Sample records for alkaline earth isotopes

  1. Alkaline earth metal thioindates

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov-Ehmin, B.N.; Ivlieva, V.I.; Filatenko, L.A.; Zajtsev, B.E.; Kaziev, G.Z.; Sarabiya, M.G.


    Alkaline earth metal thioindates of MIn/sub 2/S/sub 4/ composition were synthesized by interaction of alkaline earth metal oxoindates with hydrogen sulfide during heating. Investigation into the compounds by X-ray analysis showed that calcium compound crystallizes in cubic crystal system and strontium and barium compounds in rhombic crystal system. Lattice parameters and the number of formula units were determined. Thioindates of M/sub 3/In/sub 2/S/sub 6/ composition were synthesized, their individuality was shown.

  2. Controlled charge exchange between alkaline earth metals and their ions (United States)

    Gacesa, Marko; Côté, Robin


    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.

  3. Oxidation catalysts on alkaline earth supports

    Energy Technology Data Exchange (ETDEWEB)

    Mohajeri, Nahid


    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  4. Enhanced Magnetic Trap Loading for Alkaline-Earth Atoms (United States)

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


    We report on a technique to improve the continuous loading of atomic strontium into a magnetic trap from a Magneto-Optical Trap (MOT). This is achieved by adding a depumping laser addressing the 3P1 level. For the 3P1 -->3S1 (688-nm) transition in strontium, the depumping laser increases atom number in the magnetic trap and subsequent cooling stages by up to 65 % for the bosonic isotopes and up to 30 % for the fermionic isotope. We optimize this trap loading strategy with respect to the 688-nm laser detuning, intensity, and beam size. To understand the results, we develop a one-dimensional rate equation model of the system, which is in good agreement with the data. We discuss the use of other transitions in strontium for accelerated trap loading and the application of the technique to other alkaline-earth-like atoms.

  5. 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


    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.

  6. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

    Institute of Scientific and Technical Information of China (English)

    XUXin; ZHUTun


    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.

  7. Earth Processes: Reading the Isotopic Code (United States)

    Basu, Asish; Hart, Stan

    Publication of this monograph will coincide, to a precision of a few per mil, with the centenary of Henri Becquerel's discovery of "radiations actives" (C. R. Acad. Sci., Feb. 24, 1896). In 1896 the Earth was only 40 million years old according to Lord Kelvin. Eleven years later, Boltwood had pushed the Earth's age past 2000 million years, based on the first U/Pb chemical dating results. In exciting progression came discovery of isotopes by J. J. Thomson in 1912, invention of the mass spectrometer by Dempster (1918) and Aston (1919), the first measurement of the isotopic composition of Pb (Aston, 1927) and the final approach, using Pb-Pb isotopic dating, to the correct age of the Earth: close—2.9 Ga (Gerling, 1942), closer—3.0 Ga (Holmes, 1949) and closest—4.50 Ga (Patterson, Tilton and Inghram, 1953).

  8. Modelling the crystallisation of alkaline earth boroaluminosilicate glass ceramics

    DEFF Research Database (Denmark)

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


    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....

  9. 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: [Institute of Laboratory Medicine, University of Pecs, Pecs H-7624 (Hungary)


    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.

  10. Structural variations in layered alkaline earth metal cyclohexyl phosphonates

    Indian Academy of Sciences (India)

    Ramaswamy Murugavel; Nayanmoni Gogoi


    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.

  11. Quantum computing with alkaline-Earth-metal atoms. (United States)

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


    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.

  12. 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


    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.

  13. Proposal for Laser Cooling of Alkaline Earth Monoalkoxide Free Radicals (United States)

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


    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.

  14. Structural diversity of alkaline-earth 2,5-thiophenedicarboxylates (United States)

    Balendra; Ramanan, Arunachalam


    Exploration of the structural landscape of the system containing divalent alkaline-earth metal ion (Mg, Ca and Sr) with the rigid 2,5-thiophenedicarboxylic acid (TDC) under varying solvothermal condition (DMF, DMA and DEF) yielded five new crystals: [Mg(TDC) (DEF)2(H2O)1/2] (1), [Ca(TDC) (DMA)] (2), [Ca(TDC) (DMA) (H2O)] (3), [Sr(TDC) (DMA)] (4) and [Sr(TDC) (DMA) (H2O)] (5) and two known solids. Single crystal structures of all the solids are characteristic of extended coordination interaction between metal and carboxylate ions. While the smaller magnesium ion crystallized into a 2D coordination polymer, the larger calcium and strontium compounds resulted into the growth of 3D metal organic frameworks. All the solids show blue emission arising from intra ligand charge transfer.

  15. Alkaline Earth Core Level Photoemission Spectroscopy of High-Temperature Superconductors (United States)

    Vasquez, R.


    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.

  16. Quantum degenerate mixtures of alkali and alkaline-earth-like atoms. (United States)

    Hara, Hideaki; Takasu, Yosuke; Yamaoka, Yoshifumi; Doyle, John M; Takahashi, Yoshiro


    We realize simultaneous quantum degeneracy in mixtures consisting of the alkali and alkaline-earth-like atoms Li and Yb. This is accomplished within an optical trap by sympathetic cooling of the fermionic isotope ⁶Li with evaporatively cooled bosonic ¹⁷⁴Yb and, separately, fermionic ¹⁷³Yb. Using cross-thermalization studies, we also measure the elastic s-wave scattering lengths of both Li-Yb combinations, |a(⁶Li-¹⁷⁴Yb)| = 1.0 ± 0.2 nm and |a(⁶Li-¹⁷³Yb)| = 0.9 ± 0.2 nm. The equality of these lengths is found to be consistent with mass-scaling analysis. The quantum degenerate mixtures of Li and Yb, as realized here, can be the basis for creation of ultracold molecules with electron spin degrees of freedom, studies of novel Efimov trimers, and impurity probes of superfluid systems.

  17. Silicon isotope evidence against an enstatite chondrite Earth. (United States)

    Fitoussi, Caroline; Bourdon, Bernard


    The compositions of Earth materials are strikingly similar to those of enstatite chondrite meteorites in many isotope systems. Although this suggests that Earth largely accreted from enstatite chondrites, definitive proof of this model has been lacking. By comparing the silicon (Si) isotope signatures of several extraterrestrial materials with terrestrial samples, we show that they cannot be explained by core-formation scenarios involving a bulk Earth of enstatite chondrite composition. Si isotope similarities between the bulk silicate Earth and the Moon preclude the existence of a hidden reservoir in the lower mantle, a necessary condition of the enstatite chondrite model, and require an equilibrium process after the Moon-forming impact. A three-end-member chondritic mixing model for Earth reconciles the Si isotope similarities between enstatite chondrites and Earth.

  18. 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


    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.


    Institute of Scientific and Technical Information of China (English)

    范瑞溪; 狄俊伟


    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.

  20. [Broad excitation band alkaline-earth silicate luminescent materials activated by rare earth and its applications]. (United States)

    Xia, Wei; Lei, Ming-Kai; Luo, Xi-Xian; Xiao, Zhi-Guo


    Series of novel broad excitation band phosphors M2 MgSis O7 : Eu, Dy(M = Ca, Sr) were prepared by a high temperature solid-state reaction method. The crystal structure of compound was characterized. And the effects of part substitution of alkaline-earth on crystal structure, photoluminescence spectra and luminescence properties were also investigated. It is found that the excitation band of silicate luminescent materials extend to visible region and they exhibit yellow, green and blue long after-glow luminescence after excited by ultraviolet or visible light. Ca MgSi O7 : Eu, Dy luminescent materials can be excited effectively under the 450-480 nm range and exhibit a strong emission at 536 nm, nicely combining with blue light emitted by InGaN chips to produce white light. This promises the silicate luminescent materials a potential yellow phosphor for white LED.

  1. Isotopic evidence of Cr partitioning into Earth's core. (United States)

    Moynier, Frederic; Yin, Qing-Zhu; Schauble, Edwin


    The distribution of chemical elements in primitive meteorites (chondrites), as building blocks of terrestrial planets, provides insight into the formation and early differentiation of Earth. The processes that resulted in the depletion of some elements [such as chromium (Cr)] in the bulk silicate Earth relative to chondrites, however, remain debated between leading candidate causes: volatility versus core partitioning. We show through high-precision measurements of Cr stable isotopes in a range of meteorites, which deviate by up to ~0.4 per mil from those of the bulk silicate Earth, that Cr depletion resulted from its partitioning into Earth's core, with a preferential enrichment in light isotopes. Ab initio calculations suggest that the isotopic signature was established at mid-mantle magma ocean depth as Earth accreted planetary embryos and progressively became more oxidized.

  2. Dynamics of dipolar defects in rare earth-doped alkaline-earth fluoride crystals (United States)

    Charnock, Forrest Taylor

    Alkaline-earth fluoride crystals such as SrF2 provide an excellent sample material for investigating the physics of point defects in crystal lattices. High quality crystals are easily grown, and they readily accept many dopant ions into the lattice, particularly rare earth ions. Rare earth dopant ions (typically trivalent) occupy substitutional sites in the lattice by replacing a Sr2+ ion. Due to the extra charge of the rare earth ion, charge compensation is often provided by an extra fluoride ion (F--) located in a nearby interstitial position. If located in the nearest-neighbor (nn) interstitial position, it forms a defect with C4n symmetry; if located in the next-nearest-neighbor (nnn) intersitial position, it forms a defect with C3n symmetry. Given sufficient thermal energy, this interstitial F ion can move to adjacent interstitial sites and hence reorient the defect. The rate w at which the ion moves from one interstitial site to another is well described by a simple Arrhenius expression: w=n0e-E/kT , where n0 is the attack frequency of the F-- and E is the activation energy. This motion can profoundly affect both the electronic polarizability of the material and the polarization of light emitted or absorbed by the rare earth ion. This thesis describes the normal mode motion of interstitial ions which may occupy either nn or nnn interstitial sites. Using electron paramagnetic resonance (EPR), I observed the relative populations of nn and nnn defects in SrF2 doped with Gd3+ as a function of temperature. These measurements show that dipolar reorientation of the nnn F occurs through the nn interstitial position. Not all interstitial F-- motion is thermally driven. Fluorescence depolarization measurements of SrF2:Pr3+ indicate that optically stimulating a Pr3+ may induce interstitial motion of a nn F--. Such motion was confirmed by showing that nn defects in SrF2:Pr3+ may be polarized at very low temperatures when the sample is illuminated with resonant light. I

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

    Indian Academy of Sciences (India)

    S Sreehari Sastry; B Rupa Venkateswara Rao


    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.

  4. Isotope composition and volume of Earth's early oceans. (United States)

    Pope, Emily C; Bird, Dennis K; Rosing, Minik T


    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 δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

  5. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands. (United States)

    Dietrich, Bernard


    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. 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.


    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



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


    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.

  8. Propane selective oxidation on alkaline earth exchanged zeolite Y: room temperature in situ IR study

    NARCIS (Netherlands)

    Xu, Jiang; Mojet, Barbara L.; Ommen, van Jan G.; Lefferts, Leon


    The effect of zeolite Y ion-exchanged with a series of alkaline-earth cations on selective propane oxidation at room temperature was studied with in situ infrared spectroscopy. Isopropylhydroperoxide was observed as a reaction intermediate and can be decomposed into acetone and water. Contrary to pr

  9. Doping of graphite by an alkaline-earth metal to reduce the work function

    NARCIS (Netherlands)

    Baturin, AS; Nikolski, KN; Knyazev, AI; Tchesov, RG; Sheshin, EP


    A technique for reducing the work function of a field-emission graphite cathode by doping it by an alkaline-earth metal (barium) is suggested. A model of formation of a barium monolayer on the cathode surface is proposed. Field-emission tests show that the operating voltage of the doped cathode is l

  10. 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.


    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

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

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt


    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...

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

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


    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.

  13. Carbonatite and alkaline intrusion-related rare earth element deposits–A deposit model (United States)

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


    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.

  14. Substrate and Transition State Binding in Alkaline Phosphatase Analyzed by Computation of Oxygen Isotope Effects. (United States)

    Roston, Daniel; Cui, Qiang


    Enzymes are powerful catalysts, and a thorough understanding of the sources of their catalytic power will facilitate many medical and industrial applications. Here we have studied the catalytic mechanism of alkaline phosphatase (AP), which is one of the most catalytically proficient enzymes known. We have used quantum mechanics calculations and hybrid quantum mechanics/molecular mechanics (QM/MM) simulations to model a variety of isotope effects relevant to the reaction of AP. We have calculated equilibrium isotope effects (EIEs), binding isotope effects (BIEs), and kinetic isotope effects (KIEs) for a range of phosphate mono- and diester substrates. The results agree well with experimental values, but the model for the reaction's transition state (TS) differs from the original interpretation of those experiments. Our model indicates that isotope effects on binding make important contributions to measured KIEs on V/K, which complicated interpretation of the measured values. Our results provide a detailed interpretation of the measured isotope effects and make predictions that can test the proposed model. The model indicates that the substrate is deformed in the ground state (GS) of the reaction and partially resembles the TS. The highly preorganized active site preferentially binds conformations that resemble the TS and not the GS, which induces the substrate to adapt to the enzyme, rather than the other way around-as with classic "induced fit" models. The preferential stabilization of the TS over the GS is what lowers the barrier to the chemical step.

  15. Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study (United States)

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


    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.

  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


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

    DEFF Research Database (Denmark)

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


    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...

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

    Indian Academy of Sciences (India)

    J K Baria; A R Jani


    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.

  19. Properties of the triplet metastable states of the alkaline-earth atoms

    CERN Document Server

    Mitroy, J


    The static and dynamic properties of the alkaline-earth atoms in their metastable state are computed in a configuration interaction approach with a semi-empirical model potential for the core. Among the properties determined are the scalar and tensor polarizabilities, the quadrupole moment, some of the oscillator strengths and the dispersion coefficients of the van der Waals interaction. A simple method for including the effect of the core on the dispersion parameters is described.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sastry, S. Sreehari, E-mail: [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)


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Qiang, E-mail: [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)


    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.

  2. Spectroscopic studies of copper doped alkaline earth lead zinc phosphate glasses (United States)

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


    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.

  3. Rubidium isotopes in primitive chondrites: Constraints on Earth's volatile element depletion and lead isotope evolution (United States)

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


    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

  4. 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.


    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

  5. Magnesium stable isotope composition of Earth's upper mantle (United States)

    Handler, Monica R.; Baker, Joel A.; Schiller, Martin; Bennett, Vickie C.; Yaxley, Gregory M.


    The mantle is Earth's largest reservoir of Mg containing > 99% of Earth's Mg inventory. However, no consensus exists on the stable Mg isotope composition of the Earth's mantle or how variable it is and, in particular, whether the mantle has the same stable Mg isotope composition as chondrite meteorites. We have determined the Mg isotope composition of olivine from 22 mantle peridotites from eastern Australia, west Antarctica, Jordan, Yemen and southwest Greenland by pseudo-high-resolution MC-ICP-MS on Mg purified to > 99%. The samples include fertile lherzolites, depleted harzburgites and dunites, cryptically metasomatised ('dry') peridotites and modally metasomatised apatite ± amphibole-bearing harzburgites and wehrlites. Olivine from these samples of early Archaean through to Permian lithospheric mantle have δ25Mg DSM-3 = - 0.22 to - 0.08‰. These data indicate the bulk upper mantle as represented by peridotite olivine is homogeneous within current analytical uncertainties (external reproducibility ≤ ± 0.07‰ [2 sd]). We find no systematic δ25Mg variations with location, lithospheric age, peridotite fertility, or degree or nature of mantle metasomatism. Although pyroxene may have slightly heavier δ25Mg than coexisting olivine, any fractionation between mantle pyroxene and olivine is also within current analytical uncertainties with a mean Δ25Mg pyr-ol = +0.06 ± 0.10‰ (2 sd; n = 5). Our average mantle olivine δ25Mg DSM-3 = - 0.14 ± 0.07‰ and δ26Mg DSM-3 = - 0.27 ± 0.14‰ (2 sd) are indistinguishable from the average of data previously reported for terrestrial basalts, confirming that basalts have stable Mg isotope compositions representative of the mantle. Olivine from five pallasite meteorites have δ25Mg DSM-3 = - 0.16 to - 0.11‰ that are identical to terrestrial olivine and indistinguishable from the average δ25Mg previously reported for chondrites. These data provide no evidence for measurable heterogeneity in the stable Mg isotope

  6. Nano porous alkaline earth metal silicates as free fatty acid adsorbents from Crude Palm Oil (CPO) (United States)

    Masmur, Indra; Sembiring, Seri Bima; Bangun, Nimpan; Kaban, Jamaran; Putri, Nabila Karina


    Free fatty acids(FFA) from Crude Palm Oil (CPO) have been adsorbed by alkaline earth metal silicate (M-silicate : M = Mg, Ca, Sr and Ba) adsorbents in ethanol using batch method. The adsorbents were prepared from the chloride salts of alkaline metals and Na2SiO3. The resulting white solid of the alkaline earth metal silicates were then heated at 800°C for 3 hours to enlarge their porosities. All adsorbents were characterized by SEM-EDX, XRD and BET. The EDX spectrum of SEM-EDX showed the appearance of all elements in the adsorbents, and the XRD spectrum of all adsorbents showed that they have crystobalite structure. The porosity of the adsorbents calculated by BET method showed that the porosities of the adsorbents range from 2.0884 - 2.0969 nm. All the adsorbents were used to adsorb the FFA from CPO containing 4.79%, 7.3%, 10.37% and 13.34% of FFA. The ratio of adsorbent to CPO to be used in adsorption of FFA from CPO were made 1:1, 1:2 and 1:3, with adsorption time of 1 hour. We found that the maximum adsorption of FFA from CPO was given by Ca-Silicate adsorbent which was between 69.86 - 94.78%, while the lowest adsorption was shown by Mg-silicate adsorbent which was 49.32 -74.53%.

  7. Effects of Rare Earth and Alkaline Earth on Spheroidizing of Eutectic Carbides in Low Tungsten White Cast Iron

    Institute of Scientific and Technical Information of China (English)

    Fu Hanguang; Zou Dening


    Tungsten Alloy White Cast Iron(TAWCI) has great brittleness and narrow application scope. The influences of Rare earth element(Ce) and alkaline earth elements ( K, Na) on the microstructures and performances of TAWCI were researched, and the idea estimating spheroidizing effect of carbides using Circular Degree (C. D) were put forward. The result shows that eutectics carbide tums into sphericity from network after modification, and carbide is refined and uniformly distributed and the C. D of eutectic carbide increases. The mechanism of carbide spheroidizing was analyzed. The impact toughness and wear resistance of TAWCI obviously improve with the rise of C. D of carbides.The service life of modified TAWCI roll is 35 % higher than that of high chromium cast iron roll, and its production cost is reduced by 25 %.

  8. Creation of trapped electrons and holes in alkaline-earth fluoride crystals doped by rare-earth ions (United States)

    Radzhabov, E.


    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.


    Institute of Scientific and Technical Information of China (English)

    郅妙婵; 戴长建; 李士本


    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.

  10. Health Effects of Alkaline Diet and Water, Reduction of Digestive-tract Bacterial Load, and Earthing. (United States)

    Mousa, Haider Abdul-Lateef


    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

  11. Nanocrystalline Powders of Alkaline-Earth Phosphates as Precursors for Bioceramics

    Directory of Open Access Journals (Sweden)

    Parhi Purnendu


    Full Text Available Bone is a nanocomposite made of calcium phosphates and collagen. Collagen has a typical fibrous structure, with diameter ranging from 100 nm to 2 µm. It is suggested that calcium hydroxyapatite, Ca10(PO46(OH2 in the size range 5-50 nm embedded in the collagen framework provides mechanical strength to bone. Among calcium phosphates, apatites are found to be the most suitable for bone regeneration due to its biocompatibility. A contemporary theme is to prepare nanocrystallites of alkaline-earth phosphates that can be employed as precursors for making novel bioceramics. In this paper, we present our attempts to prepare nano-sized particles of alkaline-earth hydroxyapatites, A10(PO46(OH2 where A= Ca, Sr and Ba through a metathetical route. Our work involved the use of same reactants treated under different reaction conditions. While hydrothermal route yielded well-crystalline nanorods, microwave resulted in agglomerated hydroxyapatites and reverse micellear route gave low crystalline apatites with less agglomeration.

  12. Long-range interacting many-body systems with alkaline-earth-metal atoms. (United States)

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


    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.

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

    CERN Document Server

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


    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...

  14. Temperature-induced collapse of alkaline Earth cation-polyacrylate anion complexes. (United States)

    Lages, Sebastian; Schweins, Ralf; Huber, Klaus


    Polyacrylate anions are used to inhibit CaCO3 precipitation and may be a promising additive to control formation of inorganic nanoparticles. The origin of this applicability lies in specific interactions between the alkaline earth cations and the carboxylate functions along the polyacrylate chains. In the absence of CO32- anions, these interactions eventually cause precipitation of polyelectrolytes. Extended investigation of dilute sodium polyacrylate solutions approaching this precipitation threshold revealed a dramatic shrinking of the PA coil dimensions once the threshold is reached (Eur. Phys. J. E 2001, 5, 117). Recent isothermal calorimetric titration experiments by Antonietti et al. (Macromolecules 2004, 37, 3444) indicated that the driving force of this precipitation is entropic in nature. In the present work, we investigated the impact of temperature on the structural changes of dissolved polyacrylate chains decorated with alkaline earth cations. To this end, large polyacrylate chains were brought close to the precipitation threshold by the addition of distinct amounts of Ca2+ or Sr2+ cations. The resulting structural intermediates were then subjected to temperature variations in the range of 15 degrees C polyacrylate coils were recorded by means of light and neutron scattering. As a major result, we could unambiguously demonstrate that the coils can reversibly be collapsed and extended by increasing and decreasing the temperature, respectively.

  15. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals. (United States)

    Gagné, Olivier Charles; Hawthorne, Frank Christopher


    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

  16. Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes? (United States)

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


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hempel, Wolfgang


    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.)

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

    CERN Document Server

    Chattopadhyay, S; Angom, D


    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.

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

    González, Miriam Ferrer; Ilyina, Tatiana


    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. Lifshitz and other transitions in alkaline-earth 122 pnictides under pressure (United States)

    Quader, Khandker; Widom, Michael


    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.

  1. 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


    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.

  2. Theoretical study of the alkaline-earth (LiBe)+ ion: structure, spectroscopy and dipole moments (United States)

    Ghanmi, C.; Farjallah, M.; Berriche, H.


    We study theoretically the structure and spectroscopic properties of the alkali alkaline-earth (LiBe)+ ion. The potential energy curves and their spectroscopic parameters, permanent and transition dipole moments are determined with a quantum chemistry approach. The (LiBe)+ ion is modelled as two valence electron system moving in the field of Be2+ and Li+ cores, which are described by pseudopotentials. In addition, effective core-polarization potentials are included to correct the energy. The molecular calculations are performed using a standard quantum chemistry approach based on the pseudopotential model, Gaussian basis sets, effective core polarization potentials, and full configuration interaction (CI) calculations. The precision of our spectroscopic parameters are discussed by comparison with currently available theoretical results. A rather good agreement is observed for the ground and first excited states. The permanent dipole moments reveal many abrupt changes, which are localized at particular distances corresponding to the positions of the avoided crossings.

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

    CERN Document Server

    van Tiggelen, B A


    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.

  4. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization. (United States)

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G


    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

  5. Alkaline-earth metal hydrides as novel host lattices for Eu(II) luminescence. (United States)

    Kunkel, Nathalie; Kohlmann, Holger; Sayede, Adlane; Springborg, Michael


    Luminescence of divalent europium has been investigated for the first time in metal hydrides. A complete solid-solution series was found for the pseudobinary system Eu(x)Sr(1-x)H(2) [a = 637.6(1) pm -12.1(3)x pm, b = 387.0(1)-6.5(2)x pm, c = 732.2(2)-10.1(4)x pm]. Europium-doped alkaline-earth hydrides Eu(x)M(1-x)H(2) (M = Ca, Sr, Ba) with a small europium concentration (x = 0.005) exhibit luminescence with maximum emission wavelengths of 764 nm (M = Ca), 728 nm (M = Sr), and 750 nm (M = Ba); i.e., the emission energy of divalent europium shows an extremely large red shift compared to the emission energies of fluorides or oxides. Theoretical calculations (LDA+U) confirm decreasing band gaps with increasing europium content of the solid solutions.

  6. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene (United States)

    Sahin, H.; Peeters, F. M.


    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.

  7. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate (United States)

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


    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.

  8. 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: [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)


    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.

  9. Thermal poling of alkaline earth boroaluminosilicate glasses with intrinsically high dielectric breakdown strength (United States)

    Smith, Nicholas J.; Lanagan, Michael T.; Pantano, Carlo G.


    Per the rectification model of thermal poling, it has been proposed that intrinsic breakdown strength plays a strong limiting role in the internal DC fields supported by the glass from the poling process. One might therefore hypothesize proportionately larger second-order nonlinearity (SON) in glasses with intrinsically high dielectric breakdown strength. We test these ideas by thermal poling of two different commercial alkali-free alkaline-earth boroaluminosilicate display glasses—one with barium only (AF45 from Schott), and the other with a mixture of alkaline-earth ions (OA-10 G from NEG). Not only are such compositions relevant from a commercial standpoint, they are also interesting in that they have been recently shown to exhibit remarkably high intrinsic dielectric breakdown strengths of 11-14 MV/cm. Quantitative Maker fringe and stack Maker-fringe measurements provide an accurate evaluation of the poling-induced SON susceptibilities, and indicate maximum χ(2) values of 0.44 and 0.26 pm/V in these glasses. These values are comparable to those reported for silica and other multicomponent glasses. Thus, the hypothesis that higher χ(2) would be observed in high intrinsic breakdown strength glasses was not validated. Based on our application of the rectification model, internal fields of the order 2-4 MV/cm were calculated, which are well below the measured intrinsic breakdown strengths at room temperature. The most plausible explanation for these observations is nonlinear electronic conduction effects taking place within the depletion region at the poling temperature, limiting internal fields to a fraction of the breakdown field.

  10. 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)


    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.``

  11. Optical and electronic properties of conductive ternary nitrides with rare- or alkaline-earth elements (United States)

    Kassavetis, S.; Hodroj, A.; Metaxa, C.; Logothetidis, S.; Pierson, J. F.; Patsalas, P.


    Conductive nitrides, such as TiN, are key engineering materials for electronics, photonics, and plasmonics; one of the essential issues for such applications is the ability of tuning the conduction electron density, the resistivity, and the electron scattering. While enhancing the conduction electron density and blueshifting the intraband absorption towards the UV were easily achieved previously, reducing the conduction electron density and redshifting the intraband absorption into the infrared are still an open issue. The latter is achieved in this work by alloying TiN by rare earth (RE = Sc, Y, La) or alkaline earth (AE = Mg, Ca) atoms in Ti substitutional positions. The produced TixRE1-xN and TixAE1-xN thin film samples were grown by a hybrid arc evaporation/sputtering process, and most of them are stable in the B1 cubic structure. Their optical properties were studied in an extensive spectral range by spectroscopic ellipsometry. The ellipsometric spectra were analyzed and quantified by the Drude-Lorentz model, which provided the conduction electron density, the electron mean free path, and the resistivity. The observed interband transitions are firmly assigned, and the optical and electrical properties of TixRE1-xN and TixAE1-xN are quantitatively correlated with their composition and crystal structure.

  12. 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.


    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

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

    KAUST Repository

    Zhang, J.-Y.


    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.

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

    Directory of Open Access Journals (Sweden)

    L. S. Shirokova


    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

  15. Characterization of alkali-metal and alkaline-earth nitrates by vibrational spectroscopy

    Directory of Open Access Journals (Sweden)

    Martínez, S.


    Full Text Available Infrared spectra of sodium and potassium alkaline-metal nitrates and magnesium and calcium alkali-earth nitrates in solid phase had been recorded in order to assign the fundamental bands. The influence of the dispersal médium (alkaline halide, employed in the solid sample preparation have been discussed. The quantitative measurements of the band in ten sities at 1387 cm-1 (present in the I.R. spectra of the four nitrates in KBr médium allowed us to determine the Lambert-Beer law slopes for each compound. These values are differents (bearing in mind experimental random errors, so we have could to affirm the nonexistence of solid solution between the nitrate and the alkaline halide médium. The L-B law obtained by us can be used for the Identification differentiation and quantitative analysis of these nitrates in solid phase, even if they are present in a very low concentration.

    Se ha realizado la asignación de los espectros infrarrojo (IR de los nitratos alcalinos, sódico y potásico, y de los alcalinotérreos, magnésico y cálcico, en estado sólido. Se ha visto la influencia del medio dispersante (haluro alcalino, utilizado en la preparación de la muestra sólida. El estudio cuantitativo de la absorbencia de la banda a 1.387 cm-1 (presente en los espectros IR de los cuatro nitratos en medio KBr permite determinar las pendientes de la Ley de Lambert-Beer Se comprueba que dichas pendientes son diferentes lo que conduce a poder afirmar que no se produce disolución sólida entre el KBr y el nitrato alcalino o alcalinotérreo. La determinación de la ley de Lambert-Beer permite la identificación y el análisis cualitativo y cuantitativo por espectroscopia IR de estos nitratos cuando están presentes en bajas concentraciones en muestras sólidas.

  16. Isotopes in global change science: from isotope analytics to Earth system research; Les isotopes pour l`etude du changement du systeme terre

    Energy Technology Data Exchange (ETDEWEB)

    Oeschger, H. [Bern Univ. (Switzerland). Physikalisches Inst


    The aim of this paper is to emphasize some of the studies of Jean Charles Fontes and his role in our scientific community. Isotopes represent a powerful tool for the understanding of the Earth`s past environment and defining the envelope of natural environmental variability within which we can assess anthropogenic impact on the Earth`s biosphere, geosphere and atmosphere. The reconstruction impacts of past climatic change on the Earth`s system are a basis to validate models of the possible impacts of future climate change. Oceanic sediments, polar ice caps, continental sedimentary sequences and groundwater are archives of past climate. Their quantitative study is developed within the IGBP (International Geosphere-Biosphere Program) - Pages project, which strongly emphasizes an optimum use of isotope tools. (author) 6 refs.

  17. The lead isotopic age of the Earth can be explained by core formation alone. (United States)

    Wood, Bernard J; Halliday, Alex N


    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.

  18. 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.;


    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...... such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact....... 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....

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

    Indian Academy of Sciences (India)



    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.

  20. 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: [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)


    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.

  1. Photo-bleaching effect in divalent samarium-doped alkaline-earth fluorohalides

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Weiping [Chinese Academy of Sciences, Changchun (China); Jang, Kiwan; Cho, Hyungab; Chung, Yonghwa; Park, Seongtae; Lee, Yongill [Changwon National University, Changwon (Korea, Republic of); Kim, Changdae [Mokpo National University, Mokpo (Korea, Republic of)


    When a CW laser was focused on a sample of divalent samarium-doped alkaline-earth fluorohalides (Mg{sub 0.5}Sr{sub 0.5}FCl{sub 0.5}Br{sub 0.5} : Sm{sup 2+} or BaFCl{sub 0.5}Br{sub 0.5} : Sm{sup 2+}), the fluorescence intensity of Sm{sup +2} ions decreased rapidly. Under irradiation from a 488-nm laser with a power density of 10 W/cm{sup 2}, the intensity of the {sup 5}D{sub 0} -> {sup 7}F{sub 0} (Sm{sup 2+}) emission decreased as much as 96 % of its initial intensity in 30 minutes (for an X-ray-reduced sample). The so-called photo-bleaching effect can be influenced by the processes used for sample synthesis, such as the reduction method, the grinding process or X-ray irradiation. The decreasing curves obtained in the photo-bleaching experiments were fitted, a biexponential decreasing mode was found, which included a fast decrease (time constant {approx}tens of seconds) and a slow decrease (time constant {approx}hundreds of seconds). There was no evidence to support the divalent samarium ions being photo-ionized into trivalent samarium ions in the photobleaching process. The most probable mechanism for the photo-bleaching effect involves structural defects and color centers in the samples.

  2. Alkaline earth silicate wools - A new generation of high temperature insulation. (United States)

    Brown, Robert C; Harrison, Paul T C


    Intensive study of the natural asbestiform minerals that cause human diseases, and the consequent understanding of their hazardous characteristics, has enabled the development of manufactured fibres whose physical and/or chemical properties, in particular as they relate to biopersistence, have been adjusted to minimize possible harm to health. A strong driver for the developmentof new high temperature insulation materials wasthe perception of the toxicity of refractory ceramic fibres (RCF)and their classification in the EU as a category 2 carcinogen under Directive 67/548/EEC. Such classification carries with it the requirement for substitution by less hazardous materials. This paper focuses on the development of alkaline earth silicate (AES) wools as a new class of high temperature insulation with the capability of such substitution in a number of applications. These wools have only a low potential to cause harm because they do not persist in lung tissue once deposited, and have produced minimal effects in experimental test systems. AES wools are increasingly being used in a wide range of high temperature applications.

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

    Indian Academy of Sciences (India)

    Angelos G Kalampounias


    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.

  4. Collective non-equilibrium spin exchange in cold alkaline-earth atomic clocks (United States)

    Acevedo, Oscar Leonardo; Rey, Ana Maria


    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.

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

    DEFF Research Database (Denmark)

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


    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....

  6. Driving force for the hydration of the swelling clays: case of montmorillonites saturated with alkaline-earth cations. (United States)

    Salles, Fabrice; Douillard, Jean-Marc; Bildstein, Olivier; Gaudin, Cedric; Prelot, Benedicte; Zajac, Jerzy; Van Damme, Henri


    Important structural modifications occur in swelling clays upon water adsorption. The multi-scale evolution of the swelling clay structure is usually evidenced by various experimental techniques. However, the driving force behind such phenomena is still not thoroughly understood. It appears strongly dependent on the nature of the interlayer cation. In the case of montmorillonites saturated with alkaline cations, it was inferred that the compensating cation or the layer surface could control the hydration process and thus the opening of the interlayer space, depending on the nature of the interlayer cation. In the present study, emphasis is put on the impact of divalent alkaline-earth cations compensating the layer charge in montmorillonites. Since no experimental technique offers the possibility of directly determining the hydration contributions related to interlayer cations and layer surfaces, an approach based on the combination of electrostatic calculations and immersion data is developed here, as already validated in the case of montmorillonites saturated by alkaline cations. This methodology allows to estimate the hydration energy for divalent interlayer cations and therefore to shed a new light on the driving force for hydration process occurring in montmorillonites saturated with alkaline-earth cations. Firstly, the surface energy values obtained from the electrostatic calculations based on the Electronegativity Equalization Method vary from 450 mJ m(-2) for Mg-montmorillonite to 1100 mJ m(-2) for Ba-montmorillonite. Secondly, considering both the hydration energy for cations and layer surfaces, the driving force for the hydration of alkaline-earth saturated montmorillonites can be attributed to the interlayer cation in the case of Mg-, Ca-, Sr-montmorillonites and to the interlayer surface in the case of Ba-montmorillonites. These results explain the differences in behaviour upon water adsorption as a function of the nature of the interlayer cation

  7. The contents of alkali and alkaline earth metals in soils of the southern Cis-Ural region (United States)

    Asylbaev, I. G.; Khabirov, I. K.


    The contents and distribution patterns of alkali and alkaline earth metals in soils and rocks of the southern Cis-Ural region were studied. A database on the contents of these metals was developed, the soils were classified with respect to their provision with these metals, and corresponding schematic maps showing their distribution in soils of the region were compiled. It was found that the contents of these metals decrease from east to west (from the Yuryuzan-Aisk Piedmont Plain to the Ufa Plateau and to the Belebeevsk Upland), and their distribution patterns change. Among alkali metals, the highest accumulation in the soils is typical of potassium, sodium, and cesium; among alkaline earth metals, of strontium and barium.

  8. 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


    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。

  9. The Effect of Ormosil Matrix Composition and Alkaline Earth Metal Doping on the Photochromic Response of Ormosil-Phosphotungstate Films


    Ferreira Neto,Elias P.; Simões,Mateus B.; Noveletto,Julia C.; Yabarrena,Jean M. S. C.; Ullah,Sajjad; Ubirajara P. Rodrigues Filho


    In this study, polyoxometallate based hybrid photochromic materials were prepared by incorporating phosphotungstate anion, PW12O403−, (PW) in hybrid tetraethyl orthosilicate and (3-glycidyloxypropyl)trimethoxysilane TEOS-GPTMS derived organomodified silicates (Ormosil) matrices by sol-gel method and the resulting materials were used to prepare multilayer films by dip-coating method. The effect of alkaline earth metal cations doping and matrix composition (%GPTMS) on the photochromic res...

  10. Spin-Orbit-Coupled Correlated Metal Phase in Kondo Lattices: An Implementation with Alkaline-Earth Atoms (United States)

    Isaev, L.; Schachenmayer, J.; Rey, A. M.


    We show that an interplay between quantum effects, strong on-site ferromagnetic exchange interaction, and antiferromagnetic correlations in Kondo lattices can give rise to an exotic spin-orbit coupled metallic state in regimes where classical treatments predict a trivial insulating behavior. This phenomenon can be simulated with ultracold alkaline-earth fermionic atoms subject to a laser-induced magnetic field by observing dynamics of spin-charge excitations in quench experiments.

  11. Spin-Orbit-Coupled Correlated Metal Phase in Kondo Lattices: An Implementation with Alkaline-Earth Atoms. (United States)

    Isaev, L; Schachenmayer, J; Rey, A M


    We show that an interplay between quantum effects, strong on-site ferromagnetic exchange interaction, and antiferromagnetic correlations in Kondo lattices can give rise to an exotic spin-orbit coupled metallic state in regimes where classical treatments predict a trivial insulating behavior. This phenomenon can be simulated with ultracold alkaline-earth fermionic atoms subject to a laser-induced magnetic field by observing dynamics of spin-charge excitations in quench experiments.

  12. New neutron-deficient isotopes of barium and rare-earth elements

    CERN Document Server

    Bogdanov, D D; Karnaukhov, V A; Petrov, L A; Plochocki, A; Subbotin, V G; Voboril, J


    The authors present an investigation of the short-lived neutron- deficient isotopes of barium and rare-earth elements. By using the BEMS-2 isotope separator on a heavy ion beam, 19 new isotopes were produced with mass numbers ranging from 117 to 138. Five of these (/sup 117/Ba, /sup 129,131/Nd and /sup 133,135/Sm) turned out to be delayed proton emitters. The beta -decay probabilities for the new isotopes have been analyzed in terms of the beta -strength function. An analysis of the proton spectrum shape has been performed using the statistical model for delayed proton emission.

  13. Ocean-Based Alkalinity Enhancement: Mitigation Potential, Side Effects and the Fate of Added Alkalinity Assessed in an Earth System Model (United States)

    Gonzalez, M. F.; Ilyina, T.


    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

  14. Microstructure and creep behavior of magnesium-aluminum alloys containing alkaline and rare earth additions (United States)

    Saddock, Nicholas David

    In the past few decades governmental regulation and consumer demands have lead the automotive companies towards vehicle lightweighting. Powertrain components offer significant potential for vehicle weight reductions. Recently, magnesium alloys have shown promise for use in powertrain applications where creep has been a limiting factor. These systems are Mg-Al based, with alkaline earth or rare earth additions. The solidification, microstructure, and creep behavior of a series of Mg-4 Al- 4 X:(Ca, Ce, La, and Sr) alloys and a commercially developed AXJ530 (Mg--5 Al--3 Ca--0.15 Sr) alloy (by wt%) have been investigated. The order of decreasing freezing range of the five alloys was: AX44, AXJ530, AJ44, ALa44 and ACe44. All alloys exhibited a solid solution primary alpha-Mg phase surrounded by an interdendritic region of Mg and intermetallic(s). The primary phase was composed of grains approximately an order of magnitude larger than the cellular structure. All alloys were permanent mold cast directly to creep specimens and AXJ530 specimens were provided in die-cast form. The tensile creep behavior was investigated at 175 °C for stresses ranging from 40 to 100 MPa. The order of decreasing creep resistance was: die-cast AXJ530 and permanent mold cast AXJ530, AX44, AJ44, ALa44 and ACe44. Grain size, solute concentration, and matrix precipitates were the most significant microstructural features that influenced the creep resistance. Decreases in grain size or increases in solute concentration, both Al and the ternary addition, lowered the minimum creep rate. In the Mg-Al-Ca alloys, finely distributed Al2Ca precipitates in the matrix also improved the creep resistance by a factor of ten over the same alloy with coarse precipitates. The morphology of the eutectic region was distinct between alloys but did not contribute to difference in creep behavior. Creep strain distribution for the Mg-Al-Ca alloys developed heterogeneously on the scale of the alpha-Mg grains. As

  15. Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents. (United States)

    Fromm, Katharina M


    This overview on one of the subjects treated in our group deals with the synthesis and study of low-dimensional polymer and molecular solid state structures formed with alkaline earth metal ions in non-aqueous solvents. We have chosen several synthetic approaches in order to obtain such compounds. The first concept deals with the "cutting out" of structural fragments from a solid state structure of a binary compound, which will be explained with reference to BaI2. Depending on the size and concentration of oxygen donor ligands, used as chemical scissors on BaI2, three-, two-, one- and zero-dimensional derived adducts of BaI2 are obtained, comparable to a structural genealogy tree for BaI2. A second part deals with the supramolecular approach for the synthesis of low dimensional polymeric compounds based on alkaline earth metal iodides, obtained by the combination of metal ion coordination with hydrogen bonding between the cationic complexes and their anions. Certain circumstances allow rules to be established for the prediction of the dimensionality of a given compound, contributing to the fundamental problem of structure prediction in crystal engineering. A third section describes a synthetic approach for generating pure alkaline earth metal cage compounds as well as alkali and alkaline earth mixed metal clusters. A first step deals with different molecular solvated alkaline earth metal iodides which are investigated as a function of the ligand size in non-aqueous solvents. These are then reacted with some alkali metal compound in order to partially or totally eliminate alkali iodide and to form the targeted clusters. These unique structures of ligand stabilized metal halide, hydroxide and/or alkoxide and aryloxide aggregates are of interest as potential precursors for oxide materials and as catalysts. Approaches to two synthetic methods of the latter, sol-gel and (MO)CVD (metal-organic chemical vapour deposition), are investigated with some of our compounds. (D

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

  17. Lead isotope evidence for a young formation age of the Earth-Moon system (United States)

    Connelly, J. N.; Bizzarro, M.


    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.

  18. Eocene seasonality and seawater alkaline earth reconstruction using shallow-dwelling large benthic foraminifera (United States)

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


    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

  19. Creating an Isotopically Similar Earth-Moon System with Correct Angular Momentum from a Giant Impact

    CERN Document Server

    Wyatt, Bryant M; Sumpter, William J; Turner, Ty R; Smith, Edward L; Fain, Baylor G; Hutyra, Taylor J; Cook, Scott A; Hibbs, Michael F; Goderya, Shaukat N


    The giant impact hypothesis is the dominant theory explaining the formation of our Moon. However, its inability to produce an isotopically similar Earth-Moon system with correct angular momentum has cast a shadow on its validity. Computer-generated impacts have been successful in producing virtual systems that possess many of the physical properties we observe. Yet, addressing the isotopic similarities between the Earth and Moon coupled with correct angular momentum has proven to be challenging. Equilibration and evection resonance have been put forth as a means of reconciling the models. However, both were rejected in a meeting at The Royal Society in London. The main concern was that models were multi-staged and too complex. Here, we present initial impact conditions that produce an Earth-Moon system whose angular momentum and isotopic properties are correct. The model is straightforward and the results are a natural consequence of the impact.

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

    Directory of Open Access Journals (Sweden)

    C. E. Brennan


    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.

  1. 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


    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.

  2. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth (United States)

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


    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.).

  3. Abnormal composition of carbon isotopes in underground alkaline waters of Kuzbass (United States)

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


    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.

  4. 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 (United States)

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


    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

  5. Isotope hydrology: applied discipline in earth sciences; Hydrologie isotope: une discipline des sciences de la terre

    Energy Technology Data Exchange (ETDEWEB)

    Froehlich, K.; Rozanski, K.; Araguas Araguas, L. [Isotope Hydrology Section, International Atomic Agency, Vienna (Austria)


    The discipline `isotope hydrology` is being reviewed from the perspective of the Isotope Hydrology Section of the International Atomic Energy Agency in Vienna. The Section was created in the late fifties and is activities involved int the scientific progress of the discipline. The role of the IAEA in the development of isotope hydrology has always been of a dual nature: on one hand, the Section has been and still is heavily engaged in supporting and coordinating further development of isotope methodologies, on the other hand, it serves as an interface between the methodological development in research institutes and the applied work using proven techniques in field projects on water resources assessment and management. The paper provides a brief overview of applications of isotope-based methodologies in hydrology, with emphasis on new trends and challenges related to man`s growing impact on the water cycle. This contribution is a tribute to the memory of the former Head of the Isotope Hydrology Section, Jean-Charles Fontes, to whom we owe so much. (authors) 30 refs.

  6. Isotopic evidence for internal oxidation of the Earth's mantle during accretion (United States)

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


    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.

  7. Three interesting coordination compounds based on metalloligand and alkaline-earth ions: Syntheses, structures, thermal behaviors and magnetic property (United States)

    Zhou, Qiang; Qian, Jun; Zhang, Chi


    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.

  8. Binding and selectivity of phenazino-18-crown-6-ether with alkali, alkaline earth and toxic metal species: A DFT study (United States)

    Islam, Nasarul; Chimni, Swapandeep Singh


    The interactions of phenazino-crown ether ligands with alkali, alkaline earth and selected toxic species were investigated using density functional theory modelling by employing B3PW91/6-311G ++ (d, p) level of theory. The complex stability was analysed in terms of binding energies, perturbation energies, position of highest molecular orbital and energy gap values. In general, the complexes formed by P18C6-1a ligand with metal cations were found to be more stable than those with P18C6-1b. Among alkali and alkaline earth metals complexes having highest stability was observed for the complex formed by P18C6-1a with Be2+. Computational calculations of P18C6 ligand with toxic metal ions reveals that the P18C6-Cr6+ metal complexes acquire envelop like geometry, leading to higher binding energy values. Comparing the binding energies of neutral and monocations of Ag and Hg, the former had higher value both in neutral as well as monocation state. Thus, the stability of metal complexes is determined not only by the ligand but also by the type of metal ion. In solvent systems the stability constants of metal complexes were found increasing with decreasing permittivity of the solvent. This reflects the inherited polar character of the protic solvents stabilises the cation, resulting in decrease of effective interaction of ligand with the metal ion.

  9. 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


    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.

  10. Modification of TiO{sub 2} electrode with a series of alkaline-earth carbonates. Performance improvement of quasi-solid-state dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhan, Chun; Wang, Liduo; Wu, Xueming; Qiu, Yong [Ministry of Education, Beijing (China). Key Lab of Organic Optoelectronics and Molecular Engineering; Tsinghua Univ., Beijing (China). Dept. of Chemistry


    In this paper, alkaline-earth carbonates (CaCO{sub 3}, SrCO{sub 3} and BaCO{sub 3}) modified TiO{sub 2} electrodes are synthesized by dipping TiO{sub 2} electrode into alkaline-earth hydroxide or alkaline-earth acetate aqueous solutions. When applied to quasi-solid-state DSSC, hydroxide-treated TiO{sub 2} electrodes have increased open-circuit photovoltages (Voc). Among the three alkaline-earth hydroxides, Ba(OH){sub 2} treatment improved the DSSC performance best. The Voc improves from 0.66 V to 0.71 V and the overall conversion efficiency ({eta}) improves by 15% under100 mW/cm{sup 2}. As to acetates, not only the Voc is increased (from 0.68V to 0.74V), but also short-circuit photocurrent(Isc) is improved by Sr(OAc){sub 2} Ba(OAc){sub 2} The overall conversion efficiency improves by 22%. Dark current measurement indicate that in the presence of alkaline-earth carbonates, the TiO2 conduction band shifts to the negative direction, leading to the increase in Voc.

  11. Alkaline magmatism of the Vitim province, West Transbaikalia, Russia: Age, mineralogical, geochemical and isotope (О, C, D, Sr and Nd) data (United States)

    Doroshkevich, Anna G.; Ripp, German S.; Izbrodin, Ivan A.; Savatenkov, Valery M.


    In this paper, we study the geochronology, mineral chemistry, and whole-rock elemental, stable (O, C, D) and Sr-Nd isotopic data for alkaline ultrabasic-basic massifs of the Vitim alkaline province (Sayzhenski complex) in the Central Asian Orogenic Belt, near the boundary with the Siberian craton, to evaluate their petrogenesis and geodynamic significance. U-Pb zircon dating results in Early Paleozoic (520-486 Ma) and Late Paleozoic (306-294 Ma) stages of alkaline rock formation. The mineralogy and geochemistry exhibit a wide range of SiO2 (38-73 wt.%), enrichment in Sr, Ba, LREE and Ta and, most significantly, in Na and Al. The rocks crystallized from a parental CO2- and H2O-rich silica-undersaturated melt. Isotopically, the rocks are highly variable, with (87Sr/86Sr)i - 0.705595-0.707729 and (143Nd/144Nd)i - 0.512237-0.512643. The geochemical and isotope data suggest that the rocks were derived from a source composed of three distinct components: PREMA, EM II and marine carbonate. Additionally, stable (O, C, D) isotope data display the shifting influence of assimilated organic sediments in the source of melts and a partial secondary isotope exchange between the late-magmatic fluids and minerals.

  12. Difference of coordination between alkali- and alkaline-earth-metal ions to a symmetrical α,α',δ,δ'-tetramethylcucurbit[6]uril. (United States)

    Chen, Wen-Jian; Yu, Da-Hai; Xiao, Xin; Zhang, Yun-Qian; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu; Wei, Gang


    To explore differences in coordination between alkali- and alkaline-earth-metal ions and cucurbit[n]urils, a water-soluble α,α',δ,δ'-tetramethylcucurbit[6]uril (TMeQ[6]) was used to synthesize a series of complexes and their supramolecular assemblies, based on the coordination of TMeQ[6] with alkali- and alkaline-earth-metal ions. The complexes and corresponding supramolecular assemblies were structurally characterized by single-crystal X-ray diffraction. Unlike cucurbituril (Q[6]), which formed the metal-Q[6] polymers based on the direct coordination of carbonyl oxygen atoms to the alkali-metal ions, TMeQ[6] formed metal-TMeQ[6] polymers based on the direct coordination of carbonyl oxygen atoms with the alkaline-earth-metal ions rather than the alkali-metal ions.

  13. 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


    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...

  14. Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth's upper mantle (United States)

    Wang, Ze-Zhou; Liu, Sheng-Ao; Liu, Jingao; Huang, Jian; Xiao, Yan; Chu, Zhu-Yin; Zhao, Xin-Miao; Tang, Limei


    The zinc (Zn) stable isotope system has great potential for tracing planetary formation and differentiation processes due to its chalcophile, lithophile and moderately volatile character. As an initial approach, the terrestrial mantle, and by inference, the bulk silicate Earth (BSE), have previously been suggested to have an average δ66Zn value of ∼+0.28‰ (relative to JMC 3-0749L) primarily based on oceanic basalts. Nevertheless, data for mantle peridotites are relatively scarce and it remains unclear whether Zn isotopes are fractionated during mantle melting. To address this issue, we report high-precision (±0.04‰; 2SD) Zn isotope data for well-characterized peridotites (n = 47) from cratonic and orogenic settings, as well as their mineral separates. Basalts including mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) were also measured to avoid inter-laboratory bias. The MORB analyzed have homogeneous δ66Zn values of +0.28 ± 0.03‰ (here and throughout the text, errors are given as 2SD), similar to those of OIB obtained in this study and in the literature (+0.31 ± 0.09‰). Excluding the metasomatized peridotites that exhibit a wide δ66Zn range of -0.44‰ to +0.42‰, the non-metasomatized peridotites have relatively uniform δ66Zn value of +0.18 ± 0.06‰, which is lighter than both MORB and OIB. This difference suggests a small but detectable Zn isotope fractionation (∼0.1‰) during mantle partial melting. The magnitude of inter-mineral fractionation between olivine and pyroxene is, on average, close to zero, but spinels are always isotopically heavier than coexisting olivines (Δ66ZnSpl-Ol = +0.12 ± 0.07‰) due to the stiffer Zn-O bonds in spinel than silicate minerals (Ol, Opx and Cpx). Zinc concentrations in spinels are 11-88 times higher than those in silicate minerals, and our modelling suggests that spinel consumption during mantle melting plays a key role in generating high Zn concentrations and heavy Zn isotopic

  15. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts (United States)

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


    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.

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

    Soldán, Pavel; Zuchowski, Piotr S; Hutson, Jeremy M


    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. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis (United States)

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


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

  18. 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


    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.

  19. High-T sub c thin films on low microwave loss alkaline-rare-earth-aluminate crystals

    Energy Technology Data Exchange (ETDEWEB)

    Sobolewski, R.; Gierlowski, P.; Kula, W.; Zarembinski, S.; Lewandowski, S.J.; Berkowski, M.; Pajaczkowska, A. (Instytut Fizyki, Polska Akatlemia Nauk, Al. Lotnikow 32/46, PL-02668 Warszawa (PL)); Gorshunov, B.P.; Lyudmirsky, D.B.; Sirotinsky, O.I. (Institute of General Physics, USSR Academy of Sciences, 38 Vavilova Street, SU-117924 Moscow (SU))


    This paper reports on the alkaline-rare-earth aluminates (K{sub 2}NiF{sub 4}-type perovskites) which are an excellent choice as the substrate material for the growth of high-T{sub c} thin films suitable for microwave and far-infrared applications. The CaNdAlO{sub 4}, and SrLaAlO{sub 4} single crystals have been grown by Czochralski pulling and fabricated into the form of (001) oriented wafers. The Y-Ba-Cu-O and Bi-Sr-Ca-Cu-O films deposited on these substrates by a single-target magnetron sputtering exhibited very good superconducting and structural properties.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ceccantini, G. [Instituto de Biociencias, Sao Paulo, (Brazil). Dept. de Botanica; Figueiredo, A.M.G. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil). Div. de Radioquimica; Sondag, F.; Soubies, F. [ORSTOM, 93 - Bondy (France); Soubies, F. [Universite Paul Sabatier, 31 - Toulouse (France)


    The contents of rare earth elements (REE) and titanium in various plant species, in groundwaters and in soils from the alkaline-ultramafic complex of Salitre, have been determined. Due to the the particular mineralogy of the bedrock, REE and Ti exhibit high concentrations in the soils. Despite this, plants generally present REE concentrations within the ranges usually found in plants, and the transfer factor from soil to plant is at least ten times below the range reported in the literature, confirming that the concentrations of REE in the plants are widely independent of the soil content. All species present normalized patterns similar to those of the soils, characterized by an enrichment in light REE. Several plants show Ti concentrations about three times higher than the reference values. It is suggested that in the studied ecosystem, the plant metabolism affect the REE distribution in the groundwaters, leading to an enrichment of the superficial waters in heavy REE

  1. 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


    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.

  2. Physical and optical absorption studies of Fe3+ - ions doped lithium borate glasses containing certain alkaline earths (United States)

    Bhogi, Ashok; Kumar, R. Vijaya; Kistaiah, P.


    Iron ion doped lithium borate glasses with the composition 15RO-25Li2O-59B2O3-1Fe2O3 (where R= Ca, Sr and Ba) have been prepared by the conventional melt quenching technique and characterized to investigate the physical and optical properties using XRD, density, molar volume and UV-Visible spectroscopy. The optical absorption spectra exhibit a band at around 460 nm which is assigned to 6A1g(S) → 4Eg (G) of Fe3+ ions with distorted octahedral symmetry. From ultraviolet absorption edges, the optical band gap and Urbach energies have been evaluated. The effect of alkaline earths on these properties is discussed.

  3. Static and Dynamic Structure Factors with Account of the Ion Structure for High-temperature Alkali and Alkaline Earth Plasmas

    CERN Document Server

    Sadykova, S P; Tkachenko, I M


    The $e-e$, $e-i$, $i-i$ and charge-charge static structure factors are calculated for alkali and Be$^{2+}$ plasmas using the method described by Gregori et al. in \\cite{bibGreg2006}. The dynamic structure factors for alkali plasmas are calculated using the method of moments \\cite{bibAdam83}, \\cite{bibAdam93}. In both methods the screened Hellmann-Gurskii-Krasko potential, obtained on the basis of Bogolyubov's method, has been used taking into account not only the quantum-mechanical effects but also the ion structure \\cite{bib73}. PACS: 52.27.Aj (Alkali and alkaline earth plasmas, Static and dynamic structure factors), 52.25.Kn (Thermodynamics of plasmas), 52.38.Ph (X-ray scattering)

  4. Creating an Isotopically Similar Earth and Moon from a Giant Impact with Correct Angular Momentum (United States)

    Sumpter, William


    The giant-impact hypothesis is the dominant theory as to how the Earth-Moon system was formed, but angular momentum concerns have cast a shadow on its validity. Computer generated impacts have been successful in producing virtual Earth-Moon systems that possess many of the properties of the observed system, but when tasked with addressing the isotopic similarities between the Earth and Moon they result in systems with excessive angular momentum. Evection resonance between the Moon and the Sun has been put forth as a means of removing the excess angular momentum, but this reasoning was rejected by The Royal Society at a special session called to discuss the origin of the Moon. We show here how to use impactor spins to create an impact that preserves all the favorable aspects of previous simulations and produces an Earth-Moon system with the correct angular momentum. Evection resonance is not needed.

  5. Petrographic, geochemical and isotopic evidence of crustal assimilation processes in the Ponte Nova alkaline mafic-ultramafic massif, SE Brazil (United States)

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


    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

  6. Effects of Alkali and Alkaline Earth Metals on N-Containing Species Release during Rice Straw Pyrolysis

    Directory of Open Access Journals (Sweden)

    Pan Gao


    Full Text Available To study the effects of inherent and external alkali and alkaline earth metallic species (AAEMs, i.e., K, Ca and Mg on the behavior of N-containing species release during rice straw (RS pyrolysis, different pretreatments were applied in numerous experiments. Results indicate that ammonia (NH3 and hydrogen cyanide (HCN are the major N-containing species and that the yields of isocyanic acid (HNCO and nitric oxide (NO are relatively low. The removal of inhert AAEMs shifts N-containing species release to a high-temperature zone according to volatile release behavior because of the increase in activation energy. The formation selectivity of NH3, HNCO, and NO increases by demineralized pretreatment, whereas HCN selectivity decreases. The formation of HNCO is mainly affected by alkaline earth metal. N-containing species release occurs in low temperatures with the addition of external AAEMs. The activation energy of samples impregnated with CaCl2 and MgCl2 sharply decreases compared to the original RS. The total yields of N-containing species are reduced significantly in the presence of KCl, CaCl2, and MgCl2 as additives. The inhibition ability of AAEMs follows the sequence MgCl2 > CaCl2 > KCl. The inhibition effect of MgCl2 can be improved by solution immersion compared with solid powder mixing. The clean biomass pyrolysis and gasification technology with low N-containing species content may be developed according to the results.

  7. 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: [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)


    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.

  8. 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: [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)


    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.

  9. Stable isotope labeling confirms mixotrophic nature of streamer biofilm communities at alkaline hot springs. (United States)

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


    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

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

    Directory of Open Access Journals (Sweden)

    Florence eSchubotz


    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

  11. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth (United States)

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


    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.

  12. Isotopic constraints on the age and early differentiation of the Earth. (United States)

    McCulloch, M T


    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

  13. Carbon-bearing iron phases and the carbon isotope composition of the deep Earth. (United States)

    Horita, Juske; Polyakov, Veniamin B


    The carbon budget and dynamics of the Earth's interior, including the core, are currently very poorly understood. Diamond-bearing, mantle-derived rocks show a very well defined peak at δ(13)C ≈ -5 ± 3‰ with a very broad distribution to lower values (∼-40‰). The processes that have produced the wide δ(13)C distributions to the observed low δ(13)C values in the deep Earth have been extensively debated, but few viable models have been proposed. Here, we present a model for understanding carbon isotope distributions within the deep Earth, involving Fe-C phases (Fe carbides and C dissolved in Fe-Ni metal). Our theoretical calculations show that Fe and Si carbides can be significantly depleted in (13)C relative to other C-bearing materials even at mantle temperatures. Thus, the redox freezing and melting cycles of lithosphere via subduction upwelling in the deep Earth that involve the Fe-C phases can readily produce diamond with the observed low δ(13)C values. The sharp contrast in the δ(13)C distributions of peridotitic and eclogitic diamonds may reflect differences in their carbon cycles, controlled by the evolution of geodynamical processes around 2.5-3 Ga. Our model also predicts that the core contains C with low δ(13)C values and that an average δ(13)C value of the bulk Earth could be much lower than ∼-5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted δ(13)C values of the deep Earth have implications, not only for its accretion-differentiation history but also for carbon isotope biosignatures for early life on the Earth.

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


    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.

  15. 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


    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.

  16. Catalysis by alkali and alkaline-earth metal ions in nucleophilic attack of methoxide ion on crown ethers bearing an intra-annular acetoxy group

    NARCIS (Netherlands)

    Cacciapaglia, Roberta; Lucente, Silvia; Mandolini, Luigi; Doorn, van Arie R.; Reinhoudt, David N.; Verboom, Willem


    Rates of reaction of methoxide ion with crown ethers bearing an intra-annular acetoxy group are markedly enhanced by alkali and alkaline-earth metal bromides as a result of much stronger interactions of the metal ions with transition states than with reactants. Rates of reactions of methoxide ion w

  17. Chromium isotopes in siliciclastic sediments and sedimentary rocks as a proxy for Earth surface redox (United States)

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


    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

  18. Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol (United States)

    Shebl, Magdy; Khalil, Saied M. E.; Taha, A.; Mahdi, M. A. N.


    A new series of binuclear and mixed-ligand complexes with the general formula: [M 2(LO)yClz]; where M = Mg(II), Ca(II), Sr(II) and Ba(II); H2L = 4,6-diacetylresorcinol, the secondary ligand L' = acetylacetone (acac), 8-hydroxyquinoline (8-HQ) or 2,2'-bipyridyl (Bipy), n = 0-2, m = 1, 2, x = 0, 1, 2, 4, y = 0, 2, 4, 5 and z = 0-2; have been synthesized. They have been characterized by the analytical and spectral methods (IR, 1H NMR and mass) as well as TGA and molar conductivity measurements. The spectroscopic and conductance data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the basicity of the secondary ligand, through the two phenolic and two carbonyl groups. Binuclear octahedral geometry has been assigned to all of the prepared complexes in various molar ratios 2:2; 2:2:2; 1:2:1 and 1:2:4 (L:M:L'). Molecular orbital calculations were performed for the ligands and their complexes using Hyperchem 7.52 program on the bases of PM3 level and the results were correlated with the experimental data. The ligand and some of its alkaline metal(II) complexes showed antibacterial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

  19. Constraints on Earth degassing history from the argon isotope composition of Devonian atmosphere (United States)

    Stuart, F. M.; Mark, D.


    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)

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

    El-Nafaty, Jalo Muhammad


    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.

  1. Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations. (United States)

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


    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.

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

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


    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.

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

    CERN Multimedia


    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.

  4. Os isotopes in SNC meteorites and their implications to the early evolution of Mars and Earth (United States)

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


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

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

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


    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)).

  6. From Gene Expression to the Earth System: Isotopic Constraints on Nitrogen Cycling Across Scales (United States)

    Houlton, B. Z.


    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., ancient terrestrial plant compounds (i.e., chlorins) buried in the soil. This research aims to address the response of the nitrogen cycle to glacial-interglacial transitions over millennia, which is beyond the window of experimental testing. Together, this research highlights the utility of nitrogen isotope composition in addressing the myriad scales of this element's interaction with Earth's environment, and supports the working hypothesis that bacterial denitrification is the major fractionating pathway of nitrogen loss from the terrestrial biosphere, much like the global ocean.

  7. Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers. (United States)

    Campopiano, Antonella; Cannizzaro, Annapaola; Angelosanto, Federica; Astolfi, Maria Luisa; Ramires, Deborah; Olori, Angelo; Canepari, Silvia; Iavicoli, Sergio


    The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis.

  8. X-ray Diffraction Studies of the Structure and Thermochemistry of Alkaline-Earth Oxide-Coated Thermionic Cathodes (United States)

    Karikari, E. K.; Bassey, E.; Wintucky, Edwin G.


    NASA LeRC has a broad, active cathode technology development program in which both experimental and theoretical studies are being employed to further development of thermionic cathodes for use as electron sources in vacuum devices for communications and other space applications. One important type of thermionic cathode under development is the alkaline-earth oxide-coated (BaO, SrO, CaO) cathode. Significant improvements in the emission characteristics of this cathode have been obtained through modification of the chemical composition and morphology of the oxide coating, with the best result thus far coming from the addition of In2O3 and Sc2O3. Whereas the In2O3 produces a finer, more uniform particle structure, the exact chemical state and role of the Sc2O3 in the emission enhancement is unknown. The purpose of this cooperative agreement is to combine the studies of the surface chemistry and electron emission at NASA LeRC of chemically modified oxide coatings with a study of the thermochemistry and crystal structure using X-ray diffraction equipment and expertise at Clark Atlanta University (CAU). The study at CAU is intended to provide the description and understanding of the structure and thermochemistry needed for further improvement and optimization of the modified coatings. A description of the experimental procedure, preliminary X-ray diffraction test results, together with the design of an ultrahigh vacuum chamber necessary for high temperature thermochemistry studies will be presented.

  9. Influence of alkaline earth metals on molecular structure of 3-nitrobenzoic acid in comparison with alkali metals effect. (United States)

    Samsonowicz, M; Regulska, E; Lewandowski, W


    The influence of beryllium, magnesium, calcium, strontium and barium cations on the electronic system of 3-nitrobenzoic acid was studied in comparison with studied earlier alkali metal ions. The vibrational FT-IR (in KBr and ATR techniques) and (1)H and (13)C NMR spectra were recorded for 3-nitrobenzoic acid and its salts. Characteristic shifts in IR and NMR spectra along 3-nitrobenzoates of divalent metal series Mg→Ba were compared with series of univalent metal Li→Cs salts. Good correlations between the wavenumbers of the vibrational bands in the IR spectra for 3-nitrobenzoates and ionic potential, electronegativity, inverse of atomic mass, atomic radius and ionization energy of metals were found for alkaline earth metals as well as for alkali metals. The density functional (DFT) hybrid method B3LYP with two basis sets: 6-311++G** and LANL2DZ were used to calculate optimized geometrical structures of studied compounds. The theoretical wavenumbers and intensities of IR spectra as well as chemical shifts in NMR spectra were obtained. Geometric aromaticity indices, atomic charges, dipole moments and energies were also calculated. The calculated parameters were compared to experimental characteristic of studied compounds.

  10. Conversion of fructose, glucose, and cellulose to 5-hydroxymethylfurfural by alkaline earth phosphate catalysts in hot compressed water. (United States)

    Daorattanachai, Pornlada; Khemthong, Pongtanawat; Viriya-Empikul, Nawin; Laosiripojana, Navadol; Faungnawakij, Kajornsak


    The phosphates of alkaline earth metals (calcium and strontium) synthesized by precipitation process in acetone-water media system were used as catalysts for converting fructose, glucose, and cellulose to 5-hydroxymethylfurfural (HMF) under hot compressed water condition. It was found that the phosphates of calcium and strontium effectively catalyzed the HMF formation from fructose and glucose dehydration and cellulose hydrolysis/dehydration reaction, as compared with the non-catalytic system. The XRD analysis confirmed the CaP(2)O(6) and α-Sr(PO(3))(2) crystalline phases of the catalyst samples, while acid strength of both catalysts was in a range of +3.3 ≤ H(0) ≤ +4.8. From the study, CaP(2)O(6) and α-Sr(PO(3))(2) showed similar catalytic performance toward the dehydration of sugars, providing the HMF yields of 20-21% and 34-39% from glucose and fructose, respectively; whereas the total yield of glucose and HMF from the hydrolysis/dehydration of cellulose over α-Sr(PO(3))(2) (34%) was higher than that over CaP(2)O(6) (17.4%).

  11. A preorganized metalloreceptor for alkaline earth ions showing calcium versus magnesium selectivity in water: biological activity of selected metal complexes. (United States)

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


    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.

  12. Fragment size for calculations on alkaline-earth oxides by the crystal cluster SCF-X/sub approx. /-RW method

    Energy Technology Data Exchange (ETDEWEB)

    Lobach, V.A.; Sobolev, A.B.; Shul' gin, B.V.


    Calculations have been performed on the clusters (A/sub x/B/sub y/) (x = 1, 13; y = 6, 14), corresponding to perfect crystals of the alkaline-earth oxides (AEO) MgO, CaO, and SrO by means of methods involving molecular clusters (MC) and crystalline clusters (CC) in the SCF-X/sub approx./-RW method. It is found that MC is unsuitable for describing perfect AEO, because they have a long-range Coulomb interaction and a potential cluster effect. Even in the CC method, the nonstoichiometric composition of (A/sub x/B/sub y/) for x < 13 and y < 14 does not allow one to obtain satisfactory agreement with the observed optical and x-ray spectra. The (A/sub 13/B/sub 14/) and (B/sub 13/A/sub 14/) clusters reproduce satisfactorily the partial composition of the valence band (VB) and the conduction band (CB), as well as the widths of those bands, the fine structure of the K emission spectrum for oxygen in MgO, and the observed electron-density distribution. A study is made of the effects of varying the radii of the spheres on the error from the region between the spheres with muffin-tin averaging.

  13. Size of the fragment for crystal cluster SCF-X/sub /-SW calculations of alkaline earth metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Lobach, V.A.; Sobolev, A.B.; Shul' gin, B.V.

    Calculation of (A/sub x/B/sub y/) (x=1, 13; y=6, 14) clusters, corresponding to ideal crystals of alkaline earth metal oxides (AEMO) MgO, CaO, SrO by means of molecular cluster (MC) and crystal cluster (CC) SCF-X/sub /-SW method is carried out. MC method is not suitable for description of ideal AEMO electron structure due to long-range Coulomb interaction and potential cluster effect. Even in CC method at x < 13 and y < 14 (A/sub x/B/sub y/) cluster nonstoichiometry is inhibitory to the obtaining of satisfactory agreement with the experimental optical and X-ray spectra. (A13B14) and (B13A14) clusters satisfactorily reproduce partial composition of valence band (VB) and conduction band (CB), VB and CB widths, a fine structure of oxygen K-emission spectra in MgO and also experimental distribution of electron density. Sphere radii variation effect on the value of intersphere region error with muffin-tin averaging is considered.

  14. Fates and roles of alkali and alkaline earth metal species during the pyrolysis and gasification of a Victorian lignite

    Energy Technology Data Exchange (ETDEWEB)

    Mody, D.; Wu, H.; Li, C. [Monash University, Vic. (Australia). CRC for Clean Power from Lignite, Dept. of Chemical Engineering


    The transformation of alkali and alkaline earth metal (AAEM) species in a Victorian lignite during the pyrolysis and subsequent gasification in CO{sub 2} was studied in a novel quartz fluidised-bed reactor. Lignite samples prepared by physically adding NaCl and ion-exchanging Na{sup +} and Ca{sup ++} into the lignite were used to investigate the effects of chemical forms and valency of the AAEM species in the substrate lignite on their transformation during pyrolysis and gasification. Carboxyl-bound Na was found to be less volatile than Na present as NaCl, but more volatile than carboxyl-bound Ca during pyrolysis at temperatures between 400 and 900{sup o}C. However, the carboxyl-bound Na was volatilised to a much greater extent than the carboxyl-bound Ca in the same lignite during pyrolysis. It was seen that the loading of NaCl into the lignite did not significantly affect the char reactivity in the fluidised-bed reactor at 900{sup o}C.

  15. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides. (United States)

    Hereijgers, Bart P C; Weckhuysen, Bert M


    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.

  16. A Density Functional Theory Study of Codoping Characteristics of Sulfur with Alkaline Earth in Delafossite CuAlO2 (United States)

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


    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

  17. Tungsten isotopic evidence for disproportional late accretion to the Earth and Moon. (United States)

    Touboul, Mathieu; Puchtel, Igor S; Walker, Richard J


    Characterization of the hafnium-tungsten systematics ((182)Hf decaying to (182)W and emitting two electrons with a half-life of 8.9 million years) of the lunar mantle will enable better constraints on the timescale and processes involved in the currently accepted giant-impact theory for the formation and evolution of the Moon, and for testing the late-accretion hypothesis. Uniform, terrestrial-mantle-like W isotopic compositions have been reported among crystallization products of the lunar magma ocean. These observations were interpreted to reflect formation of the Moon and crystallization of the lunar magma ocean after (182)Hf was no longer extant-that is, more than about 60 million years after the Solar System formed. Here we present W isotope data for three lunar samples that are more precise by a factor of ≥4 than those previously reported. The new data reveal that the lunar mantle has a well-resolved (182)W excess of 20.6 ± 5.1 parts per million (±2 standard deviations), relative to the modern terrestrial mantle. The offset between the mantles of the Moon and the modern Earth is best explained by assuming that the W isotopic compositions of the two bodies were identical immediately following formation of the Moon, and that they then diverged as a result of disproportional late accretion to the Earth and Moon. One implication of this model is that metal from the core of the Moon-forming impactor must have efficiently stripped the Earth's mantle of highly siderophile elements on its way to merge with the terrestrial core, requiring a substantial, but still poorly defined, level of metal-silicate equilibration.


    Directory of Open Access Journals (Sweden)

    E. P. Lisachenko


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  20. The Use of Lead Isotope and Rare Earth Element Geochemistry for Forensic Geographic Provenancing (United States)

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


    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

  1. 1H and 23Na MAS NMR spectroscopy of cationic species in CO2 selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange (United States)

    Arévalo-Hidalgo, Ana G.; Dugar, Sneha; Fu, Riqiang; Hernández-Maldonado, Arturo J.


    The location of extraframework cations in Sr2+ and Ba2+ ion-exchanged SAPO-34 was estimated by means of 1H and 23Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO2 adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium.

  2. 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))


    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.

  3. Energetics and bonding in aluminosilicate rings with alkali metal and alkaline-earth metal charge-compensating cations. (United States)

    Gatti, Carlo; Ottonello, Giulio; Richet, Pascal


    The stabilizing effect of alkali and alkaline-earth metal ions on the oxygen donors of four- and six-membered faujausite-like rings has been calculated in terms of Kohn-Sham core-level (O1s) energy shifts with respect to these same complexes without cations. The results confirm and complement earlier investigations by Vayssilov and co-workers where Na(+) and K(+) were the only complexing cations. The oxygen donor centers in six-membered rings are stabilized by -3.6 ± 0.4, -3.9 ± 0.5, -7.3 ± 0.1, and -7.6 ± 0.2 eV by K(+), Na(+), Ca(2+), and Mg(2+) adions, respectively. The energy shifts are even greater for four-membered rings where the stabilization effects attain -3.7 ± 0.1, -4.1 ± 0.1, -8.1 ± 0.1, and -9.0 ± 0.1 eV, respectively. These effects are also observed on the low-lying σ-bonding and antibonding molecular orbitals (MOs) of the oxygen framework, but in a less systematic fashion. Clear relationships with the core-level shifts are found when the effects of alkali metal complexation are evaluated through electron localization/delocalization indices, which are defined in terms of the whole wave function and not just of the individual orbitals. Complexation with cations not only involves a small but significant electron sharing of the cation with the oxygen atoms in the ring but also enhances electron exchange among oxygen atoms while reducing that between the O atoms and the Si or Al atoms bonded to them. Such changes slightly increase from Na to K and from Mg to Ca, whereas they are significantly enhanced for alkaline-earth metals relative to alkali metals. With respect to Al-free complexes, Si/Al substitution and cation charge compensation generally enhance electron delocalization among the O atoms, except between those that are linked through an Al atom, and cause either an increased or a decreased Si-O ionicity (smaller/higher electron exchange) depending on the position of O in the chain relative to the Al atom(s). The generally increased

  4. 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


    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.

  5. 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)


    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.

  6. Ab Initio Quantum Mechanical Study of the Structure and Stability of the Alkaline Earth Metal Oxides and Peroxides (United States)

    Königstein, Markus; Catlow, C. Richard A.


    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.

  7. 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.


    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.

  8. Mixed alkali and alkaline-earth borate Li2Sr4B12O23 single crystal (United States)

    Reshak, A. H.


    A comprehensive theoretical investigation of the electronic band structure, density of states, electron charge density distribution and the optical properties for mixed alkali and alkaline-earth borate Li2Sr4B12O23 (LSBO) single crystals were performed. The experimental geometrical structure was optimized by minimizing the forces acting on each atom. Calculations were performed using the full potential linear augmented plane wave plus local orbitals (FPLAPW + lo) method within the local density approximation (LDA), generalized gradient approximation (GGA) and the recently modified Becke-Johnson potential (mBJ). Our calculations show that LSBO crystal is a direct band gap semiconductor. The calculated band gap is 4.64 eV (LDA), 4.92 eV (GGA) and 5.51 eV (mBJ). An earlier calculation using the CASTEP code within LDA obtained a band gap of about 4.66 eV. To overcome the well-known LDA underestimation of the energy gap we have used GGA and mBJ . We find that mBJ succeed by large amount in bringing the calculated bond lengths in good agreement with the experimental data. Also we found that using mBJ to calculate the optical properties gives a birefringence of about 0.068 (at λ = 586.5 nm) in excellent agreement with the experimental data (0.068 at λ = 586.5 nm). Therefore, we believe that the mBJ calculations reported here show excellent agreement with the experimental data.

  9. Ca and Mg isotope constraints on the origin of Earth's deepest δ13 C excursion (United States)

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


    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

  10. 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 (United States)

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


    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

  11. Oxidative Weathering of Earth's Surface 3.7 Billion Years ago? - A Chromium Isotope Perspective (United States)

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


    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

  12. 40Ar/39Ar ages and Sr-Nd-Pb isotopic compositions of alkaline and tholeiitic rocks from the northern Deccan Traps (United States)

    Marzoli, A.; Parisio, L.; Jourdan, F.; Melluso, L.; Sethna, S. F.; Bellieni, G.


    The Deccan large igneous province in India was emplaced close to the Cretaceous-Paleogene boundary (K-Pg; 66.0 Ma) and is formed by tholeiitic and alkaline rocks. Definition of the origin of Deccan magmatism and of its environmental impact relies on precise and accurate geochronological analyses. We present new 40Ar/39Ar ages from the northern sector of the province. In this area, tholeiitic and alkaline rocks were contemporaneously emplaced at 66.60±0.35 to 65.25±0.29 Ma in the Phenai Mata area, while rocks from Rajpipla and Mt. Pavagadh yielded ages ranging from 66.40±2.80 to 64.90±0.80 Ma. Indistinguishable ages for alkaline and tholeiitic magmatism, coupled with distinct major and trace element and Sr-Nd-Pb isotopic compositions suggest that distinct mantle sources, necessary for the two magmatic series were synchronously active. The new ages are compared with previous ages, which were carefully screened and filtered and then recalculated in order to be comparable. The entire data set of geochronological data does not support a time-related migration of the magmatism related to the northward Indian Plate movement relative to the Reunion mantle plume. The main phase of magmatism, including the newly dated rocks from the Northern Deccan occurred across the K-Pg boundary, confirming a causal link between the emplacement of the province and the K-Pg mass extinction.

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

    DEFF Research Database (Denmark)

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


    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...... for the chondrite-forming event. This ¿176 value indicates that Earth's oldest minerals were derived from melts of a mantle source with a time-integrated history of depletion rather than enrichment. The depletion event must have occurred no later than 320 Myr after planetary accretion, consistent with timing...

  14. Luminescence behaviors of Eu- and Dy-codoped alkaline earth metal aluminate phosphors through potassium carbonate coprecipitation

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Chen-Jui, E-mail:; Siao, Hao-Yi


    An electronic energy mechanism of activator and sensitizer was established to describe the luminescence behaviors of Eu- and Dy-codoped M(II)Al{sub 2}O{sub 4} (M(II) = Ba, Sr, Ca, Mg) phosphors through potassium carbonate coprecipitation. Experimental results demonstrated that the prepared phosphors exhibited superior crystallinity at a temperature lower than 950 °C. The phosphors are ordered according to emission intensity as follows Ca- > Ba- > Sr- > Mg-containing phosphors. The energy level for Eu{sup 2+} 4f{sup 6}5d{sup 1} → 4f{sup 7}, Eu{sup 3+4}D{sub 0} → {sup 7}F, and Dy{sup 3+4}F{sub 9/2} → {sup 6}H transitions and the effects of nephelauxetic and crystal field in Ba-, Sr-, and Ca-containing phosphors were discussed. The energy gap, (hv){sub em}, between 5d and 4f of Eu{sup 2+} ion is strongly affected by host composition, crystal field strength, and nephelauxetic effect. The infrared emission of 4f{sub 9/2} → 6h for Dy{sup 3+} is merely depend on the transfer of energy from Eu{sup 2+} upon excited. Ca-containing phosphor with maximum (hv){sub em} is attributed to the lowest bond length of Ca−O and highest ionization potential of Ca{sup 2+} ion, which leads to the effects of crystal field and nephelauxetic greater than that in the other phosphors. - Highlights: • The list of the collected figure captions: • Develop a new coprecipitation method to prepare high efficiency phosphors. • Obtain superior crystallinity with lower calcination temperature. • Luminescence behavior of Eu- and Dy-codoped on aluminate phosphors is discussed. • Investigate the effects of alkaline earth metal containing on crystal field and nephelauxetic.

  15. The influence of alkaline earth metal equilibria on the rheological, melting and textural properties of Cheddar cheese. (United States)

    Cooke, Darren R; McSweeney, Paul L H


    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.

  16. 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


    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.

  17. Uranium isotope evidence for temporary ocean oxygenation in the aftermath of the Sturtian Snowball Earth (United States)

    Lau, Kimberly V.; Macdonald, Francis A.; Maher, Kate; Payne, Jonathan L.


    The appearance and radiation of animals are commonly attributed to Neoproterozoic oceanic oxygenation, yet independent geochemical evidence for such an event remains equivocal. Strata deposited between the Sturtian and Marinoan Snowball Earth glaciations (660 to 640 Ma) contain the earliest animal biomarkers and possible body fossils. To quantify the extent of seafloor oxygenation during this critical interval, we present uranium isotope ratios (238U/235U denoted as δ238 U) from limestone of the Taishir Formation in Mongolia through two stratigraphic sections that are separated by ∼75 km within the same depositional basin. Above the Sturtian glacial deposits, through ∼150 m of stratigraphy, δ238 U compositions have a mean value of -0.47‰. This interval is followed by a ∼0.3‰ decrease in δ238 U, coincident with the Taishir negative carbon isotope excursion. Thereafter, δ238 U values remain relatively low until the erosional unconformity at the base of the Marinoan glacial deposits. Using a box model, we show that the best explanation for the higher δ238 U values of the post-Sturtian limestones is extensive-but temporary-oxygenation of the seafloor, and is inconsistent with a scenario involving only increased delivery of uranium to the oceans due to post-Snowball weathering. The decline in δ238 U in overlying strata, coincident with the Taishir negative δ13 C excursion, indicates a subsequent decrease in seafloor oxygenation. The U isotopic data, combined with modeling results, challenge the notion of a simple, unidirectional oxygenation of Neoproterozoic oceans.

  18. Earth's early atmosphere as seen from carbon and nitrogen isotopic analysis of Archean sediments (United States)

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


    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.

  19. Open system models of isotopic evolution in Earth's silicate reservoirs: Implications for crustal growth and mantle heterogeneity (United States)

    Kumari, Seema; Paul, Debajyoti; Stracke, Andreas


    An open system evolutionary model of the Earth, comprising continental crust (CC), upper and lower mantle (UM, LM), and an additional isolated reservoir (IR) has been developed to study the isotopic evolution of the silicate Earth. The model is solved numerically at 1 Myr time steps over 4.55 Gyr of Earth history to reproduce both the present-day concentrations and isotope ratios of key radioactive decay systems (Rb-Sr, Sm-Nd, and U-Th-Pb) in these terrestrial reservoirs. Various crustal growth scenarios - continuous versus episodic and early versus late crustal growth - and their effect on the evolution of Sr-Nd-Pb isotope systematics in the silicate reservoirs have been evaluated. Modeling results where the present-day UM is ∼60% of the total mantle mass and a lower mantle that is non-primitive reproduce the estimated geochemical composition and isotope ratios in Earth's silicate reservoirs. The isotopic evolution of the silicate Earth is strongly affected by the mode of crustal growth; only an exponential crustal growth pattern with crustal growth since the early Archean satisfactorily explains the chemical and isotopic evolution of the crust-mantle system and accounts for the so-called Pb paradoxes. Assuming that the OIB source is located in the deeper mantle, our model could, however, not reproduce its target ɛNd of +4.6 for the UM, which has been estimated from the average isotope ratios of 32 individual ocean island localities. Hence, either mantle plumes sample the LM in a non-representative way, or the simplified model set-up does not capture the full complexity of Earth's lower mantle (Nd isotope) evolution. Compared to the results obtained for a 4.55 Ga Earth, a model assuming a protracted U-Pb evolution of silicate Earth by ca. 100 Myr reproduces a slightly better fit for the Pb isotope ratios in Earth's silicate reservoirs. One notable feature of successful models is the early depletion of incompatible elements (as well as rapid decrease in Th/U) in

  20. Devonian alkaline magmatism in the northern North China Craton: Geochemistry, SHRIMP zircon U-Pb geochronology and Sr-Nd-Hf isotopes

    Directory of Open Access Journals (Sweden)

    Dingling Huang


    Full Text Available The Wulanhada pluton is among the rare suite of Devonian alkaline plutons occurring along the northern margin of the North China Craton (NCC. The intrusion is mainly composed of quartz-monzonite. Here we report zircon SHRIMP U-Pb data from this intrusion which shows emplacement age of ca. 381.5 Ma. The rock is metaluminous with high (Na2O + K2O values ranging from 8.46 to 9.66 wt.%. The REE patterns of the rocks do not show any Eu anomaly whereas the primitive-mantle-normalized spider diagram shows strong positive Sr and Ba anomalies. The Wulanhada rocks exhibit high initial values of (87Sr/86Srt = 0.70762–0.70809, low ɛNd(t = −12.76 to −12.15 values and negative values of ɛHf(t = −23.49 to −17.02 with small variations in (176Hf/177Hft (0.281873–0.282049. These geochemical features and quantitative isotopic modeling results suggest that the rocks might have been formed through the partial melting of Neoarchean basic rocks in the lower crust of the NCC. The Wulanhada rocks, together with the Devonian alkaline rocks and mafic-ultramafic complex from neighboring regions, constitute a post-collisional magmatic belt along the northern NCC.

  1. IsoNose - Isotopic Tools as Novel Sensors of Earth Surfaces Resources - A new Marie Curie Initial Training Network (United States)

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


    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

  2. Potassium isotope cosmochemistry, volatile depletion and the origin of the Earth (United States)

    Humayun, M.; Clayton, R. N.


    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.

  3. Enhanced Electroresponse of Alkaline Earth Metal-Doped Silica/Titania Spheres by Synergetic Effect of Dispersion Stability and Dielectric Property. (United States)

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


    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.

  4. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals. (United States)

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


    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.

  5. 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


    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.

  6. Chelation ion chromatography of alkaline earth and transition metals a using monolithic silica column with bonded N-hydroxyethyliminodiacetic acid functional groups. (United States)

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Jones, Phil; Paull, Brett


    A commercially available porous silica monolithic column (Onyx Monolithic Si, 100 mm×4.6 mm I.D.) was 'in-column' covalently functionalised with 2-hydroxyethyliminodiacetic acid (HEIDA) groups, and applied to the simultaneous and rapid separation of alkaline earth and transition metal ions, using high-performance chelation ion chromatography (HPCIC). With a 0.3mM dipicolinic acid (DPA) containing eluent, the baseline separation of various common transition and heavy metal ions and the four alkaline earth metal ions could be achieved in under 14 min with a flow rate of just 0.8 mL/min. Detection was achieved using spectrophotometric detection at 540 nm after post-column reaction (PCR) with 4-(2-pyridylazo)-resorcinol (PAR). Significant effects from variation of eluent nature, concentration and temperature upon selectivity and retention were demonstrated with the new monolithic silica chelating phase. Under optimised conditions (0.165 M LiNO(3) eluent, pH 2.5), peak efficiencies of 54,000, 60,000 and 64,000 N/m, for Zn(2+), Mn(2+) and Cd(2+), respectively, were recorded, far exceeding that previously reported for IDA based chelation ion exchange columns.

  7. Identifying the presence of a disulfide linkage in peptides by the selective elimination of hydrogen disulfide from collisionally activated alkali and alkaline earth metal complexes. (United States)

    Kim, Hugh I; Beauchamp, J L


    We report a new method for identifying disulfide linkages in peptides using mass spectrometry. This is accomplished by collisional activation of singly charged cationic alkali and alkaline earth metal complexes, which results in the highly selective elimination of hydrogen disulfide (H2S2). Complexes of peptides possessing disulfide bonds with sodium and alkaline earth metal are generated using electrospray ionization (ESI). Isolation followed by collision induced dissociation (CID) of singly charged peptide complexes results in selective elimination of H2S2 to leave newly formed dehydroalanine residues in the peptide. Further activation of the product yields sequence information in the region previously short circuited by the disulfide bond. For example, singly charged magnesium and calcium ion bound complexes of [Lys8]-vasopressin exhibit selective elimination of H2S2 via low-energy CID. Further isolation of the product followed by CID yields major b- and z-type fragments revealing the peptide sequence in the region between the newly formed dehydroalanine residues. Numerous model peptides provide mechanistic details for the selective elimination of H2S2. The process is initiated starting with a metal stabilized enolate anion at Cys, followed by cleavage of the S-C bond. An examination of the peptic digest of insulin provides an example of the application of the selective elimination of H2S2 for the identification of peptides with disulfide linkages. The energetics and mechanisms of H2S2 elimination from model compounds are investigated using density functional theory (DFT) calculations.

  8. 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)


    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.

  9. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals (United States)

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


    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.

  10. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals (United States)

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


    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

  11. Meteorite zircon constraints on the bulk Lu-Hf isotope composition and early differentiation of the Earth. (United States)

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


    Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The (176)Lu-(176)Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day (176)Hf/(177)Hf and (176)Lu/(177)Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess (176)Hf due to the accelerated decay of (176)Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu-Hf system. Herein we report the first, to our knowledge, high-precision Lu-Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial (176)Hf/(177)Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess (176)Hf and accurately represent the Lu-Hf system of the bulk Earth ((176)Hf/(177)Hf = 0.282793 ± 0.000011; (176)Lu/(177)Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago.


    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)


    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.

  13. Of Island Arcs and Icebergs? Strontium and Carbon Isotope Stratigraphy of Ethiopian Snowball Earth Sequences (United States)

    Miller, N. R.; Stern, R. J.; Avigad, D.; Beyth, M.; Küster, D.; Gebresilassie, S.; Mehari, K.


    Neoproterozoic low-grade metasedimentary exposures uniquely preserved in synclinoria of the Tigrai region of northern Ethiopia offer excellent opportunities to assess the sedimentary response to extreme climatic changes encompassed by the Snowball Earth Hypothesis within the framework of the tectonic evolution of the Arabian-Nubian shield. Basement exposures consist of two major sequences; an older predominantly island arc metavolcanic sequence named the Tsaliet Group, and a younger metasedimentary succession named the Tambien Group. An intervening phyllite unit displays a transitional lithology variously interpreted by previous workers as metasedimentary and metavolcanic. We report Sr and C isotope results for Tambien Group carbonates from three prospective Snowball Earth successions flanking the Mekelle outlier: Negash, Mai Kenetal, and Samre. These localities display excellent exposures of the transition from Tsaliet metavolcaniclastics into distinctive carbonate exposures of the Tambien Group. Distinctive volcanic polymict conglomerates occur close to the basal Tambien contact in the upper Tsaliet Group in two localities. Presence of evaporite pseudomorphs and persistence of microbially laminated lithologies including stromatolites suggests that Tambien carbonate deposition occurred in a shallow marine setting that was initially hypersaline. A distinct black limestone unit, with abundant organic matter and indications of variable energy conditions in a slope setting, occurs higher in the section. Accompanying this transition in gross carbonate depositional style is a pronounced enrichment of carbon isotopes from values between -4 and -1 per mil in the lower interval to values between +4 and +7 per mil in the overlying black limestone. A similar excursion to more radiogenic 87Sr/87Sr compositions is observed from values between 0.7060 to 0.7064 in the lower interval to values "plateauing" between 0.7067 and 0.7069 in the black limestone. Thus far, only the

  14. The tungsten isotopic composition of Eoarchean rocks: Implications for early silicate differentiation and core-mantle interaction on Earth (United States)

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


    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.

  15. 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


    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.

  16. 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.


    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

  17. Time Passes - Argon Isotopes as Tracers of Fluids in the Earth's Crust (United States)

    Kelley, Simon P.


    Recent experimental measurements of noble gas solubility in silicate minerals (e.g. Jackson et al. 2013, 2015) means that we can begin to explore the use of noble gas partition between minerals and fluids to understand their residence and transport in the Earth's crust. One starting point for this exploration is the distribution of noble gases and halogens in crustal fluids which was reviewed by Kendrick and Burnard (2013). In particular, K&B (2013) noted that time is a key parameter in understanding noble gas tracers in crustal processes; yielding information such as the residence time of water in a reservoir based on 4He acquired from aquifer rocks, and the 40Ar/39Ar age of fluid inclusions based on trapped fluid and minerals in quartz. Argon isotope variations in natural systems have been measured during studies of 40Ar/39Ar ages to quantify the rates and timescales of crustal processes. There are also studies of fluids in similar rocks, notably in fluid inclusions, providing the opportunity to quantify the variations in the crust. Partition of argon between mineral phases under conditions of varying fluid availability can be compared in systems where 40Ar/39Ar measurements indicate the preservation of non-radiogenic argon (both excess and atmospheric) in the minerals. Rather than a simple picture of radiogenic argon contents increasing with crustal age, and gradual depletion of atmospheric argon in deeper fluids, what emerges is a sometimes dynamic and sometimes static system in different zones of the crust. While it can be shown that the hydrous fluid in sandstone reservoirs contained excess argon, analyses of authigenic minerals rarely exhibit 40Ar/39Ar ages in excess of the growth age. In this scenario, the incompatible nature of argon means that the fluid acts as an effective infinite reservoir and radiogenic argon dominates the potassium rich authigenic minerals. The controls on noble gas distribution are also well illustrated by deep crustal rocks such as

  18. Ancient geochemical cycling in the Earth as inferred from Fe isotope studies of banded iron formations from the Transvaal Craton (United States)

    Johnson, Clark; Beard, Brian; Beukes, Nicolas; Klein, Cornelis; O'Leary, Julie


    Variations in the isotopic composition of Fe in Late Archean to Early Proterozoic Banded Iron Formations (BIFs) from the Transvaal Supergroup, South Africa, span nearly the entire range yet measured on Earth, from -2.5 to +1.0‰ in 56Fe/54Fe ratios relative to the bulk Earth. With a current state-of-the-art precision of +/-0.05‰ for the 56Fe/54Fe ratio, this range is 70 times analytical error, demonstrating that significant Fe isotope variations can be preserved in ancient rocks. Significant variation in Fe isotope compositions of rocks and minerals appears to be restricted to chemically precipitated sediments, and the range measured for BIFs stands in marked contrast to the isotopic homogeneity of igneous rocks, which have δ56Fe=0.00+/-0.05‰, as well as the majority of modern loess, aerosols, riverine loads, marine sediments, and Proterozoic shales. The Fe isotope compositions of hematite, magnetite, Fe carbonate, and pyrite measured in BIFs appears to reflect a combination of (1) mineral-specific equilibrium isotope fractionation, (2) variations in the isotope compositions of the fluids from which they were precipitated, and (3) the effects of metabolic processing of Fe by bacteria. For minerals that may have been in isotopic equilibrium during initial precipitation or early diagenesis, the relative order of δ56Fe values appears to decrease in the order magnetite > siderite > ankerite, similar to that estimated from spectroscopic data, although the measured isotopic differences are much smaller than those predicted at low temperature. In combination with on-going experimental determinations of equilibrium Fe isotope fractionation factors, the data for BIF minerals place additional constraints on the equilibrium Fe isotope fractionation factors for the system Fe(III)-Fe(II)-hematite-magnetite-Fe carbonate. δ56Fe values for pyrite are the lowest yet measured for natural minerals, and stand in marked contrast to the high δ56Fe values that are predicted from

  19. Hafnium and iron isotopes in early Archean komatiites record a plume-driven convection cycle in the Hadean Earth (United States)

    Nebel, Oliver; Campbell, Ian H.; Sossi, Paolo A.; Van Kranendonk, Martin J.


    Archean (>2.5 billion years) komatiites are considered expressions of mantle plumes that originate from and thereby sample the lowermost mantle overlying the Earth's core. Some komatiites have reported Hf isotope signatures that require a mantle source with a time-integrated Lu/Hf that is appreciably higher than average modern depleted mantle. The systematic study of the time and locus of parent-daughter fractionation of the mantle sources of these komatiites potentially constrains differentiation processes in the early Earth, and subsequent distribution and storage of early mantle reservoirs. We present radiogenic Hf and stable Fe isotopes for a series of komatiites from the Pilbara craton in Western Australia (aged 3.5 to 2.9 Ga). After careful evaluation of the effects of alteration, we find that pristine samples are characterised by a light Fe isotope mantle source and initial 176Hf/177Hf well above the age-corrected depleted mantle. Taken together these observations require a component of an old, melt-depleted reservoir in their mantle source. The Hf isotope signature of this component appears to be complementary to the first terrestrial crust, as preserved in Hadean (i.e., >4 Ga) detrital zircon cores, suggesting a causal relationship and a Hadean age for this depletion event. We propose that this Early Refractory Reservoir (ERR) is the residue formed by deep melting in hot Hadean mantle plumes, which then accumulated at the base of the first crust. Parts of this primordial lithosphere were destabilised and sank to the core-mantle boundary in cold drips and subsequently returned in hot mantle plumes, whose thermal capacity allows melting of such refractory mantle with its archetype isotope signature. The cycling of this material via cold drips and hot plumes suggests a plume-dominated convection prior to ∼3.9 Ga, which is then replaced by Archean-style plate tectonics.

  20. 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


    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.

  1. 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


    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.

  2. 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


    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.

  3. Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass: differences between sugar cane bagasse and cane trash. (United States)

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


    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.

  4. Alkaline earth metal-based metal-organic framework: hydrothermal synthesis, X-ray structure and heterogeneously catalyzed Claisen-Schmidt reaction. (United States)

    Saha, Debraj; Maity, Tanmoy; Koner, Subratanath


    Two alkaline earth metal-based carboxylate systems, [Mg(HL)(H2O)2]n (1) and [Ca(H2L)2]n (2) (H3L = chelidamic acid) have been hydrothermally synthesized, and characterized by single-crystal X-ray diffraction, IR, elemental analysis, and thermo-gravimetric analysis. Compound 1 has a 2D structure incorporating two water molecules. The dehydrated species, 1a, generated from 1 by removal of the coordinated water, has been characterized by thermo-gravimetric analysis, IR, elemental analysis and variable temperature powder X-ray diffraction. Both 1 and its dehydrated species 1a catalyze the Claisen-Schmidt reaction under heterogeneous conditions, but 1a is a more effective catalyst under environmentally friendly conditions. The catalyst can readily be recovered and reused in successive cycles without detectable loss of activity. Compound 2 has a 3D structure and is thermally stable up to 540 °C, but is inactive catalytically.

  5. Volatilisation of alkali and alkaline earth metallic species during the gasification of a Victorian brown coal in CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Quyn, Dimple Mody; Li, Chun-Zhu [CRC for Clean Power from Lignite, Department of Chemical Engineering, PO Box 36, Monash University, Victoria 3800 (Australia); Hayashi, Jun-ichiro [Centre for Advanced Research of Energy Conversion Materials, Hokkaido University, N13-W8, Kita-ku, Sapporo 060-8628 (Japan)


    A Victorian brown coal was gasified in a bench-scale quartz fluidised-bed/fixed-bed reactor in order to study the volatilisation of Na, Ca, and Mg during devolatilisation and gasification and their roles in the reactivity of chars. It was found that the majority of Na was volatilised at 900 {sup o}C under all conditions and that a Na retention limit was achieved in the char with the progress of CO{sub 2} gasification. In some cases, the presence of CO{sub 2} during devolatilisation enhanced the Na retention in the char. In contrast, the retention of Ca (and Mg) was unaffected by CO{sub 2} during devolatilisation at 900C but decreased drastically upon nascent char gasification. The fundamental differences in volatilisation between the alkali and alkaline earth metallic species are discussed in this paper.

  6. 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


    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...

  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. (United States)

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


    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. Theoretical studies of the spin Hamiltonian parameters and local distortions for Cu{sup 2+} in alkaline earth lead zinc phosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Bo-Kun; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian [University of Electronic Science and Technology of China, Chengdu (China). School of Yingcai Honors; Wu, Shao-Yi; Teng, Bao-Hua; Wu, Ming-He [University of Electronic Science and Technology of China, Chengdu (China). Dept. of Applied Physics


    The spin Hamiltonian parameters and local structures are theoretically studied for Cu{sup 2+}-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 3d{sup 9} 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 Cu{sup 2+}-O{sup 2-} 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≤Ba

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

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


    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.

  10. 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)


    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.

  11. Lack of marked cyto- and genotoxicity of cristobalite in devitrified (heated) alkaline earth silicate wools in short-term assays with cultured primary rat alveolar macrophages. (United States)

    Ziemann, Christina; Harrison, Paul T C; Bellmann, Bernd; Brown, Robert C; Zoitos, Bruce K; Class, Philippe


    Alkaline earth silicate (AES) wools are low-biopersistence high-temperature insulation wools. Following prolonged periods at high temperatures they may devitrify, producing crystalline silica (CS) polymorphs, including cristobalite, classified as carcinogenic to humans. Here we investigated the cytotoxic and genotoxic significance of cristobalite present in heated AES wools. Primary rat alveolar macrophages were incubated in vitro for 2 h with 200 µg/cm² unheated/heated calcium magnesium silicate wools (CMS1, CMS2, CMS3; heat-treated for 1 week at, or 4 weeks 150 °C below, their respective classification temperatures) or magnesium silicate wool (MS; heated for 24 h at 1260 °C). Types and quantities of CS formed, and fiber size distribution and shape were determined by X-ray diffraction and electron microscopy. Lactate dehydrogenase release and alkaline and hOGG1-modified comet assays were used, ± aluminum lactate (known to quench CS effects), for cytotoxicity/genotoxicity screening. Cristobalite content of wools increased with heating temperature and duration, paralleled by decreases in fiber length and changes in fiber shape. No marked cytotoxicity, and nearly no (CMS) or only slight (MS) DNA-strand break induction was observed, compared to the CS-negative control Al₂O₃, whereas DQ12 as CS-positive control was highly active. Some samples induced slight oxidative DNA damage, but no biological endpoint significantly correlated with free CS, quartz, or cristobalite. In conclusion, heating of AES wools mediates changes in CS content and fiber length/shape. While changes in fiber morphology can impact biological activity, cristobalite content appears minor or of no relevance to the intrinsic toxicity of heated AES wools in short-term assays with rat alveolar macrophages.

  12. sup 29 Si magic angle spinning NMR spectra of alkali metal, alkaline earth metal, and rare earth metal ion exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Chao, Kueijung; Chern, Jeryoung (Tsinghua Univ., Taiwan (China))


    The variation of the extraframework cation location in groups IA and IIA metals and rare earth metal (RE) Y zeolites as a function of the dehydration and the rehydration is monitored by {sup 29}Si MAS NMR. Unheated hydrated zeolites give similar {sup 29}Si spectra as they present the similar cation distributions. Upon dehydration a high-field shift is observed which correlates with the distortion of bond angles in silicon-oxygen tetrahedra. The line shapes of {sup 29}Si spectra depend on the nature and the location of the exchangeable cations and the occupancy of the different sites in dehydrated and rehydrated states. The correlation between the line shape of {sup 29}Si spectra and the migration of cations from the supercages to the sodalite cages after heating treatment was studied. The results of {sup 29}Si NMR agree with the known structure data.

  13. By-products of the serpentinization process on the Oman ophiolite : chemical and isotopic composition of carbonate deposits in alkaline springs, and associated secondary phases (United States)

    Sissmann, O.; Martinez, I.; Deville, E.; Beaumont, V.; Pillot, D.; Prinzhofer, A.; Vacquand, C.; Chaduteau, C.; Agrinier, P.; Guyot, F. J.


    The isotopic compositions (d13C, d18O) of natural carbonates produced by the alteration of basic and ultrabasic rocks on the Oman ophiolite have been measured in order to better understand their formation mechanisms. Fossil carbonates developed on altered peridotitic samples, mostly found in fractures, and contemporary carbonates were studied. The samples bear a large range of d13C. Those collected in veins are magnesian (magnesite, dolomite) and have a carbon signature reflecting mixing of processes and important fractionation (-11‰ to 8‰). Their association with talc and lizardite suggests they are by-products of a serpentinization process, that must have occurred as a carbon-rich fluid was circulating at depth. On the other hand, the carbonates are mostly calcic when formed in alkaline springs, most of which are located in the vicinity of lithological discontinuities such as the peridotite-gabbro contact (Moho). Aragonite forms a few meters below the surface of the ponds in Mg-poor water, and is systematically associated with brucite (Mg(OH)2). This suggests most of the Mg dissolved at depth has reprecipitated during the fluid's ascension through fractures or faults as carbonates and serpentine. Further up, on the surface waters of the ponds (depleted in Mg and D.I.C.), thin calcite films precipitate and reach extremely negative d13C values (-28‰), which could reflect either a biological carbon source, or kinetic fractionation from pumping atmospheric CO2. Their formation represent an efficient and natural process for carbon dioxide mineral sequestration. The d18O signature from all samples confirm the minerals crystallized from a low-temperature fluid. The hyperalkaline conditions (pH between 11 and 12) allowing for these fast precipitation kinetics are generated by the serpentinization process occurring at depth, as indicated by the measured associated H2-rich gas flows (over 50%) seeping out to the surface.

  14. 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.


    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.

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

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


    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.

  16. An estimate of the Bulk Silicate Earth potassium isotopic composition based on MC-ICPMS measurements of basalts (United States)

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


    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.

  17. Influence of Ce, Nd, Sm and Gd oxides on the properties of alkaline-earth borosilicate glass sealant

    Directory of Open Access Journals (Sweden)

    Nibedita Sasmal


    Full Text Available In this study, the influence of CeO2, Nd2O3, Sm2O3 and Gd2O3 on various properties of the melt-quench route derived SrO–CaO–ZnO–B2O3–SiO2 glass have been investigated. Both the precursor glasses and heat treated glasses are characterized by dilatometry, differential scanning calorimetry (DSC, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, Fourier transformed infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS. The density and coefficient of thermal expansion of the glasses varies in the range 3.557–3.804 g cm−3 and 10.5–11.2 × 10−6 K−1 (50–800 °C respectively. Decrease in crystallization tendency with increase in cationic field strength of the ions is well supported by the increasing crystallization activation energy of the glasses calculated by Kissinger, Augis–Bennett and Ozawa models. XPS study revealed the presence of both Ce3+ and Ce4+ ions and an increase in characteristic binding energy of the respective rare earth elements from their core level studies. The Knoop hardness of the glasses varies in the range 6.03–6.28 GPa. The glass transition, glass softening and crystallization temperature; density and hardness of the glasses increased with increase in cationic field strength of the incorporated ions. The thermomechanical properties of the Gd2O3 containing glass advocate its applicability as the most promising sealant in solid oxide fuel cell.

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

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


    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.

  19. The long-range non-additive three-body dispersion interactions for the rare gases, alkali, and alkaline-earth atoms. (United States)

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


    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 dipole-dipole-quadrupole, dipole-dipole-octupole, and dipole-quadrupole-quadrupole coefficients. Results for the four Z coefficients are given for the homonuclear trimers, for the trimers involving two like-rare-gas atoms, and for the trimers with all combinations of the H, He, and Li atoms. An exhaustive compilation of all coefficients between all possible atomic combinations is presented as supplementary data.

  20. 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


    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)

  1. 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


    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.

  2. Structural and spectroscopic studies of water-alkaline earth ion micro clusters: an alternate approach using genetic algorithm in conjunction with quantum chemical methods (United States)

    Ganguly Neogi, S.; Chaudhury, P.


    We present an approach of using a stochastic optimization technique namely genetic algorithm in association with quantum chemical methods to first elucidate structure and then infrared spectroscopy and thermochemistry of water-alkaline earth metal ion clusters. We show that an initial determination of structure using stochastic techniques and following it up with quantum chemical calculation can lead to much faster convergence to high quality structures for these systems. Infrared spectroscopic, thermochemical calculations and natural population analysis based charges on the central metal ions are done to further ascertain the correctness of the structures using our technique. We have done a comparative study with a pure density functional theory calculation and have shown that even for very poor starting guess geometries genetic algorithm in conjunction with density functional theory indeed converges to global structure while pure density functional theory can encounter problems in certain situations to arrive at global geometry. We have also discussed usefulness of Unimodal Normal distribution crossover for handling situation with real coded variables.

  3. 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


    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...

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

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


    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.

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

    DEFF Research Database (Denmark)

    Døssing, Lasse Nørbye

    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...

  6. 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.


    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

  7. Discovery and measurement of an isotopically distinct source of sulfate in Earth's atmosphere. (United States)

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


    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.

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


    Mitchell, K.A.


    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...

  9. Thermal effects on rare earth element and strontium isotope chemistry in single conodont elements (United States)

    Armstrong, H. A.; Pearson, D. G.; Griselin, M.


    A low-blank, high sensitivity isotope dilution, ICP-MS analytical technique has been used to obtain REE abundance data from single conodont elements weighing as little as 5 μg. Sr isotopes can also be measured from the column eluants enabling Sr isotope ratios and REE abundance to be determined from the same dissolution. Results are comparable to published analyses comprising tens to hundreds of elements. To study the effects of thermal metamorphism on REE and strontium mobility in conodonts, samples were selected from a single bed adjacent to a basaltic dyke and from the internationally used colour alteration index (CAI) "standard set." Our analyses span the range of CAI 1 to 8. Homogeneous REE patterns, "bell-shaped" shale-normalised REE patterns are observed across the range of CAI 1 to 6 in both sample sets. This pattern is interpreted as the result of adsorption during early diagenesis and could reflect original seawater chemistry. Above CAI 6 REE patterns become less predictable and perturbations from the typical REE pattern are likely to be due to the onset of apatite recrystallisation. Samples outside the contact aureole of the dyke have a mean 87Sr/ 86Sr ratio of 0.708165, within the broad range of published mid-Carboniferous seawater values. Our analysis indicates conodonts up to CAI 6 record primary geochemical signals that may be a proxy for ancient seawater.

  10. New insights from old spherules: Os-W isotope and HSE evidence for Paleoarchean meteorite bombardment of the Earth (United States)

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


    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

  11. 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


    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.

  12. 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.

  13. Elemental partitioning and isotopic fractionation of Zn between metal and silicate and geochemical estimation of the S content of the Earth's core (United States)

    Mahan, Brandon; Siebert, Julien; Pringle, Emily A.; Moynier, Frédéric


    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. Therefore, Zn provides both direct and indirect information into the origin and eventual fate of volatile and siderophile elements on Earth. However, the partitioning of Zn between metal and silicate - as well as the associated isotopic fractionation - is not well known. We have conducted a suite of partitioning experiments to characterize Zn elemental partitioning and isotopic fractionation between metal and silicate as a function of time, temperature, and composition. Experiments were conducted at 2 GPa and temperatures from 1473 K to 2273 K in a piston cylinder apparatus, with run durations from 5 to 240 min for four distinct starting materials. Chemical and isotopic equilibrium is achieved within 10 min of experimental outset. Zinc metal-silicate isotopic fractionation displays no resolvable dependence on temperature, composition, or oxygen fugacity within the data set. Therefore, the Zn isotopic composition of silicate phases can be used as a proxy for bulk telluric bodies. Partitioning results from this study and data from literature were used to robustly parameterize Zn metal-silicate partitioning as a function of temperature, pressure, and redox state. Using this parametric characterization and viable formation conditions, we have estimated a range of Zn contents in the cores of iron meteorite parent bodies (i.e. iron meteorites) of ∼0.1-150 ppm, in good agreement with natural observations. We have also calculated the first geochemical estimates for the Zn contents of the Earth's core and of the bulk Earth, at 242 ± 107 ppm and 114 ± 34 ppm (respectively), that consider the slightly siderophile behavior of Zn. These estimates of the Zn contents of the Earth's core and

  14. Isotopes as clues to the origin and earliest differentiation history of the Earth. (United States)

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


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

  15. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions. (United States)

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Song, Zhigong; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Little, Reginald B; Xu, Zhiping; Zhu, Hongwei


    Graphene and graphene oxide (G-O) have been demonstrated to be excellent filters for various gases and liquids, showing potential applications in areas such as molecular sieving and water desalination. In this paper, the selective trans-membrane transport properties of alkali and alkaline earth cations through a membrane composed of stacked and overlapped G-O sheets ("G-O membrane") are investigated. The thermodynamics of the ion transport process reveal that the competition between the generated thermal motions and the interactions of cations with the G-O sheets results in the different penetration behaviors to temperature variations for the considered cations (K(+), Mg(2+), Ca(2+), and Ba(2+)). The interactions between the studied metal atoms and graphene are quantified by first-principles calculations based on the plane-wave-basis-set density functional theory (DFT) approach. The mechanism of the selective ion trans-membrane transportation is discussed further and found to be consistent with the concept of cation-π interactions involved in biological systems. The balance between cation-π interactions of the cations considered with the sp(2) clusters of G-O membranes and the desolvation effect of the ions is responsible for the selectivity of G-O membranes toward the penetration of different ions. These results help us better understand the ion transport process through G-O membranes, from which the possibility of modeling the ion transport behavior of cellular membrane using G-O can be discussed further. The selectivity toward different ions also makes G-O membrane a promising candidate in areas of membrane separations.

  16. 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: [Department of Chemistry, Maynooth University, National University of Ireland—Maynooth, County Kildare (Ireland)


    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.

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

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


    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.

  18. Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations (United States)

    Zaghmarzi, Fatemeh Alipour; Zahedi, Mansour; Mola, Adeleh; Abedini, Saboora; Arshadi, Sattar; Ahmadzadeh, Saeed; Etminan, Nazanin; Younesi, Omran; Rahmanifar, Elham; Yoosefian, Mehdi


    Fullerenes are effective acceptor components with high electron affinity for charge transfer. The significant influences of chemical adsorption of the cations on the electrical sensitivity of pristine C60 and 15-(C2H4O)5/C60 nanocages could be the basis of new generation of electronic sensor design. The density functional theory calculation for alkali and alkaline earth cations detection by pristine C60 and 15-(C2H4O)5/C60 nanocages are considered at B3LYP level of theory with 6-31 G(d) basis set. The quantum theory of atoms in molecules analysis have been performed to understand the nature of intermolecular interactions between the cations and nanocages. Also, the natural bond orbital analysis have been performed to assess the intermolecular interactions in detail. Furthermore, the frontier molecular orbital, energy gap, work function, electronegativity, number of transferred electron (∆N), dipole moment as well as the related chemical hardness and softness are investigated and calculated in this study. The results show that the adsorption of cations (M=Na+, K+, Mg2+ and Ca2+) are exothermic and the binding energy in pristine C60 nanocage and 15-(C2H4O)5/C60 increases with respect to the cations charge. The results also denote a decrease in the energy gap and an increase in the electrical conductivity upon the adsorption process. In order to validate the obtained results, the density of state calculations are employed and presented in the end as well.

  19. 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: [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation)


    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)

  20. Promoting alkali and alkaline-earth metals on MgO for enhancing CO2 capture by first-principles calculations. (United States)

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


    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.

  1. Interaction of Rydberg atoms in circular states with the alkaline-earth Ca(4 s 2) and Sr(5 s 2) atoms (United States)

    Mironchuk, E. S.; Narits, A. A.; Lebedev, V. S.


    The resonant mechanism of interaction of alkaline-earth atoms having a low electron affinity to Rydberg atoms in circular ( l = | m| = 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(4 s 2) and Sr(5 s 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).

  2. Chondrite barium, neodymium, and samarium isotopic heterogeneity and early Earth differentiation. (United States)

    Carlson, Richard W; Boyet, Maud; Horan, Mary


    Isotopic variability in barium, neodymium, and samarium in carbonaceous chondrites reflects the distinct stellar nucleosynthetic contributions to the early solar system. We used 148Nd/144Nd to correct for the observed s-process deficiency, which produced a chondrite 146Sm-142Nd isochron consistent with previous estimates of the initial solar system abundance of 146Sm and a 142Nd/144Nd at average chondrite Sm/Nd ratio that is lower than that measured in terrestrial rocks by 21 +/- 3 parts per million. This result strengthens the conclusion that the deficiency in 142Nd in chondrites relative to terrestrial rocks reflects 146Sm decayand earlyplanetary differentiation processes.

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

    Valyaev, Boris; Dremin, Ivan


    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

  4. Earth

    CERN Document Server

    Carter, Jason


    This curriculum-based, easy-to-follow book teaches young readers about Earth as one of the eight planets in our solar system in astronomical terms. With accessible text, it provides the fundamental information any student needs to begin their studies in astronomy, such as how Earth spins and revolves around the Sun, why it's uniquely suitable for life, its physical features, atmosphere, biosphere, moon, its past, future, and more. To enhance the learning experience, many of the images come directly from NASA. This straightforward title offers the fundamental information any student needs to sp

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

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


    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

  6. 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.

  7. 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 (United States)

    Brügmann, G.; Krause, J.; Brachert, T. C.; Stoll, B.; Weis, U.; Kullmer, O.; Ssemmanda, I.; Mertz, D. F.


    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 evaporation of the lake water

  8. Rare earth elements and Nd isotopes tracing water mass mixing and particle-seawater interactions in the SE Atlantic (United States)

    Garcia-Solsona, E.; Jeandel, C.; Labatut, M.; Lacan, F.; Vance, D.; Chavagnac, V.; Pradoux, C.


    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

  9. Geological, rare earth elemental and isotopic constraints on the origin of the Banbanqiao Zn-Pb deposit, southwest China (United States)

    Li, Bo; Zhou, Jia-Xi; Huang, Zhi-Long; Yan, Zai-Fei; Bao, Guang-Ping; Sun, Hai-Rui


    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

  10. 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 (United States)

    Liu, Jingao; Touboul, Mathieu; Ishikawa, Akira; Walker, Richard J.; Graham Pearson, D.


    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

  11. {sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Arevalo-Hidalgo, Ana G. [Department of Chemical Engineering, University of Puerto Rico-Mayagueez Campus, Mayagueez, PR 00681-9000 (Puerto Rico); Dugar, Sneha; Fu, Riqiang [National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Hernandez-Maldonado, Arturo J., E-mail: [Department of Chemical Engineering, University of Puerto Rico-Mayagueez Campus, Mayagueez, PR 00681-9000 (Puerto Rico)


    The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

  12. Melt evolution beneath a rifted craton edge: 40Ar/39Ar geochronology and Sr-Nd-Hf-Pb isotope systematics of primitive alkaline basalts and lamprophyres from the SW Baltic Shield (United States)

    Tappe, Sebastian; Smart, Katie A.; Stracke, Andreas; Romer, Rolf L.; Prelević, Dejan; van den Bogaard, Paul


    A new high-precision 40Ar/39Ar anorthoclase feldspar age of 176.7 ± 0.5 Ma (2-sigma) reveals that small-volume alkaline basaltic magmatism occurred at the rifted SW margin of the Baltic Shield in Scania (southern Sweden), at a time of global plate reorganization associated with the inception of Pangea supercontinent break-up. Our combined elemental and Sr-Nd-Hf-Pb isotope dataset for representative basanite and nephelinite samples (>8 wt.% MgO) from 16 subvolcanic necks of the 30 by 40 km large Jurassic volcanic field suggests magma derivation from a moderately depleted mantle source (87Sr/86Sri = 0.7034-0.7048; εNdi = +4.4 to +5.2; εHfi = +4.7 to +8.1; 206Pb/204Pbi = 18.8-19.5). The mafic alkaline melts segregated from mixed peridotite-pyroxenite mantle with a potential temperature of ∼1400 °C at 2.7-4.2 GPa (∼90-120 km depths), which places ultimate melt generation within the convecting upper mantle, provided that the lithosphere-asthenosphere boundary beneath the southern Baltic Shield margin was at ⩽100 km depth during Mesozoic-Cenozoic rifting. Isotopic shifts and incompatible element enrichment relative to Depleted Mantle reflect involvement of at least 20% recycled oceanic lithosphere component (i.e., pyroxenite) with some minor continent-derived sediment during partial melting of well-stirred convecting upper mantle peridotite. Although pargasitic amphibole-rich metasomatized lithospheric mantle is excluded as the main source of the Jurassic magmas from Scania, hydrous ultramafic veins (i.e., hornblendite) may have caused subtle modifications to the compositions of passing sublithospheric melts. For example, modeling suggests that the more radiogenic Hf (εHfi = +6.3 to +8.1) and Pb (206Pb/204Pbi = 18.9-19.5) isotopic compositions of the more sodic and H2O-rich nephelinites, compared with relatively homogenous basanites (εHfi = +4.7 to +6.1; 206Pb/204Pbi = 18.8-18.9), originate from minor interactions between rising asthenospheric melts and

  13. 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.


    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.

  14. Syntheses, Vibrational Spectroscopy, and Crystal Structure Determination from X-Ray Powder Diffraction Data of Alkaline Earth Dicyanamides M[N(CN) 2] 2 with M=Mg, Ca, Sr, and Ba (United States)

    Jürgens, Barbara; Irran, Elisabeth; Schnick, Wolfgang


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

  15. 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


    shergottite and sea water samples. Repeated analyses of terrestrial and extraterrestrial samples demonstrate that it is possible to routinely measure the relative Mg-isotope composition of silicate materials with an external reproducibility of 2.5 and 20 ppm for the m26Mg* and m25Mg values, respectively (m......-isotope composition for Earth’s mantle – and hence that of the bulk silicate Earth – to be 25Mg/24Mg 1/4 0.126896 ¿ 0.000025 and 26Mg/24Mg 1/4 0.139652 ¿ 0.000033. Given the restricted range of m25Mg obtained for bulk planetary material by the sample-standard bracketing technique and the excellent agreement between...

  16. Rare earth elements, S and Sr isotopes and origin of barite from Bahariya Oasis, Egypt: Implication for the origin of host iron ores (United States)

    Baioumy, Hassan M.


    Based on their occurrences and relation to the host iron ores, barites are classified into: (1) fragmented barite occurs as pebble to sand-size white to yellowish white barite along the unconformity between the Bahariya Formation and iron ores, (2) interstitial barite is present as pockets and lenses of large and pure crystals inside the iron ores interstitial barite inside the iron ores, and (3) disseminated barite occurs at the top of the iron ores of relatively large crystals of barite embedded in hematite and goethite matrix. In the current study, these barites have been analyzed for their rare earth elements (REE) as well as strontium and sulfur isotopes to assess their source and origin as well as the origin of host iron ores. Barite samples from the three types are characterized by low ΣREE contents ranging between 12 and 21 ppm. Disseminated barite shows relatively lower ΣREE contents (12 ppm) compared to the fragmented (19 ppm) and interstitial (21 ppm) barites. This is probably due to the relatively higher Fe2O3 in the disseminated barite that might dilute its ΣREE content. Chondrite-normalized REE patterns for the three barite mineralizations exhibit enrichment of light rare earth elements (LREE) relative to heavy rare earth elements (HREE) as shown by the high (La/Yb)N ratios that range between 14 and 45 as well as pronounced negative Ce anomalies varying between 0.03 and 0.18. The 87Sr/86Sr ratios in the analyzed samples vary between 0.707422 and 0.712237. These 87Sr/86Sr values are higher than the 87Sr/86Sr ratios of the seawater at the time of barite formation (Middle Eocene with 87Sr/86Sr ratios of 0.70773 to 0.70778) suggesting a contribution of hydrothermal fluid of high Sr isotope ratios. The δ34S values in the analyzed barites range between 14.39‰ and 18.92‰. The lower δ34S ratios in the studied barites compared with those of the seawater at the time of barite formation (Middle Eocene with δ34S ratios of 20-22‰) is attributed to a

  17. Trapped radioactive isotopes for fundamental symmetry investigations

    Energy Technology Data Exchange (ETDEWEB)

    Willmann, Lorenz, E-mail:; Jungmann, Klaus; Onderwater, Cornelis J. G.; Timmermans, Rob G. E.; Wilschut, Hans W. [University of Groningen, KVI (Netherlands)


    Discrete symmetries tested in high precision atomic physics experiments provide guidance to model building beyond the Standard Model (SM). Here experimental opportunities arise for searches for permanent electric dipole moments (EDMs) and measurements of atomic parity violation (APV). Heavy atoms are favorable for such experiments since symmetry violating effects in atoms increase faster than the third power of the nuclear charge Z. Of special interest are isotopes of the heavy alkaline earth element radium (Z=88) since they offer large enhancement factors for EDMs and provide a new experimental road towards high precision measurements of atomic parity violation. These opportunities are exploited at the TRI{mu}P facility at KVI, Groningen.

  18. Trace Metals, Rare Earths, Carbon and Pb Isotopes as Proxies of Environmental Catastrophe at the Permian - Triassic Boundary in Spiti Himalayas, India (United States)

    Ghosh, N.; Basu, A. R.; Garzione, C. N.; Ghatak, A.; Bhargava, O. N.; Shukla, U. K.; Ahluwalia, A. D.


    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.

  19. Effect of para-substituents on alkaline earth metal ion extraction by proton di-ionizable calix[4]arene-crown-6 ligands in cone, partial-cone and 1,3-alternate conformations. (United States)

    Zhou, Hui; Liu, Dazhan; Gega, Jerzy; Surowiec, Kazimierz; Purkiss, David W; Bartsch, Richard A


    Two carboxylic acid or N-(X)sulfonyl carboxamide groups were incorporated into calix[4]arene-crown-6 compounds to afford di-ionizable ligands for use in divalent metal ion separations. Acidities of the N-(X)sulfonyl carboxamide groups were tuned by variation of the electron-withdrawing properties of X. Cone, partial-cone and 1,3-alternate conformations were obtained by different synthetic strategies and their structures verified by NMR spectroscopy. Competitive solvent extractions of alkaline earth metal cations from aqueous solutions into chloroform were performed and the results compared with those reported previously for di-ionizable p-tert-butylcalix[4]arene-crown-6 analogues to probe the influence of the para-substituent on the calix[4]arene scaffold on extraction selectivity and efficiency.

  20. Counterion influence on the vibrational wavenumbers in ternary and quaternary metal hydride salts, A2MH6 (A = alkali metal, alkaline earth, and lanthanides; M = Ir, Fe, Ru, Os, Pt, Mn). (United States)

    Gilson, Denis F R; Moyer, Ralph O


    The wavenumbers of the ν(3) metal-hydrogen stretching mode (T(1u)) in the IR spectra of both ternary and quaternary hexahydrido salts of transition metals from groups 7 to 10 ([Mn(I)H(6)](5-), [Fe(II)H(6)](4-), [Ru(II)H(6)](4-), [Os(II)H(6)](4-), [Ir(III)H(6)](3-), and [Pt(IV)H(6)](2-)) depend linearly upon the ionization energies of the counterions (alkali metal, alkaline earth, and lanthanide) with a separate line for each metal. This relationship provides quantitative support for the charge-transfer mechanism for explaining the stabilities of these compounds.

  1. 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


    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)

  2. Effect of alkaline earth oxides on the physical and spectroscopic properties of Dy3+- doped Li2O-B2O3 glasses for white emitting material application (United States)

    Shamshad, L.; Rooh, G.; Kirdsiri, K.; Srisittipokakun, N.; Damdee, B.; Kim, H. J.; Kaewkhao, J.


    Li2O-MO-B2O3:0.5Dy2O3 glasses mixed with four different alkaline earth modifier oxides MgO, CaO, SrO and BaO were synthesized by melt quench technique. Their physical properties like density, molar volume and refractive index were measured at room temperature and the effect of alkaline earth modifier oxides were studied. Also, optical absorption and photoluminescence spectra of these glasses have been acquired at room temperature. The Judd-Ofelt theory was effectively used to characterize these spectra and spectral intensities (ƒcal), Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) and certain radiative properties have been determined. Radiative life-times (τR), branching ratios (βcal), and emission cross-sections (σp) and optical gain parameters (σp × τR) were calculated from the Judd-Ofelt intensity parameters and the variation in these parameters with the variation of glass matrix are discussed. Yellow/Blue (Y/B) ratio and chromacity color coordinates (x,y) are calculated from the emission spectra which indicates the white light generation from all the investigated samples. The correlated color temperature (CCT) for the studied glasses is found to be 4418 K. The fluorescence decay time (τexp) of the 4F9/2 level of Dy3+ has been measured from the decay profiles and compared with calculated lifetimes (τcal). Among all the studied glass matrices, the glass containing BaO exhibits high value of branching ratio, large emission cross-section and high optical gain parameter for 6F9/2 → 6H13 at 575 nm. The results indicates the suitability of all the studied glasses for laser action and white light generation.

  3. Compound-specific carbon isotopes from Earth's largest flood basalt eruptions directly linked to the end-Triassic mass extinction. (United States)

    Whiteside, Jessica H; Olsen, Paul E; Eglinton, Timothy; Brookfield, Michael E; Sambrotto, Raymond N


    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.

  4. Production of the cosmogenic isotopes 3H, 7Be, 10Be, and 36Cl in the Earth's atmosphere by solar and galactic cosmic rays (United States)

    Webber, W. R.; Higbie, P. R.; McCracken, K. G.


    In a follow-up study to the earlier work of Webber and Higbie (2003) on 10Be production in the Earth's atmosphere by cosmic rays, we have calculated the atmospheric production of the cosmogenic isotopes 3H, 7Be, 10Be, and 36Cl using the FLUKA Monte Carlo code. This new calculation of atmospheric yields of these isotopes is based on 107 vertically incident protons at each of 24 logarithmically spaced energies from 10 MeV to 10 GeV, 102 times the number used in the earlier calculation, along with the latest cross sections. This permits a study of the production due to solar cosmic rays as well as galactic cosmic rays at lower energies where isotope production is a very sensitive function of energy. Solar cosmic ray spectra are reevaluated for all of the major events occurring since 1956. In terms of yearly production of 10Be, only the February 1956 solar event makes a major contribution. For 36Cl these yearly SCR production contributions are 2-5 times larger depending on the solar cosmic ray energy spectra. We have determined the yearly production of 10Be, 36Cl, and other cosmogenic isotopes above 65° geomagnetic latitude for the time period 1940-2006 covering six solar 11-year (a) cycles. The average peak-to-peak 11-a amplitude of this yearly production is 1.77. The effects of latitudinal mixing alter these direct polar production values considerably, giving an average peak-to-peak 11-a amplitude of 1.48 for the global average production.

  5. Silicon isotope fractionation during silica precipitation from aqueous solutions: Experimental and field evidence (Utrecht Studies in Earth Sciences 048)


    Geilert, S.


    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. 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


    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.

  7. The effect of the changing solar system environment on galactic cosmic ray propagation through the heliosphere: Consequences for cosmogenic isotope production in the Earth's atmosphere. (United States)

    Axford, W. I.; Florinski, V.; Zank, G. P.


    The solar system is traveling through highly inhomogeneous interstellar medium. Our galactic environment (the Local Bubble) is a vast region formed by supernova explosions filled with extremely tenuous fully ionized gas at a temperature of over a million K. Embedded in the Local Bubble are interstellar clouds ranging from cold (Twarm (T ˜ 104 K) and relatively tenuous (n ˜ 0.3 cm-1) partially ionized clouds, such as the Local Cloud where the Sun is currently located. The properties of the cloud control the size and shape of the heliosphere and, consequently, affect the propagation of galactic cosmic rays (GCRs) between the boundary of the modulation region (the heliopause) and Earth. GCRs with energies above several hundred MeV initiate nuclear reactions in the Earth's upper atmosphere producing radioactive isotopes of Beryllium and Carbon that are precipitated on the surface and eventually incorporated into sediments. It is then quite plausible that the history of the variability of the solar environment may be preserved in cosmogenic isotope records available from ice and sea sediment cores dating back more than 100,000 years. Previously, we showed that increasing the density of the cloud surrounding the solar system by a factor of 30 leads to an increase in 1 AU GCR fluxes by a factor of 1.5--3, and that cloud encounters may have been responsible for the observed peaks in 10Be records 35 and 60 thousand years ago. Extending our early model, we now calculate GCR distribution from the solution of the 2D Parker equation using the global model-calculated plasma and magnetic field parameters as a background to determine the diffusion coefficients. Initial results from a more comprehensive investigation of the global structure of the heliosphere embedded in clouds of varying density, from the present conditions in the Local Cloud to the extreme case of dense molecular clouds, are discussed.

  8. 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.


    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.)

  9. Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars (United States)

    Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.


    Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to

  10. Early differentiation of the silicate Earth : new constraints from isotopic investigation of rocks from the lunar highlands (United States)

    Boyet, M.; Carlson, R.; Borg, L.; Connelly, J.; Horan, M.


    The isotopic similarity in O, Mo, W, Si, and Fe between lunar and terrestrial samples suggests that the two planetary bodies were equilibrated in the energetic aftermath of the giant impact that gave birth to the Moon [1]. Coupled 142Nd-143Nd isotope systematics of lunar samples including both low-Ti and high-Ti mare basalts along with KREEP basalts have been used to constrain the age of crystallization of the lunar interior [2-5]. These studies show that the Sm-Nd system in the lunar mantle closed in the interval of 180-250 Ma after the beginning of solar system formation, depending on the model considered for lunar mantle differentiation (1 or 2 stage-model and initial lunar Sm/Nd ratio). Does this age represent the age of Moon formation? A prolonged lunar magma ocean (LMO) might be expected given the insulating effect of the thick plagioclase crust, so closure of the Sm-Nd system in the lunar mantle, particularly in a late stage LMO component like KREEP, might substantially post-date lunar formation. We have recently determined a new age of 4360±3 Ma for the ferroan anorthosite (FAN) 60025 using the 207Pb-206Pb, 147Sm-143Nd and 146Sm-142Nd isotope systems [6]. This study is the first in which a single sample of FAN yielded consistent ages from multiple isotope dating techniques, strongly suggesting that this age indicates the time at which the sample crystallized. In order to pursue the question of whether Moon formation occurred over 100 Ma after solar system formation, we have investigated a number of lunar rocks sampling the highland crust from both the FAN and the Mg-suite groups. Internal Sm-Nd isochron on the norite 77215 yields an age of 4296±20 Ma, in agreement with the young age determined on 60025. We will show that our new data obtained on the 146Sm-142Nd systematics of the lunar crust support the scenario of a relative young age for the Moon. Thus, these results offer a unique opportunity to better constrain the composition of the terrestrial

  11. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals. (United States)

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo


    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

  12. Synthesis and alkaline earth metal cation extraction by proton di-ionizable p-tert-butylcalix[4]arene-crown-5 compounds in cone, partial-cone and 1,3-alternate conformations. (United States)

    Zhou, Hui; Surowiec, Kazimierz; Purkiss, David W; Bartsch, Richard A


    Synthetic strategies for novel, proton di-ionizable p-tert-butylcalix[4]arene-crown-5 compounds in cone, partial-cone and 1,3-alternate conformations are reported. Selective linkage of the two diametrical phenolic oxygens in p-tert-butylcalix[4]arene with tetraethylene glycol ditosylate gave 1,3-bridged p-tert-butylcalix[4]arene-crown-5. The two remaining phenolic units were alkylated using NaH and KH as the bases to give the cone and partial-cone conformers, respectively. Preparation of the 1,3-alternate conformers utilized a different sequence in which O-alkylation was followed by crown ether ring formation. Structures of these new ligands were elucidated by (1)H and (13)C NMR spectroscopy. These proton-ionizable ligands were tested for their solvent extraction properties toward alkaline earth metal cations. Surprising differences in their extraction behaviors are noted compared to those reported previously for di-ionizable p-tert-butylcalix[4]arenecrown-6 analogues.

  13. Eu(2+)-Activated Alkaline-Earth Halophosphates, M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) for NUV-LEDs: Site-Selective Crystal Field Effect. (United States)

    Kim, Donghyeon; Kim, Sung-Chul; Bae, Jong-Seong; Kim, Sungyun; Kim, Seung-Joo; Park, Jung-Chul


    Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → Cl → Br (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

  14. Coordination of alkaline earth metal ions in the inverted cucurbit[7]uril supramolecular assemblies formed in the presence of [ZnCl4]2- and [CdCl4]2-. (United States)

    Li, Qing; Zhang, Yun-Qian; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu; Xiao, Xin


    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.

  15. 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)


    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).

  16. Effect of Ca{sup 2+} and Sr{sup 2+} alkaline earth ions on luminescence properties of BaAl{sub 12}O{sub 19}:Eu nanophosphor

    Energy Technology Data Exchange (ETDEWEB)

    Deshmukh, Abhay D., E-mail: [National Environmental Engineering Research Institute, Nagpur 440020 (India); Department of Metallurgical and Materials Engineering, VNIT, Nagpur 440011 (India); Valechha, Arti; Valechha, Dolly; Kumar, Animesh [National Environmental Engineering Research Institute, Nagpur 440020 (India); Peshwe, D.R. [Department of Metallurgical and Materials Engineering, VNIT, Nagpur 440011 (India); Dhoble, S.J. [Kamla Nehru College, Sakkardara Square, Nagpur 440009 (India)


    Nanosized barium aluminate materials was doped by divalent cations (Ca{sup 2+}, Sr{sup 2+}) and Eu{sup 2+} having nominal compositions Ba{sub 1-x}MxAl{sub 12}O{sub 19}:Eu (M=Ca and Sr) (x=0.1-0.5), were synthesized by the combustion method. These phosphors were characterized by XRD, scanning electron microscopy-energy-dispersive spectrometry (SEM-EDS) and photoluminescence measurement. The photoluminescence characterization showed the presence of Eu ion in divalent form which gave emission bands peaking at 444 nm for the 320 nm excitation (solid-state lighting excitation), while for 254 nm it gave the same emission wavelength of low intensity (1.5 times) compared to 320 nm excitation. It was also observed that alkaline earth metal (Ca{sup 2+} and Sr{sup 2+}) dopants increase the intensity of Eu{sup 2+} ion in BaAl{sub 12}O{sub 19} lattice, thus this phosphor may be useful for solid-state lighting.

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

    DEFF Research Database (Denmark)

    Kunzendorf, Helmar; Wollenberg, H.A.


    by the least-squares method to yield the fractions of La, Ce, Pr, and Nd in the samples. A calibration was established between the fractions of Ce and Nd and their abundances determined by mass spectrometry. Statistical considerations indicated that detection limits are of the order of 10 ppm. An X......-ray spectrometric scan of a longitudinally sliced drill core showed a close correlation between rare-earth abundances and appropriate minerals....

  18. PGE, Re-Os, and Mo isotope systematics in Archean and early Proterozoic sedimentary systems as proxies for redox conditions of the early Earth (United States)

    Siebert, C.; Kramers, J. D.; Meisel, Th.; Morel, Ph.; Nägler, Th. F.


    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

  19. 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


    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.)

  20. Chemical and Isotopic Heterogeneities in the Deep Earth:Importance of Lower Mantle Carbonate-rich Melts (United States)

    Collerson, K. D.; Williams, Q.; Murphy, D.


    Evolution of mantle chemical heterogeneity reflects a spectrum of processes. Nature of reservoirs has been inferred from radiogenic isotope and trace element systematics of mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) [1]. Carbonatites, kimberlites and lamproites [2-4] also sample depleted and enriched reservoirs, however, their origin remains equivocal. Secular decrease in Th/U ratio in MORB mantle (DMM), homogeneity of Th/U inferred from Pb-isotopic data, and systematic variation in Nb/Th and Nb/U ratios in MORBs [5], show that recycled components in DMM are well mixed. Thus isotopically hererogeneous domains in DMM must be transient features and are unlikely to yield HIMU and EM chemistries. Explanations for HIMU and EM OIB chemistries include involvement of: (1) subcontinental lithospheric mantle; (2) subducted oceanic lithosphere; (3) subducted sediment; or (4) an enigmatic lower mantle (LM) "plume component". Elevated 3He/4He in OIBs and kimberlites [6] and excess 129Xe and high 40Ar/39Ar [e.g., 7-8] and solar 20Ne/22Ne [9] in carbonatites indicate that they were derived from a primitive, isolated, and less degassed source than MORB. Primordial compositions show that this reservoir escaped atmospheric contamination by Ar, Xe, and Ne and pollution by 4He-rich material (from recycled 238U) during subduction. This primitive reservoir likely exists below the depth subducted slabs obviously penetrate (ca. 1700 km) e.g., [10]. That kimberlites are deeply sourced is also shown by lower mantle inclusions in diamond, e.g., [11]. Importantly, Gp. 1 and 2 kimberlites are isotopically similar to HIMU and EM-1 OIBs [4]. We interpret Gp 1 kimberlites as mixtures of HIMU and EM sources, while Gp. 2 kimberlites (close to EM-1) are interpreted as melts of a Ca perovskite-rich reservoir, possibly from slabs in the LM. We model melting of LM phases to simulate evolution of EM1 and HIMU 87Sr/86Sr, 143Nd/144Nd, 176Hf/177Hf, 207Pb/204Pb, 206Pb/204Pb and 208Pb/204

  1. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields (United States)

    Tomza, Michał


    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. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the 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 the quantum states of both reactants and products.

  2. 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 (United States)

    Zhang, Qichao; Liu, Yan; Huang, He; Wu, Zhenhan; Zhou, Qing


    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.

  3. 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


    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.

  4. The influence of different alkaline earth oxides on the structural and optical properties of undoped, Ce-doped, Sm-doped, and Sm/Ce co-doped lithium alumino-phosphate glasses (United States)

    Othman, H. A.; Arzumanyan, G. M.; Möncke, D.


    Undoped, singly Sm doped, Ce doped, and Sm/Ce co-doped lithium alumino-phosphate glasses with different alkaline earth modifiers were prepared by melt quenching. The structure of the prepared glasses was investigated by FT-IR and Raman, as well as by optical spectroscopy. The effect of the optical basicity of the host glass matrix on the added active dopants was studied, as was the effect doping had on the phosphate structural units. The optical edge shifts toward higher wavelengths with an increase in the optical basicity due to the increased polarizability of the glass matrix, but also with increasing CeO2 concentration as a result of Ce3+/Ce4+ inter valence charge transfer (IV-CT) absorption. The optical band gap for direct and indirect allowed transitions was calculated for the undoped glasses. The glass sample containing Mg2+ modifier ions is found to have the highest value (4.16 eV) for the optical band gap while Ba2+ has the lowest value (3.61 eV). The change in the optical band gap arises from the structural changes and the overall polarizability (optical basicity). Refractive index, molar refractivity Rm and molar polarizability αm values increase with increasing optical basicity of the glasses. The characteristic absorption peaks of Sm3+ were also investigated. For Sm/Ce co-doped glasses, especially at high concentration of CeO2, the absorption of Ce3+ hinders the high energy absorption of Sm3+ and this effect becomes more obvious with increasing optical basicity.

  5. 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.))


    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.

  6. Alkaline earth stannates: The next silicon?

    Energy Technology Data Exchange (ETDEWEB)

    Ismail-Beigi, Sohrab, E-mail:; Ahn, Charles H. [Department of Applied Physics, Yale University, New Haven, Connecticut 06520 (United States); Department of Physics, Yale University, New Haven, Connecticut 06520 (United States); Department of Mechanical Engineering and Materials Science, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structure and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Walker, Frederick J. [Department of Applied Physics, Yale University, New Haven, Connecticut 06520 (United States); Center for Research on Interface Structure and Phenomena, Yale University, New Haven, Connecticut 06520 (United States); Cheong, Sang-Wook [Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854 (United States); Rutgers Center for Emergent Materials, Rutgers University, Piscataway, New Jersey 08854 (United States); Rabe, Karin M. [Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854 (United States)


    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.

  7. Alkaline earth stannates: The next silicon?

    Directory of Open Access Journals (Sweden)

    Sohrab Ismail-Beigi


    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.


    decreases with increasing temperature; and the temperature dependance is stronger for SrF2. The results have been interpreted using the Simanek-Orbach theory of a phonon-induced hyperfine field. (Author)

  9. Positron elastic scattering from alkaline earth targets (United States)

    Poveda, Luis A.; Assafrão, Denise; Mohallem, José R.


    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

  10. Electrical properties of alkaline earth fluorohalide crystals

    Energy Technology Data Exchange (ETDEWEB)

    Ayachour, D. (Lab. PHASE, C.R.N., 67 - Strasbourg (France)); Sieskind, M. (Groupe d' Optique, Non-Lineaire, 67 - Strasbourg (France)); Geist, P. (C.R.N.-G.O.P.A., 67 - Strasbourg (France))


    The ionic conductivity of undoped BaFCl, BaFBr, BaFI, SrFCl, and SrFBr single crystals is measured. The activation energies for a variety of anion vacancy mechanisms and the Schottky energy are defined. They are found to be in good agreement with Baetzold's theoretical data. Partial measurements of the static dielectric constant point out that these materials show an important dipolar contribution which is connected with their antiferroelectric character. (orig.).

  11. 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 (United States)

    Kuleshova, A. I.; Dergachev, V. A.; Kudryavtsev, I. V.; Nagovitsyn, Yu. A.; Ogurtsov, M. G.


    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.

  12. Tholeiitic and calc-alkaline magma series at Adatara volcano, northesast Japan. ; Evolution mechanisms and genetic relationship. Tohoku Nippon, Adatara kazan ni okeru soreaito, karuku alkaline magma keiretsu. ; Sono shinka mechanism to seiin kankei

    Energy Technology Data Exchange (ETDEWEB)

    Fujinawa, A. (Ibaraki University, Ibaraki (Japan). Faculty of Science)


    In this report, the generation and evolution processes of coexisting low-alkali tholeiitic and calc-alkaline magmas at Adatara volcano is discussed on the basis of petrological data, and a reasonable petrological model is proposed. For the tholeiitic suite, variations of major-, trace- and rare earth-elements and Sr isotopic compositions are explained with the fractional crystallization hypothesis. These are mineralogical observations supporting this hypothesis. In contrast, for calc-alkaline suite, compositional variations of considerable numbers of major-elements and trace-elements are explained with the fractional crystallization model, but wide variations of Ni and Cr, and light REE heavy-REE ratios are inconsistent with this model. It is considered that other processes, such as mixing of magmas, assimilation and gaseous transfer, may have operated as additional processes. Also, mineralogical data are compatible with this view. 62 refs., 8 figs., 2 tabs.

  13. Chemostratigraphy of stable chromium isotopes in cap carbonate sequences - tracing the aftermath of Earth's Neoproterozoic icehouse climates (United States)

    Frei, R.; de Andrade Caxito, F.; Gaucher, C.


    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

  14. Water mass circulation and weathering inputs in the Labrador Sea based on coupled Hf-Nd isotope compositions and rare earth element distributions (United States)

    Filippova, Alexandra; Frank, Martin; Kienast, Markus; Rickli, Jörg; Hathorne, Ed; Yashayaev, Igor M.; Pahnke, Katharina


    The Labrador Sea is one of the key areas for deep water formation driving the Atlantic thermohaline circulation and thus plays an important role in Northern Hemisphere climatic fluctuations. In order to better constrain the overturning processes and the origins of the distinct water masses, combined dissolved Hf-Nd isotopic compositions and rare earth element (REE) distribution patterns were obtained from four water depth profiles along a section across the Labrador Sea. These were complemented by one surface sample off the southern tip of Greenland, three shallow water samples off the coast of Newfoundland, and two deep water samples off Nova Scotia. Although light REEs are markedly enriched in the surface waters off the coast of Newfoundland compared to north Atlantic waters, the REE concentration profiles are essentially invariant throughout the water column across the Labrador Sea. The hafnium concentrations of surface waters exhibit a narrow range between 0.6 and 1 pmol/kg but are not significantly higher than at depth. Neodymium isotope signatures (ɛNd) vary from unradiogenic values between -16.8 and -14.9 at the surface to more radiogenic values near -11.0 at the bottom of the Labrador Sea mainly reflecting the advection of the Denmark Strait Overflow Water and North East Atlantic Deep Water, the signatures of which are influenced by weathering contributions from Icelandic basalts. Unlike Nd, water column radiogenic Hf isotope signatures (ɛHf) are more variable representing diverse weathering inputs from the surrounding landmasses. The least radiogenic seawater ɛHf signatures (up to -11.7) are found in surface waters close to Greenland and near the Canadian margin. This reflects the influence of recirculating Irminger Current Waters, which are affected by highly unradiogenic inputs from Greenland. A three to four ɛHf unit difference is observed between Denmark Strait Overflow Water (ɛHf ∼ -4) and North East Atlantic Deep Water (ɛHf ∼ -0

  15. 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


    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

  16. 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


    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.

  17. 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


    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。

  18. 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


    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

  19. The Earth's early evolution. (United States)

    Bowring, S A; Housh, T


    The Archean crust contains direct geochemical information of the Earth's early planetary differentiation. A major outstanding question in the Earth sciences is whether the volume of continental crust today represents nearly all that formed over Earth's history or whether its rates of creation and destruction have been approximately balanced since the Archean. Analysis of neodymium isotopic data from the oldest remnants of Archean crust suggests that crustal recycling is important and that preserved continental crust comprises fragments of crust that escaped recycling. Furthermore, the data suggest that the isotopic evolution of Earth's mantle reflects progressive eradication of primordial heterogeneities related to early differentiation.

  20. Earth science: Extraordinary world (United States)

    Day, James M. D.


    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

  1. 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


    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

  2. Energetics and control of ultracold isotope-exchange reactions between heteronuclear dimers in external fields

    CERN Document Server

    Tomza, Michał


    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.

  3. 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 (United States)

    Stille, P.; Tatsumoto, M.


    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.

  4. Anodes for alkaline electrolysis (United States)

    Soloveichik, Grigorii Lev


    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.

  5. Oxygen isotope perspective on crustal evolution on early Earth: A record of Precambrian shales with emphasis on Paleoproterozoic glaciations and Great Oxygenation Event (United States)

    Bindeman, I. N.; Bekker, A.; Zakharov, D. O.


    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

  6. Alkaline battery operational methodology (United States)

    Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael


    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.

  7. 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


    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)

  8. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth's atmosphere. (United States)

    Whitehill, Andrew R; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei


    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.

  9. Uranium in alkaline rocks

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, M.; Wollenberg, H.; Strisower, B.; Bowman, H.; Flexser, S.; Carmichael, I.


    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.

  10. The Archean kalsilite-nepheline syenites of the Awsard intrusive massif (Reguibat Shield, West African Craton, Morocco) and its relationship to the alkaline magmatism of Africa (United States)

    Haissen, Faouziya; Cambeses, Aitor; Montero, Pilar; Bea, Fernando; Dilek, Yildirim; Mouttaqi, Abdellah


    More than 40% of the known alkaline complexes are reported from Africa. Most are ring complexes composed of syenites and associated or not, lithotypes as carbonatites, granites and mafic rocks. Radiometric dating indicates the presence of alkaline complexes with ages spanning from Precambrian to the present. In terms of outcrops, alkaline complexes are reported from cratonic zones and from belts embedded between cratonic areas. Because of the high economic potential for associated REE deposits, these alkaline complexes have received much attention from Earth scientists. These studies aim mainly to constrain the role of the mantle and the crust (and the interaction between them) in the genesis of this peculiar magmatism, and also to explain the variability observed in lithotypes and geotectonic settings. Among those alkaline complexes, Precambrian occurrences are rare. Up-to-date only a few Proterozoic examples were cited in Africa. The recently studied Awsard complex in Southern Morocco is a peculiar one with a crystallization age of 2.46 Ga and an unusual rock assemblages. This paper is a first approximation to a comparison of geochemical and isotopic fingerprints of the Awsard magmatism (as the oldest one) with other known different ages African complexes from different geotectonic settings, aiming to detect if there is any evolution in this alkaline magmatism through time. A first conclusion is that magma sources for this alkaline magmatism has been probably evaluating over geological time, from parental magmas compositions close to that of primitive mantle in these early geological time to compositions holding more and more depleted mantle and continental crust components. However, to go further in this debate more modern isotopic, geochemical and geochronological data from all these complexes are needed. Nevertheless, this comparison highlighted the peculiar character of the Awsard magmatism with an isotopic composition very close to that of Primitive mantle

  11. Methods of isotopic geochronology (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.

  12. Isotope shifts of 6s5d $^3$D-states in neutral Barium

    CERN Document Server

    Dammalapati, U; Jungmann, K; Willmann, L


    Laser spectroscopy of the low lying $^1$P and $^3$D states in atomic barium has been performed. This work contributes substantially to the development of an effective laser cooling and trapping for heavy alkaline earth elements and aims in particular for a better understanding of the atomic wave function of these systems. Isotope shifts and hyperfine structures are ideal probes for the wave functions at the position of the nucleus. This is essential input for a theoretical evaluation of the sensitivity to fundamental symmetry breaking properties like permanent electric dipole moments. We report the first isotope shift measurements of the $^3$D$_{1,2}$-$^1$P$_1$ transitions. A deviation of the King plot from its expected behavior has been observed. Further we have optically resolved the hyperfine structure of the $^3$D$_{1,2}$ states.

  13. Development and validation of a single collector ICPMS procedure to determine boron isotopeic compositions of water and food samples (United States)

    Vogl, Jochen; Rosner, Martin; Pritzkow, Wolfgang


    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.

  14. 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

    Energy Technology Data Exchange (ETDEWEB)

    Yu Kefu [South China Sea Institute of Oceanology, Chinese Academy of Sciences, 164 West Xin-Gang Road, Guangzhou 510301 (China) and Radiogenic Isotope Laboratory, Centre for Microscopy and Microanalysis (CMM), University of Queensland, Qld 4072 (Australia)]. E-mail:; Kamber, Balz S. [Radiogenic Isotope Laboratory, Centre for Microscopy and Microanalysis (CMM), University of Queensland, Qld 4072 (Australia); Department of Earth Sciences, Laurentian University, Sudbury, ONP3E2C6 (Canada); Lawrence, Michael G. [Radiogenic Isotope Laboratory, Centre for Microscopy and Microanalysis (CMM), University of Queensland, Qld 4072 (Australia); Greig, Alan [Radiogenic Isotope Laboratory, Centre for Microscopy and Microanalysis (CMM), University of Queensland, Qld 4072 (Australia); School of Earth Sciences, University of Melbourne, Vic. 3010 (Australia); Zhao Jianxin [Radiogenic Isotope Laboratory, Centre for Microscopy and Microanalysis (CMM), University of Queensland, Qld 4072 (Australia)


    Annual variations from 1982 to 1999 of a wide range of trace elements and reconnaissance Pb isotopes ({sup 207}Pb/{sup 206}Pb and {sup 208}Pb/{sup 206}Pb) 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.

  15. 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 (United States)

    Yu, Ke-Fu; Kamber, Balz S.; Lawrence, Michael G.; Greig, Alan; Zhao, Jian-Xin


    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.


    Institute of Scientific and Technical Information of China (English)


    <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 -

  17. Silicon isotopes: from cosmos to benthos


    Chakrabarti, Ramananda


    Silicon is the second most abundant element on the Earth and one of the more abundant elements in our Solar System. Variations in the relative abundance of the stable isotopes of Si (Si isotope fractionation) in different natural reservoirs, both terrestrial (surface and deep Earth) as well as extra-terrestrial (e.g. meteorites, lunar samples), are a powerful tracer of present and past processes involving abiotic as well as biotic systems. The versatility of the Si isotope tracer is reflected...

  18. 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


    % 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...

  19. Major element composition of an Early Enriched Reservoir: constraints from 142Nd/144Nd isotope systematics in the early Earth and high-pressure melting experiments of a primitive peridotite (United States)

    Kondo, Nozomi; Yoshino, Takashi; Matsukage, Kyoko N.; Kogiso, Tetsu


    The Accessible Silicate Earth (ASE) has a higher 142Nd/144Nd ratio than most chondrites. Thus, if the Earth is assumed to have formed from these chondrites, a complement low-142Nd/144Nd reservoir is needed. Such a low-142Nd/144Nd reservoir is believed to have been derived from a melt in the early Earth and is called the Early Enriched Reservoir (EER). Although the major element composition of the EER is crucial for estimating its chemical and physical properties (e.g., density) and is also essential for understanding the origin and fate of the EER, which are both major factors that determine the present composition of the Earth, it has not yet been robustly established. In order to determine the major element composition of the EER, we estimated the age and pressure-temperature conditions to form the EER that would best explain its Nd isotopic characteristics, based on Sm-Nd partitioning and its dependence on pressure, temperature, and melting phase relations. Our estimate indicates that the EER formed within 33.5 Myr of Solar System formation and at near-solidus temperatures and shallow upper-mantle pressures. We then performed high-pressure melting experiments on primitive peridotite to determine the major element composition of the EER at estimated temperature at 7 GPa and calculated the density of the EER. The result of our experiments indicates that the near-solidus melt is iron-rich komatiite. The estimated density of the near-solidus melt is lower than that of the primitive peridotite, suggesting that the EER melt would have ascended in the mantle to form an early crust. Given that high mantle potential temperatures are assumed to have existed in the Hadean, it follows that the EER melt was generated at high pressure and, therefore, its composition would have been picritic to komatiitic. As the formation age of the EER estimated in our study precedes the last giant, lunar-forming impact, the picritic to komatiitic crust (EER) would most likely have been

  20. 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


    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.

  1. 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 (United States)

    Frank, M.; Bosse, L. M.; Grasse, P.; Pahnke, K.; Hathorne, E. C.


    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.

  2. A systemic study of stepwise chlorination-chemical vapor transport characteristics of pure rare earth oxides from Sc{sub 2}O{sub 3} to Lu{sub 2}O{sub 3} mediated by alkaline chlorides as complex former

    Energy Technology Data Exchange (ETDEWEB)

    Sun Yanhui [School of Chemistry and Environment, South China Normal University, Guangzhou 510631 (China)]. E-mail:; He Peng [Department of Ecology, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Chen Huani [School of Chemistry and Environment, South China Normal University, Guangzhou 510631 (China)


    A systematic study has been carried out for the stepwise chlorination-chemical vapor transport (SC-CVT) characteristics of pure rare earth oxides from Sc{sub 2}O{sub 3} to Lu{sub 2}O{sub 3} mediated by the vapor complexes KLnCl{sub 4} and NaLnCl{sub 4} (Ln = Sc, Y and La-Lu) used NaCl and KCl as complex former, respectively. The results showed that the SC-CVT characteristics are similarly for NaCl and KCl as complex former, the main deposition temperature of the rare earth chlorides LnCl{sub 3} is in the increasing order ScCl{sub 3} < YCl{sub 3} < LaCl{sub 3}, and then with a systematically decreasing trend from the early lanthanide chlorides to the end one. The results also showed that the total transported amount of the produced chlorides is YCl{sub 3} > ScCl{sub 3}, and they are much higher than that of most lanthanoid chlorides. For lanthanoids, the total transported amount of chloride increases systematically from the early lanthanoid chlorides to the end one except for EuCl{sub 3} and GdCl{sub 3} mediated by KCl and NaCl as complex former, respectively, which showed the divergence effect of Gd in the total transport efficiency. But there are some differences in SC-CVT characteristics of pure rare earth oxide mediated by KCl and NaCl as complex former, that is the main deposition temperature region for the same rare earth element was lower for KCl than that for NaCl as complex former except for LaCl{sub 3}, CeCl{sub 3}, YbCl{sub 3} and LuCl{sub 3}, while the total transport amount of rare earth chloride for KCl as complex former is higher than that for NaCl except for LaCl{sub 3} and EuCl{sub 3}. More over, the discussion was carried out for Sc and Y on the one hand and the lanthanides contain 4f electron as another hand based on the 4f electron hybridization assumption. Further more, the transport characteristics of rare earth oxides with alkaline chlorides as complex former in this study were compared to that with AlCl{sub 3} as complex former.

  3. Alkaline broadening in Stars

    CERN Document Server

    De Kertanguy, A


    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.

  4. Stages of weathering mantle formation from carbonate rocks in the light of rare earth elements (REE) and Sr-Nd-Pb isotopes (United States)

    Hissler, Christophe; Stille, Peter


    Weathering mantles are widespread and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual high content of associated trace elements in weathering mantles originating from carbonate rocks, which have been poorly studied, compared to those developing on magmatic bedrocks. For instance, these enrichments can be up to five times the content of the underlying carbonate rocks. However, these studies also showed that the carbonate bedrock content only partially explains the soil enrichment for all the considered major and trace elements. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources. REE distribution patterns and Sr-Nd-Pb isotope ratios have been used because they are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments have been applied to identify mobile phases in the soil system and to yield information on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. All these geochemical informations indicate that the cambisol developing on such a typical weathering mantle ("terra fusca") has been formed through weathering of a condensed Bajocian limestone-marl facies. This facies shows compared to average world carbonates important trace element enrichments. Their trace element distribution patterns are similar to those of the soil

  5. Nd isotope composition and rare earth element distribution in early Paleozoic biogenic apatite from Baltoscandia: A signature of Iapetus ocean water (United States)

    Felitsyn, Sergei; Sturesson, Ulf; Popov, Leonid; Holmer, Lars


    Analyses of the Nd isotopic composition and REE distribution in biogenic apatite (organophosphatic brachiopods and conodont elements) from the Cambrian and Ordovician sequences of the Baltic plate give new insights into the development of the southeastern segment of the continental margin bounding the Iapetus ocean. The Nd isotope analyses show ɛNd(t) of ˜-8.0 for the Cambrian, indicating that the main source of the sedimentary deposition came from weathered sedimentary rocks of Vendian and Cambrian age. The increase of ɛNd(t) to ˜-5.0 for the Early Ordovician indicates the appearance of a new source of radiogenic Nd in the surrounding area—most likely a volcanic arc along the western borderland of Baltic plate from Arenigian time. Samples of Cambrian biogenic apatite show significantly lower total amounts of REE than do the Ordovician samples, and this is probably due to a shorter exposure to seawater before burial during Ordovician sedimentary accumulation in Baltoscandia. These preliminary results suggest that biogenic apatite from the Baltoscandian basin preserves geochemical signatures of the water masses that will be important for understanding the evolution of the Iapetus ocean during the early Paleozoic.

  6. The rainfall limit of the soil N cycle on Earth: stable isotopes of N and O in arid to hyperarid soils of the Atacama Desert, Chile (United States)

    Ewing, S. A.; Wankel, S. D.; Michalski, G.; Kendall, C.; Thiemens, M. H.; Amundson, R.


    Triple oxygen isotope analysis (Δ17O) provides a powerful tracer of nitrate formed by photochemical oxidation in the atmosphere. The resulting high, positive values of Δ17O are extremely sensitive to biological N cycling in the biosphere, which rapidly eliminates the photochemical signal through in-situ nitrate production (Δ17O = 0‰), coupled with uptake or other transformation of atmospheric nitrate. In surface waters, pulses of nitrate with high Δ17O values signal flushing by stormflow. In soil nitrate, high Δ17O values have provided an indicator of long-term hyperaridity in the Atacama Desert and Antarctica, where the photochemical signal is preserved as a function of extremely limited soil moisture, and thus extremely limited biology. Yet a relationship between nitrate Δ17O and nitrate δ15N values has proved elusive, despite control of both parameters by biology. We applied coupled analysis of Δ17O and δ15N in soil nitrate to a series of arid to hyperarid soils (21-2 mm rain y-1) in the Atacama Desert. These soils represent the transition from biotic soils, in which N is rapidly cycled and mostly present in organic forms (ON), to largely abiotic, hyperarid soils in which both atmospheric nitrate and ON accumulate. Detailed depth trends indicate that controls on soil non- atmospheric nitrate isotope values become increasingly abiotic as rainfall decreases and nitrate Δ17O values increase. In the most hyperarid soil, Δ17O values indicate that 80% of soil nitrate is unaltered atmospheric deposition, and vary by only ~3 ‰ with depth. Yet nitrate δ15N values increase from -2 to +8 ‰ with depth - the greatest variation among the three soils. The depth integrated nitrate δ15N value for this soil is 5.3 ‰, more enriched than surface values, likely deposition values, and values in the less arid soils. This suggests that even under conditions of accumulating atmospheric N in soils, with minimal biological activity and dissolved loss, in-situ nitrate

  7. 二价碱土金属氟化物对Er3+/Tm3+/Yb3+共掺氟氧锗酸盐玻璃热稳定性和光谱特性影响的研究%Effect of Bivalent Alkaline Earth Fluorides Introduction on Thermal Stability and Spectroscopic Properties of Er3+/Tm3+/Yb3+ Co-Doped Oxyfluorogermanate Glasses

    Institute of Scientific and Technical Information of China (English)

    胡曰博; 张新娜; 周大利; 焦清; 王荣飞; 黄劲峰; 龙晓波; 邱建备


    制备了分别含有MgF2,CaF2,SrF2或BaF2的Er3+/Tm3+/Yb3+共掺氟氧锗酸盐玻璃试样和包含BaF2纳米晶的玻璃陶瓷试样,所制备试样均具有良好的透光性.对试样的热稳定性和上转换发光特性进行了研究.通过分析试样的吸收光谱发现,随着所含二价阳离子原子量的增大,试样的紫外吸收截止波长明显向短波方向移动.结果显示:通过改变所含二价碱土金属离子的种类能够对激发光的颜色进行调节,特别值得关注的是Mg2+的影响;结果证实:通过对包含二价碱土金属的玻璃进行微晶化处理或者增加二价碱土金属的含量均能提高上转换发光的强度.%Transparent Er3+ /Tm3+ /Yb3+ co-doped oxyfluorogermanate glasses alone containing MgF2, CaF2, SrF2 or BaF2 and nano-glass-ceramics only containing BaF2 were prepared. The thermal stabilities and the up-conversion emission properties of the samples were investigated. Analyses of absorbance spectra reveal that the UV cutoff band moves slightly to shortwave band with the doping bivalent cation mass increasing. The results show that the emission color can be adjusted by changing the alkaline earth cation species in the glass matrixes, especially as Mg2+ is concerned, and the emission intensity can increase notably by heating the glass containing alkaline-earth fluoride into glass ceramic containing alkaline-earth fluoride nanocrystals or increasing the content of bivalent alkaline earth fluorides.

  8. Metasomatized lithosphere and the origin of alkaline lavas. (United States)

    Pilet, Sébastien; Baker, Michael B; Stolper, Edward M


    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.

  9. 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


    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.

  10. 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)


    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.

  11. An alkaline element

    Energy Technology Data Exchange (ETDEWEB)

    Arita, T.; Murakami, K.; Okha, K.


    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.

  12. 生物活性稀土梯度涂层在碱液环境中的电极化后处理%Electric polarized post treatment of rare earth active bioceramic gradient coating in alkaline solution

    Institute of Scientific and Technical Information of China (English)

    汪震; 刘其斌; 肖明; 杨邦成


    To improve the quality of rare earth active bioceramic gradient coatings,a method of electric polarized treatment(PAS) was used to post-process the gradient coatings fabricated by wide band laser cladding in alkali liquid.The phases and corrosion resistance of the bioceramic coatings were analyzed by XRD and an electrochemical analyzer.The bioceramic coatings were immersed in simulated body fluid(SBF) to examine its bioactivity and its electrical charge.The experimental results indicate that PAS treatment not only improves the crystallinity of the coatings,but also is favourable to transform additional phases into hydroxyapatite.PAS treatment exhibits a little effect on corrosion resistance of the bioceramic coatings.Compared with as-received coatings,the coatings treated by PAS are of better bioactivity and more negative charge.%为了改善活性生物稀土梯度涂层的质量,在碱液环境中采用电极化处理法(PAS)对宽带激光熔覆生物活性稀土梯度涂层进行后处理。利用XRD和电化学分析仪对涂层的相组成和耐腐蚀性进行了研究,通过模拟体液浸泡试验考察了生物陶瓷涂层的生物活性和涂层表面的电荷分布情况。结果表明,碱液环境中电极化处理法(PAS)能够提高涂层的结晶度,使涂层中的非晶相、杂相向羟基磷灰石转化。PAS对涂层的耐腐蚀性影响不大。与未处理涂层相比,PAS处理后的涂层生物活性更好,且涂层表面产生了更多的负电荷。

  13. Zinc isotopic compositions of breast cancer tissue. (United States)

    Larner, Fiona; Woodley, Laura N; Shousha, Sami; Moyes, Ashley; Humphreys-Williams, Emma; Strekopytov, Stanislav; Halliday, Alex N; Rehkämper, Mark; Coombes, R Charles


    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.

  14. Oxygen Isotopes in Meteorites (United States)

    Clayton, R. N.


    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 (shielding in the UV photodissociation of CO (van Dishoeck and Black, 1988). This process results from the large differences in abundance between C16O, on the one hand, and C17O and C18O on the other. Photolysis of CO occurs by absorption of stellar UV radiation in the

  15. Earth System Governance: Facing the Challenges of Climate Change

    Directory of Open Access Journals (Sweden)

    Susana Camargo Vieira


    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.

  16. Physicochemical study of alkaline earth metal and magnesium maleates

    Energy Technology Data Exchange (ETDEWEB)

    Koblova, O.E.; Vdovina, L.M.; Frolova, L.A. (Saratovskij Gosudarstvennyj Univ. (USSR); Saratovskij Gosudarstvennyj Pedagogicheskij Inst. (USSR))


    Magnesium, calcium, strontium and barium maleates are synthesized. Their thermal stability in the atmosphere of air and argon is studied. It is shown that the dehydration of initial salts proceeds in the temperature range of 100-300 deg C. The decomposition of anhydrous salts takes place in the temperature range of 380-600 deg C. The values of the effective activation energy are determined.

  17. Alkaline earth oxide nanoparticles as destructive absorbents for environmental toxins

    Energy Technology Data Exchange (ETDEWEB)

    Moscovici, J.; Latreche, K. [Univ. Paris XII, Groupe de Physique des Milieux Denses, Creteil (France); Michalowicz, A. [Univ. Paris Sud, LURE, Orsay (France); Decker, S.; Lagadic, I.; Klabunde, K. [Kansas State Univ., Chemistry Dept., Manhattan, Kansas (United States)


    Sr and Ca oxide nanoparticles are very reactive materials used to mitigate atmospheric pollution and to sequester polluting molecules. We have studied the structure of SrO nanoparticles, using Sr K-edge and Fe K-edge XAFS, that were prepared with various reactivities, with or without a Fe{sub 2}O{sub 3} coating, and before and after reaction with CCl{sub 4} or SO2. For CCl4, the polluting fraction of the reagent is totally absorbed in the bulk particle. For SO{sub 2}, the results show a total reaction for the Aerogel Preparation (AP) compound. For the coated particles before reaction, the iron oxide has a very disordered structure, and it is mixed with small metallic iron clusters for Conventional Preparation (CP) compounds. (au) 4 refs.

  18. Mixed alkaline earth effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

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


    , glass transition temperature, Vickers microhardness, and isokomtemperatures (viz., the temperatures atη=10^13.5 and 10^12.2 Pa s). The observed min-ima in fragility, glass transition temperature, and isokom temperature are ascribed to bond weakening in the local structural environment around the network...... modifiers. We suggest that, since the elastic properties of the investi-gated system are compositionally independent, the minimum in Vickers microhardness is closely correlated to the minimum in isokom temperatures. Both of these properties are related to plasticflow and the translational motion...

  19. 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.


    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

  20. The terrestrial uranium isotope cycle. (United States)

    Andersen, Morten B; Elliott, Tim; Freymuth, Heye; Sims, Kenneth W W; Niu, Yaoling; Kelley, Katherine A


    Changing conditions on the Earth's surface can have a remarkable influence on the composition of its overwhelmingly more massive interior. The global distribution of uranium is a notable example. In early Earth history, the continental crust was enriched in uranium. Yet after the initial rise in atmospheric oxygen, about 2.4 billion years ago, the aqueous mobility of oxidized uranium resulted in its significant transport to the oceans and, ultimately, by means of subduction, back to the mantle. Here we explore the isotopic characteristics of this global uranium cycle. We show that the subducted flux of uranium is isotopically distinct, with high (238)U/(235)U ratios, as a result of alteration processes at the bottom of an oxic ocean. We also find that mid-ocean-ridge basalts (MORBs) have (238)U/(235)U ratios higher than does the bulk Earth, confirming the widespread pollution of the upper mantle with this recycled uranium. Although many ocean island basalts (OIBs) are argued to contain a recycled component, their uranium isotopic compositions do not differ from those of the bulk Earth. Because subducted uranium was probably isotopically unfractionated before full oceanic oxidation, about 600 million years ago, this observation reflects the greater antiquity of OIB sources. Elemental and isotope systematics of uranium in OIBs are strikingly consistent with previous OIB lead model ages, indicating that these mantle reservoirs formed between 2.4 and 1.8 billion years ago. In contrast, the uranium isotopic composition of MORB requires the convective stirring of recycled uranium throughout the upper mantle within the past 600 million years.

  1. Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence (United States)

    Bullen, Thomas D.; Chadwick, Oliver A.


    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

  2. Investigating Carbonate System Perturbations across the Cretaceous-Palaeogene Transition using Boron Isotopes in Planktonic Foraminifera. (United States)

    Henehan, M. J.; Hull, P. M.; Planavsky, N. J.; Huber, B. T.; Thomas, E.


    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.

  3. Synthesis and acid digestion of biomorphic ceramics: determination of alkaline and alkaline earth ions. (United States)

    Bosch Ojeda, Catalina; Sánchez Rojas, Fuensanta; Cano Pavón, José Manuel


    Ceramic and glass are some of the more recent engineering materials and those that are most resistant to environmental conditions. They belong to advanced materials in that they are being developed for the aerospace and electronics industries. In the last decade, a new class of ceramic materials has been the focus of particular attention. The materials were produced with natural, renewable resources (wood or wood-based products). In this work, we have synthesised a new biomorphic ceramic material from oak wood and Si infiltration. After the material characterization, we have optimized the dissolution of the sample by acid attack in an oven under microwave irradiation. Experimental designs were used as a multivariate strategy for the evaluation of the effects of varying several variables at the same time. The optimization was performed in two steps using factorial design for preliminary evaluation and a Draper-Lin design for determination of the critical experimental conditions. Five variables (time, power, volume of HNO3, volume H2SO4 and volume of HF) were considered as factors and as a response the concentration of different metal ions in the optimization process. Interactions between analytical factors and their optimal levels were investigated using a Draper-Lin design.

  4. Moessbauer effect of the alkaline and alkaline earth metal nitroprusside powders

    CERN Document Server

    Yang, T H; Kim, H S; Hong, C Y; Kim, H B; Cho, H Y; Kim, D Y; Moon, Y S


    We observe Moessbauer spectra of Fe atoms centered in nitroprusside anions of sodium nitroprusside (Na sub 2 [Fe(CN) sub 5 NO] 2H sub 2 O). potassium-nitroprusside (K sub 2 [Fe(CN)] sub 5 NO centre dot 2.5H sub 2 O), rubidium nitroprusside (Rb sub 2 [Fe(CN) sub 5 NO centre dot H sub 2 O), magnesium nitroprusside (Mg[Fe(CN) sub 5 NO], calcium nitroprusside (Ca[Fe(CN) sub 5 NO]centre dot 4H sub 2 O), and barium nitroprusside (Ba[Fe(CN) sub 5 NO]centre dot 3H sub 2 O) samples which have photochromic properties. We compare the Moessbauer parameters, the values of the isomer shifts and the quadrupole splittings of the samples with those of a sodium nitroprusside single crystal which is a standard material. The values of the isomer shifts and the quadrupole splittings of the various compounds are close to each other. The values of the line broadening of all samples are between 2.1 GAMMA sub N and 2.5 GAMMA sub N. The Moessbauer Lamb factors (f) are between 0.252(1) and 0.340(2). These values are obtained from the s...

  5. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments (United States)

    Kitadai, Norio


    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.

  6. Contemporaneous trachyandesitic and calc-alkaline volcanism of the Huerto Andesite, San Juan Volcanic Field, Colorado, USA (United States)

    Parat, F.; Dungan, M.A.; Lipman, P.W.


    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. Catalytic Diversity in Alkaline Hydrothermal Vent Systems on Ocean Worlds (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


    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. 51

  8. Leatherback Isotopes (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 Paleoclimatology (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.

  10. Isotopic chirality

    Energy Technology Data Exchange (ETDEWEB)

    Floss, H.G. [Univ. of Washington, Seattle, WA (United States)


    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.

  11. Expanding earth

    Energy Technology Data Exchange (ETDEWEB)

    Carey, S.W.


    Arguments in favor of an expanding earth are presented. The author believes that the theory of plate tectonics is a classic error in the history of geology. The case for the expanding earth is organized in the following way: introductory review - face of the earth, development of expanding earth concept, necessity for expansion, the subduction myth, and definitions; some principles - scale of tectonic phenomena, non-uniformitarianism, tectonic profile, paleomagnetism, asymmetry of the earth, rotation of the earth, and modes of crustal extension; regional studies - western North America, Central America, South-East Asia, and the rift oceans; tests and cause of expansion. 824 references, 197 figures, 11 tables. (RWR)

  12. Handbook of environmental isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Baskaran, Mark (ed.) [Wayne State Univ., Detroit, MI (United States). Dept. Geology


    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.)

  13. When can ocean acidification impacts be detected from decadal alkalinity measurements? (United States)

    Carter, B. R.; Frölicher, T. L.; Dunne, J. P.; Rodgers, K. B.; Slater, R. D.; Sarmiento, J. L.


    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.

  14. 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: [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)


    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.

  15. 2nd Generation Alkaline Electrolysis

    DEFF Research Database (Denmark)

    Yde, Lars; Kjartansdóttir, Cecilia Kristin; Allebrod, Frank;

    This report provides the results of the 2nd Generation Alkaline Electrolysis project which was initiated in 2008. The project has been conducted from 2009-2012 by a consortium comprising Århus University Business and Social Science – Centre for Energy Technologies (CET (former HIRC)), Technical...

  16. Alkaline resistant ceramics; Alkalimotstaandskraftiga keramer

    Energy Technology Data Exchange (ETDEWEB)

    Westberg, Stig-Bjoern [Vattenfall Utveckling AB, Aelvkarleby (Sweden)


    Despite durability in several environments, ceramics and refractories can not endure alkaline environments at high temperature. An example of such an environment is when burning biofuel in modern heat and power plants in which the demand for increasing efficiency results in higher combustion temperatures and content of alkaline substances in the flue gas. Some experiences of these environments has been gained from such vastly different equipment as regenerator chambers in the glass industry and MHD-generators. The grains of a ceramic material are usually bonded together by a glassy phase which despite it frequently being a minor constituent render the materials properties and limits its use at elevated temperature. The damage is usually caused by alkaline containing low-melting phases and the decrease of the viscosity of the bonding glass phase which is caused by the alkaline. The surfaces which are exposed to the flue gas in a modern power plant are not only exposed to the high temperature but also a corroding and eroding, particle containing, gas flow of high velocity. The use of conventional refractory products is limited to 1300-1350 deg C. Higher strength and fracture toughness as well as durability against gases, slag and melts at temperatures exceeding 1700 deg C are expected of the materials of the future. Continuous transport of corrosive compounds to the surface and corrosion products from the surface as well as a suitable environment for the corrosion to occur in are prerequisites for extensive corrosion to come about. The highest corrosion rate is therefore found in a temperature interval between the dew point and the melting point of the alkaline-constituent containing compound. It is therefore important that the corrosion resistance is sufficient in the environment in which alkaline containing melts or slag may appear. In environments such as these, even under normal circumstances durable ceramics, such as alumina and silicon carbide, are attacked

  17. Iron isotopic fractionation during continental weathering

    Energy Technology Data Exchange (ETDEWEB)

    Fantle, Matthew S.; DePaolo, Donald J.


    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.

  18. Petrogenesis of coeval sodic and potassic alkaline magmas at Spanish Peaks, Colorado: Magmatism related to the opening of the Rio Grande rift (United States)

    Lord, A. Brooke Hamil; McGregor, Heath; Roden, Michael F.; Salters, Vincent J. M.; Sarafian, Adam; Leahy, Rory


    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.

  19. A novel methodology to investigate isotopic biosignatures (United States)

    Horner, T. J.; Lee, R. B. Y.; Henderson, G. M.; Rickaby, R. E. M.


    An enduring goal of trace metal isotopic studies of Earth History is to find isotopic 'fingerprints' of life or of life's individual physiochemical processes. Generally, such signatures are sought by relating an isotopic effect observed in controlled laboratory conditions or a well-characterized environment to a more complex system or the geological record. However, such an approach is ultimately limited because life exerts numerous isotopic fractionations on any one element so it is hard to dissect the resultant net fractionation into its individual components. Further, different organisms, often with the same apparent cellular function, can express different isotopic fractionation factors. We have used a novel method to investigate the isotopic fractionation associated with a single physiological process-enzyme specific isotopic fractionation. We selected Cd isotopes since only one biological use of Cd is known, CdCA (a Cd/Zn carbonic anhydrase from the coastal diatom T. Weissflogii). Thus, our investigation can also inform the long standing mystery as to why this generally toxic element appears to have a nutrient-like dissolved isotopic and concentration profile in the oceans. We used the pET-15b plasmid to insert the CdCA gene into the E. coli genome. There is no known biochemical function for Cd in E. coli, making it an ideal vector for studying distinct physiological processes within a single organism. The uptake of Cd and associated isotopic fractionation was determined for both normal cells and those expressing CdCA. It was found that whole cells always exhibited a preference for the light isotopes of Cd, regardless of the expression of CdCA; adsorption of Cd to cell surfaces was not seen to cause isotopic fractionation. However, the cleaning procedure employed exerted a strong control on the observed isotopic composition of cells. Using existing protein purification techniques, we measured the Cd isotopic composition of different subcellular fractions of E

  20. 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


    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.

  1. 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. (United States)

    Takano, Shotaro; Tanimizu, Masaharu; Hirata, Takafumi; Sohrin, Yoshiki


    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‰.

  2. U-Pb zircon geochronology, petrochemical and Sr-Nd isotopic characteristic of Late Neoproterozoic granitoid of the Bornaward Complex (Bardaskan-NE Iran) (United States)

    Bagherzadeh, R. Monazzami; Karimpour, M. H.; Farmer, G. Lang; Stern, C. R.; Santos, J. F.; Rahimi, B.; Heidarian Shahri, M. R.


    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).

  3. Silicon isotope fractionation during magmatic differentiation (United States)

    Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Burton, Kevin W.; Halliday, Alex N.


    The Si isotopic composition of Earth's mantle is thought to be homogeneous (δ 30Si = -0.29 ± 0.08‰, 2 s.d.) and not greatly affected by partial melting and recycling. Previous analyses of evolved igneous material indicate that such rocks are isotopically heavy relative to the mantle. To understand this variation, it is necessary to investigate the degree of Si isotopic fractionation that takes place during magmatic differentiation. Here we report Si isotopic compositions of lavas from Hekla volcano, Iceland, which has formed in a region devoid of old, geochemically diverse crust. We show that Si isotopic composition varies linearly as a function of silica content, with more differentiated rocks possessing heavier isotopic compositions. Data for samples from the Afar Rift Zone, as well as various igneous USGS standards are collinear with the Hekla trend, providing evidence of a fundamental relationship between magmatic differentiation and Si isotopes. The effect of fractionation has been tested by studying cumulates from the Skaergaard Complex, which show that olivine and pyroxene are isotopically light, and plagioclase heavy, relative to the Si isotopic composition of the Earth's mantle. Therefore, Si isotopes can be utilised to model the competing effects of mafic and felsic mineral fractionation in evolving silicate liquids and cumulates. At an average SiO 2 content of ˜60 wt.%, the predicted δ 30Si value of the continental crust that should result from magmatic fractionation alone is -0.23 ± 0.05‰ (2 s.e.), barely heavier than the mantle. This is, at most, a maximum estimate, as this does not take into account weathered material whose formation drives the products toward lighter δ 30Si values. Mass balance calculations suggest that removal of continental crust of this composition from the upper mantle will not affect the Si isotopic composition of the mantle.

  4. The chemical and isotopic differentiation of an epizonal magma body: Organ Needle pluton, New Mexico (United States)

    Verplanck, P.L.; Farmer, G.L.; McCurry, M.; Mertzman, S.A.


    Major and trace element, and Nd and Sr isotopic compositions of whole rocks and mineral separates from the Oligocene, alkaline Organ Needle pluton (ONP), southern New Mexico, constrain models for the differentiation of the magma body parental to this compositionally zoned and layered epizonal intrusive body. The data reveal that the pluton is rimmed by lower ??(Nd) (~-5) and higher 87Sr/86Sr (~0.7085) syenitic rocks than those in its interior (??(Nd) ~ 2, 87Sr/86Sr ~0.7060) and that the bulk compositions of the marginal rocks become more felsic with decreasing structural depth. At the deepest exposed levels of the pluton, the ??(Nd)~-5 lithology is a compositionally heterogeneous inequigranular syenite. Modal, compositional and isotopic data from separates of rare earth element (REE)-bearing major and accesory mineral phases (hornblende, titanite, apatite, zircon) demonstrate that this decoupling of trace and major elements in the inequigranular syenite results from accumulation of light REE (LREE)-bearing minerals that were evidently separated from silicic magmas as the latter rose along the sides of the magma chamber. Chemical and isotopic data for microgranular mafic enclaves, as well as for restite xenoliths of Precambrian granite wall rock, indicate that the isotopic distinction between the marginal and interior facies of the ONP probably reflects assimilation of the wall rock by ??(Nd) ~-2 mafic magmas near the base of the magma system. Fractional crystallization and crystal liquid separation of the crystally contaminated magma at the base and along the margins of the chamber generated the highly silicic magmas that ultimately pooled at the chamber top.

  5. Chlorine solubility in evolved alkaline magmas

    Directory of Open Access Journals (Sweden)

    M. R. Carroll


    Full Text Available Experimental studies of Cl solubility in trachytic to phonolitic melts provide insights into the capacity of alkaline magmas to transport Cl from depth to the earth?s surface and atmosphere, and information on Cl solubility variations with pressure, temperature and melt or fluid composition is crucial for understanding the reasons for variations in Cl emissions at active volcanoes. This paper provides a brief review of Cl solubility experiments conducted on a range of trachytic to phonolitic melt compositions. Depending on the experimental conditions the melts studied were in equilibrium with either a Cl-bearing aqueous fluid or a subcritical assemblage of low- Cl aqueous fluid + Cl-rich brine. The nature of the fluid phase(s was identified by examination of fluid inclusions present in run product glasses and the fluid bulk composition was calculated by mass balance. Chlorine concentrations in the glass increase with increasing Cl molality in the fluid phase until a plateau in Cl concentration is reached when melt coexists with aqueous fluid + brine. With fluids of similar Cl molality, higher Cl concentrations are observed in peralkaline phonolitic melts compared with peraluminous phonolitic melts; overall the Cl concentrations observed in phonolitic and trachytic melts are approximately twice those found in calcalkaline rhyolitic melts under similar conditions. The observed negative pressure dependence of Cl solubility implies that Cl contents of melts may actually increase during magma decompression if the magma coexists with aqueous fluid and Cl-rich brine (assuming melt-vapor equilibrium is maintained. The high Cl contents (approaching 1 wt% Cl observed in some melts/glasses from the Vesuvius and Campi Flegrei areas suggest saturation with a Cl-rich brine prior to eruption.

  6. Contrasting magmatic signatures in the Rairakhol and Koraput alkaline complexes, Eastern Ghats belt, India

    Indian Academy of Sciences (India)

    S Bhattacharya; M Basei


    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.

  7. Earth\\'s Mass Variability

    CERN Document Server

    Mawad, Ramy


    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.

  8. 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


    [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

  9. Isotopes a very short introduction

    CERN Document Server

    Ellam, Rob


    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...

  10. 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:; Victor, Alessandro R. [Instituto Tecnologico de Aeronautica (ITA), Sao Jose dos Campos, SP (Brazil)


    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)

  11. Isotope composition and volume of Earth’s early oceans


    Pope, Emily C.; Bird, Dennis K.; Rosing, Minik T.


    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 isotop...

  12. Alkaline Water and Longevity: A Murine Study. (United States)

    Magro, Massimiliano; Corain, Livio; Ferro, Silvia; Baratella, Davide; Bonaiuto, Emanuela; Terzo, Milo; Corraducci, Vittorino; Salmaso, Luigi; Vianello, Fabio


    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.

  13. 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


    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.

  14. Naturally occurring radionuclides and Earth sciences

    Directory of Open Access Journals (Sweden)

    G. Ferrara


    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.

  15. Martian alkaline basites chemically resemble basic rocks of the Lovozero alkaline massif, Kola peninsula (United States)

    Kochemasov, G.

    The comparative wave planetology [1, 5] successfully overcomes the most principal martian test having now analyses of alkaline rocks from Columbia Hills [2, 3, 4]. This kind of rocks was predicted earlier on basis of the wave paradigm having stated that "the higher planetary relief range - the higher density difference between lithologies composing hypsometrically (tectonically) contrasting blocks [5]. This paradigm declares that "celestial bodies are dichotomic"(Theorem 1), "celestial bodies are sectoral" (Theorem 2), "celestial bodies are granular"(Theorem 3), "angular momenta of different level blocks tend to be equal" (Theorem 4)[1, 5]. Mars is a typical terrestrial planet but the farthest from Sun and thus with the smallest tide effects. Nevertheless it has the highest relief range and seems to be most distorted (ellipsoid in shape) and broken by deep fissures. The wave approach explains this by a warping action of standing waves of 4 ortho- and diagonal directions - they are the longest and highest in the martian case. These interfering warping waves caused by the elliptic keplerian orbits implying periodically changing accelerations and inertia-gravity forces produce inevitable tectonic dichotomy (the fundamental wave 1 long 2πR), sectoring (wave 2, πR, and other overtones), granulation. A granule size depends on an orbital frequency: the higher frequency the smaller granule. The Earth's granule, as a scale, is πR/4 (see it in NASA's PIA04159), Venus ` πR/6, Mercury's πR/16, Mars' πR/2 (the sizes are strictly tied to orb. fr.). Along with the granule sizes increase relief ranges ( Mercury ˜5 km, Venus 14, Earth 20, Mars ˜30) and compositional (density) difference between lowland and highland lithologies [5]. The lowland compositions become Fericher and denser: enstatite (Mercury), Mg-basalt (Venus), tholeiite (Earth), Fe-basalt (Mars). The highland compositions get less dense, lighter: anorthosite, alkaline basalt, andesite and conditional "albitite

  16. Paleoproxies: Heavy Stable Isotope Perspectives (United States)

    Nagler, T. F.; Hippler, D.; Siebert, C.; Kramers, J. D.


    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

  17. A Teaching Exercise to Introduce Stable Isotope Fractionation of Metals into Geochemistry Courses (United States)

    Weiss, Dominik J.; Harris, Caroline; Maher, Kate; Bullen, Thomas


    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,…

  18. Earth materials and earth dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, K; Shankland, T. [and others


    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).

  19. Handbook of Indigenous Foods Involving Alkaline Fermentation

    NARCIS (Netherlands)

    Sarkar, P.K.; Nout, M.J.R.


    This book details the basic approaches of alkaline fermentation, provides a brief history, and offers an overview of the subject. The book discusses the diversity of indigenous fermented foods involving an alkaline reaction, as well as the taxonomy, ecology, physiology, and genetics of predominant m

  20. Not So Rare Earth? New Developments in Understanding the Origin of the Earth and Moon (United States)

    Righter, Kevin


    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.

  1. 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


    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.

  2. Adakitic-like magmatism in western Ossa-Morena Zone (Portugal): Geochemical and isotopic constraints of the Pavia pluton (United States)

    Lima, S. M.; Neiva, A. M. R.; Ramos, J. M. F.


    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).

  3. Isotopic mixing by magnetorotational instability in the protolunar disk (United States)

    Desch, Steven; Carballido, Augusto; Taylor, G. Jeffrey


    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.

  4. Magmatism in the Tsagaandelger, Eastern Mongolian volcanic belt: Petrological, geochemical and isotopic constraints on Mesozoic geodynamic setting (United States)

    Oidov, M.; Fujimaki, H.


    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

  5. Snowball Earth



    In the ongoing quest to better understand where life may exist elsewhere in the Universe, important lessons may be gained from our own planet. In particular, much can be learned from planetary glaciation events that Earth suffered ∼600 million years ago, so-called `Snowball Earth' episodes. I begin with an overview of how the climate works. This helps to explain how the ice-albedo feedback effect can destabilise a planet's climate. The process relies on lower temperatures causing more ice to ...

  6. Natural fractionation of uranium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Noordmann, Janine


    The topic of this thesis was the investigation of U (n({sup 238}U) / n({sup 235}U)) 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({sup 238}U) and n({sup 235}U), on Earth.

  7. 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: [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)


    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‰.

  8. Nickel isotopic composition of the mantle (United States)

    Gall, Louise; Williams, Helen M.; Halliday, Alex N.; Kerr, Andrew C.


    This paper presents a detailed high-precision study of Ni isotope variations in mantle peridotites and their minerals, komatiites as well as chondritic and iron meteorites. Ultramafic rocks display a relatively large range in δ60 Ni (permil deviation in 60 Ni /58 Ni relative to the NIST SRM 986 Ni isotope standard) for this environment, from 0.15 ± 0.07‰ to 0.36 ± 0.08‰, with olivine-rich rocks such as dunite and olivine cumulates showing lighter isotope compositions than komatiite, lherzolite and pyroxenite samples. The data for the mineral separates shed light on the origin of these variations. Olivine and orthopyroxene display light δ60 Ni whereas clinopyroxene and garnet are isotopically heavy. This indicates that peridotite whole-rock δ60 Ni may be controlled by variations in modal mineralogy, with the prediction that mantle melts will display variable δ60 Ni values due to variations in residual mantle and cumulate mineralogy. Based on fertile peridotite xenoliths and Phanerozoic komatiite samples it is concluded that the upper mantle has a relatively homogeneous Ni isotope composition, with the best estimate of δ60Nimantle being 0.23 ± 0.06‰ (2 s.d.). Given that >99% of the Ni in the silicate Earth is located in the mantle, this also defines the Ni isotope composition of the Bulk Silicate Earth (BSE). This value is nearly identical to the results obtained for a suite of chondrites and iron meteorites (mean δ60 Ni 0.26 ± 0.12‰ and 0.29 ± 0.10‰, respectively) showing that the BSE is chondritic with respect to its Ni isotope composition, with little to no Ni mass-dependent isotope fractionation resulting from core formation.

  9. Digital Earth - A sustainable Earth (United States)



    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.

  10. Association of alkaline phosphatase phenotypes with arthritides

    Directory of Open Access Journals (Sweden)

    Padmini A


    Full Text Available Arthritides, a symmetrical polyarticular disease of the bone are a heterogenous group of disorders in which hereditary and environmental factors in combination with an altered immune response appear to play a causative and pathogenic role in its occurrence. Alkaline phosphatase (ALP is an enzyme found in all tissues, with particularly high concentrations of ALP observed in the liver, bile ducts, placenta, and bone.Alkaline phosphatase is an orthophosphoric monoester phosphohydrolase catalyzing the hydrolysis of organic esters at alkaline pH, indicating that alkaline phosphatase is involved in fundamental biological processes.1 The present study envisages on identifying the specific electromorphic association of alkaline phosphatase with arthritides. Phenotyping of serum samples was carried out by PAGE (Polyacrylamide gel electrophoresis following Davies (19642 protocol on 41 juvenile arthritis, 150 rheumatoid arthritis and 100 osteo arthritis apart from, 25 normal children and 100 adult healthy subjects. Phenotyping of alkaline phosphatase revealed an increase in preponderance of p+ and p++ phenotypes in juvenile, rheumatoid and osteo arthritic patients. However a significant association of these phenotypes was observed only with rheumatoid arthritis condition (c2:17.46. Similarly, a significant increase of p+ phenotypes in female rheumatoid arthritis patients was observed (c2:14.973, suggesting that the decrease in p° (tissue non specific synthesis/secretion of alkaline phosphatase could be associated with decreased mineralization and ossification process in arthritis condition.

  11. Alkaline solution neutralization capacity of soil. (United States)

    Asakura, Hiroshi; Sakanakura, Hirofumi; Matsuto, Toshihiko


    Alkaline eluate from municipal solid waste (MSW) incineration residue deposited in landfill alkalizes waste and soil layers. From the viewpoint of accelerating stability and preventing heavy metal elution, pH of the landfill layer (waste and daily cover soil) should be controlled. On the other hand, pH of leachate from existing MSW landfill sites is usually approximately neutral. One of the reasons is that daily cover soil can neutralize alkaline solution containing Ca(2+) as cation. However, in landfill layer where various types of wastes and reactions should be taken into consideration, the ability to neutralize alkaline solutions other than Ca(OH)(2) by soil should be evaluated. In this study, the neutralization capacities of various types of soils were measured using Ca(OH)(2) and NaOH solutions. Each soil used in this study showed approximately the same capacity to neutralize both alkaline solutions of Ca(OH)(2) and NaOH. The cation exchange capacity was less than 30% of the maximum alkali neutralization capacity obtained by the titration test. The mechanism of neutralization by the pH-dependent charge can explain the same neutralization capacities of the soils. Although further investigation on the neutralization capacity of the soils for alkaline substances other than NaOH is required, daily cover soil could serve as a buffer zone for alkaline leachates containing Ca(OH)(2) or other alkaline substances.

  12. 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


    Molina-Kescher, Mario


    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. ...

  13. Stable isotope studies

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, T.


    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs.

  14. Partial radiogenic heat model for Earth revealed by geoneutrino measurements

    NARCIS (Netherlands)

    S. Abe; . et al.; M.P. Decowski


    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

  15. Clumped-isotope geochemistry of carbonates: A new tool for the reconstruction of temperature and oxygen isotope composition of seawater

    Energy Technology Data Exchange (ETDEWEB)

    Bernasconi, Stefano M., E-mail: [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Schmid, Thomas W.; Grauel, Anna-Lena [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Mutterlose, Joerg [Institut fuer Geologie, Mineralogie und Geophysik, Ruhr Universitaet Bochum, Universitaetsstr. 150, 44801 Bochum (Germany)


    Highlights: > Clumped-isotope thermometry of carbonates is discussed. > Clumped isotopes of Belemnites show higher sea surface temperatures than commonly assumed for the lower Cretaceous. > The potential of clumped-isotope measurement on foraminifera is discussed. - Abstract: Clumped-isotope geochemistry deals with State of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of the earth sciences. In particular, it allows reconstructing the temperature of formation of carbonate minerals without knowledge of the isotopic composition of the water from which they were formed. In addition, the O isotope composition of the waters from which they were formed can be calculated using the {delta}{sup 18}O of the same carbonate sample. This feature offers new approaches in paleoclimatology for reconstructing past global geochemical cycles. In this contribution two applications of this method are presented. First the potential of a new analytical method of measurement of clumped isotopes on small samples of foraminifera, for high-resolution SST and seawater {delta}{sup 18}O reconstructions from marine sediments is shown. Furthermore the potential of clumped isotope analysis of belemnites, for reconstructing seawater {delta}{sup 18}O and temperatures in the Cretaceous is shown.

  16. Prebiotic Synthesis of Glycine from Ethanolamine in Simulated Archean Alkaline Hydrothermal Vents (United States)

    Zhang, Xianlong; Tian, Ge; Gao, Jing; Han, Mei; Su, Rui; Wang, Yanxiang; Feng, Shouhua


    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.

  17. [Alkaline phosphatase in Amoeba proteus]. (United States)

    Sopina, V A


    In free-living Amoeba proteus (strain B), 3 phosphatase were found after disc-electrophoresis of 10 microg of protein in PAGE and using 1-naphthyl phosphate as a substrate a pH 9.0. These phosphatases differed in their electrophoretic mobilities - "slow" (1-3 bands), "middle" (one band) and "fast" (one band). In addition to 1-naphthyl phosphate, "slow" phosphatases were able to hydrolyse 2-naphthyl phosphate and p-nitrophenyl phosphate. They were slightly activated by Mg2+, completely inhibited by 3 chelators (EDTA, EGTA and 1,10-phenanthroline), L-cysteine, sodium dodecyl sulfate and Fe2+, Zn2+ and Mn2+ (50 mM), considerably inactivated by orthovanadate, molybdate, phosphatase inhibitor cocktail 1, p-nitrophenyl phosphate, Na2HPO4, DL-dithiothreitol and urea and partly inhibited by H2O2, DL-phenylalanine, 2-mercaptoethanol, phosphatase inhibitor cocktail 2 and Ca2+. Imidazole, L-(+)-tartrate, okadaic acid, NaF and sulfhydryl reagents -p-(hydroxy-mercuri)benzoate and N-ethylmaleimide - had no influence on the activity of "slow" phosphatases. "Middle" and "fast" phosphatases, in contrast to "slow" ones, were not inactivated by 3 chelators. The "middle" phosphatase differed from the "fast" one by smaller resistance to urea, Ca2+, Mn2+, phosphates and H2O2 and greater resistance to dithiothreitol and L-(+)-tartrate. In addition, the "fast" phosphatase was inhibited by L-cysteine but the "middle" one was activated by it. Of 5 tested ions (Mg2+, Cu2+, Mn2+, Ca2+ and Zn2+), only Zn2+ reactivated "slow" phosphatases after their inactivation by EDTA treatment. The reactivation of apoenzyme was only partial (about 35 %). Thus, among phosphatases found in amoebae at pH 9.0, only "slow" ones are Zn-metalloenzymes and may be considered as alkaline phosphatases (EC It still remains uncertain, to which particular phosphatase class "middle" and "fast" phosphatases (pH 9.0) may belong.


    Energy Technology Data Exchange (ETDEWEB)

    Hidaka, Hiroshi; Higuchi, Takuya [Department of Earth and Planetary Systems Science, Hiroshima University, Higashi-Hiroshima 739-8526 (Japan); Yoneda, Shigekazu, E-mail:, E-mail: [Department of Science and Engineering, National Museum of Nature and Science, Tsukuba 305-0005 (Japan)


    It is known that the Sayama meteorite (CM2) shows an extensive signature for aqueous alteration on the meteorite parent body, and that most of the primary minerals in the chondrules are replaced with phyllosilicates as the result of the aqueous alteration. In this paper, it is confirmed from the observation of two-dimensional Raman spectra that a part of olivine in a chondrule collected from the Sayama chondrite is serperntinized. Ion microprobe analysis of the chondrule showed that alkaline elements such as Rb and Cs are heterogeneously redistributed in the chondrule. The result of higher Rb and Cs contents in serpentinized phases in the chondrule rather than in other parts suggested the selective adsorption of alkaline elements into the serpentine in association with early aqueous activity on the meteorite parent body. Furthermore Ba isotopic analysis provided variations of {sup 135}Ba/{sup 138}Ba and {sup 137}Ba/{sup 138}Ba in the chondrule. This result was consistent with our previous isotopic data suggesting isotopic evidence for the existence of the presently extinct nuclide {sup 135}Cs in the Sayama meteorite, but the abundance of {sup 135}Cs in the solar system remains unclear because of large analytical uncertainties.

  19. Sr and Nd isotopic signature of the high-K calc-alkaline magmatism of the central Ribeira belt: the Sao Pedro Granite in Lumiar, RJ; Assinatura isotopica de Sr e Nd do magmatismo calcio-alcalino de alto-K na Faixa Ribeira central: o exemplo do Granito Sao Pedro em Lumiar, RJ

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, Julio Cezar; Medeiros, Silvia Regina de; Chaves, Eduardo Amorim, E-mail:, E-mail:, E-mail: [Departamento de Geologia, Universidade Federal do Rio de Janeiro, Rio de Janeiro (RJ) (Brazil)


    In the central-northern Ribeira belt there are many granitic to granodioritic bodies showing varied shape and size, characterizing a late- to post-collisional Ca-alkaline, cordilleran I-type province. The Sao Pedro Granite occurs in the mountain region of Rio de Janeiro State as small post-collisional bodies. It presents isotropic fabric, equigranular to seriate inequigranular texture, as well as local concentration of allanite, which gives discrete composition and texture variation to the rock. The granite has a high-K calcalkaline to alkali-calcic character and weakly peraluminous nature. Despite its short geochemical variation, high Ba, Zr and Th contents besides low concentrations of MgO and CaO are noticeable. High REE contents are associated with fractionated REE patterns showing strong negative Eu anomalies. A crustal origin for the granite can be assumed by its very negative and positive .Nd and .Sr values, respectively, as well as by 87Sr/86Sr initial ratios ranging from 0,718 to 0,740. TDM ages point to paleoproterozoic source, which agrees with geological time of intensive crust generation. (author)

  20. The discovery of isotopes a complete compilation

    CERN Document Server

    Thoennessen, Michael


    This book describes the exciting discovery of every isotope observed on earth to date, which currently numbers some 3000. For each isotope a short essay highlights the authors of the first publication for the isotope, the laboratory and year where and when the isotope was discovered, as well as details about the production and detection methods used. In controversial cases previously claims are also discussed. At the end a comprehensive table lists all isotopes sorted by elements and a complete list of references. Preliminary versions of these paragraphs have been published over the last few years as separate articles in the journal "Atomic Data and Nuclear Data Tables". The work re-evaluates all assignments judging them with a uniform set of criteria. In addition, the author includes over 100 new isotopes which have been discovered since the articles published. This book is a source of information for researchers as well as enthusiastic laymen alike. From the prepublication review: “The explanations focus ...

  1. Orogenic potassic mafic magmatism, a product of alkaline-peraluminous mixing ? Variscan 'calc-alkaline' rocks from the Central Iberian and Ossa Morena Zones, Central Spain. (United States)

    Scarrow, Jane H.; Cambeses, Aitor; Bea, Fernando; Montero, Pilar; Molina, José F.; Moreno, Juan Antonio


    Ventoso pluton, preliminary mineral chemistry, whole-rock and isotope data indicate that rather than a single-stage cogenetic calc-alkaline intrusion, the pluton is a multi-stage composite of compositionally diverse stocks. Including the metaluminous calc-alkaline Medina de las Torres gabbro and Cortijo del Pozuelo granite to the concentrically zone alkaline core though to calk-alkaline border of the main pluton. In addition, an associated older peraluminous La Jineta granite body and younger cross-cutting tholeiitic dykes crop out in the same region. Here we present new U-Pb single zircon IBERSIMS SHRIMP data which indicate that the compositionally diverse main pluton and associated stocks are contemporaneous at 334 ± 2 Ma. So, rather than reflecting reactivation of a zone of lithospheric weakness by successive magmatic events it appears that at Valencia del Ventoso diverse mantle and crustal sources were being tapped simultaneously. We suggest that this is linked to the generation of and thermal anomaly associated with the coeval ´IBERSEIS reflective body'. The question is, then, if other 'calc-alkaline' plutons have similar compositional, and so, possible tectonomagmatic complexity. To test this hypothesis studies are currently underway of the Ossa Morena Zone Burguillos del Cerro and Brovales plutons.

  2. Prophylactic treatment with alkaline phosphatase in cardiac surgery induces endogenous alkaline phosphatase release

    NARCIS (Netherlands)

    Kats, Suzanne; Brands, Ruud; Hamad, Mohamed A. Soliman; Seinen, Willem; Schamhorst, Volkher; Wulkan, Raymond W.; Schoenberger, Jacques P.; van Oeveren, Wim


    Introduction: Laboratory and clinical data have implicated endotoxin as an important factor in the inflammatory response to cardiopulmonary bypass. We assessed the effects of the administration of bovine intestinal alkaline phosphatase (bIAP), an endotoxin detoxifier, on alkaline phosphatase levels

  3. Uptake of arsenic by alkaline soils near alkaline coal fly ash disposal facilities. (United States)

    Khodadoust, Amid P; Theis, Thomas L; Murarka, Ishwar P; Naithani, Pratibha; Babaeivelni, Kamel


    The attenuation of arsenic in groundwater near alkaline coal fly ash disposal facilities was evaluated by determining the uptake of arsenic from ash leachates by surrounding alkaline soils. Ten different alkaline soils near a retired coal fly ash impoundment were used in this study with pH ranging from 7.6 to 9.0, while representative coal fly ash samples from two different locations in the coal fly ash impoundment were used to produce two alkaline ash leachates with pH 7.4 and 8.2. The arsenic found in the ash leachates was present as arsenate [As(V)]. Adsorption isotherm experiments were carried out to determine the adsorption parameters required for predicting the uptake of arsenic from the ash leachates. For all soils and leachates, the adsorption of arsenic followed the Langmuir and Freundlich equations, indicative of the favorable adsorption of arsenic from leachates onto all soils. The uptake of arsenic was evaluated as a function of ash leachate characteristics and the soil components. The uptake of arsenic from alkaline ash leachates, which occurred mainly as calcium hydrogen arsenate, increased with increasing clay fraction of soil and with increasing soil organic matter of the alkaline soils. Appreciable uptake of arsenic from alkaline ash leachates with different pH and arsenic concentration was observed for the alkaline soils, thus attenuating the contamination of groundwater downstream of the retired coal fly ash impoundment.

  4. The isotopic composition of authigenic chromium in anoxic marine sediments: A case study from the Cariaco Basin


    Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Fischer, Woodward W.; Johnson, Thomas M.; Lyons, Timothy W.


    Chromium (Cr) isotopes are an emerging proxy for tracking redox processes at the Earth's surface. However, there has been limited exploration of the Cr isotope record of modern and recent marine sediments. The basic inorganic chemistry of Cr suggests that anoxic marine basins should factor prominently in the global Cr cycle and that sediments deposited within anoxic basins may offer a valuable Cr isotope archive throughout Earth's history. Here, we present δ^(53)Cr data from sediments of the ...

  5. Statistical clumped isotope signatures

    NARCIS (Netherlands)

    Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.


    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a m

  6. Potassium isotopic evidence for a high-energy giant impact origin of the Moon. (United States)

    Wang, Kun; Jacobsen, Stein B


    The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a 'palaeo-barometer' to reveal the physical conditions during the Moon-forming event.

  7. Potassium isotopic evidence for a high-energy giant impact origin of the Moon (United States)

    Wang, Kun; Jacobsen, Stein B.


    The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a ‘palaeo-barometer’ to reveal the physical conditions during the Moon-forming event.

  8. Sulfur Earth (United States)

    de Jong, B. H.


    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  9. Transition from alkaline to calc-alkaline volcanism during evolution of the Paleoproterozoic Francevillian basin of eastern Gabon (Western Central Africa) (United States)

    Thiéblemont, Denis; Bouton, Pascal; Préat, Alain; Goujou, Jean-Christian; Tegyey, Monique; Weber, Francis; Ebang Obiang, Michel; Joron, Jean Louis; Treuil, Michel


    We report new geochemical data for the volcanic and subvolcanic rocks associated with the evolution of the Francevillian basin of eastern Gabon during Paleoproterozoic times (c. 2.1-2 Ga). Filling of this basin has proceeded through four main sedimentary or volcano-sedimentary episodes, namely FA, FB, FC and FD. Volcanism started during the FB episode being present only in the northern part of the basin (Okondja sub-basin). This volcanism is ultramafic to trachytic in composition and displays a rather constant alkaline geochemical signature. This signature is typical of a within-plate environment, consistent with the rift-setting generally postulated for the Francevillian basin during the FB period. Following FB, the FC unit is 10-20 m-thick silicic horizon (jasper) attesting for a massive input of silica in the basin. Following FC, the FD unit is a c. 200-400 m-thick volcano-sedimentary sequence including felsic tuffs and epiclastic rocks. The geochemical signatures of these rocks are totally distinct from those of the FB alkaline lavas. High Th/Ta and La/Ta ratios attest for a calc-alkaline signature and slight fractionation between heavy rare-earth suggests melting at a rather low pressure. Such characteristics are comparable to those of felsic lavas associated with the Taupo zone of New Zealand, a modern ensialic back-arc basin. Following FD, the FE detrital unit is defined only in the Okondja region, probably associated with a late-stage collapse of the northern part of the basin. It is suggested that the alkaline to calc-alkaline volcanic transition reflects the evolution of the Francevillian basin from a diverging to a converging setting, in response to the onset of converging movements in the Eburnean Belt of Central Africa.

  10. Some durability aspects of hybrid alkaline cements

    Directory of Open Access Journals (Sweden)

    Donatello S.


    Full Text Available Blended cements that contain a high content of fly ash and a low content of Portland cement typically suffer from low early strength development and long setting times. Recently, one method of overcoming these problems has been to use an alkali activator to enhance the reactivity of fly ash particles at early ages. Such cements can be grouped under the generic term “hybrid alkaline cements”, where both cement clinker and fly ash, encouraged by the presence of alkalis, are expected to contribute to cementitious gel formation. The work presented here examines some of the durability aspects of high fly ash content hybrid alkaline cement. Specifically, the aspects investigated were: exposure at high temperatures (up to 1000°C, resistance to immersion in aggressive solutions and susceptibility to the alkali aggregate reaction. All tests were repeated with a commercially available sulfate resistant Portland cement for comparison. When exposed to high temperatures, the hybrid alkaline cement showed strikingly different behaviour compared to the control Portland cement, showing fewer micro-cracks and maintaining residual compressive strengths at least equal to original strengths. Beyond 700°C, the hybrid alkaline cement began to sinter, which resulted in shrinkage of around 5% and a 100% increase in residual compressive strengths. No such sintering event was noted in the control Portland cement, which showed a drastic loss in residual compressive strengths upon heating. In immersion tests, the hybrid alkaline cement possessed excellent resistance to sulfate and seawater attack, similar to the control sulfate resistant cement. Both cements were however severely degraded by immersion in 0.1M HCl for 90 days. Both binders complied with the accelerated alkali-aggregate test but when this test was extended, the hybrid alkaline binder showed much greater dimensional stability. Possible reasons for the differences in durability behaviour in both cements

  11. Alkaline Capacitors Based on Nitride Nanoparticles (United States)

    Aldissi, Matt


    High-energy-density alkaline electrochemical capacitors based on electrodes made of transition-metal nitride nanoparticles are undergoing development. Transition- metal nitrides (in particular, Fe3N and TiN) offer a desirable combination of high electrical conductivity and electrochemical stability in aqueous alkaline electrolytes like KOH. The high energy densities of these capacitors are attributable mainly to their high capacitance densities, which, in turn, are attributable mainly to the large specific surface areas of the electrode nanoparticles. Capacitors of this type could be useful as energy-storage components in such diverse equipment as digital communication systems, implanted medical devices, computers, portable consumer electronic devices, and electric vehicles.

  12. Electrochemical behaviour of alkaline copper complexes

    Indian Academy of Sciences (India)

    C L Aravinda; S M Mayanna; V R Muralidharan


    A search for non-cyanide plating baths for copper resulted in the development of alkaline copper complex baths containing trisodium citrate [TSC] and triethanolamine [TEA]. Voltammetric studies were carried out on platinum to understand the electrochemical behaviour of these complexes. In TSC solutions, the deposition of copper involves the slow formation of a monovalent species. Adsorption of this species obeys Langmuir isotherm. In TEA solutions the deposition involves the formation of monovalent ions obeying the non-activated Temkin isotherm. Conversion of divalent to monovalent copper is also slow. In TEA and TSC alkaline copper solutions, the predominant species that undergo stepwise reduction contain only TEA ligands

  13. Isotopes in heterogeneous catalysis

    CERN Document Server

    Hargreaves, Justin SJ


    The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

  14. Generation of Radixenon Isotopes

    Energy Technology Data Exchange (ETDEWEB)

    McIntyre, Justin I.; Bowyer, Ted W.; Hayes, James C.; Heimbigner, Tom R.; Morris, Scott J.; Panisko, Mark E.; Pitts, W. K.; Pratt, Sharon L.; Reeder, Paul L.; Thomas, Charles W.


    Pacific Northwest National Laboratory has developed an automated system for separating Xe from air and can detect the following radioxenon isotopes, 131mXe, 133mXe, 133Xe, and 135Xe. This report details the techniques used to generate the various radioxenon isotopes that are used for the calibration of the detector as well as other isotopes that have the potential to interfere with the fission produced radioxenon isotopes. Fission production is covered first using highly enriched uranium followed by a description and results from an experiment to produce radioxenon isotopes from neutron activation of ambient xenon.

  15. Instability of some divalent rare earth ions and photochromic effect


    Egranov, A. V.; Sizova, T. Yu.; Shendrik, R. Yu.; Smirnova, N. A.


    It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of an...

  16. Isotope Tales: Remaining Problems, Unsolvable Questions, and Gentle Successes (United States)

    fogel, marilyn; bradley, christina; newsome, seth; filipp, fabian


    Earth's biomes function and adapt today as climate changes and ecosystems and the organisms within them adapt. Stable isotope biogeochemistry has had a major influence in understanding climate perturbations and continues to be an active area of research on many fronts. Banking on the success of compound specific stable isotope analyses of amino acids, nitrogen, carbon, and hydrogen isotopes continue to reveal subtle shifts in oceanic food webs and metabolic changes in microbes, plants, and animals. A biochemical understanding of exactly how organisms process and partition stable isotopes during metabolism remains unsolved, but is required if this field is to move beyond description to quantitation. Although the patterns of carbon and nitrogen isotopes are fairly well established in the common amino acids, we need to consider specifics: How do shifting metabolic pathways (metabolomics) influence the outcome of stable isotope partitioning? What influence does the gut microflora in animals have on isotopic labeling? What are the intramolecular isotope patterns of common amino acids and what do they tell us? What can be learned with other isotope systems, such as hydrogen? Results and ideas of how to move forward in this field will be presented starting at the molecular level and ending with ecosystems.

  17. Isotope and Nuclear Chemistry Division annual report, FY 1983

    Energy Technology Data Exchange (ETDEWEB)

    Heiken, J.H.; Lindberg, H.A. (eds.)


    This report describes progress in the major research and development programs carried out in FY 1983 by the Isotope and Nuclear Chemistry Division. It covers radiochemical diagnostics of weapons tests; weapons radiochemical diagnostics research and development; other unclassified weapons research; stable and radioactive isotope production, separation, and applications (including biomedical applications); element and isotope transport and fixation; actinide and transition metal chemistry; structural chemistry, spectroscopy, and applications; nuclear structure and reactions; irradiation facilities; advanced analytical techniques; development and applications; atmospheric chemistry and transport; and earth and planetary processes.

  18. The alkaline diet: is there evidence that an alkaline pH diet benefits health? (United States)

    Schwalfenberg, Gerry K


    This review looks at the role of an alkaline diet in health. Pubmed was searched looking for articles on pH, potential renal acid loads, bone health, muscle, growth hormone, back pain, vitamin D and chemotherapy. Many books written in the lay literature on the alkaline diet were also reviewed and evaluated in light of the published medical literature. There may be some value in considering an alkaline diet in reducing morbidity and mortality from chronic diseases and further studies are warranted in this area of medicine.

  19. The Alkaline Diet: Is There Evidence That an Alkaline pH Diet Benefits Health?

    Directory of Open Access Journals (Sweden)

    Gerry K. Schwalfenberg


    Full Text Available This review looks at the role of an alkaline diet in health. Pubmed was searched looking for articles on pH, potential renal acid loads, bone health, muscle, growth hormone, back pain, vitamin D and chemotherapy. Many books written in the lay literature on the alkaline diet were also reviewed and evaluated in light of the published medical literature. There may be some value in considering an alkaline diet in reducing morbidity and mortality from chronic diseases and further studies are warranted in this area of medicine.

  20. Petrological and Sr-Nd-Os isotopic constraints on the origin of the Fanshan ultrapotassic complex from the North China Craton (United States)

    Niu, Xiaolu; Chen, Bin; Liu, Ankun; Suzuki, K.; Ma, Xu


    The Fanshan ultramafic-syenitic complex is located on the northern margin of North China Craton, with zircon U-Pb ages of 220 Ma. It is a concentrically zoned complex, with syenite in the core, surrounded by ultramafic rocks (clinopyroxenite, glimmerite) and garnet-clinopyroxene syenite, respectively, towards the rim. Diopside, biotite, orthoclase, melanite, magnetite and apatite are the major minerals, with subordinate sphene and calcite. Mineralogy, petrology and geochemical studies point to the formation of the complex through fractional crystallization and accumulation from a SiO2-undersaturated ultrapotassic alkaline-peralkaline parent magma that is characterized by high CaO, Fe2O3, K2O and fluid compositions (P2O5, CO2, H2O, F), and by high temperature and high oxygen fugacity. Rocks from the complex are highly enriched in light rare earth elements (LREE) and large ion lithophile elements (LILE; e.g., Rb, Ba, Sr), depleted in high field strength elements (HFSE; e.g., Nb, Ta, Ti), and show relatively homogeneous Sr-Nd isotopic compositions with initial 87Sr/86Sr = 0.70513-0.70597 and ɛNd(t) = - 5.8 to - 5.3. The data suggest that the Fanshan complex originated from a phlogopite-clinopyroxenite-rich lithosphere mantle source that had previously been metasomatized by melts from carbonated oceanic crust above a subduction zone. Highly radiogenic Os isotope compositions (initial 187Os/188Os = 0.299-2.449) suggest that the parent magma to the Fanshan complex has been contaminated by Precambrian mafic crustal rocks during magma emplacement in crustal levels. The occurrence of the Fanshan complex, together with many other ultramafic/alkaline plutons of similar ages, on the northern margin of the North China Craton suggests that the northern margin of the craton entered into a large-scale extensional regime in late Triassic after the final amalgamation between Mongolian microcontinent and the craton.

  1. Biomass production on saline-alkaline soils

    Energy Technology Data Exchange (ETDEWEB)

    Chaturvedi, A.N.


    In a trial of twelve tree species (both nitrogen fixing and non-fixing) for fuel plantations on saline-alkaline soil derived from Gangetic alluvium silty clay, Leucaena leucocephala failed completely after showing rapid growth for six months. Results for other species at age two showed that Prosopis juliflora had the best productivity.

  2. Use Alkalinity Monitoring to Optimize Bioreactor Performance. (United States)

    Jones, Christopher S; Kult, Keegan J


    In recent years, the agricultural community has reduced flow of nitrogen from farmed landscapes to stream networks through the use of woodchip denitrification bioreactors. Although deployment of this practice is becoming more common to treat high-nitrate water from agricultural drainage pipes, information about bioreactor management strategies is sparse. This study focuses on the use of water monitoring, and especially the use of alkalinity monitoring, in five Iowa woodchip bioreactors to provide insights into and to help manage bioreactor chemistry in ways that will produce desirable outcomes. Results reported here for the five bioreactors show average annual nitrate load reductions between 50 and 80%, which is acceptable according to established practice standards. Alkalinity data, however, imply that nitrous oxide formation may have regularly occurred in at least three of the bioreactors that are considered to be closed systems. Nitrous oxide measurements of influent and effluent water provide evidence that alkalinity may be an important indicator of bioreactor performance. Bioreactor chemistry can be managed by manipulation of water throughput in ways that produce adequate nitrate removal while preventing undesirable side effects. We conclude that (i) water should be retained for longer periods of time in bioreactors where nitrous oxide formation is indicated, (ii) measuring only nitrate and sulfate concentrations is insufficient for proper bioreactor operation, and (iii) alkalinity monitoring should be implemented into protocols for bioreactor management.

  3. Alkaline electrochemical cells and method of making (United States)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)


    Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

  4. Presentation, calibration and validation of the low-order, DCESS Earth System Model (Version 1

    Directory of Open Access Journals (Sweden)

    J. O. Pepke Pedersen


    Full Text Available A new, low-order Earth System Model is described, calibrated and tested against Earth system data. The model features modules for the atmosphere, ocean, ocean sediment, land biosphere and lithosphere and has been designed to simulate global change on time scales of years to millions of years. The atmosphere module considers radiation balance, meridional transport of heat and water vapor between low-mid latitude and high latitude zones, heat and gas exchange with the ocean and sea ice and snow cover. Gases considered are carbon dioxide and methane for all three carbon isotopes, nitrous oxide and oxygen. The ocean module has 100 m vertical resolution, carbonate chemistry and prescribed circulation and mixing. Ocean biogeochemical tracers are phosphate, dissolved oxygen, dissolved inorganic carbon for all three carbon isotopes and alkalinity. Biogenic production of particulate organic matter in the ocean surface layer depends on phosphate availability but with lower efficiency in the high latitude zone, as determined by model fit to ocean data. The calcite to organic carbon rain ratio depends on surface layer temperature. The semi-analytical, ocean sediment module considers calcium carbonate dissolution and oxic and anoxic organic matter remineralisation. The sediment is composed of calcite, non-calcite mineral and reactive organic matter. Sediment porosity profiles are related to sediment composition and a bioturbated layer of 0.1 m thickness is assumed. A sediment segment is ascribed to each ocean layer and segment area stems from observed ocean depth distributions. Sediment burial is calculated from sedimentation velocities at the base of the bioturbated layer. Bioturbation rates and oxic and anoxic remineralisation rates depend on organic carbon rain rates and dissolved oxygen concentrations. The land biosphere module considers leaves, wood, litter and soil. Net primary production depends on atmospheric carbon dioxide concentration and

  5. Presentation, calibration and validation of the low-order, DCESS Earth System Model

    Directory of Open Access Journals (Sweden)

    J. O. P. Pedersen


    Full Text Available A new, low-order Earth system model is described, calibrated and tested against Earth system data. The model features modules for the atmosphere, ocean, ocean sediment, land biosphere and lithosphere and has been designed to simulate global change on time scales of years to millions of years. The atmosphere module considers radiation balance, meridional transport of heat and water vapor between low-mid latitude and high latitude zones, heat and gas exchange with the ocean and sea ice and snow cover. Gases considered are carbon dioxide and methane for all three carbon isotopes, nitrous oxide and oxygen. The ocean module has 100 m vertical resolution, carbonate chemistry and prescribed circulation and mixing. Ocean biogeochemical tracers are phosphate, dissolved oxygen, dissolved inorganic carbon for all three carbon isotopes and alkalinity. Biogenic production of particulate organic matter in the ocean surface layer depends on phosphate availability but with lower efficiency in the high latitude zone, as determined by model fit to ocean data. The calcite to organic carbon rain ratio depends on surface layer temperature. The semi-analytical, ocean sediment module considers calcium carbonate dissolution and oxic and anoxic organic matter remineralisation. The sediment is composed of calcite, non-calcite mineral and reactive organic matter. Sediment porosity profiles are related to sediment composition and a bioturbated layer of 0.1 m thickness is assumed. A sediment segment is ascribed to each ocean layer and segment area stems from observed ocean depth distributions. Sediment burial is calculated from sedimentation velocities at the base of the bioturbated layer. Bioturbation rates and oxic and anoxic remineralisation rates depend on organic carbon rain rates and dissolved oxygen concentrations. The land biosphere module considers leaves, wood, litter and soil. Net primary production depends on atmospheric carbon dioxide concentration and

  6. Modelling of stable water isotopes in Central Europe with COSMOiso (United States)

    Christner, Emanuel; Pfahl, Stephan; Schädler, Gerd


    Atmospheric water in form of vapor or clouds is responsible for ˜75 % of the natural greenhouse effect and carries huge amounts of latent heat. For this reason, a best possible description of the hydrological cycle is a prerequisite for reliable climate modelling. As the stable isotopes H216O, H218O and HDO differ in vapor pressure, they are fractionated during phase changes and contain information about the formation of precipitation, evaporation from the ground, etc. Therefore, the isotopic composition of atmospheric water is an useful tracer to test and improve our understanding of the extremely complex and variable hydrological cycle in Earth's atmosphere. Within the project PalMod the isotope-enabled limited-area model COSMOiso will be used for high-resolution isotope simulations of paleo-climates. For validation with modern observations we compare 12 years of modelled isotope ratios from Central Europe to observations of the Global Network of Isotopes in Precipitation (GNIP) and to observations of isotope ratios of water vapor at different locations in Germany. We find a good agreement of modelled and observed isotope ratios in summer. In winter, we observe a systematic overestimation of modelled isotope ratios in precipitation and low-level water vapor. We relate those differences to specific circulation regimes with predominantly easterly moisture transport and the corresponding strong dependence of modelled isotope ratios on lateral boundary data. Furthermore, we investigate the dependence of modelled isotope ratios in winter on the type of isotope fractionation during surface evaporation at skin temperatures close to the freezing point.

  7. Titanium corrosion in alkaline hydrogen peroxide environments (United States)

    Been, Jantje


    The corrosion of Grade 2 titanium in alkaline hydrogen peroxide environments has been studied by weight loss corrosion tests, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR) measurements and potentiodynamic polarography. Calcium ions and wood pulp were investigated as corrosion inhibitors. In alkaline peroxide, the titanium corrosion rate increased with increasing pH, temperature, and hydrogen peroxide concentration. The corrosion controlling mechanism is thought to be the reaction of the oxide with the perhydroxyl ion. No evidence of thermodynamically stable calcium titanate was found in the surface film of test coupons exposed to calcium-inhibited alkaline peroxide solutions. Calcium inhibition is probably the result of low local alkali and peroxide concentrations at the metal surface produced by reaction of adsorbed calcium with hydrogen peroxide. It has been shown that the inhibiting effect of calcium is temporary, possibly through an effect of calcium on the chemical and/or physical stability of the surface oxide. Pulp is an effective and stable corrosion inhibitor. Raising the pulp concentration decreased the corrosion rate. The inhibiting effect of pulp may be related to the adsorption and interaction of the pulp fibers with H 2O2, thereby decreasing the peroxide concentration and rendering the solution less corrosive. The presence of both pulp and calcium led to higher corrosion rates than obtained by either one inhibitor alone. Replacement of hydrofluoric acid with alkaline peroxide for pickling of titanium was investigated. Titanium corrosion rates in alkaline peroxide exceeded those obtained in the conventional hydrofluoric acid bath. General corrosion was observed with extensive roughening of the surface giving a dull gray appearance. Preferred dissolution of certain crystallographic planes was investigated through the corrosion of a titanium single crystal. Whereas the overall effect on the corrosion rate was small

  8. 外源稀土La3+对鄂尔多斯高原碱湖钝顶节旋藻生长及生理特性的影响%Effects of External Rare Earth La3+ on Growth and Physiological Property of Arthrospira in Alkaline Lake of Erdos Plateau

    Institute of Scientific and Technical Information of China (English)

    巩东辉; 李国龙; 张少英; 陈涛


    以鄂尔多斯高原碱湖的钝顶节旋藻(S1)为实验材料,采用生理与生物化学的方法测定了外源稀土元素La3+对S1生长的影响.结果表明:一定浓度的La3+对S1生长繁殖有明显的促进作用.在S1藻体细胞生长的初期La3+对其生长影响不明显;随着培养时间的延长,La3+对S1生长的影响逐渐显著(p <0.05);La3+浓度为38.53~53.94 μmol·L-1时S1的生长较快,其中La3+浓度为53.94 μmol·L-1时对S1的生物量、叶绿素含量、胞内多糖和可溶性蛋白质含量促进作用最显著(p <0.01);La3+浓度高于53.94 μmol·L-1时对S1的生长产生抑制作用.%The effects of La3 + on the growth of Arthro-spira platensis in the alkaline lake of Erdos Plateau ( S1) were studied by the physiological and biochemical method. The results showed that a certain amount of lanthanum played a catalytic role on the growth of S1. The effect of lanthanum on the algae cells in the early growth stage was not obvious, but increased significantly with time(p < 0. 05 ). The growth of S, was much quicker when the concentration of lanthanumwas between 38.53 and 53.94 μmol·L-1. The growth and the content of chlorophyll a, intracellular polysac-charide, soluble protein of S1 were most significant as the concentration of lanthanum was 53. 935μmol·L-1 (p < 0. 01). The growth of algae cell was inhibited when the concentration of lanthanum was over 53. 94 μmol·L-1.

  9. Isotopic constraints of mantle derived carbonatitic melts from Calatrava, Spain (United States)

    Humphreys, E. R.; Bailey, K.; Hawkesworth, C. J.; Wall, F.; Avanzinelli, R.


    Carbonatite volcanism is typically associated both spatially and temporally with alkaline, ultramafic volcanism (Woolley & Church, 2005). Recent discoveries in Calatrava, Spain illustrate the activity of carbonatite in the source melts of leucitite volcanism. Melilitite pyroclastic lapilli tuffs also show a clear association with volcanic carbonate. Carbonatitic activity has been shown to initiate at depths greater than 100km (Humphreys et al., 2010) despite a maximum estimate of lithospheric thickness of 80km. The presence of aragonite and abundant mantle xenoliths in many deposits are clear indication of the rapid emplacement rates of such magmas. Carbonatitic activity in the source of the leucitite melts is indicated by carbonate inclusions within olivine xenocrysts and the presence of occasional carbonatite lenses. The composition of lead and strontium isotope ratios in the bulk rock, and spatially resolved analysis of carbonate from the groundmass and from inclusions demonstrates a genetic affinity between the inclusions and the related bulk rock composition. Lead and strontium isotopic analysis suggest that such melts do not represent the composition of convecting asthenospheric mantle. 87Sr/86Sr (0.7055-0.7068) values are higher than those of MORB and most OIB. Lead isotope ratios show a trend displaced to higher 207Pb/204Pb relative to MORB and OIB. Carbonate inclusions have less radiogenic lead values than the more radiogenic bulk rocks. Our data indicate that carbonatitic activity in the mantle is intrinsic in the generation of the leucitite lava. However, petrographic and isotopic evidence suggest a complex melt history. Olivine xenocrysts are not in equilibrium with the host leucitite, despite inclusions within olivine showing an isotopic affinity to the bulk rock. We suggest that in this example, alkaline magmatism was induced by the presence of CO2 in the mantle source. Isotopic evidence shows that the mantle producing such melts was not

  10. Geochemical arguments for an Earth-like Moon-forming impactor


    Dauphas, Nicolas; Burkhardt, Christoph; Warren, Paul H.; Fang-Zhen, Teng


    Geochemical evidence suggests that the material accreted by the Earth did not change in nature during Earth's accretion, presumably because the inner protoplanetary disc had uniform isotopic composition similar to enstatite chondrites, aubrites and ungrouped achondrite NWA 5363/5400. Enstatite meteorites and the Earth were derived from the same nebular reservoir but diverged in their chemical evolutions, so no chondrite sample in meteorite collections is representative of the Earth's building...

  11. Isotope determination of sulfur by mass spectrometry in soil samples

    Directory of Open Access Journals (Sweden)

    Alexssandra Luiza Rodrigues Molina Rossete


    Full Text Available Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-, which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2- concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms was carried out by isotope ratio mass spectrometry (IRMS. In this work, the labeled material (K2(34SO4 was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

  12. 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....

  13. Xenon isotopic constraints on the timing of atmospheric volatile recycling (United States)

    Parai, R.; Mukhopadhyay, S.


    Constraints on the recycling of atmospheric volatiles into the deep Earth provide important insights into mantle temperature, cooling rate, structure and style of convection over Earth history. Studies of ancient atmospheric gases trapped in Archean cherts show that the Xe isotopic composition of the atmosphere at ~3.5 Ga differed from the modern atmosphere [1]. This suggests the atmosphere evolved in isotopic composition until it reached its present-day composition at some time after 3.5 Ga. The evolution of the atmospheric Xe isotopic composition presents an opportunity to constrain the timing of Xe recycling into the Earth's mantle. Xe isotopes measured in mid-ocean ridge basalts [MORBs; 2,3] and plume-related basalts [4,5] indicate that both the upper mantle and plume source Xe isotopic compositions are dominated by recycled Xe [e.g., 3]. We find that the mantle source Xe isotopic compositions cannot be explained by recycling ancient atmospheric Xe alone; rather, subduction and incorporation of material bearing the modern atmospheric Xe composition must dominate. We note that our findings are consistent with a number of physical reasons that recently-subducted volatiles should be more prevalent than ancient subducted volatiles. First, a higher Archean mantle potential temperature should inhibit early Xe recycling to the deep Earth. Second, since the mantle turnover time scale is estimated to be between a few hundreds of Myr and 1 Gyr, the mantle recycled atmospheric Xe budget should be primarily composed of Xe subducted after ~2.5 Ga, at which point the atmosphere approaches the modern Xe composition [1]. Therefore, even if ancient atmospheric Xe were recycled efficiently to the mantle early in Earth history, the recycled atmospheric Xe budget of the mantle should still be dominated by the modern atmospheric Xe composition. [1] Pujol et al., 2011, EPSL; [2] Tucker et al., 2012, EPSL; [3] Parai and Mukhopadhyay, 2015, G-cubed; [4] Mukhopadhyay, 2012, Nature; [5

  14. Chromium Isotopes Record Fluctuations in Precambrian Biospheric Oxygenation (United States)

    Frei, R.; Gaucher, C.; Poulton, S. W.; Canfield, D. E.


    There is a direct relationship between life, oxygen, and the surface chemistry of the Earth. Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps, near the beginning and the end of the Proterozoic Eon (2500 to 542 million years ago), but the details of this history are unclear. The geochemical behaviour of chromium (Cr) is highly sensitive to the redox state of the surface environment as oxidative weathering processes produce the oxidised hexavalent [Cr(VI)] form. Oxidation of reduced trivaltent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. The fractionated Cr isotope signature is then tranfered by riverine transport to the sea. Here, we use Cr stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of Earth’s atmosphere-hydrosphere system. Fractionated Cr isotopes indicate the accumulation of Cr(VI) in ocean surface waters ~2.8 to 2.6 billion years (Gyr) ago and a likely transient elevation in atmospheric and surface ocean oxygen prior to the first great rise of oxygen 2.45-2.2 Gyr ago (the Great Oxidation Event; GOE). In contrast, Cr isotopes in ~1.88 Gyr old BIFs are not fractionated, indicating a major decline in atmospheric oxygen and demonstrating that the GOE did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, ~800 to 542 million years (Myr) ago, we observe strong positive fractionations in Cr isotopes (δ53Cr up to +4.9 ‰) providing independent support for increased surface oxygenation at this time. This may have stimulated rapid evolution of macroscopic multicellular life. Our chromium isotope data thus provide new insights into the oxygenation history of the Earth, and highlight its use as a powerful redox tracer in aquatic systems.

  15. Chromium isotope uptake in carbonates

    DEFF Research Database (Denmark)

    Rodler, Alexandra

    composition of contemporaneous seawater. Marine carbonates are ubiquitous throughout Earth’s rock record rendering them a particularly interesting archive for constraining past changes in ocean chemistry. This thesis includes an investigation of the fractionation behavior of Cr isotopesduring coprecipitation......Chromium (Cr) is a redox sensitive element potentially capable of tracing fine-scale fluctuations of the oxygenation of Earth’s early surface environments and seawater. The Cr isotope composition of carbonates could perhaps be used as paleo-redox proxy to elucidate changes in the geological past...... related to the rise of oxygen and the evolution of the biosphere. However, before the Cr isotopesystem can be applied to faithfully delineate paleo-environmental changes, careful assessment of the signal robustness and a thorough understanding of the Cr cycle in Earth system processes is necessary...

  16. Alkaline regenerative fuel cell energy storage system for manned orbital satellites (United States)

    Martin, R. E.; Gitlow, B.; Sheibley, D. W.


    It is pointed out that the alkaline regenerative fuel cell system represents a highly efficient, lightweight, reliable approach for providing energy storage in an orbiting satellite. In addition to its energy storage function, the system can supply hydrogen and oxygen for attitude control of the satellite and for life support. A summary is presented of the results to date obtained in connection with the NASA-sponsored fuel cell technology advancement program, giving particular attention to the requirements of the alkaline regenerative fuel cell and the low-earth mission. Attention is given to system design guidelines, weight considerations, gold-platinum cathode cell performance, matrix development, the electrolyte reservoir plate, and the cyclical load profile tests.

  17. Rare Earth Market Review

    Institute of Scientific and Technical Information of China (English)


    @@ Oversupply of rare earths led to the significant price drop of rare earth mineral products and separated products in Chinese domestic market. To stabilize the price, prevent waste of resources, further improve regulation capability on domestic rare earth market and rare earth price and maintain sustaining and healthy development of rare earth industry, partial rare earth producers in Baotou and Jiangxi province projected to cease the production for one month.

  18. [Leucocyte alkaline phosphatase in normal and pathological pregnancy (author's transl)]. (United States)

    Stark, K H; Zaki, I; Sobolewski, K


    The activities of leucocyte alkaline phosphatase were determined in 511 patients with normal and pathological pregnancy. Mean values were compared and the enzyme followed up, and the conclusion was drawn that leucocyte alkaline phosphatase was no safe indicator of foetal condition. No direct relationship were found to exist between leucocyte alkaline phosphatase, total oestrogens, HSAP, HLAP, HPL, and oxytocinase.

  19. Cretaceous alkaline volcanism in south Marzanabad, northern central Alborz, Iran: Geochemistry and petrogenesis

    Directory of Open Access Journals (Sweden)

    Roghieh Doroozi


    Full Text Available The alkali-basalt and basaltic trachy-andesites volcanic rocks of south Marzanabad were erupted during Cretaceous in central Alborz, which is regarded as the northern part of the Alpine-Himalayan orogenic belt. Based on petrography and geochemistry, en route fractional crystallization of ascending magma was an important process in the evolution of the volcanic rocks. Geochemical characteristics imply that the south Marzanabad alkaline basaltic magma was originated from the asthenospheric mantle source, whereas the high ratios of (La/YbN and (Dy/YbN are related to the low degree of partial melting from the garnet bearing mantle source. Enrichment pattern of Nb and depletion of Rb, K and Y, are similar to the OIB pattern and intraplate alkaline magmatic rocks. The K/Nb and Zr/Nb ratios of volcanic rocks range from 62 to 588 and from 4.27 to 9 respectively, that are some higher in more evolved samples which may reflect minor crustal contamination. The isotopic ratios of Sr and Nd respectively vary from 0.70370 to 0.704387 and from 0.51266 to 0.51281 that suggest the depleted mantle as a magma source. The development of south Marzanabad volcanic rocks could be related to the presence of extensional phase, upwelling and decompressional melting of asthenospheric mantle in the rift basin which made the alkaline magmatism in Cretaceous, in northern central Alborz of Iran.

  20. REE characteristics and genesis of alkaline-rich porphyry, Yunnan Province

    Institute of Scientific and Technical Information of China (English)


    The Yunnan Himalayan alkaline-rich porphyry occurs as a compound rockbelt and consists of calca-alkalic, alkaline and peralkaline intrusions. Its origin is in debate. The paper deals with its origin by studying rock′s REE and Sr isotope. Although the rocks are different in their REE contents varying from 77.53 μg/g to 1 798.3 μg/g, they have very similar features in REE parameters. On the triangalar diagram of REEs, the sample dots are concentrated on the end area of light REEs, representing a product of low-degree melting of upper mantle or lower crust materials. The initial 87Sr/86Sr values of rocks vary between 0.706 4 and 0.709 8, showing a feature of mantle-crust mixed source. Moreover, REEs show a logarithmic linear positive correlation between them. This type of correlation strongly supports the fractional-partial melting model. The result of geochemistry inversion shows that the source rock of alkaline-rich porphyry is plagioclase-bearing harzburgite and of mantle-crust mixed type. At the early state of melting, some crust components of the source rock were partially melted into intermediate-acidic magma; with the crust components consumed, the magma evolved to basic.

  1. Calcium isotopic compositions of mid-ocean ridge basalts (United States)

    Zhu, H.; Zhang, Z.; Sun, W.; Wang, G. Q.


    Previous studies have demonstrated that Earth's mantle has heterogeneous calcium isotopic compositions. But the reason why mantle has its heterogeneity remains uncertain. In general, δ44/40Ca values of mantle xenolith samples have a variation of >0.45‰. While ultramafic rocks, especially dunites, have higher δ44/40Ca values than volcanic rocks, and there is a positive correlation between δ44/40Ca and Ca/Mg. These phenomena imply that the heterogeneity of Ca isotopic compositions of mantle xenolith samples might result from different degrees of melt extraction, as indicated by large Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene. However, because ancient marine carbonate has its own unique calcium isotopic characteristics, recycling of even a small amount of ancient marine carbonates into the mantle could also cause the heterogeneity of Ca isotopes in Earth's mantle. This could be the reason why oceanic island basalts (OIB) have lighter Ca isotopic compositions than the mantle xenolith. Thus, the lighter Ca isotopic compositions in the mantle source cannot only be ascribed to magmatic processes. Therefore, it is more important to know calcium isotopic characteristics during partial melting and oceanic crust contamination.Mid-ocean ridge basalts (MORB) are formed from the partial melts of the upper mantle and are rarely affected by crustal contamination. Different types of MORB, including D-MORB, N-MORB and E-MORB, have experienced different degrees of partial melting and contamination of enriched end-members. Here we report calcium isotopic characteristic of different types of MORB, we believe it will be very helpful to understand the behaviors of Ca isotopes during partial melting and it is possible to provide further information to discover the reason why calcium isotopic compositions is heterogeneous in Earth's mantle. This work was supported by Natural Science Foundation of China (No. 41373007, No. 41490632 and No. 91328204

  2. Silicon isotopes in angrites and volatile loss in planetesimals (United States)

    Moynier, Frédéric; Savage, Paul S.; Badro, James; Barrat, Jean-Alix


    Inner solar system bodies, including the Earth, Moon, and asteroids, are depleted in volatile elements relative to chondrites. Hypotheses for this volatile element depletion include incomplete condensation from the solar nebula and volatile loss during energetic impacts. These processes are expected to each produce characteristic stable isotope signatures. However, processes of planetary differentiation may also modify the isotopic composition of geochemical reservoirs. Angrites are rare meteorites that crystallized only a few million years after calcium–aluminum-rich inclusions and exhibit extreme depletions in volatile elements relative to chondrites, making them ideal samples with which to study volatile element depletion in the early solar system. Here we present high-precision Si isotope data that show angrites are enriched in the heavy isotopes of Si relative to chondritic meteorites by 50–100 ppm/amu. Silicon is sufficiently volatile such that it may be isotopically fractionated during incomplete condensation or evaporative mass loss, but theoretical calculations and experimental results also predict isotope fractionation under specific conditions of metal–silicate differentiation. We show that the Si isotope composition of angrites cannot be explained by any plausible core formation scenario, but rather reflects isotope fractionation during impact-induced evaporation. Our results indicate planetesimals initially formed from volatile-rich material and were subsequently depleted in volatile elements during accretion. PMID:25404309

  3. Silicon isotopes in angrites and volatile loss in planetesimals. (United States)

    Pringle, Emily A; Moynier, Frédéric; Savage, Paul S; Badro, James; Barrat, Jean-Alix


    Inner solar system bodies, including the Earth, Moon, and asteroids, are depleted in volatile elements relative to chondrites. Hypotheses for this volatile element depletion include incomplete condensation from the solar nebula and volatile loss during energetic impacts. These processes are expected to each produce characteristic stable isotope signatures. However, processes of planetary differentiation may also modify the isotopic composition of geochemical reservoirs. Angrites are rare meteorites that crystallized only a few million years after calcium-aluminum-rich inclusions and exhibit extreme depletions in volatile elements relative to chondrites, making them ideal samples with which to study volatile element depletion in the early solar system. Here we present high-precision Si isotope data that show angrites are enriched in the heavy isotopes of Si relative to chondritic meteorites by 50-100 ppm/amu. Silicon is sufficiently volatile such that it may be isotopically fractionated during incomplete condensation or evaporative mass loss, but theoretical calculations and experimental results also predict isotope fractionation under specific conditions of metal-silicate differentiation. We show that the Si isotope composition of angrites cannot be explained by any plausible core formation scenario, but rather reflects isotope fractionation during impact-induced evaporation. Our results indicate planetesimals initially formed from volatile-rich material and were subsequently depleted in volatile elements during accretion.

  4. Tracing recycled volatiles in a heterogeneous mantle with boron isotopes (United States)

    Walowski, Kristina; Kirstein, Linda; de Hoog, Cees-Jan; Elliot, Tim; Savov, Ivan; Devey, Colin


    Recycling of oceanic lithosphere drives the chemical evolution of the Earth's mantle supplying both solids and volatiles to the Earth's interior. Yet, how subducted material influences mantle composition remains unclear. A perfect tracer for slab recycling should be only fractionated at the Earth's surface, have a strong influence on mantle compositions but be resistant to perturbations en route back to the surface. Current understanding suggests that boron concentrations linked to B isotope determinations fulfil all these requirements and should be an excellent tracer of heterogeneity in the deep mantle. Here, we present the trace element, volatile and the B isotope composition of basaltic glasses and melt inclusions in olivine from distinct end-member ocean island basalts (OIB) to track the fate of recycled lithosphere and ultimately document how recycling contributes to mantle heterogeneity. The chosen samples represent the different end member OIB compositions and include: EMI (Pitcairn), EMII (MacDonald), HIMU (St. Helena), and FOZO (Cape Verde & Reunion). The data is derived from both submarine and subaerial deposits, with B isotope determination of both basaltic glass and melt inclusions from each locality. Preliminary results suggest OIB have B isotopic compositions that overlap the MORB array (-7.5‰±0.7; Marschall et al., 2015) but extend to both lighter and heavier values. These results suggest that B isotopes will be useful for resolving mantle source heterogeneity at different ocean islands and contribute to our understanding of the volatile budget of the deep mantle.

  5. Discovery of the Cobalt Isotopes


    Szymanski, T.; Thoennessen, M.


    Twenty-six cobalt isotopes have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  6. Discovery of the Arsenic Isotopes

    CERN Document Server

    Shore, A; Heim, M; Schuh, A; Thoennessen, M


    Twenty-nine arsenic isotopes have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  7. Intracellular Cadmium Isotope Fractionation (United States)

    Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.


    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  8. Iron isotope composition of some Archean and Proterozoic iron formations (United States)

    Planavsky, Noah; Rouxel, Olivier J.; Bekker, Andrey; Hofmann, Axel; Little, Crispin T. S.; Lyons, Timothy W.


    Fe isotopes can provide new insight into redox-dependent biogeochemical processes. Precambrian iron formations (IF) are deserving targets for Fe isotope studies because they are composed predominantly of authigenic Fe phases and record a period of unprecedented iron deposition in Earth's history. We present Fe isotope data for bulk samples from 24 Archean and Proterozoic IF and eight Phanerozoic Fe oxide-rich deposits. These data reveal that many Archean and early Paleoproterozoic iron formations were a sink for isotopically heavy Fe, in contrast to later Proterozoic and Phanerozoic Fe oxide-rich rocks. The positive δ56Fe values in IF are best explained by delivery of particulate ferric oxides formed in the water column to the sediment-water interface. Because IF are a net sink for isotopically heavy Fe, there must be a corresponding pool of isotopically light Fe in the sedimentary record. Earlier work suggested that Archean pyritic black shales were an important part of this light sink before 2.35 billion years ago (Ga). It is therefore likely that the persistently and anomalously low δ56Fe values in shales are linked with the deposition of isotopically heavy Fe in IF in the deeper parts of basins. IF deposition produced a residual isotopically light dissolved Fe pool that was captured by pyritic Fe in shales. Local dissimilatory Fe reduction in porewater and associated diagenetic reactions resulting in pyrite and carbonate precipitation may have further enhanced Fe isotope heterogeneity in marine sediments, and an 'iron shuttle' may have transported isotopically light Fe from shelf sediments to the basin. Nevertheless, water-column processing of hydrothermally delivered Fe likely had the strongest influence on the bulk iron isotope composition of Archean and Paleoproterozoic iron formations and other marine sediments.

  9. Ruthenium isotopic evidence for an inner Solar System origin of the late veneer. (United States)

    Fischer-Gödde, Mario; Kleine, Thorsten


    The excess of highly siderophile elements in the Earth's mantle is thought to reflect the addition of primitive meteoritic material after core formation ceased. This 'late veneer' either comprises material remaining in the terrestrial planet region after the main stages of the Earth's accretion, or derives from more distant asteroidal or cometary sources. Distinguishing between these disparate origins is important because a late veneer consisting of carbonaceous chondrite-like asteroids or comets could be the principal source of the Earth's volatiles and water. Until now, however, a 'genetic' link between the late veneer and such volatile-rich materials has not been established or ruled out. Such genetic links can be determined using ruthenium (Ru) isotopes, because the Ru in the Earth's mantle predominantly derives from the late veneer, and because meteorites exhibit Ru isotope variations arising from the heterogeneous distribution of stellar-derived dust. Although Ru isotopic data and the correlation of Ru and molybdenum (Mo) isotope anomalies in meteorites were previously used to argue that the late veneer derives from the same type of inner Solar System material as do Earth's main building blocks, the Ru isotopic composition of carbonaceous chondrites has not been determined sufficiently well to rule them out as a source of the late veneer. Here we show that all chondrites, including carbonaceous chondrites, have Ru isotopic compositions distinct from that of the Earth's mantle. The Ru isotope anomalies increase from enstatite to ordinary to carbonaceous chondrites, demonstrating that material formed at greater heliocentric distance contains larger Ru isotope anomalies. Therefore, these data refute an outer Solar System origin for the late veneer and imply that the late veneer was not the primary source of volatiles and water on the Earth.

  10. Mission to Very Early Earth

    Energy Technology Data Exchange (ETDEWEB)

    Hutcheon, I D; Weber, P K; Fallon, S J; Smith, J B; Aleon, J; Ryerson, F J; Harrison, T M; Cavosie, A J; Valley, J W


    The Hadean Earth is often viewed as an inhospitable and, perhaps, unlikely setting for the rise of primordial life. However, carbonaceous materials supplied by accreting meteorites and sources of chemical energy similar to those fueling life around modern deep-sea volcanic vents would have been present in abundance. More questionable are two other essential ingredients for life - liquid water and clement temperatures. Did the Hadean Earth possess a hydrosphere and temperate climate compatible with the initiation of biologic activity? If so, the popular model of an excessively hot planetary surface characterized by a basaltic crust, devoid of continental material is invalid. Similarly, establishment of an Hadean hydrosphere prior to the cessation of heavy asteroid bombardment may mean that primitive life could have evolved and then been extinguished, only to rise again. The most effective means of determining the environmental conditions on this young planet is through geochemical analysis of samples retrieved from the Early Earth. While rocks older than 4 billion years (4 Ga) have not been found, individual zircon grains, the detritus of rocks long since eroded away, have been identified with ages as old as 4.4 Ga - only {approx}160 million years younger than the Earth itself. If we can use the geochemical information contained in these unique samples to infer the nature of their source rocks and the processes that formed them, we can place constraints on the conditions prevailing at the Earth's surface shortly after formation. This project utilizes a combined analytical and experimental approach to gather the necessary geochemical data to determine the parameters required to relate the zircons to their parent materials. Mission to Early Earth involves dating, isotopic and chemical analyses of mineral and melt inclusions within zircons and of the zircons themselves. The major experimental activity at LLNL focused on the partitioning of trace elements between

  11. Hf isotope evidence for a hidden mantle reservoir

    DEFF Research Database (Denmark)

    Bizzarro, Martin; Simonetti, A.; Stevenson, R.K.;


    High-precision Hf isotopic analyses and U-Pb ages of carbonatites and kimberlites from Greenland and eastern North America, including Earth's oldest known carbonatite (3 Ga), indicate derivation from an enriched mantle source. This previously unidentified mantle reservoir-marked by an unradiogeni...

  12. Instability of some divalent rare earth ions and photochromic effect (United States)

    Egranov, A. V.; Sizova, T. Yu.; Shendrik, R. Yu.; Smirnova, N. A.


    It was shown that the divalent rare earth ions (La, Ce, Gd, Tb, Lu, and Y) in cubic sites in alkaline earth fluorides are unstable with respect to electron autodetachment since its d1(eg) ground state is located in the conduction band which is consistent with the general tendency of these ions in various compounds. The localization of doubly degenerate d1(eg) level in the conduction band creates a configuration instability around the divalent rare earth ion that leading to the formation of anion vacancy in the nearest neighborhood, as was reported in the previous paper [A. Egranov, T. Sizova, Configurational instability at the excited impurity ions in alkaline earth fluorites, J. Phys. Chem. Solids 74 (2013) 530-534]. Thus, the formation of the stable divalent ions as La, Ce, Gd, Tb, Lu, and Y (PC+ centers) in CaF2 and SrF2 crystals during x-ray irradiation occurs via the formation of charged anion vacancies near divalent ions (Re2+va), which lower the ground state of the divalent ion relative to the conductivity band. Photochromic effect occurs under thermally or optically stimulated electron transition from the divalent rare earth ion to the neighboring anion vacancy and reverse under ultraviolet light irradiation. It is shown that the optical absorption of the PC+ centers due to d → d and d → f transitions of the divalent rare-earth ion.

  13. Uranium Isotope Ratios in Modern and Precambrian Soils (United States)

    DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.


    Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

  14. Alkaline and ultrasound assisted alkaline pretreatment for intensification of delignification process from sustainable raw-material. (United States)

    Subhedar, Preeti B; Gogate, Parag R


    Alkaline and ultrasound-assisted alkaline pretreatment under mild operating conditions have been investigated for intensification of delignification. The effect of NaOH concentration, biomass loading, temperature, ultrasonic power and duty cycle on the delignification has been studied. Most favorable conditions for only alkaline pretreatment were alkali concentration of 1.75 N, solid loading of 0.8% (w/v), temperature of 353 K and pretreatment time of 6 h and under these conditions, 40.2% delignification was obtained. In case of ultrasound-assisted alkaline approach, most favorable conditions obtained were alkali concentration of 1N, paper loading of 0.5% (w/v), sonication power of 100 W, duty cycle of 80% and pretreatment time of 70 min and the delignification obtained in ultrasound-assisted alkaline approach under these conditions was 80%. The material samples were characterized by FTIR, SEM, XRD and TGA technique. The lignin was recovered from solution by precipitation method and was characterized by FTIR, GPC and TGA technique.

  15. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    is incorporated into carbonates. Hence, ancient carbonates can potentially record the Cr isotopic composition (δ53Cr ‰) of seawater in the geological past. Reliable application and interpretation of this proxy requires a detailed knowledge about processes that fractionate Cr on the Earth’s surface...... deposited during the Early Ordovician — a time of known redox instability in ancient oceans – exhibit a significant positive Cr isotope excursion of +0.5‰. This excursion is interpreted as the reductive drawn down of dissolved Cr in seawater in response to the development of a proximal anoxic sink......, and the quantification the Cr isotope composition of major Cr fluxes into and out of ocean. This thesis adds to the current knowledge of the Cr isotope system and is divided into two studies. The focus of the first study was to determine what processes control the Cr isotopic compositionof river water and to quantify...

  16. Ru isotope heterogeneity in the solar protoplanetary disk (United States)

    Fischer-Gödde, Mario; Burkhardt, Christoph; Kruijer, Thomas S.; Kleine, Thorsten


    Nucleosynthetic isotope anomalies in bulk chondrites and differentiated meteorites reflect variable proportions of isotopically diverse presolar components in bulk planetary bodies, but the origin of these heterogeneities is not well understood. Here, the Ru isotope composition of a comprehensive suite of iron meteorites and bulk samples of ordinary, enstatite and carbonaceous chondrites, as well as acid leachates and an insoluble residue of the Allende chondrite are examined using newly developed multi-collector inductively coupled plasma mass spectrometry techniques. Except for IAB iron meteorites and enstatite chondrites, all investigated meteorites show well-resolved Ru isotope anomalies. Of these, within-group Ru isotopic variations observed for samples from a given chemical group of iron meteorites reflect secondary neutron capture induced Ru isotope shifts during prolonged cosmic ray-exposure. After correction of these cosmogenic effects using Pt isotopes as a neutron-dose monitor, the remaining Ru isotope anomalies are nucleosynthetic in nature and are consistent with a deficit in s-process Ru in iron meteorite parent bodies. Similarly, Ru isotope anomalies in bulk ordinary and carbonaceous chondrites also reflect a deficiency in s-process Ru. The sequential dissolution of Allende reveals the presence of an HF-soluble s-process carrier, which is either an unidentified presolar phase or a component that incorporated s-process Ru liberated from SiC grains during nebular or parent body processes. We show that varying proportions of the s-process carrier identified in Allende resulted in the correlated Ru isotope anomalies observed for bulk meteorites, and that all meteorites (except possibly IAB irons and enstatite chondrites) are depleted in this s-process component relative to Ru from the Earth's mantle. Bulk meteorites exhibit correlated Ru and Mo isotope anomalies, reflecting variable deficits of a common s-process component, but some iron meteorites and

  17. Deselenization and detellurization of precious-metal ore concentrates by swelling oxidizing roasting and successive alkaline leaching (United States)

    Zhang, Fu-yuan; Zheng, Ya-jie; Peng, Guo-min


    A new technique of swelling oxidizing roasting and alkaline leaching was proposed for deselenization and detellurization of precious-metal ore concentrates. Alkali-metal and alkaline-earth-metal chlorides and carbonates were preliminarily selected as swelling agents. The roasting removal rate and alkaline leaching rate of selenium and tellurium were investigated, and NaCl was selected as an appropriate swelling agent. Furthermore, the effects of various factors on the selenium gasification rate and leaching rate of selenium and tellurium were investigated. The results show that the selenium gasification rate reaches 88.41% after swelling oxidizing roasting for 2 h at 510°C using an NaCl dosage coefficient of 100 and a sulfuric acid dosage coefficient of 1.3; the amorphous elemental tellurium is completely transformed into TiO2. The roasted product is subjected to alkaline leaching using a 100 g/L NaOH solution, which results in a selenium leaching rate of 10.51%, a total selenium removal rate of 98.92%, and a tellurium leaching rate of 97.64%. In the alkaline leaching residue, the contents of selenium, tellurium, gold, platinum, and palladium are 0.7825%, 5.492%, 8.333%, 0.2587%, and 1.113%, respectively; the precious metals are enriched approximately sixfold.

  18. Earth from Above (United States)

    Stahley, Tom


    Google Earth is a free online software that provides a virtual view of Earth. Using Google Earth, students can view Earth by hovering over features and locations they preselect or by serendipitously exploring locations that catch their fascination. Going beyond hovering, they can swoop forward and even tilt images to make more detailed…

  19. Cretaceous alkaline intra-plate magmatism in the Ecuadorian Oriente Basin: Geochemical, geochronological and tectonic evidence (United States)

    Barragán, Roberto; Baby, Patrice; Duncan, Robert


    Small volumes of Cretaceous alkaline basaltic magmas have been identified in the sedimentary infill of the Ecuadorian Oriente foreland basin. They are characterized by a restricted range of compositional variation, low LILE/HFSE ratios and Sr-Nd isotope values within the range of oceanic island basalts (OIB). Reflection seismic data show that a pre-existing NNE-SSW Triassic and Jurassic rift controls the location and occurrence of these alkaline eruptive sites. Radiometric ages ( 40Ar- 39Ar, incremental heating method) and the biostratigraphic record of their surrounding sediments indicate a NNE-SSW systematic age variation for the emplacement of this alkaline volcanism: from Albian (110 ± 5.2 Ma) in the northern part of the Oriente Basin, to Campanian (82.2 ± 2.0 Ma) in the west-central part. The geochemical, geochronological and tectonic evidences suggest that asthenospheric mantle has upwelled and migrated to the SSW, into the region underlying the pre-existing Triassic and Jurassic rift (thin-spot?). We propose that subduction was abandoned, subsequent to the accretion of allochthonous terranes onto the Ecuadorian and Colombian margin in the latest Jurassic-earliest Cretaceous, causing the relict slab material, corresponding to the eastwards-directed leading plate, to roll-back. Unmodified asthenospheric mantle migrated into the region previously occupied by the slab. This resulted in partial melting and the release of magmatic material to the surface in the northern part of the Oriente Basin since at least Aptian times. Then, magmatism migrated along the SSW-trending Central Wrench Corridor of the Oriente Basin during the Upper Cretaceous, probably as a consequence of the lateral propagation of the transpressive inversion of the Triassic-Jurassic rift. Eventually, the Late Cretaceous east-dipping Andean subduction system was renewed farther west, and the development of the compressional retro-foreland Oriente Basin system halted the Cretaceous alkaline

  20. Rare Earth Resolution

    Institute of Scientific and Technical Information of China (English)

    Mei Xinyu


    BEFORE the early 1970s, China had no rare earth exports, and the world rare earth market was dominated by the United States, Europe and Japan. In the 1970s, China began to enter the world rare earth market and its share has picked up sharply in the following decades. Today, having the monopoly over global rare earth production, China must improve the benefits from rare earth production, not only from producing individual rare earth products, but also from mastering the intensive processing of rare earth products.

  1. Modes of planetary-scale Fe isotope fractionation (United States)

    Schoenberg, Ronny; Blanckenburg, Friedhelm von


    A comprehensive set of high-precision Fe isotope data for the principle meteorite types and silicate reservoirs of the Earth is used to investigate iron isotope fractionation at inter- and intra-planetary scales. 14 chondrite analyses yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of - 0.015 ± 0.020‰ (2 SE) relative to the international iron standard IRMM-014. Eight non-cumulate and polymict eucrite meteorites that sample the silicate portion of the HED (howardite-eucrite-diogenite) parent body yield an average δ56Fe/ 54Fe value of - 0.001 ± 0.017‰, indistinguishable to the chondritic Fe isotope composition. Fe isotope ratios that are indistinguishable to the chondritic value have also been published for SNC meteorites. This inner-solar system homogeneity in Fe isotopes suggests that planetary accretion itself did not significantly fractionate iron. Nine mantle xenoliths yield a 2 σ envelope of - 0.13‰ to + 0.09‰ in δ56Fe/ 54Fe. Using this range as proxy for the bulk silicate Earth in a mass balance model places the Fe isotope composition of the outer liquid core that contains ca. 83% of Earth's total iron to within ± 0.020‰ of the chondritic δ56Fe/ 54Fe value. These calculations allow to interprete magmatic iron meteorites ( δ56Fe/ 54Fe = + 0.047 ± 0.016‰; N = 8) to be representative for the Earth's inner metallic core. Eight terrestrial basalt samples yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of + 0.072 ± 0.016‰. The observation that terrestrial basalts appear to be slightly heavier than mantle xenoliths and that thus partial mantle melting preferentially transfers heavy iron into the melt [S. Weyer, A.D. Anbar, G.P. Brey, C. Munker, K. Mezger and A.B. Woodland, Iron isotope fractionation during planetary differentiation, Earth and Planetary Science Letters 240(2), 251-264, 2005.] is intriguing, but also raises some important questions: first it is questionable whether the

  2. Surfactant-enhanced alkaline flooding: Buffering at intermediate alkaline pH

    Energy Technology Data Exchange (ETDEWEB)

    Rudin, J.; Wasan, D.T. (Illinois Inst. of Tech., Chicago, IL (United States))


    The alkaline flooding process involves injecting alkaline agents into the reservoir to produce more oil than is produced through conventional waterflooding. The interaction of the alkali in the flood water with the naturally occurring acids in the reservoir oil results in in-situ formation of soaps, which are partially responsible for lowering IFT and improving oil recovery. The extent to which IFT is lowered depends on the specific oil and injection water properties. Numerous investigators have attempted to clarify the relationship between system chemical composition and IFT. An experimental investigation of buffered alkaline flooding system chemistry was undertaken to determine the influence of various species present on interfacial tension (IFT) as a function of pH and ionic strength. IFT was found to go through an ultralow minimum in certain pH ranges. This synergism results from simultaneous adsorption of un-ionized and ionized acid species on the interface.

  3. Martian carbon dioxide: Clues from isotopes in SNC meteorites (United States)

    Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.


    Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

  4. Chemical Fractionation in the Silicate Vapor Atmosphere of the Earth

    CERN Document Server

    Pahlevan, Kaveh; Eiler, John; 10.1016/j.epsl.2010.10.03


    Despite its importance to questions of lunar origin, the chemical composition of the Moon is not precisely known. In recent years, however, the isotopic composition of lunar samples has been determined to high precision and found to be indistinguishable from the terrestrial mantle despite widespread isotopic heterogeneity in the Solar System. In the context of the giant-impact hypothesis, this level of isotopic homogeneity can evolve if the proto-lunar disk and post-impact Earth undergo turbulent mixing into a single uniform reservoir while the system is extensively molten and partially vaporized. In the absence of liquid-vapor separation, such a model leads to the lunar inheritance of the chemical composition of the terrestrial magma ocean. Hence, the turbulent mixing model raises the question of how chemical differences arose between the silicate Earth and Moon. Here we explore the consequences of liquid-vapor separation in one of the settings relevant to the lunar composition: the silicate vapor atmosphere...

  5. Alkaline carbonates in blast furnace process

    Directory of Open Access Journals (Sweden)

    P. Besta


    Full Text Available The production of iron in blast furnaces is a complex of physical, chemical and mechanical processes. The input raw materials contain not only metallic components, but also a number of negative elements. The most important negative elements include alkaline carbonates. They can significantly affect the course of the blast furnace process and thus the overall performance of the furnace. As a result of that, it is essential to accurately monitor the alkali content in the blast furnace raw materials. The article analyzes the alkali content in input and output raw materials and their impact on the blast furnace process.

  6. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS) (United States)

    Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.


    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

  7. Iron isotopes in an Archean ocean analogue (United States)

    Busigny, Vincent; Planavsky, Noah J.; Jézéquel, Didier; Crowe, Sean; Louvat, Pascale; Moureau, Julien; Viollier, Eric; Lyons, Timothy W.


    be tied to water column cycling—foremost to the oxidation of dissolved ferrous iron. This supports previous suggestions that enhanced iron isotope variability in the Archean may record a unique stage in Earth's history where partial ferrous iron oxidation in upwelling water masses was a common process, probably linked to oxygenic or anoxygenic photosynthesis.

  8. Long-term landscape evolution of the southeast Brazilian highlands: comparison of two alkaline intrusions areas (United States)

    Doranti Tiritan, Carolina; Hackspacher, Peter Christian; Glasmacher, Ulrich Anton


    . In the SSI area the crystalline basement registered ages 121.1±11.5 Ma and 49.4±4.8 while the alkaline stocks ages ranges 112.5±13; 91.1±11.2Ma; 89.4±13.4 88.2±8.5; 71.3±7.9. The results shows that the main difference between the areas is that PCAM region register older history then the coastal area of SSI, where thermal history starts register cooling event after the South Atlantic rifting process, while in the PCAM area register a previous history, since Carboniferous. The age-elevation relationship shows that the ages decrease systematically with increasing elevation with a break-in-slope near the 150Ma, 80Ma and around 50Ma, which means that the landscape evolution can be associated with several distinct exhumation events at the South American passive continental margin, which include the Gondwana break-up, the Late Cretaceous alkaline magmatism, and the Cenozoic evolution of a N-S trending continental graben system. We are thankful to CAPES/PROBRAL/ processo 12809/13-6, Marli Carina Siqueira Ribeiro, IGCE-UNESP; Earth Sciences Institut, Heidelberg University; References DORANTI-TIRITAN, C. , et al (2014) The Use of the Stream Length-Gradient Index in Morphotectonic Analysis of Drainage Basins in Poços de Caldas Plateau, SE Brazil. International Journal of Geosciences, 5, 1383-1394. doi: 10.4236/ijg.2014.511112 HACKSPACHER, P.C; et al. (2004) Consolidation and Break-Up of The South American Platform in Southeastern Brazil: Tectonothermal and Denudation Histories. Gondwana Research -N°1, P. 91 -101.

  9. Insights into magmatic evolution and recharge history in Capraia Volcano (Italy) from chemical and isotopic zoning in plagioclase phenocrysts

    DEFF Research Database (Denmark)

    Gagnevin, D.; Waight, Tod Earle; Daly, J.S.


    Plagioclase phenocrysts in dacites from the high-K calc-alkaline CapraiaVolcano were investigated for major, trace element and Sr isotope variations in order to gain better insight into the proposed open-system behaviour of the volcano. Repeated dissolution zone in plagioclases from the early-eru...

  10. The Lifeworld Earth and a Modelled Earth (United States)

    Juuti, Kalle


    The goal of this paper is to study the question of whether a phenomenological view of the Earth could be empirically endorsed. The phenomenological way of thinking considers the Earth as a material entity, but not as an object as viewed in science. In the learning science tradition, tracking the process of the conceptual change of the shape of the…

  11. Zirconium isotope constraints on the composition of Theia and current Moon-forming theories (United States)

    Akram, W.; Schönbächler, M.


    The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support

  12. Alkaline chemistry of transuranium elements and technetium and the treatment of alkaline radioactive wastes

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, C.H. [Westinghouse Hanford Co., Richland, WA (United States); Peretrukhin, V.F.; Shilov, V.P.; Pikaev, A.K. [Russian Academy of Sciences (Russian Federation). Inst. of Physical Chemistry


    Goal of this survey is to generalize the known data on fundamental physical-chemical properties of TRUs and Tc, methods for their isolation, and to provide recommendations that will be useful for partitioning them from alkaline high-level wastes.

  13. Perchlorate isotope forensics (United States)

    Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Horita, J.; Brown, G.M.; Jackson, W.A.; Batista, J.; Hatzinger, P.B.


    Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37Cl/35Cl and 18O/17O/ 16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method. ?? 2005 American Chemical Society.

  14. Isotope Production Facility (IPF) (United States)

    Federal Laboratory Consortium — The Los Alamos National Laboratory has produced radioactive isotopes for medicine and research since the mid 1970s, when targets were first irradiated using the 800...

  15. Isotopes in Greenland Precipitation

    DEFF Research Database (Denmark)

    Faber, Anne-Katrine

    the Arctic Ocean. A comprehensive database is created based on ice core and weather station data from Greenland within the period 1890-2014. Present day annual and seasonal mean values are computed for 326 locations in Greenland. Parameterization of the spatial distribution of temperature and δ18O are used...... of model and data can be used to improve the understanding of climate changes. This is done through analysis of isotope modelling, observations and ice core measurements. This dissertation comprises three projects: (1) Modelling the isotopic response to changes in Arctic sea surface conditions, (2......) Constructing a new Greenland database of observations and present-day ice core measurements, and (3) Performance test of isotope-enabled CAM5 for Greenland. The recent decades of rapid Arctic sea ice decline are used as a basis for an observational-based model experiment using the isotope-enabled CAM model 3...

  16. Isotopically controlled semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Haller, E.E.


    A review of recent research involving isotopically controlled semiconductors is presented. Studies with isotopically enriched semiconductor structures experienced a dramatic expansion at the end of the Cold War when significant quantities of enriched isotopes of elements forming semiconductors became available for worldwide collaborations. Isotopes of an element differ in nuclear mass, may have different nuclear spins and undergo different nuclear reactions. Among the latter, the capture of thermal neutrons which can lead to neutron transmutation doping, can be considered the most important one for semiconductors. Experimental and theoretical research exploiting the differences in all the properties has been conducted and will be illustrated with selected examples. Manuel Cardona, the longtime editor-in-chief of Solid State Communications has been and continues to be one of the major contributors to this field of solid state physics and it is a great pleasure to dedicate this review to him.

  17. Low serum alkaline phosphatase activity in Wilson's disease. (United States)

    Shaver, W A; Bhatt, H; Combes, B


    Low values for serum alkaline phosphatase activity were observed early in the course of two patients with Wilson's disease presenting with the combination of severe liver disease and Coombs' negative acute hemolytic anemia. A review of other cases of Wilson's disease revealed that 11 of 12 patients presenting with hemolytic anemia had values for serum alkaline phosphatase less than their respective sex- and age-adjusted mean values; in eight, serum alkaline phosphatase activity was less than the lower value for the normal range of the test. Low values for serum alkaline phosphatase were much less common in Wilson's disease patients with more chronic forms of presentation. Copper added in high concentration to serum in vitro did not have an important effect on serum alkaline phosphatase activity. The mechanism responsible for the decrease in serum alkaline phosphatase activity in patients is uncertain.

  18. Heterodynes dominate precipitation isotopes in the East Asian monsoon region, reflecting interaction of multiple climate factors (United States)

    Thomas, Elizabeth K.; Clemens, Steven C.; Sun, Youbin; Prell, Warren L.; Huang, Yongsong; Gao, Li; Loomis, Shannon; Chen, Guangshan; Liu, Zhengyu


    For the past decade, East Asian monsoon history has been interpreted in the context of an exceptionally well-dated, high-resolution composite record of speleothem oxygen isotopes (δ18Ocave) from the Yangtze River Valley. This record is characterized by a unique spectral response, with variance concentrated predominantly within the precession band and an enigmatic lack of variance at the eccentricity and obliquity bands. Here we examine the spectral characteristics of all existing >250-kyr-long terrestrial water isotope records in Asia, including a new water isotope record using leaf wax hydrogen isotope ratios from the Chinese Loess Plateau. There exist profound differences in spectral characteristics among all orbital-scale Asian water isotope records. We demonstrate that these differences result from latitudinal gradients in the influence of the winter and summer monsoons, both of which impact climate and water isotopes throughout East Asia. Water isotope records therefore do not reflect precipitation during a single season or from a single circulation system. Rather, water isotope records in East Asia reflect the complex interplay of oceanic and continental moisture sources, operating at multiple Earth-orbital periods. These non-linear interactions are reflected in water isotope spectra by the presence of heterodynes. Although complex, we submit that water isotope records, when paired with rapidly developing isotope-enabled model simulations, will have the potential to elucidate mechanisms causing seasonal precipitation variability and moisture source variability in East Asia.

  19. Stable isotope separation; Separations physicochimiques d'isotopes stables realisations et etudes de petites productions

    Energy Technology Data Exchange (ETDEWEB)

    Botter, F.; Molinari, Ph.; Dirian, G. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    which cooling water circulates. Studies are going forward to increase the separation factor of the cascade by using an auxiliary gas. Isotopic Exchange: A series of experiments has been performed to determine the isotopic separation factor between a lithium amalgam and an organic solvent containing a lithium salt. The various parameters which may enter into this exchange were studied: the influence of the type of solvent (the two solvents used were dimethylformamide and tetrahydrofurane), of the temperature, of the concentration and of the nature of the associated halogen. Solutions of Li metal and liquid NH{sub 3} were studied also. A number of tests were carried out to see whether there was a difference between the isotopic compositions of the Li present in the two liquid layers obtained by the dissolution of Li metal in ammonia. No difference was observed between the Li isotopic ratios in the two phases. This was also true in the case of a layer of of Li in liquid NH{sub 3} and a layer of Li I in a similar solvent. Electromigration: The method of counter current electro Migration in fused salts is a powerful isotopic enrichment technique. It can be used successfully to separate the isotopes of elements with strongly metallic character. In the case of alkalis, small quantities of isotopically pure {sup 7}Li have been obtained, while the enrichment factors obtained for potassium are of the order of 10. With regard to the alkaline earths, it has been possible to produce small quantities of calcium enriched 5 times in {sup 46}Ca. However considerable technological difficulties rise up in the way of production on a semi-industrial scale. (authors) [French] Nous avons effectue Ia separation de deuterium pur, a partir de melanges gazeux d'hydrogene et de deuterium, par chromatographie de deplacement de bande sur colonnes de palladium supporte. Les meilleures performances ont ete obtenues par des colonnes de Pd sur fritte d'alumine {alpha}. Avec une colonne de ce

  20. Isotopes through the looking glass (United States)

    Mårtensson Pendrill, Ann Marie


    Nuclear distributions affect many aspects of atomic spectra. As an example, recent experimental results for the hyperfine anomaly in Fr isotopes are considered. These depend on nuclear charge and magnetization distributions. The variations in charge radii for these isotopes were studied earlier by measuring optical isotope shifts. The hyperfine anomalies for the odd-odd isotopes involve the neutron distributions, of interest for studies of parity nonconserving effects along a chain of isotopes.

  1. Iron isotope systematics in planetary reservoirs (United States)

    Sossi, Paolo A.; Nebel, Oliver; Foden, John


    Iron is the only polyvalent major element, and controls reduction-oxidation (redox) reactions in a host of geologic processes and reservoirs, from the mineral- to planetary-scale, on Earth and in space. Mass transfer of Fe is often accompanied by changes in bonding environment, meaning the resultant variation in bond-strength in crystals, liquids and gases induces stable isotope fractionation, even at high temperatures. In the absence of iron exchange, electron transfer can also affect iron's valence state and calculated oxygen fugacity (fO2), however its isotope composition remains unchanged. Thus, iron isotopes are a powerful tool to investigate processes that involve mass transfer, redox reactions and changes in bonding environment in planetary systems. Primitive chondritic meteorites show remarkable isotopic homogeneity, δ57 Fe = - 0.01 ± 0.01 ‰ (2SE), over a wide range of Fe/Mg vs Ni/Mg, a proxy for fO2 in the solar nebula. In chondrites, there are iron isotope differences between metal and silicates that become more pronounced at higher metamorphic grades. However, on a planetary scale, Mars and Vesta overlap with chondrites, preserving no trace of core formation or volatile depletion on these bodies. Upon assessment of pristine lherzolites, the Bulk Silicate Earth is heavier than chondrites (δ57 Fe = + 0.05 ± 0.01 ‰; 2SE), and similar to or slightly lighter than the Moon. That the mantles of some differentiated inner solar system bodies extend to heavier compositions (+ 0.2 ‰) than chondrites may principally result from volatile depletion either at a nebular or late accretion stage. Within terrestrial silicate reservoirs, iron isotopes provide insight into petrogenetic and geodynamic processes. Partial melting of the upper mantle produces basalts that are heavier than their sources, scaling with degree of melting and driving the increasingly refractory peridotite to lighter compositions. Mid-Ocean Ridge Basalts (MORBs) are homogeneous to δ57 Fe


    Energy Technology Data Exchange (ETDEWEB)



    Physical and chemical agents in the environment, those used in clinical applications, or encountered during recreational exposures to sunlight, induce damages in DNA. Understanding the biological impact of these agents requires quantitation of the levels of such damages in laboratory test systems as well as in field or clinical samples. Alkaline gel electrophoresis provides a sensitive (down to {approx} a few lesions/5Mb), rapid method of direct quantitation of a wide variety of DNA damages in nanogram quantities of non-radioactive DNAs from laboratory, field, or clinical specimens, including higher plants and animals. This method stems from velocity sedimentation studies of DNA populations, and from the simple methods of agarose gel electrophoresis. Our laboratories have developed quantitative agarose gel methods, analytical descriptions of DNA migration during electrophoresis on agarose gels (1-6), and electronic imaging for accurate determinations of DNA mass (7-9). Although all these components improve sensitivity and throughput of large numbers of samples (7,8,10), a simple version using only standard molecular biology equipment allows routine analysis of DNA damages at moderate frequencies. We present here a description of the methods, as well as a brief description of the underlying principles, required for a simplified approach to quantitation of DNA damages by alkaline gel electrophoresis.

  3. The Nolans Bore rare-earth element-phosphorus-uranium mineral system: geology, origin and post-depositional modifications (United States)

    Huston, David L.; Maas, Roland; Cross, Andrew; Hussey, Kelvin J.; Mernagh, Terrence P.; Fraser, Geoff; Champion, David C.


    Nolans Bore is a rare-earth element (REE)-U-P fluorapatite vein deposit hosted mostly by the ~1805 Ma Boothby Orthogneiss in the Aileron Province, Northern Territory, Australia. The fluorapatite veins are complex, with two stages: (1) massive to granular fluorapatite with inclusions of REE silicates, phosphates and (fluoro)carbonates, and (2) calcite-allanite with accessory REE-bearing phosphate and (fluoro)carbonate minerals that vein and brecciate the earlier stage. The veins are locally accompanied by narrow skarn-like (garnet-diopside-amphibole) wall rock alteration zones. SHRIMP Th-Pb analyses of allanite yielded an age of 1525 ± 18 Ma, interpreted as the minimum age of mineralisation. The maximum age is provided by a ~1550 Ma SHRIMP U-Pb age for a pegmatite that predates the fluorapatite veins. Other isotopic systems yielded ages from ~1443 to ~345 Ma, implying significant post-depositional isotopic disturbance. Calculation of initial ɛNd and 87Sr/86Sr at 1525 Ma and stable isotope data are consistent with an enriched mantle or lower crust source, although post-depositional disturbance is likely. Processes leading to formation of Nolans Bore began with north-dipping subduction along the south margin of the Aileron Province at 1820-1750 Ma, producing a metasomatised, volatile-rich, lithospheric mantle wedge. About 200 million years later, near the end of the Chewings Orogeny, this reservoir and/or the lower crust sourced alkaline low-degree partial melts which passed into the mid- and upper-crust. Fluids derived from these melts, which may have included phosphatic melts, eventually deposited the Nolans Bore fluorapatite veins due to fluid-rock interaction, cooling, depressurisation and/or fluid mixing. Owing to its size and high concentration of Th (2500 ppm), in situ radiogenic heating caused significant recrystallisation and isotopic resetting. The system finally cooled below 300 °C at ~370 Ma, possibly in response to unroofing during the Alice Springs

  4. The effect of alkaline agents on retention of EOR chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Lorenz, P.B.


    This report summarizes a literature survey on how alkaline agents reduce losses of surfactants and polymers in oil recovery by chemical injection. Data are reviewed for crude sulfonates, clean anionic surfactants, nonionic surfactants, and anionic and nonionic polymers. The role of mineral chemistry is briefly described. Specific effects of various alkaline anions are discussed. Investigations needed to improve the design of alkaline-surfactant-polymer floods are suggested. 62 refs., 28 figs., 6 tabs.

  5. On the use of Li isotopes as a proxy for water-rock interaction in fractured crystalline rocks: A case study from the Gotthard rail base tunnel (United States)

    Wanner, Christoph; Bucher, Kurt; Pogge von Strandmann, Philip A. E.; Waber, H. Niklaus; Pettke, Thomas


    We present Li isotope measurements of groundwater samples collected during drilling of the 57 km long Gotthard rail base tunnel in Switzerland, to explore the use of Li isotope measurements for tracking water-rock interactions in fractured crystalline rocks at temperatures of up to 43 °C. The 17 groundwater samples originate from water-conducting fractures within two specific crystalline rock units, which are characterized by a similar rock mineralogy, but significantly different fluid composition. In particular, the aqueous Li concentrations observed in samples from the two units vary from 1-4 mg/L to 0.01-0.02 mg/L. Whereas δ7Li values from the unit with high Li concentrations are basically constant (δ7Li = 8.5-9.1‰), prominent variations are recorded for the samples from the unit with low Li concentrations (δ7Li = 10-41‰). This observation demonstrates that Li isotope fractionation can be highly sensitive to aqueous Li concentrations. Moreover, δ7Li values from the unit with low Li concentrations correlate well with reaction progress parameters such as pH and [Li]/[Na] ratios, suggesting that δ7Li values are mainly controlled by the residence time of the fracture groundwater. Consequently, 1D reactive transport modeling was performed to simulate mineral reactions and associated Li isotope fractionation along a water-conducting fracture system using the code TOUGHREACT. Modeling results confirm the residence time hypothesis and demonstrate that the absence of δ7Li variation at high Li concentrations can be well explained by limitation of the amount of Li that is incorporated into secondary minerals. Modeling results also suggest that Li uptake by kaolinite forms the key process to cause Li isotope fractionation in the investigated alkaline system (pH >9), and that under slow flow conditions (mineral reaction rates if more thermodynamic data about the temperature-dependent incorporation of Li in secondary minerals as well as corresponding fractionation

  6. NASA Earth Exchange (NEX) (United States)

    National Aeronautics and Space Administration — The NASA Earth Exchange (NEX) represents a new platform for the Earth science community that provides a mechanism for scientific collaboration and knowledge sharing....

  7. Earth on the Move. (United States)

    Naturescope, 1987


    Provides background information on the layers of the earth, the relationship between changes on the surface of the earth and its insides, and plate tectonics. Teaching activities are included, with some containing reproducible worksheets and handouts to accompany them. (TW)

  8. EarthKAM (United States)

    National Aeronautics and Space Administration — Sponsored by NASA, EarthKAM (Earth Knowledge Acquired by Middle School Students) is an educational outreach program allowing middle school students to take pictures...

  9. Earth Sciences Division annual report 1990

    Energy Technology Data Exchange (ETDEWEB)



    This Annual Report presents summaries of selected representative research activities grouped according to the principal disciplines of the Earth Sciences Division: Reservoir Engineering and Hydrogeology, Geology and Geochemistry, and Geophysics and Geomechanics. Much of the Division`s research deals with the physical and chemical properties and processes in the earth`s crust, from the partially saturated, low-temperature near-surface environment to the high-temperature environments characteristic of regions where magmatic-hydrothermal processes are active. Strengths in laboratory and field instrumentation, numerical modeling, and in situ measurement allow study of the transport of mass and heat through geologic media -- studies that now include the appropriate chemical reactions and the hydraulic-mechanical complexities of fractured rock systems. Of particular note are three major Division efforts addressing problems in the discovery and recovery of petroleum, the application of isotope geochemistry to the study of geodynamic processes and earth history, and the development of borehole methods for high-resolution imaging of the subsurface using seismic and electromagnetic waves. In 1989 a major DOE-wide effort was launched in the areas of Environmental Restoration and Waste Management. Many of the methods previously developed for and applied to deeper regions of the earth will in the coming years be turned toward process definition and characterization of the very shallow subsurface, where man-induced contaminants now intrude and where remedial action is required.

  10. A nucleosynthetic origin for the Earth's anomalous (142)Nd composition. (United States)

    Burkhardt, C; Borg, L E; Brennecka, G A; Shollenberger, Q R; Dauphas, N; Kleine, T


    A long-standing paradigm assumes that the chemical and isotopic compositions of many elements in the bulk silicate Earth are the same as in chondrites. However, the accessible Earth has a greater (142)Nd/(144)Nd ratio than do chondrites. Because (142)Nd is the decay product of the now-extinct (146)Sm (which has a half-life of 103 million years), this (142)Nd difference seems to require a higher-than-chondritic Sm/Nd ratio for the accessible Earth. This must have been acquired during global silicate differentiation within the first 30 million years of Solar System formation and implies the formation of a complementary (142)Nd-depleted reservoir that either is hidden in the deep Earth, or lost to space by impact erosion. Whether this complementary reservoir existed, and whether or not it has been lost from Earth, is a matter of debate, and has implications for determining the bulk composition of Earth, its heat content and structure, as well as for constraining the modes and timescales of its geodynamical evolution. Here we show that, compared with chondrites, Earth's precursor bodies were enriched in neodymium that was produced by the slow neutron capture process (s-process) of nucleosynthesis. This s-process excess leads to higher (142)Nd/(144)Nd ratios; after correction for this effect, the (142)Nd/(144)Nd ratios of chondrites and the accessible Earth are indistinguishable within five parts per million. The (142)Nd offset between the accessible silicate Earth and chondrites therefore reflects a higher proportion of s-process neodymium in the Earth, and n