherent AAEMs could also significantly enhance the decomposition of levoglucosan, and alkaline earth metals showed greater effect than alkali metals. PMID:26005925

  16. Helical ternary complexes of alkaline earth picrates with open-chain crown ether

    Institute of Scientific and Technical Information of China (English)

    刘伟生; 温永红; 刘雪原; 谭民裕

    2003-01-01

    Four solid complexes of alkaline earth picrates with N,N,N′,N′-tetraphenyl-3,6,9-tri- oxaundecanediamide (TTD), M (Pic)2TTD (1, M = Mg; 2, M = Ca; 3, M = Sr; 4, M = Ba), have been prepared and characterized by elemental analysis, conductivity measurement, IR spectra, 1H NMR spectra and TG-DTA techniques. Crystal structure of complex 3 shows that the Sr(Ⅱ) ion is 9-coordinated by five oxygen atoms from TTD and four oxygen atoms from two bidentate picrates, and the coordination polyhedron is distorted tricapped trigonal prism. TTD as a pentadentate ligand forms a right-handed helical coordination structure. The chelating helical chain has a relative fixed radius and then shows a high coordination selectivity to metal ion. The high selectivity of TTD to alkaline earth ions is explained elementarily from the special coordination structures.

  17. Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

    Science.gov (United States)

    Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

    2016-09-01

    Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

  18. Role of elastic deformation in determining the mixed alkaline earth effect of hardness in silicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Potuzak, M.;

    2015-01-01

    show that the mixed alkaline earth effect manifests itself as deviations from linearity in shear modulus, Poisson’s ratio, glass transition temperature, liquid fragility index, hardness, volume of densification, and volume of plastic flow. We find no correlation between the elastic part...... of the indentation and hardness, and we thus infer that elastic deformation does not play a dominant role in determining the mixed alkaline earth effect of hardness. However, interestingly, we find a strong correlation between Poisson’s ratio, volume of plastic flow, and hardness, by which the minimum in hardness......Glasses deform permanently as a result of indentation and the total resistance to deformation consists of three individual resistances, i.e., those to elastic deformation, densification, and plastic flow. The link between Vickers hardness and the resistances to densification and plastic flow has...

  19. Environmental effects on fatigue of alkaline earth aluminosilicate glass with varying fictive temperature

    DEFF Research Database (Denmark)

    Striepe, Simon; Deubener, Joachim; Smedskjær, Morten Mattrup;

    2013-01-01

    The influence of relative humidity on microhardness, stress intensity, crack resistance, and sub-critical crack growth of an alkaline earth aluminosilicate glass has been studied by Vickers indentation. Quenched and annealed glasses with a wide range of fictive temperatures (ΔTf ≈ 130 K) are comp......The influence of relative humidity on microhardness, stress intensity, crack resistance, and sub-critical crack growth of an alkaline earth aluminosilicate glass has been studied by Vickers indentation. Quenched and annealed glasses with a wide range of fictive temperatures (ΔTf ≈ 130 K......) are compared in order to determine the influence of the thermal history on these properties. Vickers hardness is found to be essentially unaffected by the environmental conditions, while the stress intensity factor (fracture toughness) and the crack resistance decrease significantly with increasing humidity...

  20. Long-range interactions between the alkali-metal atoms and alkaline earth ions

    CERN Document Server

    Kaur, Jasmeet; Arora, Bindiya; Sahoo, B K

    2014-01-01

    Accurate knowledge of interaction potentials among the alkali atoms and alkaline earth ions is very useful in the studies of cold atom physics. Here we carry out theoretical studies of the long-range interactions among the Li, Na, K, and Rb alkali atoms with the Ca$^+$, Ba$^+$, Sr$^+$, and Ra$^+$ alkaline earth ions systematically which are largely motivated by their importance in a number of applications. These interactions are expressed as a power series in the inverse of the internuclear separation $R$. Both the dispersion and induction components of these interactions are determined accurately from the algebraic coefficients corresponding to each power combination in the series. Ultimately, these coefficients are expressed in terms of the electric multipole polarizabilities of the above mentioned systems which are calculated using the matrix elements obtained from a relativistic coupled-cluster method and core contributions to these quantities from the random phase approximation. We also compare our estim...

  1. Tryptophan fluorescence quenching by alkaline earth metal cations in deionized bacteriorhodopsin.

    Science.gov (United States)

    Wang, G; Wang, A J; Hu, K S

    2000-12-01

    Tryptophan quenching by the addition of alkaline earth metal cations to deionized bacteriorhodopsin suspensions was determined. The results show that the addition of cation primarily quenches fluorescence from surface tryptophan residues. The quenched intensity exhibits a 1/R dependence, where R is the ionic radius of the corresponding metal ion. This observation results from a stronger energy transfer coupling between the tryptophan and the retinal. The membrane curvature may be involved as a result of cations motion and correlated conformational changes. PMID:11332888

  2. Removal of phosphorous through roasting of oolitic iron ore with alkaline earth additives

    OpenAIRE

    Ionkov, Krassimir; GAYDARDZHIEV, Stoyan; Bastin, David; de Araujo, Armando Correa; Lacoste, Marine

    2012-01-01

    The present study is devoted to improvement of the leaching efficiency during phosphorous removal from high phosphorous gravity-magnetic concentrate. Before leaching the concentrate has been subjected to roasting with the addition of either Ca(OH)2 or CaO. The oolitic iron ore is roasted at 900°C for one hour. This reflects in reaction between alkaline earth additive and quartz, aluminosilicates, phosphorus, and some other minor components of the gangue minerals. The application of leaching, ...

  3. Adsorption of Alkali, Alkaline Earth and Transition Metal Atoms on Silicene

    OpenAIRE

    Sahin, Hasan; Peeters, Francois M.

    2013-01-01

    The adsorption characteristics of alkali, alkaline earth and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon, are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, workfuncti...

  4. TL and XRD correlation studies of RE3+ doped alkaline earth sulphate phosphors

    International Nuclear Information System (INIS)

    Alkaline earth sulphate phosphors activated with ambient weight percentage composition of rare earth (RE) ions were prepared from Indian mineral gypsum and from synthesized sulphate compounds. The results of TL studies have been interpreted in terms of defect levels and the results of X-ray diffraction (XRD) studies are considered in terms of possible sites and population of activator ions in the host lattice. The correlation studies reveal some interesting results and they lead to suggest some suitable model. (author). 5 refs., 3 figs

  5. Density functional study on the ferromagnetism of alkaline earth doped InN

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai-Cheng, E-mail: kczhang@yeah.net [College of Mathematics and Physics, Bohai University, Jinzhou 121013 (China); Li, Yong-Feng [Key laboratory of Integrated Exploitation of Bayan Obo Multi-Metal Resources, Inner Mongolia University of Science and Technology, Baotou 014010 (China); School of Mathematics, Physics and Biological Engineering, Inner Mongolia University of Science and Technology, Baotou 014010 (China); Liu, Yong [State Key Laboratory of Metastable Materials Science and Technology and College of Science, Yanshan University, Qinhuangdao, Hebei 066004 (China); Zhu, Yan [Department of Physics, Nanjing University of Aeronautics and Astronautics, Nanjing 210016 (China)

    2015-03-15

    Highlights: • The magnetic properties of alkaline earth doped InN were systematically investigated. • The doped system transits from nonmagnetic state to half-metallic state. • Strong ferromagnetism can be expected in Sr- or Ba-doped InN. • Under nitrogen-rich condition, the defect is more stable. - Abstract: Recently, p-type conduction of InN doped by alkaline earth was reported in experiments. However, the magnetic property of the doped systems has not been studied. We systematically investigate the magnetic property of alkaline-earth doped InN by density-functional theory. Our results reveal that the ground state of the doped system transits from nonmagnetic state to spin-polarized state, and the holes introduced into the valence band become more localized as the defect ranges from Be to Ba. As a result, strong half-metallic ferromagnetism emerges for Sr- or Ba-doped InN. Our calculations reveal that the formation energy of defect is much lower for nitrogen-rich condition, under which the doped system can be favorably synthesized.

  6. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan); Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan); Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro [Department of Research Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, Miyamae cho-7, Kofu 400-8511 (Japan); Sato, Tsugio [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku Sendai 980-8577 (Japan)

    2015-09-15

    Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.

  7. Spectroscopic studies of copper doped alkaline earth lead zinc phosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Sastry, S. Sreehari, E-mail: sreeharisastry@yahoo.com [Department of Physics, Acharya Nagarjuna University, Nagarjunanagar 522510 (India); Rao, B. Rupa Venkateswara [Department of Physics, Acharya Nagarjuna University, Nagarjunanagar 522510 (India); Department of Physics, V.R. Siddhartha Engineering College, Vijayawada 52007 (India)

    2014-02-01

    In this paper spectroscopic investigation of Cu{sup 2+} doped alkaline earth lead zinc phosphate glasses was done through the spectroscopic techniques like X-ray diffraction, Ultra Violet (UV) absorption Spectroscopy, Electron Paramagnetic Resonance (EPR – X band), Fourier Transform Infra Red (FTIR) and Raman Spectroscopy. Alkaline earth lead zinc phosphate glasses containing 0.1% copper oxide (CuO) were prepared by the melt quenching technique. Spectroscopic studies indicated that there is a greater possibility for the copper ions to exist in Cu{sup 2+} state in these glasses. The optical absorption spectra indicated that the absorption peak of Cu{sup 2+} is a function of composition. The maxima absorption peak was reported at 862 nm for strontium lead zinc phosphate glass. Bonding parameters were calculated for the optical and EPR data. All these spectral results indicated clearly that there are certain structural changes in the present glass system with different alkaline earth contents. The IR and Raman spectra noticed the breaking of the P–O–P bonds and creating more number of new P–O–Cu bonds.

  8. Spectroscopic studies of copper doped alkaline earth lead zinc phosphate glasses

    Science.gov (United States)

    Sastry, S. Sreehari; Rao, B. Rupa Venkateswara

    2014-02-01

    In this paper spectroscopic investigation of Cu2+ doped alkaline earth lead zinc phosphate glasses was done through the spectroscopic techniques like X-ray diffraction, Ultra Violet (UV) absorption Spectroscopy, Electron Paramagnetic Resonance (EPR - X band), Fourier Transform Infra Red (FTIR) and Raman Spectroscopy. Alkaline earth lead zinc phosphate glasses containing 0.1% copper oxide (CuO) were prepared by the melt quenching technique. Spectroscopic studies indicated that there is a greater possibility for the copper ions to exist in Cu2+ state in these glasses. The optical absorption spectra indicated that the absorption peak of Cu2+ is a function of composition. The maxima absorption peak was reported at 862 nm for strontium lead zinc phosphate glass. Bonding parameters were calculated for the optical and EPR data. All these spectral results indicated clearly that there are certain structural changes in the present glass system with different alkaline earth contents. The IR and Raman spectra noticed the breaking of the P-O-P bonds and creating more number of new P-O-Cu bonds.

  9. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    International Nuclear Information System (INIS)

    Alkaline earth metal doped tin oxide (SnO2) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl4·5H2O and A(NO3)2·xH2O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO2 and A-doped SnO2 hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO2 hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m2 g−1 exhibited the considerably high OSC of 457 μmol-O g−1 and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material

  10. Ca isotope fractionation in a high-alkalinity lake system: Mono Lake, California

    Science.gov (United States)

    Nielsen, Laura C.; DePaolo, Donald J.

    2013-10-01

    Precipitation of calcium carbonate minerals from aqueous solutions causes surface-controlled kinetic stable Ca isotope fractionation. The magnitude of fractionation depends on the relative rates of ion attachment to and detachment from the mineral surface, which in turn is predicted to depend on both the saturation state and the solution stoichiometry or the Ca:CO32- activity ratio. Experimental studies have not directly investigated the effects of varying solution stoichiometry on calcium isotope partitioning during calcite or aragonite growth, but natural alkaline lake systems such as Mono Lake, California provide a test bed for the hypothesized stoichiometry dependence. Mono Lake has a Ca:CO32- activity ratio of about 0.0001, seven orders of magnitude lower than ocean water and typical terrestrial freshwater. We present chemical and isotopic measurements of streams, springs, lake water, and precipitated carbonates from the Mono Basin that yield evidence of stoichiometry-dependent Ca isotope fractionation during calcite, aragonite and Mg-calcite precipitation from the alkaline lake water. To estimate the Ca isotope fractionation factors, it is necessary to characterize the lake Ca balance and constrain the variability of lake water chemistry both spatially and temporally. Streams and springs supply Ca to the lake, and a substantial fraction of this supply is precipitated along the lake shore to form tufa towers. Lake water is significantly supersaturated with respect to carbonate minerals, so CaCO3 also precipitates directly from the water column to form carbonate-rich bottom sediments. Growth rate inhibition by orthophosphate likely preserves the high degree of supersaturation in the lake. Strontium isotope ratios are used to estimate the proportions of fresh and alkaline lake water from which each solid carbonate sample precipitated. Carbonate minerals that precipitate directly from lake water (low Ca:CO32-) experience relatively large Ca isotope fractionation

  11. Effects of alkaline earth metal ion complexation on amino acid zwitterion stability: Results from infrared action spectroscopy

    NARCIS (Netherlands)

    Bush, M. F.; Oomens, J.; Saykally, R. J.; Williams, E. R.

    2008-01-01

    The structures of isolated alkaline earth metal cationized amino acids are investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theory. These results indicate that arginine, glutamine, proline, serine, and valine all adopt zwitterionic structures when complexed with diva

  12. Enhancement effect of alkaline earth metal on the determination of aluminium by atomic absorption spectrometry with a graphite furnace

    OpenAIRE

    Matsusaki, Koji

    1987-01-01

    In the determination of aluminium by atomic absorption spectrometry with a graphite furnace, coexisting oxyanion salts of alkaline earth metal enhanced the aluminium atomic absorption. The relative absorbance was increased with decreasing of the ramp atomization rate and with decreasing of the sheathing gas flow rate less than 51 min^. These results show that the enhancement effect is caused by the reductivity of the carbide of alkaline earth metal which is formed in the furnace at ashing and...

  13. Creation of trapped electrons and holes in alkaline-earth fluoride crystals doped by rare-earth ions

    Science.gov (United States)

    Radzhabov, E.

    2002-06-01

    Defects in Ce 3+- and Eu 2+-doped alkaline-earth fluorides, created by vacuum ultraviolet (VUV) photons with energy lower than that of the band gap, were investigated by various methods: thermostimulated luminescence, photostimulated luminescence and optical absorption. The CaF 2:Eu 2+ thermoluminescence curves in the range of 60-330 K due to various types of trapped holes were the same after VUV illumination as after X-ray irradiation. Thermoluminescence curves of Ce 3+-doped alkaline-earth fluorides created by VUV illumination or X-ray irradiation were generally similar. However, Vk thermoluminescence peaks were absent in VUV-illuminated CaF 2:Ce 3+ and SrF 2:Ce 3+ crystals. Creation of Ce 2+ characteristic bands was observed in photostimulated luminescence spectra as well as in optical absorption spectra of vacuum ultraviolet-illuminated or X-ray-irradiated Ce 3+-doped crystals. The proposed mechanism of creation of trapped hole and trapped electron defects by vacuum ultraviolet illumination involves charge transfer-type transitions, in which the electron transfers from valence band to an impurity level, lying in the band gap. Comparison of all involved energies of transitions in the crystals investigated shows that the sum of all transition energies is less than that of the band gap by 1-3 eV. This energy difference can be considered as the energy of lattice relaxation around created Ce 2+ or Eu + ions.

  14. Electronic structures, mechanical and thermodynamic properties of cubic alkaline-earth hexaborides from first principles calculations

    International Nuclear Information System (INIS)

    Highlights: • The band gaps for CaB6, SrB6 and BaB6 depend sensitively on the values of lattice constant a and positional parameter z. • The order in elastic anisotropy is CaB6 > SrB6 > BaB6. • There are LO/TO splitting lines in the range of 5–10 THz at G point. - Abstract: The electronic structures, mechanical and thermodynamic properties of alkaline-earth hexaborides MB6 (M = Ca, Sr or Ba) are calculated from first principles using density functional theory combined with the quasi-harmonic approximation. These three alkaline-earth hexaborides are semiconductors with a slightly increased trend for their band gaps as M orders from Ca to Ba. Their band gaps depend sensitively on the values of lattice constant a and internal parameter z. The polycrystalline values of the elastic constants and bulk, shear and Young’s moduli are consistent with those determined experimentally. All alkaline-earth hexaborides have strongly anisotropic elastic properties in the order of CaB6 > SrB6 > BaB6. By using the phonon calculations, the thermodynamic properties are investigated. The obtained phonon dispersion relations for CaB6, SrB6, and BaB6 show similar features and there are LO/TO splitting lines in the range of 5–10 THz. Finally, the thermal conductivities of CaB6, SrB6 and BaB6 are evaluated via Clarke’s model and Cahill’s model

  15. Rubidium isotopes in primitive chondrites: Constraints on Earth's volatile element depletion and lead isotope evolution

    Science.gov (United States)

    Nebel, O.; Mezger, K.; van Westrenen, W.

    2011-05-01

    The bulk silicate Earth (BSE) shows substantial deficits in volatile elements compared to CI-chondrites and solar abundances. These deficits could be caused by pre-accretionary depletion in the solar nebula during condensation of solids, or by later heat-driven evaporation during collision of small bodies that later accreted to form the Earth. The latter is considered to result in isotope fractionation for elements with low condensation temperatures that correlates with the degree of depletion. Here, we report first high-precision isotope ratio measurements of the moderately volatile and lithophile trace element Rb. Data from seventeen chondrite meteorites show that their Rb isotope abundances are nearly indistinguishable from Earth, not deviating more than 1 per mil in their 87Rb/85Rb. The almost uniform solar system Rb isotope pool suggests incomplete condensation or evaporation in a single stage is unlikely to be the cause of the volatile element deficit of the Earth. As Rb and Pb have similar condensation temperatures, we use their different degrees of depletion in the BSE to address the mechanisms and timing of terrestrial volatile depletion. The Rb isotope data are consistent with a scenario in which the volatile budget of the Earth was generated by a mixture of a highly volatile-element depleted early Proto-Earth with undepleted material in the course of terrestrial accretion. Observed Pb and Rb abundances and U-Pb and Rb-Sr isotope systematics suggest that volatile addition occurred at approximately the same time at which last core-mantle equilibration was achieved. In line with previous suggestions, this last equilibration involved a second stage of Pb (but not Rb) depletion from the BSE. The timing of this second Pb loss event can be constrained to ~ 110 Ma after the start of the solar system. This model supports a scenario with core storage of Pb in the aftermath of a putative Moon forming giant impact that also delivered the bulk of the volatile

  16. STARK STRUCTURE OF THE RYDBERG STATES OF ALKALINE-EARTH ATOMS

    Institute of Scientific and Technical Information of China (English)

    郅妙婵; 戴长建; 李士本

    2001-01-01

    The Stark effects of the Rydberg states in the alkaline-earth atoms are studied theoretically. Using a method similar to the treatment of alkali atoms, the properties of the Stark states of Mg, Ca, Sr and Ba atoms in the regions far away from the perturbers are investigated. The Stark maps for Mg (n=16, M=0), Ca (n=10, M=0), Sr (n=12,M=0) and Ba (n=13, |M|=0,1) are presented. Topics such as the general methods of calculation, the treatment of fine structure, and the structure of level anti-crossings are discussed. The comparison between the theoretical and experimental Stark maps is satisfactory.

  17. Comparison of Ce$^{3+}$ and Pr$^{3+}$ activators in alkaline-earth fluoride crystals

    OpenAIRE

    Radzhabov, E.; Nepomnyaschikh, A.

    2012-01-01

    The emission spectra of Ce$^{3+}$ or Pr$^{3+}$ doped CaF$_2$, SrF$_2$, BaF$_2$ excited by vacuum ultraviolet photons or by x-ray as well as excitation and absorption spectra in vacuum ultraviolet region (6-13 eV) were studied. The transfer of exciton energy is the main channel for Ce$^{3+}$ excitation in alkaline-earth fluorides. Three different stages of energy transfer were observed. Pr$^{3+}$ excited by two processes, slow f-f luminescence excited by excitons, fast d-f luminescence excited...

  18. Optical tuning of the scattering length of cold alkaline earth atoms

    OpenAIRE

    Ciurylo, R.; Tiesinga, E.; P.S. Julienne

    2004-01-01

    It is possible to tune the scattering length for the collision of ultra-cold 1S0 ground state alkaline-earth atoms using an optical Feshbach resonance. This is achieved with a laser far detuned from an excited molecular level near the frequency of the atomic intercombination 1S0--3P1 transition. Simple resonant scattering theory, illustrated by the example of 40Ca, allows an estimate of the magnitude of the effect. Unlike alkali metal species, large changes of the scattering length are possib...

  19. Calculated Structural Phase-Transitions in the Alkaline-Earth Metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt

    1982-01-01

    The local-density approximation and the linear muffin-tin orbital method have been used within the atomic-sphere approximation to calculate structural energy differences for all the alkaline earth metals at zero temperature. At ordinary pressure the calculations predict the crystal structure sequ...... sequence hcp→fcc→bcc as a function of atomic number. As a function of pressure they predict the structure sequence fcc→bcc→hcp. The structural transitions and the onset of superconductivity under pressure are correlated with the d occupation number....

  20. Health Effects of Alkaline Diet and Water, Reduction of Digestive-tract Bacterial Load, and Earthing.

    Science.gov (United States)

    Mousa, Haider Abdul-Lateef

    2016-04-01

    In the article, the author discusses the issue of chronic, low-grade acidosis that is thought to be brought about primarily by 2 factors: (1) advancing age, with a consequent decline in renal function; and (2) diet. An acid-forming diet can induce low-grade metabolic acidosis, which causes very small decreases in blood pH and plasma bicarbonate (HCO3-) that remain within the range considered to be normal. However, if the duration of the acidosis is prolonged or chronically present, even a low degree of acidosis can become significant. This article reviews supporting evidence in the literature that has shown that consumption of abundant alkaline-forming foods can result in improvement in bone mineral density (BMD) and muscle mass, protection from chronic illnesses, reduced tumor-cell invasion and metastasis, and effective excretion of toxins from the body. In addition, a large number of studies showing the benefits of alkaline water (mineral water) have revealed that people consuming water with a high level of total dissolved solids (TDS) (ie, with a high mineral content) have shown a lower incidence of coronary heart disease (CHD), cardiovascular disease (CVD), and cancer and lower total mortality rates. Consumption of alkaline water also may prevent osteoporosis and protect pancreatic beta cells with its antioxidant effects. In addition, this article discusses the literature that shows that reducing digestive-tract bacterial load can play an important role in increasing blood alkalinity toward the normal upper limit. That change occurs through good oral hygiene, flossing of teeth, perfect chewing of food, and bowel evacuation as soon as possible. Finally, the author reviews the literature that shows that earthing (ie, the direct contact of the human body with the earth) can supply a current of plentiful electrons. Earthing has been shown to reduce acute and chronic inflammation, blood glucose in patients with diabetes, red blood cell (RBC) aggregation, and blood

  1. Health Effects of Alkaline Diet and Water, Reduction of Digestive-tract Bacterial Load, and Earthing.

    Science.gov (United States)

    Mousa, Haider Abdul-Lateef

    2016-04-01

    In the article, the author discusses the issue of chronic, low-grade acidosis that is thought to be brought about primarily by 2 factors: (1) advancing age, with a consequent decline in renal function; and (2) diet. An acid-forming diet can induce low-grade metabolic acidosis, which causes very small decreases in blood pH and plasma bicarbonate (HCO3-) that remain within the range considered to be normal. However, if the duration of the acidosis is prolonged or chronically present, even a low degree of acidosis can become significant. This article reviews supporting evidence in the literature that has shown that consumption of abundant alkaline-forming foods can result in improvement in bone mineral density (BMD) and muscle mass, protection from chronic illnesses, reduced tumor-cell invasion and metastasis, and effective excretion of toxins from the body. In addition, a large number of studies showing the benefits of alkaline water (mineral water) have revealed that people consuming water with a high level of total dissolved solids (TDS) (ie, with a high mineral content) have shown a lower incidence of coronary heart disease (CHD), cardiovascular disease (CVD), and cancer and lower total mortality rates. Consumption of alkaline water also may prevent osteoporosis and protect pancreatic beta cells with its antioxidant effects. In addition, this article discusses the literature that shows that reducing digestive-tract bacterial load can play an important role in increasing blood alkalinity toward the normal upper limit. That change occurs through good oral hygiene, flossing of teeth, perfect chewing of food, and bowel evacuation as soon as possible. Finally, the author reviews the literature that shows that earthing (ie, the direct contact of the human body with the earth) can supply a current of plentiful electrons. Earthing has been shown to reduce acute and chronic inflammation, blood glucose in patients with diabetes, red blood cell (RBC) aggregation, and blood

  2. Long-range interacting many-body systems with alkaline-earth-metal atoms.

    Science.gov (United States)

    Olmos, B; Yu, D; Singh, Y; Schreck, F; Bongs, K; Lesanovsky, I

    2013-04-01

    Alkaline-earth-metal atoms can exhibit long-range dipolar interactions, which are generated via the coherent exchange of photons on the (3)P(0) - (3)D(1) transition of the triplet manifold. In the case of bosonic strontium, which we discuss here, this transition has a wavelength of 2.6 μm and a dipole moment of 4.03 D, and there exists a magic wavelength permitting the creation of optical lattices that are identical for the states (3)P(0) and (3)D(1). This interaction enables the realization and study of mixtures of hard-core lattice bosons featuring long-range hopping, with tunable disorder and anisotropy. We derive the many-body master equation, investigate the dynamics of excitation transport, and analyze spectroscopic signatures stemming from coherent long-range interactions and collective dissipation. Our results show that lattice gases of alkaline-earth-metal atoms permit the creation of long-lived collective atomic states and constitute a simple and versatile platform for the exploration of many-body systems with long-range interactions. As such, they represent an alternative to current related efforts employing Rydberg gases, atoms with large magnetic moment, or polar molecules.

  3. Modelling three-dimensional-quench cooling for alkaline-earth atoms

    CERN Document Server

    Mehlstaeubler, T E; Douillet, A; Rehbein, N; Rasel, E M; Ertmer, W

    2003-01-01

    Quench cooling is a promising technique to reach ultra-cold temperatures in alkaline-earth atoms by Doppler cooling on ultra-narrow transitions. The principles of quench cooling are derived from an effective two-level system with a linewidth adjustable by the quenching laser. A tunable linewidth reconciles the contradictory requirements of a fast cooling rate and a high velocity selectivity at high and low temperatures, respectively. In this paper, we investigate the efficiency of quench cooling in alkaline-earth systems. We present a one-dimensional analytical description of the quenching process. Cooling and trapping in three dimensions is studied with semi-classical Monte Carlo simulations. Our results for magnesium indicate a loading efficiency of up to 40% of pre-cooled atoms at 2 mK into a QuenchMOT. Final temperatures of 9 mu K and an increase in phase-space density by almost five orders of magnitude are observed in the simulations.

  4. Long-range interacting many-body systems with alkaline-earth-metal atoms

    CERN Document Server

    Olmos, B; Singh, Y; Schreck, F; Bongs, K; Lesanovsky, I

    2012-01-01

    Alkaline-earth-metal atoms exhibit long-range dipolar interactions, which are generated via the coherent exchange of photons on the 3P_0-3D_1-transition of the triplet manifold. In case of bosonic strontium, which we discuss here, this transition has a wavelength of 2.7 \\mu m and a dipole moment of 2.46 Debye, and there exists a magic wavelength permitting the creation of optical lattices that are identical for the states 3P_0 and 3D_1. This interaction enables the realization and study of mixtures of hard-core lattice bosons featuring long-range hopping, with tuneable disorder and anisotropy. We derive the many-body Master equation, investigate the dynamics of excitation transport and analyze spectroscopic signatures stemming from coherent long-range interactions and collective dissipation. Our results show that lattice gases of alkaline-earth-metal atoms permit the creation of long-lived collective atomic states and constitute a simple and versatile platform for the exploration of many-body systems with lon...

  5. Calculation of the lowest electronic excitations of the alkaline earth metals using the relativistic polarization propagator

    Energy Technology Data Exchange (ETDEWEB)

    Brandt, Sven; Pernpointner, Markus, E-mail: Markus.Pernpointner@pci.uni-heidelberg.de

    2015-07-09

    Highlights: • We perform four-component correlated excitation spectra calculations of the alkaline earth metals. • We stress the relevance of a relativistic treatment in case of heavy systems. • The excellent performance of two-component variants is shown. • The wide applicability of propagators for accurate electronic structure calculations is demonstrated. - Abstract: In this work we use the recently implemented four-component polarization propagator for accurate single excitation calculations of alkaline earth metals and compare our results to experimental data. Various approximations to the Dirac–Coulomb Hamiltonian are additionally tested. In Ca spin–orbit coupling already leads to noticeable zero field splitting, which gradually increases for the heavier homologs finally invalidating the singlet and triplet state characterizations. For all systems we observe a very good agreement with experimental transition energies in the considered energy range. For Sr, Ba and Ra non-relativistic approaches already exhibit unacceptable deviations in the reproduction of transition energies and spectral structure. The obtained excited final states are analyzed in terms of atomic donor and acceptor orbital contributions. Our results stress the necessity to use relativistic implementations of the polarization propagator for an accurate description of both electron correlation and relativistic effects contributing to excitation spectra of heavy systems.

  6. Porphyrin-Alkaline Earth MOFs with the Highest Adsorption Capacity for Methylene Blue.

    Science.gov (United States)

    Hou, Yuxia; Sun, Junshan; Zhang, Daopeng; Qi, Dongdong; Jiang, Jianzhuang

    2016-04-25

    A series of four porphyrin-alkaline earth metal- organic frameworks [Mg(HDCPP)2 (DMF)2 ]n ⋅(H2 O)7 n (1), [Ca(HDCPP)2 (H2 O)2 ]n (DMF)1.5 n (2), [Sr(DCPP)(H2 O)(DMA)]n (3), and [Ba(DCPP)(H2 O)(DMA)]n (4) was isolated for the first time from solvothermal reaction between metal-free 5,15-di(4- carboxyphenyl)porphyrin (H2 DCPP) and alkaline earth ions. Single-crystal X-ray diffraction analysis reveals the 2D and 3D supramolecular network with periodic nanosized porosity for 1/2 and 3/4, respectively. The whole series of MOFs, in particular, compounds 1 and 2 with intrinsic low molecular formula weight, exhibit superior adsorption performance for methylene blue (MB) with excellent capture capacity as represented by the thus far highest adsorption amount of 952 mg g(-1) for 2 and good selectivity, opening a new way for the potential application of the main group metal-based MOFs. PMID:27002679

  7. Three-photon process for producing a degenerate gas of metastable alkaline-earth-metal atoms

    Science.gov (United States)

    Barker, D. S.; Pisenti, N. C.; Reschovsky, B. J.; Campbell, G. K.

    2016-05-01

    We present a method for creating a quantum degenerate gas of metastable alkaline-earth-metal atoms. This has yet to be achieved due to inelastic collisions that limit evaporative cooling in the metastable states. Quantum degenerate samples prepared in the 1S0 ground state can be rapidly transferred to either the 3P2 or 3P0 state via a coherent three-photon process. Numerical integration of the density-matrix evolution for the fine structure of bosonic alkaline-earth-metal atoms shows that transfer efficiencies of ≃90 % can be achieved with experimentally feasible laser parameters in both Sr and Yb. Importantly, the three-photon process can be set up such that it imparts no net momentum to the degenerate gas during the excitation, which will allow for studies of metastable samples outside the Lamb-Dicke regime. We discuss several experimental challenges to successfully realizing our scheme, including the minimization of differential ac Stark shifts between the four states connected by the three-photon transition.

  8. A 3-photon process for producing degenerate gases of metastable alkaline-earth atoms

    Science.gov (United States)

    Barker, Daniel S.; Pisenti, Neal C.; Reschovsky, Benjamin J.; Campbell, Gretchen K.

    2016-05-01

    We present a method for creating quantum degenerate gases of metastable alkaline-earth atoms. A degenerate gas in any of the 3 P metastable states has not previously been obtained due to large inelastic collision rates, which are unfavorable for evaporative cooling. Samples prepared in the 1S0 ground state can be rapidly transferred to either the 3P2 or 3P0 state via a coherent 3-photon process. Numerical integration of the density matrix evolution for the fine structure of bosonic alkaline-earth atoms shows that transfer efficiencies of ~= 90 % can be achieved with experimentally feasible laser parameters in both Sr and Yb. Importantly, the 3-photon process does not impart momentum to the degenerate gas during excitation, which allows studies of these metastable samples outside the Lamb-Dicke regime. We discuss several experimental challenges to the successful realization of our scheme, including the minimization of differential AC Stark shifts between the four states connected by the 3-photon transition.

  9. Short-life neutronodeficient isotopes of rare-earth elements

    International Nuclear Information System (INIS)

    In this work the following isotopes and isomers of the rare-earth elements were identified mostly for the first time and some verified: 157Tm(Tsub(1/2) = 3.6 min), 158Yb(Tsub(1/2) = 1.1 min), 159Yb(Tsub(1/2) = 1.75 min), 160Yb(Tsub(1/2) = 4.8 min), 148sup(m)Tb(Tsub(1/2) = 2.1 min), 149sup(m)Tb(Tsub(1/2) = 4.5 min), 150sup(m)Tb(Tsub(1/2) = 6.0 min) and 152Tb(Tsub(1/2) = 4.0 min). All of them were obtained in the spallation reactions on thin tantalum targets bombarded with a 660 MeV proton beam. The terbium isomers were also obtained in the heavy-ion reactions 141Pr(12C,xn) Tb and 139La(16O,xn)Tb. A method of fast extraction of rare-earth element isobars by direct separation from the tantalum targets was developed. The tantalum targets were placed in the ion source with surface ionization of the mass-separator. Semiconductor detectors were used for X-ray and γ-ray as well as α-particle spectra measurements. On the basis of experimental results, decay schemes of investigated isotopes (except 159Yb) were prepared. Some regularities in the α-decay energies were observed for isotones with N = 84 and N = 86. Two-quasiparticle states of the multiplets [π(hsub(11/2)) v (fsub(7/2))] in odd-odd Tb isotopes and [v(hsub(9/2)) v (fsub(7/2)) in even-even Gd isotopes were observed. Existence of these states indicates that the pure collective models are not sufficient to explain properties of nuclei in the region of N = 82 and Z = 64. Conclusions are presented on the method of fast isotope separation, techniques of measurements, methods of isotope (isomer) identification and their application in work with mass-separators on high-energy proton beams. (author)

  10. Dark-state suppression and optimization of laser cooling and fluorescence in a trapped alkaline-earth-metal single ion

    CERN Document Server

    Lindvall, T; Tittonen, I; Madej, A A; 10.1103/PhysRevA.86.033403

    2012-01-01

    We study the formation and destabilization of dark states in a single trapped 88Sr+ ion caused by the cooling and repumping laser fields required for Doppler cooling and fluorescence detection of the ion. By numerically solving the time-dependent density matrix equations for the eight-level system consisting of the sublevels of the 5s 2S1/2, 5p 2P1/2, and 4d 2D3/2 states, we analyze the different types of dark states and how to prevent them in order to maximize the scattering rate, which is crucial for both the cooling and the detection of the ion. The influence of the laser linewidths and ion motion on the scattering rate and the dark resonances is studied. The calculations are then compared with experimental results obtained with an endcap ion trap system located at the National Research Council of Canada and found to be in good agreement. The results are applicable also to other alkaline earth ions and isotopes without hyperfine structure.

  11. Metal based synthetic routes to heavy alkaline earth aryloxo complexes involving ligands of moderate steric bulk.

    Science.gov (United States)

    Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Guino-o, Marites; Ruhlandt-Senge, Karin

    2009-07-01

    Treatment of an alkaline earth metal (Ca, Sr, Ba) with 2,4,6-trimethylphenol (HOmes) at elevated temperatures in the presence of mercury under solvent-free conditions, followed by extraction of the reaction mixture with 1,2-dimethoxyethane (dme), afforded dinuclear alkaline earth aryloxo complexes [Ae2(Omes)4(dme)4] (Ae = Ca 1, Sr 3, Ba 6). Extraction of the Ca metal and HOmes reaction mixture with thf afforded [Ca3(Omes)6(thf)] 2. In contrast, redox transmetallation ligand exchange reactions between an alkaline earth metal, diphenylmercury and HOmes in dme yielded solely 1 for Ca metal, a mixture of 3 and the methoxide bridged cage [Sr5(Omes)5(OMe)5(dme)4] x 2dme 4 for Sr metal, and solely [Ba5(Omes)5(OMe)5(dme)4] x dme 7 for Ba metal. The methoxide ligands originate from the C-O activation of the dme solvent. Treatment of liquid ammonia activated Sr or Ba metal with HOmes in thf afforded the linear species [Ae3(Omes)6(thf)6] (Ae = Sr 5, Ba 8), and 8 was also obtained from barium metal and HOmes in refluxing thf. The structures of 1 and 3, determined by X-ray crystallography, consist of two six coordinate Ae metal atoms, to each of which is bound a terminal aryloxide ligand, two bridging aryloxide ligands, and chelating and unidentate dme ligands. The structures of 4 and 7 contain five Ae metal atoms arranged on the vertices of a distorted square based pyramid. The Ae atoms are linked by four mu3-OMe ligands and a mu4-OMe ligand. Four bridging aryloxide ligands and four chelating dme ligands complete the coordination spheres of the four seven coordinate Ae atoms at the base of the pyramid, and a terminal aryloxide ligand is bound to the five coordinate apical Ae atom. The structures of 5 and 8 consist of a trinuclear linear array of Ae metal atoms, and contain solely bridging aryloxide ligands. Three thf ligands are bound to each terminal Ae atom, giving all Ae atoms a coordination number of six. PMID:19662279

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  14. Relations between structure and material properties in earth alkaline silicate basing phosphors; Struktureigenschaftsbeziehungen in Erdalkalisilikat basierenden Leuchtstoffen

    Energy Technology Data Exchange (ETDEWEB)

    Hempel, Wolfgang

    2008-03-19

    This work is basing on the relation between structure and luminescence of Eu{sup 2+} doped Earth-Alkaline-Silicates. After an overview of Earth-Alkaline-Silicates silicates with an additional cation (Li{sup +}, Al{sup 3+}) and an additional anion (Cl{sup -}, N{sup 3-}) are examined in chapter 4 and 5. Basing on this data an relation between structural influence - like ion-radii, anion and coordination polyeder - and phosphor luminescence is set up. The ability of using as an industrial phosphor is made in the final chapter. (orig.)

  15. Structure elucidation of alkaline earth impregnated MCM-41 type mesoporous materials obtained by direct synthesis: An experimental and theoretical study

    Science.gov (United States)

    Paz, Gizeuda L.; Silva, Francisco das Chagas M.; Araújo, Maciel M.; Lima, Francisco das Chagas A.; Luz, Geraldo E.

    2014-06-01

    In this work, MCM-41 were synthesized hydrothermally and functionalized with calcium and strontium salts by direct method, using the Si/M = 50 molar ratio, in order to elucidate the way as the alkaline earth is incorporated on MCM-41 molecular sieve. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, nitrogen adsorption-desorption and theoretical calculations by DFT method. Experimental results and computer simulations showed that the alkaline earths were incorporated on MCM-41 through a complex structure, which negatively influences on basic sites formation.

  16. Prospects for sympathetic cooling of polar molecules: NH with alkali-metal and alkaline-earth atoms - a new hope

    CERN Document Server

    Soldán, Pavel; Hutson, Jeremy M

    2009-01-01

    We explore the potential energy surfaces for NH molecules interacting with alkali-metal and alkaline-earth atoms using highly correlated ab-initio electronic structure calculations. The surfaces for interaction with alkali-metal atoms have deep wells dominated by covalent forces. The resulting strong anisotropies will produce strongly inelastic collisions. The surfaces for interaction with alkaline-earth atoms have shallower wells that are dominated by induction and dispersion forces. For Be and Mg the anisotropy is small compared to the rotational constant of NH, so that collisions will be relatively weakly inelastic. Be and Mg are thus promising coolants for sympathetic cooling of NH to the ultracold regime.

  17. Electric dipole polarizability of alkaline-Earth-metal atoms from perturbed relativistic coupled-cluster theory with triples

    CERN Document Server

    Chattopadhyay, S; Angom, D

    2014-01-01

    The perturbed relativistic coupled-cluster (PRCC) theory is applied to calculate the electric dipole polarizabilities of alkaline Earth metal atoms. The Dirac-Coulomb-Breit atomic Hamiltonian is used and we include the triple excitations in the relativistic coupled-cluster (RCC) theory. The theoretical issues related to the triple excitation cluster operators are described in detail and we also provide details on the computational implementation. The PRCC theory results are in good agreement with the experimental and previous theoretical results. We, then, highlight the importance of considering the Breit interaction for alkaline Earth metal atoms.

  18. Lifshitz and other transitions in alkaline-earth 122 pnictides under pressure

    Science.gov (United States)

    Quader, Khandker; Widom, Michael

    2014-10-01

    We carry out T =0 first-principles total energy calculations in the entire set of alkaline 122-pnictides (A Fe2As2 ; A = alkaline-earth element Ca, Sr, Ba, Ra) as a function of hydrostatic pressure. We find multiple distinct transitions to occur, namely an enthalpic transition in which the zero-pressure striped antiferromagnetic orthorhombic (OR-AFM) phase becomes thermodynamically less stable than a competing tetragonal (T) phase, a magnetic transition in which the OR-AFM phase loses its magnetism and orthorhombicity, and a lattice parameter anomaly in which the tetragonal c-axis collapses and a collapsed tetragonal (cT) phase becomes stable. Our results for energy band dispersions and spectra, lattice parameters, enthalpies, magnetism, and elastic constants over a wide range of hydrostatic pressure provide a coherent understanding of these experimentally observed transitions. In particular, the T-cT transition and anomalies in lattice parameters and elastic properties, observed at finite temperatures, are interpreted as arising from proximity to T =0 Lifshitz transitions, wherein pressure causes nontrivial changes in the Fermi surface topology in these materials.

  19. Impacts of artificial ocean alkalinization on the carbon cycle and climate in Earth system simulations

    Science.gov (United States)

    González, Miriam Ferrer; Ilyina, Tatiana

    2016-06-01

    Using the state-of-the-art emissions-driven Max Planck Institute Earth system model, we explore the impacts of artificial ocean alkalinization (AOA) with a scenario based on the Representative Concentration Pathway (RCP) framework. Addition of 114 Pmol of alkalinity to the surface ocean stabilizes atmospheric CO2 concentration to RCP4.5 levels under RCP8.5 emissions. This scenario removes 940 GtC from the atmosphere and mitigates 1.5 K of global warming within this century. The climate adjusts to the lower CO2 concentration preventing the loss of sea ice and high sea level rise. Seawater pH and the carbonate saturation state (Ω) rise substantially above levels of the current decade. Pronounced differences in regional sensitivities to AOA are projected, with the Arctic Ocean and tropical oceans emerging as hot spots for biogeochemical changes induced by AOA. Thus, the CO2 mitigation potential of AOA comes at a price of an unprecedented ocean biogeochemistry perturbation with unknown ecological consequences.

  20. Laser-Induced Kondo Effect in Ultracold Alkaline-Earth Fermions.

    Science.gov (United States)

    Nakagawa, Masaya; Kawakami, Norio

    2015-10-16

    We demonstrate that laser excitations can coherently induce a novel Kondo effect in ultracold atoms in optical lattices. Using a model of alkaline-earth fermions with two orbitals, it is shown that the optically coupled two internal states are dynamically entangled to form the Kondo-singlet state, overcoming the heating effect due to the irradiation. Furthermore, a lack of SU(N) symmetry in the optical coupling provides a peculiar feature in the Kondo effect, which results in spin-selective renormalization of effective masses. We also discuss the effects of interorbital exchange interactions, and reveal that they induce novel crossover or reentrant behavior of the Kondo effect owing to control of the coupling anisotropy. The laser-induced Kondo effect is highly controllable by tuning the laser strength and the frequency, and thus offers a versatile platform to study the Kondo physics using ultracold atoms.

  1. Theoretical study of the dipole moments of selected alkaline-earth halides

    Science.gov (United States)

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

    1986-01-01

    Ab initio calculations at the self-consistent-field (SCF), singles-plus-doubles configuration-interaction (SDCI), and coupled-pair functional (CPF) level, are reported for the dipole moments and dipole derivatives of the X2Sigma(+) ground states of BeF, BeCl, MgF, MgCl, CaF, CaCl, and SrF. For comparison, analogous calculations are performed for the X1Sigma(+) state of KCl. The CPF results are found to be in remarkably better agreement with experiment than are the SCF and SDCI results. Apparently higher excitations are required to properly describe the radial extent along the bond axis of the remaining valence electron on the alkaline-earth metal.

  2. Preparations of Pure Alkaline Earth Molybdate Phases from Single Molecular Precursors

    Institute of Scientific and Technical Information of China (English)

    JIANG Ya-qi; ZHAO Hong; FANG Zhi-min; WAN Hui-lin; XIONG Ming; ZHOU Zhao-hui

    2004-01-01

    The pure phases of alkaline earth molybdates MMoO4, where M=Mg, Ca, Sr or Ba, were synthesized via the calcination of the related citrato oxomolybdate complexes. The mixed metal oxides can be highly dispersed at the atomic level due to the existence of uniform citrato oxomolybdenum precursors in definite composition. The complexing effect helps to produce the fine-grained oxides with particle size in the ultrafine scale(<100 nm) at heat-treatment temperatures below 500 ℃. The structures of the precursor complexes and the finally heat-treated particles were studied by means of IR, XRD, DSC, DTA and TG techniques. The morphologies of the particles were observed by using the SEM technique. The average particle sizes were calculated to be in the range of 30-50 nm based on X-ray diffraction line-broadening and SEM images, indicating the poor conglomeration of crystallite at low temperatures.

  3. State-dependent lattices for quantum computing with alkaline-earth-metal atoms

    CERN Document Server

    Daley, Andrew J; Zoller, Peter

    2011-01-01

    Recent experimental progress with Alkaline-Earth atoms has opened the door to quantum computing schemes in which qubits are encoded in long-lived nuclear spin states, and the metastable electronic states of these species are used for manipulation and readout of the qubits. Here we discuss a variant of these schemes, in which gate operations are performed in nuclear-spin-dependent optical lattices, formed by near-resonant coupling to the metastable excited state. This provides an alternative to a previous scheme [A. J. Daley, M. M. Boyd, J. Ye, and P. Zoller, Phys. Rev. Lett 101, 170504 (2008)], which involved independent lattices for different electronic states. As in the previous case, we show how existing ideas for quantum computing with Alkali atoms such as entanglement via controlled collisions can be freed from important technical restrictions. We also provide additional details on the use of collisional losses from metastable states to perform gate operations via a lossy blockade mechanism.

  4. Core-Shell Magneto-Optical Trap for Alkaline-Earth-Metal-Like Atoms

    CERN Document Server

    Lee, Jeongwon; Noh, Jiho; Mun, Jongchul

    2014-01-01

    We propose and demonstrate a new magneto-optical trap (MOT) for alkaline-earth-metal-like (AEML) atoms where the narrow $^{1}S_{0}\\rightarrow$$^{3}P_{1}$ transition and the broad $^{1}S_{0}\\rightarrow$$^{1}P_{1}$ transition are spatially arranged into a core-shell configuration. Our scheme resolves the main limitations of previously adopted MOT schemes, leading to a significant increase in both the loading rate and the steady state atom number. We apply this scheme to $^{174}$Yb MOT, where we show about a hundred-fold improvement in the loading rate and ten-fold improvement in the steady state atom number compared to reported cases that we know of to date. This technique could be readily extended to other AEML atoms to increase the statistical sensitivity of many different types of precision experiments.

  5. Optical tuning of the scattering length of cold alkaline earth atoms

    CERN Document Server

    Ciurylo, R; Julienne, P S

    2004-01-01

    It is possible to tune the scattering length for the collision of ultra-cold 1S0 ground state alkaline-earth atoms using an optical Feshbach resonance. This is achieved with a laser far detuned from an excited molecular level near the frequency of the atomic intercombination 1S0--3P1 transition. Simple resonant scattering theory, illustrated by the example of 40Ca, allows an estimate of the magnitude of the effect. Unlike alkali metal species, large changes of the scattering length are possible while atom loss remains small, because of the very narrow line width of the molecular photoassociation transition. This raises prospects for control of atomic interactions for a system without magnetically tunable Feshbach resonance levels.

  6. Photon Hall Scattering from Alkaline-earth-like atoms and Alkali-like ions

    CERN Document Server

    van Tiggelen, B A

    2016-01-01

    We investigate the possibility of observing a magneto-transverse scattering of photons from alkaline-earth-like atoms as well as alkali-like ions and provide orders of magnitude. The transverse magneto-scattering is physically induced by the interference between two possible quantum transitions of an outer electron in a S-state, one dispersive electric-dipole transition to a P-orbital state and a second resonant electric-quadrupole transition to a P-orbital state. In contrast with previous mechanisms proposed for such an atomic photonic Hall effect, no real photons are scattered by the electric-dipole allowed transition, which increases the ratio of Hall current to background photons significantly. The main experimental challenge is to overcome the small detection threshold, with only 10^{-5} photons scattered per atom per second.

  7. Calculation of the lowest electronic excitations of the alkaline earth metals using the relativistic polarization propagator

    Science.gov (United States)

    Brandt, Sven; Pernpointner, Markus

    2015-07-01

    In this work we use the recently implemented four-component polarization propagator for accurate single excitation calculations of alkaline earth metals and compare our results to experimental data. Various approximations to the Dirac-Coulomb Hamiltonian are additionally tested. In Ca spin-orbit coupling already leads to noticeable zero field splitting, which gradually increases for the heavier homologs finally invalidating the singlet and triplet state characterizations. For all systems we observe a very good agreement with experimental transition energies in the considered energy range. For Sr, Ba and Ra non-relativistic approaches already exhibit unacceptable deviations in the reproduction of transition energies and spectral structure. The obtained excited final states are analyzed in terms of atomic donor and acceptor orbital contributions. Our results stress the necessity to use relativistic implementations of the polarization propagator for an accurate description of both electron correlation and relativistic effects contributing to excitation spectra of heavy systems.

  8. Zircon U-Pb age, geochemical, and Sr-Nd-Pb isotopic constraints on the origin of alkaline intrusions in eastern Shandong Province, China

    Science.gov (United States)

    Liu, Shen; Feng, Caixia; Hu, Ruizhong; Gao, Shan; Wang, Tao; Feng, Guangying; Qi, Youqiang; Coulson, Ian M.; Lai, Shaocong

    2013-08-01

    Alkaline intrusions in the eastern Shandong Province consist of quartz monzonite and granite. U-Pb zircon ages, geochemical data, and Sr-Nd-Pb isotopic data for these rocks are reported in the present paper. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb zircon analyses yielded consistent ages ranging from 114.3 ± 0.3 to 122.3 ± 0.4 Ma for six samples of the felsic rocks. The felsic rocks are characterised by a wide range of chemical compositions (SiO2 = 55.14-77.63 wt. %, MgO = 0.09-4.64 wt. %, Fe2O3 = 0.56-7.6 wt. %, CaO = 0.40-5.2 wt. %), light rare earth elements (LREEs) and large ion lithophile elements (LILEs) (i.e., Rb, Pb, U) enrichment, as well as significant rare earth elements (HREEs) and heavy field strength (HFSEs) (Nb, Ta, P and Ti) depletion, various and high (87Sr/86Sr) i ranging from 0.7066 to 0.7087, low ɛ Nd (t) values from -14.1 to -17.1, high neodymium model ages (TDM1 = 1.56-2.38Ga, TDM2 = 2.02-2.25Ga), 206Pb/204Pb = 17.12-17.16, 207Pb/204Pb = 15.44-15.51, and 208Pb/204Pb = 37.55-37.72. The results suggested that these rocks were derived from an enriched crustal source. In addition, the alkaline rocks also evolved as the result of the fractionation of potassium feldspar, plagioclase, +/- ilmenite or rutile and apatite. However, the alkaline rocks were not affected by crustal contamination. Moreover, the generation of the alkaline rocks can be attributed to the structural collapse of the Sulu organic belt due to various processes.

  9. Raman and Rietveld structural characterization of sintered alkaline earth doped ceria

    Energy Technology Data Exchange (ETDEWEB)

    Siqueira Junior, Jose Marcio; Brum Malta, Luiz Fernando; Garrido, Francisco M.S. [Departamento de Quimica Inorganica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Centro de Tecnologia, Bloco A, room 632, CEP 68563, 21941-909 Rio de Janeiro, RJ (Brazil); Ogasawara, Tsuneharu [Programa de Engenharia Metalurgica e de Materiais, Coordenacao dos Programas de Pos - Graduacao de Engenharia, Centro de Tecnologia, Universidade Federal do Rio de Janeiro, Ilha do Fundao, CEP 68505, 21941-972 Rio de Janeiro, RJ (Brazil); Medeiros, Marta Eloisa, E-mail: chico@iq.ufrj.br [Departamento de Quimica Inorganica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Centro de Tecnologia, Bloco A, room 632, CEP 68563, 21941-909 Rio de Janeiro, RJ (Brazil)

    2012-08-15

    Nanocrystalline calcium and strontium singly doped ceria and co-doped ceria materials for solid electrolytes were prepared via a hydrothermal route. The effect of the hydrothermal treatment time on the solid solution composition was evaluated. Sr doped ceria was the most difficult to form, due to the Sr{sup 2+} large ionic radius. The small crystal size (12-16 nm) of powders allowed sintering into dense ceramic pellets at 1350 Degree-Sign C for 5 h. Raman spectroscopy evidenced a great lattice distortion for Sr doped and co-doped ceria materials, explaining the deterioration of the electrical properties for these ceramics. Besides that, a second phase was detected for Sr doped ceria pellet by using X-ray powder diffraction and Rietveld refinement of XRD data. Impedance measurements showed that Ca-doped ceria behaves as the best ionic conductor ({sigma}{sub g} 390 Degree-Sign C = 1.0 Multiplication-Sign 10{sup -3} S cm{sup -1}) since the nominal composition was achieved; on the other hand, Sr doped ceria performed as resistive materials since Sr incorporation into ceria lattice was critical. These results enhance the close interlace between electrical performance and chemical composition of alkaline earth doped ceria. -- Highlights: Black-Right-Pointing-Pointer Hydrothermally synthesized calcium doped ceria nanoparticles. Black-Right-Pointing-Pointer Incorporation of alkaline earth dopant into ceria lattice. Black-Right-Pointing-Pointer Raman and Rietveld structural characterization. Black-Right-Pointing-Pointer Calcium doped ceria ceramic pellets with high ionic conductivity. Black-Right-Pointing-Pointer Problems associated with the Sr{sup 2+} incorporation into ceria lattice.

  10. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene

    Science.gov (United States)

    Sahin, H.; Peeters, F. M.

    2013-02-01

    The adsorption characteristics of alkali, alkaline-earth, and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, work function, and dipole moment of the metal adsorbed silicene sheets. Alkali metals, Li, Na, and K, adsorb to hollow sites without any lattice distortion. As a consequence of the significant charge transfer from alkalis to silicene, metalization of silicene takes place. Trends directly related to atomic size, adsorption height, work function, and dipole moment of the silicene/alkali adatom system are also revealed. We found that the adsorption of alkaline-earth metals on silicene is entirely different from their adsorption on graphene. The adsorption of Be, Mg, and Ca turns silicene into a narrow gap semiconductor. Adsorption characteristics of eight transition metals Ti, V, Cr, Mn, Fe, Co, Mo, and W are also investigated. As a result of their partially occupied d orbital, transition metals show diverse structural, electronic, and magnetic properties. Upon the adsorption of transition metals, depending on the adatom type and atomic radius, the system can exhibit metal, half-metal, and semiconducting behavior. For all metal adsorbates, the direction of the charge transfer is from adsorbate to silicene, because of its high surface reactivity. Our results indicate that the reactive crystal structure of silicene provides a rich playground for functionalization at nanoscale.

  11. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    Science.gov (United States)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-10-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg2+, Ca2+ and Ba2+) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO)4, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (44·62)3(49·66)2. The calcium compound consists of 1D infinite "Ca-O" inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D "Ba-O" inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions' influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies.

  12. Effect of Composition and Impurities on the Phosphorescence of Green-Emitting Alkaline Earth Aluminate Phosphor.

    Directory of Open Access Journals (Sweden)

    Doory Kim

    Full Text Available Recent improvements to SrAl2O4:Eu2+, Dy3+ phosphors have enabled the use of luminescent hosts with a stable crystal structure and high physical and chemical stability, thus overcoming the bottleneck in the applicability of ZnS:Cu phosphors. However, enhancement of afterglow lifetime and brightness in SrAl2O4:Eu2+, Dy3+ phosphors remains a challenging task. Here, we have improved the afterglow characteristics in terms of persistence time and brightness by a systematic investigation of the composition of Eu-doped alkaline earth aluminate SrAl2O4:Eu2+, Dy3+ crystals. We found that a Dy3+/Eu2+ ratio of ~2.4 and ~0.935 mol Eu2+ (per mol of SrAl2O4 gave the brightest and longest emissions (11% and 9% increase for each. Doping with Si4+ also resulted in a slight increase in brightness up to ~15%. Doping with alkali metal or alkaline earth metal significantly enhanced the phosphorescence intensity. In particular, doping with 0.005 mol Li+ (per mol of SrAl2O4 alone boosted the phosphorescence intensity to 239% of the initial value, as compared to that observed for the non-doped crystal, while doping with 0.01 mol Mg2+ and 0.005 mol Li+ (per 1 mol SrAl2O4 boosted the phosphorescence intensity up to 313% of the initial value. The results of this investigation are expected to act as a guideline for the synthesis of bright and long persistent phosphors, and facilitate the development of persistent phosphors with afterglow characteristics superior to those of conventional phosphors.

  13. Effect of Composition and Impurities on the Phosphorescence of Green-Emitting Alkaline Earth Aluminate Phosphor

    Science.gov (United States)

    Kim, Doory; Kim, Han-Eol; Kim, Chang-Hong

    2016-01-01

    Recent improvements to SrAl2O4:Eu2+, Dy3+ phosphors have enabled the use of luminescent hosts with a stable crystal structure and high physical and chemical stability, thus overcoming the bottleneck in the applicability of ZnS:Cu phosphors. However, enhancement of afterglow lifetime and brightness in SrAl2O4:Eu2+, Dy3+ phosphors remains a challenging task. Here, we have improved the afterglow characteristics in terms of persistence time and brightness by a systematic investigation of the composition of Eu-doped alkaline earth aluminate SrAl2O4:Eu2+, Dy3+ crystals. We found that a Dy3+/Eu2+ ratio of ~2.4 and ~0.935 mol Eu2+ (per mol of SrAl2O4) gave the brightest and longest emissions (11% and 9% increase for each). Doping with Si4+ also resulted in a slight increase in brightness up to ~15%. Doping with alkali metal or alkaline earth metal significantly enhanced the phosphorescence intensity. In particular, doping with 0.005 mol Li+ (per mol of SrAl2O4) alone boosted the phosphorescence intensity to 239% of the initial value, as compared to that observed for the non-doped crystal, while doping with 0.01 mol Mg2+ and 0.005 mol Li+ (per 1 mol SrAl2O4) boosted the phosphorescence intensity up to 313% of the initial value. The results of this investigation are expected to act as a guideline for the synthesis of bright and long persistent phosphors, and facilitate the development of persistent phosphors with afterglow characteristics superior to those of conventional phosphors. PMID:26731086

  14. The nature of Earth's building blocks as revealed by calcium isotopes

    Science.gov (United States)

    Valdes, Maria C.; Moreira, Manuel; Foriel, Julien; Moynier, Frédéric

    2014-05-01

    Calcium is the fifth most abundant element in the Earth and in chondrites and is a pure lithophile element which does not partition into planetary cores. Therefore, the calcium isotopic composition of the mantle represents the bulk Earth and calcium isotopes have the potential to reveal genetic links between Earth and meteorites. However, whether calcium exhibits significant mass-dependent variations among Earth and the various chondrite groups, and the magnitude of these variations, is still contentious. Here we have developed a new method to analyze calcium isotope ratios with high precision using multiple-collector inductively-coupled-plasma mass-spectrometry. The method has been applied to a range of terrestrial and meteoritic samples. We find that the Earth, the Moon, and the aubrite parent body are indistinguishable from enstatite, ordinary, and CO chondritic meteorites. Therefore, enstatite chondrites cannot be excluded as components of Earth's building blocks based on calcium isotopes, as has been proposed previously. In contrast, CI, CV, CM and CR carbonaceous chondrites are largely enriched in lighter calcium isotopes compared to Earth, and, overall, exhibit a wide range in calcium isotopic composition. Calcium is the only major element, along with oxygen, for which isotopic variations are observed among carbonaceous chondrite groups. These calcium isotope variations cannot be attributed to volatility effects, and it is difficult to ascribe them to the abundance of isotopically light refractory inclusions. The calcium isotope data presented in this study suggest that both ordinary and enstatite chondrites are representative of the bulk of the refractory materials that formed Earth. On the basis of calcium isotopes, carbonaceous chondrites (with the exception of CO) are not representative of the fraction of condensable material that accreted to form the terrestrial planets and can be excluded as unique contenders for the building blocks of Earth; however

  15. Variation in Isotopic Biosignatures From Carbonate Rich, Microbial Mats in Saline, Alkaline Lakes on the Cariboo Plateau, B.C.

    Science.gov (United States)

    Brady, A.; Slater, G.; Druschel, G.; Lim, D.

    2009-05-01

    Cyanobacteria dominated, carbonate rich microbial mats found in saline, alkaline lakes on the Cariboo Plateau, B.C. represent potential analogues of the evaporative systems that might have occurred on early Earth or Mars. These evaporative lakes generally have pH values > 10, salinities of up to 33 psu and alkalinities of > 15, 000 mg CaCO3/L but differ in other geochemical parameters. The ability to understand natural variations in microbial activity and biosignatures in such modern analogues is central to our understanding of the capabilities and limits of life, the interpretation of the geologic record and potentially one day to the interpretation of astrobiological data. Phospholipid fatty acid (PLFA) profiling, voltammetry, and stable isotope analysis of organic and inorganic carbon pools highlighted the spatial and seasonal variability that exists in modern evaporative microbial mat dominated lakes. Variations in microbial PLFA distribution demonstrated that Cariboo Plateau microbial mat community composition varied seasonally and spatially. Voltammetry results showed that photosynthetic oxygen production occurred in the upper 5 mm of mats resulting in supersaturation of oxygen in surface waters. Depletion of oxygen generally occurred just below 5 mm and sulfide production began at 10 - 15 mm from the mat surface. Isotope analysis (13C) of Cariboo microbial mats showed inorganic (dissolved inorganic carbon) to organic (bulk cell) isotopic discriminations of 23-25 ‰, indicating non-CO2 limited photosynthesis. These results are in contrast to high organic content analogue mats previously reported that show evidence of CO2 limitation. Further, the Cariboo mats demonstrated significant intra- and inter-mat variations in carbonate δ13C values with respect to dissolved inorganic carbon (DIC) ranging from enrichment to 13C-depleted carbonate. In Deer Lake, isotopic enrichment of surface water DIC by 2-3 ‰ above atmospheric equilibrium indicated microbial

  16. The evolution of the earth climate. Marine paleoclimatology using oxygen isotopes

    International Nuclear Information System (INIS)

    It is shown how the discovery of isotopic fractionation enabled the development of a method for measuring the earth climate evolution. The method, based on paleotemperature formula, requires the isotope analysis of oceanic sediments and enables the earth climate evolution during the last million years to be determined

  17. Ab Initio Calculation of 19F NMR Chemical Shielding for Alkaline-earth-metal Fluorides

    Institute of Scientific and Technical Information of China (English)

    CAI,Shu-Hui(蔡淑惠); CHEN,Zhong,(陈忠); LU,Xin(吕鑫); CHEN,Zhi-Wei(陈志伟); WAN,Hui-Lin(万惠霖)

    2001-01-01

    Gauge-independent atomic orbital (GIAO) method atHartree-Fock (HF) and density functional theory (DFr) lev-els,respectively,was employed to calculate 19F NMR chemi-cal shieldings of solid state alkaline-earth-metal fluorides MF2 (M = Mg,Ca,Sr,Ba).The results show that,although thecalculated19F chemical shieldings tend to be larger than the experinental values,they have a fairly good linear relation-ship with the observed ones.The calculated results based on different combinations of basis sets show that the B3LYP (ahybrid of DFT with HF) predictions are greatly superior tothe I-IF predictions.When a basis set of metal atom with ef- fecfive core potential (ECP) has well representation of valencewavefunction,especially wavefuncfion of d component,andproper definition of core electron nmnher,it can be applied toobtain 19F chemical shielding which is dose to that of all-elec-tron calculation.Tne variation of 19F chemical shielding of al-kaline-earth-metal fluorides correlates well with the latticefactor A/R2.``

  18. Long-range interactions of excited He atoms with the alkaline earth atoms Mg, Ca, and Sr

    KAUST Repository

    Zhang, J.-Y.

    2013-04-05

    Dispersion coefficients for the long-range interactions of the first four excited states of He, i.e., He(2 1, 3 S) and He(2 1, 3 P), with the low-lying states of the alkaline earth atoms Mg, Ca, and Sr are calculated by summing over the reduced matrix elements of multipole transition operators.

  19. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides

    NARCIS (Netherlands)

    Hereijgers, B.P.C.; Weckhuysen, B.M.

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with al

  20. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 1. Introduction, Be and Mg

    Science.gov (United States)

    De Visscher, Alex; Vanderdeelen, Jan; Königsberger, Erich; Churagulov, Bulat R.; Ichikuni, Masami; Tsurumi, Makoto

    2012-03-01

    The alkaline earth carbonates are an important class of minerals. This volume compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1, the present paper, outlines the procedure adopted in this volume in detail, and presents the beryllium and magnesium carbonates. For the minerals magnesite (MgCO3), nesquehonite (MgCO3.3H2O), and lansfordite (MgCO3.5H2O), a critical evaluation is presented based on curve fits to empirical and/or thermodynamic models. Useful side products of the compilation and evaluation of the data outlined in the introduction are new relationships for the Henry constant of CO2 with Sechenov parameters, and for various equilibria in the aqueous phase including the dissociation constants of CO2(aq) and the stability constant of the ion pair MCO30(aq) (M = alkaline earth metal). Thermodynamic data of the alkaline earth carbonates consistent with two thermodynamic model variants are proposed. The model variant that describes the Mg2+-HCO3- ion interaction with Pitzer parameters was more consistent with the solubility data and with other thermodynamic data than the model variant that described the interaction with a stability constant.

  1. Influence of base strength on the catalytic performance of nano-sized alkaline earth metal oxides supported on carbon nanofibers

    NARCIS (Netherlands)

    Frey, A.M.; Yang, J.; Feche, C.; Essayem, N.; Stellwagen, D.R.; Figueras, F.; Jong, de K.P.; Bitter, J.H.

    2013-01-01

    Nano-sized (3 nm) alkaline earth metal oxides supported on carbon nanofibers were prepared by a facile impregnation and heat treatment method of the corresponding nitrates. These supported catalysts showed a significant improved activity for the aldol reaction and transesterification compared to the

  2. Electric dipole polarizabilities at imaginary frequencies for the alkali-metal, alkaline-earth, and inert gas atoms

    CERN Document Server

    Derevianko, Andrei; Babb, James F

    2009-01-01

    The electric dipole polarizabilities evaluated at imaginary frequencies for hydrogen, the alkali-metal atoms, the alkaline earth atoms, and the inert gases are tabulated along with the resulting values of the atomic static polarizabilities, the atom-surface interaction constants, and the dispersion (or van der Waals) constants for the homonuclear and the heteronuclear diatomic combinations of the atoms.

  3. Clumped isotope disequilibrium during rapid CO2 uptake and carbonate precipitation in subaerial alkaline springs associated with ongoing serpentinization

    Science.gov (United States)

    Falk, E. S.; Guo, W.; Kelemen, P. B.

    2014-12-01

    Ongoing serpentinization in tectonically exposed ultramafic bodies is manifested at the surface in alkaline springs (pH >11). Where these high-pH waters come in contact with CO2 at the surface, rapid calcite precipitation forms extensive travertines. We study natural travertine samples from Oman and synthetic witherite (BaCO3) from high-pH experiments to identify disequilibrium signals in δ18O, δ13C and clumped isotopes (measured as Δ47) that characterize rapid uptake of atmospheric CO2 and carbonate precipitation from high pH fluids. Kinetic effects preclude the use of clumped or oxygen isotopes for carbonate thermometry in these environments, but trends in δ18O, δ13C and Δ47 could help identify extinct alkaline systems or distinguish CO2 sources. Oman travertines formed at peridotite-hosted alkaline springs have long been known to exhibit a large range of kinetically depleted δ18O and δ13C values. We find fresh carbonate precipitated at these alkaline springs also exhibit large enrichments in Δ47 that covary with the depletions in δ18O and δ13C, thought to arise during hydroxylation of CO2 in high-pH fluids. Witherite precipitated during rapid CO2 uptake and carbonate precipitation in high pH experiments also exhibits disequilibrium values in δ18O, δ13C and Δ47, with the Δ47 of carbonate precipitates strongly affected by the Δ47 the reactant CO2. δ18O, δ13C and Δ47 trends could serve as a marker for carbonates formed in subaerial alkaline environments and track carbon sources in these systems. For example, the δ18O-δ13C slope in carbonates from Martian meteorites is similar to that observed in carbonates from terrestrial alkaline springs, so if corresponding enrichments in Δ47 could be identified in Martian carbonates, it could suggest that alkaline springs were present on the surface of Mars. Clumped isotope signals could also help distinguish carbon sources: kinetic enrichments in Δ47 would be absent or diminished in high-pH carbonates

  4. Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes?

    Science.gov (United States)

    Shirokova, L. S.; Mavromatis, V.; Bundeleva, I.; Pokrovsky, O. S.; Bénézeth, P.; Pearce, C.; Gérard, E.; Balor, S.; Oelkers, E. H.

    2011-07-01

    The fractionation of Mg isotopes was determined during the cyanobacterial mediated precipitation of hydrous magnesium carbonate precipitation in both natural environments and in the laboratory. Natural samples were obtained from Lake Salda (SE Turkey), one of the few modern environments on the Earth's surface where hydrous Mg-carbonates are the dominant precipitating minerals. This precipitation was associated with cyanobacterial stromatolites which were abundant in this aquatic ecosystem. Mg isotope analyses were performed on samples of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments. Laboratory Mg carbonate precipitation experiments were conducted in the presence of purified Synechococcus sp cyanobacteria that were isolated from the lake water and stromatolites. The hydrous magnesium carbonates nesquehonite (MgCO3·3H2O) and dypingite (Mg5(CO3)4(OH)25(H2O)) were precipitated in these batch reactor experiments from aqueous solutions containing either synthetic NaHCO3/MgCl2 mixtures or natural Lake Salda water, in the presence and absence of live photosynthesizing Synechococcus sp. Bulk precipitation rates were not to affected by the presence of bacteria when air was bubbled through the system. In the stirred non-bubbled reactors, conditions similar to natural settings, bacterial photosynthesis provoked nesquehonite precipitation, whilst no precipitation occurred in bacteria-free systems in the absence of air bubbling, despite the fluids achieving a similar or higher degree of supersaturation. The extent of Mg isotope fractionation (Δ26Mgsolid-solution) between the mineral and solution in the abiotic experiments was found to be identical, within uncertainty, to that measured in cyanobacteria-bearing experiments, and ranges from -1.4 to -0.7 ‰. This similarity refutes the use of Mg isotopes to validate microbial mediated precipitation of hydrous Mg carbonates.

  5. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1)

    OpenAIRE

    A. Jahn; Lindsay, K; Giraud, X.; Gruber, N.; Otto-Bliesner, B. L.; Liu, Z.; E. C. Brady

    2014-01-01

    Carbon isotopes in the ocean are frequently used as paleo climate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized dataset, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "ab...

  6. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1)

    OpenAIRE

    A. Jahn; Lindsay, K; Giraud, X.; Gruber, N.; Otto-Bliesner, B. L.; Liu, Z.; E. C. Brady

    2015-01-01

    Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "ab...

  7. Isotope dating of alkaline rocks from the Urals using U-Pb zircon data

    International Nuclear Information System (INIS)

    Uranium-lead isotope-geochronologic studying of zircons from miaskites and carbonatites of the ilmenorock-wischnevorock complex is carried out by methods and low-background analysis technique. A tendency to inverse relationship between the degree of U-Pb-dating discordanticity and uranium concentration in a sample. The point positions in discordanticity correlate with morphological zircon peculiarities. The two-stage history of zircon (crystallization-metamorphism) and the model of its U-Pb system, in which is assumed to be U, Th and radiogenic Pb concentrations in microinclusions of Th-U-mineral in zircon are based. Synchronism of events in miaskite and carbonatite history is shown. Rock metamorphization accompanied by Pbrad loss is dated by concordia in 261 ± 14 and 261 ± 6 for miaskite and carbonatites. The age of zircon crystallization is determined 422 ± 10 and 432 ± 12 mln years correspondingly. Pre-folded (Ordovician) age of alkaline rocks of the Urals and manifestation of their metamorphism in the Variscian epoch of regional folding is based

  8. Late Cenozoic alkaline volcanism in the northwestern Caribbean - Tectonic setting and Sr isotopic characteristics

    Science.gov (United States)

    Wadge, G.; Wooden, J. L.

    1982-01-01

    The northwestern corner of the Caribbean plate has at least sixteen centers of alkalic volcanism, most of which is Quaternary in age. Sr-87/Sr-86 ratios of the rocks in these centers are used to distinguish three geographical groups: a low-ratio group (0.7026-0.7031) at the Nicaraguan Rise, an intermediate-ratio group (0.7036-0.7038) in northeastern Costa Rica, and a high-ratio group (0.7047-0.7063) in Hispaniola. It is suggested that the increased radiogenic strontium in both Costa Rica and Hispaniola may have come from volatile-rich fluids escaping from adjacent subducting slabs of oceanic crust. The isotopic differences between the two areas is explained by the relative longevity and high rate of subduction in Costa Rica compared to that in Hispaniola. The Costa Rican alkaline rocks cover a segment of the Cocos plate which is being subducted at a smaller angle (about 35 deg) than at the rest of the Central American arc.

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

    Science.gov (United States)

    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.

  10. Structure of alkaline-earth pentafluoroantimonates(III), MSbF5(M=Sr, Ba)

    International Nuclear Information System (INIS)

    Strontium pentafluoroantimonate(III), SrSbF5, Mr=304.36, orthorhombic, Pbcm, a=4.378 (1), b=8.853 (3), c=11.233 (4) A, V=435.4 (3) A3, Z=4, Dm=4.60, Dx=4.64 Mg m-3, Mo Kα, λ=0.71069 A, μ=18.9 mm-1, F(000)=536, T=298 K, R=0.028 for 596 independent reflections with I>3α(I). Barium pentafluoroantimonate(III), BaSbF5, Mr=354.08, orthorhombic, Pbcm, a=4.676 (1), b=9.313 (2), c=11.213 (3) A, V=488.3 (2) A3, Z=4, Dm=4.77, Dx=4.82 Mg m-3, Mo Kα, λ=0.71069 A, μ=13.6 mm-1, F(000)=608, T=298 K, R=0.015 for 914 independent reflections with I>3σ(I). SrSbF5 and BaSbF5 are isostructural compounds. The three-dimensional network consists of isolated SbF52- units which are connected by ten-coordinated alkaline-earth ions Sr2+ or Ba2+. The geometry of these pentafluoroantimonate ions is approximately square pyramidal with the Sb atom outside the pyramid, below the four F atoms constituting the basal plane. (orig.)D

  11. CP(N-1) Quantum Field Theories with Alkaline-Earth Atoms in Optical Lattices

    CERN Document Server

    Laflamme, C; Dalmonte, M; Gerber, U; Mejía-Díaz, H; Bietenholz, W; Wiese, U -J; Zoller, P

    2015-01-01

    We propose a cold atom implementation to attain the continuum limit of (1+1)-d CP(N-1) quantum field theories. These theories share important features with (3+1)-d QCD, such as asymptotic freedom and $\\theta$ vacua. Moreover, their continuum limit can be accessed via the mechanism of dimensional reduction. In our scheme, the CP(N-1) degrees of freedom emerge at low energies from a ladder system of SU(N) quantum spins, where the N spin states are embodied by the nuclear Zeeman states of alkaline-earth atoms, trapped in an optical lattice. Based on Monte Carlo results, we establish that the continuum limit can be demonstrated by an atomic quantum simulation by employing the feature of asymptotic freedom. We discuss a protocol for the adiabatic state preparation of the ground state of the system, the real-time evolution of a false $\\theta$-vacuum state after a quench, and we propose experiments to unravel the phase diagram at non-zero density.

  12. Thermodynamic properties of titanates, zirconates and hafnates of alkaline earth metals

    International Nuclear Information System (INIS)

    The problems are considered arising in critical analysis and choosing recommended values of thermodynamic constants of the series of the most important perovskites-ferroelectrics-titanates, zirconates, and hafnates of alkaline-earth metals finding application in modern radioelectronics. Recommended values of standard thermodynamic values are given: heat capacity Csub(p,298) , enthalpy change H298-H0, entropy S298, heat formation ΔHsub(f,298 ), free energy formation ΔGsub(f,298) , temperatures and heats of phase transitions with indication of errors for the adopted values. The effect of impurities on thermal constants of phase transitions is discussed. The relationships between thermodynamic characteristics of perovskites and crystal structure as well as the effect of orthorhombic distortions of ideal perovskite lattice on entropy of the compounds have been considered. Along with thermodynamic methods of investigation, a great attention is given to other physical methods which have been used for finding temperature regions of phase transitions, Curie points, and temperatures of transition from ferroelectric to paraelectric state. The importance of physical methods is emphasized in those cases when phase transitions are accompanied by small energy changes and are not fixed in measuring heat capacity

  13. CP(N - 1) quantum field theories with alkaline-earth atoms in optical lattices

    Science.gov (United States)

    Laflamme, C.; Evans, W.; Dalmonte, M.; Gerber, U.; Mejía-Díaz, H.; Bietenholz, W.; Wiese, U.-J.; Zoller, P.

    2016-07-01

    We propose a cold atom implementation to attain the continuum limit of (1 + 1) -d CP(N - 1) quantum field theories. These theories share important features with (3 + 1) -d QCD, such as asymptotic freedom and θ-vacua. Moreover, their continuum limit can be accessed via the mechanism of dimensional reduction. In our scheme, the CP(N - 1) degrees of freedom emerge at low energies from a ladder system of SU(N) quantum spins, where the N spin states are embodied by the nuclear Zeeman states of alkaline-earth atoms, trapped in an optical lattice. Based on Monte Carlo results, we establish that the continuum limit can be demonstrated by an atomic quantum simulation by employing the feature of asymptotic freedom. We discuss a protocol for the adiabatic preparation of the ground state of the system, the real-time evolution of a false θ-vacuum state after a quench, and we propose experiments to unravel the phase diagram at non-zero density.

  14. Syntheses, structure and properties of Alkaline-earth metal salts of 4-Nitrophenylacetic acid

    Indian Academy of Sciences (India)

    BIKSHANDARKOIL R SRINIVASAN; KIRAN T DHAVSKAR; CHRISTIAN NÄTHER

    2016-11-01

    The synthesis, crystal structure, spectral characteristics and thermal properties of alkaline-earth metal salts of 4-nitrophenylacetic acid (4-npaH) namely, [Mg(H₂O)₆](4-npa)₂·4H₂O (4-npa = 4-nitrophenylacetate) (1), [Ca(H₂O)₂(4-npa)₂] (2) and [Sr(H₂O)₃(4-npa)₂]·4.5H₂O(3) are reported. In 1, the 4-npa ion functions as a charge balancing counter anion for the octahedral [Mg(H₂O)6]²⁺ unit with the Mg(II) ion situated on a centre of inversion. The two unique lattice water molecules link the [Mg(H₂O)₆]²⁺ cations and 4-npa anions with the aid of O-H· · ·O interactions. Compounds 2 and 3 are one-dimensional (1-D) coordination polymers containing an eight coordinated Ca(II) situated in a general position and a nine coordinated Sr(II) located on a twofold axis. The μ₂-bridging tridentate binding modes of the crystallographically independent 4-npa ligands in 2 and the unique 4-npa ligand in 3 link the bivalent metal ions into an infinite chain with alternating Ca· · · Ca separations of 3.989 and 4.009 Å, respectively, and a single Sr· · · Sr separation of 4.194Å in the 1-D chain.

  15. Surface fractal dimensions and textural properties of mesoporous alkaline-earth hydroxyapatites

    Energy Technology Data Exchange (ETDEWEB)

    Vilchis-Granados, J. [Instituto Nacional de Investigaciones Nucleares, Departamento de Química, A.P. 18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, DF (Mexico); Universidad Autónoma del Estado de México, Facultad de Química, Av. Paseo Colón esquina con Paseo Tollocan s/n Toluca, México (Mexico); Granados-Correa, F., E-mail: francisco.granados@inin.gob.mx [Instituto Nacional de Investigaciones Nucleares, Departamento de Química, A.P. 18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, DF (Mexico); Barrera-Díaz, C.E. [Universidad Autónoma del Estado de México, Facultad de Química, Av. Paseo Colón esquina con Paseo Tollocan s/n Toluca, México (Mexico)

    2013-08-15

    This work examines the surface fractal dimensions (D{sub f}) and textural properties of three different alkaline-earth hydroxyapatites. Calcium, strontium and barium hydroxyapatite compounds were successfully synthesized via chemical precipitation method and characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, and N{sub 2}-physisorption measurements. Surface fractal dimensions were determined using single N{sub 2}-adsorption/desorption isotherms method to quantify the irregular surface of as-prepared compounds. The obtained materials were also characterized through their surface hydroxyl group content, determined by the mass titration method. It was found that the D{sub f} values for the three materials covered the range of 0.77 ± 0.04–2.33 ± 0.11; these results indicated that the materials tend to have smooth surfaces, except the irregular surface of barium hydroxyapatite. Moreover, regarding the synthesized calcium hydroxyapatite exhibited better textural properties compared with the synthesized strontium and barium hydroxyapatites for adsorbent purposes. However, barium hydroxyapatite shows irregular surface, indicating a high population of active sites across the surface, in comparison with the others studied hydroxyapatites. Finally, the results showed a linear correlation between the surface hydroxyl group content at the external surface of materials and their surface fractal dimensions.

  16. Collective non-equilibrium spin exchange in cold alkaline-earth atomic clocks

    Science.gov (United States)

    Acevedo, Oscar Leonardo; Rey, Ana Maria

    2016-05-01

    Alkaline-earth atomic (AEA) clocks have recently been shown to be reliable simulators of two-orbital SU(N) quantum magnetism. In this work, we study the non-equilibrium spin exchange dynamics during the clock interrogation of AEAs confined in a deep one-dimensional optical lattice and prepared in two nuclear levels. The two clock states act as an orbital degree of freedom. Every site in the lattice can be thought as populated by a frozen set of vibrational modes collectively interacting via predominantly p-wave collisions. Due to the exchange coupling, orbital state transfer between atoms with different nuclear states is expected to happen. At the mean field level, we observe that in addition to the expected suppression of population transfer in the presence of a large magnetic field, that makes the single particle levels off-resonance, there is also an interaction induced suppression for initial orbital population imbalance. This suppression resembles the macroscopic self-trapping mechanism seen in bosonic systems. However, by performing exact numerical solutions and also by using the so-called Truncated Wigner Approximation, we show that quantum correlations can significantly modify the mean field suppression. Our predictions should be testable in optical clock experiments. Project supported by NSF-PHY-1521080, JILA-NSF-PFC-1125844, ARO, AFOSR, and MURI-AFOSR.

  17. IR and Raman spectroscopic studies of sol–gel derived alkaline-earth silicate glasses

    Indian Academy of Sciences (India)

    Angelos G Kalampounias

    2011-04-01

    IR and Raman spectroscopies have been utilized to study the structure and vibrational modes of sol–gel-derived binary silicate glasses. The present study is motivated by the immense geological significance and focuses on the MO–SiO2 (M = Ca, Mg) binary systems in an effort to unveil the role of the CaO and MgO modifiers when incorporated to the 3D silica structure. Glasses in the composition range = 0, 0.1, 0.2, 0.3 and 0.4 prepared by the sol–gel method were compared with the corresponding glasses formed by appropriate mixing of SiO2 and MO powders through melting and fast cooling. The vibrational spectra of the sol–gel-derived glasses have revealed considerable changes in relative intensities as a function of the MO mole fraction. These changes signify structural modifications on the silica network. The population of the 3 species was found to increase for both modified silicate systems. The rate of increase is more pronounced in the CaO–SiO2 glasses. The extent of network depolymerization in the porous glass is higher at the same content of alkaline earth oxide compared to the bulk glass. The results are indicative of a more `defective’ nature of the sol–gel glasses compared to the corresponding melt-quenched ones.

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

    Science.gov (United States)

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

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (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(α02-), 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 (α02-), and (Λ) increases with increasing of K2O content and electronic 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 K2O 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).

  19. Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes?

    Directory of Open Access Journals (Sweden)

    L. S. Shirokova

    2011-07-01

    Full Text Available The fractionation of Mg isotopes was determined during the cyanobacterial mediated precipitation of hydrous magnesium carbonate precipitation in both natural environments and in the laboratory. Natural samples were obtained from Lake Salda (SE Turkey, one of the few modern environments on the Earth's surface where hydrous Mg-carbonates are the dominant precipitating minerals. This precipitation was associated with cyanobacterial stromatolites which were abundant in this aquatic ecosystem. Mg isotope analyses were performed on samples of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments. Laboratory Mg carbonate precipitation experiments were conducted in the presence of purified Synechococcus sp cyanobacteria that were isolated from the lake water and stromatolites. The hydrous magnesium carbonates nesquehonite (MgCO3·3H2O and dypingite (Mg5(CO34(OH25(H2O were precipitated in these batch reactor experiments from aqueous solutions containing either synthetic NaHCO3/MgCl2 mixtures or natural Lake Salda water, in the presence and absence of live photosynthesizing Synechococcus sp. Bulk precipitation rates were not to affected by the presence of bacteria when air was bubbled through the system. In the stirred non-bubbled reactors, conditions similar to natural settings, bacterial photosynthesis provoked nesquehonite precipitation, whilst no precipitation occurred in bacteria-free systems in the absence of air bubbling, despite the fluids achieving a similar or higher degree of supersaturation. The extent of Mg isotope fractionation (Δ26Mgsolid-solution between the mineral and solution in the abiotic experiments was found to be identical, within uncertainty, to that measured in cyanobacteria-bearing experiments, and ranges from −1.4 to −0.7 ‰. This similarity refutes

  20. The etching process of boron nitride by alkali and alkaline earth fluorides under high pressure and high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Guo, W., E-mail: guowei1982cry@163.com [College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024 (China); National Key Lab of Superhard Materials, Jilin University, Changchun 130012 (China); Ma, H.A.; Jia, X. [National Key Lab of Superhard Materials, Jilin University, Changchun 130012 (China)

    2014-03-01

    Graphical abstract: - Highlights: • Appropriate etch processes of hBN and cBN under HPHT are proposed. • The degree of the crystallization of hBN was decreased. • A special cBN growth mechanism with a triangular unit is proposed. • Plate-shape cBN crystals with large ratio of length to thickness were obtained. • A strategy provides useful guidance for controlling the cBN morphology. - Abstract: Some new etching processes of hexagonal boron nitride (hBN) and cubic boron nitride (cBN) under high pressure and high temperature in the presence of alkali and alkaline earth fluorides have been discussed. It is found that hBN is etched distinctly by alkali and alkaline earth fluorides and the morphology of hBN is significantly changed from plate-shape to spherical-shape. Based on the “graphitization index” values of hBN, the degree of the crystallization of hBN under high pressure and high temperature decreases in the sequence of LiF > CaF{sub 2} > MgF{sub 2}. This facilitates the formation of high-quality cBN single crystals. Different etch steps, pits, and islands are observed on cBN surface, showing the strong etching by alkali and alkaline earth fluorides and the tendency of layer-by-layer growth. A special layer growth mechanism of cBN with a triangular unit has been found. Furthermore, the morphologies of cBN crystals are apparently affected by a preferential surface etching of LiF, CaF{sub 2} and MgF{sub 2}. Respectively, the plate-shape and tetrahedral cBN crystals can be obtained in the presence of different alkali and alkaline earth fluorides.

  1. The etching process of boron nitride by alkali and alkaline earth fluorides under high pressure and high temperature

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Appropriate etch processes of hBN and cBN under HPHT are proposed. • The degree of the crystallization of hBN was decreased. • A special cBN growth mechanism with a triangular unit is proposed. • Plate-shape cBN crystals with large ratio of length to thickness were obtained. • A strategy provides useful guidance for controlling the cBN morphology. - Abstract: Some new etching processes of hexagonal boron nitride (hBN) and cubic boron nitride (cBN) under high pressure and high temperature in the presence of alkali and alkaline earth fluorides have been discussed. It is found that hBN is etched distinctly by alkali and alkaline earth fluorides and the morphology of hBN is significantly changed from plate-shape to spherical-shape. Based on the “graphitization index” values of hBN, the degree of the crystallization of hBN under high pressure and high temperature decreases in the sequence of LiF > CaF2 > MgF2. This facilitates the formation of high-quality cBN single crystals. Different etch steps, pits, and islands are observed on cBN surface, showing the strong etching by alkali and alkaline earth fluorides and the tendency of layer-by-layer growth. A special layer growth mechanism of cBN with a triangular unit has been found. Furthermore, the morphologies of cBN crystals are apparently affected by a preferential surface etching of LiF, CaF2 and MgF2. Respectively, the plate-shape and tetrahedral cBN crystals can be obtained in the presence of different alkali and alkaline earth fluorides

  2. Investigation on Alkaline-Earth Houses in Jilin Province%吉林碱土民居考察

    Institute of Scientific and Technical Information of China (English)

    王红燕; 朴玉顺

    2012-01-01

    Through extensive research on the residential alkali soil houses in places of the of Yilibao, Sanli bad in the Daan Town,the New Peace Town and Anguang Town, the article clears the distribution and characteristics of the Jilin province alkaline earth houses. Through the residents of the area of alkali land survey- ing and mapping field exploration and focus, the article summarizes the status of the use of alkaline-earth res- idence and makes a detailed analysis of characteristics of alkaline-earth residence. These characteristics are as follows:the alkaline-earth residents living with the ease of local materials, low cost, good thermal insulation properties ,cool, short lifetime, difficult to maintain ,easily damaged and unsightly appearance.%通过对吉林省大安市平安镇一里堡、三里堡、新平安镇、安广镇等地的碱土民居的广泛调研,厘清了吉林省境内碱土民居的分布规律和特点。通过对该地区碱土民居的实地踏勘和重点测绘,总结归纳了碱土民居的使用现状,详细剖析了碱土民居所具有的便于就地取材、造价低廉,保温隔热性能好、冬暖夏凉,使用寿命短、维护困难,易受损、外观不美观等特点。

  3. Microcalorimetric study on host-guest complexation of naphtho-15-crown-5 with four ions of alkaline earth metal*

    OpenAIRE

    Song, Ming-Zhi; Zhu, Lan-ying; Gao, Xi-ke; Dou, Jian-Min; Sun, De-zhi

    2004-01-01

    Thermodynamic parameters of complexation of naphto-15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of sta...

  4. The lead isotopic age of the Earth can be explained by core formation alone.

    Science.gov (United States)

    Wood, Bernard J; Halliday, Alex N

    2010-06-10

    The meaning of the age of the Earth defined by lead isotopes has long been unclear. Recently it has been proposed that the age of the Earth deduced from lead isotopes reflects volatile loss to space at the time of the Moon-forming giant impact rather than partitioning into metallic liquids during protracted core formation. Here we show that lead partitioning into liquid iron depends strongly on carbon content and that, given a content of approximately 0.2% carbon, experimental and isotopic data both provide evidence of strong partitioning of lead into the core throughout the Earth's accretion. Earlier conclusions that lead is weakly partitioned into iron arose from the use of carbon-saturated (about 5% C) iron alloys. The lead isotopic age of the Earth is therefore consistent with partitioning into the core and with no significant late losses of moderately volatile elements to space during the giant impact.

  5. The significance of secondary interactions during alkaline earth-promoted dehydrogenation of dialkylamine-boranes.

    Science.gov (United States)

    Bellham, Peter; Anker, Mathew D; Hill, Michael S; Kociok-Köhn, Gabriele; Mahon, Mary F

    2016-09-21

    a modified mechanism for group 2-mediated dimethylamine borane dehydrocoupling that is dependent on the intermediacy of key derivatives of the [NMe2·BH3](-) and [NMe2BH2NMe2BH3](-) anions but does not require the formation of high energy alkaline earth hydride intermediates. Although these results are specifically focussed on the applications of alkaline earth species, this mechanistic insight may also be relevant to other redox-inactive main group element-based systems and to our understanding of hydrogen evolution from saline derivatives of ammonia borane. PMID:27529536

  6. Ocean-Based Alkalinity Enhancement: Mitigation Potential, Side Effects and the Fate of Added Alkalinity Assessed in an Earth System Model

    Science.gov (United States)

    Gonzalez, M. F.; Ilyina, T.

    2014-12-01

    Artificial ocean alkalinization (AOA) has been proposed as a mean to mitigate climate change and ocean acidification. Whilst the mitigation potential of this geo-engineering technology may sound promising, it poses environmental risks. Within the Priority Program "Climate Engineering" of the German Science Foundation (DFG), we investigate the mitigation potential of AOA to reduce atmospheric CO2 and counteract the consequences of ocean acidification. We are particularly interested in the residence time of the added alkalinity at the ocean surface because it must stay in the upper ocean in order to increase the oceanic CO2 uptake. The mitigation potential, risks and the unintended consequences of this geo-engineering method are also exhaustively studied. These questions are tackled through the analysis of different alkalinity enhancement scenarios in the state-of-the-art Earth system model of the Max Planck Institute for Meteorology (MPI-ESM) in a configuration based on the fifth phase of the Coupled Model Intercomparison Project (CMIP5). Model scenarios are designed so that AOA is performed to keep the atmospheric CO2 concentrations similar to values of the stabilization scenario RCP4.5, while fossil fuel CO2 emissions follow the pathway of the high-CO2 scenario RCP8.5. Alkalinity is added globally into the upper 12 meters of the ocean in different seasons and years. We found that on the time scale of relevance (i.e. from years to decades), season and location are key aspects to take into account in the implementation of AOA. This is because of inhomogeneous vertical mixing of added alkalinity due to the mixed layer depth which is established by the season. We also show that the rate of addition greatly determines impact and outcome of this geo-engineering method. Changes driven by the implementation of this method in the ocean biogeochemistry are also discussed. For instance, the associated changes in the carbon cycle, marine oxygen levels, saturation state of

  7. Isotope composition and volume of Earth´s early oceans

    DEFF Research Database (Denmark)

    Pope, Emily Catherine; Bird, Dennis K.; Rosing, Minik Thorleif

    2012-01-01

    Oxygen and hydrogen isotope compositions of Earth´s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs......, but hydrogen´s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as Î...... in Earth´s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth....

  8. Electron emission of alkaline and alkaline-earth vapors adsorbed on refractory metals; Emission electronique des metaux alcalins et alcalino-terreux adsorbes sur les metaux refractaires

    Energy Technology Data Exchange (ETDEWEB)

    Alleau, Th.; Desplat, J.L. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    This work has been carried out as an aid to research on thermionic converter electrodes. The improvement of the converter efficiency makes it necessary to explain physically the adsorption process, and to determine theoretically its laws. The Gyftopoulos, Levine, Steiner's latest theory has been used to plot, by means of a computer, the 'S' shaped curves which bind the electron emission of adsorbed alkaline and alkaline-earth metals to their temperature and to the substrate temperature. 21 examples are presented, some of them being studied with crystallographic orientation. (authors) [French] Cette etude a ete realisee dans le cadre des recherches effectuees sur les electrodes des convertisseurs thermoioniques. L'explication physique des phenomenes d'adsorption et la connaissance theorique de leurs lois, est indispensable a l'amelioration du rendement des convertisseurs. Il a ete fait appel a la recente theorie de E.P. Gyftopoulos, J.D. Levine, D. Steiner pour tracer par ordinateur les courbes en 'S' qui lient l'emission electronique des metaux alcalins ou alcalino-terreux a leur temperature et a la temperature des metaux refractaires sur lesquels ils sont adsorbes. 21 cas sont etudies, dont certains en fonction de l'orientation cristalline. (auteurs)

  9. Synthesis and crystal structures of novel LaOAgS-type alkaline earth – Zinc, manganese, and cadmium fluoride pnictides

    Energy Technology Data Exchange (ETDEWEB)

    Charkin, Dmitri O., E-mail: charkin@inorg.chem.msu.ru; Urmanov, Arthur V.; Plokhikh, Igor V.; Korshunov, Alexander D.; Kuznetsov, Alexey N.; Kazakov, Sergey M.

    2014-02-05

    Highlights: • Sight new alkaline earth – Mn, Zn, Cd fluoride pnictides were prepared. • All new compounds adopt the LaOAgS structure type. • Bond distances in their structures are transferable within 2–3%. • Very close similarities are observed in structural chemistry of LaOAgS- and HfCuSi{sub 2}-type compounds of Mn, Cu, Zn, Ag, and Cd. -- Abstract: Systematic studies of the LaOAgS-type compounds among alkaline earth – Zn/Cd/Mn fluoride pnictides revealed the existence of new representatives SrFMnP, SrFMnAs, SrFMnSb, SrFZnAs, SrFZnSb, BaFZnAs, BaFCdP, and BaFCdAs. Similar to rare-earth oxide compounds and contrary to isolobal chalcogenides of Cu/Ag, not all possible compositions could be realized. No compound of the structure type is formed for calcium; strontium forms fluoride pnictides only with zinc and manganese, while for barium, new representatives are also formed with cadmium. This trend, which possibly has a geometrical origin, is corroborated by quantum chemical calculations. Formation of NdOZnP-type compounds also was not observed suggesting the structure to be characteristic only for rare earth – zinc oxide phosphides.

  10. The MCVD synthesis and characterization of water tolerant fiber optic waveguides based on alkaline earth-doped silicas

    Science.gov (United States)

    Farley, Kevin F.

    Optical fibers that transmit throughout the entire telecommunications spectrum (1.2--1.7 mum) are presently manufactured by the removal of hydrogen or OH from the host preform glass. Hydrogen-oxygen torches are utilized in the conventional preform manufacturing process, but result in the formation of hydroxyls in germanium-doped silica fiber. The hydroxyl species generate unacceptably high losses for long haul telecommunications systems. This thesis has explored an alternative strategy for reducing OH-related absorption in silica-based glasses. Alkaline earth modifiers have been introduced via the modified chemical vapor deposition (MCVD) process to successfully damp out and dramatically reduce the extrinsic attenuation associated with both water and hydrogen. Specifically, alkaline earth ions were introduced into alumino-silicate glasses to form MgO-Al2O3-SiO2, CaO-Al 2O3-SiO2, and SrO-Al2O3-SiO 2 compositions. The utilization of halide precursors based on the vapor delivery of rare earths was incorporated into the existing MCVD set-up to fabricate these optical preforms. Both the bulk preforms and fibers drawn from them were characterized to determine relevant optical properties, including the attenuation, index profiles and extinction coefficients arising from OH in each host. The data indicate that modification of the silica glass structure through the additions of modifying ions can significantly reduce OH related absorption. For example, the doping of alkaline earth ions decreased the extinction coefficient measured at the 1.39 mum) OH overtone, to values reinforced by a series of experiments documenting their resistance to hydrogen induced losses.

  11. Monte Carlo simulations of electron thermalization in alkali iodide and alkaline-earth fluoride scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Wang Zhiguo; Gao Fei; Kerisit, Sebastien [Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Xie Yulong [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Campbell, Luke W. [National Security Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

    2012-07-01

    A Monte Carlo model of electron thermalization in inorganic scintillators, which was developed and applied to CsI in a previous publication [Wang et al., J. Appl. Phys. 110, 064903 (2011)], is extended to another material of the alkali halide class, NaI, and to two materials from the alkaline-earth halide class, CaF{sub 2} and BaF{sub 2}. This model includes electron scattering with both longitudinal optical (LO) and acoustic phonons as well as the effects of internal electric fields. For the four pure materials, a significant fraction of the electrons recombine with self-trapped holes and the thermalization distance distributions of the electrons that do not recombine peak between approximately 25 and 50 nm and extend up to a few hundreds of nanometers. The thermalization time distributions of CaF{sub 2}, BaF{sub 2}, NaI, and CsI extend to approximately 0.5, 1, 2, and 7 ps, respectively. The simulations show that the LO phonon energy is a key factor that affects the electron thermalization process. Indeed, the higher the LO phonon energy is, the shorter the thermalization time and distance are. The thermalization time and distance distributions show no dependence on the incident {gamma}-ray energy. The four materials also show different extents of electron-hole pair recombination due mostly to differences in their electron mean free paths (MFPs), LO phonon energies, initial densities of electron-hole pairs, and static dielectric constants. The effect of thallium doping is also investigated for CsI and NaI as these materials are often doped with activators. Comparison between CsI and NaI shows that both the larger size of Cs{sup +} relative to Na{sup +}, i.e., the greater atomic density of NaI, and the longer electron mean free path in NaI compared to CsI contribute to an increased probability for electron trapping at Tl sites in NaI versus CsI.

  12. Monte Carlo simulations of electron thermalization in alkali iodide and alkaline-earth fluoride scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhiguo; Xie, YuLong; Campbell, Luke W.; Gao, Fei; Kerisit, Sebastien N.

    2012-07-01

    A Monte Carlo model of electron thermalization in inorganic scintillators, which was developed and applied to CsI in a previous publication [Wang et al., J. Appl. Phys. 110, 064903 (2011)], is extended to another material of the alkali halide class, NaI, and to two materials from the alkaline-earth halide class, CaF2 and BaF2. This model includes electron scattering with both longitudinal optical (LO) and acoustic phonons as well as the effects of internal electric fields. For the four pure materials, a significant fraction of the electrons recombine with self-trapped holes and the thermalization distance distributions of the electrons that do not recombine peak between approximately 25 and 50 {per_thousand}nm and extend up to a few hundreds of nanometers. The thermalization time distributions of CaF2, BaF2, NaI, and CsI extend to approximately 0.5, 1, 2, and 7 ps, respectively. The simulations show that the LO phonon energy is a key factor that affects the electron thermalization process. Indeed, the higher the LO phonon energy is, the shorter the thermalization time and distance are. The thermalization time and distance distributions show no dependence on the incident {gamma}-ray energy. The four materials also show different extents of electron-hole pair recombination due mostly to differences in their electron mean free paths (MFPs), LO phonon energies, initial densities of electron-hole pairs, and static dielectric constants. The effect of thallium doping is also investigated for CsI and NaI as these materials are often doped with activators. Comparison between CsI and NaI shows that both the larger size of Cs+ relative to Na+, i.e., the greater atomic density of NaI, and the longer electron mean free path in NaI compared to CsI contribute to an increased probability for electron trapping at Tl sites in NaI versus CsI.

  13. Influence of doping with alkaline earth metals on the optical properties of thermochromic VO2

    Science.gov (United States)

    Dietrich, Marc K.; Kramm, Benedikt G.; Becker, Martin; Meyer, Bruno K.; Polity, Angelika; Klar, Peter J.

    2015-05-01

    Thin films of doped VO2 were deposited, analyzed, and optimized with regard to their solar energy transmittance (Tsol) and visible/luminous light transmittance (Tlum) which are important parameters in the context of smart window applications in buildings. The doping with alkaline earth metals (AEM) like Mg, Ca, Sr, or Ba increased both Tsol and Tlum due to a bandgap widening and an associated absorption edge blue-shift. Thereby, the brown-yellowish color impression of pure VO2 thin films, which is one major hindrance limiting the usage of VO2 as thermochromic window coating, was overcome. Transparent thin films with excellent switching behavior were prepared by sputtering. Highly doped V1-xMexO2 (Me = Ca, Sr, Ba) kept its excellent thermochromic switching behavior up to x(Me) = Me/(Me + V) = 10 at. % doping level, while the optical bandgap energy was increased from 1.64 eV for undoped VO2 to 2.38 eV for x(Mg) = 7.7 at. %, 1.85 eV for x(Ca) = 7.4 at. %, 1.84 eV for x(Sr) = 6.4 at. % and 1.70 eV for x(Ba) = 6.8 at. %, as well as the absorption edge is blue shifted by increasing AEM contents. Also, the critical temperature ϑc, at which the semiconductor-to-metal transition (SMT) occurs, was decreased by AEM doping, which amounted to about -0.5 K/at. % for all AEM on average. The critical temperature was determined by transmittance-temperature hysteresis measurements. Furthermore, Tsol and Tlum were calculated and were found to be significantly enhanced by AEM doping. Tlum increased from 32.0% in undoped VO2 to 43.4% in VO2 doped with 6.4 at. % Sr. Similar improvements were found for other AEM. The modulation of the solar energy transmittance ΔTsol, which is the difference of the Tsol values in the low and high temperature phase, was almost constant or even slightly increased when the doping level was increased up to about 10 at. % Ca, Sr, or Ba.

  14. Eocene seasonality and seawater alkaline earth reconstruction using shallow-dwelling large benthic foraminifera

    Science.gov (United States)

    Evans, David; Müller, Wolfgang; Oron, Shai; Renema, Willem

    2013-11-01

    Intra-test variability in Mg/Ca and other (trace) elements within large benthic foraminifera (LBF) of the family Nummulitidae have been investigated using laser-ablation inductively-coupled plasma mass spectrometry (LA-ICPMS). These foraminifera have a longevity and size facilitating seasonal proxy retrieval and a depth distribution similar to 'surface-dwelling' planktic foraminifera. Coupled with their abundance in climatically important periods such as the Paleogene, this means that this family of foraminifera are an important but under-utilised source of palaeoclimatic information. We have calibrated the relationship between Mg/Ca and temperature in modern Operculina ammonoides and observe a ˜2% increase in Mg/Ca °C-1. O. ammonoides is the nearest living relative of the abundant Eocene genus Nummulites, enabling us to reconstruct mid-Eocene tropical sea surface temperature seasonality by applying our calibration to fossil Nummulites djokdjokartae from Java. Our results indicate a 5-6 °C annual temperature range, implying greater than modern seasonality in the mid-Eocene (Bartonian). This is consistent with seasonal surface ocean cooling facilitated by enhanced Eocene tropical cyclone-induced upper ocean mixing, as suggested by recent modelling results. Analyses of fossil N. djokdjokartae and Operculina sp. from the same stratigraphic interval demonstrate that environmental controls on proxy distribution coefficients are the same for these two genera, within error. Using previously published test-seawater alkaline earth metal distribution coefficients derived from an LBF of the same family (Raitzsch et al., 2010) and inorganic calcite, with appropriate correction systematics for secular Mg/Casw variation (Evans and Müller, 2012), we use our fossil data to produce a more accurate foraminifera-based Mg/Casw reconstruction and an estimate of seawater Sr/Ca. We demonstrate that mid-Eocene Mg/Casw was ≲2 molmol, which is in contrast to the model most

  15. The oxygen isotope composition of earth's oldest rocks and evidence of a terrestrial magma ocean

    DEFF Research Database (Denmark)

    Rumble, D.; Bowring, S.; Iizuka, T.;

    2013-01-01

    Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce....... But other sources of heat for global melting cannot be excluded such as bolide impacts during early accretion of proto-Earth, the decay of short-lived radioactive isotopes, or the energy released during segregation of core from mantle....

  16. Rare Isotopes in Cosmic Explosions and Accelerators on Earth

    International Nuclear Information System (INIS)

    Rare isotopes are nature's stepping stones to produce the heavy elements, and they are produced in large quantities in stellar explosions. Despite their fleeting existence, they shape the composition of the universe and the observable features of stellar explosions. The challenge for nuclear science is to produce and study the very same rare isotopes so as to understand the origin of the elements and a range of astronomical observations. I will review the progress that has been made to date in astronomy and nuclear physics, and the prospects of finally addressing many of the outstanding issues with the future Facility for Rare Isotope Beams (FRIB), which DOE will build at Michigan State University.

  17. Optical Feshbach resonances of Alkaline-Earth atoms in a 1D or 2D optical lattice

    OpenAIRE

    Naidon, Pascal; Julienne, Paul S.

    2006-01-01

    Motivated by a recent experiment by Zelevinsky et al. [Phys. Rev. Lett. 96, 203201], we present the theory for photoassociation and optical Feshbach resonances of atoms confined in a tight one-dimensional (1D) or two-dimensional (2D) optical lattice. In the case of an alkaline-earth intercombination resonance, the narrow natural width of the line makes it possible to observe clear manifestations of the dimensionality, as well as some sensitivity to the scattering length of the atoms. Among po...

  18. Microcalorimetric study on host-guest complexation of naphtho-15-crown-5 with four ions of alkaline earth metal

    Institute of Scientific and Technical Information of China (English)

    SONG Ming-zhi; ZHU Lan-ying; GAO Xi-ke; DOU Jian-min; SUN De-zhi

    2005-01-01

    Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.

  19. Preparation of decarboxylic-functionalized weak cation exchanger and application for simultaneous separation of alkali, alkaline earth and transition metals.

    Science.gov (United States)

    Peng, Yahui; Gan, Yihui; He, Chengxia; Yang, Bingcheng; Guo, Zhimou; Liang, Xinmiao

    2016-06-01

    A novel weak cation exchanger (WCX) with dicarboxyl groups functionalized has been developed by clicking mercaptosuccinic acid onto silica gel. The simple synthesis starts with modification of silica gel with triethoxyvinylsilane, followed by efficient coupling vinyl-bonded silica with mercaptosuccinic acid via a "thiol-ene" click reaction. The obtained WCX demonstrated good separation and high selectivity towards common metals. Simultaneous separation of 10 alkali, alkaline earth and transition metals was achieved within 12min. Ion exchange and complex mechanism dominates the separation process. Its utility was demonstrated for determination of metals in tap water. PMID:27130093

  20. Lead isotope evidence for a young formation age of the Earth-Moon system

    Science.gov (United States)

    Connelly, J. N.; Bizzarro, M.

    2016-10-01

    A model of a giant impact between two planetary bodies is widely accepted to account for the Earth-Moon system. Despite the importance of this event for understanding early Earth evolution and the inventory of Earth's volatiles critical to life, the timing of the impact is poorly constrained. We explore a data-based, two-stage Pb isotope evolution model in which the timing of the loss of volatile Pb relative to refractory U in the aftermath of the giant impact is faithfully recorded in the Pb isotopes of bulk silicate Earth. Constraining the first stage Pb isotopic evolution permits calculating an age range of 4.426-4.417 Ga for the inflection in the U/Pb ratio related to the giant impact. This model is supported by Pb isotope data for angrite meteorites that we use to demonstrate volatility-driven, planetary-scale Pb loss was an efficient process during the early Solar System. The revised age is ∼100 Myr younger than most current estimates for the age of the Moon but fully consistent with recent ages for lunar ferroan anorthosite and the timing of Earth's first crust inferred from the terrestrial zircon record. The estimated loss of ∼98% of terrestrial Pb relative to the Solar System bulk composition by the end of the Moon-forming process implies that the current inventory of Earth's most volatile elements, including water, arrived during post-impact veneering by volatile-rich bodies.

  1. Novel alkaline earth copper germanates with ferro and antiferromagnetic S=1/2 chains

    International Nuclear Information System (INIS)

    Two new alkaline earth copper(II) germanates were hydrothermally synthesized: CaCuGeO4·H2O (1) and BaCu2Ge3O9·H2O (2), and their structures determined by single crystal X-ray diffraction. Compound (1) crystallizes in space group P21/c with a=5.1320(2) Å, b=16.1637(5) Å, c=5.4818(2) Å, β=102.609(2)°, V=443.76(3) Å3 and Z=4. This copper germanate contains layers of composition [CuGeO4]∞2− comprising CuO4 square planes and GeO4 tetrahedra with calcium and water molecules in the inter-layer space. Compound (2) crystallizes in the Cmcm space group with a=5.5593(3) Å, b=10.8606(9) Å, c=13.5409(8) Å, V=817.56(9) Å3 and Z=4. This structure contains GeO6 and CuO6 octahedra as well as GeO4 tetrahedra, forming a three-dimensional network of interconnecting six-membered ring channels. The magnetic susceptibility for both samples can be interpreted as S=1/2 chains, in agreement with the copper topology observed in the crystal structure. The susceptibility of (1) exhibits a Bonner–Fisher type behavior, resulting from antiferromagnetic intra-chain interactions without three-dimensional ordering down to 5 K—the lowest measured temperature. This observation, together with the absence of super-exchange paths between the copper chains, make this system particularly promising for the study of low dimensional magnetism. The magnetic properties of (2) show a very weak ferromagnetic near-neighbor interaction along the chain. In this compound a peak the χT plot seems to indicate the onset of interchain antiferromagentic correlations. However, no ordering temperature is detected in the susceptibility data. - Graphical abstract: Copper chains present in CaCuGeO4·H2O and BaCu2Ge3O9·H2O, two novel copper germanates synthesized hydrothermally, showing antiferromagnetic and ferromagnetic intra-chain interactions respectively. Highlights: ► The structure of two new chain containing copper germinates is reported. ► The calcium compound CaCuGeO4·H2O contains

  2. Three interesting coordination compounds based on metalloligand and alkaline-earth ions: Syntheses, structures, thermal behaviors and magnetic property

    Science.gov (United States)

    Zhou, Qiang; Qian, Jun; Zhang, Chi

    2016-09-01

    Based on metalloligand LCu ([Cu(2,4-pydca)2]2-, 2,4-pydca2- = pyridine-2,4-dicarboxylate) and alkaline-earth ions (Ca2+, Sr2+, and Ba2+), three interesting coordination compounds, [Ca(H2O)7][LCu·H2O]·H2O (1), {Sr[LCu·H2O]·4H2O}n (2), and {Ba[LCu·H2O]·8H2O}n (3), have been synthesized and well-characterized by elemental analysis, infrared spectroscopy, thermogravimetric and single-crystal X-ray diffraction analysis. X-ray crystallographic studies reveal that 1 features a discrete 0D coordination compound, while 2 and 3 exhibit the 2D network and 1D chain structures, respectively. Compound 2 is constructed from {LCu}2 dimers connected with {Sr2} units, which is fabricated by two Sr2+ ions bridged via two μ2-O bridges, while compound 3 is formed by 1D {Ba}n chain linked with metalloligands LCu and exhibits an interesting sandwich like chain structure. It is noted that the coordination numbers of alkaline-earth ions are in positive correlation with their radiuses. Moreover, the magnetic property of compound 2 has been studied.

  3. Modelling oxygen isotopes in the University of Victoria Earth System Climate Model

    Directory of Open Access Journals (Sweden)

    C. E. Brennan

    2011-09-01

    Full Text Available Implementing oxygen isotopes (H218O, H216O in coupled climate models provides both an important test of the individual model's hydrological cycle, and a powerful tool to mechanistically explore past climate changes while producing results directly comparable to isotope proxy records. Here we describe the addition of oxygen isotopes in the University of Victoria Earth System Climate Model (UVic ESCM. Equilibrium simulations are performed for preindustrial and Last Glacial Maximum conditions. The oxygen isotope content in the model preindustrial climate is compared against observations for precipitation and seawater. The distribution of oxygen isotopes during the LGM is compared against available paleo-reconstructions.

  4. Dipole Polarizability of Alkali-Metal (Na, K, Rb) - Alkaline-Earth-Metal (Ca,Sr) Polar molecules - Prospects of Alignment

    CERN Document Server

    Gopakumar, Geetha; Hada, Masahiko; Kajita, Masatoshi

    2014-01-01

    Electronic open-shell ground-state properties of selected alkali-metal (AM) - alkaline-earth-metal (AEM) polar molecules are investigated. We determine potential energy curves of the 2{\\Sigma}+ ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes (23Na, 39K, 85Rb) - (40Ca, 88Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  5. Geochemistry, geochronology and zircon Hf isotopic study of peralkaline-alkaline intrusions along the northern margin of the North China Craton and its tectonic implication for the southeastern Central Asian Orogenic Belt

    Science.gov (United States)

    Zhao, Pan; Jahn, Bor-ming; Xu, Bei; Liao, Wen; Wang, Yanyang

    2016-09-01

    A giant Permian alkaline magmatic belt has recently been identified in southern Inner Mongolia, along the northern margin of the North China Craton (NCC). This belt is mainly composed of syenite, quartz syenite, alkaline granite and mafic microgranular enclaves (MME)-bearing granodiorite. In order to study the petrogenesis and tectonic implications of these rocks, we undertook zircon U-Pb dating and geochemical analysis of two Permian alkaline plutons. The first Guangxingyuan Pluton occurs in the Hexigten area and is composed of MME-bearing tonalite, K-feldspar granite and syenite. The second Durenwuliji Pluton, located in the Xianghuangqi area, comprises syenite, quartz syenite and K-feldspar granite. Zircon U-Pb dating on tonalite, K-feldspar granite, syenite and quartz syenite from the two plutons yielded a tight range of ages from 259 to 267 Ma. The peralkaline-alkaline rocks show high abundance of total alkalis (K2O + Na2O = 7.9-12.9%) and K2O contents (3.9-8.0%), enrichment in large ion lithophile elements (LILE) and light rare earth element (LREE), and depletion of high field strength elements (HFSE). The associated tonalite and MMEs display I-type granitic geochemical affinity, with less total abundance of trace elements than the peralkaline-alkaline rocks. Zircon Hf isotopic analysis of the Guangxingyuan pluton yielded a large range of εHf(t) values from - 15.5 to + 6.7 and model ages (TDMC) from 781 to 2012 Ma. By contrast, the Hf isotopic data of the Durenwuliji pluton shows a small range of εHf(t) from + 6.2 to + 8.9 and TDMC from 667 to 816 Ma. The geochemical and Hf isotopic characteristics indicate that the parental magma was derived from a mixing of metasomatic mantle-derived mafic magma with different amount of crust-derived felsic magma, and followed by fractional crystallization. Considering previous tectonic studies in Inner Mongolia, a Permian post-orogenic extension was proposed to account for these peralkaline-alkaline intrusions following

  6. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

    Science.gov (United States)

    Chen, Heng; Savage, Paul S.; Teng, Fang-Zehn; Helz, Rosalind T.; Moynier, Frédéric

    2013-01-01

    he zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰66Zn66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe–Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰66Zn66Zn=0.28±0.05‰ (2s.d.).

  7. Colorimetric and bare-eye detection of alkaline earth metal ions based on the aggregation of silver nanoparticles functionalized with thioglycolic acid

    International Nuclear Information System (INIS)

    We describe a simple and rapid method for colorimetric and bare-eye detection of the alkaline earth metal ions Mg(II), Ca(II), Sr(II) and Ba(II) based on the use of silver nanoparticles (AgNPs) functionalized with thioglycolic acid (TGA). The TGA ligand was self-assembled onto the AgNPs to form a probe that undergoes a color change from yellow to orange or red on exposure to the alkaline earth ions. It is presumed that the color change is a result of the aggregation of the AgNPs caused by the interaction of the bivalent ions with the carboxy groups on the AgNPs. The color change can be used for bare-eye and colorimetric determination of the alkaline earth metal ions, for example to rapidly determine water hardness. (author)

  8. Dispersion coefficients for the interaction of inert gas atoms with alkali and alkaline earth ions and alkali atoms with their singly ionized ions

    CERN Document Server

    Singh, Sukhjit; Sahoo, B K; Arora, Bindiya

    2016-01-01

    We report the dispersion coefficients for the interacting inert gas atoms with the alkali ions, alkaline earth ions and alkali atoms with their singly charged ions. We use our relativistic coupled-cluster method to determine dynamic dipole and quadrupole polarizabilities of the alkali atoms and singly ionized alkaline earth atoms, whereas a relativistic random phase approximation approach has been adopted to evaluate these quantities for the closed-shell configured inert gas atoms and the singly and doubly ionized alkali and alkaline earth atoms, respectively. Accuracies of these results are adjudged from the comparison of their static polarizability values with their respective experimental results. These polarizabilities are further compared with the other theoretical results. Reason for the improvement in the accuracies of our estimated dispersion coefficients than the data listed in [At. Data and Nucl. Data Tables 101, 58 (2015)] are discussed. Results for some of the atom-ion interacting systems were not...

  9. Abnormal composition of carbon isotopes in underground alkaline waters of Kuzbass

    Science.gov (United States)

    Shvartsev, S. L.; Lepokurova, O. E.; Ponomarchuk, V. A.; Domrocheva, E. V.; Sizikov, D. A.

    2016-08-01

    The first data on abnormally high δ13C values in hydrocarbonates (HCO 3 - ) dissolved in underground waters of coal deposits of Kuzbass (up to +30.9‰) are reported. It is shown that such an unusual isotope composition of waters results from the long, strictly directed interaction in the water-rock-gas-organic material system occurring under the conditions of hindered water exchange. Extensive fractionation of C isotopes is the result of the evolution of the water-rock-gas-coal system after penetration of infiltration waters into the coal deposits and their long interaction with all these components, rather than metamorphism of organic material upon its transformation into coal. With respect to such an approach, the isotope composition of dissolved C may indicate the duration of the evolution in the water-rock-gas-organic material system.

  10. Titanium stable isotope investigation of magmatic processes on the Earth and Moon

    Science.gov (United States)

    Millet, Marc-Alban; Dauphas, Nicolas; Greber, Nicolas D.; Burton, Kevin W.; Dale, Chris W.; Debret, Baptiste; Macpherson, Colin G.; Nowell, Geoffrey M.; Williams, Helen M.

    2016-09-01

    We present titanium stable isotope measurements of terrestrial magmatic samples and lunar mare basalts with the aims of constraining the composition of the lunar and terrestrial mantles and evaluating the potential of Ti stable isotopes for understanding magmatic processes. Relative to the OL-Ti isotope standard, the δ49Ti values of terrestrial samples vary from -0.05 to +0.55‰, whereas those of lunar mare basalts vary from -0.01 to +0.03‰ (the precisions of the double spike Ti isotope measurements are ca. ±0.02‰ at 95% confidence). The Ti stable isotope compositions of differentiated terrestrial magmas define a well-defined positive correlation with SiO2 content, which appears to result from the fractional crystallisation of Ti-bearing oxides with an inferred isotope fractionation factor of ΔTi49oxide-melt = - 0.23 ‰ ×106 /T2. Primitive terrestrial basalts show no resolvable Ti isotope variations and display similar values to mantle-derived samples (peridotite and serpentinites), indicating that partial melting does not fractionate Ti stable isotopes and that the Earth's mantle has a homogeneous δ49Ti composition of +0.005 ± 0.005 (95% c.i., n = 29). Eclogites also display similar Ti stable isotope compositions, suggesting that Ti is immobile during dehydration of subducted oceanic lithosphere. Lunar basalts have variable δ49Ti values; low-Ti mare basalts have δ49Ti values similar to that of the bulk silicate Earth (BSE) while high-Ti lunar basalts display small enrichment in the heavy Ti isotopes. This is best interpreted in terms of source heterogeneity resulting from Ti stable isotope fractionation associated with ilmenite-melt equilibrium during the generation of the mantle source of high-Ti lunar mare basalts. The similarity in δ49Ti between terrestrial samples and low-Ti lunar basalts provides strong evidence that the Earth and Moon have identical stable Ti isotope compositions.

  11. Isotopic evidence for internal oxidation of the Earth's mantle during accretion

    Science.gov (United States)

    Williams, Helen M.; Wood, Bernard J.; Wade, Jon; Frost, Daniel J.; Tuff, James

    2012-03-01

    The Earth's mantle is currently oxidised and out of chemical equilibrium with the core. The reasons for this and for the relatively oxidised state of Earth's mantle relative to the mantles of other terrestrial planets are unclear. It has been proposed that the oxidised nature and high ferric iron (Fe3 +) content of Earth's mantle was produced internally by disproportionation of ferrous iron (Fe2 +) into Fe3 + and metallic iron by perovskite crystallisation during accretion. Here we show that there is substantial Fe isotope fractionation between experimentally equilibrated metal and Fe3 +-bearing perovskite (≥ 0.45‰/amu), which can account for the heavy Fe isotope compositions of terrestrial basalts relative to equivalent samples derived from Mars and Vesta as the latter bodies are too small to stabilise significant perovskite. Mass balance calculations indicate that all of the mantle's Fe3 + could readily have been generated from a single disproportionation event, consistent with dissolution of perovskite in the lower mantle during a process such as the Moon-forming giant impact. The similar Fe isotope compositions of primitive terrestrial and low-titanium lunar basalts is consistent with models of equilibration between the mantles of the Earth and Moon in the aftermath of the giant impact and suggests that the heavy Fe isotope composition of the Earth's mantle was established prior to, or during the giant impact. The oxidation state and ferric iron content of the Earth's mantle was therefore plausibly set by the end of accretion, and may be decoupled from later volatile additions and the rise of oxygen in the Earth's atmosphere at 2.45 Ga.

  12. Activation analysis and isotope dilution applied to the determination of rare earth elements in ytrium oxides

    International Nuclear Information System (INIS)

    A method for determining rare earth elements from matrix constituted by sample of ytrium oxide is shown. Ion exchange technique and electron with chelating agent have been chosen for chemical separations. The method consists of using isotope dilution followed by activation analysis in order to determine the amounts of the elements

  13. Modifying the size and uniformity of upconversion Yb/Er:NaGdF4 nanocrystals through alkaline-earth doping.

    Science.gov (United States)

    Lei, Lei; Chen, Daqin; Huang, Ping; Xu, Ju; Zhang, Rui; Wang, Yuansheng

    2013-11-21

    NaGdF4 is regarded as an ideal upconversion (UC) host material for lanthanide (Ln(3+)) activators because of its unique crystal structure, high Ln(3+) solubility, low phonon energy and high photochemical stability, and Ln(3+)-doped NaGdF4 UC nanocrystals (NCs) have been widely investigated as bio-imaging and magnetic resonance imaging agents recently. To realize their practical applications, controlling the size and uniformity of the monodisperse Ln(3+)-doped NaGdF4 UC NCs is highly desired. Unlike the routine routes by finely adjusting the multiple experimental parameters, herein we provide a facile and straightforward strategy to modify the size and uniformity of NaGdF4 NCs via alkaline-earth doping for the first time. With the increase of alkaline-earth doping content, the size of NaGdF4 NCs increases gradually, while the size-uniformity is still retained. We attribute this "focusing" of size distribution to the diffusion controlled growth of NaGdF4 NCs induced by alkaline-earth doping. Importantly, adopting the Ca(2+)-doped Yb/Er:NaGdF4 NCs as cores, the complete Ca/Yb/Er:NaGdF4@NaYF4 core-shell particles with excellent size-uniformity can be easily achieved. However, when taking the Yb/Er:NaGdF4 NCs without Ca(2+) doping as cores, they could not be perfectly covered by NaYF4 shells, and the obtained products are non-uniform in size. As a result, the UC emission intensity of the complete core-shell NCs increases by about 30 times in comparison with that of the cores, owing to the effective surface passivation of the Ca(2+)-doped cores and therefore protection of Er(3+) in the cores from the non-radiative decay caused by surface defects, whereas the UC intensity of the incomplete core-shell NCs is enhanced by only 3 times. PMID:24096887

  14. Alkaline earth lead and tin compounds Ae2Pb, Ae2Sn, Ae = Ca, Sr, Ba, as thermoelectric materials

    Directory of Open Access Journals (Sweden)

    David Parker and David J Singh

    2013-01-01

    Full Text Available We present a detailed theoretical study of three alkaline earth compounds Ca2Pb, Sr2Pb and Ba2Pb, which have undergone little previous study, calculating electronic band structures and Boltzmann transport and bulk moduli using density functional theory. We also study the corresponding tin compounds Ca2Sn, Sr2Sn and Ba2Sn. We find that these are all narrow band gap semiconductors with an electronic structure favorable for thermoelectric performance, with substantial thermopowers for the lead compounds at temperature ranges from 300 to 800 K. For the lead compounds, we further find very low calculated bulk moduli—roughly half of the values for the lead chalcogenides, suggestive of soft phonons and hence low lattice thermal conductivity. All these facts indicate that these materials merit experimental investigation as potential high performance thermoelectrics. We find good potential for thermoelectric performance in the environmentally friendly stannide materials, particularly at high temperature.

  15. Two-band superfluidity and intrinsic Josephson effect in alkaline-earth-metal Fermi gases across an orbital Feshbach resonance

    Science.gov (United States)

    Iskin, M.

    2016-07-01

    We first show that the many-body Hamiltonian governing the physical properties of an alkaline-earth 173Yb Fermi gas across the recently realized orbital Feshbach resonance is exactly analogous to that of two-band s -wave superconductors with contact interactions; i.e., even though the free-particle bands have a tunable energy offset in between and are coupled by a Josephson-type attractive interband pair scattering, the intraband interactions have exactly the same strength. We then introduce two intraband order parameters within the BCS mean-field approximation and investigate the competition between their in-phase and out-of-phase (i.e., the so-called π -phase) solutions in the entire BCS-BEC evolution at zero temperature.

  16. Quantum mechanical study of molecular collisions at ultra-low energy: applications to alkali and alkaline-earth systems

    International Nuclear Information System (INIS)

    In order to investigate the collisional processes which occur during the formation of molecular Bose-Einstein condensates, a time-independent quantum mechanical formalism, based on hyperspherical coordinates, has been applied to the study of atom-diatom dynamics at ultra-low energies. We present theoretical results for three alkali systems, each composed of lithium, sodium or potassium atoms, and for an alkaline-earth system composed of calcium atoms. We also study dynamics at large and positive atom-atom scattering length. Evidence for the suppression of inelastic processes in a fermionic system is given, as well as a linear relation between the atom-diatom scattering length and the atom-atom scattering length. (author)

  17. Optical Feshbach resonances of Alkaline-Earth atoms in a 1D or 2D optical lattice

    CERN Document Server

    Naidon, P; Julienne, Paul S.; Naidon, Pascal

    2006-01-01

    Motivated by a recent experiment by Zelevinsky et al. [Phys. Rev. Lett. 96, 203201], we present the theory for photoassociation and optical Feshbach resonances of atoms confined in a tight one-dimensional (1D) or two-dimensional (2D) optical lattice. In the case of an alkaline-earth intercombination resonance, the narrow natural width of the line makes it possible to observe clear manifestations of the dimensionality, as well as some sensitivity to the scattering length of the atoms. Among possible applications, a 2D lattice may be used to increase the spectroscopic resolution by about one order of magnitude. Furthermore, a 1D lattice induces a shift which provides a new way of determining the strength of a resonance by spectroscopic measurements.

  18. Electric dipole polarizabilities of doubly ionized alkaline Earth metal ions from perturbed relativistic coupled-cluster theory

    CERN Document Server

    Chattopadhyay, S; Angom, D

    2013-01-01

    Using perturbed relativistic coupled-cluster (PRCC) theory we compute the ground state electric dipole polarizability, $\\alpha$, of doubly ionized alkaline earth metal ions $\\rm{Mg}^{2+}$, $\\rm{Ca}^{2+}$, $\\rm{Sr}^{2+}$, $\\rm{Ba}^{2+}$ and $\\rm{Ra}^{2+}$. In the present work we use the Dirac-Coulomb-Breit atomic Hamiltonian and we also include the Uehling potential, which is the leading order term in the vacuum polarization corrections. We examine the correction to the orbital energies arising from the Uehling potential in the self-consistent field calculations as well as perturbatively. Our results of $\\alpha$ are in very good agreement with the experimental data, and we observe a change in the nature of the orbital energy corrections arising from the vacuum polarization as we go from $\\rm{Mg}^{2+}$ to Ra$^{2+}$.

  19. Main group chemistry of 9-hydroxophenalenone: Syntheses and structural characterization of the alkaline earth and zinc complexes

    Indian Academy of Sciences (India)

    Arup Mukherjee; Prinson P Samuel; Carola Schulzke; Swadhin K Mandal

    2014-09-01

    Herein, we report the synthesis and characterization of 9-hydroxophenalenone based alkaline earth and zinc complexes.The reaction of 9-hydroxophenalenone (HO,O-PLY (1)) with one equivalent of KN(SiMe3)2 and MI2 in THF yields heteroleptic complexes [(O,O-PLY)M(THF)]I [M= Mg (2), Ca (3), Sr (4), Ba (5); n = 1-4], while use of two equivalents of KN(SiMe3)2 in THF (with respect to PLY) produces homoleptic complex (O,O-PLY)2Mg(THF)2 (6). Moreover, reaction between two equivalents of 1 with one equivalent of ZnMe2 in THF produces complex (O,O-PLY)2Zn(THF)2 (7). All these complexes were characterized by NMR spectroscopy and elemental analyses. The solid state structures of complexes 2, 6 and 7 were established by single crystal X-ray diffraction analysis.

  20. Frontier Orbital Engineering of Metal-Organic Frameworks with Extended Inorganic Connectivity: Porous Alkaline-Earth Oxides.

    Science.gov (United States)

    Hendon, Christopher H; Walsh, Aron; Dincă, Mircea

    2016-08-01

    The development of conductive metal-organic frameworks is challenging owing to poor electronic communication between metal clusters and the organic ligands that bridge them. One route to overcoming this bottleneck is to extend the inorganic dimensionality, while using the organic components to provide chemical functionality. Using density functional theory methods, we demonstrate how the properties of the alkaline-earth oxides SrO and BaO are transformed upon formation of porous solids with organic oxygen sources (acetate and trifluoroacetate). The electron affinity is significantly enhanced in the hybrid materials, while the ionization potential can be tuned over a large range with the polarity of the organic moiety. Furthermore, because of their high-vacuum fraction, these materials have dielectric properties suitable for low-κ applications. PMID:27267149

  1. Influence of alkali and alkaline earth elements on the uptake of radionuclides by Pleurototus eryngii fruit bodies

    Energy Technology Data Exchange (ETDEWEB)

    Guillen, J., E-mail: fguillen@unex.es [LARUEX, Dpt. Applied Physics, Faculty of Veterinary Science, University of Extremadura, Avda. Universidad, s/n, 10071 Caceres (Spain); Baeza, A.; Salas, A. [LARUEX, Dpt. Applied Physics, Faculty of Veterinary Science, University of Extremadura, Avda. Universidad, s/n, 10071 Caceres (Spain)

    2012-04-15

    In the literature, there are many data available on radionuclide contents and their transfer to different species of mushrooms. There are some variables, however, which affect the transfer but are very difficult to observe in collected wild mushrooms. An example is the effect of different concentrations of alkali and alkaline earth elements in the soil. Modification of these concentrations in the soil solution has traditionally been used as a countermeasure to deal with radioactively contaminated areas. In the present work, fruiting bodies of Pleurotus eryngii, a saprophytic mushroom, were grown under controlled laboratory conditions, varying the content of alkali (potassium and caesium) and alkaline earth (calcium and strontium) elements. The transfer of {sup 134}Cs, {sup 85}Sr, and {sup 60}Co (added to the cultures) and of natural {sup 210}Pb was analysed by increasing the content of each stable element considered. A significant, but nonlinear, enhancement of stable caesium and {sup 134}Cs was observed with increasing content of stable caesium in the substrate/mycelium. The transfer of {sup 85}Sr decreased with the addition of each stable cation, whereas the {sup 60}Co and {sup 210}Pb transfers were unaffected. - Highlights: Black-Right-Pointing-Pointer The addition of stable potassium did not affect the uptake of radiocaesium. Black-Right-Pointing-Pointer The addition of stable caesium increased the stable caesium and {sup 134}Cs content in the fruiting bodies of Pleurotus eryngii. Black-Right-Pointing-Pointer The addition of calcium reduced the content of calcium and {sup 85}Sr in the fruiting bodies. Black-Right-Pointing-Pointer These countermeasures did not work properly in the case of {sup 60}Co and {sup 210}Pb, no effect was observed.

  2. Characterization of alkaline-earth oxide additions to the MnO2 cathode in an aqueous secondary battery

    International Nuclear Information System (INIS)

    Highlights: → Adding MgO in MnO2 cathode enhances the battery discharge capacity. → Mechanism appears to be different with those of our previously published results. → Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. → Transferred the primary battery into a secondary while using LiOH as electrolyte. - Abstract: The effect of alkaline-earth oxide additions on aqueous rechargeable battery is investigated using microscopic and spectroscopic techniques. The alkaline-earth oxide additions such as magnesium oxide (MgO) and barium oxide (BaO) were physically mixed to the manganese dioxide (MnO2) cathode of a cell comprising zinc as an anode and aqueous lithium hydroxide as the electrolyte. The results showed that such additions greatly improved the discharge capacity of the battery (from 145 to 195 for MgO and 265 mAh/g for BaO). Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. With an aim to understand the role of these additives and its improvement in cell performance, we have used microscopy, spectroscopy, ion beam analysis and diffraction based techniques to study the process. Transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy analysis (EDS) results showed evidence of crystalline MnO2 particles for MgO as additive, whereas, MnO2 particles with diffused structure leading to mixture of phases is observed for BaO additives which is in agreement with X-ray diffraction (XRD) data. This work relates to improvement in the electrochemical behaviour of the Zn-MnO2 battery while the MgO additive helps to reduce the formation of manganese and zinc such as hetaerolite that hinders the lithium intercalation.

  3. Characterization of alkaline-earth oxide additions to the MnO{sub 2} cathode in an aqueous secondary battery

    Energy Technology Data Exchange (ETDEWEB)

    Minakshi, Manickam, E-mail: minakshi@murdoch.edu.au [Extractive Metallurgy, Murdoch University, Murdoch, WA 6150 (Australia); Blackford, Mark [Institute of Materials Engineering, ANSTO, Lucas Heights, NSW 2234 (Australia); Ionescu, Mihail [Institute for Environment Research, ANSTO, Lucas Heights, NSW 2234 (Australia)

    2011-05-19

    Highlights: > Adding MgO in MnO{sub 2} cathode enhances the battery discharge capacity. > Mechanism appears to be different with those of our previously published results. > Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. > Transferred the primary battery into a secondary while using LiOH as electrolyte. - Abstract: The effect of alkaline-earth oxide additions on aqueous rechargeable battery is investigated using microscopic and spectroscopic techniques. The alkaline-earth oxide additions such as magnesium oxide (MgO) and barium oxide (BaO) were physically mixed to the manganese dioxide (MnO{sub 2}) cathode of a cell comprising zinc as an anode and aqueous lithium hydroxide as the electrolyte. The results showed that such additions greatly improved the discharge capacity of the battery (from 145 to 195 for MgO and 265 mAh/g for BaO). Capacity fade with subsequent cycling is reduced only for MgO but not for BaO. With an aim to understand the role of these additives and its improvement in cell performance, we have used microscopy, spectroscopy, ion beam analysis and diffraction based techniques to study the process. Transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy analysis (EDS) results showed evidence of crystalline MnO{sub 2} particles for MgO as additive, whereas, MnO{sub 2} particles with diffused structure leading to mixture of phases is observed for BaO additives which is in agreement with X-ray diffraction (XRD) data. This work relates to improvement in the electrochemical behaviour of the Zn-MnO{sub 2} battery while the MgO additive helps to reduce the formation of manganese and zinc such as hetaerolite that hinders the lithium intercalation.

  4. Decay studies of neutron deficient rare earth isotopes with OASIS

    International Nuclear Information System (INIS)

    We report results on the decay of 124Pr, /sup 124,125/Ce, /sup 124,125/La, /sup 134-136/Eu, /sup 134-136/Sm, /sup 134-136/Pm, 144Ho, /sup 141,142,144/Dy, /sup 140,141,142,144/Tb, /sup 140-142/Gd, and /sup 140-142/Eu, produced by 92Mo(H.I.,xpyn) reactions at the Berkeley SuperHILAC, and studied with the OASIS on-line mass separator facility. Half-lives, delayed proton branching ratios, γ-ray energies and intensities, partial decay schemes and several J/sup π/ assignments are presented. Level systematics of the even mass Nd and Sm isotopes and of the nu h/sub 11/2/ - nu s/sub 1/2/ isomers for N = 77 are discussed

  5. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1

    Directory of Open Access Journals (Sweden)

    A. Jahn

    2015-08-01

    Full Text Available Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM, containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air–sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

  6. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1)

    Science.gov (United States)

    Jahn, A.; Lindsay, K.; Giraud, X.; Gruber, N.; Otto-Bliesner, B. L.; Liu, Z.; Brady, E. C.

    2015-08-01

    Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air-sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

  7. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1

    Directory of Open Access Journals (Sweden)

    A. Jahn

    2014-11-01

    Full Text Available Carbon isotopes in the ocean are frequently used as paleo climate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized dataset, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM, containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air–sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly less computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example a too sluggish ventilation of the deep Pacific Ocean.

  8. Effects of alternating current imposition and alkaline earth elements on modification of primary Mg_2Si crystals in hypereutectic Mg-Si alloy

    Institute of Scientific and Technical Information of China (English)

    DU Jun; K. IWAI; LI Wen-fang; PENG Ji-hua

    2009-01-01

    The effects of alternating current imposition and/or alkaline earth elements on modification of the primary Mg_2Si crystals in the hypereutectic Mg-Si alloy were investigated. An alternating current of 60 A with frequency of 1 kHz was applied into the hypereutectic Mg-Si melt which was alloyed with alkaline earth elements or not in the fixed temperature range from 700 to 630 ℃. The results show that the primary Mg_2Si crystals could be refined by imposing alternating current or adding alkaline elements. Compared with the samples treated by adding 0.4% Ca or 0.4% Sr, higher modification efficiency could be obtained for the samples treated by imposing alternating current. No further modification efficiency could be obtained for the samples treated by imposing alternating current combined with 0.4% Ca or 0.4% Sr addition.

  9. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts

    Science.gov (United States)

    Rizo, Hanika; Walker, Richard J.; Carlson, Richard W.; Horan, Mary F.; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G.

    2016-05-01

    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth’s primary accretionary period have survived to the present.

  10. Design of a novel optically stimulated luminescent dosimeter using alkaline earth sulfides doped with SrS:Eu,Sm materials

    Institute of Scientific and Technical Information of China (English)

    Yanping Liu; Zhaoyang Chen; Yanwei Fan; Weizhen Ba; Wu Lu; Qi Guo; Shilie Pan; Aimin Chang; Xinqiang Tang

    2008-01-01

    Optically stimulated luminescence (OSL) is the luminescence emitted from an irradiated insulator or semiconductor during exposure to light.The OSL intensity is a function of the dose of radiation absorbed by the sample and thus can be used as the basis of a radiation dosimetry method.Alkaline earth sulfides doped with rare-earth elements such as Ce,Sm and Eu are OSL dosimeters having very high sensitivity,and the OSL with a short time constant is separated from the stimulated light.In this paper,a novel OSL dosimeter designed with SrS:Eu,Sm materials is described.The dosimeter takes advantage of the characteristics of charge trapping materials SrS:Eu,Sm that exhibit OSL.The measuring range of the dosimeter is from 0.01 to 100Gy.The equipment,which is relatively simple and small in size,is promising for applications in space exploration and high dose radiation dosimetry.

  11. Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

    Science.gov (United States)

    Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

    2016-08-01

    The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Bacontaining copper dopants.

  12. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids%有机磷(膦)酸对碱土金属的萃取

    Institute of Scientific and Technical Information of China (English)

    许新; 朱屯

    2002-01-01

    Solvent extraction equilibria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester,di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent on the e/r value and hydration energy of the metal ions. The minor shift of the P-O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P-O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compounds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effect is explained by using IR spectra of the loaded organic phase.

  13. Synthesis of a new family of ionophores based on aluminum-dipyrrin complexes (ALDIPYs) and their strong recognition of alkaline earth ions.

    Science.gov (United States)

    Saikawa, Makoto; Daicho, Manami; Nakamura, Takashi; Uchida, Junji; Yamamura, Masaki; Nabeshima, Tatsuya

    2016-03-14

    Mononuclear and dinuclear aluminum-dipyrrin complexes (ALDIPYs) were synthesized as a new family of ionophores. They exhibited colorimetric and fluorometric responses to alkaline earth ions in an aqueous mixed solvent. The strong recognition was achieved via multipoint interactions with the oxygen atoms appropriately incorporated into the ligand framework. PMID:26935409

  14. Petrographic, geochemical and isotopic evidence of crustal assimilation processes in the Ponte Nova alkaline mafic-ultramafic massif, SE Brazil

    Science.gov (United States)

    Azzone, Rogério Guitarrari; Montecinos Munoz, Patricio; Enrich, Gaston Eduardo Rojas; Alves, Adriana; Ruberti, Excelso; Gomes, Celsode Barros

    2016-09-01

    Crustal assimilation plus crystal fractionation processes of different basanite magma batches control the evolution of the Ponte Nova cretaceous alkaline mafic-ultramafic massif in SE Brazil. This massif is composed of several intrusions, the main ones with a cumulate character. Disequilibrium features in the early-crystallized phases (e.g., corrosion and sieve textures in cores of clinopyroxene crystals, spongy-cellular-textured plagioclase crystals, gulf corrosion texture in olivine crystals) and classical hybridization textures (e.g., blade biotite and acicular apatite crystals) provide strong evidence of open-system behavior. All samples are olivine- and nepheline-normative rocks with basic-ultrabasic and potassic characters and variable incompatible element enrichments. The wide ranges of whole-rock 87Sr/86Sri and 143Nd/144Ndi ratios (0.70432-0.70641 and 0.512216-0.512555, respectively) are indicative of crustal contribution from the Precambrian basement host rocks. Plagioclase and apatite 87Sr/86Sr ratios (0.70422-0.70927) obtained for the most primitive samples of each intrusion indicate disequilibrium conditions from early- to principal-crystallization stages. Isotope mixing-model curves between the least contaminated alkaline basic magma and heterogeneous local crustal components indicate that each intrusion of the massif is differentiated from the others by varied degrees of crustal contribution. The primary mechanisms of crustal contribution to the Ponte Nova massif involve the assimilation of host rock xenoliths during the development of the chamber environment and the assimilation of partial melts from the surrounding host rocks. Thermodynamic models using the melts algorithm indicate that parental alkaline basic magmas can be strongly affected by contamination processes subsequently to their initial stages of crystallization when there is sufficient energy to assimilate partial melts of crustal host rocks. The assimilation processes are considered to

  15. EVALUATION OF RADIOLOGICAL SIGNIFICANCE OF RARE-EARTH METALS WITH NATURAL RADIOACTIVE ISOTOPES

    OpenAIRE

    E. P. Lisachenko

    2013-01-01

    Among the rare-earth metals with natural radioactive isotopes, lantan, lutetium and samarium are allocated a relatively high specific activity. The formation of the additional external radiation keep it close to the significance of the materials to the radiation categories of materials with a high content of natural radionuclides of uranium and thorium family, lanthanum value is much less. Samarium, with acceptable toxicology content in the working area, forms the internal exposure to the lim...

  16. Re-Os geochronology and coupled Os-Sr isotope constraints on the Sturtian snowball Earth.

    Science.gov (United States)

    Rooney, Alan D; Macdonald, Francis A; Strauss, Justin V; Dudás, Francis Ö; Hallmann, Christian; Selby, David

    2014-01-01

    After nearly a billion years with no evidence for glaciation, ice advanced to equatorial latitudes at least twice between 717 and 635 Mya. Although the initiation mechanism of these Neoproterozoic Snowball Earth events has remained a mystery, the broad synchronicity of rifting of the supercontinent Rodinia, the emplacement of large igneous provinces at low latitude, and the onset of the Sturtian glaciation has suggested a tectonic forcing. We present unique Re-Os geochronology and high-resolution Os and Sr isotope profiles bracketing Sturtian-age glacial deposits of the Rapitan Group in northwest Canada. Coupled with existing U-Pb dates, the postglacial Re-Os date of 662.4 ± 3.9 Mya represents direct geochronological constraints for both the onset and demise of a Cryogenian glaciation from the same continental margin and suggests a 55-My duration of the Sturtian glacial epoch. The Os and Sr isotope data allow us to assess the relative weathering input of old radiogenic crust and more juvenile, mantle-derived substrate. The preglacial isotopic signals are consistent with an enhanced contribution of juvenile material to the oceans and glacial initiation through enhanced global weatherability. In contrast, postglacial strata feature radiogenic Os and Sr isotope compositions indicative of extensive glacial scouring of the continents and intense silicate weathering in a post-Snowball Earth hothouse.

  17. Stable isotope labeling confirms mixotrophic nature of streamer biofilm communities at alkaline hot springs

    Directory of Open Access Journals (Sweden)

    Florence eSchubotz

    2015-02-01

    Full Text Available Streamer biofilm communities (SBC are often observed within chemosynthetic zones of Yellowstone hot spring outflow channels, where temperatures exceed those conducive to photosynthesis. Nearest the hydrothermal source (75-88°C SBC comprise thermophilic Archaea and Bacteria, often mixed communities including Desulfurococcales and uncultured Crenarchaeota, as well as Aquificae, Thermus, each carrying diagnostic membrane lipid biomarkers. We tested the hypothesis that SBC can alternate their metabolism between autotrophy and heterotrophy depending on substrate availability. Feeding experiments were performed at two alkaline hot springs in Yellowstone National Park: Octopus Spring and ‘Bison Pool’, using various 13C-labeled substrates (bicarbonate, formate, acetate and glucose to determine the relative uptake of these different carbon sources. Highest 13C uptake, at both sites, was from acetate into almost all bacterial fatty acids, particularly into methyl-branched C15, C17 and C19 fatty acids that are diagnostic for Thermus/Meiothermus and some Firmicutes as well as into universally common C16:0 and C18:0 fatty acids. 13C-glucose showed a similar, but a 10 to 30 times lower uptake across most fatty acids. 13C bicarbonate uptake, signifying the presence of autotrophic communities was only significant at ‘Bison Pool’ and was observed predominantly in non-specific saturated C16, C18, C20 and C22 fatty acids. Incorporation of 13C-formate occurred only at very low rates at ‘Bison Pool’ and was almost undetectable at Octopus Spring, suggesting that formate is not an important carbon source for SBC. 13C uptake into archaeal lipids occurred predominantly with 13C acetate, suggesting also that archaeal communities at both springs have primarily heterotrophic carbon assimilation pathways. We hypothesize that these communities are energy-limited and predominantly nurtured by input of exogenous organic material, with only a small fraction being

  18. Stable isotope labeling confirms mixotrophic nature of streamer biofilm communities at alkaline hot springs.

    Science.gov (United States)

    Schubotz, Florence; Hays, Lindsay E; Meyer-Dombard, D'Arcy R; Gillespie, Aimee; Shock, Everett L; Summons, Roger E

    2015-01-01

    Streamer biofilm communities (SBC) are often observed within chemosynthetic zones of Yellowstone hot spring outflow channels, where temperatures exceed those conducive to photosynthesis. Nearest the hydrothermal source (75-88°C) SBC comprise thermophilic Archaea and Bacteria, often mixed communities including Desulfurococcales and uncultured Crenarchaeota, as well as Aquificae and Thermus, each carrying diagnostic membrane lipid biomarkers. We tested the hypothesis that SBC can alternate their metabolism between autotrophy and heterotrophy depending on substrate availability. Feeding experiments were performed at two alkaline hot springs in Yellowstone National Park: Octopus Spring and "Bison Pool," using various (13)C-labeled substrates (bicarbonate, formate, acetate, and glucose) to determine the relative uptake of these different carbon sources. Highest (13)C uptake, at both sites, was from acetate into almost all bacterial fatty acids, particularly into methyl-branched C15, C17 and C19 fatty acids that are diagnostic for Thermus/Meiothermus, and some Firmicutes as well as into universally common C16:0 and C18:0 fatty acids. (13)C-glucose showed a similar, but a 10-30 times lower uptake across most fatty acids. (13)C-bicarbonate uptake, signifying the presence of autotrophic communities was only significant at "Bison Pool" and was observed predominantly in non-specific saturated C16, C18, C20, and C22 fatty acids. Incorporation of (13)C-formate occurred only at very low rates at "Bison Pool" and was almost undetectable at Octopus Spring, suggesting that formate is not an important carbon source for SBC. (13)C-uptake into archaeal lipids occurred predominantly with (13)C-acetate, suggesting also that archaeal communities at both springs have primarily heterotrophic carbon assimilation pathways. We hypothesize that these communities are energy-limited and predominantly nurtured by input of exogenous organic material, with only a small fraction being sustained by

  19. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

    Science.gov (United States)

    Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I. F.; Nogueira, Afonso C. R.; Agrinier, Pierre; Ader, Magali

    2016-07-01

    The terminal Neoproterozoic Era (850-542 Ma) is characterized by the most pronounced positive sulfur isotope (34S/32S) excursions in Earth's history, with strong variability and maximum values averaging δ34S~+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33S/32S, 34S/32S and 36S/32S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere.

  20. Isotopic constraints on the age and early differentiation of the Earth.

    Science.gov (United States)

    McCulloch, M T

    1996-03-01

    The Earth's age and early differentiation history are re-evaluated using updated isotopic constraints. From the most primitive terrestrial Pb isotopic compositions found at Isua Greenland, and the Pilbara of Western Australia, combined with precise geochronology of these localities, an age 4.49 +/- 0.02 Ga is obtained. This is interpreted as the mean age of core formation as U/Pb is fractionated due to sequestering of Pb into the Earth's core. The long-lived Rb-Sr isotopic system provides constraints on the time interval for the accretion of the Earth as Rb underwent significant depletion by volatile loss during accretion of the Earth or its precursor planetesimals. A primitive measured 87Sr/86Sr initial ratio of 0.700502 +/- 10 has been obtained for an early Archean (3.46 Ga) barite from the Pilbara Block of Western Australia. Using conservative models for the evolution of Rb/Sr in the early Archean mantle allows an estimate to be placed on the Earth's initial Sr ratio at approximately 4.50 Ga, of 0.69940 +/- 10. This is significantly higher than that measured for the Moon (0.69900 +/- 2) or in the achondrite, Angra dos Reis (0.69894 +/- 2) and for a Rb/Sr ratio of approximately 1/2 of chondrites corresponds to a mean age for accretion of the Earth of 4.48 + /- 0.04 Ga. The now extinct 146Sm-142Nd (T1/2(146)=103 l0(6)yrs) combined with the long-lived 147Sm-143Nd isotopic systematics can also be used to provide limits on the time of early differentiation of the Earth. High precision analyses of the oldest (3.8-3.9 Ga) Archean gneisses from Greenland (Amitsoq and Akilia gneisses), and Canada (Acasta gneiss) do not show measurable (> +/- l0ppm) variations of 142Nd, in contrast to the 33 ppm 142Nd excess reported for an Archean sample. The general lack of 142Nd variations, combined with the presence of highly positive epsilon 143 values (+4.0) at 3.9 Ga, indicates that the record of large-scale Sm/Nd fractionation events was not preserved in the early-Earth from 4

  1. Sm{sup 3+}-doped alkaline earth borate glasses as UV→visible photon conversion layer for solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Shen, L.F. [School of Textile and Material Engineering, Dalian Polytechnic University, Dalian 116034 (China); Department of Electronic Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China); Chen, B.J.; Pun, E.Y.B. [Department of Electronic Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China); Lin, H., E-mail: lhai8686@yahoo.com [School of Textile and Material Engineering, Dalian Polytechnic University, Dalian 116034 (China); Department of Electronic Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong (China)

    2015-04-15

    Intense multi-peak red fluorescence emissions of Sm{sup 3+} are exhibited in alkaline-earth borate (LKZBSB) glasses under UV radiation. The spontaneous emission probabilities A{sub rad} corresponding to the {sup 4}G{sub 5/2}→{sup 6}H{sub J} (J=5/2, 7/2, 9/2 and 11/2) transitions are derived to be 24.74, 129.72, 117.03 and 32.23 s{sup −1}, respectively, and the relevant stimulated emission cross-sections σ{sub em} are 0.77×10{sup −22}, 4.46×10{sup −22}, 5.05×10{sup −22} and 1.38×10{sup −22} cm{sup 2}, confirming the effectiveness of red luminescence in Sm{sup 3+}-doped LKZBSB glasses. Quantitative characterization through the evaluation of absolute spectral parameters reveals that the quantum yield of Sm{sup 3+}-doped LKZBSB glasses is as high as 13.29%. Furthermore, with the introduction of Ce{sup 3+}, the effective excitation wavelength range and the emission intensity of Sm{sup 3+} in LKZBSB glasses are remarkably expanded and improved by a maximum sensitization factor of 9.02 in the UVB region. These results demonstrate that the present glass system has promising potential as an efficient UV→visible photon conversion layer for the enhancement of solar cell efficiency, including appealing applications in outer space. - Highlights: • Intense multi-peak red fluorescence emissions of Sm{sup 3+} are exhibited under UV radiation. • Effectiveness of red luminescence is confirmed by stimulated emission cross-sections. • Quantum yield of Sm{sup 3+}-doped LKZBSB glasses is 13.29% by quantitative characterization. • Effective excitation wavelength range and emission intensity are improved with Ce{sup 3+} doping. • Alkaline-earth borate glass has potential as solar cell UV→Vis photon conversion layer.

  2. From snowball earth to the cambrian explosion: the interpretative potential of the isotope record

    Science.gov (United States)

    Shields, G.

    2003-04-01

    The interval in Earth history between 750 Ma and 530 Ma represents the erratic transition between the distinctly different "Earth systems" of the Proterozoic and the Phanerozoic. Geologists have developed several indirect methods to study this key interval but perhaps none with as much wanton enthusiasm as isotope geochemistry. Here I attempt a review of the isotope record across this key transition period, with special emphasis on the interpretative role that isotopes can play in understanding events such as the "Snowball Earth" glaciations and the "Cambrian Explosion". The marine isotope record reveals the Proterozoic-Phanerozoic transition to have been a unique period in Earth history with first-order features in all three of the major isotope proxies: 87Sr/86Sr, 34S/32S and 13C/12C ratios. Seawater 87Sr/86Sr, increased sharply between about 900 Ma and 500 Ma from 0.704 to 0.709, the largest rise ever. Although attributed to increasing rates of continental erosion, this remains only the most plausible explanation because few aspects of the rise have been satisfactorily linked to particular tectonic events. Much of the uncertainty surrounding the Proterozoic 87Sr/86Sr record is due to poor age dating and discrepancies in stratigraphic correlation schemes, which together with diagenetic alteration have led to the current inability to realise the potential of the 87Sr/86Sr record for global stratigraphic correlation. Carbon isotopes have played a key role in recent palaeoenvironmental interpretations of the Proterozoic-Phanerozoic transition, most of which have already been discarded or merely forgotten. Nevertheless, it is clear that the extraordinary δ13C values of the later Neoproterozoic (and the earliest Cambrian) demand extraordinary explanations, for which there is still much scope for future invention. Carbon isotopes may also play an important supporting role in correlation, however, the role that δ13C may play in global stratigraphic correlation has

  3. Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada: an alkaline, meromictic lake

    International Nuclear Information System (INIS)

    Distribution and isotopic composition (delta13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake, an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion, reached uniform concentrations in the monimolimnion and again increased with depth in monimolimnion bottom sediments. The delta13C[CH4] values in bottom sediment below 1 m sub-bottom depth increased with vertical distance up the core. Monimolimnion delta13C[CH4] values were greater than most delta13C[CH4] values found in the anoxic mixolimnion. No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50 to 60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4/[C2H6 + C3H8] were high in the anoxic mixolimnion, decreased in the monimolimnion and increased with depth in the sediment. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. (author)

  4. Isotope effect of potassium in an aqueous/amalgam system

    International Nuclear Information System (INIS)

    The isotope fractionation of potassium in an aqueous (KOH)/amalgam system has been studied. Two types of isotope effects with opposite isotope enrichment directions were observed in the electrolysis of potassium from the aqueous into the amalgam phase under constant electrolytic potentials. It was found that the first isotope effect causing the light isotope enriched in the amalgam is related to the kinetic process of the mass transfer through the aqueous/amalgam interface, while the second one leading to the enrichment of the heavy isotope in the amalgam phase is produced by the isotope-exchange equilibrium. The temperature dependence of the equilibrium isotope effect was also investigated using single-stage and multi-stage techniques. It was observed that the equilibrium isotope effect increases as the temperature increases in the range of 293-371 K. An empirical equation was used to fit the variations of the isotope effects with temperature for potassium together with the other alkaline and alkaline earth metals studied in the same system. The origin of the equilibrium isotope fractionation in the electron-exchange system was discussed. Furthermore, the mass dependence of the separation coefficients of the alkaline and alkaline earth metals observed in aqueous/amalgam and ion-exchange systems were compared. At 293 K the equilibrium isotope separation coefficient for the 39K/41K isotopes in the amalgam system was determined as (5.6 ± 0.6).10-3. (author)

  5. Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations.

    Science.gov (United States)

    Redondo, Pilar; Largo, Antonio; Rayón, Víctor Manuel; Molpeceres, Germán; Sordo, José Ángel; Barrientos, Carmen

    2014-08-14

    The reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory. In the reactions of Mg(+) with either chloro- or bromomethane the transition structure lies in energy clearly above the reactants rendering thermal activation of CH3Cl or CH3Br extremely improbable. The remaining reactions are exothermic and barrierless processes; thus carbon-halogen bonds in chloro- or bromomethane can be activated by calcium, strontium or barium monocations to obtain the metal halogen cation and the methyl radical. The Mulliken population analysis for the stationary points of the potential energy surfaces supports a "harpoon"-like mechanism for the halogen-atom abstraction processes. An analysis of the bonding situation for the stationary points on the potential energy surface has also been performed in the framework of the quantum theory of atoms in molecules.

  6. Chromium isotopes in siliciclastic sediments and sedimentary rocks as a proxy for Earth surface redox

    Science.gov (United States)

    Reinhard, C. T.; Planavsky, N. J.; Wang, X.; Owens, J. D.; Johnson, T. M.; Fischer, W. W.; Lyons, T. W.

    2013-12-01

    Chromium (Cr) isotopes are an emerging and potentially promising proxy for tracking redox processes at Earth's surface. However, recent efforts to reconstruct the Cr isotope record through time have primarily focused on sporadically deposited iron-rich chemical sediments, with large temporal gaps and limited capacity to explore the Cr isotope record relative to modern and recent marine processes. However, the basic inorganic chemistry of Cr suggests that anoxic marine basins factor prominently in the global Cr cycle, and that likewise sediments deposited within anoxic basins may offer an unexplored Cr isotope archive throughout Earth's history. We present authigenic δ53Cr data from sediments of the Cariaco Basin, Venezuela--a ';type' environment on the modern Earth for large, perennially anoxic basins with relatively strong hydrological connections to the global ocean. Combined with currently available constraints on the δ53Cr composition of modern Atlantic seawater, these data are consistent with the hypothesis that anoxic marine basins can serve as a chemical archive of the first-order features of seawater δ53Cr variation. We employ a simple quantitative model to explore the implications of this hypothesis for global Cr isotope mass balance and the possible utility of authigenic δ53Cr in anoxically deposited siliciclastic sediments and sedimentary rocks as a global paleoredox proxy. Our focus is a basic analysis of the primary controls on seawater δ53Cr as related to both the marine redox landscape and the processes involved in the weathering and aqueous-particulate transport of Cr at Earth's surface. As a case study, we provide analysis of new bulk δ53Cr data through a Cretaceous Oceanic Anoxic Event (OAE-2), which shows a well-defined ~1.0‰ negative excursion during the event coupled with evidence for a drawdown of the marine Cr reservoir. We present a conceptual model to explain these observations, and interpret this shift to suggest a shutdown of

  7. A new N-hydroxyethyliminodiacetic acid modified core-shell silica phase for chelation ion chromatography of alkaline earth, transition and rare earth elements.

    Science.gov (United States)

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Stack, Elaine M; Omamogho, Jesse O; Glennon, Jeremy D; Paull, Brett

    2013-12-20

    Bare core-shell silica (1.7μm) has been modified with iminodiacetic acid functional groups via standard silane chemistry, forming a new N-hydroxyethyliminodiacetic acid (HEIDA) functionalised core-shell stationary phase. The column was applied in high-performance chelation ion chromatography and evaluated for the retention of alkaline earth, transition and heavy metal cations. The influence of nitric acid eluent concentration, addition of complexing agent dipicolinic acid, eluent pH and column temperature on the column performance was investigated. The efficiencies obtained for transition and heavy metal cations (and resultant separations) were comparable or better than those previously obtained for alternative fully porous silica based chelation stationary phases, and a similarly modified monolithic silica column, ranging from ∼15 to 56μm HETP. Increasing the ionic strength of the eluent with the addition of KNO3 (0.75M) and increasing the column temperature (70°C) facilitated the isocratic separation of a mixture of 14 lanthanides and yttrium in under 12min, with HETP averaging 18μm (7μm for Ce(III)).

  8. Transfer of alkaline earth elements in mothers' milk and doses from 45Ca, 90Sr and 226Ra

    International Nuclear Information System (INIS)

    An international programme of work is currently under way to develop methods for calculating doses to infants from ingestion of radionuclides present in mothers' milk. This paper considers the special case of the alkaline earth elements. Models have been developed for 45Ca, 90Sr and 226Ra and the sensitivity of results to various changes in parameter values is discussed. A complication when calculating doses from intakes of radium is that the International Commission on Radiological Protection has previously recommended that doses from decay products of radium should be calculated using element-specific biokinetic models (so-called independent biokinetics). An extension of this method to the models for breastfeeding is proposed. Preliminary estimates of the doses received by the infant for a number of maternal intake scenarios show that doses to the infant can exceed the corresponding adult dose, such as for 45Ca (ratio = 3.1) while, in other cases such as 90Sr, the infant dose can be a significant fraction of the adult dose. (author)

  9. Electronic structures and second hyperpolarizabilities of alkaline earth metal complexes end-capped with NA2 (A = H, Li, Na).

    Science.gov (United States)

    Banerjee, Paramita; Nandi, Prasanta K

    2016-05-14

    The ground state structures and NLO properties of a number of alkaline earth metal complexes end-capped with NA2 groups (A = H, Li, Na) are calculated by employing the CAM-B3LYP, wB97XD and B2PLYP functionals along with MP2 and CCSD(T) for 6-311++G(d,p), 6-311++G(3df,3pd), aug-cc-pVTZ, aug-pc-2 and Hypol basis sets. The complexes are found to be significantly stable. The magnitude of second hyperpolarizability enhances appreciably with increase in the number of magnesium and calcium atoms in the chain, which has been indicated by the power law dependence γ = a + bn(c) with c values ranging from 2.4-4.3 for Mg and 2.4-3.7 for Ca complexes, respectively. The largest second-hyperpolarizability (10(9) au) is obtained for the complex Ca7(NNa2)2 at the CAM-B3LYP level. The two state model has been used to explain the variation of hyperpolarizabilities. PMID:27088138

  10. A preorganized metalloreceptor for alkaline earth ions showing calcium versus magnesium selectivity in water: biological activity of selected metal complexes.

    Science.gov (United States)

    Amatori, Stefano; Ambrosi, Gianluca; Fanelli, Mirco; Formica, Mauro; Fusi, Vieri; Giorgi, Luca; Macedi, Eleonora; Micheloni, Mauro; Paoli, Paola; Rossi, Patrizia

    2014-08-25

    The N,N'-bis[(3-hydroxy-4-pyron-2-yl)methyl]-N,N'-dimethylethylendiamine (Malten = L) forms the highly stable [CuH(-2)L] species in water, in which the converging maltol oxygen atoms form an electron-rich area able to host hard metal ions. When considering the alkaline earth series (AE), the [Cu(H(-2)L)] species binds all metal ions, with the exception of Mg(2+), exhibiting the relevant property to discriminate Ca(2+) versus Mg(2+) at physiological pH 7.4; the binding of the AE metal is visible to the naked eye. The stability constant values of the trinuclear [AE{Cu(H(-2)L)}2](2+) species formed reach the maximum for Ca(2+) (log K=7.7). Ca(2+) also forms a tetranuclear [Ca{Cu(H(-2)L)}]2(4+) species at a high Ca(2+) concentration. Tri- and tetranuclear calcium complexes show blue- and pink-colored crystals, respectively. [Cu(H(-2)L)] is the most active species in inducing DNA alterations. The DNA damages are compatible with its hydrolytic cleavages.

  11. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides.

    Science.gov (United States)

    Hereijgers, Bart P C; Weckhuysen, Bert M

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with all studied catalyst materials, however, the selectivity for hydrogen increased from 15 % to 51 % when going from the unpromoted to a BaO-promoted catalyst. The formation of the undesired byproducts CO, methane, and dimethyl ether was considerably reduced as well. The observed trend in catalyst performance follows the trend in increasing basicity of the studied promoter elements, indicating a chemical effect of the promoter material. Superior catalytic performance, in terms of H(2) and CO selectivity, was obtained with a Au/La(2)O(3) catalyst. At 300 degrees C the hydrogen selectivity reached 80 % with only 2 % CO formation, and the catalyst displayed a stable performance over at least 24 h on-stream. Furthermore, the formation of CO was found to be independent of the oxygen concentration in the feed. The commercial lanthanum oxide used in this study had a low specific surface area, which led to the formation of relative large gold particles. Therefore, the catalytic activity could be enhanced by decreasing the gold particle size through deposition on lanthanum oxide supported on high-surface-area alumina.

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

    Science.gov (United States)

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

    2016-04-01

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

  13. Rare earth elements and neodymium isotopes in world river sediments revisited

    Science.gov (United States)

    Bayon, G.; Toucanne, S.; Skonieczny, C.; André, L.; Bermell, S.; Cheron, S.; Dennielou, B.; Etoubleau, J.; Freslon, N.; Gauchery, T.; Germain, Y.; Jorry, S. J.; Ménot, G.; Monin, L.; Ponzevera, E.; Rouget, M.-L.; Tachikawa, K.; Barrat, J. A.

    2015-12-01

    Over the past decades, rare earth elements (REE) and their radioactive isotopes have received tremendous attention in sedimentary geochemistry, as tracers for the geological history of the continental crust and provenance studies. In this study, we report on elemental concentrations and neodymium (Nd) isotopic compositions for a large number of sediments collected near the mouth of rivers worldwide, including some of the world's major rivers. Sediments were leached for removal of non-detrital components, and both clay and silt fractions were retained for separate geochemical analyses. Our aim was to re-examine, at the scale of a large systematic survey, whether or not REE and Nd isotopes could be fractionated during Earth surface processes. Our results confirmed earlier assumptions that river sediments do not generally exhibit any significant grain-size dependent Nd isotopic variability. Most sediments from rivers draining old cratonic areas, sedimentary systems and volcanic provinces displayed similar Nd isotopic signatures in both clay and silt fractions, with ΔεNd(clay-silt) flat shale-normalized patterns. However, clay fractions were almost systematically characterized by a progressive enrichment from the heavy to the light REE and a positive europium (Eu) anomaly. In agreement with results from previous soil investigations, the observed REE fractionation between clays and silts is probably best explained by preferential alteration of feldspars and/or accessory mineral phases. Importantly, this finding clearly indicates that silicate weathering can lead to decoupling of REE between different grain-size fractions, with implications for sediment provenance studies. Finally, we propose a set of values for a World River Average Clay (WRAC) and Average Silt (WRAS), which provide new estimates for the average composition of the weathered and eroded upper continental crust, respectively, and could be used for future comparison purposes.

  14. Early history of Earth's crust-mantle system inferred from hafnium isotopes in chondrites

    DEFF Research Database (Denmark)

    Bizzarro, Martin; Haack, Henning; Rosing, M.;

    2003-01-01

    The Lu to Hf decay series has been widely used to understand the nature of Earth's early crust-mantle system. The interpretation, however, of Lu-Hf isotope data requires accurate knowledge of the radioactive decay constant of Lu (¿176), as well as bulk-Earth reference parameters. A recent...... calibration of the ¿176 value calls for the presence of highly unradiogenic hafnium in terrestrial zircons with ages greater than 3.9 Gyr, implying widespread continental crust extraction from an isotopically enriched mantle source more than 4.3 Gyr ago, but does not provide evidence for a complementary...... depleted mantle reservoir. Here we report Lu-Hf isotope measurements of different Solar System objects including chondrites and basaltic eucrites. The chondrites define a Lu-Hf isochron with an initial Hf/Hf ratio of 0.279628 ± 0.000047, corresponding to ¿176 = 1.983 ± 0.033 x 10yr using an age of 4.56 Gyr...

  15. Constraints on Earth degassing history from the argon isotope composition of Devonian atmosphere

    Science.gov (United States)

    Stuart, F. M.; Mark, D.

    2012-04-01

    The primordial and radiogenic isotopes of the noble gases combine to make them a powerful tool for determining the time and tempo of the outgassing of the Earth's interior. The outgassing history of the Earth is largely constrained from measurements of the isotopic composition of He, Ne, Ar and Xe in samples of modern mantle, crust and atmosphere. There have been few unequivocal measurement of the isotopic composition of noble gases in ancient atmosphere. We have re-visited whether ancient Ar is trapped in the ~400 Ma Rhynie chert [1]. We have analysed samples of pristine Rhynie chert using the ARGUS multi-collector mass spectrometer calibrated against the new determination of atmospheric Ar isotope ratios [2]. 40Ar/36Ar ratios are low, with many lower than the modern air value (298.8). Importantly these are accompanied by atmospheric 38Ar/36Ar ratios indicating that the low 40Ar/36Ar are not due to mass fractionation. We conclude that the Rhynie chert has captured Devonian atmosphere-derived Ar. The data indicate that the Devonian atmosphere 40Ar/36Ar was at least 3 % lower than the modern air value. Thus the Earth's atmosphere has accumulated at least 5 ± 0.2 x 1016 moles of 40Ar in the last 400 million years, at an average rate of 1.24 ± 0.06 x 108 mol 40Ar/year. This overlaps the rate determined from ice cores for the last 800,000 years [3] and implies that there has been no resolvable temporal change in Earth outgassing rate since mid-Palaeozoic times. The new data require the Earth outgassed early, and suggests that pristine samples of Archaean and Proterozoic chert may prove useful as palaeo-atmosphere tracers. [1] G. Turner, J. Geol. Soc. London 146, 147-154 (1989) [2] D. Mark, F.M. Stuart, M. de Podesta, Geochim. Cosmochim. Acta 75, 7494-7501 [3] M. Bender et al., Proc. Nat. Acad. Sci. 105, 8232-8237 (2008)

  16. Rare earth element and stable sulphur (δ 34S) isotope study of baryte-copper mineralization in Gulani area, Upper Benue Trough, NE Nigeria

    Science.gov (United States)

    El-Nafaty, Jalo Muhammad

    2015-06-01

    The geology of Gulani area comprises of inliers of diorite and granites of the Older Granite suite of the Pan-African (600 ± 150 Ma) age within Cretaceous sediments of the Bima, Yolde and Pindiga Formations and the Tertiary/Quaternary basalts of the Biu Plateau. Epigenetic baryte-copper mineralization occurs as baryte veins within the Bima and Yolde sandstones and fracture-filling malachite in Pan-African granites. Unaltered (distal), hydrothermally altered (proximal) granites and sandstones and vein materials (mineral separates of baryte and chalcopyrite/malachite mineralized rocks) were analysed for rare earth elements (REE) and stable sulphur isotopes. The REE patterns of the unaltered rocks (both granites and sandstones) indicate background values before mineralization, depicted by enriched LREE, depleted HREE and weak negative Eu anomalies typical of Pan-African (calc-alkaline) granites and sandstones derived from them. On the other hand, the hydrothermally altered and mineralized rocks and mineral separates show a distinct baryte and copper mineralization sub-systems characterized by similar high LREE and corresponding low HREE abundances. However, the negative Eu anomalies of the copper sub-system hosted by granites are typical of Pan-African (calc-alkaline) granites. The sandstone host rocks of the baryte sub-system are marked by positive Eu anomalies interpreted as reflecting the injection and subsequent deposition of the baryte-bearing hydrothermal solutions under oxidizing conditions. The baryte mineral separates show δ (34S) isotope range of 12.3-13.1‰ (CDT) indicating sulphur from sedimentary formation sources. This ruled out magmatic source of the sulphur from the nearby Tertiary/Quaternary volcanic rocks of the Biu Plateau as well as ocean water. However, the stable sulphur isotopic determination of the sulphides (chalcopyrite/malachite mineral separates and mineralized rocks) did not yield peaks and therefore no inferences drawn in this regard.

  17. Synthesis, characterization and solubility of alkaline earth uranyl carbonates M2[UO2(CO3)3].xH20; M: Mg, Ca, Sr, Ba

    International Nuclear Information System (INIS)

    The release and dispersion of uranium from closed uranium mining sites and the resulting uranium contamination of the natural environment of such sites is a major problem examined in this dissertation. Knowledge of the pollution pathways and processes is indispensable for an assessment of the radiological implications for the human population, to be taken into account in the planning of site rehabilitation work. The formation of secondary uranium minerals may contribute to an immobilization of the uranium, but it is possible as well that such secondary uranium minerals will release uranium. A major task of this dissertation therefore was to examine the conditions of formation of alkaline earth uranyl carbonates in the context of their natural occurrence as observed at some sites, and to answer the question of whether hitherto unknown alkaline earth uranyl carbonates may form in the natural environment, and ought to be taken into account as new source terms. (orig./CB)

  18. Earth-atmosphere evolution based on new determination of Devonian atmosphere Ar isotopic composition

    Science.gov (United States)

    Stuart, Finlay M.; Mark, Darren F.; Gandanger, Pierre; McConville, Paul

    2016-07-01

    The isotopic composition of the noble gases, in particular Ar, in samples of ancient atmosphere trapped in rocks and minerals provides the strongest constraints on the timing and rate of Earth atmosphere formation by degassing of the Earth's interior. We have re-measured the isotopic composition of argon in the Rhynie chert from northeast Scotland using a high precision mass spectrometer in an effort to provide constraints on the composition of Devonian atmosphere. Irradiated chert samples yield 40Ar/36Ar ratios that are often below the modern atmosphere value. The data define a 40Ar/36Ar value of 289.5 ± 0.4 at K/36Ar = 0. Similarly low 40Ar/36Ar are measured in un-irradiated chert samples. The simplest explanation for the low 40Ar/36Ar is the preservation of Devonian atmosphere-derived Ar in the chert, with the intercept value in 40Ar-39Ar-36Ar space representing an upper limit. In this case the Earth's atmosphere has accumulated only 3% (5.1 ± 0.4 ×1016 mol) of the total 40Ar inventory since the Devonian. The average accumulation rate of 1.27 ± 0.09 ×108 mol40Ar/yr overlaps the rate over the last 800 kyr. This implies that there has been no resolvable temporal change in the outgassing rate of the Earth since the mid-Palaeozoic despite the likely episodicity of Ar degassing from the continental crust. Incorporating the new Devonian atmosphere 40Ar/36Ar into the Earth degassing model of Pujol et al. (2013) provides the most precise constraints on atmosphere formation so far. The atmosphere formed in the first ∼100 Ma after initial accretion during a catastrophic degassing episode. A significant volume of 40Ar did not start to accumulate in the atmosphere until after 4 Ga which implies that stable K-rich continental crust did not develop until this time.

  19. The use of alkaline hydrolysis as a novel strategy for chloroform remediation: the feasibility of using construction wastes and evaluation of carbon isotopic fractionation.

    Science.gov (United States)

    Torrentó, Clara; Audí-Miró, Carme; Bordeleau, Geneviève; Marchesi, Massimo; Rosell, Mònica; Otero, Neus; Soler, Albert

    2014-01-01

    Laboratory and field-scale pilot experiments were performed to evaluate the feasibility of chloroform degradation by alkaline hydrolysis and the potential of δ(13)C values to assess this induced reaction process at contaminated sites. In batch experiments, alkaline conditions were induced by adding crushed concrete (pH 12.33 ± 0.07), a filtered concrete solution (pH 12.27 ± 0.04), a filtered cement solution (pH 12.66 ± 0.02) and a pH 12 buffer solution (pH 11.92 ± 0.11). The resulting chloroform degradation after 28 days was 94, 96, 99, and 72%, respectively. The experimental data were described using a pseudo-first-order kinetic model, resulting in pseudo-first-order rate constant values of 0.10, 0.12, 0.20, and 0.05 d(-1), respectively. Furthermore, the significant chloroform carbon isotopic fractionation associated with alkaline hydrolysis of chloroform (-53 ± 3‰) and its independence from pH in the admittedly limited tested pH range imply a great potential for the use of δ(13)C values for in situ monitoring of the efficacy of remediation approaches based on alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30-40% of chloroform degradation was achieved during the two studied recharge periods. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits. PMID:24410407

  20. The use of alkaline hydrolysis as a novel strategy for chloroform remediation: the feasibility of using construction wastes and evaluation of carbon isotopic fractionation.

    Science.gov (United States)

    Torrentó, Clara; Audí-Miró, Carme; Bordeleau, Geneviève; Marchesi, Massimo; Rosell, Mònica; Otero, Neus; Soler, Albert

    2014-01-01

    Laboratory and field-scale pilot experiments were performed to evaluate the feasibility of chloroform degradation by alkaline hydrolysis and the potential of δ(13)C values to assess this induced reaction process at contaminated sites. In batch experiments, alkaline conditions were induced by adding crushed concrete (pH 12.33 ± 0.07), a filtered concrete solution (pH 12.27 ± 0.04), a filtered cement solution (pH 12.66 ± 0.02) and a pH 12 buffer solution (pH 11.92 ± 0.11). The resulting chloroform degradation after 28 days was 94, 96, 99, and 72%, respectively. The experimental data were described using a pseudo-first-order kinetic model, resulting in pseudo-first-order rate constant values of 0.10, 0.12, 0.20, and 0.05 d(-1), respectively. Furthermore, the significant chloroform carbon isotopic fractionation associated with alkaline hydrolysis of chloroform (-53 ± 3‰) and its independence from pH in the admittedly limited tested pH range imply a great potential for the use of δ(13)C values for in situ monitoring of the efficacy of remediation approaches based on alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30-40% of chloroform degradation was achieved during the two studied recharge periods. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits.

  1. THEORETICAL-ANALYSIS OF THE O(1S) BINDING-ENERGY SHIFTS IN ALKALINE-EARTH OXIDES - CHEMICAL OR ELECTROSTATIC CONTRIBUTIONS

    NARCIS (Netherlands)

    PACCHIONI, G; BAGUS, PS

    1994-01-01

    We report results from ab initio cluster-model calculations on the O(1s) binding energy (BE) in the alkaline-earth oxides, MgO, CaO, SrO, and BaO; all these oxides have a cubic lattice structure. We have obtained values for both the initial- and final-state BE's. A simple point-charge model, where a

  2. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals

    OpenAIRE

    Liu, Yuanyue; Merinov, Boris V.; Goddard III, William A.

    2016-01-01

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same...

  3. Evaluation of AA5052 alloy anode in alkaline electrolyte with organic rare-earth complex additives for aluminium-air batteries

    Science.gov (United States)

    Wang, Dapeng; Li, Heshun; Liu, Jie; Zhang, Daquan; Gao, Lixin; Tong, Lin

    2015-10-01

    Behaviours of the AA5052 aluminium alloy anode of the alkaline aluminium-air battery are studied by the hydrogen evolution test, the electrochemical measurements and the surface analysis method. The combination of amino-acid and rare earth as electrolyte additives effectively retards the self-corrosion of AA5052 aluminium alloy in 4 M NaOH solution. It shows that the combination of L-cysteine and cerium nitrate has a synergistic effect owing to the formation of a complex film on AA5052 alloy surface. The organic rare-earth complex can decrease the anodic polarisation, suppress the hydrogen evolution and increase the anodic utilization rate.

  4. Production of Rare Earth Isotope Beams for Radiotracer-DLTS on SiC

    CERN Multimedia

    2002-01-01

    Electrical properties of semiconductors are extremely sensitive to minor traces of impurities and defects. This fact allows to intentionally modify material properties and is thus the very basis of semiconductor electronics and optoelectronics. In the present project, electronic properties and doping effects of rare-earth elements in the technologically important semiconductor SiC are to be investigated using optical and electrical characterization techniques like Photoluminescence, Deep Level Transient Spectroscopy and Thermal Admittance Spectroscopy. By using the elemental transmutation of radioactive isotopes as a tracer, it will be guaranteed that the impurity-related band gap states can definitively be distinguished from intrinsic or process-induced defects. For SiC up to now only detailed investigation of Er- related deep levels have been reported, preliminary data exist for Sm- and Gd- impurities. In this project we propose the implantation of Pr and Eu isotopes for detailed level studies.

  5. Structural criteria for the rational design of selective ligands. Extension of the MM3 force field to aliphatic ether complexes of the alkali and alkaline earth cations

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P.; Rustad, J.R. (Pacific Northwest Lab., Richland, WA (United States))

    1994-07-13

    Structural requirements for strain-free metal ion complexation by an aliphatic ether group are investigated through the use of both ab initio molecular orbital and molecular mechanics calculations. Hartree-Fock calculations on simple models, M-O(Me)[sub 2] and M-O(Me)(Et), reveal a preference for trigonal planar geometry when aliphatic ether oxygens are coordinated to alkali and alkaline earth cations. This preference is found to be strongest in small, high-valent cations and weakest in large, low-valent cations. Results from the Hartree-Fock calculations are used to extend the MM3 force field for calculation on aliphatic ether complexes with the alkali (Li to Cs) and alkaline earth (Mg to Ba) cations. The resulting molecular model (i) reproduces the experimental crystal structures of 51 different complexes of multidentate ethers with alkali and alkaline earth cations, (ii) explains experimental trends in the structure of five-membered chelate rings of aliphatic ethers, (iii) reveals a fundamental difference between the metal ion size selectivity of five-membered chelate rings of ethers versus that of amines, and (iv) rationalizes trends in the stability of four potassium complexes with the diasteriomers of dicyclohexyl-18-crown-6. 40 refs., 9 figs., 5 tabs.

  6. Synthesis of monomeric and polymeric alkali and alkaline earth metal complexes using a phosphinoselenoic amide ligand in metal coordination sphere

    Indian Academy of Sciences (India)

    Jayeeta Bhattacharjee; Ravi K Kottalanka; Harinath Adimulam; Tarun K Panda

    2014-09-01

    We report the monomeric complexes of magnesium and calcium of composition [M(THF){2-Ph2P(Se)N(CMe3)}2] [M= Mg (3), n = 1 andM = Ca (4), n = 2)] and polymeric complexes of potassium and barium of composition [K(THF)2{Ph2P(Se)N(CMe3)}] (2) and [K(THF)Ba{Ph2P(Se)N(CMe3)}3](5) respectively. The potassium complex 2 was readily prepared by the reaction of potassium bis(trimethylsilyl)amide with phosphinoselenoic amide ligand (1) at ambient temperature. The calcium complex 4 was prepared by two synthetic routes: in the first method, commonly known as salt metathesis reaction, the potassium complex 2 was made to react with alkaline earth metal diiodide at room temperature to afford the corresponding calcium complex. The metal bis(trimethylsilyl)amides were made to react with protic ligand 1 in the second method to eliminate the volatile bis(trimethyl)silyl amine. The magnesium complex 3 and barium complex 5 were prepared only through the first method. Solid-state structures of all the new complexes were established by single crystal X-ray diffraction analysis. The smaller ionic radii of Mg2+ (0.72Å) and Ca2+ (0.99Å) ions form the monomeric complex, whereas the larger ions K+ (1.38Å) and Ba2+ (1.35Å) were found to form onedimensional polymeric complexes with monoanionic ligand 1. Compound 2 serves an example of magnesium complex with a Mg-Se direct bond.

  7. Band structure and electrical properties of MBE grown HfO{sub 2} - based alkaline earth Perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Peter, Dudek; Grzegorz, Lupina; Grzegorz, Kozlowski; Jarek, Dabrowski; Gunther, Lippert; Hans-Joachim, Muessig; Thomas, Schroeder [IHP-Microelectronics, Frankfurt, Oder (Germany); Dieter, Schmeisser [BTU, Cottbus (Germany)

    2010-07-01

    Ultra thin dielectric films (<20 nm) deposited on TiN electrodes are interesting for MIM capacitor application. High capacitance density and dielectric permittivity must be accompanied by extremely low leakage currents (10{sup -8} A/cm{sup 2}) at bias 0.5 V. To achieve such low leakage currents, high band gap and proper band alignment is required. Occupied electronic states can be probed with standard laboratory photoemission methods. Probing of unoccupied states is more challenging. Synchrotron based PES in combination with XAS forms a powerful method to study the band alignment. ASAM end station located at the U 49/2 PGM 2 beamline of BESSY II (Berlin) offers excellent conditions for performing such measurements. We investigated HfO{sub 2} - based alkaline earth perovskite - BaHfO{sub 3} with subsequent admixture of TiO{sub 2}, resulting in formation of BaHf{sub 0.5}Ti{sub 0.5}O{sub 3} compound. The analysis of data indicates that band gap for HfO{sub 2} is similar to BaHfO{sub 3} and amounts 5.8 eV; for BaHf{sub 0.5}Ti{sub 0.5}O{sub 3} it decreases to 3.8 eV. We conclude that the addition of TiO{sub 2} to BaHfO{sub 3} increases significantly the dielectric permittivity but also impacts the band gap alignment. The conduction band offset shrinks, influencing the leakage current behavior.

  8. Ab Initio Quantum Mechanical Study of the Structure and Stability of the Alkaline Earth Metal Oxides and Peroxides

    Science.gov (United States)

    Königstein, Markus; Catlow, C. Richard A.

    1998-10-01

    We report a detailed computationally study of the stability of the alkaline earth metal peroxidesMO2(M=Ba, Sr, Ca, Mg, Be) with respect to decomposition into the corresponding oxidesMOand molecular oxygen using Hartree-Fock and density functional theory (DFT) techniques. A comparison between calculated and experimental binding energies indicates that the DFT method is most suitable for a correct description of the peroxide bond. The DFT reaction energies for the peroxide decompositionMO2→MO+{1}/{2}O2show that only BaO2and SrO2are thermodynamically stable compounds, while CaO2(in the calcium carbide structure), MgO2, and BeO2(in the pyrite structure) are energetically unstable with reaction energies of -24.7, -26.8, and -128.7kJ/mol, respectively, and are therefore unlikely to exist as pure compounds. The published calcium carbide structure for CaO2is probably incorrect, at least for pure calcium peroxide, since apart from the thermodynamical instability the compound is more stable in the pyrite structure by 25.5 kJ/mol. Our analysis suggests that the water and/or hydrogen peroxide content of experimentally prepared MgO2samples is necessary for the stabilization of the structure, while BeO2is clearly unstable under ambient conditions. We studied also the effect of the zero point energies and the entropies on the decomposition free energies and, for this purpose, performed atomistic lattice simulations based on interatomic potentials, which we derived from ourab initiodata; the results indicate a negligible effect of the zero point energies, while the entropy terms favor the decomposition reaction by ca. 20 kJ/mol at 298.15 K.

  9. Ab initio quantum mechanical study of the structure and stability of the alkaline earth metal oxides and peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Koenigstein, M.; Catlow, C.R.A. [Royal Institution of Great Britain, London (United Kingdom). Davy Faraday Research Lab.

    1998-10-01

    The authors report a detailed computational study of the stability of the alkaline earth metal peroxides MO{sub 2} (M = Ba, Sr, Ca, Mg, Be) with respect to decomposition into the corresponding oxides Mo and molecular oxygen using Hartree-Fock and density functional theory (DFT) techniques. A comparison between calculated and experimental binding energies indicates that the DFT method is most suitable for a correct description of the peroxide bond. The DFT reaction energies for the peroxide decomposition MO{sub 2} {yields} MO + {1/2}O{sub 2} show that only BaO{sub 2} and SrO{sub 2} are thermodynamically stable compounds, while CaO{sub 2} (in the calcium carbide structure), MgO{sub 2}, and BeO{sub 2} (in the pyrite structure) are energetically unstable with reaction energies of {minus}24.7, {minus}26.8, and {minus}128.7 kJ/mol, respectively, and are therefore unlikely to exist as pure compounds. The published calcium carbide structure for CaO{sub 2} is probably incorrect, at least for pure calcium peroxide, since apart from the thermodynamical instability the compound is more stable in the pyrite structure by 25.5 kJ/mol. The analysis suggests that the water and/or hydrogen peroxide content of experimentally prepared MgO{sub 2} samples is necessary for the stabilization of the structure, while BeO{sub 2} is clearly unstable under ambient conditions. The authors studied also the effect of the zero point energies and the entropies on the decomposition free energies and, for this purpose, performed atomistic lattice simulations based on interatomic potentials, which they derived from their ab initio data; the results indicate a negligible effect of the zero point energies, while the entropy terms favor the decomposition reaction by ca. 20 kJ/mol at 298.15 K.

  10. Decay spectroscopy of neutron-rich rare-earth isotopes and collectivity around double midshell

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Hiroshi, E-mail: hiroshi@ribf.riken.jp [IRCNPC, School of Physics and Nuclear Energy Engineering, Beihang University, Beijing 100191 (China); RIKEN Nishina Center, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan)

    2015-10-15

    Neutron-rich rare-earth isotopes with A ≈ 170, which locate near the middle of the major shells for both proton and neutron between the doubly magic nuclei {sup 132}Sn and {sup 208}Pb, have been investigated by means of decay spectroscopy techniques at the RIBF facility at RIKEN. The nuclei of interest were produced by in-flight fission of a high-intensity {sup 238}U beam at 345 MeV/u. In this contribution, scientific motivations, the details of experimental procedures, and some prospects of the data analysis are reported.

  11. EVALUATION OF RADIOLOGICAL SIGNIFICANCE OF RARE-EARTH METALS WITH NATURAL RADIOACTIVE ISOTOPES

    Directory of Open Access Journals (Sweden)

    E. P. Lisachenko

    2013-01-01

    Full Text Available Among the rare-earth metals with natural radioactive isotopes, lantan, lutetium and samarium are allocated a relatively high specific activity. The formation of the additional external radiation keep it close to the significance of the materials to the radiation categories of materials with a high content of natural radionuclides of uranium and thorium family, lanthanum value is much less. Samarium, with acceptable toxicology content in the working area, forms the internal exposure to the limits for professionals. The use of these elements in science and industry requires the radiation-hygienic evaluation.

  12. Photoelectron Experiments and Studies of X-Ray Absorption Near Edge Structure in Alkaline-Earth and Rare - Fluorides.

    Science.gov (United States)

    Gao, Yuan

    Alkaline-earth fluorides and rare-earth trifluorides possess technological importance for applications in multi -layer electronic device structures and opto-electronic devices. Interfaces between thin films of YbF _3 and Si(111) substrates were studied by photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. Results of YbF_3 /Si(111) were compared with those of TmF _3/Si(111). While electrons in the Si valence band are prevented from occupying the empty 4f levels in TmF_3 at the interface by the on -site Coulomb repulsion energy, the charge transfer from Si to YbF_3 is possible because the totally filled 4f states in Yb still lie below the Si valence band maximum. The theory of x-ray absorption near edge structure (XANES) is incomplete except for a few particularly simple special cases. A Bragg reflection model was developed to qualitatively explain the oscillations in XANES, in terms of the scattering of the photoelectron wave between families of lattice planes as set out by the Bragg condition for backscattering. The model was found to represent the data for systems with nearly free electron like conduction bands reasonably well. High resolution CaF_2 fluorine K edge XANES was used as a prototype to understand XANES in more depth on systems with strong core hole effects. Unlike previous work which involved multiple scattering cluster calculations that include only short range order effects, both the long range order and the symmetry breaking core holes are included in a new bandstructure approach in which the core hole is treated with a supercell technique. A first principles calculation with the use of pseudopotentials successfully reproduced all the main features of the first 15 eV of the fluorine K edge in CaF_2 which had not been explained with the cluster calculations. A comparison of the theoretical and experimental fluorine K edges in CaF_2 and BaF _2 was used to identify the structure related features. The possibility

  13. Rare earth elements and neodymium isotopes in world river sediments revisited

    Science.gov (United States)

    Bayon, G.; Toucanne, S.; Skonieczny, C.; André, L.; Bermell, S.; Cheron, S.; Dennielou, B.; Etoubleau, J.; Freslon, N.; Gauchery, T.; Germain, Y.; Jorry, S. J.; Ménot, G.; Monin, L.; Ponzevera, E.; Rouget, M.-L.; Tachikawa, K.; Barrat, J. A.

    2015-12-01

    Over the past decades, rare earth elements (REE) and their radioactive isotopes have received tremendous attention in sedimentary geochemistry, as tracers for the geological history of the continental crust and provenance studies. In this study, we report on elemental concentrations and neodymium (Nd) isotopic compositions for a large number of sediments collected near the mouth of rivers worldwide, including some of the world's major rivers. Sediments were leached for removal of non-detrital components, and both clay and silt fractions were retained for separate geochemical analyses. Our aim was to re-examine, at the scale of a large systematic survey, whether or not REE and Nd isotopes could be fractionated during Earth surface processes. Our results confirmed earlier assumptions that river sediments do not generally exhibit any significant grain-size dependent Nd isotopic variability. Most sediments from rivers draining old cratonic areas, sedimentary systems and volcanic provinces displayed similar Nd isotopic signatures in both clay and silt fractions, with ΔεNd(clay-silt) volcanic and/or sedimentary rocks relative to more resistant lithologies may occur in river basins, possibly leading locally to Nd isotopic decoupling between different size fractions. Except for volcanogenic sediments, silt fractions generally displayed homogeneous REE concentrations, exhibiting relatively flat shale-normalized patterns. However, clay fractions were almost systematically characterized by a progressive enrichment from the heavy to the light REE and a positive europium (Eu) anomaly. In agreement with results from previous soil investigations, the observed REE fractionation between clays and silts is probably best explained by preferential alteration of feldspars and/or accessory mineral phases. Importantly, this finding clearly indicates that silicate weathering can lead to decoupling of REE between different grain-size fractions, with implications for sediment provenance

  14. The Use of Lead Isotope and Rare Earth Element Geochemistry for Forensic Geographic Provenancing

    Science.gov (United States)

    Carey, A.; Darrah, T.; Harrold, Z.; Prutsman-Pfeiffer, J.; Poreda, R.

    2008-12-01

    Lead isotope and rare earth element composition of modern human bones are analyzed to explore their utility for geographical provenancing. DNA analysis is the standard for identification of individuals. DNA analysis requires a DNA match for comparison. Thus, DNA analysis is of limited use in cases involving unknown remains. Trace elements are incorporated into bones and teeth during biomineralization, recording the characteristics of an individual's geochemical environment. Teeth form during adolescence, recording the geochemical environment of an individual's youth. Bones remodel throughout an individual's lifetime. Bones consist of two types of bone tissue (cortical and trabecular) that remodel at different rates, recording the geochemical environment at the time of biomineralization. Cortical bone tissue, forming the outer surface of bones, is dense, hard tissue that remodels in 25-30 yrs. Conversely, trabecular bone tissue, the inner cavity of bones, is low density, porous and remodels in 2-5 years. Thus, analyzing teeth and both bone tissues allows for the development of a geographical time line capable of tracking immigration patterns through time instead of only an individual's youth. Geochemical isotopic techniques (Sr, O, C, N) have been used for geographical provenancing in physical anthropology. The isotopic values of Sr, C, O, N are predominantly a function of soil compositions in areas where food is grown or water is consumed. Application of these provenancing techniques has become difficult as an individual's diet may reflect the isotopic composition of foods obtained at the local grocer as opposed to local soil compositions. Thus, we explore the use of REEs and Pb isotopes for geographical provenancing. Pb and REEs are likely more reliable indicators of modern geographical location as their composition are high in bio-available sources such as local soils, atmospheric aerosols, and dust as opposed to Sr, C, O, N that are controlled by food and

  15. From Gene Expression to the Earth System: Isotopic Constraints on Nitrogen Cycling Across Scales

    Science.gov (United States)

    Houlton, B. Z.

    2015-12-01

    A central motivation of the Biogeosciences is to understand the cycling of biologically essential elements over multiple scales of space and time. This charge is vital to basic knowledge of Earth system functioning. It is also relevant to many of the global challenges we face, such as climate change, biodiversity conservation, and the multifaceted role of global fertilizer use in maximizing human health and well-being. Nitrogen is connected to all of these; yet it has been one of the more vexing elements to quantitatively appraise across systems and scales. Here I discuss how research in my group has been exploring the use of natural nitrogen isotope abundance (15N/14N) as a biogeochemical tracer - from the level of gene expression to nitrogen's role in global climate change. First, I present evidence for a positive correlation between the bacterial genes that encode for gaseous nitrogen production (i.e., nirS) and the 15N/14N of soil extractable nitrate pools across an array of terrestrial ecosystems. Second, I demonstrate how these local-scale results fit with our work on ecosystem-scale nitrogen isotope budgets, where we quantify a uniformly small isotope effect (i.e., working hypothesis that bacterial denitrification is the major fractionating pathway of nitrogen loss from the terrestrial biosphere, much like the global ocean.

  16. The influence of alkaline earth metal equilibria on the rheological, melting and textural properties of Cheddar cheese.

    Science.gov (United States)

    Cooke, Darren R; McSweeney, Paul L H

    2013-11-01

    The total calcium content of cheese, along with changes in the equilibrium between soluble and casein (CN)-bound calcium during ripening can have a major impact on its rheological, functional and textural properties; however, little is known about the effect of other alkaline earth metals. NaCl was partially substituted with MgCl2 or SrCl2 (8·7 and 11·4 g/kg curd, respectively) at the salting stage of cheesemaking to study their effects on cheese. Three cheeses were produced: Mg supplemented (+Mg), Sr supplemented (+Sr) and a control Cheddar cheese. Ca, Mg and Sr contents of cheese and expressible serum obtained therefrom were determined by atomic absorption spectroscopy. Addition of Mg2+ or Sr2+ had no effect on % moisture, protein, fat and extent of proteolysis. A proportion of the added Mg2+ and Sr2+ became CN-bound. The level of CN-bound Mg was higher in the +Mg cheese than the control throughout ripening. The level of CN-bound Ca and Mg decreased during ripening in all cheeses, as did % CN-bound Sr in the +Sr cheese. The presence of Sr2+ increased % CN-bound Ca and Mg at a number of ripening times. Adding Mg2+ had no effect on % CN-bound Ca. The +Sr cheese exhibited a higher G' at 70 °C and a lower LTmax than the control and +Mg cheeses throughout ripening. The +Sr cheese had significantly lower meltability compared with the control and +Mg cheeses after 2 months of ripening. Hardness values of the +Sr cheese were higher at week 2 than the +Mg and control cheeses. Addition of Mg2+ did not influence the physical properties of cheese. Supplementing cheese with Sr appeared to have effects analogous to those previously reported for increasing Ca content. Sr2+ may form and/or modify nanocluster crosslinks causing an increase in the strength of the para-casein matrix.

  17. Structures and Spectroscopy Studies of Two M(II-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg

    Directory of Open Access Journals (Sweden)

    Kui-Rong Ma

    2013-01-01

    Full Text Available The two examples of alkaline-earth M(II-phosphonate coordination polymers, [Ba2(L(H2O9]·3H2O (1 and [Mg1.5(H2O9]·(L-H21.5·6H2O (2 (H4L = H2O3PCH2N(C4H8NCH2PO3H2, N,N′-piperazinebis(methylenephosphonic acid, (L-H2 = O3PH2CHN(C4H8NHCH2PO3 have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound 1 possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4 shows two types of coordination modes reported rarely at the same time. In 1, both crystallographic distinct Ba(1 and Ba(2 ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound 2 possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II ions. Free metal cations   [MgO6]n2+ and uncoordinated anions (L-H2n2- are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for 1 and 302 nm, 378 nm, and 434.5 nm for 2 (λex=235 nm, respectively. The high energy emissions could be derived from the intraligand π∗-n transition stations of H4L (310 nm and 382 nm, λex=235 nm, while the low energy emission (>400 nm of 1-2 may be due to the coordination effect with metal(II ions.

  18. 40Ar/39Ar Geochronology, Isotope Geochemistry (Sr, Nd, Pb), and petrology of alkaline lavas near Yampa, Colorado: migration of alkaline volcanism and evolution of the northern Rio Grande rift

    Science.gov (United States)

    Cosca, Michael A.; Thompson, Ren A.; Lee, John P.; Turner, Kenzie J.; Neymark, Leonid A.; Premo, Wayne R.

    2014-01-01

    Volcanic rocks near Yampa, Colorado (USA), represent one of several small late Miocene to Quaternary alkaline volcanic fields along the northeast margin of the Colorado Plateau. Basanite, trachybasalt, and basalt collected from six sites within the Yampa volcanic field were investigated to assess correlations with late Cenozoic extension and Rio Grande rifting. In this paper we report major and trace element rock and mineral compositions and Ar, Sr, Nd, and Pb isotope data for these volcanic rocks. High-precision 40Ar/39Ar geochronology indicates westward migration of volcanism within the Yampa volcanic field between 6 and 4.5 Ma, and the Sr, Nd, and Pb isotope values are consistent with a primary source in the Proterozoic subcontinental lithospheric mantle. Relict olivine phenocrysts have Mg- and Ni-rich cores, whereas unmelted clinopyroxene cores are Na and Si enriched with finely banded Ca-, Mg-, Al-, and Ti-enriched rims, thus tracing their crystallization history from a lithospheric mantle source region to one in contact with melt prior to eruption. A regional synthesis of Neogene and younger volcanism within the Rio Grande rift corridor, from northern New Mexico to southern Wyoming, supports a systematic overall southwest migration of alkaline volcanism. We interpret this Neogene to Quaternary migration of volcanism toward the northeast margin of the Colorado Plateau to record passage of melt through subvertical zones within the lithosphere weakened by late Cenozoic extension. If the locus of Quaternary alkaline magmatism defines the current location of the Rio Grande rift, it includes the Leucite Hills, Wyoming. We suggest that alkaline volcanism in the incipient northern Rio Grande rift, north of Leadville, Colorado, represents melting of the subcontinental lithospheric mantle in response to transient infiltration of asthenospheric mantle into deep, subvertical zones of dilational crustal weakness developed during late Cenozoic extension that have been

  19. Ca and Mg isotope constraints on the origin of Earth's deepest δ13 C excursion

    Science.gov (United States)

    Husson, Jon M.; Higgins, John A.; Maloof, Adam C.; Schoene, Blair

    2015-07-01

    Understanding the extreme carbon isotope excursions found in carbonate rocks of the Ediacaran Period (635-541 Ma), where δ13 C of marine carbonates (δ13 Ccarb) reach their minimum (- 12 ‰) for Earth history, is one of the most vexing problems in Precambrian geology. Known colloquially as the 'Shuram' excursion, the event has been interpreted by many as a product of a profoundly different Ediacaran carbon cycle. More recently, diagenetic processes have been invoked, with the very negative δ13 C values of Ediacaran carbonates explained via meteoric alteration, late-stage burial diagenesis or growth of authigenic carbonates in the sediment column, thus challenging models which rely upon a dramatically changing redox state of the Ediacaran oceans. Here we present 257 δ 44 / 40 Ca and 131 δ26 Mg measurements, along with [Mg], [Mn] and [Sr] data, from carbonates of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia to bring new isotope systems to bear on understanding the 'Shuram' excursion. Data from four measured sections spanning the basin reveal stratigraphically coherent trends, with variability of ∼1.5‰ in δ26 Mg and ∼1.2‰ in δ 44 / 40 Ca. This Ca isotope variability dwarfs the 0.2-0.3 ‰ change seen coeval with the Permian-Triassic mass extinction, the largest recorded in the rock record, and is on par with putative changes in the δ 44 / 40 Ca value of seawater seen over the Phanerozoic Eon. Changes in both isotopic systems are too large to explain with changes in the isotopic composition of Ca and Mg in global seawater given modern budgets and residence times, and thus must be products of alternative processes. Relationships between δ 44 / 40 Ca and [Sr] and δ26 Mg and [Mg] are consistent with mineralogical control (e.g., aragonite vs. calcite, limestone vs. dolostone) on calcium and magnesium isotope variability. The most pristine samples in the Wonoka dataset, preserving Sr concentrations (in the 1000s of ppm range) and δ 44 / 40

  20. Mass-Independent Fractionation of Oxygen Isotope in Earth Wind: First Principle Calculations for Photodissociation

    Science.gov (United States)

    Yamada, A.; Nanbu, S.; Kasai, Y.; Ozima, M.

    2009-12-01

    Mass-independently fractionated oxygen isotope were reported on metal particles extracted from Apollo lunar soils [1, 2], but these origins are still unknown. Since the substantial fraction of Earth-escaping O+ flux (Earth Wind, EW hereafter), comparable to the amount of the anomalous oxygen implanted on the metal particles, could reach the lunar surface [3], Ozima et al. [4] suggested that EW may be responsible to the anomalous oxygen. The purpose is to test this EW hypothesiss, we study oxygen isotopic ratios of O+ at the upper atmosphere. From quantum chemical calculations of photo-dissociation of O2, we show the results in mass-independent isotopic fractionation of oxygen, thereby in conformity with the EW hypothesis. First principles reaction dynamics simulations were performed to compute the photolysis rate for the B3Σu- ← X3Σg- electronic transition, for Schumann-Runge band. With the assumption of the Born-Oppenheimer approximation, we performed the wave-packet dynamics for the nuclei-motion in the potential energy curves determined by the first step calculation. Quantum chemical program package [5] was used for the first step calculation, and the quantum dynamics was carried out by our own program package. Assuming the quantum yield of the corresponding photolysis is unity, the photo-absorption cross section can be correlated with the photolysis rate. Therefore, following the time dependent approach, the autocorrelation function (A(t) = ) was numerically computed by the second step calculation. Finally, the theoretical spectrum as a function of wavelength of excitation light was estimated by the Fourier transform of the autocorrelation function A(t) [6]. Calculated absorption cross sections for C16O showed similar wavelength dependence with experiment [7], although the absolute magnitude was yet to be calibrated for a quantitative comparison. Assuming Boltzmann distribution at 1200 K, we estimated enrichment factors defined as σι(λ)/σ16(λ) - 1 (i

  1. Oxidative Weathering of Earth's Surface 3.7 Billion Years ago? - A Chromium Isotope Perspective

    Science.gov (United States)

    Frei, R.; Crowe, S.; Bau, M.; Polat, A.; Fowle, D. A.; Døssing, L. N.

    2015-12-01

    The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth's earliest surface chemistry and the low oxygen primordial biosphere. We find positive Cr isotope values (average δ53Cr = +0.05 +/- 0.10 permil; δ53Cr = (53Cr/52Cr)sample/(53Cr/52Cr)SRM 979 - 1) x 1000, where SRM 979 denotes Standard Reference Material 979 in both the Fe and Si-rich mesobands of 7 compositionally distinct quartz-magnetite and magnesian banded iron formation (BIF) samples collected from the eastern portion of the Isua BIF (Western Greenland). These postively fractioned Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed BIFs from Isua indicate oxidative Cr cycling 3.8-3.7 Gyr ago. We also examined the distribution of U, which is immobile in its reduced state but mobile when it is oxidized. Elevated U/Th ratios (mean U/Th ratio of 0.70 ± 0.29) in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species (ROS) accumulated in Earth's surface environment inducing the oxidative weathering of rocks during the deposition of the Isua BIFs. The precise threshold atmospheric O2 concentrations for the induction of Cr isotope fractionation remain uncertain, but we argue that our data are consistent with the very low levels of oxygen or other ROS indicated by other proxies. Importantly, any trace of Cr that cycled through redox reactions on land would tend both to be heavy, and to mobilize into the contemporaneous run-off more readily than Cr weathered directly as Cr(III). Once having reached the oceans, this fractionated Cr would have been stripped from seawater by Fe (oxy)hydroxides formed during the deposition of BIFs from low oxygen oceans. The

  2. Meteorite zircon constraints on the bulk Lu−Hf isotope composition and early differentiation of the Earth

    OpenAIRE

    Iizuka, Tsuyoshi; Yamaguchi, Takao; Hibiya, Yuki; Amelin, Yuri

    2015-01-01

    The radioactive decay of lutetium-176 to hafnium-176 has been used to study Earth’s crust−mantle differentiation that is the primary agent of the chemical and thermal evolution of the silicate Earth. Yet the data interpretation requires a well-defined hafnium isotope growth curve of the bulk Earth, which is notoriously difficult to reconstruct from the variable bulk compositions of undifferentiated chondrite meteorites. Here we use lutetium–hafnium systematics of meteorite zircon crystals to ...

  3. Determination of rare-earth elements in rocks by isotope-excited X-ray fluorescence spectrometry

    DEFF Research Database (Denmark)

    Kunzendorf, Helmar; Wollenberg, H.A.

    1970-01-01

    Isotope-excited X-ray fluorescence spectrometry furnishes a rapid determination of rare-earth elements in unprepared rock samples. The samples are excited by 241Am γ-rays, generating X-ray spectra on a multichannel pulse-height analyser. Gaussian peaks of the Kα and Kβ X-ray energies are treated......-ray spectrometric scan of a longitudinally sliced drill core showed a close correlation between rare-earth abundances and appropriate minerals....

  4. Electronic structure, optical properties and bonding in alkaline earth halo-fluoride scintillators: BaClF, BaBrF and BaIF

    Energy Technology Data Exchange (ETDEWEB)

    Yedukondalu, N. [University of Hyderabad; Babu, K. Ramesh [University of Hyderabad; Bheemalingam, Ch. [University of Hyderabad; Singh, David J [ORNL; Vaitheeswaran, G. [University of Hyderabad; Kanchana, V. [IIT Hyderabad

    2011-01-01

    We report first-principles studies of the structural, electronic, and optical properties of the alkaline-earth halofluorides, BaXF (X = Cl, Br, and I), including pressure dependence of structural properties. The band structures show clear separation of the halogen p derived valence bands into higher binding energy F and lower binding energy X derived manifolds reflecting the very high electronegativity of F relative to the other halogens. Implications of this for bonding and other properties are discussed. We find an anisotropic behavior of the structural parameters especially of BaIF under pressure. The optical properties on the other hand are almost isotropic, in spite of the anisotropic crystal structures.

  5. An {\\it ab initio} relativistic coupled-cluster theory of dipole and quadrupole polarizabilities: Applications to a few alkali atoms and alkaline earth ions

    CERN Document Server

    Sahoo, B K

    2006-01-01

    We present a general approach within the relativistic coupled-cluster theory framework to calculate exactly the first order wave functions due to any rank perturbation operators. Using this method, we calculate the static dipole and quadrupole polarizabilities in some alkali atoms and alkaline earth-metal ions. This may be a good test of the present theory for different rank and parity interaction operators. This shows a wide range of applications including precise calculations of both parity and CP violating amplitudes due to rank zero and rank one weak interaction Hamiltonians. We also give contributions from correlation effects and discuss them in terms of lower order many-body perturbation theory.

  6. Earth's early atmosphere as seen from carbon and nitrogen isotopic analysis of Archean sediments

    Science.gov (United States)

    Gibson, E. K., Jr.; Carr, L. P.; Gilmour, I.; Pillinger, C. T.

    1986-01-01

    The origin and evolution of the Earth's early atmosphere has long been a topic of great interest but determination of actual compositions over geologic time is a difficult problem. However, recent systematic studies of stromatolite deposits (Precambrian Paleobiology Research Group) has extended our knowledge of Archean ecosystems. It has been shown that many stromatolite deposits have undergone negligible alteration since their time of formation. The discovery of primary fluid inclusions within unaltered 3.5 b.y. old Archiean sediments and the observation that the 3.3 b.y. old Barberton cherts have remained closed to argon loss and have not been subjected to thermal metamorphism suggests that an opportunity exists for the direct measurement of the volatile constituents present at their time of formation. Of primary interest to this study was the possibility that the stromatolites and other Archean sediments might retain a vestige of the atmosphere and thus afford an indication of the variations in carbon dioxide and nitrogen isotopic compositions with time. A suite of essentially unaltered Archean stromatolites and the cherts of different ages and geologic sites have been analyzed for their trapped carbon dioxide and nitrogen compositions by the stepped combustion extraction tech nique utilizing static mass spectrometers for the isotope measurements.

  7. Global-scale modelling of melting and isotopic evolution of Earth's mantle: melting modules for TERRA

    Science.gov (United States)

    van Heck, Hein J.; Davies, J. Huw; Elliott, Tim; Porcelli, Don

    2016-04-01

    Many outstanding problems in solid-Earth science relate to the geodynamical explanation of geochemical observations. Currently, extensive geochemical databases of surface observations exist, but satisfying explanations of underlying mantle processes are lacking. One way to address these problems is through numerical modelling of mantle convection while tracking chemical information throughout the convective mantle. We have implemented a new way to track both bulk compositions and concentrations of trace elements in a finite-element mantle convection code. Our approach is to track bulk compositions and trace element abundances via particles. One value on each particle represents bulk composition and can be interpreted as the basalt component. In our model, chemical fractionation of bulk composition and trace elements happens at self-consistent, evolving melting zones. Melting is defined via a composition-dependent solidus, such that the amount of melt generated depends on pressure, temperature and bulk composition of each particle. A novel aspect is that we do not move particles that undergo melting; instead we transfer the chemical information carried by the particle to other particles. Molten material is instantaneously transported to the surface layer, thereby increasing the basalt component carried by the particles close to the surface and decreasing the basalt component in the residue. The model is set to explore a number of radiogenic isotopic systems, but as an example here the trace elements we choose to follow are the Pb isotopes and their radioactive parents. For these calculations we will show (1) the evolution of the distribution of bulk compositions over time, showing the buildup of oceanic crust (via melting-induced chemical separation in bulk composition), i.e. a basalt-rich layer at the surface, and the transportation of these chemical heterogeneities through the deep mantle; (2) the amount of melt generated over time; (3) the evolution of the

  8. Syntheses, Vibrational Spectroscopy, and Crystal Structure Determination from X-Ray Powder Diffraction Data of Alkaline Earth Dicyanamides M[N(CN)

    Energy Technology Data Exchange (ETDEWEB)

    Juergens, Barbara; Irran, Elisabeth; Schnick, Wolfgang

    2001-03-01

    The alkaline earth dicyanamides Mg[N(CN){sub 2}]{sub 2}, Ca[N(CN){sub 2}]{sub 2}, Sr[N(CN){sub 2}]{sub 2}, and Ba[N(CN){sub 2}]{sub 2} were synthesized by ion exchange using Na[N(CN){sub 2}] and the respective nitrates or bromides as starting materials. The crystal structures were determined from X-ray powder diffractometry: Mg[N(CN){sub 2}]{sub 2}, Pnnm, Z=2, a=617.14(3), b=716.97(3), and c=740.35(5) pm; Ca[N(CN){sub 2}]{sub 2} and Sr[N(CN){sub 2}]{sub 2}, C2/c, Z=4; Ca[N(CN){sub 2}]{sub 2}, a=1244.55(3), b=607.97(1), and c=789.81(1) pm, {beta}=98.864(2){degree}; Sr[N(CN){sub 2}]{sub 2}, a=1279.63(2), b=624.756(8), and c=817.56(1) pm, {beta}=99.787(1){degree}; Ba[N(CN){sub 2}]{sub 2}, Pnma, Z=4, a=1368.68(7), b=429.07(7), and c=1226.26(2) pm. The dicyanamides consist of the respective alkaline earth cations and bent planar [N(CN){sub 2}]{sup -} ions. The structural features were correlated with vibrational spectroscopic data. The thermal behavior was studied by thermoanalytical experiments.

  9. Enhanced Electroresponse of Alkaline Earth Metal-Doped Silica/Titania Spheres by Synergetic Effect of Dispersion Stability and Dielectric Property.

    Science.gov (United States)

    Yoon, Chang-Min; Lee, Seungae; Cheong, Oug Jae; Jang, Jyongsik

    2015-09-01

    A series of alkaline earth metal-doped hollow SiO2/TiO2 spheres (EM-HST) are prepared as electrorheological (ER) materials via sonication-mediated etching method with various alkaline earth metal hydroxides as the etchant. The EM-HST spheres are assessed to determine how their hollow interior and metal-doping affects the ER activity. Both the dispersion stability and the dielectric properties of these materials are greatly enhanced by the proposed one-step etching method, which results in significant enhancement of ER activity. These improvements are attributed to increased particle mobility and interfacial polarization originating from the hollow nature of the EM-HST spheres and the effects of EM metal-doping. In particular, Ca-HST-based ER fluid exhibits ER performance which is 7.1-fold and 3.1-fold higher than those of nonhollow core/shell silica/titania (CS/ST) and undoped hollow silica/titania (HST)-based ER fluids, respectively. This study develops a versatile and simple approach to enhancing ER activity through synergetic effects arising from the combination of dispersion stability and the unique dielectric properties of hollow EM-HST spheres. In addition, the multigram scale production described in this experiment can be an excellent advantage for practical and commercial ER application.

  10. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

    Science.gov (United States)

    Liu, Yuanyue; Merinov, Boris V; Goddard, William A

    2016-04-01

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems. PMID:27001855

  11. Coordination and ion-ion interactions of chromium centers in alkaline earth zinc borate glasses probed by electron paramagnetic resonance and optical spectroscopy

    Science.gov (United States)

    Sumalatha, B.; Omkaram, I.; Rajavardana Rao, T.; Linga Raju, Ch

    2013-05-01

    Electron paramagnetic resonance (EPR), optical absorption and FT-IR studies have been carried out on chromium ions incorporated in alkaline earth zinc borate glasses. The EPR spectra exhibit two resonance signals with effective g values at g ≈ 1.99 and ≈1.97. The resonance signal at g ≈ 1.99 is attributed to the contribution from both the exchange coupled Cr3+-Cr3+ ion pairs and the isolated Cr3+ ions and the resonance signal at g ≈ 1.97 is due to Cr5+ ions. The paramagnetic susceptibility (χ) was calculated from the EPR data at various (123-303 K) temperatures and the Curie temperature (θp) was calculated from the 1/χ-T graph. The optical absorption spectra exhibit three bands at ˜360 nm, ˜440 nm and a broad band at ˜615 nm characteristic of Cr3+ ions in an octahedral symmetry. From the observed band positions, the crystal-field splitting parameter Dq and the Racah parameters (B and C) have been evaluated. From the ultraviolet edges, the optical band gap energies (Eopt) and Urbach energy (ΔE) are calculated. The theoretical optical basicity (Λth) of these glasses has also been evaluated. Chromium ions doped alkaline earth zinc borate glasses show BO3 and BO4 structural units in the FT-IR studies.

  12. Coordination and ion–ion interactions of chromium centers in alkaline earth zinc borate glasses probed by electron paramagnetic resonance and optical spectroscopy

    International Nuclear Information System (INIS)

    Electron paramagnetic resonance (EPR), optical absorption and FT-IR studies have been carried out on chromium ions incorporated in alkaline earth zinc borate glasses. The EPR spectra exhibit two resonance signals with effective g values at g ≈ 1.99 and ≈1.97. The resonance signal at g ≈ 1.99 is attributed to the contribution from both the exchange coupled Cr3+–Cr3+ ion pairs and the isolated Cr3+ ions and the resonance signal at g ≈ 1.97 is due to Cr5+ ions. The paramagnetic susceptibility (χ) was calculated from the EPR data at various (123–303 K) temperatures and the Curie temperature (θp) was calculated from the 1/χ–T graph. The optical absorption spectra exhibit three bands at ∼360 nm, ∼440 nm and a broad band at ∼615 nm characteristic of Cr3+ ions in an octahedral symmetry. From the observed band positions, the crystal-field splitting parameter Dq and the Racah parameters (B and C) have been evaluated. From the ultraviolet edges, the optical band gap energies (Eopt) and Urbach energy (ΔE) are calculated. The theoretical optical basicity (Λth) of these glasses has also been evaluated. Chromium ions doped alkaline earth zinc borate glasses show BO3 and BO4 structural units in the FT-IR studies. (paper)

  13. Enhanced Electroresponse of Alkaline Earth Metal-Doped Silica/Titania Spheres by Synergetic Effect of Dispersion Stability and Dielectric Property.

    Science.gov (United States)

    Yoon, Chang-Min; Lee, Seungae; Cheong, Oug Jae; Jang, Jyongsik

    2015-09-01

    A series of alkaline earth metal-doped hollow SiO2/TiO2 spheres (EM-HST) are prepared as electrorheological (ER) materials via sonication-mediated etching method with various alkaline earth metal hydroxides as the etchant. The EM-HST spheres are assessed to determine how their hollow interior and metal-doping affects the ER activity. Both the dispersion stability and the dielectric properties of these materials are greatly enhanced by the proposed one-step etching method, which results in significant enhancement of ER activity. These improvements are attributed to increased particle mobility and interfacial polarization originating from the hollow nature of the EM-HST spheres and the effects of EM metal-doping. In particular, Ca-HST-based ER fluid exhibits ER performance which is 7.1-fold and 3.1-fold higher than those of nonhollow core/shell silica/titania (CS/ST) and undoped hollow silica/titania (HST)-based ER fluids, respectively. This study develops a versatile and simple approach to enhancing ER activity through synergetic effects arising from the combination of dispersion stability and the unique dielectric properties of hollow EM-HST spheres. In addition, the multigram scale production described in this experiment can be an excellent advantage for practical and commercial ER application. PMID:26266695

  14. MB82- (M=Be,Mg,Ca,Sr,and Ba):Planar octacoordinate alkaline earth metal atoms enclosed by boron rings

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Complexes involving planar octacoordinate alkaline earth metal atoms in the centers of eight-membered boron rings have been investigated by two density functional theory (DFT) methods.BeB82-with D8h symmetry is predicted to be stable,both geometrically and electronically,since a good match is achieved between the size of the central beryllium atom and the eight-membered boron ring.By contrast,the other alkaline earth metal atoms cannot be stabilized in the center of a planar eight-membered boron ring because of their large radii.By following the out-of-plane imaginary vibrational frequency,pyramidal C8v MgB82-,CaB82-,SrB82-,and BaB82-structures are obtained.The presence of delocalized π and σ valence molecular orbitals in D8h BeB82-gives rise to aromaticity,which is reflected by the value of the nucleus-independent chemical shift.The D8h BeB82-structure is confirmed to be the global minimum on the potential energy surface.

  15. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals

    Science.gov (United States)

    Liu, Yuanyue; Merinov, Boris V.; Goddard, William A., III

    2016-04-01

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

  16. The role of magma mixing in the evolution of high-K calc-alkaline granitoid suites: in situ trace element and Sr-Nd-Hf isotope constraints

    Science.gov (United States)

    Laurent, Oscar; Zeh, Armin; Gerdes, Axel; Slaby, Ewa; Villaros, Arnaud

    2015-04-01

    The so-called "I-type", high-K calc-alkaline granitoids are often considered as "hybrid" in origin, i.e. involving both mantle and crustal components in their petrogenesis. The interactions between both components either take place (1) at mantle levels (i.e. enriched mantle source); (2) at emplacement levels (i.e. crustal contamination and/or magma mixing with crustal melts) or (3) both. Magma mixing is, in particular, frequently invoked to explain the compositional range of high-K calc-alkaline granitoid suites, especially phases of intermediate composition (SiO2 = 60-65 wt.%) such as quartz-diorites or granodiorites. We investigated the role of magma mixing in the origin of such rocks using elemental and isotope (Sr-Nd-Hf) chemistry of magmatic minerals (plagioclase, zircon, apatite, titanite, epidote), measured in situ by LA-(MC-)ICPMS, allowing a much greater spatial resolution than classical whole-rock geochemistry. We focused on a suite of late-Archaean (2.69 Ga-old) high-K, calc-alkaline granitoids from the Pietersburg block, northern Kaapvaal Craton (South Africa): the Mashashane, Matlala, Matok and Moletsi plutons. Those plutons range from diorites to monzogranites, emplaced at different crustal levels but all within a relatively short time span and showing evidence for interactions (mingling), both at the outcrop and mineral scale. Hf isotope data on zircon confirm that all rocks are cogenetic (identical ɛHf(t)), but trace element and Sr isotopes in plagioclase point to the involvement of several components in their petrogenesis, at different stages of the magma evolution. The most mafic rocks (diorites) derive from the interaction, at mantle levels, between depleted peridotite and a sedimentary component of quartzofeldspathic nature. The mineral chemistry of more felsic rocks can be explained by (1) differentiation from the diorite magmas through Amp + Plag fractionation; (2) interactions with magmas derived from melting of local crust (tonalites

  17. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

    Science.gov (United States)

    Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2016-04-01

    Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

  18. Rare-earth nuclei: Radii, isotope-shifts and deformation properties in the relativistic mean field theory

    International Nuclear Information System (INIS)

    A systematic study of the ground-state properties of even-even rare earth nuclei has been performed in the framework of the Relativistic Mean-Field (RMF) theory using the parameter set NL-Sh. Nuclear radii, isotope shifts and deformation properties of the heavier rare-earth nuclei have been obtained, which encompass atomic numbers ranging from Z=60 to Z=70 and include a large range of isospin. It is shown that RMF theory is able to provide a good and comprehensive description of the empirical binding energies of the isotopic chains. At the same time the quadrupole deformations β2 obtained in the RMF theory are found to be in good agreement with the available empirical values. The theory predicts a shape transition from prolate to oblate for nuclei at neutron number N=78 in all the chains. A further addition of neutrons up to the magic number 82 brings about the spherical shape. For nuclei above N-82, the RMF theory predicts the well-known onset of prolate deformation at about N-88, which saturates at about N-102. The deformation properties display an identical behaviour for all the nuclear chains. A good description of the above deformation transitions in the RMF theory in all the isotopic chains leads to a successful reproduction of the anomalous behaviour of the empirical isotopic shifts of the rare-earth nuclei. The RMF theory exhibits a remarkable success in providing a unified and microscopic description of various empirical data. (orig.)

  19. Comparative investigation on the effect of alkaline earth oxides on the intensity of absorption bands due to Cu2+, Mn3+ and Cr3+ ions in ternary silicate glasses

    Indian Academy of Sciences (India)

    S P Singh; Aman; Anal Tarafder

    2004-06-01

    Absorption characteristics of Cu2+, Mn3+ and Cr3+ ions in ternary silicate (20Na2O.10RO.70SiO2, where R=Ca, Sr, Ba) glasses were investigated. The intensities of absorption bands due to Cu2+ ion was found to increase with increasing ionic radii of the alkaline earth ions whereas it was found to decrease in case of Mn3+ and Cr3+ ions with increasing ionic radii of the alkaline earth ions. The results were discussed in the light of relation between linear extinction coefficients of these ions and coulombic force of alkaline earth ions. The change in intensities of Cu2+, Mn3+ and Cr3+ ion is attributed due to change in silicate glass compositions.

  20. Deep sources of salinisation of Lake Kinneret, Israel - An isotope and rare earth approach

    International Nuclear Information System (INIS)

    Full text: Salinisation of fresh groundwater reservoirs is a widespread problem, especially in arid regions. As a first step for protection it is crucial to identify its sources and mechanisms. The Jordan Rift Valley between Israel and Jordan is the deepest land depression on earth with the Dead Sea with -410 m below sea level, functioning as a receiving reservoir for the surrounding highlands. Groundwater quality changes drastically within sharp boundaries indicating an admixture of saline groundwater components of different origins. Lake Kinneret (Sea of Galilee), situated in the northern part of the Jordan Rift Graben, serves as an important drinking water reservoir for Israel and by treaty also for Jordan. The water quality is affected by an influx of saline groundwater by salty springs located at the lake shore but also within the lake and by an up welling seepage via the lake floor. More or less two main groups of theories exist about the primary origin of the salinity. One is that the salinisation derives by dilution of an ancient, intensively evaporated brine developed in a lake formed in the Rift Valley following seawater intrusion during late Miocene. The other is that the salinisation derives from dissolved evaporative sediments in a depth of 2000 meters or more. The existence of these sediments is not proven but strong hints exists. Based on isotope, Rare Earth elements and chemical data at least three different water types can be distinguished which all can be explained by mixing of more or less one original brine with recent young groundwater. (author)

  1. Potassium isotope cosmochemistry, volatile depletion and the origin of the Earth

    Science.gov (United States)

    Humayun, M.; Clayton, R. N.

    1993-01-01

    We report the first results obtained by our techniques for the precise and accurate determination of the isotopic composition of potassium to constrain the mechanism of volatile element depletion in the formation of the Earth, Moon, and meteorites. Our measurements of delta(K-41) for six chondrites and ten terrestrial rocks attained an average precision of the individual measurement of plus or minus 0.4 percent (2 sigma; plus or minus 0.2 percent/a.m.u. and yield a net chondrite-Earth difference unresolved at the 99 percent confidence limit, delta(K-41) = 0.32 plus or minus 0.35 percent (3 delta). This sets a firm upper limit of 1.3 plus or minus 1.4 percent Rayleigh evaporation of terrestrial potassium (using alpha = square root of 41/39), compared with an observed approximately equals 85 percent chemical depletion of K relative to C1 chondrites. Similar conclusions are reached for the SNC meteorites, Shergotty and Zagami, for 15495 (lunar mare gabbro), and for the eucrite Juvinas. Our conclusion is that direct evaporation of volatile elements from planets (e.g. from silicate vapor atmospheres following giant impact) can be ruled out, and the cause of volatile loss must be sought elsewhere, e.g. nebular processes. Our present findings do not support the conclusions of Hinton et al., the discrepancy to be resolved at a later date. We also find lunar soil 64801, delta(K-41) = +4.99 plus or minus 0.53 percent, to be distinctly heavy in accord with Garner et al.

  2. IsoNose - Isotopic Tools as Novel Sensors of Earth Surfaces Resources - A new Marie Curie Initial Training Network

    Science.gov (United States)

    von Blanckenburg, Friedhelm; Bouchez, Julien; Bouman, Caludia; Kamber, Balz; Gaillardet, Jérôme; Gorbushina, Anna; James, Rachael; Oelkers, Eric; Tesmer, Maja; Ashton, John

    2015-04-01

    The Marie Curie Initial Training Network »Isotopic Tools as Novel Sensors of Earth Surfaces Resources - IsoNose« is an alliance of eight international partners and five associated partners from science and industry. The project is coordinated at the Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences and will run until February 2018. In the last 15 years advances in novel mass-spectrometric methods have opened opportunities to identify "isotopic fingerprints" of virtually all metals and to make use of the complete information contained in these fingerprints. The understanding developed with these new tools will ultimately guide the exploitation of Earth surface environments. However, progress in bringing these methods to end-users depends on a multi transfer of knowledge between (1) isotope Geochemistry and Microbiology, Environmental Sciences (2), Economic Geology and (3) instrument developers and users in the development of user-friendly and new mass spectrometric methods. IsoNose will focus on three major Earth surface resources: soil, water and metals. These resources are currently being exploited to an unprecedented extent and their efficient management is essential for future sustainable development. Novel stable isotope techniques will disclose the processes generating (e.g. weathering, mineral ore formation) and destroying (e.g. erosion, pollution) these resources. Within this field the following questions will be addressed and answered: - How do novel stable isotope signatures characterize weathering processes? - How do novel stable isotope signatures trace water transport? - How to use novel stable isotope as environmental tracers? - How to use novel stable isotope for detecting and exploring metal ores? - How to improve analytical capabilities and develop robust routine applications for novel stable isotopes? Starting from the central questions mentioned above the IsoNose activities are organized in five scientific work packages: 1

  3. Chlorine isotope enrichment on a strong alkaline anion exchanger in dependence of type and concentration of the strange electrolytic solution

    International Nuclear Information System (INIS)

    Chlorine isotope enrichment for heterogenous ionexchange equilibria was studied. The dependence of element separation effects on the anion of the strange electrolyte (for same cation), on the cation of the strange electrolyte (for same anion), on the concentration of the strange electrolyte and also on the acetone: water ratio of the solvent was investigated. (orig./HBR)

  4. Astrophysical Shrapnel: Discriminating Among Near-Earth Stellar Explosion Sources of Live Radioactive Isotopes

    CERN Document Server

    Fry, Brian J; Ellis, John R

    2015-01-01

    We consider the production and deposition on Earth of isotopes with half-lives in the range 10$^{5}$ to 10$^{8}$ years that might provide signatures of nearby stellar explosions, extending previous analyses of Core-Collapse Supernovae (CCSNe) to include Electron-Capture Supernovae (ECSNe), Super-Asymptotic Giant Branch (SAGBs) stars, Thermonuclear/Type Ia Supernovae (TNSNe), and Kilonovae/Neutron Star Mergers (KNe). We revisit previous estimates of the $^{60}$Fe and $^{26}$Al signatures, and extend these estimates to include $^{244}$Pu and $^{53}$Mn. We discuss interpretations of the $^{60}$Fe signals in terrestrial and lunar reservoirs in terms of a nearby stellar ejection ~2.2 Myr ago, showing that (i) the $^{60}$Fe yield rules out the TNSN and KN interpretations, (ii) the $^{60}$Fe signals highly constrain a SAGB interpretation but do not completely them rule out, (iii) are consistent with a CCSN origin, and (iv) are highly compatible with an ECSN interpretation. Future measurements could resolve the radio...

  5. ASTROPHYSICAL SHRAPNEL: DISCRIMINATING AMONG NEAR-EARTH STELLAR EXPLOSION SOURCES OF LIVE RADIOACTIVE ISOTOPES

    Energy Technology Data Exchange (ETDEWEB)

    Fry, Brian J.; Fields, Brian D. [Department of Astronomy, University of Illinois, Urbana, IL 61801 (United States); Ellis, John R. [Theoretical Physics and Cosmology Group, Department of Physics, King' s College London, London WC2R 2LS (United Kingdom)

    2015-02-10

    We consider the production and deposition on Earth of isotopes with half-lives in the range 10{sup 5}-10{sup 8} yr that might provide signatures of nearby stellar explosions, extending previous analyses of Core-Collapse Supernovae (CCSNe) to include Electron-Capture Supernovae (ECSNe), Super-Asymptotic Giant Branch (SAGB) stars, Thermonuclear/Type Ia Supernovae (TNSNe), and Kilonovae/Neutron Star Mergers (KNe). We revisit previous estimates of the {sup 60}Fe and {sup 26}Al signatures, and extend these estimates to include {sup 244}Pu and {sup 53}Mn. We discuss interpretations of the {sup 60}Fe signals in terrestrial and lunar reservoirs in terms of a nearby stellar ejection ∼2.2 Myr ago, showing that (1) the {sup 60}Fe yield rules out the TNSN and KN interpretations, (2) the {sup 60}Fe signals highly constrain SAGB interpretations but do not completely them rule out, (3) are consistent with a CCSN origin, and (4) are highly compatible with an ECSN interpretation. Future measurements could resolve the radioisotope deposition over time, and we use the Sedov blast wave solution to illustrate possible time-resolved profiles. Measuring such profiles would independently probe the blast properties including distance, and would provide additional constraints for the nature of the explosion.

  6. ASTROPHYSICAL SHRAPNEL: DISCRIMINATING AMONG NEAR-EARTH STELLAR EXPLOSION SOURCES OF LIVE RADIOACTIVE ISOTOPES

    International Nuclear Information System (INIS)

    We consider the production and deposition on Earth of isotopes with half-lives in the range 105-108 yr that might provide signatures of nearby stellar explosions, extending previous analyses of Core-Collapse Supernovae (CCSNe) to include Electron-Capture Supernovae (ECSNe), Super-Asymptotic Giant Branch (SAGB) stars, Thermonuclear/Type Ia Supernovae (TNSNe), and Kilonovae/Neutron Star Mergers (KNe). We revisit previous estimates of the 60Fe and 26Al signatures, and extend these estimates to include 244Pu and 53Mn. We discuss interpretations of the 60Fe signals in terrestrial and lunar reservoirs in terms of a nearby stellar ejection ∼2.2 Myr ago, showing that (1) the 60Fe yield rules out the TNSN and KN interpretations, (2) the 60Fe signals highly constrain SAGB interpretations but do not completely them rule out, (3) are consistent with a CCSN origin, and (4) are highly compatible with an ECSN interpretation. Future measurements could resolve the radioisotope deposition over time, and we use the Sedov blast wave solution to illustrate possible time-resolved profiles. Measuring such profiles would independently probe the blast properties including distance, and would provide additional constraints for the nature of the explosion

  7. [Effect of processes in the earth's crust on evolution of photosynthesis (as indicated by data on carbon isotopic composition)].

    Science.gov (United States)

    Ivlev, A A

    2010-01-01

    A probable mechanism of effect of processes occurring in the Earth's crust on evolution of photosynthesis is considered. According to the hypothesis, this effect is realized through entrance to the Earth's atmosphere of carbon dioxide that stimulates photosynthesis. Supply of CO2 is irregular and is due to irregular movements of the Earth's crust plates. This is accompanied by destruction of carbonates and conversion of carbon of the organic matter to CO2 due to processes of reduction of sulfates. The CO2 content in atmosphere rises for relatively short orogenic periods, due to intensive crust plate movement, while for the subsequent long periods, called the geosynclinal ones, of the relatively slow plate movement, the CO2 content falls due to the higher rate of its consumption for photosynthesis. Owing to the carbon isotopic fractionation accompanying photosynthesis, regular isotopic differences appear between the atmospheric CO2 and the "living" matter (Relay's effect); these differences are then transformed to isotope differences of the carbonate and organic carbon. At the appearance in atmosphere of free oxygen--product of photosynthesis--in organisms there appears photorespiration that also is accompanied by fractionation of carbon isotopes, but with effect of opposite sign. This leads to enrichment of the photosynthesizing biomass with 13C isotope at the orogenic periods. As a result, the initially pronounced isotope differences of the carbonate and organic carbon decrease by the end of the geosyclinal periods. According to the proposed model, concentrations of CO2 and O2 are exchanged in the antiphase. They lead to alternation of periods of warning up and cooling off on the Earth. The former coincide with the orogenic periods, the latter appear at the end of geosyclinal periods when oxygen is accumulated in atmosphere, while organic substance in sediments. Accumulation of organic substance leads to formation of petroleum-maternal masses. To substantiate the

  8. The tungsten isotopic composition of Eoarchean rocks: Implications for early silicate differentiation and core-mantle interaction on Earth

    Science.gov (United States)

    Iizuka, Tsuyoshi; Nakai, Shun'ichi; Sahoo, Yu Vin; Takamasa, Asako; Hirata, Takafumi; Maruyama, Shigenori

    2010-03-01

    We have measured 182W/ 184W for Eoarchean rocks from the Itsaq Gneiss Complex (3.8-3.7 Ga pillow meta-basalts, a meta-tonalite, and meta-sediments) and Acasta Gneiss Complex (4.0-3.6 Ga felsic orthogneisses) to assess possible W isotopic heterogeneity within the silicate Earth and to constrain W isotopic evolution of the mantle. The data reveal that 182W/ 184W values in the Eoarchean samples are uniform within the analytical error and indistinguishable from the modern accessible mantle signature, suggesting that the W isotopic composition of the upper mantle has not changed significantly since the Eoarchean era. The results imply either that chemical communication between the mantle and core has been insignificant in post-Hadean times, or that a lowermost mantle with a distinctive W isotope signature has been isolated from mantle convective cycling. Most terrestrial rock samples have a 0.2 ɛ142Nd/ 144Nd higher than the chondrite average. This requires either the presence of a hidden enriched reservoir formed within the first 30 Ma of the Solar System, or the bulk Earth having a ˜ 5% higher Sm/Nd than the chondrite average. We explored the relevance of the 182Hf- 182W isotope system to the 146Sm- 142Nd isotope system during early silicate differentiation events on Earth. In this context, we demonstrate that the lack of resolvable 182W excesses in the Itsaq rocks, despite 142Nd excesses compared to the modern accessible mantle, is more consistent with the view that the bulk Earth has a non-chondritic Sm/Nd. In the non-chondritic Sm/Nd Earth model, the 182W- 142Nd chronometry constrains the age of the source mantle depletion for the Itsaq samples to more than ˜ 40 Ma after the Solar System origin. Our results cannot confirm the previous report of 182W anomalies in the Eoarchean Itsaq meta-sediments, which were interpreted as reflecting an impact-derived meteoritic component.

  9. Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass: differences between sugar cane bagasse and cane trash.

    Science.gov (United States)

    Keown, Daniel M; Favas, George; Hayashi, Jun-ichiro; Li, Chun-Zhu

    2005-09-01

    Sugar cane bagasse and cane trash were pyrolysed in a novel quartz fluidised-bed/fixed-bed reactor. Quantification of the Na, K, Mg and Ca in chars revealed that pyrolysis temperature, heating rate, valence and biomass type were important factors influencing the volatilisation of these alkali and alkaline earth metallic (AAEM) species. Pyrolysis at a slow heating rate (approximately 10 K min(-1)) led to minimal (often biomass samples. Fast heating rates (>1000 K s(-1)), encouraging volatile-char interactions with the current reactor configuration, resulted in the volatilisation of around 80% of Na, K, Mg and Ca from bagasse during pyrolysis at 900 degrees C. Similar behaviour was observed for monovalent Na and K with cane trash, but the volatilisation of Mg and Ca from cane trash was always restricted. The difference in Cl content between bagasse and cane trash was not sufficient to fully explain the difference in the volatilisation of Mg and Ca.

  10. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS2

    Directory of Open Access Journals (Sweden)

    X. D. Li

    2015-05-01

    Full Text Available Single adsorption of different atoms on pristine two-dimensional monolayer MoS2 have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS2. Additionally, local or long-range magnetic moments of two-dimensional MoS2 sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS2 monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

  11. Production of Synthesis Gas via Methane Reforming with CO2 on Ni/SiO2 Catalysts Promoted by Alkali and Alkaline Earth Metals

    Institute of Scientific and Technical Information of China (English)

    陈平; 侯昭胤; 郑小明

    2005-01-01

    Ni/SiO2 catalysts promoted by alkali metals K and Cs or alkaline earth metals Mg, Ca, Sr and Ba were prepared, characterized by H2-TPR and XRD, and used for the production of synthesis gas via methane reforming with CO2. Though K and Cs promoted Ni catalysts could eliminate coke deposition, the reforming activity of these promoted catalysts was decreased heavily. Mg and Ca promoted Ni/SiO2 catalysts exhibited excellent coke resistance ability with minor loss of the reforming activity of Ni/SiO2. Ba showed poor coke resistance ability and small amount of Sr increased the formation of coke. The possible mechanism of these promoters was discussed.

  12. Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al2O3 in methane catalytic partial oxidation

    Institute of Scientific and Technical Information of China (English)

    Changlin Yu; Weizheng Weng; Qing Shu; Xiangjie Meng; Bin Zhang; Xirong Chen; Xiaochun Zhou

    2011-01-01

    Nano-sized γ-alumina(γ-Al2O3)was first prepared by a precipitation method.Then,active component of cobalt and a series of alkalineearth metal promoters or nickel(Ni)with different contents were loaded on the γ-Al2O3 support.The catalysts were characterized by N2 adsorption-desorption,X-ray diffraction(XRD)and thermogravimetry analysis(TGA).The activity and selectivity of the catalysts in catalytic partial oxidation(CPO)of methane have been compared with Co/γ-Al2O3,and it is found that the catalytic activity,selectivity,and stability are enhanced by the addition of alkaline-earth metals and nickel.The optimal loadings of strontium(Sr)and Ni were 6 and 4 wt%,respectively.This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane.

  13. Dispersion coefficients for the interactions of the alkali and alkaline-earth ions and inert gas atoms with a graphene layer

    CERN Document Server

    Kaur, Kiranpreet; Sahoo, B K

    2015-01-01

    Largely motivated by a number of applications, the van der Waals dispersion coefficients ($C_3$s) of the alkali ions (Li$^+$, Na$^+$, K$^+$ and Rb$^+$), the alkaline-earth ions (Ca$^+$, Sr$^+$, Ba$^+$ and Ra$^+$) and the inert gas atoms (He, Ne, Ar and Kr) with a graphene layer are determined precisely within the framework of Dirac model. For these calculations, we have evaluated the dynamic polarizabilities of the above atomic systems very accurately by evaluating the transition matrix elements employing relativistic many-body methods and using the experimental values of the excitation energies. The dispersion coefficients are, finally, given as functions of the separation distance of an atomic system from the graphene layer and the ambiance temperature during the interactions. For easy extraction of these coefficients, we give a logistic fit to the functional forms of the dispersion coefficients in terms of the separation distances at the room temperature.

  14. Dispersion coefficients for the interactions of the alkali-metal and alkaline-earth-metal ions and inert-gas atoms with a graphene layer

    Science.gov (United States)

    Kaur, Kiranpreet; Arora, Bindiya; Sahoo, B. K.

    2015-09-01

    Largely motivated by a number of applications, the van der Waals dispersion coefficients C3 of the alkali-metal ions Li+,Na+,K+, and Rb+, the alkaline-earth-metal ions Ca+,Sr+,Ba+, and Ra+, and the inert-gas atoms He, Ne, Ar, and Kr with a graphene layer are determined precisely within the framework of the Dirac model. For these calculations, we evaluate the dynamic polarizabilities of the above atomic systems very accurately by evaluating the transition matrix elements employing relativistic many-body methods and using the experimental values of the excitation energies. The dispersion coefficients are given as functions of the separation distance of an atomic system from the graphene layer and the ambiance temperature during the interactions. For easy extraction of these coefficients, we give a logistic fit to the functional forms of the dispersion coefficients in terms of the separation distances at room temperature.

  15. Determination of rare earth elements, uranium and thorium in geological samples by ICP-MS, using an automatic fusion machine as an alkaline digestion tool.

    Science.gov (United States)

    Granda, Luis; Rivera, Maria; Velasquez, Colon; Barona, Diego; Carpintero, Natalia

    2014-05-01

    At the present time, rare earth elements deposits have became in strategic resources for extraction of raw materials in order to manufacture high tech devices (computers, LCD, cell phones, batteries for hybrid vehicles, fiber optics and wind turbines) (1).The appropriate analytical determination of the REE ( rare earth elements) in sediment and rock samples , is important to find potential deposits and to recognize geological environments for identifying possible alterations and mineral occurrences. The alkaline fusion, which aim is to move the entire sample from solid to liquid state by forming water soluble complexes of boron and lithium, as a previous procedure for the determination of these elements, usually takes a lot of time due to the complexity of the analysis phase and by the addition of other reagents (Tm and HF ) (2) to compensate the lack of strict temperature control. The objective of this work is to develop an efficient alternative to alkaline digestion using an electrical fusion machine, which allows to create temperature programs with advanced process control and supports up to 5 samples simultaneously, which generates a reproducibility of the method and results during the melting step. Additionally, this new method permits the processing of a larger number of samples in a shorter time. The samples analyzed in this method were weighed into porcelain crucibles and subjected to calcination for 4 hours at 950 ° C in order to determine the Lost on Ignition (LOI ) , that serves to adjust the analytical results and to preserve the shelf life of the platinum ware. Subsequently, a fraction of the calcined sample was weighed into platinum crucibles and mixed with ultra-pure lithium metaborate ( flux ) 1:4 . The crucible was then placed in the fusion machine, which was programmed to take the sample from room temperature to 950 ° C in five minutes, make a small ramp to 970 ° C maintain that temperature for five minutes and download the melt in a 10 % v / v

  16. Enhanced NH{sub 3} gas sensing performance based on electrospun alkaline-earth metals composited SnO{sub 2} nanofibers

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Shuang [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Key Laboratory of Physical Chemistry, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); Kan, Kan [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Key Laboratory of Physical Chemistry, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); Daqing Branch, Heilongjiang Academy of Sciences, Daqing 163319 (China); Yang, Ying; Jiang, Chao [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Key Laboratory of Physical Chemistry, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); Gao, Jun [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Key Laboratory of Physical Chemistry, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); Department of Chemistry, Harbin Normal University, Harbin 150025 (China); Jing, Liqiang [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Key Laboratory of Physical Chemistry, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); Shen, Peikang [Department of Physics and Engineering Sun Yat-sen University, Guangzhou 510275 (China); Li, Li, E-mail: llwjjhlju@sina.cn [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Key Laboratory of Physical Chemistry, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); Key Laboratory of Chemical Engineering Process and Technology for High-efficiency Conversion, School of Chemistry and Material Science, Heilongjiang University, Harbin 150080 (China); and others

    2015-01-05

    Highlights: • The small-sized SnO{sub 2} (5–7 nm) were obtained by adding the alkaline-earth. • Sr-composited SnO{sub 2} nanofibers showed uniform nanotubes structure (Sr/SnO{sub 2}). • Sr/SnO{sub 2} showed an excellent sensing performance to NH{sub 3} at room temperature. - Abstract: One-dimensional alkaline-earth metals composited SnO{sub 2} (Ae/SnO{sub 2}) nanofibres were fabricated via electrospinning technique, followed by thermal treatment at 600 °C for 5 h. Transmission electron microscopy (TEM) studies showed that the nanoparticles size of Ae/SnO{sub 2} was 5–7 nm, which was smaller than the pristine SnO{sub 2} nanorods attached by 20 nm nanoparticles. Moreover, Sr/SnO{sub 2} nanocomposites showed uniform nanotubes structure with the wall thickness of about 30 nm, in which all the nanoparticles were connected to their neighbors by necks. The Sr/SnO{sub 2} nanotubes exhibited an excellent sensing response toward NH{sub 3} gas at room temperature, lower detection limit (10 ppm), faster response time (6 s towards 2000 ppm∼16 s towards 10 ppm) and better reversibility compared to the pristine SnO{sub 2} nanorods. The enhanced sensor performances were attributed to the higher conductivity of the Sr/SnO{sub 2}. Mott–Schottky plots (M–S) and electrochemical impedance spectroscopy (EIS) measurements indicated that the carrier density of Sr/SnO{sub 2} nanotubes was 3 fold of that pristine SnO{sub 2}.

  17. Syntheses and characterization of energetic compounds constructed from alkaline earth metal cations (Sr and Ba) and 1,2-bis(tetrazol-5-yl)ethane

    International Nuclear Information System (INIS)

    Two new energetic compounds, [M(BTE)(H2O)5]n (M=Sr(1), Ba(2)) [H2BTE=1,2-bis(tetrazol-5-yl)ethane], have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isomorphous and exhibit 2D (4,4) net framework, generated by 4-connected Sr2(H2O)10/Ba2(H2O)10 SBUs linked up by two independent binding modes of H2BTE, and the resulting 2D structure is interconnected by hydrogen-bond and strong face to face π-π stacking interactions between two tetrazole rings to lead to a 3D supramolecular architecture. DSC measurements show that they have significant catalytic effects on thermal decomposition of ammonium perchlorate. Moreover, the photoluminescence properties, thermogravimetric analyses, and flame colors of the as-prepared compounds are also investigated in this paper. - Graphical abstract: Two novel 2D isomorphous alkaline earth metal complexes were assembled by 4-connected Sr2(H2O)10/Ba2(H2O)10 SBUs and two independent binding modes of H2BTE ligands, and the catalytic performances toward thermal decomposition of ammonium perchlorate and photoluminescent properties of them were investigated. Highlights: → Two novel alkaline earth energetic coordination polymers have been prepared.→ Both structures are layered based on 4-connected Sr2(H2O)10/Ba2(H2O)10 SBUs and two distinct H2BTE coordination modes.→ The dehydrated products of the compounds possess good thermostability and significant catalytic effects on thermal decomposition of AP.

  18. Origin and Dynamics of Rare Earth Elements during Flood Events in Contaminated River Basins: Sr-Nd-Pb Isotopic Evidence.

    Science.gov (United States)

    Hissler, Christophe; Stille, Peter; Iffly, Jean François; Guignard, Cédric; Chabaux, François; Pfister, Laurent

    2016-05-01

    In order to precisely quantify the contribution of anthropogenic activities and geogenic sources to the dissolved and suspended loads of rivers we have combined for the first time Rare Earth Element (REE) concentrations with Sr-Nd-Pb isotope ratios. We observed enrichments in Anthropogenic Rare Earth Elements (AREE) for dissolved (Gd) and suspended (Ce and Nd) loads of river water. During flood events, AREE anomalies progressively disappeared and gave way to the geogenic chemical signature of the basin in both dissolved and suspended loads. The isotopic data confirm these observations and shed new light on the trace elements sources. On the one hand, dissolved loads have peculiar isotopic characteristics and carry mainly limestone-derived and anthropogenic Sr and Nd as well as significant amounts of anthropogenic Pb. On the other hand, the results clearly indicate that anthropogenic contributions impact the suspended loads in all hydrological conditions. This study demonstrates that anthropogenic contributions to the river may change not only Pb but also Sr and Nd isotopic compositions in both dissolved and suspended loads. This is of importance for future provenance studies. PMID:27045616

  19. Hydrogen and carbon abundances and isotopic ratios in apatite from alkaline intrusive complexes, with a focus on carbonatites

    Energy Technology Data Exchange (ETDEWEB)

    Nadeau, S.L.; Epstein, S.; Stolper, E. [California Inst. of Tech., Pasadena, CA (United States). Div. of Geological and Planetary Sciences

    1999-06-01

    The authors report H and C contents and {delta}D and {delta}{sup 13}C values of apatites from 15 alkaline intrusive complexes ranging in age from 110 Ma to 2.6 Ga. Sampling focused on carbonatites, but included silicate rocks as well. Heating temperatures up to 1,500 C is needed to extract fully H{sub 2}O and CO{sub 2} from these apatites. Apatites from carbonatite-rich intrusive complexes contain 0.2--1.1 wt% H{sub 2}O and 0.05--0.70 wt% CO{sub 2}; apatites from two silicate-rich alkaline complexes with little or no carbonatite are generally poorer in both volatile components (0.1--0.2% H{sub 2}O and 0.01--0.11% CO{sub 2}). D/H ratios in apatites from these rocks are bimodally distributed. The authors suggest that the {delta}D values of group I apatites represent primitive, mantle-derived values and that the group II apatites crystallized from degassed magmas, resulting in lower H{sub 2}O contents and {delta}D values. In contrast to H{sub 2}O contents and {delta}D values, CO{sub 2} contents and {delta}{sup 13}C values of gas released at high temperatures from multiple aliquots of these apatite samples are variable. This suggests the presence of more than one C-bearing component in these apatites, one of which is proposed to be dissolved carbonate; the other could be associated with hydrocarbons.

  20. Geology and stable isotope geochemistry of Paleoarchean sulfur. Formation, preservation and geobiology of ancient pyrite and barite. (Utrecht Studies in Earth Sciences 031)

    NARCIS (Netherlands)

    Roerdink, D.L.

    2013-01-01

    Sulfur isotopes in ancient sulfate and sulfide minerals provide a comprehensive record of microbial processes involved in the early sulfur cycle on Earth. However, the interpretation of these isotopic signatures requires information on the geological context of such samples, because abiotic reaction

  1. Comparisons between adsorption and diffusion of alkali, alkaline earth metal atoms on silicene and those on silicane: Insight from first-principles calculations

    Science.gov (United States)

    Bo, Xu; Huan-Sheng, Lu; Bo, Liu; Gang, Liu; Mu-Sheng, Wu; Chuying, Ouyang

    2016-06-01

    The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory. Silicane is staler against the metal adatoms than silicene. Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene. Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed. However, the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate. Combining the adsorption energy with the diffusion energy barriers, it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage. In order to avoid forming a metal cluster, we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane. Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials. Project supported by the Natural Science Foundation of Jiangxi Province, China (Grant Nos. 20152ACB21014, 20151BAB202006, and 20142BAB212002) and the Fund from the Jiangxi Provincial Educational Committee, China (Grant No. GJJ14254). Bo Xu is also supported by the Oversea Returned Project from the Ministry of Education, China.

  2. Rare earth elements and titanium in plants, soils and groundwaters in the alkaline-ultramafic complex of Salitre, MG, Brazil

    OpenAIRE

    Ceccantini, G.; Figueiro, A.M.G.; Sondag, Francis; Soubiès, François

    1997-01-01

    The contents of Rare Earth Elements (REE) and titanium in various species of plants, in groundwaters and in soils from the ultramafic complex of Salitre, MG, Brazil, were determined. Due to the particular mineralogy of the bedrock, REE and Ti present high concentrations in the soils. The transfer factors of the REE from soil to plants were calculated, giving values ranging from 0.0001 to 0.0028, much lower than the values reported elsewhere in Brazil. Furthermore, as suggested by other author...

  3. Shoshonite and sub-alkaline magmas from an ultrapotassic volcano: Sr-Nd-Pb isotope data on the Roccamonfina volcanic rocks, Roman Magmatic Province, Southern Italy

    Science.gov (United States)

    Conticelli, Sandro; Marchionni, Sara; Rosa, Davide; Giordano, Guido; Boari, Elena; Avanzinelli, Riccardo

    2009-01-01

    The Roccamonfina volcano is characterised by two stages of volcanic activity that are separated by volcano-tectonic caldera collapses. Ultrapotassic leucite-bearing rocks are confined to the pre-caldera stage and display geochemical characteristics similar to those of other volcanoes in the Roman Province. After the major sector collapse of the volcano, occurred at ca. 400 ka, shoshonitic rocks erupted from cinder cones and domes both within the caldera and on the external flanks of the pre-caldera Roccamonfina volcano. On the basis of new trace element and Sr-Nd-Pb isotope data, we show that the Roccamonfina shoshonitic rocks are distinct from shoshonites of the Northern Roman Province, but are very similar to those of the Neapolitan volcanoes. The last phases of volcanic activity erupted sub-alkaline magmas as enclaves in trachytic domes, and as lavas within the Monte Santa Croce dome. Ultrapotassic rocks of the pre-caldera composite volcano are plagioclase-bearing leucitites characterised by high levels of incompatible trace elements with an orogenic signature having troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of 87Sr/86Sr range from 0.70926 to 0.70999, 143Nd/144Nd ranges from 0.51213 to 0.51217, while the lead isotope rations vary between 18.788-18.851 for 206Pb/204Pb, 15.685-15.701 for 207Pb/204Pb, and 39.048-39.076 for 208Pb/204Pb. Shoshonites show a similar pattern of trace element depletions and enrichments to the earlier ultrapotassic leucite-bearing rocks but have a larger degree of differentiation and lower concentrations of incompatible trace elements. On the other hand, shoshonitic rocks have Sr, Nd, and Pb isotopes consistently different than pre-caldera ultrapotassic leucite-bearing rocks. 87Sr/86Sr ranges from 0.70665 to 0.70745, 143Nd/144Nd ranges from 0.51234 to 0.51238, 206Pb/204Pb ranges from 18.924 to 19.153, 207Pb/204Pb ranges from 15.661 to 15.694, and 208Pb/204Pb ranges from 39.084 to 39.212. High-K calc-alkaline

  4. Water concentrations and hydrogen isotope compositions of alkaline basalt-hosted clinopyroxene megacrysts and amphibole clinopyroxenites: the role of structural hydroxyl groups and molecular water

    Science.gov (United States)

    Kovács, István; Demény, Attila; Czuppon, György; Lécuyer, Christophe; Fourel, Francois; Xia, Qun-Ke; Liu, Jia; Pintér, Zsanett; Király, Edit; Török, Kálmán; Szabó, Ábel; Deloule, Etienne; Falus, György; Fancsik, Tamás; Zajacz, Zoltán; Sándorné Kovács, Judit; Udvardi, Beatrix

    2016-05-01

    The aim of this study was to determine both `water' contents (as OH- and H2O) and δD values of several clinopyroxene samples from alkaline basalts. These parameters were first obtained from five clinopyroxene samples using both the classical `off-line' vacuum extraction technique and the `on-line' high-temperature pyrolysis technique. Blanks measured with the `on-line' gas extraction techniques were low enough to prevent any contamination by atmospheric water vapour. The comparison of data has revealed that our `on-line' procedure is more effective for the extraction of `water' from clinopyroxenes and, consequently, this `on-line' technique was applied to ten additional clinopyroxene samples. Sample δD values cover a similar range from -95 to -45 ‰ (VSMOW) regardless of the studied locations, whereas the total `water' content varies from ~115 to ~2570 ppm. The structural hydroxyl content of clinopyroxene samples measured by micro-FTIR spectrometry varies from ~0 to 476 ppm expressed in molecular water equivalent. The total `water' concentrations determined by mass spectrometry differ considerably from structural hydroxyl contents constrained by micro-FTIR, thus indicating that considerable proportion of the `water' may be present in (nano)-inclusions. The structural hydroxyl concentration—apart from clinopyroxenes separated from amphibole clinopyroxenite xenoliths—correlates positively with the δD values of clinopyroxene megacrysts for each locality, indicating that structurally bond hydrogen in clinopyroxenes may have δD values higher than molecular water in inclusions. This implies that there may be a significant hydrogen isotope fractionation for structural hydroxyl during crystallization of clinopyroxene, while for molecular water there may be no or only negligible isotope fractionation.

  5. Elemental partitioning and isotopic fractionation of Zn between metal and silicate and geochemical estimation of the S content of the Earth's core

    CERN Document Server

    Mahan, B; Pringle, E A; Moynier, F

    2016-01-01

    Zinc metal-silicate fractionation provides experimental access to the conditions of core formation and Zn has been used to estimate the S contents of the Earth's core and of the bulk Earth, assuming that they share similar volatility and that Zn was not partitioned into the Earth's core. We have conducted a suite of partitioning experiments to characterize Zn metal-silicate elemental and isotopic fractionation as a function of time, temperature, and composition. Experiments were conducted at temperatures from 1473-2273K, with run durations from 5-240 minutes for four starting materials. Chemical and isotopic equilibrium is achieved within 10 minutes. Zinc metal-silicate isotopic fractionation displays no resolvable dependence on temperature, composition, or oxygen fugacity. Thus, the Zn isotopic composition of silicate phases can be used as a proxy for bulk telluric bodies. Results from this study and literature data were used to parameterize Zn metal-silicate partitioning as a function of temperature, pressu...

  6. Oxygen-18 leaving group kinetic isotope effects on the hydrolysis of nitrophenyl glycosides. 2. Lysozyme and beta-glucosidase: acid and alkaline hydrolysis.

    Science.gov (United States)

    Rosenberg, S; Kirsch, J F

    1981-05-26

    Oxygen-18 leaving group kinetic isotope effects (KIEs) have been measured for a set of glycosyl transfer reactions with p-nitrophenyl beta-D-glycosides as substrates. Acid-catalyzed hydrolysis and alkaline hydrolysis exhibit KIEs of K16/k18 = 1.0355 +/- 0.0015 and 1.0386 +/- 0.0032, respectively. Lysozyme and beta-glucosidase A show KIEs on Vmax/Km (V/K) of (V/KI)16/(V/K)18 = 1.0467 +/- 0.0015 and 1.0377 +/0 0.0061, respectively. The large magnitude of these KIEs requires that carbon-oxygen bond scission be far advanced in the transition states for these reactions; therefore in the transition states for the first irreversible steps in these reaction sequences, scission of the glycosidic bond must be essentially complete for the reactions catalyzed by lysozyme and beta-glucosidase A, which are thought to proceed via SN1 and SN2 mechanisms, respectively. Acid-catalyzed hydrolysis is shown to proceed through a transition state involving at least 80% C-O bond cleavage and only partially proton transfer to the leaving p-nitrophenyl oxygen atom. PMID:6788083

  7. Sr, C and O isotopes as markers of alkaline disturbances in the Toarcian argillites of the Tournemire experimental platform (France). Case of a 15-years old engineered analogue.

    Science.gov (United States)

    Techer, I.; Boulvais, P.; Bartier, D.; Tinseau, E.

    2009-04-01

    argillites close to the cement-concrete contact. These data are detailed in another session of this meeting (Techer et al., ERE6 session). In order to precise the spatial extent of the disturbances and to discuss the nature of the responsible fluids, a systematic chemical and isotopic study was performed focusing on the Sr, C and O isotopes known to be very good markers of alkaline fluids percolation (Fourcade et al. 2006). Four studied levels were selected according to their location on the DM overcore and the nature of the cementitious material in contact to the argillites: -155 cm level (DM155) and -180 cm level (DM180) where argillites were in contact with a 1.5 to 3 cm thick concrete; -245 cm level (DM245) and -300 cm level (DM300) where the cementitious material was represented by a fine grained Portland cement 2 to 5 cm thick. Samples of the cementitious materials were collected at each level. Argillites were sampled perpendicularly to the cement-concrete contact with a continuous sampling every 2 to 5 mm millimeters (P1). Micro-fissures developed perpendicularly to the cement-concrete contact were opened and infilling secondary minerals were collected by scrap as a function of the distance to the cement-concrete (P3). Along P1 and P3, no significant variation of the carbonates d18O isotopic values was observed in the argillites. On the opposite d13C and 87Sr/86Sr values of these minerals changed significantly in the direct contact with the cement-concrete over a distance of 15 to 25 mm. Beyond this distance, argillites were again well bedded and showed values similar to those measured in a reference sample. Negative d13C values measured in the disturbed zone and close to those encountered in the cement and the concrete argued for a perturbation induced by an alkaline solution. 87Sr/86Sr isotopic ratios showed a progressive evolution in the disturbed zone, with increasing trends towards the cementitious material. Thanks to complementary Sr elementary contents

  8. C and O stable isotopic signatures of fast-growing dripstones on alkaline substrates: reflection of growth mechanism, carbonate sources and environmental conditions.

    Science.gov (United States)

    Zavadlav, Saša; Mazej, Darja; Zavašnik, Janez; Rečnik, Aleksander; Dominguez-Víllar, David; Cukrov, Neven; Lojen, Sonja

    2012-06-01

    Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments--Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave)--were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ(13)C (average-28.2‰) and δ(18)O (average-18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO(2) in a highly alkaline solution and consequent disequilibrium precipitation of CaCO(3). The main source of carbon is atmospheric or biogenic CO(2) in the poorly ventilated karstic cave, which is reflected in even lower δ(13)C values. Statistical analysis of δ(13)C and δ(18)O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate. PMID:22316094

  9. In-situ buildup of cosmogenic isotopes at the earth`s surface: measurement of erosion rates and exposure times

    Energy Technology Data Exchange (ETDEWEB)

    Fifield, L.K.; Allan, G.L.; Stone, J.O.H.; Evans, J.M.; Cresswell, R.G.; Ophel, T.R. [Australian National Univ., Canberra, ACT (Australia)

    1993-12-31

    Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes {sup 10}Be (t{sub 1/2} = 1.5Ma), {sup 26}Al (0.7Ma) and {sup 36}Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on {sup 36}Cl. The accumulation of cosmogenic {sup 36}Cl in calcite (CaCO{sub 3}) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of {sup 36}Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of {sup 36}Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of {sup 36}Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs.

  10. Chromium stable isotope systematic – implications for the redox evolution of the earth

    DEFF Research Database (Denmark)

    Døssing, Lasse Nørbye

    isotopes as modern soil profiles and indicate that oxidative weathering in the terrestrial environment started well before and after the Great Oxidation Event ~2.3 billion years ago. The signals of oxidative weathering on land are traceable in contemporaneous marine sediments such as Banded Iron Formations......The isotopic composition of chromium (Cr) holds great promise as a paleo-redox proxy.Whereas the reduction of oxidized Cr(VI) to Cr(III) yields a well-defined kineticfractionation, the fractionation imparted during oxidative weathering is only described theoretically. This thesis demonstrates...... that Cr isotopes fractionate during oxidative weathering of modern soil systems. The result is the retention of light Cr(III) and the release of heavy Cr(VI) to runoff. Deviations in Cr isotope compositions from mantle inventory values are ultimately attributed to oxidative weathering in modern systems...

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

    CERN Document Server

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

    2012-01-01

    The long-range non-additive three-body dispersion interaction coefficients $Z_{111}$, $Z_{112}$, $Z_{113}$, and $Z_{122}$ 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 $Z_{111}$, arising from three mutual dipole interactions is known as the Axilrod-Teller-Muto coefficient or the DDD (dipole-dipole-dipole) coefficient. Similarly, the terms $Z_{112}$, $Z_{113}$, and $Z_{122}$ arise from the mutual combinations of dipole (1), quadrupole (2), and octupole (3) interactions between atoms and they are sometimes known, respectively, as DDQ, DDO, and DQQ 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, Li atoms. An exhaustive compilation of all coefficients between all possible atomic combinations is presented as supp...

  12. CO{sub 2} Capture Properties of Alkaline-earth Metal Oxides and Hydroxides: A Combined Density Functional Theory and Lattice Phonon Dynamics Study

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Yuhua; Sorescu, Dan

    2010-01-01

    By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO{sub 2} absorption/desorption reactions with alkaline earth metal oxides MO and hydroxides M(OH){sub 2} (where M = Be,Mg,Ca,Sr,Ba) are analyzed. The heats of reaction and the chemical potential changes of these solids upon CO{sub 2} capture reactions have been calculated and used to evaluate the energy costs. Relative to CaO, a widely used system in practical applications, MgO and Mg(OH){sub 2} systems were found to be better candidates for CO{sub 2} sorbent applications due to their lower operating temperatures (600–700 K). In the presence of H{sub 2}O, MgCO{sub 3} can be regenerated into Mg(OH){sub 2} at low temperatures or into MgO at high temperatures. This transition temperature depends not only on the CO{sub 2} pressure but also on the H{sub 2}O pressure. Based on our calculated results and by comparing with available experimental data, we propose a general computational search methodology which can be used as a general scheme for screening a large number of solids for use as CO{sub 2} sorbents.

  13. CO2 capture properties of alkaline earth metal oxides and hydroxides: A combined density functional theory and lattice phonon dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Yuhua [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Sorescu, Dan C. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

    2010-01-01

    By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO2 absorption/desorption reactions with alkaline earth metal oxides MO and hydroxides M(OH)2 (where M = Be, Mg, Ca, Sr, Ba) are analyzed. The heats of reaction and the chemical potential changes of these solids upon CO2 capture reactions have been calculated and used to evaluate the energy costs. Relative to CaO, a widely used system in practical applications, MgO and Mg(OH)2 systems were found to be better candidates for CO2 sorbent applications due to their lower operating temperatures (600-700 K). In the presence of H2O, MgCO3 can be regenerated into Mg(OH)2 at low temperatures or into MgO at high temperatures. This transition temperature depends not only on the CO2 pressure but also on the H2O pressure. Based on our calculated results and by comparing with available experimental data, we propose a general computational search methodology which can be used as a general scheme for screening a large number of solids for use as CO2 sorbents.

  14. CO(2) capture properties of alkaline earth metal oxides and hydroxides: A combined density functional theory and lattice phonon dynamics study.

    Science.gov (United States)

    Duan, Yuhua; Sorescu, Dan C

    2010-08-21

    By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO(2) absorption/desorption reactions with alkaline earth metal oxides MO and hydroxides M(OH)(2) (where M=Be,Mg,Ca,Sr,Ba) are analyzed. The heats of reaction and the chemical potential changes of these solids upon CO(2) capture reactions have been calculated and used to evaluate the energy costs. Relative to CaO, a widely used system in practical applications, MgO and Mg(OH)(2) systems were found to be better candidates for CO(2) sorbent applications due to their lower operating temperatures (600-700 K). In the presence of H(2)O, MgCO(3) can be regenerated into Mg(OH)(2) at low temperatures or into MgO at high temperatures. This transition temperature depends not only on the CO(2) pressure but also on the H(2)O pressure. Based on our calculated results and by comparing with available experimental data, we propose a general computational search methodology which can be used as a general scheme for screening a large number of solids for use as CO(2) sorbents. PMID:20726653

  15. Mechanochemical synthesis, structure, and properties of solid solutions of alkaline earth metal fluorides: Ma1-xMbxF2 (M: Ca, Sr, Ba)

    Science.gov (United States)

    Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

    2016-10-01

    The capability of mechanochemical synthesis for the formation of solid solutions of alkaline earth metal fluorides Ma1-xMbxF2 (M: Ca, Sr, Ba) was tested by fluorination of metal acetates and metal hydroxides with ammonium fluoride directly at milling. Evidence was found for a mutual substitution of cations on their lattice positions in Ca1-xSrxF2 and Ba1-xSrxF2 samples. For the Ba/Ca-system this synthesis route is only partially successful. X-ray diffraction and 19F MAS NMR spectroscopy were used to characterize all samples concerning their crystal structure and local fluorine coordination. Calculations of 19F chemical shifts with the superposition model along with probability calculations for the intensity of the individual 19F lines, performed in dependence on the molar composition of the samples, perfectly agree with the experimental findings. The fluoride ion conductivity of as-prepared samples, determined by temperature dependent DC conductivity measurements, is significantly higher than those of crystalline binary fluorides. Moreover, a higher F- ion conductivity is observed for samples with higher mixing grade in the Ca/Sr-and the Ba/Sr-systems.

  16. [High current microsecond pulsed hollow cathode lamp excited ionic fluorescence spectrometry of alkaline earth elements in inductively coupled plasma with a Fassel-torch].

    Science.gov (United States)

    Zhang, Shao-Yu; Gong, Zhen-Bin; Huang, Ben-Li

    2006-02-01

    High current microsecond pulsed hollow cathode lamp (HCMP-HCL) excited ionic fluorescence spectrometry (IFS) of alkaline earth elements in inductively coupled plasma (ICP) with a Fassel-torch has been investigated. In wide condition ranges only IFS was observed, whilst atomic fluorescence spectrometry (AFS) was not detectable. More intense ionic fluorescence signal was observed at lower observation heights and at lower incident RF powers. Without introduction of any reduction organic gases into the ICP, the limit of detection (LOD, 3sigma) of Ba was improved by 50-fold over that of a conventional pulsed (CP) HCL with the Baird sleeve-extended torch. For Ca and Sr, the LODs by HCMP-HCL-ICP-IFS and CP-HCL-ICP-AFS show no significant difference. Relative standard deviations were 0.6%-1.4% (0.1-0.2 microg x mL(-1), n = 10) for 5 ionic fluorescence lines. Preliminary studies showed that the intensity of ionic fluorescence could be depressed in the presence of K, Al and P.

  17. Transfer of alkaline earth elements in mothers' milk and doses from {sup 45}Ca, {sup 90}Sr and {sup 226}Ra

    Energy Technology Data Exchange (ETDEWEB)

    Smith, T.J.; Phipps, A.W.; Fell, T.P.; Harrison, J.D

    2003-07-01

    An international programme of work is currently under way to develop methods for calculating doses to infants from ingestion of radionuclides present in mothers' milk. This paper considers the special case of the alkaline earth elements. Models have been developed for {sup 45}Ca, {sup 90}Sr and {sup 226}Ra and the sensitivity of results to various changes in parameter values is discussed. A complication when calculating doses from intakes of radium is that the International Commission on Radiological Protection has previously recommended that doses from decay products of radium should be calculated using element-specific biokinetic models (so-called independent biokinetics). An extension of this method to the models for breastfeeding is proposed. Preliminary estimates of the doses received by the infant for a number of maternal intake scenarios show that doses to the infant can exceed the corresponding adult dose, such as for {sup 45}Ca (ratio = 3.1) while, in other cases such as {sup 90}Sr, the infant dose can be a significant fraction of the adult dose. (author)

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

    Directory of Open Access Journals (Sweden)

    Jin-Gang Ma

    2015-08-01

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

  19. Ab initio properties of the ground-state polar and paramagnetic europium-alkali-metal-atom and europium-alkaline-earth-metal-atom molecules

    CERN Document Server

    Tomza, Michał

    2014-01-01

    The properties of the electronic ground state of the polar and paramagnetic europium-$S$-state-atom molecules have been investigated. Ab initio techniques have been applied to compute the potential energy curves for the europium-alkali-metal-atom, Eu$X$ ($X$=Li, Na, K, Rb, Cs), europium-alkaline-earth-metal-atom, Eu$Y$ ($Y$=Be, Mg, Ca, Sr, Ba), and europium-ytterbium, EuYb, molecules in the Born-Oppenheimer approximation for the high-spin electronic ground state. The spin restricted open-shell coupled cluster method restricted to single, double, and noniterative triple excitations, RCCSD(T), was employed and the scalar relativistic effects within the small-core energy-consistent pseudopotentials were included. The permanent electric dipole moments and static electric dipole polarizabilities were computed. The leading long-range coefficients describing the dispersion interaction between atoms at large internuclear distances $C_6$ are also reported. The EuK, EuRb, and EuCs molecules are examples of species poss...

  20. Strontium isotopes and rare-earth element geochemistry of hydrothermal carbonate deposits from Lake Tanganyika, East Africa

    Energy Technology Data Exchange (ETDEWEB)

    Barrat, J.A.; Boulegue, J.; Tiercelin, J.J.; Lesourd, M.

    2000-01-01

    At Cape Banza (North Tanganyika Lake), fluids and aragonite chimneys have been collected many times since the discovery of this sublacustrine field in 1987. This sampling has been investigated here for the Sr isotopic compositions and the rare-earth element features of the carbonates and a few fluid samples. The {sup 87}Sr/{sup 86}Sr ratios of the chimneys indicate that they have precipitated from a mixture of lake water (more than 95%) and hydrothermal fluids. No zoning in the chimneys was detected with the Sr data. For the rare-earth elements, the situation is more complex. The external walls of the chimneys are rare-earth-element-poor (La {approx} 500 ppb, Yb {approx} 200 ppb, La/Yb = 2 to 3.4). Their shale normalized rare-earth element patterns suggest that they are in equilibrium with the inferred carbonate-depositing fluids. The rare-earth element concentrations of the internal walls of the chimneys are significantly light rare earth elements (LREE)-enriched with La contents sometimes up to 5 ppm. The authors suggest that they contain more vent-fluid rare-earth elements than the external wall samples, possibly adsorbed on the surface of growing crystals or simply hosted by impurities. It was not possible to constrain the nature of these phases, but the variations of the compositions of the internal wall materials of the active chimneys with time, as well as data obtained on an inactive chimney indicate that this rare-earth element excess is mobile. Partition coefficients were calculated between the external wall aragonite and carbonate-depositing fluid. The results are strikingly similar to the values obtained by Sholkovitz and Shen (1995) on coral aragonite, and suggest that there is no significant biologic effect on the incorporation of rare-earth elements into coral aragonite and that the various carbonate complexes involved Me(CO{sub 3}{sup +}) complexes are the main LREE carriers in seawater instead of Me(CO{sub 3}){sub 2}{sup {minus}} in Banza fluids

  1. Study of the effect hydrogen binding in the solvation of alkaline earth cations with MeOH in nitromethane using 1 H NMR technique and determination of ionic solvation number

    CERN Document Server

    Alizadeh, N

    2001-01-01

    A proton NMR method for the study of the effect hydrogen binding and determination of solvation numbers of alkaline earth cations with methanol (MeOH) in in tromethane (NM) as diluent is described. The method is based on monitoring the resonance frequency of MeOH protons as a function of MeOH to metal ion mole ratio at constant metal ion concentration. the average solvation number of cation, n, at any MeOH/ metal ion mole ration was calculated from the NMR chemical shift-mole ration data and was plotted against the mole ration values. The solvation numbers of alkaline earth cations were obtained from the limiting values of the corresponding n, vs. mole ratio plots.

  2. Contamination in mafic mineral-rich calc-alkaline granites: a geochemical and Sr-Nd isotope study of the Neoproterozoic Piedade Granite, SE Brazil

    Directory of Open Access Journals (Sweden)

    Leite Renato J.

    2006-01-01

    Full Text Available The Piedade Granite (~600 Ma was emplaced shortly after the main phase of granite magmatism in the Agudos Grandes batholith, Apiaí-Guaxupé Terrane, SE Brazil. Its main units are: mafic mineral-rich porphyritic granites forming the border (peraluminous muscovite-biotite granodiorite-monzogranite MBmg unit and core (metaluminous titanite-bearing biotite monzogranite BmgT unit and felsic pink inequigranular granite (Bmg unit between them. Bmg has high LaN/YbN (up to 100, Th/U (>10 and low Rb, Nb and Ta, and can be a crustal melt derived from deep-seated sources with residual garnet and biotite. The core BmgT unit derived from oxidized magmas with high Mg# (~45, Ba and Sr, fractionated REE patterns (LaN/YbN= 45, 87Sr/86Sr(t~ 0.710, epsilonNd(t ~ -12 to -14, interpreted as being high-K calc-alkaline magmas contaminated with metasedimentary rocks that had upper-crust signature (high U, Cs, Ta. The mafic-rich peraluminous granites show a more evolved isotope signature (87Sr/86Sr(t = 0.713-0.714; epsilonNd(t= -14 to -16, similar to Bmg, and Mg# and incompatible trace-element concentrations intermediate between Bmg and BmgT. A model is presented in whichMBmgis envisaged as the product of contamination between a mafic mineral-rich magma consanguineous with BmgT and pure crustal melts akin to Bmg.

  3. Isotopic ages for alkaline igneous rocks, including a 26 Ma ignimbrite, from the Peshawar plain of northern Pakistan and their tectonic implications

    Science.gov (United States)

    Ahmad, Irshad; Khan, Shuhab; Lapen, Thomas; Burke, Kevin; Jehan, Noor

    2013-01-01

    New isotopic ages on zircons from rocks of the Peshawar Plain Alkaline Igneous Province (PPAIP) reveal for the first time the occurrence of ignimbritic Cenozoic (Oligocene) volcanism in the Himalaya at 26.7 ± 0.8 Ma. Other new ages confirm that PPAIP rift-related igneous activity was Permian and lasted from ˜290 Ma to ˜250 Ma. Although PPAIP rocks are petrologically and geochemically typical of rifts and have been suggested to be linked to rifting on the Pangea continental margin at the initiation of the Neotethys Ocean, there are no documented rift-related structures mapped in Permian rocks of the Peshawar Plain. We suggest that Permian rift-related structures have been dismembered and/or reactivated during shortening associated with India-Asia collision. Shortening in the area between the Main Mantle Thrust (MMT) and the Main Boundary Thrust (MBT) may be indicative of the subsurface northern extension of the Salt Range evaporites. Late Cenozoic sedimentary rocks of the Peshawar Plain deposited during and after Himalayan thrusting occupy a piggy-back basin on top of the thrust belt. Those sedimentary rocks have buried surviving evidence of Permian rift-related structures. Igneous rocks of the PPAIP have been both metamorphosed and deformed during the Himalayan collision and Cenozoic igneous activity, apart from the newly recognized Gohati volcanism, has involved only the intrusion of small cross-cutting granitic bodies concentrated in areas such as Malakand that are close to the MMT. Measurements on Chingalai Gneiss zircons have confirmed the occurrence of 816 ± 70 Ma aged rocks in the Precambrian basement of the Peshawar Plain that are comparable in age to rocks in the Malani igneous province of the Rajasthan platform ˜1000 km to the south.

  4. An estimate of the Bulk Silicate Earth potassium isotopic composition based on MC-ICPMS measurements of basalts

    Science.gov (United States)

    Wang (王昆), Kun; Jacobsen, Stein B.

    2016-04-01

    We report a method for high-precision potassium isotope measurements that improves by an order of magnitude the precision compared to previous methods. The purification of K is achieved through ion exchange chromatography on AG50W-X8 cation exchange resins. The 41K/39K ratios are analyzed with a GV Instruments IsoProbe P Multiple-Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICP-MS) equipped with a hexapole collision gas cell. With this technique, the argon-hydride interferences as well as the large 40Ar+ peak from the Ar-plasma are eliminated. The 41K/39K ratios can thus be obtained with a precision of 0.05 per mil. The precision and accuracy of this method is validated with gravimetrically determined 41K or 39K enriched standards. New precise K isotopic compositions of three terrestrial basalts (BCR-2, BHVO-1 and a MORB) are also reported. These basalts have indistinguishable K isotopic compositions and are used to define a reference value of -0.479 ± 0.027 per mil for the 41K/39K ratio of the Bulk Silicate Earth (BSE) relative to a Merck Suprapur potassium nitrate standard. Seawater and sylvites from evaporite deposits have similar 41K/39K ratios, but higher by up to 0.227 per mil compared to the Merck Suprapur standard. Other commercially available K-salts/solutions also have 41K/39K ratios similar to the Merck standard, while a SPEX K-chloride was higher by 0.384 per mil. This shows that K isotope variations will be useful as a tracer in low-temperature geochemistry processes.

  5. Global-scale modelling of melting and isotopic evolution of Earth's mantle: Melting modules for TERRA

    NARCIS (Netherlands)

    Van Heck, H.J.; Huw Davies, J.; Elliott, T.; Porcelli, D.

    2016-01-01

    Many outstanding problems in solid-Earth science relate to the geodynamical explanation of geochemical observations. Currently, extensive geochemical databases of surface observations exist, but satisfying explanations of underlying mantle processes are lacking. One way to address these problems is

  6. Strontium isotopes and rare earth elements as tracers of groundwater-lake water interactions, Lake Naivasha, Kenya

    Energy Technology Data Exchange (ETDEWEB)

    Bwire Ojiambo, S.; Berry Lyons, W.; Welch, Kathy A.; Poreda, Robert J.; Johannesson, Karen H

    2003-11-01

    Strontium isotope compositions and rare earth element (REE) concentrations are presented for groundwater and surface water samples collected from the Lake Naivasha watershed in the East African Rift, Kenya. The chief objective of the study is to test the suitability of REEs, in conjunction with Sr isotopes, as tools for investigating groundwater-lake water interactions. In general, the REE concentrations and {sup 87}Sr/{sup 86}Sr ratios support the authors' earlier investigations where Cl mass balance, {delta}{sup 18}O, {delta}D, and He isotopes were employed to study groundwater-lake water interactions in the Naivasha watershed. The REE data suggest that a significant amount of the groundwater south of Lake Naivasha (i.e., 50-85%) consists of lake water recharge to the aquifer system. Specifically, mixing calculations conducted using REE data of Lake Naivasha water and groundwaters indicate that between 70 and 85% of groundwater directly south of the lake is likely lake water. These values are somewhat higher than the authors' previous estimates determined with conservative stable H isotopes ({delta}D, 50-70%). For both cases, however, the data demonstrate that water originating in Lake Naivasha contributes significantly to the underlying groundwater flow system, hence supporting earlier evidence that the lake's freshness reflects rapid loss of water and dissolved solutes to the local groundwater system. Overall, lake and groundwater Sr isotope compositions support seepage of lake water into the underlying aquifer along the lake's south shore. The {sup 87}Sr/{sup 86}Sr data also provide additional insight into the geochemical evolution of waters of the Lake Naivasha watershed indicating that the initial source of Sr to these waters is likely chemical weathering reactions involving basaltic rocks within the recharge zones of the watershed along the Rift Valley flanks. Furthermore, with increasing residence time of groundwaters within the aquifer

  7. Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices—CCSD(T) calculations and atomic site occupancies

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Barry M.; McCaffrey, John G., E-mail: john.mccaffrey@nuim.ie [Department of Chemistry, Maynooth University, National University of Ireland—Maynooth, County Kildare (Ireland)

    2016-01-28

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y{sup 1}P←a{sup 1}S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ⋅ RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (<130 cm{sup −1}). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr{sub 2} while this transition is quenched in Ba{sub 2}. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba{sub 2} indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications.

  8. Interaction of Rydberg atoms in circular states with the alkaline-earth Ca(4s{sup 2}) and Sr(5s{sup 2}) atoms

    Energy Technology Data Exchange (ETDEWEB)

    Mironchuk, E. S.; Narits, A. A.; Lebedev, V. S., E-mail: vlebedev@sci.lebedev.ru [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation)

    2015-11-15

    The resonant mechanism of interaction of alkaline-earth atoms having a low electron affinity to Rydberg atoms in circular (l = vertical bar m vertical bar = n–1) and near-circular states has been studied. To describe the dynamics of resonant processes accompanied by nonadiabatic transitions between ionic and Rydberg covalent terms of a quasimolecule, an approach based on the integration of coupled equations for the probability amplitudes has been developed taking into account the possibility of the decay of an anion in the Coulomb field of the positive ionic core of a highly excited atom. The approach involves the specific features of the problem associated with the structure of the wavefunction of a Rydberg electron in states with high orbital angular momenta l ∼ n–1. This approach provides a much more accurate description of the dynamics of electronic transitions at collisions between atoms than that within the modified semiclassical Landau–Zener model. In addition, this approach makes it possible to effectively take into account many channels of the problem. The cross sections for resonant quenching of Rydberg states of the Li(nlm) atom with given principal n, orbital l = n–1, and magnetic m quantum numbers at thermal collisions with the Ca(4s{sup 2}) and Sr(5s{sup 2}) atoms have been calculated. The dependences of the results on n, m, and angle α between the relative velocity of the atoms and the normal to the plane of the orbit of the Rydberg electron have been obtained. The influence of orientational effects on the efficiency of the collisional destruction of circular and near-circular states has been studied. The results indicate a higher stability of such states to their perturbations by neutral particles as compared to usually studied nl states with low values of l (l ≪ n)

  9. Promoting alkali and alkaline-earth metals on MgO for enhancing CO2 capture by first-principles calculations.

    Science.gov (United States)

    Kim, Kiwoong; Han, Jeong Woo; Lee, Kwang Soon; Lee, Won Bo

    2014-12-01

    Developing next-generation solid sorbents to improve the economy of pre- and post-combustion carbon capture processes has been challenging for many researchers. Magnesium oxide (MgO) is a promising sorbent because of its moderate sorption-desorption temperature and low heat of sorption. However, its low sorption capacity and thermal instability need to be improved. Various metal-promoted MgO sorbents have been experimentally developed to enhance the CO2 sorption capacities. Nevertheless, rigorous computational studies to screen an optimal metal promoter have been limited to date. We conducted first-principles calculations to select metal promoters of MgO sorbents. Five alkali (Li-, Na-, K-, Rb-, and Cs-) and 4 alkaline earth metals (Be-, Ca-, Sr-, and Ba-) were chosen as a set of promoters. Compared with the CO2 adsorption energy on pure MgO, the adsorption energy on the metal-promoted MgO sorbents is higher, except for the Na-promoter, which indicates that metal promotion on MgO is an efficient approach to enhance the sorption capacities. Based on the stabilized binding of promoters on the MgO surface and the regenerability of sorbents, Li, Ca, and Sr were identified as adequate promoters among the 9 metals on the basis of PW91/GGA augmented with DFT+D2. The adsorption energies of CO2 on metal-promoted MgO sorbents for Li, Ca, and Sr atoms are -1.13, -1.68, and -1.48 eV, respectively. PMID:25319405

  10. Alkaline Earth Metal Zirconate Perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)) Derived from Molecular Precursors and Doped with Eu(3+) Ions.

    Science.gov (United States)

    Drąg-Jarząbek, Anna; John, Łukasz; Petrus, Rafał; Kosińska-Klähn, Magdalena; Sobota, Piotr

    2016-03-24

    The effect of alkaline earth metal alkoxides on the protonation of zirconocene dichloride was investigated. This approach enabled the design of compounds with preset molecular structures for generating high-purity binary metal oxide perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)). Single-source molecular precursors [Ba4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2(η(2) -HOR)2 (HOR)2 Cl4], [Sr4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2 (HOR)4 Cl4], [Ca4 Zr2 (μ6-O)(μ3 ,η(2)-OR)8 (OR)2 Cl4], and [Ca6 Zr2 (μ2 ,η(2)-OR)12 (μ-Cl)2 (η(2) -HOR)4 Cl6 ]⋅8 CH2 Cl2 were prepared via elimination of the cyclopentadienyl ring from Cp2 ZrCl2 as CpH in the presence of M(OR)2 and alcohol ROH (ROH=CH3OCH2 CH2OH) as a source of protons. The resulting complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray diffraction. The compounds were then thermally decomposed to MCl2 /MZrO3 mixtures. Leaching of MCl2 from the raw powder with deionized water produced highly pure perovskite-like oxide particles of 40-80 nm in size. Luminescence studies on Eu(3+)-doped MZrO3 revealed that the perovskites are attractive host lattices for potential applications in display technology. PMID:26891039

  11. Isotopic geology

    International Nuclear Information System (INIS)

    Born from the application to geology of nuclear physics techniques, the isotopic geology has revolutionized the Earth's sciences. Beyond the dating of rocks, the tracer techniques have permitted to reconstruct the Earth's dynamics, to measure the temperatures of the past (giving birth to paleoclimatology) and to understand the history of chemical elements thanks to the analysis of meteorites. Today, all domains of Earth sciences appeal more or less to the methods of isotopic geology. In this book, the author explains the principles, methods and recent advances of this science: 1 - isotopes and radioactivity; 2 - principles of isotope dating; 3 - radio-chronological methods; 4 - cosmogenic isotope chronologies; 5 - uncertainties and radio-chronological results; 6 - geochemistry of radiogenic isotopes; 7 - geochemistry of stable isotopes; 8 - isotopic geology and dynamical analysis of reservoirs. (J.S.)

  12. Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere.

    Science.gov (United States)

    Dominguez, Gerardo; Jackson, Terri; Brothers, Lauren; Barnett, Burton; Nguyen, Bryan; Thiemens, Mark H

    2008-09-01

    Sulfate (SO(4)) and its precursors are significant components of the atmosphere, with both natural and anthropogenic sources. Recently, our triple-isotope ((16)O, (17)O, (18)O) measurements of atmospheric sulfate have provided specific insights into the oxidation pathways leading to sulfate, with important implications for models of the sulfur cycle and global climate change. Using similar isotopic measurements of aerosol sulfate in a polluted marine boundary layer (MBL) and primary sulfate (p-SO(4)) sampled directly from a ship stack, we quantify the amount of p-SO(4) found in the atmosphere from ships. We find that ships contribute between 10% and 44% of the non-sea-salt sulfate found in fine [diameter (D) international maritime law, and atmospheric chemistry.

  13. Biogeochemistry of selenium isotopes: processes, cycling and paleoenvironmental applications. (Utrecht Studies in Earth Sciences 24)

    OpenAIRE

    Mitchell, K.A.

    2012-01-01

    Selenium (Se) is an essential trace element, which, with multiple oxidation states and six stable isotopes, has been suggested as a potentially powerful environmental tracer and paleoenvironmental proxy. Chapter 1 provides a literature review of the Se cycle. While the Se cycle shares some similarities with the S cycle, there are major differences that become apparent from a synthesis of the existing literature, we therefore compare the oceanic cycles of Se and S in Chapter 2. The biogeochemi...

  14. Shape transition and coexistence in neutron-deficient rare earth isotopes

    CERN Multimedia

    We propose to study spectroscopic quadrupole moments of excited states and electromagnetic transition rates between them in the neutron-deficient rare earth nuclei $^{140}$Sm and $^{142}$Gd using projectile Coulomb excitation at energies of 4.7 MeV per nucleon. The rare earth nuclei below the N=82 shell closure form one of the few regions of the nuclear chart where oblate shapes are expected to occur near the ground state. Nuclear shapes are expected to change rapidly in this region, with coexistence of oblate and prolate shapes in some nuclei. The measurement of electromagnetic matrix elements represents therefore a particularly sensitive test of theoretical nuclear structure models.

  15. New insights from old spherules: Os-W isotope and HSE evidence for Paleoarchean meteorite bombardment of the Earth

    Science.gov (United States)

    Schulz, T.; Luguet, A. A.; Koeberl, C.

    2014-12-01

    Introduction: Although still debated, spherule beds in the Barberton Mountain Land (~3.4 Ga) are suspected to represent remnants of impact-generated and ballistically emplaced silicate melt droplets [e.g. 1]. Such deposits provide the only window into the late stages of the heavy meteorite bombardment on Earth as their source craters have long since been obliterated. In order to identify a possible meteoritic component and, if successful, to discuss potential projectile materials, we are performing a detailed Os-W isotope as well as HSE abundance study on spherule layers from the recently drilled ICDP BARB5 core (grid location 25°30`50.76``S, 31°33`10.08``E). Samples and Methods: Samples were taken from a spherule-containing meta-sedimentary core section discovered between 510 and 512 m depth. About 100 mg of homogenized sample powders were spiked with a mixed 190Os, 185Re, 191Ir and 194Pt tracer and treated in a high pressure asher using inverse aqua regia, followed by conventional extraction schemes for Os and the other HSEs [4]. Chemical and Os isotope measurements (via N-TIMS) were performed in Vienna, whereas HSE measurements were undertaken via ICP MS in Bonn. Results and Discussion: Our preliminary Os isotope data reveal a trend between samples exhibiting high spherule to matrix ratios (187Os/188Os ~0.106 and Os ~0.4 ppm) and samples with lower ones (187Os/188Os up to ~0.304 and Os ~0.008 ppm). Notably, the most unradiogenic samples exhibit carbonaceous-chondrite-like initial 187Os/188Os and HSE ratios, whereas all other samples are clear non-chondritic. These findings support an extraterrestrial contribution in the spherules and can be interpreted compared to conclusions drawn from a Cr isotope study performed on similar samples [3], possibly representing a different impact event and favouring a chondritic projectile. However, further considerations based on precise Os/W ratio determinations and high-precision 182W isotope data, will be presented at the

  16. Surprisingly Different Reaction Behavior of Alkali and Alkaline Earth Metal Bis(trimethylsilyl)amides toward Bulky N-(2-Pyridylethyl)-N'-(2,6-diisopropylphenyl)pivalamidine.

    Science.gov (United States)

    Kalden, Diana; Oberheide, Ansgar; Loh, Claas; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias

    2016-07-25

    N-(2,6-Diisopropylphenyl)-N'-(2-pyridylethyl)pivalamidine (Dipp-N=C(tBu)-N(H)-C2 H4 -Py) (1), reacts with metalation reagents of lithium, magnesium, calcium, and strontium to give the corresponding pivalamidinates [(tmeda)Li{Dipp-N=C(tBu)-N-C2 H4 -Py}] (6), [Mg{Dipp-N=C(tBu)-N-C2 H4 -Py}2 ] (3), and heteroleptic [{(Me3 Si)2 N}Ae{Dipp-N=C(tBu)-N-C2 H4 -Py}], with Ae being Ca (2 a) and Sr (2 b). In contrast to this straightforward deprotonation of the amidine units, the reaction of 1 with the bis(trimethylsilyl)amides of sodium or potassium unexpectedly leads to a β-metalation and an immediate deamidation reaction yielding [(thf)2 Na{Dipp-N=C(tBu)-N(H)}] (4 a) or [(thf)2 K{Dipp-N=C(tBu)-N(H)}] (4 b), respectively, as well as 2-vinylpyridine in both cases. The lithium derivative shows a similar reaction behavior to the alkaline earth metal congeners, underlining the diagonal relationship in the periodic table. Protonation of 4 a or the metathesis reaction of 4 b with CaI2 in tetrahydrofuran yields N-(2,6-diisopropylphenyl)pivalamidine (Dipp-N=C(tBu)-NH2 ) (5), or [(thf)4 Ca{Dipp-N=C(tBu)-N(H)}2 ] (7), respectively. The reaction of AN(SiMe3 )2 (A=Na, K) with less bulky formamidine Dipp-N=C(H)-N(H)-C2 H4 -Py (8) leads to deprotonation of the amidine functionality, and [(thf)Na{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 a) or [(thf)K{Dipp-N=C(H)-N-C2 H4 -Py}]2 (9 b), respectively, are isolated as dinuclear complexes. From these experiments it is obvious, that β-metalation/deamidation of N-(2-pyridylethyl)amidines requires bases with soft metal ions and also steric pressure. The isomeric forms of all compounds are verified by single-crystal X-ray structure analysis and are maintained in solution. PMID:27355970

  17. Characterization and activity of alkaline earth metals loaded CeO{sub 2}–MO{sub x} (M = Mn, Fe) mixed oxides in catalytic reduction of NO

    Energy Technology Data Exchange (ETDEWEB)

    Mousavi, Seyed Mahdi [Department of Applied Chemistry and Chemical Engineering, Faculty of Chemistry, University of Tabriz, 5166616471 Tabriz (Iran, Islamic Republic of); Niaei, Aligholi, E-mail: niaei@yahoo.com [Department of Applied Chemistry and Chemical Engineering, Faculty of Chemistry, University of Tabriz, 5166616471 Tabriz (Iran, Islamic Republic of); Illán Gómez, María José [Carbon Materials and Environment Research Group, Department of Inorganic Chemistry, Faculty of Science, Universidad de Alicante, Alicante (Spain); Salari, Dariush; Nakhostin Panahi, Parvaneh [Department of Applied Chemistry and Chemical Engineering, Faculty of Chemistry, University of Tabriz, 5166616471 Tabriz (Iran, Islamic Republic of); Abaladejo-Fuentes, Vicente [Carbon Materials and Environment Research Group, Department of Inorganic Chemistry, Faculty of Science, Universidad de Alicante, Alicante (Spain)

    2014-02-14

    Nanocrystalline CeO{sub 2}–MO{sub x} mixed oxides (M = Mn, Fe) with different M/(M + Ce) molar ratio are prepared by sol–gel combustion method. X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), Temperature Programmed Reduction with H{sub 2} (H{sub 2}-TPR) and N{sub 2}-adsorption (BET) analyses are conducted to characterize the physical–chemical properties of the catalysts. The activity of catalysts for reduction of NOx with ammonia has been evaluated. The CeO{sub 2}–MnO{sub x} catalysts showed better low temperature activity than CeO{sub 2}–FeO{sub x}. The superior activity of CeO{sub 2}–MnO{sub x} with Mn/(Mn + Ce) molar ratio of 0.25 respect to other catalysts (with 83% NO conversion and 68% N{sub 2} yield at 200 °C) is associated to nanocrystalline structure, reducibility at low temperature and synergistic effect between Ce and Mn that are observed by XRD, TEM and H{sub 2}-TPR. The CeO{sub 2}–FeO{sub x} catalysts were found to be active at high temperature, being Ce–Fe the best catalyst yielded 82% NO conversion at 300 °C. The effect of alkaline earth metals (Ca, Mg, Sr and Ba) loading on the structure and catalytic activity of cerium mixed oxides are also investigated. Loading of Ba enhanced the NO reduction activity of mixed oxides due to the increase of number of basic sites. Highest performance with 91% NO conversion and 80% N{sub 2} yield attained over CeO{sub 2}–MnO{sub x} (0.25)-Ba (7%) catalyst at 200 °C. - Highlights: • CeO{sub 2}–MO{sub x} mixed oxides (M = Mn, Fe) were synthesized by sol–gel combustion method. • The activity of mixed oxides is evaluated in catalytic reduction of NO with NH{sub 3}. • The CeO{sub 2}–MnO{sub x} showed better activity than CeO{sub 2}–FeO{sub x} due to better redox properties. • Ba loading enhanced the activity due to the increase of number of basic sites. • 91% NO conversion and 80% N{sub 2} yield attained over 7%Ba–Ce{sub 0.75}Mn{sub 0.25}O{sub 2} at 200 °C.

  18. Hydrocarbon degassing of the earth and origin of oil-gas fields (isotope-geochemical and geodynamic aspects)

    Science.gov (United States)

    Valyaev, Boris; Dremin, Ivan

    2016-04-01

    More than half a century ago, Academician PN Kropotkin substantiated the relationship of the formation and distribution of oil and gas fields with the processes of emanation hydrocarbon degassing of the Earth. Over the years, the concept of PN Kropotkin received further development and recognition of studies based on new factual material. Of particular importance are the following factors: a) the results of studies on global and regional uneven processes of traditional oil and gas and the role of deep faults in controlling the spread of oil and gas fields; b) the results of the research on gigantic volumes and localization of the discharges of hydrocarbon fluids (mud volcanoes, seeps) on land and into the atmosphere and through the bottom of the World ocean; c) the results of the studies on grand volumes of the spread of unconventional hydrocarbon resources in their non-traditional fields, especially on near-surface interval of unconventional oil and gas accumulation with gas hydrates, heavy oil and bitumen, as well as extraordinary resources of oil and gas in the shale and tight rocks. Deep mantle-crust nature of oil and gas in traditional and nontraditional deposits thus received further substantiation of geological and geophysical data and research results. However, isotopic and geochemical data are still interpreted in favor of the concept of the genesis of oil and gas in the processes of thermal catalytic conversion of organic matter of sedimentary rocks, at temperatures up to 200°C. In this report an alternative interpretation of the isotope carbon-hydrogen system (δ13C-δD) for gas and of oil deposits, isotope carbon system for methane and carbon dioxide (δ13C1-δ13C0) will be presented. An alternative interpretation will also be presented for the data on carbon-helium isotope geochemical system for oil and gas fields, volcanoes and mud volcanoes. These constructions agree with the geological data on the nature of deep hydrocarbon fluids involved in the

  19. Petrogenesis of coeval silica-saturated and silica-undersaturated alkaline rocks: Mineralogical and geochemical evidence from the Saima alkaline complex, NE China

    Science.gov (United States)

    Zhu, Yu-Sheng; Yang, Jin-Hui; Sun, Jin-Feng; Zhang, Ji-Heng; Wu, Fu-Yuan

    2016-03-01

    A combined study of zircon U-Pb ages, mineral chemistry, whole-rock elements and Sr-Nd-Hf isotopes was carried out for the Saima alkaline complex in the northeastern China, in order to investigate the source and petrogenesis of coeval silica-saturated and silica-undersaturated alkaline rocks. The Saima alkaline complex consists of nepheline syenites, quartz-bearing syenites and alkaline volcanic rocks (i.e., phonolite and trachyte), with minor mafic dikes and carbonatitic veins. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and secondary ion mass spectrometry (SIMS) zircon U-Pb dating gives consistent ages of 230-224 Ma for these rocks, suggesting that they are coeval. All alkaline rocks in the Saima complex are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depleted in high field strength elements (HFSEs) with significant negative Nb, Ta and Ti anomalies. Geochemical data and Sr-Nd-Hf isotopic compositions indicate that the various alkaline rocks were all derived from partial melting of an ancient, re-enriched lithospheric mantle in the garnet stability field, but experienced variable siliceous- or carbonate-rich crustal contamination. Based on petrographic evidence, mineral compositions, and whole-rock geochemical data, two distinct magmatic evolutionary trends are proposed to explain the coeval emplacement of the various rock types within the Saima alkaline complex. The silica-undersaturated rocks (nepheline syenites and phonolites) result from alkali feldspar + apatite + titanite crystal fractionation of an alkaline mafic parental melt combined with assimilation of marine carbonate host rocks. In contrast, the generation of silica-saturated rocks (quartz-bearing syenites and trachytes) may be attributed to subsequent and continued clinopyroxene + apatite + biotite crystal fractionation coupled with assimilation of siliceous sediments.

  20. Hf and Nd Isotope Evidence for Production of an Incompatible Trace Element Enriched Crustal Reservoir in Early Earth (Invited)

    Science.gov (United States)

    Brandon, A. D.; Debaille, V.; Lapen, T. J.

    2010-12-01

    The final significant stage of accretion of the Earth was likely a collision between proto-Earth and a Mars sized impactor that formed the Moon. This event is thought to have produced enough thermal energy to melt all or most of the Earth, with a consequent magma ocean (MO). During subsequent cooling, the Earth would have formed its protocrust and corresponding mantle lithosphere, consisting of solidified basalt-komatiitic melt, in combination with buoyant cumulates and late stage residual melts from the MO. Relative to the convecting mantle, portions of this protolithosphere are likely to have been enriched in incompatible trace elements (ITE) in sufficient quantities to contain a significant amount of the bulk Earth’s budget for rare earth elements, U, Th, and Hf. If the protolithosphere was negatively buoyant, it may have overturned at or near the final stages of MO crystallization and a significant portion of that material may have been transported into the deep mantle where it resided and remixed into the convecting mantle over Earth history [1,2]. If the protolithosphere remained positively buoyant, its crust would have likely begun to erode from surface processes, and subsequently recycled back into the mantle over time as sediment and altered crust, once a subduction mechanism arose. The Nd and Hf isotopic compositions of Earth’s earliest rocks support the idea that an early-formed ITE-enriched reservoir was produced. The maxima in 142Nd/144Nd for 3.85 to 3.64 Ga rocks from Isua, Greenland decreases from +20 ppm to +12 ppm relative to the present day mantle value, respectively [3]. This indicates mixing of an early-formed ITE enriched reservoir back into the convecting mantle. In addition, zircons from the 3.1 Ga Jack Hills conglomerate indicate that material with an enriched 176Lu/177Hf of ~0.02 and an age of 4.4 Ga or greater was present at the Earth’s surface over the first 2 Ga of Earth history, supporting the scenario of a positively buoyant

  1. Study of oblate nuclear shapes and shape coexistence in neutron-deficient rare earth isotopes

    CERN Multimedia

    Guttormsen, M S; Reiter, P; Larsen, A; Korten, W; Clement, E; Siem, S; Renstrom, T; Buerger, A; Jenkins, D G

    We propose to investigate nuclear shapes and shape coexistence in neutron-deficient rare earth nuclei below the N=82 shell closure at the ISOLDE facility by employing Coulomb excitation of Nd, Sm, Gd, and Dy beams from the REX accelerator and the Miniball experiment. Nuclear shapes are expected to change rapidly in this region of the nuclear chart. The measurement of electric quadrupole moments of excited states and the transition rates between them serves as a stringent test of theoretical models and effective nucleon-nucleon interactions.

  2. Mixed ligand complexes of alkaline earth metals: Part XII. Mg(II, Ca(II, Sr(II and Ba(II complexes with 5-chlorosalicylaldehyde and salicylaldehyde or hydroxyaromatic ketones

    Directory of Open Access Journals (Sweden)

    MITHLESH AGRAWAL

    2002-04-01

    Full Text Available The reactions of alkaline earth metal chlorides with 5-chlorosalicylaldehyde and salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been carried out in 1 : 1 : 1 mole ratio and the mixed ligand complexes of the type MLL’(H2O2 (where M = Mg(II, Ca(II, Sr(II and Ba(II, HL = 5-chlorosalicylaldehyde and HL’ = salicylaldehyde, 2-hydroxyacetophenone or 2-hydroxypropiophenone have been isolated. These complexes were characterized by TLC, conductance measurements, IR and 1H-NMR spectra.

  3. Three Isotopes of Oxygen in Lunar Samples - The Same as Earth or Different?

    Science.gov (United States)

    Pillinger, C. T.; Greenwood, R. C.; Johnson, D.; Gibson, E. K.; Miller, M. F.; Franchi, I. A.

    2014-01-01

    One of the most important measurements that can be made for any extraterrestrial sample is determination of the relative abundance of O-16, O-17 and O-18. To make the comparison, investigators report their results as delta (d) values compared to terrestrial delta O-17 vs delta O-18 for a suite of specimens because for any given reservoir, i.e. a planetary parent body such as the Earth or Mars, the numbers should define a line of gradient approximately one half. Different bodies should be identified from their delta O-17 which has traditionally been defined by the equation delta O-17 = delta O-17 - (a constant, ca. 0.52) × delta O-18.

  4. Rare earth elements and Nd isotopes tracing water mass mixing and particle-seawater interactions in the SE Atlantic

    Science.gov (United States)

    Garcia-Solsona, E.; Jeandel, C.; Labatut, M.; Lacan, F.; Vance, D.; Chavagnac, V.; Pradoux, C.

    2014-01-01

    Distributions of dissolved and particulate rare earth elements (REEs) and seawater neodymium isotopic composition (εNd) were established in samples from the BONUS GoodHope (BGH) IPY-GEOTRACES cruise in the SE Atlantic sector of the Southern Ocean (36°S-13°E to 57°S-0°, Feb.-Mar. 2008). Close to the South African continent in the subtropical domain, particulate REEs show the highest concentrations and flat PAAS-normalized patterns, clearly tracing their lithogenic origin. Active cerium oxidation onto suspended particles is evidenced by the mirror-image relationship of the cerium anomaly between dissolved and particulate phases. Unradiogenic dissolved neodymium in surface waters (εNd = -17.1) traces the influence of old sedimentary material brought by the Agulhas current and rings to the Cape Basin area. A mass balance calculation suggests that the release of Nd from dissolution of lithogenic material corresponds to a remobilization of 154 × 106 T of sediment per year, i.e., 5% of the total sediment delivered to the southeast African coast annually. At open ocean stations, both dissolved and particulate REEs present negative cerium anomalies, indicating that particles have acquired a marine signature. The increasing REE concentrations with depth, and the strong linear correlations of dissolved REE with silica, indicate that surface removal and deep re-mineralisation of REEs are partially related to the biogeochemical cycle of silicate, which involves biogenic silica (diatoms). Combined with marine carbonates, these authigenic phases could explain the observed REE patterns in suspended particles, except for La. We suggest that the positive La anomalies in both phases are linked to the oceanic barium cycle and the partial dissolution of barite crystals, especially in the Polar Frontal Zone. The εNd composition behaves conservatively in intermediate and deep waters, while input processes affect the isotopic signal of subtropical surface waters and Weddell Gyre

  5. Geological, rare earth elemental and isotopic constraints on the origin of the Banbanqiao Zn-Pb deposit, southwest China

    Science.gov (United States)

    Li, Bo; Zhou, Jia-Xi; Huang, Zhi-Long; Yan, Zai-Fei; Bao, Guang-Ping; Sun, Hai-Rui

    2015-11-01

    The newly discovered Banbanqiao Zn-Pb deposit in the southeastern part of the Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province is located on the western Yangtze Block, southwest China. Ore bodies of the Banbanqiao deposit are stratiform type, host in dolomitic limestone and dolostone of the Lower Carboniferous Dapu Formation and occur within the NNE-trending Banbanqiao anticline. More than 1.5 million tones (Mt) Zn-Pb ores at grades of 0.26-10.32 wt.% Pb and 0.81-28.8 wt.% Zn have been controlled until now. δ13CPDB and δ18OSMOW values of calcite separates range from -2.8‰ to -0.7‰ (average -1.1‰) and +14.1‰ to +17.0‰ (average +15.5‰), respectively. The δ13CPDB values are similar to those of marine carbonate rocks, but higher than those of mantle and significantly different from those of sedimentary organic matter. However, the δ18OSMOW values are among those of mantle, marine carbonate rocks and sedimentary organic matter. δ34SCDT values of sulfide separates range from +3.2‰ to +9.9‰ (average +6.5‰), unlike mantle-derived sulfur (0 ± 3‰), whilst lower than evaporites (+22‰ to +28‰) within host strata. 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values of country shale and dolostone whole-rock samples are 18.47, 15.66 and 38.70, and 18.44-18.60, 15.66-15.85 and 38.70-39.14, respectively. Sulfide separates have 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values ranging from 18.03 to 18.73, 15.65 to 15.78 and 38.15 to 39.14, respectively. These Pb isotopic data indicate a clearly crustal source of Pb in the plot of 207Pb/204Pb vs. 206Pb/204Pb. Total REE (ΣREE) contents of country shale and dolostone whole-rock samples are 2.63 ppm and 0.72-86.2 ppm with δEu values are 2.79 and 0.34-0.70, respectively. Pyrite, sphalerite, galena and calcite samples have ΣREE contents of 5.3-36.4 ppm, 0.29-3.39 ppm, 0.52 ppm and 22.0-41.1 ppm, respectively, and δEu values of 0.64-0.86, 0.94-2.86, 0.32 and 0.21-0.45, respectively. These rare earth

  6. Widespread tungsten isotope anomalies and W mobility in crustal and mantle rocks of the Eoarchean Saglek Block, northern Labrador, Canada: Implications for early Earth processes and W recycling

    Science.gov (United States)

    Liu, Jingao; Touboul, Mathieu; Ishikawa, Akira; Walker, Richard J.; Graham Pearson, D.

    2016-08-01

    Well-resolved 182W isotope anomalies, relative to the present mantle, in Hadean-Archean terrestrial rocks have been interpreted to reflect the effects of variable late accretion and early mantle differentiation processes. To further explore these early Earth processes, we have carried out W concentration and isotopic measurements of Eoarchean ultramafic rocks, including lithospheric mantle rocks, meta-komatiites, a layered ultramafic body and associated crustal gneisses and amphibolites from the Uivak gneiss terrane of the Saglek Block, northern Labrador, Canada. These analyses are augmented by in situ W concentration measurements of individual phases in order to examine the major hosts of W in these rocks. Although the W budget in some rocks can be largely explained by a combination of their major phases, W in other rocks is hosted mainly in secondary grain-boundary assemblages, as well as in cryptic, unidentified W-bearing 'nugget' minerals. Whole rock W concentrations in the ultramafic rocks show unexpected enrichments relative, to elements with similar incompatibilities. By contrast, W concentrations are low in the Uivak gneisses. These data, along with the in situ W concentration data, suggest metamorphic transport/re-distribution of W from the regional felsic rocks, the Uivak gneiss precursors, to the spatially associated ultramafic rocks. All but one sample from the lithologically varied Eoarchean Saglek suite is characterized by generally uniform ∼ + 11 ppm enrichments in 182W relative to Earth's modern mantle. Modeling shows that the W isotopic enrichments in the ultramafic rocks were primarily inherited from the surrounding 182W-rich felsic precursor rocks, and that the W isotopic composition of the original ultramafic rocks cannot be determined. The observed W isotopic composition of mafic to ultramafic rocks in intimate contact with ancient crust should be viewed with caution in order to plate constraints on the early Hf-W isotopic evolution of the

  7. The alkaline and alkaline-carbonatite magmatism from Southern Brazil

    Science.gov (United States)

    Ruberti, E.; Gomes, C. D. B.; Comin-Chiaramonti, P.

    2015-12-01

    Early to Late Cretaceous lasting to Paleocene alkaline magmatism from southern Brazil is found associated with major extensional structural features in and around the Paraná Basin and grouped into various provinces on the basis of several data. Magmatism is variable in size, mode of occurrence and composition. The alkaline rocks are dominantly potassic, a few occurrences showing sodic affinity. The more abundant silicate rocks are evolved undersaturated to saturated in silica syenites, displaying large variation in igneous forms. Less evolved types are restricted to subvolcanic environments and outcrops of effusive suites occur rarely. Cumulatic mafic and ultramafic rock types are very common, particularly in the alkali-carbonatitic complexes. Carbonatite bodies are represented by Ca-carbonatites and Mg-carbonatites and more scarcely by Fe-carbonatites. Available radiometric ages for the alkaline rocks fit on three main chronological groups: around 130 Ma, subcoveal with the Early Cretaceous flood tholeiites of the Paraná Basin, 100-110 Ma and 80-90 Ma (Late Cretaceous). The alkaline magmatism also extends into Paleocene times, as indicated by ages from some volcanic lavas. Geochemically, alkaline potassic and sodic rock types are distinguished by their negative and positive Nb-Ta anomalies, respectively. Negative spikes in Nb-Ta are also a feature common to the associated tholeiitic rocks. Sr-Nd-Pb systematics confirm the contribution of both HIMU and EMI mantle components in the formation of the alkaline rocks. Notably, Early and Late Cretaceous carbonatites have the same isotopic Sr-Nd initial ratios of the associated alkaline rocks. C-O isotopic Sr-Nd isotopic ratios indicate typical mantle signature for some carbonatites and the influence of post-magmatic processes in others. Immiscibility of liquids of phonolitic composition, derived from mafic alkaline parental magmas, has been responsible for the origin of the carbonatites. Close association of alkaline

  8. Alkaline quinone flow battery.

    Science.gov (United States)

    Lin, Kaixiang; Chen, Qing; Gerhardt, Michael R; Tong, Liuchuan; Kim, Sang Bok; Eisenach, Louise; Valle, Alvaro W; Hardee, David; Gordon, Roy G; Aziz, Michael J; Marshak, Michael P

    2015-09-25

    Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy. PMID:26404834

  9. Iridium, sulfur isotopes and rare earth elements in the Cretaceous-Tertiary boundary clay at Stevns Klint, Denmark

    Energy Technology Data Exchange (ETDEWEB)

    Schmitz, B.; Andersson, P.; Dahl, J.

    1988-01-01

    Microbial activity and redox-controlled precipitation have been of major importance in the process of metal accumulation in the strongly Ir-enriched Cretaceous-Tertiary (K-T) boundary clay, the Fish Clay, at Stevns Klint in Denmark. Two important findings support this view: (1) Kerogen, recovered by leaching the Fish Clay in HCl and HF, shows an Ir concentration of 1100 ppb; this represents about 50% of the Ir present in the bulk sample Fish clay. Strong organometallic complexes is the most probable carrier phase for this fraction of Ir. Kerogen separated from the K-T boundary clay at Caravaca, Spain, similarly exhibits enhanced Ir concentrations. (2) Sulfur isotope analyses of metal-rich pyrite spherules, which occur in extreme abundance (about 10% by weight) in the basal Fish Clay, give a delta/sup 34/S value of -32 per thousand. This very low value shows that sulfide formation by anaerobic bacteria was intensive in the Fish Clay during early diagenesis. Since the pyrite spherules are major carriers of elements such as Ni, Co, As, Sb and Zn, microbial activity may have played an important role for concentrating these elements. In the Fish Clay large amounts of rare earth elements have precipitated from sea water on fish scales. Analyses reveal that, compared with sea water, the Fish Clay is only about four times less enriched in sea-water derived lanthanides than in Ir. This shows that a sea-water origin is plausible for elements that are strongly enriched in the clay, but whose origin cannot be accounted for by a lithogenic precursor.

  10. Re-evaluation of interferences of doubly charged ions of heavy rare earth elements on Sr isotopic analysis using multi-collector inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    We re-evaluate the interference of doubly charged heavy rare earth elements during Sr isotopic analysis using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). A series of mixed solutions of standard reference material SRM 987, rare earth elements, and Sr separated from rock reference materials are measured to assess the influence of isobaric interferences on the MC-ICP-MS analysis of Sr isotopes. After sample dissolution, conventional cation-exchange chromatography is employed for Sr purification of rock reference materials prior to MC-ICP-MS measurement. It has been demonstrated that if the natural abundances of Er and Yb are used to correct for doubly charged ion interferences on Sr, an overcorrection results. In contrast, the use of measured doubly charged ion ratios results in an accurate and precise correction of isobaric interference. This finding is confirmed by analytical results for several certified reference materials from mafic (basaltic) to felsic (granitic) silicate rocks. It is noteworthy that, because Er is more prone to doubly charged ion formation, it dominates over Yb doubly charged ions as an interference source. - Highlights: • We re-investigated interference of doubly charged HREE ion on Sr isotope. • Natural abundance of Er and Yb to correct the interference leads to an overcorrection. • Er is more prone to doubly charged ion formation than Yb

  11. Quantum mechanical study of molecular collisions at ultra-low energy: applications to alkali and alkaline-earth systems; Etude quantique de collisions moleculaires a ultra-basse energie: applications aux alcalins et alcalino-terreux

    Energy Technology Data Exchange (ETDEWEB)

    Quemener, G

    2006-10-15

    In order to investigate the collisional processes which occur during the formation of molecular Bose-Einstein condensates, a time-independent quantum mechanical formalism, based on hyperspherical coordinates, has been applied to the study of atom-diatom dynamics at ultra-low energies. We present theoretical results for three alkali systems, each composed of lithium, sodium or potassium atoms, and for an alkaline-earth system composed of calcium atoms. We also study dynamics at large and positive atom-atom scattering length. Evidence for the suppression of inelastic processes in a fermionic system is given, as well as a linear relation between the atom-diatom scattering length and the atom-atom scattering length. (author)

  12. An Unprecedented 1D Zigzag Chain Alkaline Earth Metal Derivative {[Ba(DMF)3(H2O)2][Ba(DMF)4]2(P2W18O62)}n Containing Dawson Heteropolyanion

    Institute of Scientific and Technical Information of China (English)

    Jing Ping WANG; Jian Ru MA; Jing Yang NIU

    2006-01-01

    An unprecedented 1D zigzag chain alkaline earth metal derivative, {[Ba(DMF)3(H2O)2][Ba(DMF)4]2(P2W18O62)}n, (DMF=N, N-dimethyl formamide) containing Dawson heteropolyanion has been successfully synthesized and characterized by X-ray crystallography. Two barium cations bridged by three DMF ligands in parallel combination with the Dawson-type heteropolyanion [P2W18O62]6- and then the resulting subunits {[Ba(DMF)4]2(P2W18O62)}2+ are alternately linked together via another [Ba(DMF)3(H2O)2]2+ ions, constructing a 1D zigzag chain architecture.

  13. IS THE SUN LIGHTER THAN THE EARTH? ISOTOPIC CO IN THE PHOTOSPHERE, VIEWED THROUGH THE LENS OF THREE-DIMENSIONAL SPECTRUM SYNTHESIS

    Energy Technology Data Exchange (ETDEWEB)

    Ayres, Thomas R. [Center for Astrophysics and Space Astronomy, University of Colorado, Boulder, CO 80309 (United States); Lyons, J. R. [Department of Earth and Space Sciences, University of California, Los Angeles, CA (United States); Ludwig, H.-G.; Caffau, E. [Zentrum fuer Astronomie der Universitaet Heidelberg, Heidelberg (Germany); Wedemeyer-Boehm, S., E-mail: Thomas.Ayres@Colorado.edu [Institute of Theoretical Astrophysics, University of Oslo, Oslo (Norway)

    2013-03-01

    We consider the formation of solar infrared (2-6 {mu}m) rovibrational bands of carbon monoxide (CO) in CO5BOLD 3D convection models, with the aim of refining abundances of the heavy isotopes of carbon ({sup 13}C) and oxygen ({sup 18}O, {sup 17}O), to compare with direct capture measurements of solar wind light ions by the Genesis Discovery Mission. We find that previous, mainly 1D, analyses were systematically biased toward lower isotopic ratios (e.g., R {sub 23} {identical_to} {sup 12}C/{sup 13}C), suggesting an isotopically 'heavy' Sun contrary to accepted fractionation processes that were thought to have operated in the primitive solar nebula. The new 3D ratios for {sup 13}C and {sup 18}O are R {sub 23} = 91.4 {+-} 1.3 (R {sub Circled-Plus} = 89.2) and R {sub 68} = 511 {+-} 10 (R {sub Circled-Plus} = 499), where the uncertainties are 1{sigma} and 'optimistic'. We also obtained R {sub 67} = 2738 {+-} 118 (R {sub Circled-Plus} = 2632), but we caution that the observed {sup 12}C{sup 17}O features are extremely weak. The new solar ratios for the oxygen isotopes fall between the terrestrial values and those reported by Genesis (R {sub 68} = 530, R {sub 67} = 2798), although including both within 2{sigma} error flags, and go in the direction favoring recent theories for the oxygen isotope composition of Ca-Al inclusions in primitive meteorites. While not a major focus of this work, we derive an oxygen abundance, {epsilon}{sub O} {approx} 603 {+-} 9 ppm (relative to hydrogen; log {epsilon} {approx} 8.78 on the H = 12 scale). The fact that the Sun is likely lighter than the Earth, isotopically speaking, removes the necessity of invoking exotic fractionation processes during the early construction of the inner solar system.

  14. Synthesis, crystal and band structures, and optical properties of a new lanthanide-alkaline earth tellurium(IV) oxide: La2Ba(Te3O8)(TeO3)2

    International Nuclear Information System (INIS)

    A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La2Ba(Te3O8)(TeO3)2, has been prepared by the solid-state reaction and structurally characterized. The compound crystallizes in monoclinic space group C2/c with a=19.119(3), b=5.9923(5), c=13.2970(19) A, β=107.646(8)o, V=1451.7(3) A3 and Z=4. La2Ba(Te3O8)(TeO3)2 features a 3D network structure in which the cationic [La2Ba(TeO3)2]4+ layers are cross-linked by Te3O84- anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La2Ba(Te3O8)(TeO3)2 is a wide band-gap semiconductor. - Graphical abstract: A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La2Ba(Te3O8)(TeO3)2, has been prepared by the solid-state reaction and structurally characterized. The structure of La2Ba(Te3O8)(TeO3)2 is 3D network in which the cationic [La2Ba(TeO3)2]4+ layers are cross-linked by Te3O84- anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La2Ba(Te3O8)(TeO3)2 is a wide band-gap semiconductor

  15. Trace Metals, Rare Earths, Carbon and Pb Isotopes as Proxies of Environmental Catastrophe at the Permian - Triassic Boundary in Spiti Himalayas, India

    Science.gov (United States)

    Ghosh, N.; Basu, A. R.; Garzione, C. N.; Ghatak, A.; Bhargava, O. N.; Shukla, U. K.; Ahluwalia, A. D.

    2015-12-01

    Himalayan sediments from Spiti Valley, India preserve geochemical signatures of the Permian - Triassic (P-Tr) mass extinction in the Neo-Tethys Ocean. We integrate new sedimentological and fossil record with high-resolution geochemical-isotopic data from Spiti that reveals an ecological catastrophe of global proportions. Trace elements of U, Th, Nb, Ta, Zr, Hf, the rare earths (REE) and carbon, oxygen and lead isotopes measured across the P-Tr boundary in Spiti are used as proxies for evaluating abrupt changes in this continental shelf environment. δ13Corg excursions of 2.4‰ and 3.1‰ in Atargu and Guling P-Tr sections in Spiti Valley are associated with an abrupt fall of biological productivity while δ13Ccarb and δ18Ocarb record of these sediments shows effects of diagenesis. Here, the P-Tr boundary is compositionally distinct from the underlying Late Permian gray shales, as a partly gypsiferous ferruginous layer that allows additional geochemical-isotopic investigation of sedimentary sources. Conspicuous Ce - Eu anomalies in the light REE-enriched Late Permian shales reflect the source composition of the adjacent Panjal Trap basalts of Kashmir. An abrupt change of this source to continental crust is revealed by Nb - Ta and Zr - Hf anomalies at the P-Tr ferruginous layer and continuing through the overlying Early Triassic carbonate rocks. Pb concentration and isotope ratios of 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb identify changes in the sedimentary element flux, distinguishing the Late Permian shales from the distinct siliciclastic continental crustal signature in the Early Triassic carbonates. These geochemical-isotopic constraints on the sedimentary geochemistry of one of the most critical transitions in geological record establish the utility of multi-proxy datasets for paleoenvironmental reconstructions.

  16. Hawaiian imprint on dissolved Nd and Ra isotopes and rare earth elements in the central North Pacific: Local survey and seasonal variability

    Science.gov (United States)

    Fröllje, Henning; Pahnke, Katharina; Schnetger, Bernhard; Brumsack, Hans-Jürgen; Dulai, Henrietta; Fitzsimmons, Jessica N.

    2016-09-01

    Dissolved neodymium isotopes (143Nd/144Nd, expressed as εNd) and rare earth elements (REEs) have the potential to trace the provenance of lithogenic material as well as water masses. The central North Pacific is poorly investigated with respect to its Nd isotope signature and REE cycling, and little is known about the contributions of volcanic islands, such as Hawaii, relative to dust input from Asian deserts to the surface water REE budgets. Here we present dissolved Nd isotope and REE data along with long-lived radium isotope activities from Hawaii Ocean Time-Series Station ALOHA and coastal waters from Oahu, sampled for a GEOTRACES process study in February 2011. The data are supplemented with seasonal samples from ALOHA. Our results show a clear influence of the Hawaiian Islands on the coastal ocean and surface waters at ALOHA during February, expressed by higher surface water Ra activities, radiogenic surface εNd (εNd = +1.4 to -1.0), and elevated Eu anomalies (Eu/Eu∗ ⩾ 1.3). Seasonal cycles of Asian dust deposition most likely contribute to the seasonal εNd variability of surface waters at ALOHA, as suggested by more negative εNd and the lack of Eu anomalies in summer. Neodymium isotopes in the intermediate and deep water column at ALOHA trace typical North Pacific water masses, such as North Pacific Intermediate Water and North Pacific Deep Water. We suggest that a radiogenic εNd excursion in 1000-2000 m water depth, observed in various North Pacific profiles, is controlled by advection of a modified Upper Circumpolar Deep Water or North Equatorial Pacific Intermediate Water. We further present an updated average εNd signature of -3.5 ± 0.5 for North Pacific Deep Water and show that REE patterns of deep waters at ALOHA are dominantly controlled by vertical processes.

  17. In-situ chemical, U-Pb dating, and Hf isotope investigation of megacrystic zircons, Malaita (Solomon Islands): Evidence for multi-stage alkaline magmatic activity beneath the Ontong Java Plateau

    Science.gov (United States)

    Simonetti, Antonio; Neal, Clive R.

    2010-06-01

    Previous investigations of pipe-like intrusions of alnöite within northern Malaita (Solomon Islands) have detailed the chemical and isotopic nature of the alnöite and entrained megacrysts/xenoliths. Alnöite emplacement is poorly constrained since available ages include an Ar-Ar date of 34 Ma (phlogopite) from a mantle xenolith, and a 206Pb/238U date of 33.9 Ma for a zircon megacryst. Hence, we report chemical data, in-situ U-Pb age determinations and Hf isotope compositions for megacrystic zircons recovered from alnöite-derived, ilmenite-rich gravels in the Auluta, Kwainale, and Faufaumela rivers of Malaita. The Zr/Hf ratio (39 to 50) is variable for zircons from Auluta and Faufaumela, whereas it is relatively uniform (40 to 42) in most zircons from Kwainale. Chemical imaging reveals the homogeneous nature for all of the 16 grains analyzed. Trace element compositions obtained by LA-ICP-MS indicate parallel chondrite-normalized REE patterns at variable levels of enrichment; these patterns combined with their low abundances (< 1 to 10 ppm) of U, Th, and Pb confirm their mantle origin. In-situ U-Pb dating conducted by LA-ICP-MS (n = 94 analyses) define a total range in weighted mean (WM) 206Pb/238U ages between ∼ 35 and ∼ 52 Ma. The zircons from Auluta define a range of WM 206Pb/238U ages between 34.9 ± 2.0 Ma and 45.1 ± 2.5 Ma (2σ) that correlate negatively with Zr/Hf ratios and total REE contents. Conversely, the chemically homogeneous zircons from Kwainale define a uniform age spectrum yielding a WM 206Pb/238U age of 36.7 ± 0.5 Ma (2σ). In-situ Hf isotope analyses (n = 30) are uniform and define a WM 176Hf/177Hf value of 0.282933 ± 0.000013 (2σ), which is identical to the previously reported whole rock value for the Malaitan alnöite (0.282939 ± 0.000007). Correlations between ages and chemical compositions (i.e., Auluta zircons), and the uniform Hf isotope compositions are consistent with zircon formation from a common Ontong Java Plateau (OJP

  18. Compound-specific carbon isotopes from Earth's largest flood basalt eruptions directly linked to the end-Triassic mass extinction.

    Science.gov (United States)

    Whiteside, Jessica H; Olsen, Paul E; Eglinton, Timothy; Brookfield, Michael E; Sambrotto, Raymond N

    2010-04-13

    A leading hypothesis explaining Phanerozoic mass extinctions and associated carbon isotopic anomalies is the emission of greenhouse, other gases, and aerosols caused by eruptions of continental flood basalt provinces. However, the necessary serial relationship between these eruptions, isotopic excursions, and extinctions has never been tested in geological sections preserving all three records. The end-Triassic extinction (ETE) at 201.4 Ma is among the largest of these extinctions and is tied to a large negative carbon isotope excursion, reflecting perturbations of the carbon cycle including a transient increase in CO(2). The cause of the ETE has been inferred to be the eruption of the giant Central Atlantic magmatic province (CAMP). Here, we show that carbon isotopes of leaf wax derived lipids (n-alkanes), wood, and total organic carbon from two orbitally paced lacustrine sections interbedded with the CAMP in eastern North America show similar excursions to those seen in the mostly marine St. Audrie's Bay section in England. Based on these results, the ETE began synchronously in marine and terrestrial environments slightly before the oldest basalts in eastern North America but simultaneous with the eruption of the oldest flows in Morocco, a CO(2) super greenhouse, and marine biocalcification crisis. Because the temporal relationship between CAMP eruptions, mass extinction, and the carbon isotopic excursions are shown in the same place, this is the strongest case for a volcanic cause of a mass extinction to date.

  19. Isotopic geology; Geologie isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Allegre, C. [Paris-7 Univ. Denis Diderot, 75 (France); Institut de physique du globe de Paris, 75 - Paris (France)

    2005-07-01

    Born from the application to geology of nuclear physics techniques, the isotopic geology has revolutionized the Earth's sciences. Beyond the dating of rocks, the tracer techniques have permitted to reconstruct the Earth's dynamics, to measure the temperatures of the past (giving birth to paleoclimatology) and to understand the history of chemical elements thanks to the analysis of meteorites. Today, all domains of Earth sciences appeal more or less to the methods of isotopic geology. In this book, the author explains the principles, methods and recent advances of this science: 1 - isotopes and radioactivity; 2 - principles of isotope dating; 3 - radio-chronological methods; 4 - cosmogenic isotope chronologies; 5 - uncertainties and radio-chronological results; 6 - geochemistry of radiogenic isotopes; 7 - geochemistry of stable isotopes; 8 - isotopic geology and dynamical analysis of reservoirs. (J.S.)

  20. Ion transport in alkaline and earth alkaline hydrogen fluorides

    NARCIS (Netherlands)

    Kroger, C; Niggemeier, H; Wiemhofer, HD; Glumov, O; Murin, [No Value

    2002-01-01

    The impedance of the hydrogen fluorides KHF2, NH4HF2 and BaHF3 was investigated as a function of temperature and in the presence of HF and H2O. A comparison of results on different electrode materials. (graphite, silver, palladium, Sn \\ SnF2, and Sn \\ SnF2 \\ LaF3) was used to elucidate the contribut

  1. Coordination of alkaline earth metal ions in the inverted cucurbit[7]uril supramolecular assemblies formed in the presence of [ZnCl4]2- and [CdCl4]2-.

    Science.gov (United States)

    Li, Qing; Zhang, Yun-Qian; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu; Xiao, Xin

    2015-05-01

    A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water-soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H(+) form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE(2+)) in aqueous HCl solutions in the presence of [ZnCl(4)](2-) and [CdCl(4)](2-) anions as structure-directing agents. Single-crystal X-ray diffraction analysis revealed that both iQ[7]-AE(2+) -[ZnCl(4)](2-) -HCl and iQ[7]-AE(2+) -[CdCl(4)](2-) -HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl(4)](2-) and [CdCl(4)](2-) anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE(2+) coordination polymers through outer-surface interactions of Q[n]s.

  2. Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF2, SrF2, and BaF2)

    International Nuclear Information System (INIS)

    The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF2, SrF2, and BaF2 is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF2 crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of ∼2 × 103 pA/cm2). In BaF2 samples, the transformation of BaO into Ba(OH)2 was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH)2 into BaO. In the initial stage of irradiation of all MF2 compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF2 matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF2 destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of ∼20 nm in the sample.

  3. [Treatment of chronic inflammation of the upper respiratory airways by inhalation thermal therapy with sulfur-sulfate-bicarbonate- carbonate-alkaline earth mineral water: a study of nasal cytology].

    Science.gov (United States)

    Cristalli, G; Abramo, A; Pollastrini, L

    1996-12-01

    The purpose of the paper is to better characterise changes occurred in nose cytology in a group of 50 subjects affected by chronic inflammation of upper respiratory airway. The patients were random shared in two groups: group A 40 subjects treated using sulphurous thermal water and a group B (control), 10 cases, treated using placebo saline solution. The post-therapy evaluation of nasal cytology showed an improvement of the chronic inflammation in 65% of group A patients (diminution of bacterial dust 65%, diminution of PMN cells in 60% of cases and disappearance of metaplasy notes in all the cases of group A. No statistical modifications were observed in control group. Moreover were observed a increase of plasma-cell number much more in group A. The author conclusion is that a period of thermal therapy using sulphur-sulphate-alkaline-earth metals water in chronic inflammation of the nose, throw pharmacological and physical actions, cause an improvement of the chronic inflammation and a normalisation of nose cytology. PMID:9381939

  4. High hydrogen loading of thin palladium wires through alkaline earth carbonates' precipitation on the cathodic surface - evidence of a new phase in the Pd-H system

    Energy Technology Data Exchange (ETDEWEB)

    Celani, F.; Spallone, A.; Di Gioacchino, D. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, Frascati, RM (Italy); Marini, P.; Di Stefano, V.; Nakamura, M. [EURESYS, Rome (Italy); Pace, S. [Salerno Univ., Salerno (Italy). Dept. of Physics, Istituto Nazionale per la Fisica della Materia; Mancini, A. [ORIM S.r.l., Piediripa, MC (Italy); Tripodi, P. [Stanford Research Institut International, Stanford, CA (United States)

    2000-07-01

    A new protocol for the electrolytic loading of hydrogen (H) in thin palladium (Pd) wires has been developed. In order to increase the cathodic overvoltage, which is known to be the main parameter capable to enhance the electrolytic H loading of Pd, the catalytic action of the Pd surface versus H-H recombination has been strongly reduced by precipitation of a thin layer of alkaline-earth carbonates on the cathode. A set of electrolytes has been employed, containing small amounts of hydrochloric or sulfuric acid and strontium or calcium ions. The H loading has been continuously evaluated through ac measurements of the Pd wire resistance. Uncommonly low resistivity values, leading to an estimate of exceptionally high H loading, have been observed. Evidence of the existence of a new phase in the very high H content region of the Pd-H system has been inferred on the basis of the determination of the temperature coefficient of the electrical resistivity. Mainly for this purpose a thin layer of Hg was galvanically deposed on the cathodic surface, in order to prevent any H deloading during the measurements. The results have been fully reproduced in other 2 well equipped and experienced Laboratories (Italy, USA).

  5. Silicon isotope fractionation during silica precipitation from aqueous solutions: Experimental and field evidence (Utrecht Studies in Earth Sciences 048)

    OpenAIRE

    Geilert, S.

    2013-01-01

    Climate conditions during Earth’s earliest history were very different from today. Knowledge about this issue is crucial for understanding the development of life on our planet. Billions of years ago, silica-rich rocks formed on the ocean floor, and a small volume is still preserved in surface exposures. They carry traces that provide insight into the properties of ancient seawater. Measuring the proportions of silicon isotopes in these rocks is considered as a promising approach to determine...

  6. Concentrations and isotope ratios of helium and other noble gases in the Earth's atmosphere during 1978-2011

    CERN Document Server

    Brennwald, Matthias S; Figura, Simon; Vollmer, Martin K; Langenfelds, Ray; Steele, L Paul; Kipfer, Rolf

    2012-01-01

    The evolution of the atmospheric noble gas composition during the past few decades has hardly been studied because, in contrast to many other atmospheric gases, systematic time-series measurements have not been available. Based on theoretical considerations, the atmospheric noble gas isotope composition is assumed to be stable on time scales of up to about 10^6 years, with the potential exception of anthropogenic changes predicted for the He concentration and the 3He/4He ratio. However, experimental assessments of the predicted changes in the atmospheric He isotope composition are controversial. To empirically test these assumptions and predictions, we analysed the noble gas isotope composition in samples of the Cape Grim Air Archive, a well-defined archive of marine boundary layer air in the southern hemisphere. The resulting time series of the 20Ne, 40Ar, 86Kr and 136Xe concentrations and 20Ne/22Ne and 40Ar/36Ar ratios during 1978-2011 demonstrate the stability of the atmospheric Ne, Ar, Kr and Xe compositi...

  7. Study of conformational and acid-base properties of norbadione A and pulvinic derivatives: Consequences on their complexation properties of alkaline and alkaline earth cations; Etude des proprietes conformationnelles et acido-basiques de la norbadione A et de derives pulviniques: consequences sur leurs proprietes complexantes de cations alcalins et alcalino-terreux

    Energy Technology Data Exchange (ETDEWEB)

    Kuad, P

    2006-01-15

    This work deals with the study of norbadione A, a pigment extracted from mushrooms and known to complex cesium cations. The study of the acid-base properties of norbadione A has allowed to determine the relative acidity of the seven protonable functions of the molecule and to reveal a reversible isomerization of the double exocyclic bond of the pulvinic moieties. The observed change of configuration is induced by a hydrogen bond of the H-O-H type and by electrostatic interactions. Moreover, the microscopic protonation mechanism of the norbadione A has been analyzed, considering three different study media where the acid-base properties of the norbadione A are compared. In the presence of 0.15 mol.l{sup -1} of NaCl, it has been observed a remarkable cooperativity in the protonation of the enol groups. At last, the use of different analytical methods (NMR, potentiometry and calorimetry) has allowed to study the complexing properties of the norbadione A towards cesium and other alkaline and rare earth cations. (O.M.)

  8. Soils Developed from Different Volcanic Rocks from the Fernando de Noronha Island: Rare-Earth Element Patterns and Isotopic Lead Composition

    Directory of Open Access Journals (Sweden)

    Sonia Maria Barros de Oliveira

    2011-12-01

    Full Text Available This study examines the infl uence of pedogenesis on the distribution of rare earth elements in soils derived fromdifferent rock types and formed under tropical humid climate, as well as the possible contribution of airborne Pb to thesesoils. We studied 5 soil profi les developed from different volcanic rocks cropping out in the Fernando de Noronha island.Results show that in the course of weathering, the soils were enriched in REE. The REE patterns of the soils are similarto those of the parent material, except for a slight HREE enrichment. Lead-isotope data indicate the presence of a nonradiogenicanthropogenic component in the upper horizons of the soil profi les.

  9. Oxygen isotope fractionation in divalent metal carbonates

    Science.gov (United States)

    O'Neil, J.R.; Clayton, R.N.; Mayeda, T.K.

    1969-01-01

    Equilibrium fractionation factors for the distribution of 18O between alkaline-earth carbonates and water have been measured over the temperature range 0-500??C. The fractionation factors ?? can be represented by the equations CaCO3-H2O, 1000 ln??=2.78(106 T-2)-3.39, SrCO3-H 2O, 1000 ln??=2.69(106 T-2)-3.74, BaCO3-H2O, 1000 ln??=2.57(106 T -2)-4.73. Measurements on MnCO3, CdCO3, and PbCO3 were made at isolated temperatures. A statistical-mechanical calculation of the isotopic partition function ratios gives reasonably good agreement with experiment. Both cationic size and mass are important in isotopic fractionation, the former predominantly in its effect on the internal vibrations of the anion, the latter in its effect on the lattice vibrations.

  10. Magnesium isotope fractionation during carbonatite magmatism at Oldoinyo Lengai, Tanzania

    Science.gov (United States)

    Li, Wang-Ye; Teng, Fang-Zhen; Halama, Ralf; Keller, Jörg; Klaudius, Jurgis

    2016-06-01

    To investigate the behaviour of Mg isotopes during carbonatite magmatism, we analyzed Mg isotopic compositions of natrocarbonatites and peralkaline silicate rocks from Oldoinyo Lengai, Tanzania. The olivine melilitites from the vicinity of Oldoinyo Lengai have homogeneous and mantle-like Mg isotopic compositions (δ26Mg of -0.30 to -0.26‰), indicating limited Mg isotope fractionation during mantle melting. The highly evolved peralkaline silicate rocks not related to silicate-carbonatite liquid immiscibility, including phonolites from the unit Lengai I, combeite-wollastonite nephelinites (CWNs) from the unit Lengai II A and carbonated combeite-wollastonite-melilite nephelinites (carbCWMNs), have δ26Mg values (from -0.25 to -0.10‰) clustered around the mantle value. By contrast, the CWNs from the unit Lengai II B, which evolved from the silicate melts that were presumably generated by silicate-carbonatite liquid immiscibility, have heavier Mg isotopes (δ26Mg of -0.06 to +0.09‰). Such a difference suggests Mg isotope fractionation during liquid immiscibility and implies, based on mass-balance calculations, that the original carbonatite melts at Lengai were isotopically light. The variable and positive δ26Mg values of natrocarbonatites (from +0.13 to +0.37‰) hence require a change of their Mg isotopic compositions subsequent to liquid immiscibility. The negative correlations between δ26Mg values and contents of alkali and alkaline earth metals of natrocarbonatites suggest Mg isotope fractionation during fractional crystallization of carbonatite melts, with heavy Mg isotopes enriched in the residual melts relative to fractionated carbonate minerals. Collectively, significant Mg isotope fractionation may occur during both silicate-carbonatite liquid immiscibility and fractional crystallization of carbonatite melts, making Mg isotopes a potentially useful tracer of these processes relevant to carbonatite petrogenesis.

  11. A normalised seawater strontium isotope curve. Possible implications for Neoproterozoic-Cambrian weathering rates and the further oxygenation of the Earth

    Energy Technology Data Exchange (ETDEWEB)

    Shields, G.A. [Muenster Univ. (Germany). Geologisch-Palaeontologisches Inst.

    2007-07-01

    The strontium isotope composition of seawater is strongly influenced on geological time scales by changes in the rates of continental weathering relative to ocean crust alteration. However, the potential of the seawater {sup 87}Sr/{sup 86}Sr curve to trace globally integrated chemical weathering rates has not been fully realised because ocean {sup 87}Sr/{sup 86}Sr is also influenced by the isotopic evolution of Sr sources to the ocean. A preliminary attempt is made here to normalise the seawater {sup 87}Sr/{sup 86}Sr curve to plausible trends in the {sup 87}Sr/{sup 86}Sr ratios of the three major Sr sources: carbonate dissolution, silicate weathering and submarine hydrothermal exchange. The normalised curve highlights the Neoproterozoic-Phanerozoic transition as a period of exceptionally high continental influence, indicating that this interval was characterised by a transient increase in global weathering rates and/or by the weathering of unusually radiogenic crustal rocks. Close correlation between the normalised {sup 87}Sr/{sup 86}Sr curve, a published seawater {delta}{sup 34}S curve and atmospheric pCO{sub 2} models is used here to argue that elevated chemical weathering rates were a major contributing factor to the steep rise in seawater {sup 87}Sr/{sup 86}Sr from 650 Ma to 500 Ma. Elevated weathering rates during the Neoproterozoic-Cambrian interval led to increased nutrient availability, organic burial and to the further oxygenation of Earth's surface environment. Use of normalised seawater {sup 87}Sr/{sup 86}Sr curves will, it is hoped, help to improve future geochemical models of Earth System dynamics. (orig.)

  12. Alkaline sorbent injection for mercury control

    Science.gov (United States)

    Madden, Deborah A.; Holmes, Michael J.

    2003-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  13. Influence of alkali and alkaline earth ions on the -alkylation of the lower rim phenolic-OH groups of -tert-butyl-calix[4]arene to result in amide-pendants: Template action of K+ and the structure of K+ bound tetra-amide derivative crystallized with a -tert-butylcalix[4]arene anion

    Indian Academy of Sciences (India)

    Amjad Ali; Chebrolu P Rao; Philippe Guionneau

    2008-03-01

    Role of alkali and alkaline earth ions on the formation of calix[4]arene-amide derivatives through -alkylation of the lower rim phenolic-OH groups in general and template action of K+ in particular have been explored. Na+ and K+ ions among alkali, and Ca2+ and Sr2+ ions among alkaline earth have shown tetra-amide derivatives bound to metal ion species. Among all these, potassium salts act as template and yields a K+ bound tetra-amide derivative where the charge is counter balanced by a calix[4] arene-monoanion and the product is crystallographically characterized. Change in the amide precursor used in these -alkylation reactions has no effect on the type of the amide derivative formed. Also demonstrated is a direct one-step reaction for the preparation of 1,3-di-amide derivative in high yield and low reaction period using CsHCO3.

  14. PGE, Re-Os, and Mo isotope systematics in Archean and early Proterozoic sedimentary systems as proxies for redox conditions of the early Earth

    Science.gov (United States)

    Siebert, C.; Kramers, J. D.; Meisel, Th.; Morel, Ph.; Nägler, Th. F.

    2005-04-01

    Re-Os data and PGE concentrations as well as Mo concentrations and isotope data are reported for suites of fine clastic sediments and black shales from the Barberton Greenstone Belt, South Africa (Fig Tree and Moodies Groups, 3.25-3.15 Ga), the Belingwe Greenstone Belt, Zimbabwe (Manjeri Formation, ca. 2.7 Ga) and shales from the Witwatersrand, Ventersdorp and Transvaal Supergroups, South Africa ranging from 2.95 to 2.2 Ga. Moderately oxidizing conditions are required to mobilize Re and Mo in the environment, Mo fractionation only occurs in solution, and these parameters thus have potential use as paleoredox proxies for the early Earth. PGE + Re abundance patterns of Barberton Greenstone Belt sediments are uniform and very similar in shape to those of komatiites. This indicates (1) that the PGE came from a source of predominantly ultramafic composition and, (2) that PGE were transported and deposited essentially in particulate form. Sediments from the younger Belingwe Greenstone Belt show more fractionated PGE + Re patterns and have Re/Os ratios 10 to 100× higher than those of Barberton sediments. Their PGE abundance patterns and Re/Os ratios are intermediate between those of the mid-Archean shales and Neoproterozoic to Recent black shales. They reflect scavenging of Re from solution in the sedimentary environment. δ 98/95Mo values of black shales of all ages correlate with their concentrations. The Barberton Greenstone Belt samples have ˜1-3 ppm Mo, similar to a granitoid-basaltic source. This Mo has δ 98/95Mo between -1.9 and -2.4‰ relative to present day mean ocean water molybdenum, MOMO and is thus not isotopically fractionated relative to such a source. Similar to the PGE this indicates transport in solid form. Sediments from the Belingwe Greenstone Belt show in part enhanced Mo concentrations (up to 6 ppm) and Mo isotope fractionation (δ 98/95Mo up to -1.4‰ relative to MOMO). The combined PGE + Re and Mo data show mainly reducing conditions in the

  15. ALP (Alkaline Phosphatase) Test

    Science.gov (United States)

    ... Also known as: ALK PHOS; Alkp Formal name: Alkaline Phosphatase Related tests: AST ; ALT ; GGT ; Bilirubin ; Liver Panel ; Bone Markers ; Alkaline Phosphatase Isoenzymes; Bone Specific ALP All content on ...

  16. Petrogenesis and tectonic implications of the high-K Alamas calc-alkaline granitoids at the northwestern margin of the Tibetan Plateau: Geochemical and Sr-Nd-Hf-O isotope constraints

    Science.gov (United States)

    Zhang, Qichao; Liu, Yan; Huang, He; Wu, Zhenhan; Zhou, Qing

    2016-09-01

    The Alamas granitoid pluton in the eastern part of the Western Kunlun Orogen, the northwestern margin of the Tibetan Plateau, is composed of quartz diorite. Zircon separates from the pluton has SIMS U-Pb age of ∼446 Ma. Rocks from the pluton have a narrow range of SiO2 (56.84-62.57 wt%), MgO (1.76-2.94 wt%), and total alkalis (Na2O + K2O = 5.14-9.59 wt%), and are metaluminous and high-K calc-alkaline to shoshonitic in composition. They are enriched in light rare earth elements (LREEs), with (La/Yb)N = 14-25, and show weakly negative Eu anomalies. These rocks are relatively enriched in Sr (472-676 ppm) and Ba (435-2388 ppm), and depleted in Nb, Ta, Th, and Ti. Their εNd(t) values range from -6.4 to -8.4, and (87Sr/86Sr)i = 0.7184-0.7200. Zircons from the pluton show εHf(t) values of -1.4 to -8.8, and δ18O = 6.4-9.0‰. Geochemical data indicate that the granitoids were likely derived from the reworking of an ancient, deep crustal source, influenced by a minor mantle-derived component. Magmatic differentiation was dominated by the fractional crystallization of hornblende, biotite, and accessory minerals such as apatite, allanite, and Fe-Ti oxides. In summary, the Late Ordovician Alamas pluton is an I-type granitoid that was emplaced in a post-collisional environment, suggesting that this tectonic stage had already initiated prior to ∼445 Ma.

  17. Positron elastic scattering from alkaline earth targets

    Science.gov (United States)

    Poveda, Luis A.; Assafrão, Denise; Mohallem, José R.

    2016-07-01

    A previously reported model potential approach [Poveda et al., Phys. Rev. A 87, 052702 (2013)] was extended to study low energy positron elastic scattering from beryllium and magnesium. The cross sections were computed for energies ranging from 10-5 eV up to well above the positronium formation threshold. The present results are in good agreement with previous reports, including the prediction of a p-wave resonance in the cross section for magnesium. The emergence of this shape resonance is connected to a trend observed in the evolution of the partial wave cross section in going from Be to Mg target. This trend lead us to speculate that a sharp d-wave resonance should be observed in positron elastic scattering from calcium. The positron-target binding energies are investigated in detail, both using the scattering information and by direct computation of the bound state energies using the model potentials. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2016-70120-y

  18. Alkaline earth stannates: The next silicon?

    International Nuclear Information System (INIS)

    Semiconductor materials are being used in an increasingly diverse array of applications, with new device concepts being proposed each year for solar cells, flat-panel displays, sensors, memory, and spin transport. This rapid progress of invention outpaces the development of new semiconductor materials with the required properties and performance. In many applications, high carrier mobility at room temperature is required in addition to specific functional properties critical to the device concept. We review recent developments on high mobility stannate perovskite oxide materials and devices

  19. Alkaline earth stannates: The next silicon?

    Directory of Open Access Journals (Sweden)

    Sohrab Ismail-Beigi

    2015-06-01

    Full Text Available Semiconductor materials are being used in an increasingly diverse array of applications, with new device concepts being proposed each year for solar cells, flat-panel displays, sensors, memory, and spin transport. This rapid progress of invention outpaces the development of new semiconductor materials with the required properties and performance. In many applications, high carrier mobility at room temperature is required in addition to specific functional properties critical to the device concept. We review recent developments on high mobility stannate perovskite oxide materials and devices.

  20. Alkaline earth stannates: The next silicon?

    OpenAIRE

    Sohrab Ismail-Beigi; Walker, Frederick J.; Sang-Wook Cheong; Rabe, Karin M.; Ahn, Charles H.

    2015-01-01

    Semiconductor materials are being used in an increasingly diverse array of applications, with new device concepts being proposed each year for solar cells, flat-panel displays, sensors, memory, and spin transport. This rapid progress of invention outpaces the development of new semiconductor materials with the required properties and performance. In many applications, high carrier mobility at room temperature is required in addition to specific functional properties critical to the device con...

  1. Chemical composition of modern and fossil Hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation – Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    Directory of Open Access Journals (Sweden)

    I. Ssemmanda

    2012-03-01

    Full Text Available For reconstructing environmental change in terrestrial realms the geochemistry of fossil bioapatite in bones and teeth is among the most promising applications. This study demonstrates that alkaline earth elements in enamel of Hippopotamids, in particular Ba and Sr are tracers for water provenance and hydrochemistry. The studied specimens are molar teeth from Hippopotamids found in modern and fossil lacustrine settings of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi and from modern fluvial environments of the Nile River. Concentrations in enamel vary by ca. two orders of magnitude for Ba (120–9336 μg g−1 as well as for Sr (9–2150 μg g−1. Concentration variations in enamel are partly induced during post-mortem alteration and during amelogenesis, but the major contribution originates from the variable water chemistry in the habitats of the Hippopotamids which is dominated by the lithologies and weathering processes in the watershed areas. Amelogenesis causes a distinct distribution of Ba and Sr in modern and fossil enamel, in that element concentrations increase along profiles from the outer rim towards the enamel-dentin junction by a factor of 1.3–1.5. These elements are well correlated with MgO and Na2O in single specimens, thus suggesting that their distribution is determined by a common, single process. Presuming that the shape of the tooth is established at the end of the secretion process and apatite composition is in equilibrium with the enamel fluid, the maturation process can be modeled by closed system Rayleigh crystallization. Enamel from many Hippopotamid specimens has Sr/Ca and Ba/Ca which are typical for herbivores, but the compositions extend well into the levels of plants and carnivores. Within enamel from single specimens these element ratios covary and provide a specific fingerprint of the Hippopotamid habitat. All specimens together, however, define subparallel

  2. Possible influence of climate factors on the reconstruction of the cosmogenic isotope 14C production rate in the earth's atmosphere and solar activity in past epochs

    Science.gov (United States)

    Kuleshova, A. I.; Dergachev, V. A.; Kudryavtsev, I. V.; Nagovitsyn, Yu. A.; Ogurtsov, M. G.

    2015-12-01

    The paper considers the probable influence of variations of the global temperature and carbon dioxide concentration in the Earth's atmosphere on the results of reconstruction of the production rate of the cosmogenic isotope 14C in the terrestrial atmosphere for the period from the early 15th to the mid 19th century. This time interval covers the Spörer, Maunder, and Dalton minima of solar activity, as well as the Little Ice Age. It was shown that the climate changes that occurred during the Little Ice Age should be taken into account. In the Maunder and Spörer minima of solar activity, the 14C generation rate may be comparable to the values for the Dalton minimum, while exclusion of the climate effect yields extremely large values of the 14C production rate for these grand minima. In the solar activity reconstruction for past epochs, this circumstance should be taken into consideration via measurements of the 14C concentration on a long time scale.

  3. Chemostratigraphy of stable chromium isotopes in cap carbonate sequences - tracing the aftermath of Earth's Neoproterozoic icehouse climates

    Science.gov (United States)

    Frei, R.; de Andrade Caxito, F.; Gaucher, C.

    2012-12-01

    fluctuations can be interpreted to reflect increased continentally-derived input into the shallow seawater (increasing δ18O and increasingly positively fractionated (δ53Cr values thought to mirror increased mobilization of hexavalent [Cr(VI)] from the landmasses. Photosynthetic algae blooms in the aftermath of the icehouse climate would likely explain the increasing δ13C values of the studied carbonates deposited atop the cap dolostones. Chromium stable isotopes prove to be a suitable tracer for hydrothermal vs. continental influx into shallow seawater and have the potential to connect to the degree of oxidative weathering conditions on land. Schoenberg et al. (2008) Chemical Geology, 249, 294-306 Caxito et al. (2012) Precambrian Research, 200-203, 38

  4. Decomposition kinetics of alkaline earth carbonates by integral approximation method Cinética de decomposição de carbonatos de terra alcalina pelo método de aproximação integral

    Directory of Open Access Journals (Sweden)

    S. Maitra

    2008-09-01

    Full Text Available The decomposition kinetics of four synthetic alkaline earth metal carbonates (MgCO3, CaCO3, SrCO3 and BaCO3 was studied under non-isothermal conditions from thermo-gravimetric measurements as compared to. The integral approximation method of Coats and Redfern was used to determine the kinetic parameters for the decomposition processes. The decomposition reactions followed mostly first order kinetics and the activation energy of the decomposition reactions increased with the increase in the molecular mass of the carbonates. The change in enthalpy for the decomposition processes was also calculated and compared with the activation energies for the decomposition processes. The activation energy of the decomposition process for all the carbonates was higher than the enthalpy of the reaction excepting SrCO3.A cinética de decomposição de quatro carbonatos sintéticos de metais de terra alcalina (MgCO3, CaCO3, SrCO3 e BaCO3 foi estudada sob condições não isotérmicas por meio de medidas de termogravimétricas e feita sua comparação. O método de aproximação integral de Coats e Redfern foi usado para determinar os parâmetros cinéticos dos processos de decomposição. As reações de decomposição seguiram principalmente cinética de primeira ordem e a energia de ativação para as reações de decomposição aumentou com o aumento da massa molecular dos carbonatos. A variação na entalpia para os processos de decomposição foi também calculada e comparada com as energias de ativação. A energia de ativação dos processos de decomposição de todos os carbonatos foi maior que a entalpia da reação excepto para SrCO3.

  5. 中温商业SCR催化剂碱和碱土中毒特性研究%Study on alkali and alkaline earths poisoning characteristics for a commercial SCR catalyst

    Institute of Scientific and Technical Information of China (English)

    沈伯雄; 卢凤菊; 高兰君; 岳时吉

    2016-01-01

    The poisoning of a commercial selective catalytic reduction ( SCR ) catalysts by alkali ( K ) and alkaline earths ( Ca) has been simulated in the laboratory. The techniques of N2 adsorption, scanning electronic microscopy, X-ray photoelectron spectroscopy, NH3-temperature program desorption, H2-temperature program reduction were used to identify the changes of physical chemical characteristics of the catalysts before and after the simulated poisoning. The results indicated that the poisoning of K and Ca did not damage the basic pore structure of the SCR catalyst, but decreased the BET surface area and pore volume. The poisoning by K and Ca changed the chemical valence state of V and decreased the reducibility of V. The poisoning by K and Ca decreased the amount of chemically adsorbed oxygen on the catalyst surface as well as acidity of the catalysts. The poisoning by K and Ca lowered the SCR activity of the catalysts and the poisoning by Ca was more serious than K.%在实验室条件下对选择性催化还原( SCR)商业催化剂的碱( K)和碱土( Ca)中毒进行了模拟,并采用液氮吸附、扫描电镜、能谱分析、NH3-程序升温脱附、H2-程序升温还原等方法对催化剂中毒前后的物理化学性质变化进行了表征。结果表明, K和Ca的中毒没有破坏商业中温SCR催化剂孔的基本结构,但K和Ca的中毒使催化剂的比表面积和孔容减小。 K和Ca的中毒在一定程度上改变了催化剂表面钒的价态,导致了钒的还原能力减弱,同时降低催化剂表面化学吸附氧。钾中毒和钙中毒使催化剂的表面酸量降低。钾和钙中毒造成中温SCR催化剂的脱硝活性降低,并且Ca中毒造成的催化剂活性降低要明显高于K中毒。

  6. Chemical composition of modern and fossil hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation – Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    Directory of Open Access Journals (Sweden)

    I. Ssemmanda

    2012-11-01

    Full Text Available This study demonstrates that alkaline earth elements in enamel of hippopotamids, in particular Ba and Sr, are tracers for water provenance and hydrochemistry in terrestrial settings. The studied specimens are permanent premolar and molar teeth found in modern and fossil lacustrine sediments of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi and from modern fluvial environments of the Nile River. Concentrations in enamel vary by two orders of magnitude for Ba (120–9336 μg g−1 as well as for Sr (9–2150 μg g−1. The variations are partially induced during post-mortem alteration and during amelogenesis, but the major contribution originates ultimately from the variable water chemistry in the habitats of the hippopotamids which is controlled by the lithologies and weathering processes in the watershed areas. Amelogenesis causes a distinct distribution of MgO, Ba and Sr in modern and fossil enamel, in that element concentrations increase along profiles from the outer rim towards the enamel–dentin junction by a factor of 1.3–1.9. These elements are well correlated in single specimens, thus suggesting that their distribution is determined by a common, single process, which can be described by closed system Rayleigh crystallization of bioapatite in vivo. Enamel from most hippopotamid specimens has Sr/Ca and Ba/Ca which are typical for herbivores. However, Ba/Sr ranges from 0.1 to 3 and varies on spatial and temporal scales. Thus, Sr concentrations and Ba/Sr in enamel differentiate between habitats having basaltic mantle rocks or Archean crustal rocks as the ultimate sources of Sr and Ba. This provenance signal is modulated by climate change. In Miocene to Pleistocene enamel from the Lake Albert region, Ba/Sr decreases systematically with time from 2 to 0.5. This trend can be correlated with changes in climate from humid to arid, in vegetation from C3 to C4 biomass as well as with increasing

  7. Operation of a high temperature ion source at the helium-jet on-line isotope separator facility HELIOS

    Energy Technology Data Exchange (ETDEWEB)

    Bruegger, M.; Hildebrand, N.; Karlewski, T.; Trautmann, N. (Mainz Univ. (Germany, F.R.). Inst. fuer Kernchemie); Mazumdar, A.K. (Marburg Univ. (Germany, F.R.). Fachbereich Physik); Herrmann, G. (Mainz Univ. (Germany, F.R.). Inst. fuer Kernchemie; Gesellschaft fuer Schwerionenforschung m.b.H., Darmstadt (Germany, F.R.))

    1985-02-01

    The performance of a high temperature ion source coupled to a helium gas-jet transport system for an efficient mass separation of neutron-rich alkaline earth and lanthanide isotopes is reported and the results of overall efficiency measurements using different cluster materials in the gas-jet are given. A fast, microprocessor controlled tape transport system for ..gamma..-spectroscopic studies on short-lived isotopes is described. Some results on the decay of 3.8sub(-s) /sup 152/Pr are presented.

  8. Earth science: Extraordinary world

    Science.gov (United States)

    Day, James M. D.

    2016-09-01

    The isotopic compositions of objects that formed early in the evolution of the Solar System have been found to be similar to Earth's composition -- overturning notions of our planet's chemical distinctiveness. See Letters p.394 & p.399

  9. Isotopic age dating of the alkaline intrusive complex and its related molybdenum polymetallic deposit at Hekanzi, western Liaoning Province%辽西河坎子碱性侵入杂岩体及钼多金属矿床同位素年代学研究

    Institute of Scientific and Technical Information of China (English)

    刘勇; 聂凤军; 方俊钦

    2012-01-01

    The newly discovered Hekanzi deposit is a medium-size porphyry molybdenum deposit in western Liaoning Province. Intrusive complexes are widely distributed in the study area, with the Mesozoic alkaline and calc-alka-line rocks being the most developed alkaline rocks. They intruded into the Precambrian and Paleozoic volcanic-sedimentary rocks in the forms of batholiths, stocks, and dykes. Alkaline intrusive rocks are mainly miascite, alkaline syenite and alkaline diabase. The calc-alkaline rocks are mainly granite porphyry, granodiorite, biotite granite and K-feldspar granite. Isotopic ages of the Hekanzi alkaline granite and its related Mo polymetallic deposit have been determined. The rock-forming age of the biotite-orthoclase granite is (235.3 ± 1.0) Ma with MSWD value of 0.68. Re-Os isotopic data of six molybdenite separates define a correlation line corresponding to an age of (224.0 ?1.3) Ma with MSWD value of 0.72. The metallic minerals in the ore are pyrite, chalcopy-rite, molybdenite, pyrrhotite, marcasite and a little scheetine. Gangue minerals are mainly calcite, fluorite, garnet, serpentine, peridotite, dolomite, feldspar, plagioclase and quartz. The NE-trending, NS-trending and NW-trending fault zones are widely distributed in the alkaline intrusive complex and its related molybdenum polymetallic deposit at Hekanzi.%对辽西河坎子地区与碱性杂岩体相关的钼多金属矿床进行了同位素年代学研究.所获黑云母正长花岗岩锆石LA-ICP-MS U-Pb同位素加权平均年龄为(235.3±1.0) Ma,MSWD值为0.68;河坎子钼多金属矿床内辉钼矿的Re-Os同位素等时线年龄为(224.0±1.3) Ma,MSWD值为0.72.碱性杂岩体与相关的钼多金属矿床具有密切的空间关系,两者的形成时间亦比较接近,据此可推测,河坎子碱性杂岩体与相关的钼多金属矿床均为印支期构造-岩浆作用及流体活动的产物.印支期内频繁的岩浆-热液活动为该地区内钼、铜、金多金属元素的活

  10. Anodes for alkaline electrolysis

    Science.gov (United States)

    Soloveichik, Grigorii Lev

    2011-02-01

    A method of making an anode for alkaline electrolysis cells includes adsorption of precursor material on a carbonaceous material, conversion of the precursor material to hydroxide form and conversion of precursor material from hydroxide form to oxy-hydroxide form within the alkaline electrolysis cell.

  11. Alkaline "Permanent" Paper.

    Science.gov (United States)

    Pacey, Antony

    1991-01-01

    Discussion of paper manufacturing processes and their effects on library materials focuses on the promotion of alkaline "permanent" paper, with less acid, by Canadian library preservation specialists. Standards for paper acidity are explained; advantages of alkaline paper are described, including decreased manufacturing costs; and recyclability is…

  12. Inlfuence of Mixed Alkali-Alkaline Earth Effect on Alkali Resistance of Medium Temperature Fritted Glaze%混合碱/碱土金属效应对中温熔块釉耐碱性的影响

    Institute of Scientific and Technical Information of China (English)

    秦立邦; 卢希龙; 曹春娥; 陈云霞; 沈华荣; 黄钢

    2014-01-01

    In order to improve the alkali resistance of medium temperature fritted glaze, a large number of experiments were carried out to get a better base fritted glaze. Then, inlfuence of mixed alkali metal effect and mixed alkaline earth metal effect on alkali resistance of the glaze was studied. Results show that mixed alkali effect existed in two alkali metal oxides-Li2O and Na2O. When the Li+/Na+molar ratio was equal to 1, the frit had the best alkali resistance. Calcium oxide had obvious suppression effect on alkali metal oxides. When the CaO/(Li2O+Na2O) molar ratio was equal to 1.22, the frit had the best alkali resistance. For binary mixed alkali metal oxides, when both the molar ratios of CaO/BaO and CaO/MgO were equal to 8.2, the frit had the best alkali resistance, but BaO worked better than MgO. For ternary mixed alkali metal oxides, when the molar ratio of CaO:MgO:BaO was equal to 14:3.3:1, both the frit and fritted glaze had the best alkali resistance.%为了提高中温熔块釉的耐碱性,通过大量实验得到较好的基础熔块釉组成,在此基础上,探讨混合碱金属效应、混合碱土金属效应对熔块耐碱性的影响。结果表明:Li2O和Na2O两种碱金属氧化物存在“混合碱金属效应”,其摩尔比为1时,熔块耐碱性最佳。氧化钙对碱金属(Li2O+Na2O)的压制效应明显,当CaO/(Li2O+Na2O)为1.22时,熔块耐碱性最好。二元碱土金属混合时,CaO/BaO、CaO/MgO摩尔比均为8.2时耐碱性最好,但BaO的效果要大于MgO;三元碱土混合中, CaO∶MgO∶BaO摩尔比为14∶3.3∶1时,熔块耐碱性最高,且此时釉的耐碱性也最强。

  13. Precambrian tholeiitic-dacitic rock-suites and Cambrian ultramafic rocks in the Pennine nappe system of the Alps: Evidence from Sm-Nd isotopes and rare earth elements

    Science.gov (United States)

    Stille, P.; Tatsumoto, M.

    1985-01-01

    Major element, trace element and Sm-Nd isotope analyses were made of polymetamorphic hornblendefelses, plagioclase amphibolites and banded amphibolites from the Berisal complex in the Simplon area (Italy, Switzerland) to determine their age, origin and genetic relationships. In light of major and rare earth element data, the hornblendefelses are inferred to have originally been pyroxene-rich cumulates, the plagioclase amphibolites and the dark layers of the banded amphibolites to have been tholeiitic basalts and the light layers dacites. The Sm-Nd isotope data yield isochron ages of 475??81 Ma for the hornblendefelses, 1,018??59 Ma for the plagioclase amphibolites and 1,071??43 Ma for the banded amphibolites. The 1 Ga magmatic event is the oldest one ever found in the crystalline basement of the Pennine nappes. The Sm -Nd isotope data support the consanguinity of the tholeiitic dark layers and the dacitic light layers of the banded amphibolites with the tholeiitic plagioclase amphibolites and the ultramafic hornblendefelses. The initial e{open}Nd values indicate that all three rock types originated from sources depleted in light rare earth elements. We suggest that plagioclase and banded amphibolites were a Proterozoic tholeiite-dacite sequence that was strongly deformed and flattened during subsequent folding. The hornblendefelses are thought to be Cambrian intrusions of pyroxene-rich material. ?? 1985 Springer-Verlag.

  14. Quantum mechanics and molecular dynamics simulations of complexation of alkaline-earth and lanthanide cations by poly-amino-carboxylate ligands; Simulations par mecanique quantique et dynamique moleculaire de la complexation de cations alcalino-terreux et lanthanides par des ligands polyaminocarboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Durand, S

    1999-07-01

    Molecular dynamics (MD) simulations on lanthanide(III) and alkaline-earth(II) complexes with poly-amino-carboxylates (ethylene-diamino-tetra-acetate EDTA{sup 4-}, ethylene-diamino-tri-acetate-acetic acid EDTA(H){sup 3-}, tetra-aza-cyclo-dodecane-tetra-acetate DOTA{sup 4-}, methylene-imidine-acetate MIDA{sup 2-}) are reported. First, a consistent set of Lennard-Jones parameters for La{sup 3+}, Eu{sup 3+} and Lu{sup 3+} cations has been derived from free energy calculations in aqueous solution. Observed differences in hydration free energies, coordination distances and hydration numbers are reproduced. Then, the solution structures of 1:1 complexes of alkaline-earth and/or lanthanide cations with EDTA{sup 4-}, EDTA(H){sup 3-}, DOTA{sup 4-} and 1:2 complexes of lanthanide cations with MIDA{sup 2-} were studied by MD in water. In addition, free energy calculations were performed to study, for each ligand, the relative thermodynamic stabilities of complexes with Ca{sup 2+} vs Sr{sup 2+} and vs Ba{sup 2+} on the one hand, and with La{sup 3+} vs Eu{sup 3+} and vs Lu{sup 3+} on the other hand. Model does not take into account explicitly polarization and charge transfer. However, the results qualitatively agree with experimental complexation data (structure and selectivities). (author)

  15. Energetics and control of ultracold isotope-exchange reactions between heteronuclear dimers in external fields

    CERN Document Server

    Tomza, Michał

    2015-01-01

    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000$\\,$MHz thus resulting in cold or ultracold products. For these chemical reactions there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. The exothermic isotope-exchange reactions can be tuned to become endothermic by employing a laser-induced state-selective Stark shift control thus providing a ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over quantum states of both reactants and products.

  16. Alkaline battery operational methodology

    Energy Technology Data Exchange (ETDEWEB)

    Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael

    2016-08-16

    Methods of using specific operational charge and discharge parameters to extend the life of alkaline batteries are disclosed. The methods can be used with any commercial primary or secondary alkaline battery, as well as with newer alkaline battery designs, including batteries with flowing electrolyte. The methods include cycling batteries within a narrow operating voltage window, with minimum and maximum cut-off voltages that are set based on battery characteristics and environmental conditions. The narrow voltage window decreases available capacity but allows the batteries to be cycled for hundreds or thousands of times.

  17. Fluid inclusion, rare earth element geochemistry, and isotopic characteristics of the eastern ore zone of the Baiyangping polymetallic Ore district, northwestern Yunnan Province, China

    Science.gov (United States)

    Feng, Caixia; Bi, Xianwu; Liu, Shen; Hu, Ruizhong

    2014-05-01

    The Baiyangping Cu-Ag polymetallic ore district is located in the northern part of the Lanping-Simao foreland fold belt, which lies between the Jinshajiang-Ailaoshan and Lancangjiang faults in western Yunnan Province, China. The source of ore-forming fluids and materials within the eastern ore zone were investigated using fluid inclusion, rare earth element (REE), and isotopic (C, O, and S) analyses undertaken on sulfides, gangue minerals, wall rocks, and ores formed during the hydrothermal stage of mineralization. These analyses indicate: (1) The presence of five types of fluid inclusion, which contain various combinations of liquid (l) and vapor (v) phases at room temperature: (a) H2O (l), (b) H2O (l) + H2O (v), (c) H2O (v), (d) CmHn (v), and (e) H2O (l) + CO2 (l), sometimes with CO2 (v). These inclusions have salinities of 1.4-19.9 wt.% NaCl equivalents, with two modes at approximately 5-10 and 16-21 wt.% NaCl equivalent, and homogenization temperatures between 101 °C and 295 °C. Five components were identified in fluid inclusions using Raman microspectrometry: H2O, dolomite, calcite, CH4, and N2. (2) Calcite, dolomitized limestone, and dolomite contain total REE concentrations of 3.10-38.93 ppm, whereas wall rocks and ores contain REE concentrations of 1.21-196 ppm. Dolomitized limestone, dolomite, wall rock, and ore samples have similar chondrite-normalized REE patterns, with ores in the Huachangshan, Xiaquwu, and Dongzhiyan ore blocks having large negative δCe and δEu anomalies, which may be indicative of a change in redox conditions during fluid ascent, migration, and/or cooling. (3) δ34S values for sphalerite, galena, pyrite, and tetrahedrite sulfide samples range from -7.3‰ to 2.1‰, a wide range that indicates multiple sulfur sources. The basin contains numerous sources of S, and deriving S from a mixture of these sources could have yielded these near-zero values, either by mixing of S from different sources, or by changes in the geological

  18. Uranium in alkaline rocks

    International Nuclear Information System (INIS)

    Geologic and geochemical criteria were developed for the occurrence of economic uranium deposits in alkaline igneous rocks. A literature search, a limited chemical analytical program, and visits to three prominent alkaline-rock localities (Ilimaussaq, Greenland; Pocos de Caldas, Brazil; and Powderhorn, Colorado) were made to establish criteria to determine if a site had some uranium resource potential. From the literature, four alkaline-intrusive occurrences of differing character were identified as type-localities for uranium mineralization, and the important aspects of these localities were described. These characteristics were used to categorize and evaluate U.S. occurrences. The literature search disclosed 69 U.S. sites, encompassing nepheline syenite, alkaline granite, and carbonatite. It was possible to compare two-thirds of these sites to the type localities. A ranking system identified ten of the sites as most likely to have uranium resource potential

  19. Uranium in alkaline rocks

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, M.; Wollenberg, H.; Strisower, B.; Bowman, H.; Flexser, S.; Carmichael, I.

    1978-04-01

    Geologic and geochemical criteria were developed for the occurrence of economic uranium deposits in alkaline igneous rocks. A literature search, a limited chemical analytical program, and visits to three prominent alkaline-rock localities (Ilimaussaq, Greenland; Pocos de Caldas, Brazil; and Powderhorn, Colorado) were made to establish criteria to determine if a site had some uranium resource potential. From the literature, four alkaline-intrusive occurrences of differing character were identified as type-localities for uranium mineralization, and the important aspects of these localities were described. These characteristics were used to categorize and evaluate U.S. occurrences. The literature search disclosed 69 U.S. sites, encompassing nepheline syenite, alkaline granite, and carbonatite. It was possible to compare two-thirds of these sites to the type localities. A ranking system identified ten of the sites as most likely to have uranium resource potential.

  20. Oxygen isotope perspective on crustal evolution on early Earth: A record of Precambrian shales with emphasis on Paleoproterozoic glaciations and Great Oxygenation Event

    Science.gov (United States)

    Bindeman, I. N.; Bekker, A.; Zakharov, D. O.

    2016-03-01

    We present stable isotope and chemical data for 206 Precambrian bulk shale and tillite samples that were collected mostly from drillholes on all continents and span the age range from 0.5 to 3.5 Ga with a dense coverage for 2.5-2.2 Ga time interval when Earth experienced four Snowball Earth glaciations and the irreversible rise in atmospheric O2. We observe significant, downward shift of several ‰ and a smaller range of δ18 O values (7 to 9‰) in shales that are associated with the Paleoproterozoic and, potentially, Neoproterozoic glaciations. The Paleoproterozoic samples consist of more than 50% mica minerals and have equal or higher chemical index of alteration than overlying and underlying formations and thus underwent equal or greater degrees of chemical weathering. Their pervasively low δ18 O and δD (down to - 85 ‰) values provide strong evidence of alteration and diagenesis in contact with ultra-low δ18 O glacial meltwaters in lacustrine, deltaic or periglacial lake (sikussak-type) environments associated with the Paleoproterozoic glaciations. The δDsilicate values for the rest of Precambrian shales range from -75 to - 50 ‰ and are comparable to those for Phanerozoic and Archean shales. Likewise, these samples have similar ranges in δ13Corg values (-23 to - 33 ‰ PDB) and Corg content (0.0 to 10 wt%) to Phanerozoic shales. Precambrian shales have a large range of δ18 O values comparable to that of the Phanerozoic shales in each age group and formation, suggesting similar variability in the provenance and intensity of chemical weathering, except for the earliest 3.3-3.5 Ga Archean shales, which have consistently lower δ18 O values. Moreover, Paleoproterozoic shales that bracket in age the Great Oxidation Event (GOE) overlap in δ18 O values. Absence of a step-wise increase in δ18 O and δD values suggests that despite the first-order change in the composition of the atmosphere, weathering cycle was not dramatically affected by the GOE at ∼2

  1. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth's atmosphere.

    Science.gov (United States)

    Whitehill, Andrew R; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

    2013-10-29

    Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ((16)O,(17)O,(18)O) and sulfur ((32)S, (33)S, (34)S, (36)S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ(33)S up to 78‰ and Δ(36)S up to 110‰, from the broadband excitation of SO2 in the 250-350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 ( (3)B1), which results from intersystem crossing from the excited singlet ( (1)A2/ (1)B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin-orbit interaction between the singlet ( (1)A2/ (1)B1) and triplet ( (3)B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for (33)SO2 and (36)SO2 for the low vibrational levels of the (1)A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems.

  2. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth's atmosphere.

    Science.gov (United States)

    Whitehill, Andrew R; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

    2013-10-29

    Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ((16)O,(17)O,(18)O) and sulfur ((32)S, (33)S, (34)S, (36)S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ(33)S up to 78‰ and Δ(36)S up to 110‰, from the broadband excitation of SO2 in the 250-350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 ( (3)B1), which results from intersystem crossing from the excited singlet ( (1)A2/ (1)B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin-orbit interaction between the singlet ( (1)A2/ (1)B1) and triplet ( (3)B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for (33)SO2 and (36)SO2 for the low vibrational levels of the (1)A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems. PMID:23836655

  3. New approaches to the Moon's isotopic crisis

    OpenAIRE

    Melosh, H. J.

    2014-01-01

    Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offe...

  4. High-precision Mg isotope measurements of terrestrial and extraterrestrial material by HR-MC-ICPMS - implications for the relative and absolute Mg isotope composition of the bulk silicate Earth

    DEFF Research Database (Denmark)

    Bizzarro, Martin; Paton, Chad; Larsen, Kirsten Kolbjørn;

    2011-01-01

    We report novel methods for the chemical purification of Mg from silicate rocks by ion-exchange chromatography, and high-precision analysis of Mg-isotopes by high-resolution multiple collector inductively coupled plasma source mass spectrometry (HR-MC-ICPMS). Using these methods, we have measured...

  5. Is the Sun Lighter than the Earth? Isotopic CO in the Photosphere, Viewed through the Lens of 3D Spectrum Synthesis

    CERN Document Server

    Ayres, Thomas R; Ludwig, H -G; Caffau, E; Wedemeyer-Böhm, S

    2013-01-01

    We consider the formation of solar infrared (2-6 micron) rovibrational bands of carbon monoxide (CO) in CO5BOLD 3D convection models, with the aim to refine abundances of the heavy isotopes of carbon (13C) and oxygen (18O,17O), to compare with direct capture measurements of solar wind light ions by the Genesis Discovery Mission. We find that previous, mainly 1D, analyses were systematically biased toward lower isotopic ratios (e.g., R23= 12C/13C), suggesting an isotopically "heavy" Sun contrary to accepted fractionation processes thought to have operated in the primitive solar nebula. The new 3D ratios for 13C and 18O are: R23= 91.4 +/- 1.3 (Rsun= 89.2); and R68= 511 +/- 10 (Rsun= 499), where the uncertainties are 1 sigma and "optimistic." We also obtained R67= 2738 +/- 118 (Rsun= 2632), but we caution that the observed 12C17O features are extremely weak. The new solar ratios for the oxygen isotopes fall between the terrestrial values and those reported by Genesis (R68= 530, R6= 2798), although including both...

  6. Methods of isotopic geochronology

    Science.gov (United States)

    Gorokhov, I. M.; Levchenkov, O. A.

    Papers are presented on such topics as the age of the chemical elements; the age of meteorites, the moon, and the earth; isotopic ages of the most ancient terrestrial formations; and the Archean evolution of Enderby Land in the Antarctic as evidenced by isotopic dating. Consideration is also given to a uranium-lead geochronology technique for investigating Precambrian ore deposits, a Pb-Pb technique of zircon dating, and the potentials and limitations of Sm-Nd geochronology.

  7. Isotopic and geochemical studies of fluid-rock interactions and the chemical evolution of the oceans

    Energy Technology Data Exchange (ETDEWEB)

    Derry, L.A.

    1989-01-01

    The isotopic compositions of Sr and Nd, and the abundances of rare earth elements (REE) are used to study various types of fluid-rock interactions in the Earth's crust. The isotopic compositions of Sr and Nd and REE patterns in marine chemical sediments of Precambrian age are used to estimate the relative importance of continental weathering versus submarine hydrothermal activity in determining the chemical mass balance of the Precambrian oceans. Major and trace element abundances and Sr and Nd isotopes are used to quantify the degree of interaction of a carbonatite fluid-magmatic system with felsic crust, and to constrain the isotopic characteristics of the mantle source region. The isotopic composition of Sr is reported from a well characterized sequence of Upper Proterozoic carbonates from Svalbard and east Greenland. A simple model of carbonate recycling and isotopic mass balance calculations illustrate that sedimentary recycling can have a strong influence on Sr in the oceans. REE patterns from Precambrian banded iron formations (BIFs) are very similar to modern metalliferous sediments, and imply that the overall REE pattern of Precambrian seawater was similar to today. The mantle-like {var epsilon}{sub Nd} values and positive Eu anomalies imply that the source of the REE in the BIFs was submarine hydrothermal activity. The implications of a large hydrothermal flux of reduced Fe on the redox controls of the Precambrian atmosphere are explored, and a testable hypothesis is developed. The mass balance of Eu in the oceans is affected by preferential scavenging at hydrothermal sites. Data from the Cherry Hill, CA mineralizing system imply a complex plumbing system and a long residence time for the water. Isotopic data from the Fen alkaline complex, Norway, define mixing trends between mantle derived magmas or magmatic fluids and old crust.

  8. Alkaline broadening in Stars

    CERN Document Server

    De Kertanguy, A

    2015-01-01

    Giving new insight for line broadening theory for atoms with more structure than hydrogen in most stars. Using symbolic software to build precise wave functions corrected for ds;dp quantum defects. The profiles obtained with that approach, have peculiar trends, narrower than hydrogen, all quantum defects used are taken from atomic database topbase. Illustration of stronger effects of ions and electrons on the alkaline profiles, than neutral-neutral collision mechanism. Keywords : Stars: fundamental parameters - Atomic processes - Line: profiles.

  9. High-precision analysis on annual variations of heavy metals, lead isotopes and rare earth elements in mangrove tree rings by inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Yu, Ke-Fu; Kamber, Balz S.; Lawrence, Michael G.; Greig, Alan; Zhao, Jian-Xin

    2007-02-01

    Annual variations from 1982 to 1999 of a wide range of trace elements and reconnaissance Pb isotopes ( 207Pb/ 206Pb and 208Pb/ 206Pb) were analyzed by solution ICP-MS on digested ash from mangrove Rhizophora apiculata, obtained from Leizhou Peninsula, along northern coast of South China Sea. The concentrations of the majority of elements show a weak declining trend with growth from 1982 to 1999, punctuated by several high concentration spikes. The declining trends are positively correlated with ring width and negatively correlated with inferred water-use efficiency, suggesting a physiological control over metal-uptake in this species. The episodic metal concentration-peaks cannot be interpreted with lateral movement or growth activities and appear to be related to environmental pollution events. Pb isotope ratios for most samples plot along the 'Chinese Pb line' and clearly document the importance of gasoline Pb as a source of contaminant. Shale-normalised REE + Y patterns are relatively flat and consistent across the growth period, with all patterns showing a positive Ce anomaly and elevated Y/Ho ratio. The positive Ce anomaly is observed regardless of the choice of normaliser, in contrast to previously reported REE patterns for terrestrial and marine plants. This pilot study of trace element, REE + Y and Pb isotope distribution in mangrove tree rings indicates the potential use of mangroves as monitors of historical environmental change.

  10. Determination of rare earth elements, thorium and uranium by inductively coupled plasma mass spectrometry and strontium isotopes by thermal ionization mass spectrometry in soil samples of Bryansk region contaminated due to Chernobyl accident

    International Nuclear Information System (INIS)

    Inductively coupled plasma mass spectrometric (ICP-MS) determination of rare earth elements (REEs), thorium and uranium in forest, pasture, field and kitchen garden soils from a Russian territory and in certified reference materials (JLK-1, JSD-2 and BCR-1) is described. In addition to concentration data, strontium isotopic composition of the soil samples were measured by thermal ionization mass spectrometry. The measurements contributed to the understanding of the background levels of these elements in an area contaminated due to Chernobyl accident. There was not a significant variation in the concentration of REEs at different depth levels in forest soil samples, however, the ratio of Th/U varied from 3.32 to 3.60. Though concentration of U and Th varied to some extent, the ratio did not show much variation. The value of 87Sr/86Sr ratio, was in the top layer soil sample relatively higher than in the lower layers. (author)

  11. Development and validation of a single collector ICPMS procedure to determine boron isotopeic compositions of water and food samples

    Science.gov (United States)

    Vogl, Jochen; Rosner, Martin; Pritzkow, Wolfgang

    2010-05-01

    Authenticity and provenance studies as well as issues in environmental- and geo-sciences are hot topics in nowadays isotope research. Elements being known for their natural isotopic variation, such as lead and strontium, are being used to assign the provenance of artefacts, food and other products. A recent study revealed the potential of boron (B) isotopes for delivering information on the provenance of crop plants. To offer alternative analytical instrumentations beside the classical TIMS procedures a single collector ICPMS procedure for B isotope analyses has been developed and validated. This procedure should enable more B isotope studies, as single collector ICPMS intruments are more widepread in the relevant laboratories compared to TIMS. The developed procedures for the determination of B isotopic compositions use a magnetic sector ICPMS and consist of one low resolution (LR) and one medium resolution (MR) procedure. The absolute standard deviation for the δ11B determination in three independently measured samples lies between 0.2 and 0.8 ‰ for the LR and between 0.3 and 1.5 ‰ for the MR. The expanded uncertainties with a coverage factor of k=2 range between 1.4 and 1.6 ‰ for the LR and between 2.9 and 3.2 ‰ for the MR. The trueness, expressed as average deviation from the reference values, is less than 1.1 ‰ for LR and 0.8 ‰ for MR. To test the practicability of the procedure the matrix tolerance has been investigated. Using a measurement solution containing 100 µg/kg boron a matrix of 2 mg/kg of alkaline and earth alkaline elements was found as a limit for stable instrumental mass discrimination. Thus a highly efficient matrix separation is required, similar to TIMS. The developed procedure is well suited for the for B isotope studies of various matrices and especially the LR procedure offers relatively small uncertainties combined with high sample throughput.

  12. Use of Radioactive Ion Beams for Biomedical Research 2. in-vivo dosimetry using positron emitting rare earth isotopes with the rotating prototype PET scanner at the Geneva Cantonal Hospital

    CERN Multimedia

    2002-01-01

    % IS331 \\\\ \\\\ The use of radioactive metal ions (such as $^{90}$Y, $^{153}$Sm or $^{186}$Re) in cancer therapy has made some progress, but has been hampered by factors that could be addressed at CERN with a greater likelihood of success than at any other installation in the world. The present proposal seeks to use the unique advantage of CERN ISOLDE to get round these problems together with the PET scanners at the Cantonal Hospital Geneva (PET~=~positron emission tomography). Radioisotope production by spallation at ISOLDE makes available a complete range of isotopes having as complete a diversity of types and energy of radiation, of half-life, and of ionic properties as one would wish. Among these isotopes several positron-emitters having clinical relevance are available.\\\\ \\\\Some free rare earth chelatas are used presently in palliation of painful bone metastases. Curative effects are not able for the moment with this kind of radiopharmaceuticals. More and better data on the biokinetics and bio-distribution...

  13. Strong Input and Removal of Rare Earth Elements (REEs) Affect Dissolved Nd Isotope Composition of Seawater in the Panama Basin and the Eastern Equatorial Pacific

    Science.gov (United States)

    Frank, M.; Bosse, L. M.; Grasse, P.; Pahnke, K.; Hathorne, E. C.

    2014-12-01

    The distributions of dissolved REEs and Nd isotopes are controlled by inputs from land and water mass mixing. We present new data from the Panama Basin in the Eastern Equatorial Pacific (EEP) extending previous studies in the frame of the German SFB 754 project. The samples were taken following GEOTRACES protocols along a section from close to the Panamanian coast into the deep Panama Basin during FS Meteor cruise M90 in October/November 2012. Elevated Nd concentrations near 13 pmol/kg are found at the surface, which rapidly decrease to a subsurface minimum of 8 pmol/kg near 100m depth and then increase with water depth reaching maximum values of 18 pmol/kg at 3000 m water depth. However, these deep water concentrations are more than a factor of 2 lower than observed for North Pacific Deep Water (NPDW), which is the prevailing Pacific deep water mass at the sampling locations. All the REEs are depleted compared to NPDW suggesting that efficient uptake and scavenging dominate compared to release from remineralized particles. The surface waters show the most radiogenic Nd isotope values (ɛNd = +4.3) so far obtained globally. In combination with the Nd concentration maxima at the surface this suggests riverine dissolved and fine grained particulate inputs from southern Panama and Colombia where highly radiogenic volcanic rocks are exposed. Elevated ɛNd values above -1 in the entire water column are more radiogenic than in NPDW in the Central Pacific and in waters further south in the EEP, which confirms that release of REEs from the sinking volcanogenic material affects the entire water column. These data clearly document that significant inputs from land combined with efficient scavenging and removal in surface and deep waters control the distribution of REEs and Nd isotopes in the Panama Basin and the adjacent EEP (Grasse et al., 2012), which also has important implications for the distribution of other trace metals.

  14. Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano, Italy

    International Nuclear Information System (INIS)

    This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and 87Sr/86Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and 87Sr/86Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water-rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average 87Sr/86Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704-0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher 87Sr/86Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO4 and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites)

  15. GEOCHRONOMETRY ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20040631 Chen Jiangfeng (School of Earth and Space Sciences, University of Science and Technology of China, Hefei, Anhui) ; Xie Zhi Relationships Between Rb-Sr, Ar - Ar Geochronometers and Oxygen Isotopic Equilibrium of Intrusions from Eastern Anhui Province, China (Geological Journal of China Universities, ISSN 1006 - 7493, CN 32 -

  16. Alkaline Phosphatase in Stem Cells

    Directory of Open Access Journals (Sweden)

    Kateřina Štefková

    2015-01-01

    Full Text Available Alkaline phosphatase is an enzyme commonly expressed in almost all living organisms. In humans and other mammals, determinations of the expression and activity of alkaline phosphatase have frequently been used for cell determination in developmental studies and/or within clinical trials. Alkaline phosphatase also seems to be one of the key markers in the identification of pluripotent embryonic stem as well as related cells. However, alkaline phosphatases exist in some isoenzymes and isoforms, which have tissue specific expressions and functions. Here, the role of alkaline phosphatase as a stem cell marker is discussed in detail. First, we briefly summarize contemporary knowledge of mammalian alkaline phosphatases in general. Second, we focus on the known facts of its role in and potential significance for the identification of stem cells.

  17. Alkaline fuel cells applications

    Science.gov (United States)

    Kordesch, Karl; Hacker, Viktor; Gsellmann, Josef; Cifrain, Martin; Faleschini, Gottfried; Enzinger, Peter; Fankhauser, Robert; Ortner, Markus; Muhr, Michael; Aronson, Robert R.

    On the world-wide automobile market technical developments are increasingly determined by the dramatic restriction on emissions as well as the regimentation of fuel consumption by legislation. Therefore there is an increasing chance of a completely new technology breakthrough if it offers new opportunities, meeting the requirements of resource preservation and emission restrictions. Fuel cell technology offers the possibility to excel in today's motive power techniques in terms of environmental compatibility, consumer's profit, costs of maintenance and efficiency. The key question is economy. This will be decided by the costs of fuel cell systems if they are to be used as power generators for future electric vehicles. The alkaline hydrogen-air fuel cell system with circulating KOH electrolyte and low-cost catalysed carbon electrodes could be a promising alternative. Based on the experiences of Kordesch [K. Kordesch, Brennstoffbatterien, Springer, Wien, 1984, ISBN 3-387-81819-7; K. Kordesch, City car with H 2-air fuel cell and lead-battery, SAE Paper No. 719015, 6th IECEC, 1971], who operated a city car hybrid vehicle on public roads for 3 years in the early 1970s, improved air electrodes plus new variations of the bipolar stack assembly developed in Graz are investigated. Primary fuel choice will be a major issue until such time as cost-effective, on-board hydrogen storage is developed. Ammonia is an interesting option. The whole system, ammonia dissociator plus alkaline fuel cell (AFC), is characterised by a simple design and high efficiency.

  18. Metasomatized lithosphere and the origin of alkaline lavas.

    Science.gov (United States)

    Pilet, Sébastien; Baker, Michael B; Stolper, Edward M

    2008-05-16

    Recycled oceanic crust, with or without sediment, is often invoked as a source component of continental and oceanic alkaline magmas to account for their trace-element and isotopic characteristics. Alternatively, these features have been attributed to sources containing veined, metasomatized lithosphere. In melting experiments on natural amphibole-rich veins at 1.5 gigapascals, we found that partial melts of metasomatic veins can reproduce key major- and trace-element features of oceanic and continental alkaline magmas. Moreover, experiments with hornblendite plus lherzolite showed that reaction of melts of amphibole-rich veins with surrounding lherzolite can explain observed compositional trends from nephelinites to alkali olivine basalts. We conclude that melting of metasomatized lithosphere is a viable alternative to models of alkaline basalt formation by melting of recycled oceanic crust with or without sediment.

  19. Calcium stable isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gausonne, Nikolaus [Muenster Univ. (Germany). Inst. fuer Mineralogie; Schmitt, Anne-Desiree [Strasbourg Univ. (France). LHyGeS/EOST; Heuser, Alexander [Bonn Univ. (Germany). Steinmann-Inst. fuer Geologie, Mineralogie und Palaeontologie; Wombacher, Frank [Koeln Univ. (Germany). Inst. fuer Geologie und Mineralogie; Dietzel, Martin [Technische Univ. Graz (Austria). Inst. fuer Angewandte Geowissenschaften; Tipper, Edward [Cambridge Univ. (United Kingdom). Dept. of Earth Sciences; Schiller, Martin [Copenhagen Univ. (Denmark). Natural History Museum of Denmark

    2016-08-01

    This book provides an overview of the fundamentals and reference values for Ca stable isotope research, as well as current analytical methodologies including detailed instructions for sample preparation and isotope analysis. As such, it introduces readers to the different fields of application, including low-temperature mineral precipitation and biomineralisation, Earth surface processes and global cycling, high-temperature processes and cosmochemistry, and lastly human studies and biomedical applications. The current state of the art in these major areas is discussed, and open questions and possible future directions are identified. In terms of its depth and coverage, the current work extends and complements the previous reviews of Ca stable isotope geochemistry, addressing the needs of graduate students and advanced researchers who want to familiarize themselves with Ca stable isotope research.

  20. Genesis of the Madang Cenozoic sodic alkaline basalt in the eastern margin of the Tibetan Plateau and its continental dynamic implications

    Institute of Scientific and Technical Information of China (English)

    LAI; ShaoCong; ZHANG; GuoWei; LI; YongFei; QIN; JiangFeng

    2007-01-01

    The Madang Cenozoic sodic alkaline basalt occurred in the eastern margin of the Tibetan Plateau, where is a key tectonic transform region of Tibet, North China, and Yangtze blocks. The basalts are characterized by the variation in SiO2=42%―51%, Na2O/K2O>4, belonging to the sodic alkaline basalt series. The rocks are enriched in Ba, Th, Nb, Ta, relative to a slight depletion in K, Rb in the trace and rare earth element (REE) spider diagrams that are similar to the typical oceanic island alkaline basalt. The Sr-Nd-Pb isotopic compositions suggest that they are derived from a mixed mantle reservoir. The western Qinling-Songpan tectonic region was controlled by Tibet, North China and Yangtze blocks since Cenozoic, therefore, the region was in the stage of the substance converge from the mantle to upper crust, producing a mixed mantle reservoir in the studied area. The Madang basalts occurred in the specific tectonic background, they result from partial melting of a mixed asthenospheric mantle reservoir in the western Qinling-Songpan tectonic node.

  1. Bifunctional alkaline oxygen electrodes

    Science.gov (United States)

    Swette, L.; Kackley, N.; Mccatty, S. A.

    1991-01-01

    The authors describe the identification and testing of electrocatalysts and supports for the positive electrode of moderate-temperature, single-unit, rechargeable alkaline fuel cells. Recent work on Na(x)Pt3O4, a potential bifunctional catalyst, is described, as well as the application of novel approaches to the development of more efficient bifunctional electrode structures. The three dual-character electrodes considered here showed similar superior performance; the Pt/RhO2 and Rh/RhO2 electrodes showed slightly better performance than the Pt/IrO2 electrode. It is concluded that Na(x)Pt3O4 continues to be a promising bifunctional oxygen electrode catalyst but requires further investigation and development.

  2. Silica in alkaline brines

    Science.gov (United States)

    Jones, B.F.; Rettig, S.L.; Eugster, H.P.

    1967-01-01

    Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

  3. An alkaline element

    Energy Technology Data Exchange (ETDEWEB)

    Arita, T.; Murakami, K.; Okha, K.

    1983-04-28

    A cathode with a dual layer active mass is installed in the disk shaped alkaline silver and zinc element. The first layer, which is turned towards the anode, contains 85 parts Ag2O, 5 parts electrolytic MnO2 and 10 parts graphite. The second layer, which contacts the bottom of the element, contains 35 parts Ag2O, 60 parts electrolytic MnO2 and 5 parts graphite. The electrical capacity of the first and second layers is 60 and 40, respectively. The first layer may be discharged with a high current density and the second layer with less current density. The element has high characteristics with comparatively low cost.

  4. Rare earth element and Nd isotope geochemistry of an ombrotrophic peat bog at Karukinka (Chile, 53.9° S): a palaeo-record of Holocene dust deposition in Tierra del Fuego.

    Science.gov (United States)

    Vanneste, Heleen; De Vleeschouwer, François; Vanderstraeten, Aubry; Mattielli, Nadine; Triquet, Delphine; Piotrowska, Natalia; Le Roux, Gael

    2013-04-01

    The value of ombrotrophic peat bogs as past atmospheric dust records, has been increasingly recognized over the past 10 years. Their high accumulation rates provide high resolution archives of natural atmospheric dust deposition since the Late Glacial, often missing in marine, lake and ice core records. Consequently, peat deposits can be used as a proxy for atmospheric circulation patterns and thus palaeoclimate. In the Southern Hemisphere, the climate is considered to be driven by the Southern Westerly Wind belt (SSW), as it significantly affects the Antarctic Circumpolar Current and hence atmospheric CO2 levels. Palaeo SSW belt migrations have been observed in palaeoclimate records but, reconstructions of SSW shifts and associated climatic changes are incoherent, in particular for the Holocene. As peatlands thrive in southwest Tierra del Fuego due to its high annual precipitation, a remote ombrotrophic peat bog at Karukinka (southwest on the Isla Grande de Tierra del Fuego) was sampled, to investigate the Holocene palaeoclimate in southern South America based on dust deposition records. A 4,5 m long Russian D-core was recovered and subsequently subsampled for elemental and isotope geochemistry in addition to density and radiocarbon dating measurements. Initial results show a number of layers enriched in scandium, indicating the presence of lithogenic material, i.e. dust. Rare earth element patterns indicate at least 2 different sources. The most significant dust peak occurs at the base of the core at ~7300 Cal years B.P and has a neodymium isotopic composition of 2.2, suggesting a volcanic origin.

  5. Strontium Isotope Study of Coal Untilization By-products Interacting with Environmental Waters

    Energy Technology Data Exchange (ETDEWEB)

    Spivak-Birndorf, Lev J; Stewart, Brian W; Capo, Rosemary C; Chapman, Elizabeth C; Schroeder, Karl T; Brubaker, Tonya M

    2011-09-01

    Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements—including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc—during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ({sup 87}Sr/{sup 86}Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-{sup 87}Sr/{sup 86}Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB–water interaction.

  6. Microbes: Agents of Isotopic Change

    Science.gov (United States)

    Fogel, M. L.

    2012-12-01

    Microbes drive many of the important oxidation and reduction reactions on Earth; digest almost all forms of organic matter; and can serve as both primary and secondary producers. Because of their versatile biochemistry and physiology, they impart unique isotopic signatures to organic and inorganic materials, which have proven to be key measurements for understanding elemental cycling now and throughout Earth's history. Understanding microbial isotope fractionations in laboratory experiments has been important for interpreting isotopic patterns measured in natural settings. In fact, the pairing of simple experiment with natural observation has been the pathway for interpreting the fingerprint of microbial processes in ancient sediments and rocks. Examples of how key experiments have explained stable isotope fractionations by microbes and advanced the field of microbial ecology will be presented. Learning the isotopic signatures of Earth's microbes is a valuable exercise for predicting what isotopic signatures could be displayed by possible extant or extinct extraterrestrial life. Given the potential for discovery on Mars, Enceladus, and other solar system bodies, new methods and techniques for pinpointing what is unique about microbial isotope signatures is particularly relevant.

  7. Climate and isotopic tracers

    International Nuclear Information System (INIS)

    The applications of natural radioactivity and isotopic measurements in the sciences concerning Earth and its atmosphere, are numerous: carbon 14 dating with the Tandetron apparatus at the Cea, measurement of oxygen 18 in coral or sediment limestone for the determination of ocean temperature and salinity, carbon 14 dating of corals for the determination of sea level variations, deuterium content in polar ice-cap leads to temperature variations determination; isotopic measurements also enable the determination of present climate features such as global warming, oceanic general circulation

  8. Modulators of intestinal alkaline phosphatase.

    Science.gov (United States)

    Bobkova, Ekaterina V; Kiffer-Moreira, Tina; Sergienko, Eduard A

    2013-01-01

    Small molecule modulators of phosphatases can lead to clinically useful drugs and serve as invaluable tools to study functional roles of various phosphatases in vivo. Here, we describe lead discovery strategies for identification of inhibitors and activators of intestinal alkaline phosphatases. To identify isozyme-selective inhibitors and activators of the human and mouse intestinal alkaline phosphatases, ultrahigh throughput chemiluminescent assays, utilizing CDP-Star as a substrate, were developed for murine intestinal alkaline phosphatase (mIAP), human intestinal alkaline phosphatase (hIAP), human placental alkaline phosphatase (PLAP), and human tissue-nonspecific alkaline phosphatase (TNAP) isozymes. Using these 1,536-well assays, concurrent HTS screens of the MLSMR library of 323,000 compounds were conducted for human and mouse IAP isozymes monitoring both inhibition and activation. This parallel screening approach led to identification of a novel inhibitory scaffold selective for murine intestinal alkaline phosphatase. SAR efforts based on parallel testing of analogs against different AP isozymes generated a potent inhibitor of the murine IAP with IC50 of 540 nM, at least 65-fold selectivity against human TNAP, and >185 selectivity against human PLAP. PMID:23860652

  9. Alkaline battery, separator therefore

    Science.gov (United States)

    Schmidt, George F. (Inventor)

    1980-01-01

    An improved battery separator for alkaline battery cells has low resistance to electrolyte ion transfer and high resistance to electrode ion transfer. The separator is formed by applying an improved coating to an electrolyte absorber. The absorber, preferably, is a flexible, fibrous, and porous substrate that is resistant to strong alkali and oxidation. The coating composition includes an admixture of a polymeric binder, a hydrolyzable polymeric ester and inert fillers. The coating composition is substantially free of reactive fillers and plasticizers commonly employed as porosity promoting agents in separator coatings. When the separator is immersed in electrolyte, the polymeric ester of the film coating reacts with the electrolyte forming a salt and an alcohol. The alcohol goes into solution with the electrolyte while the salt imbibes electrolyte into the coating composition. When the salt is formed, it expands the polymeric chains of the binder to provide a film coating substantially permeable to electrolyte ion transfer but relatively impermeable to electrode ion transfer during use.

  10. 与碳酸岩-碱性杂岩体相关的内生稀土矿床成矿作用研究进展%Review of the Metallogenesis of the Endogenetic Rare Earth Elements Deposits Related to Carbonatite-Alkaline Complex

    Institute of Scientific and Technical Information of China (English)

    宋文磊; 许成; 王林均; 吴敏; 曾亮; 王丽泽; 冯梦

    2013-01-01

    The geological characteristics and mineralization of the endogenetic rare earth elements (REE) deposits related with carbonatite-alkaline complexes are reviewed.The REE deposits mainly include primary magmatic and hydrothermal types.The former is relatively rare,and REE minerals crystallized from carbonatite magma.The REE minerals in hydrothermal deposits are intergrowth with calcite,fluorite,barite,quartz.They occur as ore veins intruding carbonatite-alkaline complexes and wall rocks,or as fracture or void filling fine-grained,polycrystalline aggregates overprinting earlier carbonatitic minerals.Previous researches showed that REE mineralization was controlled by the crystallization and accumulation of carbonate minerals during carbonatitc magma-hydrothermal processes.However,REE enrichment mechanism is still debate,i.e.liquid immiscibility of carbonate-silicate magmas,fractional crystallization of carbonate minerals from carbonatite magma,extraction of carbonatitic liquids,and hydrothermal alteration of carbonatites.Note carbonatites normally show light REE enrichment and mineralization,and absent heavy REE minerals.Therefore,high temperature and pressure experiments on REE partition coefficients between volatile-rich carbonate and alkaline silicate melts or fluids,and REE partition behavior between carbonate and co-precipitating minerals during carbonatite magma evolution,will be a key to reveal the REE mineralization mechanism.%综述与碳酸岩-碱性杂岩体相关的内生稀土矿床的基本特征和成矿作用研究进展.根据矿化特征,该类矿床大体可以分为原生岩浆型和热液型,前者稀土矿物是从碳酸岩岩浆中直接结晶出来,矿化主要产于碳酸岩岩体中;后者稀土矿物通常与方解石、萤石、重晶石、石英等矿物共生形成脉体,穿插于碳酸岩杂岩体及围岩中,或作为裂隙或空洞充填物,或呈细粒多晶集合体叠加在碳酸岩中早期形成的矿物之上.以往的研究

  11. CLIMB: cosmic light isotopes and muons with balloons

    Energy Technology Data Exchange (ETDEWEB)

    Pearce, M. E-mail: pearce@particle.kth.se; Adriani, O.; Boezio, M.; Bonvicini, V.; Carlson, P.; Mocchiutti, E.; Papini, P.; Straulino, S.; Vacchi, A.; Vannuccini, E.; Zampa, G.; Zampa, N

    2004-06-01

    A new balloon-borne experiment is proposed which will measure high-energy light isotopes at the top of the Earth's atmosphere and cosmic ray muons at fixed altitudes within the Earth's atmosphere.

  12. Iron isotope biosignatures

    Science.gov (United States)

    Beard, B. L.; Johnson, C. M.; Cox, L.; Sun, H.; Nealson, K. H.; Aguilar, C.

    1999-01-01

    The (56)Fe/(54)Fe of Fe-bearing phases precipitated in sedimentary environments varies by 2.5 per mil (delta(56)Fe values of +0.9 to -1. 6 per mil). In contrast, the (56)Fe/(54)Fe of Fe-bearing phases in igneous rocks from Earth and the moon does not vary measurably (delta(56)Fe = 0.0 +/- 0.3 per mil). Experiments with dissimilatory Fe-reducing bacteria of the genus Shewanella algae grown on a ferrihydrite substrate indicate that the delta(56)Fe of ferrous Fe in solution is isotopically lighter than the ferrihydrite substrate by 1.3 per mil. Therefore, the range in delta(56)Fe values of sedimentary rocks may reflect biogenic fractionation, and the isotopic composition of Fe may be used to trace the distribution of microorganisms in modern and ancient Earth.

  13. Alkaline earth-gold-aluminides. Synthesis and structure of SrAu{sub 3}Al{sub 2}, SrAu{sub 2.83}Al{sub 2.17}, BaAu{sub 2.89}Al{sub 2.11} and BaAu{sub 7.09}Al{sub 5.91}

    Energy Technology Data Exchange (ETDEWEB)

    Gerke, Birgit; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2015-07-01

    New alkaline earth-gold-aluminides were synthesized from the elements in sealed tantalum or quartz ampoules in muffle furnaces at maximum annealing temperatures of 1325 K. The structures were refined from single crystal X-ray diffractometer data. SrAu{sub 3}Al{sub 2} crystallizes in an ordered version of the LT-SrZn{sub 5} structure: Pnma, a = 1315.9(3), b = 549.0(1), c = 684.5(3) pm, wR2 = 0.0232, 930 F{sup 2} values, 35 variables. SrAu{sub 2.83}Al{sub 2.17} (a = 1065.0(2), b = 845.0(2), c = 548.1(1) pm, wR2 = 0.0416, 452 F{sup 2} values, 22 variables) and BaAu{sub 2.89}Al{sub 2.11} (a = 1096.1(3), b = 835.7(3), c = 554.0(1) pm, wR2 = 0.0280, 501 F{sup 2} values, 22 variables) both adopt the BaZn{sub 5} type, space group Cmcm with Au/Al mixing on the 4c site. The gold and aluminum atoms in both types form three-dimensional networks of condensed tetrahedra with the strontium and barium atoms in large cavities. BaAu{sub 7.09}Al{sub 5.91} is a new member of the NaZn{sub 13} type: Fm anti 3c, a = 1257.6(2) pm, wR2 = 0.0267, 168 F{sup 2} values, 12 variables. Both the 96i and 8b sites show Au/Al mixing. The crystal chemical details are discussed.

  14. Isotopic clusters

    International Nuclear Information System (INIS)

    Spectra of isotopically mixed clusters (dimers of SF6) are calculated as well as transition frequencies. The result leads to speculations about the suitability of the laser-cluster fragmentation process for isotope separation. (Auth.)

  15. Neutron skin in Osmium isotopes

    International Nuclear Information System (INIS)

    Here we have made an attempt to calculate neutron skin thickness in rare earth even-even osmium isotopes. The selected isotopes ranges from 2-p to 2-n drip line. Neutron skin is an important feature of neutron rich nuclei. The ground state proton and neutron rms radii have been calculated using HFB approximation. A comparison of calculated radii have been done by using two different Skyrme parameterizations and two different basis

  16. Earth System Governance: Facing the Challenges of Climate Change

    Directory of Open Access Journals (Sweden)

    Susana Camargo Vieira

    2013-01-01

    Full Text Available YOUNG, Oran R. Institutional Dynamics: Emergent Patterns in International Environmental Governance. Cambridge (Massachusets, USA: The MIT Press, 2010. Earth System Governance Series. 225p. (Paperback; alkaline paper. ISBN 978-0-262-51440-8.

  17. Destructive Adsorption of Carbon Tetrachloride on Alkaline Earth Metal Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Mestl, Gerhard; Rosynek, Michael P.; Krawietz, Thomas R.; Haw, James F.; Lunsford, Jack H.

    2001-01-01

    The destructive adsorption of CCl4 on MgO, CaO, SrO, and BaO has been studied as a function of the reaction temperature and the amount of CCl4 injected. The reaction was followed using in situ Raman spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and 13 C mag

  18. Alkaline earth alkyl insertion chemistry of in situ generated aminoboranes.

    Science.gov (United States)

    Bellham, Peter; Hill, Michael S; Kociok-Köhn, Gabriele; Liptrot, David J

    2013-01-21

    Reactions of equimolar quantities of secondary amine boranes, R(2)NH·BH(3), with the homoleptic group 2 alkyl compounds [M{CH(SiMe(3))(2)}(2)(THF)(2)] (M = Mg, Ca, Sr) provide the alkyl group 2 amido borane derivatives [M{CH(SiMe(3))(2)}{NR(2)BH(3)}(THF)](2). While the strontium derivatives of reactions with dimethylamine and pyrrolidine borane are stable and isolable compounds, the analogous magnesium and calcium compounds are found to be unstable at room temperature. Studies of the thermolysis of the alkylstrontium derivatives have allowed this instability to be rationalised as a result of β-hydride elimination, the facility of which varies with changing M(2+) charge density, to form the products of M-C insertion of H(2)B=NR(2). Subsequent to this process, alkylaminoboranes, [HB(NR(2)){CH(SiMe(3))(2)}], are observed to form through a further suggested β-hydride elimination reaction. This chemistry is also extended to the reaction of the primary amine borane (t)BuNH(2)·BH(3) with [Sr{CH(SiMe(3))(2)}(2)(THF)(2)]. In this case the crystal structure of a heteroleptic species, which may be considered as a tetrameric aggregate of two [Sr{CH(SiMe(3))(2)}{(NH(t)Bu)BH(3)}(2)] anions and two cationic [Sr{(NH(t)Bu)(BH(3))}(THF)(2)] components, has been determined. Kinetic studies of the reactions of [M{CH(SiMe(3))(2)}(2)(THF)(2)] (M = Mg, Ca, Sr) with dimethylamine borane have also been undertaken and describe a complex mechanism in which the barriers to formation of the various intermediate species are a consequence of M(2+) radius and resultant charge density as well as the steric demands of the coordinated amidoborane ligands. PMID:23070304

  19. Aluminum/alkaline earth metal composites and method for producing

    Science.gov (United States)

    Russell, Alan M; Anderson, Iver E; Kim, Hyong J; Freichs, Andrew E

    2014-02-11

    A composite is provided having an electrically conducting Al matrix and elongated filaments comprising Ca and/or Sr and/or Ba disposed in the matrix and extending along a longitudinal axis of the composite. The filaments initially comprise Ca and/or Sr and/or Ba metal or allow and then may be reacted with the Al matrix to form a strengthening intermetallic compound comprising Al and Ca and/or Sr and/or Ba. The composite is useful as a long-distance, high voltage power transmission conductor.

  20. Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

    Science.gov (United States)

    Fantle, M.S.; Bullen, T.D.

    2009-01-01

    The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a

  1. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

    Science.gov (United States)

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  2. Zinc isotopic compositions of breast cancer tissue.

    OpenAIRE

    Larner, F; Woodley, LN; Shousha, S; Moyes, A; Humphreys-Williams, E; Strekopytov, S; Halliday, AN; Rehkämper, M; Coombes, RC

    2015-01-01

    An early diagnostic biomarker for breast cancer is essential to improve outcome. High precision isotopic analysis, originating in Earth sciences, can detect very small shifts in metal pathways. For the first time, the natural intrinsic Zn isotopic compositions of various tissues in breast cancer patients and controls were determined. Breast cancer tumours were found to have a significantly lighter Zn isotopic composition than the blood, serum and healthy breast tissue in both groups. The Zn i...

  3. Catalytic Diversity in Alkaline Hydrothermal Vent Systems on Ocean Worlds

    Science.gov (United States)

    Cameron, Ryan D.; Barge, Laura; Chin, Keith B.; Doloboff, Ivria J.; Flores, Erika; Hammer, Arden C.; Sobron, Pablo; Russell, Michael J.; Kanik, Isik

    2016-10-01

    Hydrothermal systems formed by serpentinization can create moderate-temperature, alkaline systems and it is possible that this type of vent could exist on icy worlds such as Europa which have water-rock interfaces. It has been proposed that some prebiotic chemistry responsible for the emergence of life on Earth and possibly other wet and icy worlds could occur as a result ofredox potential and pH gradients in submarine alkaline hydrothermal vents (Russell et al., 2014). Hydrothermal chimneys formed in laboratory simulations of alkaline vents under early Earth conditions have precipitate membranes that contain minerals such as iron sulfides, which are hypothesized to catalyze reduction of CO2 (Yamaguchi et al. 2014, Roldan et al. 2014) leading to further organic synthesis. This CO2 reduction process may be affected by other trace components in the chimney, e.g. nickel or organic molecules. We have conducted experiments to investigate catalytic properties of iron and iron-nickel sulfides containing organic dopants in slightly acidic ocean simulants relevant to early Earth or possibly ocean worlds. We find that the electrochemical properties of the chimney as well as the morphology/chemistry of the precipitate are affected by the concentration and type of organics present. These results imply that synthesis of organics in water-rock systems on ocean worlds may lead to hydrothermal precipitates which can incorporate these organic into the mineral matrix and may affect the role of gradients in alkaline vent systems.Therefore, further understanding on the electroactive roles of various organic species within hydrothermal chimneys will have important implications for habitability as well as prebiotic chemistry. This work is funded by NASA Astrobiology Institute JPL Icy Worlds Team and a NAI Director's Discretionary Fund award.Yamaguchi A. et al. (2014) Electrochimica Acta, 141, 311–318.Russell, M. J. et al. (2014), Astrobiology, 14, 308-43.Roldan, A. (2014) Chem. Comm

  4. Geology and petrology of Lages Alkaline District, Santa Catarina State

    International Nuclear Information System (INIS)

    A 1:100.000 geological map shows the main outcrops, covering about 50 Km2, of the leucocratic alkaline rocks, ultra basic alkaline rocks, carbonatites and volcanic breccias which intruded the Gondwanic sedimentary rocks within a short time interval and characterize the Alkaline District of Lages. Chemical analyses of 33 whole-rock samples confirm the petrographic classification, but the agpaitic indexes, mostly below 1.0, do not reflect the mineralogical variations of the leucocratic alkaline rocks adequately. Partial REE analyses indicate that the light as well as the heavy rare earth contents decrease from the basic to the more evolved rocks, the La/Y ratio remaining approximately constant. Eleven new K/Ar ages from porphyritic nepheline syenites porphyritic phonolites, ultra basic alkaline rocks and pipe-breccias, together with six already available ages, show a major concentration in the range 65 to 75 Ma, with a mode at ca. 70 Ma. But one Rb/Sr whole-rock reference isochron diagram gives an age of 82+-6 Ma for the agpaitic phonolites of the Serra Chapada, which are considered younger than the miaskitic porphyriric nepheline syenites. The 87 Sr/86 Sr ratios of 0.705-0.706 are compatible with a sub continental mantelic origin, devoid of crustal contamination. A petrogenetic model based on subtraction diagrams and taking into consideration the geologic, petrographic, mineralogic and petrochemical characteristics of the alkaline rocks of Lages consists of limited partial melting with CO2, contribution of the previously metasomatized upper mantle, in a region submitted to decompression. (author)

  5. Variability of the earth's climate

    International Nuclear Information System (INIS)

    In this paper, the global evolution of the Earth's climate since the Precambrian is described and the reconstruction of the last major oscillations generally referred to as the last climatic cycles which occurred during the Quarternary is presented: isotope geochemistry, micropaleontological transfer functions; ice volume and sea level, temperatures, deep water circulation of the last climatic cycle

  6. Contemporaneous trachyandesitic and calc-alkaline volcanism of the Huerto Andesite, San Juan Volcanic Field, Colorado, USA

    Science.gov (United States)

    Parat, F.; Dungan, M.A.; Lipman, P.W.

    2005-01-01

    Locally, voluminous andesitic volcanism both preceded and followed large eruptions of silicic ash-flow tuff from many calderas in the San Juan volcanic field. The most voluminous post-collapse lava suite of the central San Juan caldera cluster is the 28 Ma Huerto Andesite, a diverse assemblage erupted from at least 5-6 volcanic centres that were active around the southern margins of the La Garita caldera shortly after eruption of the Fish Canyon Tuff. These andesitic centres are inferred, in part, to represent eruptions of magma that ponded and differentiated within the crust below the La Garita caldera, thereby providing the thermal energy necessary for rejuvenation and remobilization of the Fish Canyon magma body. The multiple Huerto eruptive centres produced two magmatic series that differ in phenocryst mineralogy (hydrous vs anhydrous assemblages), whole-rock major and trace element chemistry and isotopic compositions. Hornblende-bearing lavas from three volcanic centres located close to the southeastern margin of the La Garita caldera (Eagle Mountain - Fourmile Creek, West Fork of the San Juan River, Table Mountain) define a high-K calc-alkaline series (57-65 wt % SiO2) that is oxidized, hydrous and sulphur rich. Trachyandesitic lavas from widely separated centres at Baldy Mountain-Red Lake (western margin), Sugarloaf Mountain (southern margin) and Ribbon Mesa (20 km east of the La Garita caldera) are mutually indistinguishable (55-61 wt % SiO2); they are characterized by higher and more variable concentrations of alkalis and many incompatible trace elements (e.g. Zr, Nb, heavy rare earth elements), and they contain anhydrous phenocryst assemblages (including olivine). These mildly alkaline magmas were less water rich and oxidized than the hornblende-bearing calc-alkaline suite. The same distinctions characterize the voluminous precaldera andesitic lavas of the Conejos Formation, indicating that these contrasting suites are long-term manifestations of San Juan

  7. Alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} with large nonlinear optical properties in the deep-ultraviolet region

    Energy Technology Data Exchange (ETDEWEB)

    Reshak, A. H., E-mail: maalidph@yahoo.com [New Technologies—Research Centre, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Huang, Hongwei [School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Kamarudin, H. [Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Auluck, S. [Council of Scientific and Industrial Research—National Physical Laboratory, Dr. K S Krishnan Marg, New Delhi 110012, India and Physics Department, Indian Institute of Technology - Delhi, Hauz Khas, New Delhi 110016 (India)

    2015-02-28

    The linear optical response and second harmonic generation (SHG) in alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} are investigated by means of density functional theory. Calculations are performed using four types of exchange correlations: Ceperley-Alder local density approximation, Perdew Burke and Ernzerhof general gradient approximation, Engel-Vosko generalized gradient approximation, and the recently modified Becke-Johnson potential (mBJ). The mBJ approach brings the calculated band gap (7.20 eV) in excellent agreement with the experimental one (7.28 eV). The calculated values of the uniaxial anisotropy δε=−0.076 and the birefringence Δn(0)=0.052 indicate considerable anisotropy in the linear optical properties, which makes it favorable for the second harmonic generation. The dominant component of the second harmonic generation is χ{sub 111}{sup (2)}(ω). The value of |χ{sub 111}{sup (2)}(ω)| is about 1.2 pm/V at λ = 1064 nm in agreement with previous calculations. To analyze the origin of the high SHG of NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} single crystals, we have correlated the features of |χ{sub 111}{sup (2)}(ω)| spectra with the features of ε{sub 2}(ω) spectra as a function of ω/2 and ω. From the calculated dominant component |χ{sub 111}{sup (2)}(ω)|, we find that the microscopic first hyperpolarizability, β{sub 111}, the vector components along the dipole moment direction is 0.5 × 10{sup −30} esu at static limit and 0.6 × 10{sup −30} esu at λ = 1064 nm.

  8. When can ocean acidification impacts be detected from decadal alkalinity measurements?

    Science.gov (United States)

    Carter, B. R.; Frölicher, T. L.; Dunne, J. P.; Rodgers, K. B.; Slater, R. D.; Sarmiento, J. L.

    2016-04-01

    We use a large initial condition suite of simulations (30 runs) with an Earth system model to assess the detectability of biogeochemical impacts of ocean acidification (OA) on the marine alkalinity distribution from decadally repeated hydrographic measurements such as those produced by the Global Ship-Based Hydrographic Investigations Program (GO-SHIP). Detection of these impacts is complicated by alkalinity changes from variability and long-term trends in freshwater and organic matter cycling and ocean circulation. In our ensemble simulation, variability in freshwater cycling generates large changes in alkalinity that obscure the changes of interest and prevent the attribution of observed alkalinity redistribution to OA. These complications from freshwater cycling can be mostly avoided through salinity normalization of alkalinity. With the salinity-normalized alkalinity, modeled OA impacts are broadly detectable in the surface of the subtropical gyres by 2030. Discrepancies between this finding and the finding of an earlier analysis suggest that these estimates are strongly sensitive to the patterns of calcium carbonate export simulated by the model. OA impacts are detectable later in the subpolar and equatorial regions due to slower responses of alkalinity to OA in these regions and greater seasonal equatorial alkalinity variability. OA impacts are detectable later at depth despite lower variability due to smaller rates of change and consistent measurement uncertainty.

  9. Investigating Carbonate System Perturbations across the Cretaceous-Palaeogene Transition using Boron Isotopes in Planktonic Foraminifera.

    Science.gov (United States)

    Henehan, M. J.; Hull, P. M.; Planavsky, N. J.; Huber, B. T.; Thomas, E.

    2014-12-01

    The interval spanning the latest Maastrichtian to the early Palaeocene has great potential in helping to elucidate the stabilising mechanisms on the Earth's carbonate system on both long and very short geological timescales, from the geologically-instantaneous production of sulphate-rich aerosols and nitrogen oxides from the K-Pg bolide impact to the relatively more gradual degassing from Deccan volcanism in the latest Maastrichtian. The extent to which ocean pH (and atmospheric CO2 concentrations) changed in response to these contrasting acidification pressures, and the timescales of their recovery, may provide unique insight into the efficiency of the Earth's oceans in buffering greenhouse gas increases (through carbonate dissolution, weathering-derived alkalinity flux, and biological carbon cycling). The boron isotope palaeo-pH proxy in planktic foraminifera is well suited to such investigations, but its application over this interval has been problematic, not least due to a scarcity of sample material and a near-complete turnover of planktonic foraminiferal species across the K-Pg boundary. To attempt to circumvent these issues, we investigate the biological influences on boron isotope signals in Maastrichtian and Danian planktonic foraminifera, with the goal of producing more accurate palaeo-pH reconstructions. With these findings in mind, we present preliminary constraints on ocean pH and carbonate system dynamics across this critical interval of geological time.

  10. Zinc isotopic compositions of breast cancer tissue.

    Science.gov (United States)

    Larner, Fiona; Woodley, Laura N; Shousha, Sami; Moyes, Ashley; Humphreys-Williams, Emma; Strekopytov, Stanislav; Halliday, Alex N; Rehkämper, Mark; Coombes, R Charles

    2015-01-01

    An early diagnostic biomarker for breast cancer is essential to improve outcome. High precision isotopic analysis, originating in Earth sciences, can detect very small shifts in metal pathways. For the first time, the natural intrinsic Zn isotopic compositions of various tissues in breast cancer patients and controls were determined. Breast cancer tumours were found to have a significantly lighter Zn isotopic composition than the blood, serum and healthy breast tissue in both groups. The Zn isotopic lightness in tumours suggests that sulphur rich metallothionein dominates the isotopic selectivity of a breast tissue cell, rather than Zn-specific proteins. This reveals a possible mechanism of Zn delivery to Zn-sequestering vesicles by metallothionein, and is supported by a similar signature observed in the copper isotopic compositions of one breast cancer patient. This change in intrinsic isotopic compositions due to cancer has the potential to provide a novel early biomarker for breast cancer.

  11. Measurement of C and N isotopes of geological samples using Delta V Plus Stable Isotope Ratio Mass Spectrometer via different preparatory systems

    Digital Repository Service at National Institute of Oceanography (India)

    Karapurkar, S.; Methar, A.; Agnihotri, R.

    Stable isotope studies have proven their unique potential in unraveling several key biogeochemical processes occurring on solid earth as well as in world oceans. In addition, measurements of stable isotopes of lighter elements viz. C, N, O have...

  12. Petrogenesis of Permian alkaline lamprophyres and diabases from the Spanish Central System and their geodynamic context within western Europe

    OpenAIRE

    Orejana García, David; Villaseca González, Carlos; Billstrom, Kjell; Paterson, Bruce A.

    2008-01-01

    Basic to ultrabasic alkaline lamprophyres and diabases intruded within the Spanish Central System (SCS) during Upper Permian. Their high LREE, LILE and HFSE contents, together with positive Nb–Ta anomalies, link their origin with the infiltration of sublithospheric K-rich fluids. These alkaline dykes may be classified in two distinct groups according to the Sr–Nd isotope ratios: (1) a depleted PREMA-like asthenospheric component, and (2) a BSE-like lithospheric compone...

  13. Structural studies of human alkaline phosphatase in complex with strontium: Implication for its secondary effect in bones

    OpenAIRE

    Llinas, Paola; Masella, Michel; Stigbrand, Torgny; Ménez, André; Stura, Enrico A.; Le Du, Marie Hélène

    2006-01-01

    Strontium is used in the treatment of osteoporosis as a ranelate compound, and in the treatment of painful scattered bone metastases as isotope. At very high doses and in certain conditions, it can lead to osteomalacia characterized by impairment of bone mineralization. The osteomalacia symptoms resemble those of hypophosphatasia, a rare inherited disorder associated with mutations in the gene encoding for tissue-nonspecific alkaline phosphatase (TNAP). Human alkaline phosphatases have four m...

  14. Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

    Science.gov (United States)

    Bullen, Thomas D.; Chadwick, Oliver A.

    2016-01-01

    Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils, and indeed at all but the wettest site across the climosequence, to represent the complement of an isotopically light Ba fraction removed from these soils by plant roots consistent with the biolifting hypothesis. We further suggest that

  15. Oxygen Isotopes in Meteorites

    Science.gov (United States)

    Clayton, R. N.

    2003-12-01

    Oxygen isotope abundance variations in meteorites are very useful in elucidating chemical and physical processes that occurred during the formation of the solar system (Clayton, 1993). On Earth, the mean abundances of the three stable isotopes are 16O: 99.76%, 17O: 0.039%, and 18O: 0.202%. It is conventional to express variations in abundances of the isotopes in terms of isotopic ratios, relative to an arbitrary standard, called SMOW (for standard mean ocean water), as follows:The isotopic composition of any sample can then be represented by one point on a "three-isotope plot," a graph of δ17O versus δ18O. It will be seen that such plots are invaluable in interpreting meteoritic data. Figure 1 shows schematically the effect of various processes on an initial composition at the center of the diagram. Almost all terrestrial materials lie along a "fractionation" trend; most meteoritic materials lie near a line of "16O addition" (or subtraction). (4K)Figure 1. Schematic representation of various isotopic processes shown on an oxygen three-isotope plot. Almost all terrestrial materials plot along a line of "fractionation"; most primitive meteoritic materials plot near a line of "16O addition." The three isotopes of oxygen are produced by nucleosynthesis in stars, but by different nuclear processes in different stellar environments. The principal isotope, 16O, is a primary isotope (capable of being produced from hydrogen and helium alone), formed in massive stars (>10 solar masses), and ejected by supernova explosions. The two rare isotopes are secondary nuclei (produced in stars from nuclei formed in an earlier generation of stars), with 17O coming primarily from low- and intermediate-mass stars (radiation in the wavelength range 90-100 nm. The reaction proceeds by a predissociation mechanism, in which the excited electronic state lives long enough to have well-defined vibrational and rotational energy levels. As a consequence, the three isotopic species - C16O, C17O

  16. Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano, Italy

    Energy Technology Data Exchange (ETDEWEB)

    Barbieri, Maurizio; Morotti, Marco

    2003-01-01

    This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and {sup 87}Sr/{sup 86}Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and {sup 87}Sr/{sup 86}Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water-rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average {sup 87}Sr/{sup 86}Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704-0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher {sup 87}Sr/{sup 86}Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO{sub 4} and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites)

  17. Nucleotide sequences encoding a thermostable alkaline protease

    Science.gov (United States)

    Wilson, David B.; Lao, Guifang

    1998-01-01

    Nucleotide sequences, derived from a thermophilic actinomycete microorganism, which encode a thermostable alkaline protease are disclosed. Also disclosed are variants of the nucleotide sequences which encode a polypeptide having thermostable alkaline proteolytic activity. Recombinant thermostable alkaline protease or recombinant polypeptide may be obtained by culturing in a medium a host cell genetically engineered to contain and express a nucleotide sequence according to the present invention, and recovering the recombinant thermostable alkaline protease or recombinant polypeptide from the culture medium.

  18. Earth\\'s Mass Variability

    OpenAIRE

    Mawad, Ramy

    2014-01-01

    The perturbation of the Earth caused by variability of mass of Earth as additional reason with gravity of celestial bodies and shape of the Earth. The Earth eating and collecting matters from space and loss or eject matters to space through its flying in the space around the Sun. The source of the rising in the global sea level is not closed in global warming and icebergs, but the outer space is the additional important source for this rising. The Earth eats waters from space in unknown mecha...

  19. Discover Earth

    Science.gov (United States)

    Steele, Colleen

    1998-01-01

    Discover Earth is a NASA-sponsored project for teachers of grades 5-12, designed to: (1) enhance understanding of the Earth as an integrated system; (2) enhance the interdisciplinary approach to science instruction; and (3) provide classroom materials that focus on those goals. Discover Earth is conducted by the Institute for Global Environmental Strategies in collaboration with Dr. Eric Barron, Director, Earth System Science Center, The Pennsylvania State University; and Dr. Robert Hudson, Chair, the Department of Meteorology, University of Maryland at College Park. The enclosed materials: (1) represent only part of the Discover Earth materials; (2) were developed by classroom teachers who are participating in the Discover Earth project; (3) utilize an investigative approach and on-line data; and (4) can be effectively adjusted to classrooms with greater/without technology access. The Discover Earth classroom materials focus on the Earth system and key issues of global climate change including topics such as the greenhouse effect, clouds and Earth's radiation balance, surface hydrology and land cover, and volcanoes and climate change. All the materials developed to date are available on line at (http://www.strategies.org) You are encouraged to submit comments and recommendations about these materials to the Discover Earth project manager, contact information is listed below. You are welcome to duplicate all these materials.

  20. On the apparent CO2 absorption by alkaline soils

    Directory of Open Access Journals (Sweden)

    X. Chen

    2014-02-01

    Full Text Available Alkaline soils in the Gubantonggut Desert were recently demonstrated socking away large quantities of CO2 in an abiotic form. This demands a better understanding of abiotic CO2 exchange in alkaline sites. Reaction of CO2 with the moisture or dew in the soil was conjectured as a potential mechanism. The main goal of this study is to determine the extent to which the dew deposition modulates Land–Atmosphere CO2 exchange at highly alkaline sites (pH ~ 10. Experiments were conducted at the most barren sites (canopy coverage 2 fluxes were measured using a micro-lysimeters and an automated flux system (LI-COR, Lincoln, Nebraska, USA, respectively. There is an evident increase of dew deposition in nocturnal colder temperatures and decrease in diurnal warmer temperatures. Variations of soil CO2 flux are almost contrary, but the increase in diurnal warmer temperatures is obscure. It was shown that the accumulation and evaporation of dew in the soil motivates the apparent absorption and release of CO2. It was demonstrated that dew amounts in the soil has an exponential relation with the part in Fc beyond explanations of the worldwide utilized Q10 model. Therefore dew deposition in highly alkaline soils exerted a potential CO2 sink and can partly explain the apparent CO2 absorption. This implied a crucial component in the net ecosystem carbon balance (NECB at alkaline sites which occupies approximately 5% of the Earth's land surface (7 million km. Further explorations for its mechanisms and representativeness over other arid climate systems have comprehensive perspectives in the quaternary research.

  1. Development of alkaline fuel cells.

    Energy Technology Data Exchange (ETDEWEB)

    Hibbs, Michael R.; Jenkins, Janelle E.; Alam, Todd Michael; Janarthanan, Rajeswari [Colorado School of Mines, Golden, CO; Horan, James L. [Colorado School of Mines, Golden, CO; Caire, Benjamin R. [Colorado School of Mines, Golden, CO; Ziegler, Zachary C. [Colorado School of Mines, Golden, CO; Herring, Andrew M. [Colorado School of Mines, Golden, CO; Yang, Yuan [Colorado School of Mines, Golden, CO; Zuo, Xiaobing [Argonne National Laboratory, Argonne, IL; Robson, Michael H. [University of New Mexico, Albuquerque, NM; Artyushkova, Kateryna [University of New Mexico, Albuquerque, NM; Patterson, Wendy [University of New Mexico, Albuquerque, NM; Atanassov, Plamen Borissov [University of New Mexico, Albuquerque, NM

    2013-09-01

    This project focuses on the development and demonstration of anion exchange membrane (AEM) fuel cells for portable power applications. Novel polymeric anion exchange membranes and ionomers with high chemical stabilities were prepared characterized by researchers at Sandia National Laboratories. Durable, non-precious metal catalysts were prepared by Dr. Plamen Atanassov's research group at the University of New Mexico by utilizing an aerosol-based process to prepare templated nano-structures. Dr. Andy Herring's group at the Colorado School of Mines combined all of these materials to fabricate and test membrane electrode assemblies for single cell testing in a methanol-fueled alkaline system. The highest power density achieved in this study was 54 mW/cm2 which was 90% of the project target and the highest reported power density for a direct methanol alkaline fuel cell.

  2. Development of alkaline fuel cells.

    Energy Technology Data Exchange (ETDEWEB)

    Hibbs, Michael R.; Jenkins, Janelle E.; Alam, Todd Michael; Janarthanan, Rajeswari; Horan, James L.; Caire, Benjamin R.; Ziegler, Zachary C.; Herring, Andrew M.; Yang, Yuan; Zuo, Xiaobing; Robson, Michael H.; Artyushkova, Kateryna; Patterson, Wendy; Atanassov, Plamen Borissov

    2013-09-01

    This project focuses on the development and demonstration of anion exchange membrane (AEM) fuel cells for portable power applications. Novel polymeric anion exchange membranes and ionomers with high chemical stabilities were prepared characterized by researchers at Sandia National Laboratories. Durable, non-precious metal catalysts were prepared by Dr. Plamen Atanassovs research group at the University of New Mexico by utilizing an aerosol-based process to prepare templated nano-structures. Dr. Andy Herrings group at the Colorado School of Mines combined all of these materials to fabricate and test membrane electrode assemblies for single cell testing in a methanol-fueled alkaline system. The highest power density achieved in this study was 54 mW/cm2 which was 90% of the project target and the highest reported power density for a direct methanol alkaline fuel cell.

  3. Petrogenesis of coeval sodic and potassic alkaline magmas at Spanish Peaks, Colorado: Magmatism related to the opening of the Rio Grande rift

    Science.gov (United States)

    Lord, A. Brooke Hamil; McGregor, Heath; Roden, Michael F.; Salters, Vincent J. M.; Sarafian, Adam; Leahy, Rory

    2016-07-01

    Approximately coeval, relatively primitive (∼5-10% MgO with exception of a trachyandesite) alkaline mafic dikes and sills at or near Spanish Peaks, CO are divided into relatively sodic and potassic varieties on the basis of K2O/Na2O. Many of these dikes are true lamprophyres. In spite of variable alkali element ratios, the alkaline rocks share a number of geochemical similarities: high LIL element contents, high Ba and similar Sr, Nd and Hf isotope ratios near that of Bulk Earth. One important difference is that the potassic rocks are characterized by lower Al2O3 contents, typically less than 12 wt.%, than the sodic dikes/sills which typically have more than 13 wt.% Al2O3, and this difference is independent of MgO content. We attribute the distinct Al2O3 contents to varying pressure during melting: a mica-bearing, Al-poor vein assemblage for the potassic magmas melted at higher pressure than an aluminous amphibole-bearing vein assemblage for the sodic magmas. Remarkable isotopic and trace element similarities with approximately contemporaneous, nearby Rio Grande rift-related basalts in the San Luis Valley, indicate that the magmatism at Spanish Peaks was rift-related, and that lithosphere sources were shared between some rift magmas and those at Spanish Peaks. High Zn/Fe ratios in the Spanish Peaks mafic rocks point to a clinopyroxene- and garnet-rich source such as lithosphere veined by pyroxenite or eclogite. Lithospheric melting was possibly triggered by foundering of cool, dense lithosphere beneath the Rio Grande rift during the initiation of rifting with the potassic parent magmas generated by higher pressure melting of the foundered lithosphere than the sodic parent magmas. This process, caused by gravitational instability of the lithosphere (Elkins-Tanton, 2007) may be common beneath active continental rifts.

  4. Analysis of gases in the Earth's crust

    Science.gov (United States)

    Jenden, P. D.

    1986-05-01

    To investigate the origin and fate of natural gas in the Earth's crust, approximately 700 gas samples have been analyzed for chemical composition and stable isotopic ratios of carbon, hydrogen, nitrogen, sulfur and oxygen. During the current reporting period, helium isotope measurements confirmed the presence of mantle volatiles in the Sacramento basin, a dry gas province in northern California. Methane carbon isotope ratios and N2/Ar ratios suggest that Sacramento basin commercial gases with up to 88% nitrogen are derived from metasedimentary rocks. Studies of seep gases in Los Angeles indicate that ethane and higher hydrocarbons may be retarded during natural gas migration and the propane is selectively attacked during bacterial alteration. Carbon dioxide reduction and acetate dissimilation, the two main pathways for microbial methane formation, are characterized by different methane hydrogen isotope ratios. Hydrogen isotope ratios of methane and carbon isotope ratios of carbon dioxide and ethane help to distinguish microbial gases, thermogenic gases, and mixed gases.

  5. Earth\\'s Mass Variability

    CERN Document Server

    Mawad, Ramy

    2014-01-01

    The perturbation of the Earth caused by variability of mass of Earth as additional reason with gravity of celestial bodies and shape of the Earth. The Earth eating and collecting matters from space and loss or eject matters to space through its flying in the space around the Sun. The source of the rising in the global sea level is not closed in global warming and icebergs, but the outer space is the additional important source for this rising. The Earth eats waters from space in unknown mechanism. The mass of the Earth become greater in November i.e. before transit apoapsis two months, and become latter in February i.e. after transit apoapsis to two months.

  6. Ce3+/Tb3+ Doped Alkaline-Earth Borate Glasses Employed in Enhanced Solar Cells%增强型太阳能电池用Ce3+/Tb3+掺杂碱土硼酸盐玻璃

    Institute of Scientific and Technical Information of China (English)

    杨朋; 赵昕; 王志强; 林海

    2015-01-01

    Ce3+ and Tb3+ doped alkaline earth borate (LKZBSB) glasses and the photoluminescence properties of glass system have been fabricated and investigated ,and the observed violet and green fluorescences are originated from Ce3+ and Tb3+ emit-ting centers ,respectively .Four emission bands peaked at 487 ,543 ,586 and 621 nm are attributed to the emission transitions 5 D4 → 7 F6 ,5 D4 → 7 F5 ,5 D4 → 7 F4 and 5 D4 → 7 F3 of Tb3+ ,respectively ,and consists of a broad emission band peaking at 389 nm attributed to 5 d→4 f electric dipole allowed transition of Ce3+ .With the introduction of Ce3+ ,the effective excitation wavelength range of Tb3+ in LKZBSB glasses are remarkably expanded ,and the enhanced factor of green fluorescence of Tb3+ in Ce3+ /Tb3+co-doped LKZBSB glasses is up to 73 times in medium-wavelength ultraviolet (UVB) excitation region ,compared with that in Tb3+ single-doped case .The results show that the conversion from ultraviolet (UV) radiation to visible light is efficient in Ce3+ /Tb3+ doped LKZBSB glasses ,demonstrating that the glasses have potential values in developing enhanced solar cell as a conver-sion layer .%制备并研究了Ce3+和Tb3+掺杂碱土硼酸盐(LKZBSB)玻璃及该体系玻璃的光致发光特性,观察到起源于Ce3+和T b3+发光中心的蓝紫色和绿色荧光。波长为487,543,586和621 nm的发射峰分别归属于Tb3+的5D4→7F6,5D4→7F5,5D4→7F4和5D4→7F3发射跃迁,389nm的宽带发射峰归属于Ce3+的5d→4f电偶级允许跃迁。通过Ce3+引入,LKZBSB玻璃中Tb3+可见光发射的有效激发波长范围显著扩大,尤其在中波紫外激发下,Ce3+/T b3+共掺样品中T b3+的绿光发射强度相对于T b3+单掺样品,增强系数高达73倍。结果表明,在Ce3+/Tb3+掺杂LKZBSB玻璃中,紫外辐射可有效转换成可见光,作为光转换层对增强型太阳能电池的研发具有重要的应用价值。

  7. Handbook of environmental isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Baskaran, Mark (ed.) [Wayne State Univ., Detroit, MI (United States). Dept. Geology

    2011-07-01

    Applications of radioactive and stable isotopes have revolutionized our understanding of the Earth and near-earth surface processes. The utility of the isotopes are ever-increasing and our sole focus is to bring out the applications of these isotopes as tracers and chronometers to a wider audience so that they can be used as powerful tools to solve environmental problems. New developments in this field remain mostly in peer-reviewed journal articles and hence our goal is to synthesize these findings for easy reference for students, faculty, regulators in governmental and non-governmental agencies, and environmental companies. While this volume maintains its rigor in terms of its depth of knowledge and quantitative information, it contains the breadth needed for wide variety problems and applications in the environmental sciences. This volume presents all of the newer and older applications of isotopes pertaining to the environmental problems in one place that is readily accessible to readers. This book not only has the depth and rigor that is needed for academia, but it has the breadth and case studies to illustrate the utility of the isotopes in a wide variety of environments (atmosphere, oceans, lakes, rivers and streams, terrestrial environments, and sub-surface environments) and serves a large audience, from students and researchers, regulators in federal, state and local governments, and environmental companies. (orig.)

  8. Leatherback Isotopes

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — SWFSC is currently working on a project identifying global marine isotopes using leatherback turtles (Dermochelys coriacea) as the indicator species. We currently...

  9. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

    Floss, H.G. [Univ. of Washington, Seattle, WA (United States)

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  10. Isotopic Paleoclimatology

    Science.gov (United States)

    Bowen, R.

    Paleotemperature scales were calculated by H. C. Urey and others in the 1950s to assess past temperatures, and later work using the stable isotopes of oxygen, hydrogen, and carbon employed standards such as Peedee belemnite (PDB) and Standard Mean Ocean Water (SMOW). Subsequently, subjects as diverse as ice volume and paleotemperatures, oceanic ice and sediment cores, Pleistocene/Holocene climatic changes, and isotope chronostratigraphy extending back to the Precambrian were investigated.

  11. Iron isotopic fractionation during continental weathering

    Energy Technology Data Exchange (ETDEWEB)

    Fantle, Matthew S.; DePaolo, Donald J.

    2003-10-01

    The biological activity on continents and the oxygen content of the atmosphere determine the chemical pathways through which Fe is processed at the Earth's surface. Experiments have shown that the relevant chemical pathways fractionate Fe isotopes. Measurements of soils, streams, and deep-sea clay indicate that the {sup 56}Fe/{sup 54}Fe ratio ({delta}{sup 56}Fe relative to igneous rocks) varies from +1{per_thousand} for weathering residues like soils and clays, to -3{per_thousand} for dissolved Fe in streams. These measurements confirm that weathering processes produce substantial fractionation of Fe isotopes in the modern oxidizing Earth surface environment. The results imply that biologically-mediated processes, which preferentially mobilize light Fe isotopes, are critical to Fe chemistry in weathering environments, and that the {delta}{sup 56}Fe of marine dissolved Fe should be variable and negative. Diagenetic reduction of Fe in marine sediments may also be a significant component of the global Fe isotope cycle. Iron isotopes provide a tracer for the influence of biological activity and oxygen in weathering processes through Earth history. Iron isotopic fractionation during weathering may have been smaller or absent in an oxygen-poor environment such as that of the early Precambrian Earth.

  12. Natural fractionation of uranium isotopes

    International Nuclear Information System (INIS)

    The topic of this thesis was the investigation of U (n(238U) / n(235U)) isotope variations in nature with a focus on samples (1) that represent the continental crust and its weathering products (i.e. granites, shales and river water) (2) that represent products of hydrothermal alteration on mid-ocean ridges (i.e. altered basalts, carbonate veins and hydrothermal water) and (3) from restricted euxinic basins (i.e. from the water column and respective sediments). The overall goal was to explore the environmental conditions and unravel the mechanisms that fractionate the two most abundant U isotopes, n(238U) and n(235U), on Earth.

  13. Contrasting magmatic signatures in the Rairakhol and Koraput alkaline complexes, Eastern Ghats belt, India

    Indian Academy of Sciences (India)

    S Bhattacharya; M Basei

    2010-04-01

    The relation between alkaline magmatism and tectonism has been a contentious issue, particularly for the Precambrian continental regions. Alkaline complexes at the southwestern margin of Eastern Ghats belt, India, have been interpreted as rift-valley magmatism. However, those complexes occurring in granulite ensemble in the interior segments of the Eastern Ghats belt could not possibly be related to the rift-system, assumed for the western margin of the Eastern Ghats belt. Koraput complex was emplaced in a pull-apart structure, dominated by magmatic fabrics and geochemically similar to a fractionated alkaline complex, compatible with an alkalibasalt series. Rairakhol complex, on the other hand, shows dominantly solid-state deformation fabrics and geochemically similar to a fractionated calc-alkaline suite. Isotopic data for the Koraput complex indicate ca. 917 Ma alkaline magmatism from a depleted mantle source and postcrystalline thermal overprint at ca. 745 Ma, also recorded from sheared metapelitic country rocks. The calc-alkaline magmatism of the Rairakhol complex occurred around 938 Ma, from an enriched mantle source, closely following Grenvillian granulite facies imprint in the charnockitic country rocks.

  14. U-Pb zircon geochronology, petrochemical and Sr-Nd isotopic characteristic of Late Neoproterozoic granitoid of the Bornaward Complex (Bardaskan-NE Iran)

    Science.gov (United States)

    Bagherzadeh, R. Monazzami; Karimpour, M. H.; Farmer, G. Lang; Stern, C. R.; Santos, J. F.; Rahimi, B.; Heidarian Shahri, M. R.

    2015-11-01

    The Bornaward Granitoid Complex (BGC) in the Taknar Zone is located in the northeast of Central Iranian Block. The BGC consists of granite, alkaligranite, syenogranite, leucogranite, granophyre, monzogranite, granodiorite, tonalite and diorite that have intruded into the center of Taknar Zone. These intrusive rocks affected by low grade metamorphism. Because of there are no reliable isotope dating data, for the Bornaward Granitoid Complex rocks have been proposed discordant ages (Jurassic, Cretaceous or even younger ages) by many studies. In the present study, new isotopic information based on zircon U-Pb dating has revealed the origin and time of the formation of the BGC. These new results do not confirm previously proposed ages. The results obtained from zircon U-Pb dating of the BGC rocks suggest late-Neoproterozoic (Precambrian) age (540-550 Ma). The Bornaward Granitoid Complex is middle-high metaluminous to lower-middle peraluminous and belongs to tholeiite, calc-alkaline to high-K calc-alkaline rock series with enrichment in LIL (Cs, Rb and Ba, U, K, Zr, Y, Th) and depletion in HIL (Sr and Nb, Ta, Ti) elements. Chondrite-normalized Rare Earth Elements (REE) plots indicate minor enrichment of LREE compared to HREE, and strong negative anomaly of Eu compared to other Rare Earth Elements. Furthermore, initial 87Sr/86Sr and 143Nd/144Nd range from 0.70351 to 0.71689 and 0.511585 to 0.512061, respectively, and initial εNd isotope values for granite, granodiorite and diorite range from -6.73 to 2.52. These all indicate that the BGC has derived from partial melting of distinct basement source regions with very high initial 87Sr/86Sr and undergoing extensive crustal contamination (S-type granite).

  15. Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin.

    Science.gov (United States)

    Takano, Shotaro; Tanimizu, Masaharu; Hirata, Takafumi; Sohrin, Yoshiki

    2013-06-19

    Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n=6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved δ(65)Cu was 0.40-0.68‰.

  16. Alkaline fuel cell performance investigation

    Science.gov (United States)

    Martin, R. E.; Manzo, M. A.

    1988-01-01

    An exploratory experimental fuel cell test program was conducted to investigate the performance characteristics of alkaline laboratory research electrodes. The objective of this work was to establish the effect of temperature, pressure, and concentration upon performance and evaluate candidate cathode configurations having the potential for improved performance. The performance characterization tests provided data to empirically establish the effect of temperature, pressure, and concentration upon performance for cell temperatures up to 300 F and reactant pressures up to 200 psia. Evaluation of five gold alloy cathode catalysts revealed that three doped gold alloys had more that two times the surface areas of reference cathodes and therefore offered the best potential for improved performance.

  17. Red-emitting alkaline-earth rare-earth pentaoxometallates powders prepared by metal carboxylates solution

    Indian Academy of Sciences (India)

    Kyu-Seog Hwang; Sung-Dae Kim; Seung Hwangbo; Jin-Tae Kim

    2013-06-01

    Moisture-insensitive metal carboxylates that are mostly liquids at room temperature have been first applied to the preparation of strontium europium aluminate (Sr2EuAlO5) powders for red-emitting phosphor under near ultraviolet radiation. Strontium naphthenate, aluminium-2-ethylhexanoate and europium-2-ethylhexanoate were dissolved with toluene to prepare starting solution. Precursor pyrolyzed at 500 °C for 240 min was finally annealed at 900–1200 °C for 240 min in Ar. X-ray diffraction analysis, field emission–scanning electron microscope and fluorescent spectrophotometer were used to evaluate structural and optical properties. For the 1000 °C-annealed powders with regular shape and narrow size distribution confirmed by FE–SEM observation, strong red emission at 615nm under the excitation of 395nm maximum was reached, then the higher annealed samples at above 1100 °C gave the lower emission intensities.

  18. Alkaline Water and Longevity: A Murine Study.

    Science.gov (United States)

    Magro, Massimiliano; Corain, Livio; Ferro, Silvia; Baratella, Davide; Bonaiuto, Emanuela; Terzo, Milo; Corraducci, Vittorino; Salmaso, Luigi; Vianello, Fabio

    2016-01-01

    The biological effect of alkaline water consumption is object of controversy. The present paper presents a 3-year survival study on a population of 150 mice, and the data were analyzed with accelerated failure time (AFT) model. Starting from the second year of life, nonparametric survival plots suggest that mice watered with alkaline water showed a better survival than control mice. Interestingly, statistical analysis revealed that alkaline water provides higher longevity in terms of "deceleration aging factor" as it increases the survival functions when compared with control group; namely, animals belonging to the population treated with alkaline water resulted in a longer lifespan. Histological examination of mice kidneys, intestine, heart, liver, and brain revealed that no significant differences emerged among the three groups indicating that no specific pathology resulted correlated with the consumption of alkaline water. These results provide an informative and quantitative summary of survival data as a function of watering with alkaline water of long-lived mouse models.

  19. Rare earth optogalvanic spectroscopy: preliminary results

    Energy Technology Data Exchange (ETDEWEB)

    Destro, Marcelo G.; Neri, Jose W.; Rodrigues, Nicolau A.S.; Silveira, Carlos A.B.; Riva, Rudimar [Instituto de Estudos Avancados (IEAv/EFO), Sao Jose dos Campos, SP (Brazil). Div. de Fotonica]. E-mail: destro@ieav.cta.br; Victor, Alessandro R. [Instituto Tecnologico de Aeronautica (ITA), Sao Jose dos Campos, SP (Brazil)

    2008-07-01

    The IEAv has special interest in the studies of rare earth isotope applications in laser medium and integrated optics as well as aerospace research. We are starting to work with Ytterbium, Erbium, Dysprosium and Neodymium laser selective photoionization research. This paper describes the preliminary results of emission and optogalvanic spectroscopy obtained from a Neodymium hollow cathode lamps. Furthermore these results were used to setup our laser systems to work to leads a Nd isotopes selective laser photoionization. (author)

  20. Rare earth optogalvanic spectroscopy: preliminary results

    International Nuclear Information System (INIS)

    The IEAv has special interest in the studies of rare earth isotope applications in laser medium and integrated optics as well as aerospace research. We are starting to work with Ytterbium, Erbium, Dysprosium and Neodymium laser selective photoionization research. This paper describes the preliminary results of emission and optogalvanic spectroscopy obtained from a Neodymium hollow cathode lamps. Furthermore these results were used to setup our laser systems to work to leads a Nd isotopes selective laser photoionization. (author)

  1. Earth materials and earth dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, K; Shankland, T. [and others

    2000-11-01

    In the project ''Earth Materials and Earth Dynamics'' we linked fundamental and exploratory, experimental, theoretical, and computational research programs to shed light on the current and past states of the dynamic Earth. Our objective was to combine different geological, geochemical, geophysical, and materials science analyses with numerical techniques to illuminate active processes in the Earth. These processes include fluid-rock interactions that form and modify the lithosphere, non-linear wave attenuations in rocks that drive plate tectonics and perturb the earth's surface, dynamic recrystallization of olivine that deforms the upper mantle, development of texture in high-pressure olivine polymorphs that create anisotropic velocity regions in the convecting upper mantle and transition zone, and the intense chemical reactions between the mantle and core. We measured physical properties such as texture and nonlinear elasticity, equation of states at simultaneous pressures and temperatures, magnetic spins and bonding, chemical permeability, and thermal-chemical feedback to better characterize earth materials. We artificially generated seismic waves, numerically modeled fluid flow and transport in rock systems and modified polycrystal plasticity theory to interpret measured physical properties and integrate them into our understanding of the Earth. This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL).

  2. Nuclear geophysiology: Isotopes in Australian environmental analysis

    International Nuclear Information System (INIS)

    Lovelock introduced the term 'geophysiology' to describe the holistic study of the Earth systems. By analogy with medicine, and the corresponding field of nuclear medicine, 'nuclear geophysiology' describes the application of nuclear techniques to Earth system science. Injections of radioisotopes into the Earth's systems occur naturally and continuously, while artificial radionuclides have been injected at times as a result of human activities. Here, we provide some examples of Australian investigations into the physiology of the Earth derived from the study of these isotopes. (author)

  3. Grace DAKASEP alkaline battery separator

    Science.gov (United States)

    Giovannoni, R. T.; Lundquist, J. T.; Choi, W. M.

    1987-01-01

    The Grace DAKASEP separator was originally developed as a wicking layer for nickel-zinc alkaline batteries. The DAKASEP is a filled non-woven separator which is flexible and heat sealable. Through modification of formulation and processing variables, products with a variety of properties can be produced. Variations of DAKASEP were tested in Ni-H2, Ni-Zn, Ni-Cd, and primary alkaline batteries with good results. The properties of DAKASEP which are optimized for Hg-Zn primary batteries are shown in tabular form. This separator has high tensile strength, 12 micron average pore size, relatively low porosity at 46-48 percent, and consequently moderately high resistivity. Versions were produced with greater than 70 percent porosity and resistivities in 33 wt percent KOH as low as 3 ohm cm. Performance data for Hg-Zn E-1 size cells containing DAKASEP with the properties shown in tabular form, are more reproducible than data obtained with a competitive polypropylene non-woven separator. In addition, utilization of active material is in general considerably improved.

  4. Progress of research on the influence of alkaline cation and alkaline solution on bentonite properties

    International Nuclear Information System (INIS)

    Based on the previous laboratory studies and numerical simulation on bentonite in alkaline environments, the effects of alkaline cation and alkaline solution on mineral composition, microstructure, swelling capacity and hydraulic properties of bentonite are emphasized in this paper, temperature, pH values and concentration are discussed as main affecting factors. When bentonite is exposed to alkaline cation or alkaline solution, microstructure of bentonite will be changed due to the dissolution of montmorillonite and the formation of secondary minerals, which results in the decrease of swelling pressure. The amount of the reduction of swelling pressure depends on the concentration of alkaline solution. Temperature, polyvalent cation, salinity and concentration are the main factors affecting hydraulic properties of bentonite under alkaline conditions. Therefore, future research should focus on the mechanism of coupling effects of weak alkaline solutions on the mineral composition, microstructure, swelling capacity and hydraulic properties of bentonite under different temperatures and different pH values. (authors)

  5. Naturally occurring radionuclides and Earth sciences

    Directory of Open Access Journals (Sweden)

    G. Ferrara

    1997-06-01

    Full Text Available Naturally occurring radionuclides are used in Earth sciences for two fundamental purposes: age determination of rocks and minerals and studies of variation of the isotopic composition of radiogenic nuclides. The methodologies that are in use today allow us to determine ages spanning from the Earth's age to the late Quaternary. The variations of isotopic composition of radiogenic nuclides can be applied to problems of mantle evolution, magma genesis and characterization with respect to different geodynamic situations and can provide valuable information not obtainable by elemental geochemistry.

  6. Early Earth differentiation [rapid communication

    Science.gov (United States)

    Walter, Michael J.; Trønnes, Reidar G.

    2004-09-01

    The birth and infancy of Earth was a time of profound differentiation involving massive internal reorganization into core, mantle and proto-crust, all within a few hundred million years of solar system formation ( t0). Physical and isotopic evidence indicate that the formation of iron-rich cores generally occurred very early in planetesimals, the building blocks of proto-Earth, within about 3 million years of t0. The final stages of terrestrial planetary accretion involved violent and tremendously energetic giant impacts among core-segregated Mercury- to Mars-sized objects and planetary embryos. As a consequence of impact heating, the early Earth was at times partially or wholly molten, increasing the likelihood for high-pressure and high-temperature equilibration among core- and mantle-forming materials. The Earth's silicate mantle harmoniously possesses abundance levels of the siderophile elements Ni and Co that can be reconciled by equilibration between iron alloy and silicate at conditions comparable to those expected for a deep magma ocean. Solidification of a deep magma ocean possibly involved crystal-melt segregation at high pressures, but subsequent convective stirring of the mantle could have largely erased nascent layering. However, primitive upper mantle rocks apparently have some nonchondritic major and trace element refractory lithophile element ratios that can be plausibly linked to early mantle differentiation of ultra-high-pressure mantle phases. The geochemical effects of crystal fractionation in a deep magma ocean are partly constrained by high-pressure experimentation. Comparison between compositional models for the primitive convecting mantle and bulk silicate Earth generally allows, and possibly favors, 10-15% total fractionation of a deep mantle assemblage comprised predominantly of Mg-perovskite and with minor but geochemically important amounts of Ca-perovskite and ferropericlase. Long-term isolation of such a crystal pile is generally

  7. Isotope Spectroscopy

    CERN Document Server

    Caffau, E; Bonifacio, P; Ludwig, H -G; Monaco, L; Curto, G Lo; Kamp, I

    2013-01-01

    The measurement of isotopic ratios provides a privileged insight both into nucleosynthesis and into the mechanisms operating in stellar envelopes, such as gravitational settling. In this article, we give a few examples of how isotopic ratios can be determined from high-resolution, high-quality stellar spectra. We consider examples of the lightest elements, H and He, for which the isotopic shifts are very large and easily measurable, and examples of heavier elements for which the determination of isotopic ratios is more difficult. The presence of 6Li in the stellar atmospheres causes a subtle extra depression in the red wing of the 7Li 670.7 nm doublet which can only be detected in spectra of the highest quality. But even with the best spectra, the derived $^6$Li abundance can only be as good as the synthetic spectra used for their interpretation. It is now known that 3D non-LTE modelling of the lithium spectral line profiles is necessary to account properly for the intrinsic line asymmetry, which is produced ...

  8. Alkaline azide mutagenicity in cowpea

    International Nuclear Information System (INIS)

    Sodium azide is known as a potent mutagen in cereals and legumes. It is very effective in acidic medium in barley. Here an attempt is made to measure the effectiveness of sodium azide in alkaline medium (pH 7.4) on cowpea (Vigna unguiculata (L.) Walp., variety FS-68). Seeds pre-soaked in distilled water for 5 hours were treated with different concentrations (10-6, 10-5, 10-4 and 10-3M) of sodium azide (NaN3) for 4 hours at 28± 2 deg. C. Bottles were intermittently shaken, then the seeds were thoroughly washed in running tap water and subsequently planted in pots. The treatment caused significant biological damage such as reduction in seed germination, length of root and shoot, number of nodules and pods per plant and morphological leaf variations. Morphological, as well as chlorophyll mutants, were detected in M2

  9. Sr isotope evolution during chemical weathering of granites -- impact of relative weathering rates of minerals

    Institute of Scientific and Technical Information of China (English)

    MA; Yingjun

    2001-01-01

    [1]Ma, Y. J., Liu, C. Q., Geochemistry of strontium isotopes in the crust weathering system, Acta Mineralogica Sinica (in Chinese), 1998, 18(3): 350.[2]Ma, Y. J., Liu, C. Q., Using strontium isotopes to trace nutrient element circulation and hydrochemical evolution within an ecosystem, Advance in Earth Sciences (in Chinese), 1999, 14 (4): 377.[3]Brantley, S. L., Chesley, J. T., Stillings, L. L., Isotopic ratios and release rates of strontium from weathering feldspars, Geochim. Cosmochim. Acta, 1998, 62(9): 1493.[4]Blum, J. D., Erel, Y., A silicate weathering mechanism linking increases in marine 87Sr/86Sr with global glaciation, Nature, 1995, 373: 415.[5]Blum, J. D., Erel, Y., Rb-Sr isotope systematics of granitic soil chronosequence: The importance of biotite weathering, Geochim. Cosmochim. Acta, 1997, 61(15): 3193.[6]Bullen, T., Krabbenhoft, D., Kendall, C., Kinetic and mineralogic controls on the evolution of groundwater chemistry and 87Sr/86Sr in a sandy silicate aquifer, northern Wisconsin, USA, Geochim. Cosmochim. Acta, 1996, 60: 1807.[7]Bullen, T., White, A., Blum, A. et al., Chemical weathering of a soil chronosequence on granitoid alluvium: Ⅱminer-alogic and isotopic constraints on the behavior of strontium, Geochim. Cosmochim. Acta, 1997, 61: 291.[8]Blum, J. D., Erel, Y., Brown, K., 87Sr/86Sr ratios of Sierra Nevada stream waters: Implications for relative mineral weath-ering rates, Geochim. Cosmochim. Acta, 1993, 57: 5019.[9]Ma Yingjun, Trace element and strontium isotope geochemistry during chemical weathering, Ph. D. Dissertation, 1999, Institute of Geochemistry, Chinese Academy of Sciences.[10]Nesbitt, H. W., Markovics, G., Price, R. C., Chemical processes affecting alkalis and alkaline earths during continental weathering, Geochim. Cosmochim. Acta, 1980, 44: 1659.[11]Clauer, N., Strontium and argon isotopes in naturally weathered biotites, muscovites and feldspars, Chem. Geol., 1981, 31: 325.[12

  10. Earth's earliest biosphere: Its origin and evolution

    International Nuclear Information System (INIS)

    Some of the subjects discussed are related to the early biogeologic history, the nature of the earth prior to the oldest known rock record, the early earth and the Archean rock record, the prebiotic organic syntheses and the origin of life, Precambrian organic geochemistry, the biochemical evolution of anaerobic energy conversion, the isotopic inferences of ancient biochemistries, Archean stromatolites providing evidence of the earth's earliest benthos, Archean microfossils, the geologic evolution of the Archean-Early Proterozoic earth, and the environmental evolution of the Archean-Early Proterozoic earth. Other topics examined are concerned with geochemical evidence bearing on the origin of aerobiosis, biological and biochemical effects of the development of an aerobic environment, Early Proterozoic microfossils, the evolution of earth's earliest ecosystems, and geographic and geologic data for processed rock samples. Attention is given to a processing procedure for abiotic samples and calculation of model atmospheric compositions, and procedures of organic geochemical analysis

  11. Not So Rare Earth? New Developments in Understanding the Origin of the Earth and Moon

    Science.gov (United States)

    Righter, Kevin

    2007-01-01

    A widely accepted model for the origin of the Earth and Moon has been a somewhat specific giant impact scenario involving an impactor to proto-Earth mass ratio of 3:7, occurring 50-60 Ma after T(sub 0), when the Earth was only half accreted, with the majority of Earth's water then accreted after the main stage of growth, perhaps from comets. There have been many changes to this specific scenario, due to advances in isotopic and trace element geochemistry, more detailed, improved, and realistic giant impact and terrestrial planet accretion modeling, and consideration of terrestrial water sources other than high D/H comets. The current scenario is that the Earth accreted faster and differentiated quickly, the Moon-forming impact could have been mid to late in the accretion process, and water may have been present during accretion. These new developments have broadened the range of conditions required to make an Earth-Moon system, and suggests there may be many new fruitful avenues of research. There are also some classic and unresolved problems such as the significance of the identical O isotopic composition of the Earth and Moon, the depletion of volatiles on the lunar mantle relative to Earth's, the relative contribution of the impactor and proto-Earth to the Moon's mass, and the timing of Earth's possible atmospheric loss relative to the giant impact.

  12. Study of alpha activity in the region of rare earths

    International Nuclear Information System (INIS)

    The alpha decay half-lives of the Nd144, Cd152 and Er162 isotopes were redetermined using Ilford L4 nuclear emulsions charged with rare earth complexes of natural isotopic composition. The results were compared to results obtained by other authors, and with results calculated by potential barrier penetration theory. (M.C.K.)

  13. Digital Earth - A sustainable Earth

    Science.gov (United States)

    Mahavir

    2014-02-01

    All life, particularly human, cannot be sustainable, unless complimented with shelter, poverty reduction, provision of basic infrastructure and services, equal opportunities and social justice. Yet, in the context of cities, it is believed that they can accommodate more and more people, endlessly, regardless to their carrying capacity and increasing ecological footprint. The 'inclusion', for bringing more and more people in the purview of development is often limited to social and economic inclusion rather than spatial and ecological inclusion. Economic investment decisions are also not always supported with spatial planning decisions. Most planning for a sustainable Earth, be at a level of rural settlement, city, region, national or Global, fail on the capacity and capability fronts. In India, for example, out of some 8,000 towns and cities, Master Plans exist for only about 1,800. A chapter on sustainability or environment is neither statutorily compulsory nor a norm for these Master Plans. Geospatial technologies including Remote Sensing, GIS, Indian National Spatial Data Infrastructure (NSDI), Indian National Urban Information Systems (NUIS), Indian Environmental Information System (ENVIS), and Indian National GIS (NGIS), etc. have potential to map, analyse, visualize and take sustainable developmental decisions based on participatory social, economic and social inclusion. Sustainable Earth, at all scales, is a logical and natural outcome of a digitally mapped, conceived and planned Earth. Digital Earth, in fact, itself offers a platform to dovetail the ecological, social and economic considerations in transforming it into a sustainable Earth.

  14. Nickel isotopes as a new geochemical tracer

    Science.gov (United States)

    Gall, L.; Williams, H. M.; Siebert, C.; Halliday, A.

    2010-12-01

    Research into "non-traditional" stable isotope systems has been of great interest over the past decade. The stable isotope system of nickel (Ni) has not been studied as intensively as other transition metals (e.g. Fe, Cr, Cu, Zn, and Mo), even though it is a ubiquitous element in geological environments and is a bioessential trace metal, e.g. for production of methane by methanogens. We have developed a novel chemical separation procedure to isolate Ni from most geological matrices. Because of its chemical behavior during ion-exchange chromatography complete separation of Ni is very complex. We therefore make use of a Ni double spike that allows us to optimize the chemical separation and correct instrumental mass bias during mass spectrometry analysis. This technique allows high precision Ni isotope measurements resulting in long term external reproducibility of USGS rock standard BHVO-2 of 0.09‰ (2s.d.) on δ60/58Ni with typical measurement errors as low as 0.04‰ (2s.d.). We have measured the isotope composition of Ni in a variety of terrestrial samples demonstrating significant isotope variation. In magmatic rocks Ni isotopes appear to be largely homogeneous, with only small variations (no more than 0.2‰) between different rock types, from ultramafic to felsic. There is no evidence of significant isotopic fractionation during melting and differentiation of the silicate Earth. In contrast we find significant systematic isotope variations (up to 1.5‰) between magmatic rocks and FeMn crusts, shales and sulphides. Our data clearly demonstrate mass-dependent fractionation of Ni isotopes in the marine and terrestrial environment by inorganic processes, in addition to the biological fractionations already reported by others, highlighting the potential of Ni isotopes as a powerful new tracer for Earth Surface processes.

  15. Rare—Earth Elements and Genesis of Lamprophyres in the Laowangzhai Gold Orefield,Yunnan Province

    Institute of Scientific and Technical Information of China (English)

    黄智龙; 朱成明; 等

    1996-01-01

    The Laowangzhai super-large gold orefield,which is situated in northern Mt.Ailao tectonic zone,Yunnan Province,is a typical gold orefield where lamprophyres are temporally and spatially related to gold mineralization.Major element data show that lamprophyres in the orefield are of alkalic series and can be divided into potassic and K-rich calc-alkaline lamprophyres.The rocks are enriched in rare-earth elements as compared with the primary mantle and mid-ocean ridge basalts(MORB).Modelled calculations by the least squares method of Petrological Mixing show that the mantle-source for the lamprophyres in enriched in rarc earth elemeots.The geotectonic development of western Yunnan,Sr and Nd isotopic compositions,incompatible element patterns and linear programing calculations indicate that the fluids were derived from dehydration of submaine sediments which are enriched in ALK,LREE and incompatible elements and then were carried to mantle wedges as a result of plate subduction.That is the main factor leading to the formation of a metasonatic fertile mantle in the area studied.

  16. Isotopes a very short introduction

    CERN Document Server

    Ellam, Rob

    2016-01-01

    An isotope is a variant form of a chemical element, containing a different number of neutrons in its nucleus. Most elements exist as several isotopes. Many are stable while others are radioactive, and some may only exist fleetingly before decaying into other elements. In this Very Short Introduction, Rob Ellam explains how isotopes have proved enormously important across all the sciences and in archaeology. Radioactive isotopes may be familiar from their use in nuclear weapons, nuclear power, and in medicine, as well as in carbon dating. They have been central to establishing the age of the Earth and the origins of the solar system. Combining previous and new research, Ellam provides an overview of the nature of stable and radioactive isotopes, and considers their wide range of modern applications. ABOUT THE SERIES: The Very Short Introductions series from Oxford University Press contains hundreds of titles in almost every subject area. These pocket-sized books are the perfect way to get ahead in a new subjec...

  17. The importance of being alkaline

    OpenAIRE

    M. J. Russell

    2003-01-01

    The earliest forms of "protolife" on Earth must have been able to reproduce and replicate; it is likely that they were also cellular. How might such systems have formed? In his Perspective, Russell highlights the report by Hanczyc et al., who show that clay particles can catalyze the formation of lipid vesicles. These particles also adsorb RNA. If the vesicles are forced to divide, RNA is distributed among the daughter vesicles. Similar conditions to those used in the experiments may have exi...

  18. Hf isotope evidence for a hidden mantle reservoir

    DEFF Research Database (Denmark)

    Bizzarro, Martin; Simonetti, A.; Stevenson, R.K.;

    2002-01-01

    Hf isotopic composition and preserved in the deep mantle for at least 3 b.y.-may account for the mass imbalance in Earth's Hf-Nd budget. The Hf isotopic data presented here support a common mantle source region and genetic link between carbonatite and some oceanic-island basalt volcanoes....

  19. Studies on sulphur isotope variations in nature

    International Nuclear Information System (INIS)

    The variations of sulphur isotopes in natural compounds (and of oxygen isotopes in sulphates) provide a powerful method of investigation in various fields of earth sciences such as hydrology, geochemistry, geothermal exploration, volcanology, oceanography, sedimentology, ore formation, environmental sciences and others, although probably the method is not equally mature in all these fields, because of the inherent complexity and, sometimes, insufficient basic data. To review the current situation, and to identify trends of research and application of sulphur isotopes, the International Atomic Energy Agency held an Advisory Group Meeting on the Hydrology and Geochemistry of Sulphur Isotopes, which took place in Vienna at the IAEA Headquarters from 17 to 20 June 1985. Most of the papers presented at the meeting are included in this publication under the following titles: Isotopic composition of dissolved oceanic sulphate; Sulphur isotopes in the water of Lake Neusiedl, Austria; Relationships between the sulphur and oxygen isotope composition of dissolved sulphate; Sulphur and sulphate-oxygen isotopes in New Zealand geothermal systems and volcanic discharges; Isotopic composition and origin of sulphur compounds in groundwaters and brines in the Po Valley (northern Italy); Two case studies on the origin of aqueous sulphate in deep crystalline rocks; Sulphur and oxygen isotopic compositions of groundwater - and sabkha - sulphate in the Middle East; Radiolytic oxidation of sulphides and geochemical behaviour of sulphur isotopes in uranium deposits; On bias in 34S/32S data obtained using SO2 gas in mass spectrometry; Sulphur isotope analyses of trace sulphide and sulphate in various materials using Kiba reagent. Refs, figs and tabs

  20. A Teaching Exercise to Introduce Stable Isotope Fractionation of Metals into Geochemistry Courses

    Science.gov (United States)

    Weiss, Dominik J.; Harris, Caroline; Maher, Kate; Bullen, Thomas

    2013-01-01

    Variations in the isotopic composition of elements have been widely used to study earth's climate, biosphere, and interior, and more recently to track the fate of contaminants. Within the broad range of elements that exhibit measureable isotopic variations, metal stable isotopes are increasingly applied across the biological, geological,…

  1. Inorganic-organic separators for alkaline batteries

    Science.gov (United States)

    Sheibley, D. W. (Inventor)

    1978-01-01

    A flexible separator is reported for use between the electrodes of Ni-Cd and Ni-Zn batteries using alkaline electrolytes. The separator was made by coating a porous substrate with a battery separator composition. The coating material included a rubber-based resin copolymer, a plasticizer and inorganic and organic fillers which comprised 55% by volume or less of the coating as finally dried. One or more of the filler materials, whether organic or inorganic, is preferably active with the alkaline electrolyte to produce pores in the separator coating. The plasticizer was an organic material which is hydrolyzed by the alkaline electrolyte to improve conductivity of the separator coating.

  2. Partial radiogenic heat model for Earth revealed by geoneutrino measurements

    NARCIS (Netherlands)

    S. Abe; . et al.; M.P. Decowski

    2011-01-01

    The Earth has cooled since its formation, yet the decay of radiogenic isotopes, and in particular uranium, thorium and potassium, in the planet’s interior provides a continuing heat source. The current total heat flux from the Earth to space is 44.2±1.0 TW, but the relative contributions from residu

  3. Paleoproxies: Heavy Stable Isotope Perspectives

    Science.gov (United States)

    Nagler, T. F.; Hippler, D.; Siebert, C.; Kramers, J. D.

    2002-12-01

    Recent advances in isotope ratio mass spectrometry, namely multiple collector ICP-MS and refined TIMS techniques, will significantly enhance the ability to measure heavy stable isotope fractionation, which will lead to the development of a wide array of process-identifying (bio)-geochemical tools. Thus far research in this area is not easily assessable to scientists outside the isotope field. This is due to the fact that analyzing heavy stable isotopes does not provide routine numbers which are per se true (the preciser the truer) but is still a highly experimental field. On the other hand resolving earth science problems requires specialists familiar with the environment being studied. So what is in there for paleoceanographers? In a first order approach, relating isotope variations to physical processes is straightforward. A prominent example are oxygen isotope variations with temperature. The total geological signal is of course far more complicated. At low temperatures, heavy stable isotopes variations have been reported for e.g. Ca, Cr, Fe, Cu, Zn, Mo and Tl. Fractionation mechanisms and physical parameters responsible for the observed variations are not yet resolved for most elements. Significant equilibrium isotope fractionation is expected from redox reactions of transition metals. However a difference in coordination number between two coexisting speciations of an element in the same oxidation state can also cause fractionation. Protonation of dissolved Mo is one case currently discussed. For paleoceanography studies, a principal distinction between transition metals essential for life (V to Zn plus Mo) or not will be helpful. In case of the former group, distinction between biogenic and abiogenic isotope fractionation will remain an important issue. For example, abiotic Fe redox reactions result in isotope fractionations indistinguishable in direction and magnitude from microbial effects. Only a combination of different stable isotope systems bears the

  4. Eruption of Alkaline Basalts Prior to the Calc-alkaline Lavas of Mt. Cleveland Volcano, Aleutian Arc, Alaska

    Science.gov (United States)

    Bridges, D. L.; Nicolaysen, K. P.

    2005-12-01

    Mt. Cleveland is a 1,730 m stratovolcano, located on Chuginadak Island, that has erupted at least 23 times historically, with the latest occurring in August 2005. Major, trace, and REE analyses of 63 samples from Mt. Cleveland, including 8 from proximal cinder cones and 4 from andesitic domes on the lower flanks, identify two distinct lava suites. Modern Cleveland (MC) basalts to dacites (50.5-66.7 wt.% SiO2) exhibit a calc-alkaline differentiation trend. Major element trends suggest crystal fractionation of plagioclase +/- ortho- and clinopyroxene in MC lavas and olivine in cinder cone deposits. Resorption textures on plagioclase and olivine phenocrysts and multiple populations of plagioclase predominate throughout the MC suite suggesting magma mixing is a major process at Cleveland. Frothy white xenoliths of plagioclase + quartz + biotite are encased in glass and erupted as small pumiceous fragments in 2001. The partial resorption of the xenocrysts indicates assimilation is also an active crustal process at Cleveland. MC trace element spider diagrams exhibit a typical arc pattern in which HFS elements including Nb are depleted, and Pb and LIL elements are enriched. Th/La, Sm/La, and Sr, Nd, Pb, and Hf isotopic ratios indicate both a North Pacific MORB and a sediment component in the source of modern Cleveland lavas, consistent with sediment flux estimates of 90 to 95 m3/m/yr and an updip sediment thickness of 1300 to 1400 meters. Average 206Pb/204Pb, 207Pb/204Pb, 87Sr/86Sr, and 143Nd/144Nd values for the calc-alkaline suite are 18.93, 15.58, 0.70345, and 0.51303 respectively. The second suite consists of 3 olivine-rich, mildly alkaline basalts (48.5-49.4 wt.% SiO2), of older stratigraphic position than MC lavas representing deposits from an older phase of activity (ancestral Cleveland, AC). La/Yb, Sr/Y, and Th/Nb ratios indicate lower degrees of partial melting, relative to MC lavas, and suggests presence of garnet in the source region. The AC lavas, however, are

  5. Magmatism in the Tsagaandelger, Eastern Mongolian volcanic belt: Petrological, geochemical and isotopic constraints on Mesozoic geodynamic setting

    Science.gov (United States)

    Oidov, M.; Fujimaki, H.

    2008-12-01

    The vast territory of Mongolia lies in the heart of the Central Asian Orogenic Belt, one of largest provinces of the Phanerozoic continental growth on Earth (Jahn et al., 2004). We present new petrographic, geochemical and Sr-Nd isotopic analyses on Mesozoic igneous rocks emplaced in Central Mongolia. The Mesozoic igneous suites, those exposed in the Tsagaandelger area, pass upwards from alkaline series trachytic rocks and overlain by tuffaceous sediments. Those are intruded by calc alkaline leucocratic granites and covered by Late Mesozoic calc alkaline bimodal volcanic rocks consisting of basalts and rhyolite. Alkaline series volcanic sequences were erupted in Early-Middle Triassic (241 Ma) and characterized by LILE, LREE enrichment and significant Nb-Ta depletion. Rocks have weakly enriched initial 87Sr86Sr ratios of 0.705 to 0.706 and positive ɛNd(t) values (0.7 to 4). The crystallization age of intrusive rocks is 231 Ma. The majority of samples is slightly peraluminous and can be classified as granite, including monzogranite, granodiorite and aplite. Granites are characterized by near- zero ɛNd(t) values (0.7 to 2) and tetrad effect in their REE distribution patterns. Further Cretaceous volcanic sequences have lower contents of LILE and higher contents of HFS and REE, comparing with Triassic volcanic sequences. The Cretaceous volcanic rocks have the initial 87Sr86Sr ratios between 0.705 and 0.719 and near-zero ɛNd(t) values (-0.7 to 1.6). Trace element geochemistry indicates that Mesozoic volcanic rocks from the studied area are arc related. The Triassic volcanic and plutonic rocks could be emplaced in active continental margin settings. Post collisional extensional regime could be started with Early Cretaceous volcanism. The mass balance calculation suggests that the all Mesozoic volcanic and plutonic rocks were derived from sources composed of more than 80% juvenile mantle-derived component. Our data confirm the earlier observations of similar isotopic

  6. Deep-water circulation and detrital provenance in the South Pacific, from the present day until 240 000 years ago : evidence from Nd, Sr and Pb isotopes and Rare Earth Elements

    OpenAIRE

    Molina-Kescher, Mario

    2014-01-01

    Present and past climate of the Earth has strongly depended on oceanic circulation and marine biological productivity. The formation of deep and bottom waters in high latitudes as a consequence of density changes and their pathways through the global ocean, the so called thermohaline circulation (THC) have been of primary importance for the redistribution of heat, for the Earth’s albedo through control on the sea ice distribution, and it serves as a reservoir of greenhouse gases such as CO2. ...

  7. Adakitic-like magmatism in western Ossa-Morena Zone (Portugal): Geochemical and isotopic constraints of the Pavia pluton

    Science.gov (United States)

    Lima, S. M.; Neiva, A. M. R.; Ramos, J. M. F.

    2013-02-01

    Granitic rocks are a major component of the Earth's continental crust and occur in a wide variety of tectonic settings. Their chemical and isotopic characterization is crucial to the recognition of the potential sources and mechanisms involved in their generation. In this study, we present the first whole rock chemical and isotopic (Sr-Nd-O) data for the Pavia pluton (328-317 Ma), located near the western border of the Ossa-Morena Zone (Évora Massif, Portugal). Major and trace element geochemistry suggests that the different granitic phases composing this intrusive body (enclaves, granites (s.l.) and crosscutting dikes) represent independent magma pulses and the majority is similar to TTGs and adakites. The little Sr-Nd-O isotopic variation, with (87Sr/86Sr)328 = 0.70428-0.70560, ɛNd328 ranging between - 3.4 and + 0.4 and δ18O varying from + 5.6‰ to + 8.4‰ implies an isotopically similar protolith for all phases. The most viable mechanism for the generation of the Pavia pluton adakitic-like magmatism is assimilation-fractional crystallization of a mantle-derived magma. This mechanism was also invoked to explain the genesis of other plutons within the Évora Massif but they have a distinct chemistry (typical arc calc-alkaline rocks). The chemical differences between them and the Pavia pluton granitic rocks are interpreted as the result of lower degrees of crustal assimilation and higher degrees of contamination of mantle-derived magmas by the sinking slab (after subduction blocking and subsequent slab break-off).

  8. Real-time materials evolution visualized within intact cycling alkaline batteries

    Energy Technology Data Exchange (ETDEWEB)

    Gallaway, JW; Erdonmez, CK; Zhong, Z; Croft, M; Sviridov, LA; Sholklapper, TZ; Turney, DE; Banerjee, S; Steingart, DA

    2014-01-01

    The scientific community has focused on the problem of inexpensive, safe, and sustainable large-scale electrical energy storage, which is needed for a number of emerging societal reasons such as stabilizing intermittent renewables-based generation like solar and wind power. The materials used for large-scale storage will need to be low cost, earth-abundant, and safe at the desired scale. The Zn-MnO2 "alkaline" battery chemistry is associated with one-time use, despite being rechargeable. This is due to material irreversibilities that can be triggered in either the anode or cathode. However, as Zn and MnO2 have high energy density and low cost, they are economically attractive even at limited depth of discharge. As received, a standard bobbin-type alkaline cell costs roughly $20 per kW h. The U. S. Department of Energy ARPA-E $100 per kW h cost target for grid storage is thus close to the cost of alkaline consumer primary cells if re-engineered and/or cycled at 5-20% nominal capacity. Herein we use a deeply-penetrating in situ technique to observe ZnO precipitation near the separator in an alkaline cell anode cycled at 5% DOD, which is consistent with cell failures observed at high cycle life. Alkaline cells designed to avoid such causes of cell failure could serve as a low-cost baseload for large-scale storage.

  9. Prebiotic Synthesis of Glycine from Ethanolamine in Simulated Archean Alkaline Hydrothermal Vents

    Science.gov (United States)

    Zhang, Xianlong; Tian, Ge; Gao, Jing; Han, Mei; Su, Rui; Wang, Yanxiang; Feng, Shouhua

    2016-09-01

    Submarine hydrothermal vents are generally considered as the likely habitats for the origin and evolution of early life on Earth. In recent years, a novel hydrothermal system in Archean subseafloor has been proposed. In this model, highly alkaline and high temperature hydrothermal fluids were generated in basalt-hosted hydrothermal vents, where H2 and CO2 could be abundantly provided. These extreme conditions could have played an irreplaceable role in the early evolution of life. Nevertheless, sufficient information has not yet been obtained for the abiotic synthesis of amino acids, which are indispensable components of life, at high temperature and alkaline condition. This study aims to propose a new method for the synthesis of glycine in simulated Archean submarine alkaline vent systems. We investigated the formation of glycine from ethanolamine under conditions of high temperature (80-160 °C) and highly alkaline solutions (pH = 9.70). Experiments were performed in an anaerobic environment under mild pressure (0.1-8.0 MPa) at the same time. The results suggested that the formation of glycine from ethanolamine occurred rapidly and efficiently in the presence of metal powders, and was favored by high temperatures and high pressures. The experiment provides a new pathway for prebiotic glycine formation and points out the phenomenal influence of high-temperature alkaline hydrothermal vents in origin of life in the early ocean.

  10. Clinopyroxene-host disequilibrium (Sr-Nd-Pb isotope systematics) in ultra-potassic magmas from East-African Rift: Implications for magma mixing and source heterogeneity

    Science.gov (United States)

    Muravyeva, Natalya; Belyatsky, Boris; Senin, Valeriy

    2014-05-01

    Nd, Pb and Sr isotope ratios have been determined for kamafugite lava and clinopyroxene and phlogopite phenocrysts from Toro-Ankole and Virunga volcanic fields of the East African Rift. The whole rock Sr - Nd isotopic signatures of kamafugites (87Sr/86Sr: 0.70463 - 0.70536; 143Nd/144Nd: 0.51249 - 0.51255) suggest derivation from an EM1-type mantle source. In contrast, Pb isotopic compositions of the same samples (206Pb/204Pb: 19.00 - 19.57; 207Pb/204Pb: 15.69 - 15.74; 208Pb/204Pb: 39.30 - 40.26) reveal a similarity to EM2-type mantle. New Nd, Pb and Sr isotopic data for clinopyroxene (87Sr/86Sr: 0.70473 - 0.70503; 143Nd/144Nd: 0.51250 - 0.51254; 206Pb/204Pb: 18.04 - 18.17; 207Pb/204Pb: 15.58 - 15.60; 208Pb/204Pb: 38.09 - 38.23) suggest derivation from an EM1-like source, and indicate Sr and Pb isotope disequilibrium between clinopyroxene and corresponding host rock. Moreover, clinopyroxenes demonstrating a greater degree of isotopic disequilibrium with their host rock are more sodic in composition. The isotopic disequilibrium is corroborated by the presence of chemical zoning within clinopyroxene, which suggests rapid magma ascent rates preventing melt homogenization. The Pb isotopic ratios for both mineral and corresponding whole rock, together with published data on East African rift-related alkaline centers, define a trend interpreted to represent a mixing line for melts derived from sources such as EM1 and as HIMU. The similar isotopic compositions for clinopyroxene from the different volcanic rocks within the East African Rift suggest the existence of a common, older mantle source for their parental melts. The origin of these melts can be attributed to an enrichment event ~ 400-500 Ma, i.e., significantly prior the younger (Quaternary) ultrapotassic magmatism. Our preferred interpretation for the results reported here involves the mixing of the melts derived from EM1- and HIMU-like sources, which were rapidly transported to the Earth's surface. The primary

  11. Technetium recovery from high alkaline solution

    Science.gov (United States)

    Nash, Charles A.

    2016-07-12

    Disclosed are methods for recovering technetium from a highly alkaline solution. The highly alkaline solution can be a liquid waste solution from a nuclear waste processing system. Methods can include combining the solution with a reductant capable of reducing technetium at the high pH of the solution and adding to or forming in the solution an adsorbent capable of adsorbing the precipitated technetium at the high pH of the solution.

  12. Alkaline tolerant dextranase from streptomyces anulatus

    Science.gov (United States)

    Decker, Stephen R.; Adney, William S.; Vinzant, Todd B.; Himmel, Michael E.

    2003-01-01

    A process for production of an alkaline tolerant dextranase enzyme comprises culturing a dextran-producing microorganism Streptomyces anulatus having accession no. ATCC PTA-3866 to produce an alkaline tolerant dextranase, Dex 1 wherein the protein in said enzyme is characterized by a MW of 63.3 kDa and Dex 2 wherein its protein is characterized by a MW of 81.8 kDa.

  13. Distinctly different parental magmas for calc-alkaline plutons and tholeiitic lavas in the central and eastern Aleutian arc

    Science.gov (United States)

    Cai, Yue; Rioux, Matthew; Kelemen, Peter B.; Goldstein, Steven L.; Bolge, Louise; Kylander-Clark, Andrew R. C.

    2015-12-01

    Cenozoic calc-alkaline plutons that comprise the middle crust of the central and eastern Aleutians have distinct isotopic and elemental compositions compared to Holocene tholeiitic lavas in the same region, including those from the same islands. Therefore the Holocene lavas are not representative of the net magmatic transfer from the mantle into the arc crust. Compared to the lavas, the Eocene to Miocene (9-39 Ma) intermediate to felsic plutonic rocks show higher SiO2 at a given Fe/Mg ratio, and have higher εNd-εHf values and lower Pb-Sr isotope ratios. However, the plutonic rocks strongly resemble calc-alkaline Holocene volcanics with more "depleted" isotope ratios in the western Aleutians, whose composition has been attributed to significant contributions from partial melting of subducted basaltic oceanic crust. These data could reflect a temporal variation of central and eastern Aleutian magma source compositions, from predominantly calc-alkaline compositions with more "depleted" isotope ratios in the Paleogene, to tholeiitic compositions with more "enriched" isotopes more recently. Alternatively, the differences between central Aleutian plutonic and volcanic rocks may reflect different transport and emplacement processes for the magmas that form plutons versus lavas. Calc-alkaline parental magmas, with higher SiO2 and high viscosity, are likely to form plutons after extensive mid-crustal degassing of initially high water contents. This conclusion has overarching importance because the plutonic rocks are chemically similar to bulk continental crust. Formation of similar plutonic rocks worldwide may play a key role in the genesis and evolution of continental crust.

  14. Alkaline regenerative fuel cell systems for energy storage

    Science.gov (United States)

    Schubert, F. H.; Reid, M. A.; Martin, R. E.

    1981-01-01

    A description is presented of the results of a preliminary design study of a regenerative fuel cell energy storage system for application to future low-earth orbit space missions. The high energy density storage system is based on state-of-the-art alkaline electrolyte cell technology and incorporates dedicated fuel cell and electrolysis cell modules. In addition to providing energy storage, the system can provide hydrogen and oxygen for attitude control of the satellite and for life support. During the daylight portion of the orbit the electrolysis module uses power provided by the solar array to generate H2 and O2 from the product water produced by the fuel cell module. The fuel cell module supplies electrical power during the dark period of the orbit.

  15. Origin and evolution of overlapping calc-alkaline and alkaline magmas: The Late Palaeozoic post-collisional igneous province of Transbaikalia (Russia)

    Science.gov (United States)

    Litvinovsky, B. A.; Tsygankov, A. A.; Jahn, B. M.; Katzir, Y.; Be'eri-Shlevin, Y.

    2011-08-01

    The Late Palaeozoic voluminous magmatism in Transbaikalia, Russia (a territory of > 600,000 km 2 to the east of Lake Baikal) is highly diverse and complex. Of special interest are (1) the significant overlap in time between magmatic suites commonly ascribed to post-collisional and within-plate settings and (2) the provenance of the coeval, but distinct, granitoid magmas that are closely spaced within a large region. Magmatic activity lasted almost continuously from ~ 330 Ma to ~ 275 Ma and included five igneous suites occupying a total area of ~ 200,000 km 2: (1) the Barguzin suite of high-K calc-alkaline granite (330-310 Ma); (2 and 3) the coeval Chivyrkui suite of low-silica calc-alkaline granitoids and the Zaza suite of high-K calc-alkaline to alkaline granite and quartz syenite which were emplaced between 305 and 285 Ma; and (4 and 5) the partially overlapped in time Lower-Selenga monzonite-syenite suite (285-278 Ma) and the Early-Kunalei suite of alkali-feldspar and peralkaline quartz syenite and granite (281-275 Ma). The overall increase in alkalinity of the granitoids with time reflects the progress from post-collisional to within-plate settings. However, a ~ 20 m.y. long transitional period during which both calc-alkaline and alkaline granitoids were emplaced indicates the coexistence of thickened (batholiths) and thinned (rift) crustal tracts. Sr-Nd-O isotope and elemental geochemical data suggest that the relative contribution of mantle-derived components to the generation of silicic magmas progressively increased with time. The high-K calc-alkaline granite magmas that formed the Angara-Vitim batholith were generated by high degree melting of supracrustal metamorphic rocks [ɛNd(t) = - 5.7 to - 7.7; δ 18O(Qtz) = 12‰], with minor contribution of H 2O and K from the underplated mafic magma (the convective diffusion model). The coeval calc-alkaline Chivyrkui suite and the transitional to alkaline Zaza suite formed as a result of mixing of crustal silicic

  16. Rare earths

    International Nuclear Information System (INIS)

    General mineralogical-geochemical and analytical characteristics of (lanthanides and yttrium) are presented. It is pointed out that individual RE in complex chemical composition samples are successfully determined by physical methods of the analysis (emission spectral method, spark mass spectrometry method, neutron + activation analysis). RE sum determination is performed by spectrophotometric titrimetric or gravimetric methods. Principal methods of RE separation and concentration, methods of analytical samples dissolution are considered. Detailed descriptions of some specific techniques of determining rare earths in rocks, ores and minerals are presented

  17. Isotopic mixing by magnetorotational instability in the protolunar disk

    Science.gov (United States)

    Desch, Steven; Carballido, Augusto; Taylor, G. Jeffrey

    2016-10-01

    One explanation for the striking similarity in isotopic ratios between the Earth and Moon is that isotopes were efficiently mixed in the protolunar disk and between the disk and the Earth. We examine the ability of the magnetorotational instability to act in the protolunar disk, calculating the ionization fraction of the vapor component and the resultant Elsasser numbers. We perform shearing box magnetohydrodynamic simulations to calculate the rate of turbulent mixing. We conclude that mixing of isotopes in the disk is effective on ~ 102 yr timescales, faster than the time for the disk to evolve and the Moon to form. We also consider the effectiveness of isotopic mixing between the disk and the Earth.

  18. Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin

    Energy Technology Data Exchange (ETDEWEB)

    Takano, Shotaro, E-mail: shotaro@inter3.kuicr.kyoto-u.ac.jp [Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan); Tanimizu, Masaharu [Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology, 200 Monobe Otsu, Nankoku 783-8502 (Japan); Hirata, Takafumi [Laboratory for Planetary Sciences, Division of Earth and Planetary Sciences, Kyoto University, Kitashirakawa Oiwake-cho, Kyoto 606-8502 (Japan); Sohrin, Yoshiki [Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan)

    2013-06-19

    Graphical abstract: -- Highlights: •A simple analytical method for determining the Cu isotopic composition in seawater using an ethylenediaminetriacetic acid chelating resin was developed. •The accuracy was evaluated via addition of NIST SRM976 or {sup 65}Cu-enriched standard to seawater. •δ{sup 65}Cu of seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples from the northwestern Pacific Ocean were firstly determined. -- Abstract: Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2 L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n = 6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved δ{sup 65}Cu was 0.40–0.68‰.

  19. Improved electrodes and gas impurity investigations on alkaline electrolysers

    DEFF Research Database (Denmark)

    Reissner, R.; Schiller, G.; Knoeri, T.;

    Alkaline water electrolysis for hydrogenproduction is a well-established techniquebut some technological issues regarding thecoupling of alkaline water electrolysis andRenewable Energy Sources (RES) remain tobe improved.......Alkaline water electrolysis for hydrogenproduction is a well-established techniquebut some technological issues regarding thecoupling of alkaline water electrolysis andRenewable Energy Sources (RES) remain tobe improved....

  20. 21 CFR 864.7660 - Leukocyte alkaline phosphatase test.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Leukocyte alkaline phosphatase test. 864.7660... Leukocyte alkaline phosphatase test. (a) Identification. A leukocyte alkaline phosphatase test is a device used to identify the enzyme leukocyte alkaline phosphatase in neutrophilic granulocytes...