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Sample records for alkaline earth carbonates

  1. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

    SciTech Connect

    De Visscher, Alex; Vanderdeelen, Jan

    2012-06-15

    The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO{sub 3} types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO{sub 3}{center_dot} H{sub 2}O), the hexahydrate ikaite (CaCO{sub 3}{center_dot}6H{sub 2}O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

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

    NASA Astrophysics Data System (ADS)

    González, Miriam Ferrer; Ilyina, Tatiana

    2016-06-01

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

  3. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

    USGS Publications Warehouse

    Chen, S.G.; Yang, R.T.

    1997-01-01

    From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

  4. Alkaline earth metal catalysts for asymmetric reactions.

    PubMed

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

    The group 2 alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) are among the most common elements on Earth, abundant in both the sea and the Earth's crust. Although they are familiar in our daily lives, their application to organic synthesis has, so far, been limited. Some particularly useful properties of these elements include (i) low electronegativity, (ii) a stable oxidation state of +2, meaning that they can potentially form two covalent bonds with anions, and (iii) the ability to occupy a variety of coordination sites due to their large ionic radius. Furthermore, the alkaline earth metals, found between the group 1 and group 3 elements, show mild but significant Lewis acidity, which can be harnessed to control coordinative molecules via a Lewis acid-base interaction. Taken together, these characteristics make the metals Ca, Sr, and Ba very promising components of highly functionalized acid-base catalysts. In this Account, we describe the development of chiral alkaline earth metal catalysts for asymmetric carbon-carbon bond-forming reactions. Recently prepared chiral alkaline earth metal complexes have shown high diastereo- and enantioselectivities in fundamental and important chemical transformations. We chose chiral bisoxazoline (Box) derivatives bearing a methylene tether as a ligand for chiral modification. These molecules are very useful because they can covalently coordinate to alkaline earth metals in a bidentate fashion through deprotonation of the tether portion. It was found that chiral calcium-Box complexes could successfully promote catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions with high diastereo- and enantioselectivities. Both the calcium-Box complexes and chiral strontium-bis-sulfonamide and chiral barium-BINOLate complexes could catalyze asymmetric 1,4-addition reactions with high enantioselectivities. Furthermore, we designed a calcium-neutral coordinative ligand complex as a new type of chiral alkaline

  5. Method of increasing the sulfation capacity of alkaline earth sorbents

    DOEpatents

    Shearer, J.A.; Turner, C.B.; Johnson, I.

    1980-03-13

    A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

  6. Method of increasing the sulfation capacity of alkaline earth sorbents

    DOEpatents

    Shearer, John A.; Turner, Clarence B.; Johnson, Irving

    1982-01-01

    A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

  7. Alkaline earth filled nickel skutterudite antimonide thermoelectrics

    DOEpatents

    Singh, David Joseph

    2013-07-16

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

  8. Alkaline and alkaline earth metal phosphate halides and phosphors

    DOEpatents

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

    2012-11-13

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

  9. The alkaline earth intercalates of molybdenum disulfide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.; Samson, S.; Woollam, J. A.

    1975-01-01

    Molybdenum disulfide has been intercalated with calcium and strontium by means of the liquid ammonia technique. Chemical, X-ray, and superconductivity data are presented. The X-ray data reveal a lowering of crystal symmetry and increase of complexity of the structure upon intercalation with the alkaline earth metals. The Ca and Sr intercalates start to superconduct at 4 and 5.6 K, respectively, and show considerable anisotropy regarding the critical magnetic field.

  10. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

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

  11. Oxidation catalysts on alkaline earth supports

    DOEpatents

    Mohajeri, Nahid

    2017-03-21

    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.

  12. Carbon cycling and snowball Earth.

    PubMed

    Goddéris, Yves; Donnadieu, Yannick

    2008-12-18

    The possibility that Earth witnessed episodes of global glaciation during the latest Precambrian challenges our understanding of the physical processes controlling the Earth's climate. Peltier et al. suggest that a 'hard snowball Earth' state may have been prevented owing to the release of CO(2) from the oxidation of dissolved organic carbon (DOC) in the ocean as the temperature decreased. Here we show that the model of Peltier et al. is not self-consistent as it implies large fluctuations of the ocean alkalinity content without providing any processes to account for it. Our findings suggest that the hard snowball Earth hypothesis is still valid.

  13. Diclofenac salts. III. Alkaline and earth alkaline salts.

    PubMed

    Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

    2005-11-01

    Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

  14. Study of point defects in alkaline-earth sulfides

    SciTech Connect

    Pandey, R.; Kunz, A.B.; Vail, J.M.

    1988-11-01

    The results of a computer simulation study of point defects including vacancy, interstitial, and F/sup +/ center in alkaline-earth sulfides are presented. The study is based on ICECAP/HADES simulation procedures and uses empirical interionic potentials obtained from the analysis of macroscopic data for these materials. The results predict the dominance of Schottky disorder and suggest that vacancy migration predominates in alkaline-earth sulfides. Furthermore, the calculated F/sup +/ center absorption energy is in good agreement with the experimental data deduced from the optical stimulated studies in these materials.

  15. Tuning NaYF4 Nanoparticles through Alkaline Earth Doping

    PubMed Central

    Chen, Xian; Peng, Dengfeng; Wang, Feng

    2013-01-01

    Phase and size of lanthanide-doped nanoparticles are the most important characteristics that dictate optical properties of these nanoparticles and affect their technological applications. Herein, we present a systematic study to examine the effect of alkaline earth doping on the formation of NaYF4 upconversion nanoparticles. We show that alkaline earth doping has a dual function of tuning particle size of hexagonal phase NaYF4 nanoparticles and stabilizing cubic phase NaYF4 nanoparticles depending on composition and concentration of the dopant ions. The study described here represents a facile and general strategy to tuning the properties of NaYF4 upconversion nanoparticles. PMID:28348353

  16. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  17. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

  18. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

  19. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  20. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  1. Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals.

    PubMed

    Westerhausen, Matthias

    2006-10-28

    Heterobimetallic compounds of the alkaline-earth metals show a wide structural variety with strongly differing reactivity patterns. The combination of magnesium and alkali metal amides yields cyclic molecules with an extreme high reactivity which often are considered as "inverse crowns" with the metal atoms as coordination sites for Lewis bases. In other metallates of the alkaline-earth metals an activation of alkyl groups succeeds. In alkaline-earth metal zincates an inverse coordination of the type M(2)[(mu-R)(2)ZnR](2) is observed and the alkyl groups are in bridging positions between zinc and the s-block metals thus forming a very reactive M-C-Zn three-center-two-electron bond. Furthermore, the metals of the carbon group form alkaline-earth metal-silicon, -germanium and -tin bonds or, in the presence of very strong Lewis bases, even solvent-separated ion pairs. For electronegative substituents at tin an inverse coordination mode such as M[(mu-R)(2)SnR](2) is observed.

  2. Specialties of distributions of alkaline-earth metals in coal

    SciTech Connect

    Fan Jinchuan; Fan Minqiang

    1997-12-31

    Four different ranks of coal have been sampled and separated into different density fractions by Float-Sink. The contents of some trace elements in each density fraction has been analyzed by ICAP. The analyzed data show that the alkaline-earth metals (Be, Sr, and Ba) have their special distributions in coal: Be and Sr may exist in the form of organic matter. Ba often has the highest content in the middle density fraction (1.4--1.5). The relative relationship between ash (or sulfur) and the trace element in a certain type of coal was obtained by using linear regression approach. Results show that there is no significant correlation between the contents of ash or sulfur and those of Be, Sr, and Ba. On the other hand, the linear regression was done among the trace elements of 17 types of coal. The results also show that there is no significant correlation between ash or sulfur and alkaline-earth metals.

  3. Theoretical study of the alkali and alkaline-earth monosulfides

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  4. Steady-state superradiance with alkaline-earth-metal atoms

    SciTech Connect

    Meiser, D.; Holland, M. J.

    2010-03-15

    Alkaline-earth-metal-like atoms with ultranarrow transitions open the door to a new regime of cavity quantum electrodynamics. That regime is characterized by a critical photon number that is many orders of magnitude smaller than what can be achieved in conventional systems. We show that it is possible to achieve superradiance in steady state with such systems. We discuss the basic underlying mechanisms as well as the key experimental requirements.

  5. Preservation of primary lake signatures in alkaline earth carbonates of the Eocene Green River Wilkins Peak-Laney Member transition zone

    NASA Astrophysics Data System (ADS)

    Murphy, John T.; Lowenstein, Tim K.; Pietras, Jeffrey T.

    2014-12-01

    Significant changes in carbonate mineralogy, texture, and stable isotope composition occur at the transition from the Wilkins Peak Member to the Laney Member in the Eocene Green River Formation, Bridger Basin, Wyoming, which reflect evolution of inflow waters, lake waters, and paleoenvironments. The top of the Wilkins Peak Member contains heterogeneous laminae of calcite and dolomite. Evaporites associated with these layers suggest deposition in hypersaline lakes. Diagenetic carbonate mineral textures include euhedral cement overgrowths and interlocking mosaics of calcite and dolomite crystals, 20-70 μm in size. Electron microprobe analyses indicate diagenetic overgrowth of Fe-rich dolomite on cloudy Fe-poor cores. δ18O values of carbonate laminae in the upper Wilkins Peak Member vary by ~ 6‰ with no depth dependent or mineralogic trends, which also suggests diagenetic overprinting. Alternating organic-rich and primary aragonite, calcite, and dolomite laminae were identified from the lower Laney Member. Primary lacustrine aragonite consists of well sorted, prismatic crystals 5-10 μm in length, with micro-lamination defined by crystal size variation. Primary precipitated calcite and dolomite laminae are monominerallic, with well sorted polyhedral crystals, ~ 10 μm in size. Primary mineralogy of the lower Laney Member changes from calcite to aragonite and dolomite stratigraphically upward. Along the same 15 m thick stratigraphic interval, δ18O values decrease upward by ~ 3‰, all of which suggests (1) lake waters underwent evaporative concentration, which together with calcite precipitation increased the lake water Mg/Ca ratios and led to formation of aragonite and dolomite, (2) source waters became lower in δ18O, possibly as inflow changed to higher altitude foreland rivers. The results from this study show that understanding the primary lacustrine versus diagenetic origin of Green River carbonate minerals is essential for paleoenvironmental and

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

    DOEpatents

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

    1995-01-01

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

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

    DOEpatents

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

    1995-01-31

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  10. Enhanced Magnetic Trap Loading for Alkaline-Earth Atoms

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  11. Structural diversity of alkaline-earth 2,5-thiophenedicarboxylates

    NASA Astrophysics Data System (ADS)

    Balendra; Ramanan, Arunachalam

    2017-03-01

    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.

  12. Multi proxy approach for the formation of calcium carbonates in alkaline man-made environments

    NASA Astrophysics Data System (ADS)

    Rinder, T.; Dietzel, M.; Leis, A.

    2009-04-01

    The formation of calcium carbonates, e.g. in drainage systems of tunnels, may be induced by degassing of CO2-rich groundwater which enters the building. However, the dissolution of portlandite (Ca(OH)2) from cements or the shotcrete of the tunnel wall bears an additional and immense potential for the formation of carbonates from alkaline solutions. Variations in trace element incorporation and distribution of the stable isotopes of carbon and oxygen in the precipitated calcium carbonates may represent powerful tools to identify individual mechanisms for carbonate formation. As portlandite dissolves, highly alkaline solutions are obtained. In this case, precipitation of calcium carbonate can be related to the absorption of CO2 from the atmosphere. Isotopic analyses of the calcite show that fixation of CO2 from the Earth's atmosphere leads to significantly lighter ^13Ccalcite values (down to -25 o/oo, VPDB) as expected for the fixation of groundwater carbonate (typical ^13Ccalcite values between -10 and -16o/oo, VPDB). The evolution of Sr/Ca ratios in the alkaline drainage solutions and in the corresponding calcium carbonate precipitation provides insight into the dissolution process at the concrete with respect to the amount of primarily dissolved portlandite from the cement. Moreover, an inverse relationship between Mg/Ca and Sr/Ca ratios is observed due to the liberation of aqueous strontium by the dissolution of portlandite and the formation of brucite (Mg(OH)2) at alkaline conditions. Less incorporation of magnesium in the calcite structure is a strong indicator for carbonate precipitation from highly alkaline environments. Applications of such multi proxy approaches are discussed with case studies. Main tasks are the reconstruction of the environmental conditions during primary CaCO3 formation and monitoring of ongoing precipitation of calcium carbonates and cement-water interaction in alkaline man-made environments.

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

    NASA Technical Reports Server (NTRS)

    Vasquez, R.

    1993-01-01

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

  14. Isotopic fractionation of alkali earth metals during carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Yotsuya, T.; Ohno, T.; Muramatsu, Y.; Shimoda, G.; Goto, K. T.

    2014-12-01

    The alkaline earth metals such as magnesium, calcium and strontium play an important role in a variety of geochemical and biological processes. The element ratios (Mg/Ca and Sr/Ca) in marine carbonates have been used as proxies for reconstruction of the past environment. Recently several studies suggested that the study for the isotopic fractionation of the alkaline earth metals in marine carbonates has a potentially significant influence in geochemical research fields (e.g. Eisenhauer et al., 2009). The aim of this study is to explore the influence of carbonate polymorphs (Calcite and Aragonite) and environmental factors (e.g., temperature, precipitation rate) on the level of isotopic fractionation of the alkaline earth metals. We also examined possible correlations between the level of isotopic fractionation of Ca and that of other alkaline earth metals during carbonate precipitation. In order to determine the isotope fractionation factor of Mg, Ca and Sr during carbonate precipitation, calcite and aragonite were synthesized from calcium bicarbonate solution in which the amount of magnesium was controlled based on Kitano method. Calcium carbonates were also prepared from the mixture of calcium chlorite and sodium hydrogen carbonate solutions. The isotope fractionation factors were measured by MC-ICPMS. Results suggested that the level of isotopic fractionation of Mg during carbonate precipitation was correlated with that of Sr and that the change of the carbonate crystal structure could make differences of isotopic fractionations of Mg and Ca, however no difference was found in the case of Sr. In this presentation, the possible mechanism will be discussed.

  15. Improvement of thermoelectric properties of alkaline-earth hexaborides

    SciTech Connect

    Takeda, Masatoshi . E-mail: takeda@mech.nagaokaut.ac.jp; Terui, Manabu; Takahashi, Norihito; Ueda, Noriyoshi

    2006-09-15

    Thermoelectric (TE) and transport properties of alkaline-earth hexaborides were examined to investigate the possibility of improvement in their TE performance. As carrier concentration increased, electrical conductivity increased and the absolute value of the Seebeck coefficient decreased monotonically, while carrier mobility was almost unchanged. These results suggest that the electrical properties of the hexaboride depend largely on carrier concentration. Thermal conductivity of the hexaboride was higher than 10 W/m K even at 1073 K, which is relatively high among TE materials. Alloys of CaB{sub 6} and SrB{sub 6} were prepared in order to reduce lattice thermal conductivity. Whereas the Seebeck coefficient and electrical conductivity of the alloys were intermediate between those of CaB{sub 6} and SrB{sub 6} single phases, the thermal conductivities of the alloys were lower than those of both single phases. The highest TE performance was obtained in the vicinity of Ca{sub 0.5}Sr{sub 0.5}B{sub 6}, indicating that alloying is effective in improving the performance. - Graphical abstract: Thermoelectric figure-of-merit, ZT, for (Ca,Sr)B{sub 6} alloys. The highest ZT value of 0.35 at 1073 K was obtained due to effective reduction of thermal conductivity by alloying.

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

    DOEpatents

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

    1995-01-24

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

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

    DOEpatents

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

    1995-01-01

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

  18. Effect of alkaline-earth ions on the dynamics of alkali ions in bismuthate glasses

    NASA Astrophysics Data System (ADS)

    Dutta, A.; Ghosh, A.

    2005-12-01

    The effect of alkaline earth ions on the dynamics of Li+ ions in bismuthate glasses has been studied in the temperature range 353-503K and in the frequency range 10Hz-2MHz . The dc conductivity increases and activation energy decreases with the increase of a particular alkaline earth content for the glasses with a fixed alkali content. The increased modification of the network due to the increase in alkaline earth content in the compositions is responsible for the increasing conductivity. Also the compositions with smaller alkaline earth ions were found to exhibit higher conductivity. Although the conductivity increases with the decrease of ionic radii of alkaline earth ions, the activation energy shows a maximum for the Sr ion. The electric modulus and the conductivity formalisms have been employed to study the relaxation dynamics of charge carriers in these glasses. The alkali ions were observed to change their dynamics with the change of the alkaline earth ions. The same anomalous trend for activation energy for the conductivity relaxation frequency and the hopping frequency was also observed for glasses containing SrO. It was also observed that the mobile lithium ion concentrations are independent of nature of alkaline earth ions in these glasses.

  19. Physical and electrochemical properties of alkaline earth doped, rare earth vanadates

    SciTech Connect

    Adijanto, Lawrence; Balaji Padmanabhan, Venu; Holmes, Kevin J.; Gorte, Raymond J.; Vohs, John M.

    2012-06-15

    The effect of partial substitution of alkaline earth (AE) ions, Sr{sup 2+} and Ca{sup 2+}, for the rare earth (RE) ions, La{sup 3+}, Ce{sup 3+}, Pr{sup 3+}, and Sm{sup 3+}, on the physical properties of REVO{sub 4} compounds were investigated. The use of the Pechini method to synthesize the vanadates allowed for high levels of AE substitution to be obtained. Coulometric titration was used to measure redox isotherms for these materials and showed that the addition of the AE ions increased both reducibility and electronic conductivity under typical solid oxide fuel cell (SOFC) anode conditions, through the formation of compounds with mixed vanadium valence. In spite of their high electronic conductivity, REVO{sub 4}-yttira stabilized zirconia (YSZ) composite anodes exhibited only modest performance when used in SOFCs operating with H{sub 2} fuel at 973 K due to their low catalytic activity. High performance was obtained, however, after the addition of a small amount of catalytically active Pd to the anode. - Graphical abstract: Coulometric titration isotherms for ({open_square}) LaVO{sub 4}, ( White-Circle ) PrVO{sub 4}, ( Lozenge ) CeVO{sub 4}, ( Black-Up-Pointing-Triangle ) Ce{sub 0.7}Sr{sub 0.3}VO{sub 3.85}, and ( Black-Square ) Ce{sub 0.7}Ca{sub 0.3}VO{sub 3.85}, at 973 K. Highlights: Black-Right-Pointing-Pointer Infiltration procedures were used to prepare SOFC anodes from various vanadates. Black-Right-Pointing-Pointer Doping of Alkaline Earth to Rare Earth Vanadates showed to improve conductivity and chemical stability. Black-Right-Pointing-Pointer Alkaline Earth Doped Rare Earth Vanadates-YSZ composites showed conductivities as high as 5 S cm{sup -1} at 973 K. Black-Right-Pointing-Pointer As with other ceramic anodes, the addition of a catalyst was required to achieve low anode impedance.

  20. Physical and electrochemical properties of alkaline earth doped, rare earth vanadates

    NASA Astrophysics Data System (ADS)

    Adijanto, Lawrence; Balaji Padmanabhan, Venu; Holmes, Kevin J.; Gorte, Raymond J.; Vohs, John M.

    2012-06-01

    The effect of partial substitution of alkaline earth (AE) ions, Sr2+ and Ca2+, for the rare earth (RE) ions, La3+, Ce3+, Pr3+, and Sm3+, on the physical properties of REVO4 compounds were investigated. The use of the Pechini method to synthesize the vanadates allowed for high levels of AE substitution to be obtained. Coulometric titration was used to measure redox isotherms for these materials and showed that the addition of the AE ions increased both reducibility and electronic conductivity under typical solid oxide fuel cell (SOFC) anode conditions, through the formation of compounds with mixed vanadium valence. In spite of their high electronic conductivity, REVO4-yttira stabilized zirconia (YSZ) composite anodes exhibited only modest performance when used in SOFCs operating with H2 fuel at 973 K due to their low catalytic activity. High performance was obtained, however, after the addition of a small amount of catalytically active Pd to the anode.

  1. Release characteristics of alkali and alkaline earth metallic species during biomass pyrolysis and steam gasification process.

    PubMed

    Long, Jiang; Song, Hu; Jun, Xiang; Sheng, Su; Lun-Shi, Sun; Kai, Xu; Yao, Yao

    2012-07-01

    Investigating the release characteristics of alkali and alkaline earth metallic species (AAEMs) is of potential interest because of AAEM's possible useful service as catalysts in biomass thermal conversion. In this study, three kinds of typical Chinese biomass were selected to pyrolyse and their chars were subsequently steam gasified in a designed quartz fixed-bed reactor to investigate the release characteristics of alkali and alkaline earth metallic species (AAEMs). The results indicate that 53-76% of alkali metal and 27-40% of alkaline earth metal release in pyrolysis process, as well as 12-34% of alkali metal and 12-16% of alkaline earth metal evaporate in char gasification process, and temperature is not the only factor to impact AAEMs emission. The releasing characteristics of AAEMs during pyrolysis and char gasification process of three kinds of biomass were discussed in this paper.

  2. More arrows in the quiver: new pathways and old problems with heavy alkaline earth metal diphenylmethanides.

    PubMed

    Alexander, Jacob S; Ruhlandt-Senge, Karin

    2004-03-05

    Progress in the field of sigma-bonded alkaline earth organometallics has been handicapped by numerous complications, such as high reactivity, low solubility, and the limited availability of suitable starting materials. Here we present two synthetic methods, hydrocarbon elimination and desilylation, as alternative routes into this chemistry. A novel barium diphenylmethanide was prepared using these routes delineating that both methods provide a powerful, versatile synthetic access route to an extended library of organometallic alkaline earth derivatives.

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

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  4. Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses

    SciTech Connect

    Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

    2015-08-15

    A series of mixed cation silicate glasses of the composition A2O – 2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observed that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.

  5. ALKALINE CARBONATE LEACHING PROCESS FOR URANIUM EXTRACTION

    DOEpatents

    Thunaes, A.; Brown, E.A.; Rabbitts, A.T.

    1957-11-12

    A process for the leaching of uranium from high carbonate ores is presented. According to the process, the ore is leached at a temperature of about 200 deg C and a pressure of about 200 p.s.i.g. with a solution containing alkali carbonate, alkali permanganate, and bicarbonate ion, the bicarbonate ion functionlng to prevent premature formation of alkali hydroxide and consequent precipitation of a diuranate. After the leaching is complete, the uranium present is recovered by precipitation with NaOH.

  6. [Broad excitation band alkaline-earth silicate luminescent materials activated by rare earth and its applications].

    PubMed

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

    2008-01-01

    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.

  7. Dynamics of dipolar defects in rare earth-doped alkaline-earth fluoride crystals

    NASA Astrophysics Data System (ADS)

    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

  8. Rare-earth-doped bifunctional alkaline-earth metal fluoride nanocrystals via a facile microwave-assisted process.

    PubMed

    Pang, Min; Liu, Dapeng; Lei, Yongqian; Song, Shuyan; Feng, Jing; Fan, Weiqiang; Zhang, Hongjie

    2011-06-20

    Rare-earth-doped magnetic-optic bifunctional alkaline-earth metal fluoride nanocrystals have been successfully synthesized via a facile microwave-assisted process. The as-prepared nanocrystals were monodisperse and could form stable colloidal solutions in polar solvents, such as water and ethanol. They show bright-green fluorescence emisson. Furthermore, Gd(3+)-doped ones exhibit paramagnetic behavior at room temperature and superparamagnetic behavior at 2 K.

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

    PubMed

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

    2009-01-01

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

  10. Depolarizing collisions with hydrogen: Neutral and singly ionized alkaline earths

    SciTech Connect

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

    2014-06-20

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

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

    NASA Astrophysics Data System (ADS)

    Gonzalez, M. F.; Ilyina, T.

    2014-12-01

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

  12. IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline Earth Metal Pseudohalides

    NASA Astrophysics Data System (ADS)

    Hála, Jiri

    2004-03-01

    This volume presents solubility data of azides, cyanides, cyanates, and thiocyanates of alkali metals, alkaline earth metals, and ammonium. Covered are binary and ternary systems in all solvents. No solubility data have been found for some of the compounds of alkali metals, alkaline metals, and ammonium. These include beryllium and magnesium azides, lithium, rubidium cesium, ammonium, and alkaline earth cyanates and cyanides, and beryllium thiocyanate. Likewise, no solubility data seem to exist for selenocyanates of the mentioned metals and ammonium. The literature has been covered up to the middle of 2001, and there was a great effort to have the literature survey as complete as possible. The few documents which remained unavailable to the editor, and could not be included in the volume, are listed in the Appendix. For some compounds it was not possible to show the Chemical Abstracts registry numbers since these have not been assigned. For this reason, the registry number index is incomplete.

  13. Systematic studies of the mass spectrometric properties of alkaline earth metal cationized amino acids and peptides

    NASA Astrophysics Data System (ADS)

    Küjckelmann, Ulrich; Müller, Dietrich; Weber, Carsten

    1997-07-01

    The results of a systematic study of the gas phase interactions of α-amino acids and peptides (4-15 amino acids) with alkaline earth metals, observed with mass spectrometric techniques, are presented. Furthermore, a model for the cationization with calcium at the C-terminal amino acid arginine in rotaviral polypeptides is presented.

  14. Homoleptic alkaline earth metal bis(trifluoromethanesulfonyl)imide complex compounds obtained from an ionic liquid.

    PubMed

    Babai, Arash; Mudring, Anja-Verena

    2006-04-17

    The first homoleptic alkaline earth bis(trifluoromethanesulfonyl)imide (Tf2N) complexes [mppyr]2[Ca(Tf2N)4], [mppyr]2[Sr(Tf2N)4], and [mppyr][Ba(Tf2N)3] were crystallized from a solution of the respective alkaline earth bis(trifluoromethanesulfonyl)imide and the ionic liquid [mppyr][Tf2N] (mppyr = 1,1-N-methyl-N-propylpyrrolidinium). In the calcium and strontium compounds, the alkaline earth metal (AE) is coordinated by four bidentately chelating Tf2N ligands to form isolated (distorted) square antiprismatic [AE(Tf2N)4]2- complexes which are separated by N-methyl-N-propylpyrrolidinium cations. In contrast, the barium compound, [mppyr][Ba(Tf2N)3], forms an extended structure. Here the alkaline earth cation is surrounded by six oxygen atoms belonging to three Tf2N- anions which coordinate in a bidentate chelating fashion. Three further oxygen atoms of the same ligands are linking the Ba2+ cations to infinite (infinity)(1)[Ba(Tf2N)3] chains.

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

    ERIC Educational Resources Information Center

    Dietrich, Bernard

    1985-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Takahashi, Yuriko

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

  17. Carbon Dioxide Carbonates in the Earth;s Mantle: Implications to the Deep Carbon Cycle

    SciTech Connect

    Yoo, Choong-Shik; Sengupta, Amartya; Kim, Minseob

    2012-05-22

    An increase in the ionic character in C-O bonds at high pressures and temperatures is shown by the chemical/phase transformation diagram of CO{sub 2}. The presence of carbonate carbon dioxide (i-CO{sub 2}) near the Earth's core-mantle boundary condition provides insights into both the deep carbon cycle and the transport of atmospheric CO{sub 2} to anhydrous silicates in the mantle and iron core.

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

    USGS Publications Warehouse

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

    2011-01-01

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

  19. Ab initio study of the alkali and alkaline-earth monohydroxides

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

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

    DOEpatents

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

    1993-01-01

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

  1. Ab initio calculations on the positive ions of the alkaline-earth oxides, fluorides, and hydroxides

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

    Theoretical dissociation energies are presented for the alkaline-earth fluoride, hydroxide, and oxide positive ions that are considered to be accurate to 0.1-0.2 eV. The r(e) for the positive ions are found to be consistently shorter than the corresponding neutrals by 0.07 + or -0.02 A. The bonding in the ground states is demonstrated to be of predominantly M + 2 X - character. The a 3 Pi and A 1 Pi are found to lie considerably above the X 1 Sigma + ground states of the alkaline-earth fluoride and hydroxide positive ions. The overall agreement of the theoretical ionization potentials with the available experimental appearance potentials is satisfactory; these values should represent the most accurate and consistent set available.

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

    PubMed

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

    2015-09-01

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

  3. Advances in the growth of alkaline-Earth halide single crystals for scintillator detectors

    NASA Astrophysics Data System (ADS)

    Boatner, L. A.; Ramey, J. O.; Kolopus, J. A.; Neal, J. S.; Cherepy, N. J.; Beck, P. R.; Payne, S. A.; Burger, A.; Rowe, E.; Bhattacharya, P.

    2014-09-01

    Alkaline-earth scintillators such as strontium iodide and other alkaline-earth halides activated with divalent europium represent some of the most efficient and highest energy resolution scintillators for use as gamma-ray detectors in a wide range of applications. These applications include the areas of nuclear nonproliferation, homeland security, the detection of undeclared nuclear material, nuclear physics and materials science, medical diagnostics, space physics, high energy physics, and radiation monitoring systems for first responders, police, and fire/rescue personnel. Recent advances in the growth of large single crystals of these scintillator materials hold the promise of higher crystal yields and significantly lower detector production costs. In the present work, we describe new processing protocols that, when combined with our molten salt filtration methods, have led to advances in achieving a significant reduction of cracking effects during the growth of single crystals of SrI2:Eu2+. In particular, we have found that extended pumping on the molten crystalgrowth charge under vacuum for time periods extending up to 48 hours is generally beneficial in compensating for variations in the alkaline-earth halide purity and stoichiometry of the materials as initially supplied by commercial sources. These melt-pumping and processing techniques are now being applied to the purification of CaI2:Eu2+ and some mixed-anion europium-doped alkaline-earth halides prior to single-crystal growth by means of the vertical Bridgman technique. The results of initial studies of the effects of aliovalent doping of SrI2:Eu2+ on the scintillation characteristics of this material are also described.

  4. Surface energetics of alkaline-earth metal oxides: Trends in stability and adsorption of small molecules

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-04-01

    We present a systematic theoretical investigation of the surface properties, stability, and reactivity of rocksalt type alkaline-earth metal oxides including MgO, CaO, SrO, and BaO. The accuracy of commonly used exchange-correlation density functionals (LDA, PBE, RPBE, PBEsol, BEEF-vdW, and hybrid HSE) and random-phase approximation (RPA) is evaluated and compared to existing experimental values. Calculated surface energies of the four most stable surface facets under vacuum conditions, the (100) surface, the metal and oxygen terminated octopolar (111), and the (110) surfaces, exhibit a monotonic increase in stability from MgO to BaO. On the MgO(100) surface, adsorption of CO, NO, and CH4 is characterized by physisorption while H2O chemisorbs, which is in agreement with experimental findings. We further use the on-top metal adsorption of CO and NO molecules to map out the surface energetics of each alkaline-earth metal oxide surface. The considered functionals all qualitatively predict similar adsorption energy trends. The ordering between the adsorption energies on different surface facets can be attributed to differences in the local geometrical surface structure and the electronic structure of the metal constituent of the alkaline-earth metal oxide. The striking observation that CO adsorption strength is weaker than NO adsorption on the (100) terraces as the period of the alkaline-earth metal in the oxide increases is analyzed in detail in terms of charge redistribution within the σ and π channels of adsorbates. Finally, we also present oxygen adsorption and oxygen vacancy formation energies in these oxide systems.

  5. Properties of the triplet metastable states of the alkaline-earth-metal atoms

    SciTech Connect

    Mitroy, J.; Bromley, M.W.J.

    2004-11-01

    The static and dynamic properties of the alkaline-earth-metal atoms in their metastable state are computed in a configuration interaction approach with a semiempirical 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.

  6. Advances in the growth of alkaline-earth halide single crystals for scintillator detectors

    SciTech Connect

    Boatner, Lynn A; Ramey, Joanne Oxendine; Kolopus, James A; Neal, John S; Cherepy, Nerine; Payne, Stephen A.; Beck, P; Burger, Arnold; Rowe, E; Bhattacharya, P.

    2014-01-01

    Alkaline-earth scintillators such as strontium iodide and other alkaline-earth halides activated with divalent europium represent some of the most efficient and highest energy resolution scintillators for use as gamma-ray detectors in a wide range of applications. These applications include the areas of nuclear nonproliferation, homeland security, the detection of undeclared nuclear material, nuclear physics and materials science, medical diagnostics, space physics, high energy physics, and radiation monitoring systems for first responders, police, and fire/rescue personnel. Recent advances in the growth of large single crystals of these scintillator materials hold the promise of higher crystal yields and significantly lower detector production costs. In the present work, we describe new processing protocols that, when combined with our molten salt filtration methods, have led to advances in achieving a significant reduction of cracking effects during the growth of single crystals of SrI2:Eu2+. In particular, we have found that extended pumping on the molten crystal-growth charge under vacuum for time periods extending up to 48 hours is generally beneficial in compensating for variations in the alkaline-earth halide purity and stoichiometry of the materials as initially supplied by commercial sources. These melt-pumping and processing techniques are now being applied to the purification of CaI2:Eu2+ and some mixed-anion europium-doped alkaline-earth halides prior to single-crystal growth by means of the vertical Bridgman technique. The results of initial studies of the effects of aliovalent doping of SrI2:Eu2+ on the scintillation characteristics of this material are also described.

  7. Energetics of alkali and alkaline earth ion-exchanged zeolite A

    DOE PAGES

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

    2016-06-30

    Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential (Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A) to –48.02more » ± 1.85 kJ/mol per TO2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

  8. Energetics of alkali and alkaline earth ion-exchanged zeolite A

    SciTech Connect

    Sun, Hui; Wu, Di; Liu, Kefeng; Guo, Xiaofeng; Navrotsky, Alexandra

    2016-06-30

    Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential (Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A) to –48.02 ± 1.85 kJ/mol per TO2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.

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

    SciTech Connect

    Dong, Qiang; Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin; Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro; Sato, Tsugio

    2015-09-15

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

  10. Carbon Dioxide Removal and Conversion to Ocean Alkalinity: Why and How

    NASA Astrophysics Data System (ADS)

    Rau, G. H.

    2014-12-01

    Drastic reduction in anthropogenic CO2 emissions is the most obvious way to stabilize atmospheric CO2. However, there is growing risk that effective emissions reduction policies and technologies will not engage soon enough to avoid significant CO2-induced climate and ocean acidification impacts. This realization has lead to increased interest (e.g., IPCC AR5, 2014; NRC/NAS, 2014) in the possibility of pro-actively increasing CO2 removal (CDR) from the atmosphere above the 55% of our emissions that are already removed from air by natural land and ocean processes. While a variety of biotic, abiotic, and hybrid CDR methods have been proposed, those involving geochemistry have much to recommend them. These methods employ the same geochemical reactions that naturally and effectively remove excess planetary CO2 and neutralize ocean acidity on geologic time scales. These reactions proceed when the hydrosphere, acidified by excess air CO2, contacts and reacts with carbonate and silicate minerals (>90% of the Earth's crust), producing dissolved bicarbonates and carbonates, i.e., ocean alkalinity. This alkalinity is eventually removed and the excess carbon stored via carbonate precipitation. So while the importance and global effectiveness of such reactions are not in question, it remains to be seen if this very slow, natural CDR could be safely and cost-effectively accelerated to help manage air CO2 levels on human rather than geologic time scales. Various terrestrial and marine, geochemistry-based CDR methods will be reviewed including: 1) the addition of minerals to soils and the ocean, 2) removal of CO2 from waste streams, esp. from biomass energy, via wet mineral contacting, and 3) the production and use of mineral derivatives, e.g. oxides or hydroxides, as CDR agents. The additional potential environmental benefits (e.g., reversal of ocean carbonate saturation loss) and impacts (e.g., increased mineral extraction), as well as potential economics will also be discussed.

  11. The Effect of Alkaline Earth Metal on the Cesium Loading of Ionsiv(R) IE-910 and IE-911

    SciTech Connect

    Fondeur, F.F.

    2001-01-16

    This study investigated the effect of variances in alkaline earth metal concentrations on cesium loading of IONSIV(R) IE-911. The study focused on Savannah River Site (SRS) ''average'' solution with varying amounts of calcium, barium and magnesium.

  12. Enhancement of accelerated carbonation of alkaline waste residues by ultrasound.

    PubMed

    Araizi, Paris K; Hills, Colin D; Maries, Alan; Gunning, Peter J; Wray, David S

    2016-04-01

    The continuous growth of anthropogenic CO2 emissions into the atmosphere and the disposal of hazardous wastes into landfills present serious economic and environmental issues. Reaction of CO2 with alkaline residues or cementitius materials, known as accelerated carbonation, occurs rapidly under ambient temperature and pressure and is a proven and effective process of sequestering the gas. Moreover, further improvement of the reaction efficiency would increase the amount of CO2 that could be permanently sequestered into solid products. This paper examines the potential of enhancing the accelerated carbonation of air pollution control residues, cement bypass dust and ladle slag by applying ultrasound at various water-to-solid (w/s) ratios. Experimental results showed that application of ultrasound increased the CO2 uptake by up to four times at high w/s ratios, whereas the reactivity at low water content showed little change compared with controls. Upon sonication, the particle size of the waste residues decreased and the amount of calcite precipitates increased. Finally, the sonicated particles exhibited a rounded morphology when observed by scanning electron microscopy.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    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%.

  14. Moving Carbon, Changing Earth: Bringing the Carbon Cycle to Life

    NASA Astrophysics Data System (ADS)

    Zabel, I.; Duggan-Haas, D.; Ross, R. M.; Stricker, B.; Mahowald, N. M.

    2014-12-01

    The carbon cycle presents challenges to researchers - in how to understand the complex interactions of fluxes, reservoirs, and systems - and to outreach professionals - in how to get across the complexity of the carbon cycle and still make it accessible to the public. At Cornell University and the Museum of the Earth in Ithaca, NY, researchers and outreach staff tackled these challenges together through a 2013 temporary museum exhibition: Moving Carbon, Changing Earth. Moving Carbon, Changing Earth introduced visitors to the world of carbon and its effect on every part of our lives. The exhibit was the result of the broader impacts portion of an NSF grant awarded to Natalie Mahowald, Professor in the Department of Earth and Atmospheric Sciences at Cornell University, who has been working with a team to improve simulations of regional and decadal variability in the carbon cycle. Within the exhibition, visitors used systems thinking to understand the distribution of carbon in and among Earth's systems, learning how (and how quickly or slowly) carbon moves between and within these systems, the relative scale of different reservoirs, and how carbon's movement changes climate and other environmental dynamics. Five interactive stations represented the oceans, lithosphere, atmosphere, biosphere, and a mystery reservoir. Puzzles, videos, real specimens, and an interview with Mahowald clarified and communicated the complexities of the carbon cycle. In this talk we'll present background information on Mahowald's research as well as photos of the exhibition and discussion of the components and motivations behind them, showing examples of innovative ways to bring a complex topic to life for museum visitors.

  15. Intermolecular hydroamination of vinylarenes by iminoanilide alkaline-earth catalysts: a computational scrutiny of mechanistic pathways.

    PubMed

    Tobisch, Sven

    2014-07-14

    A thorough computational exploration of the mechanistic intricacies of the intermolecular hydroamination (HA) of vinylarenes by a recently reported class of kinetically stabilised iminoanilide [{N^N}Ae{N(SiMe3)2}⋅(THF)n] alkaline-earth amido compounds (Ae = Ca, Sr, Ba) is presented. Two distinct mechanistic pathways for catalytic HA mediated by alkaline-earth and rare-earth compounds have emerged over the years that account equally well for the specific features of the process. On one hand, a concerted proton-assisted pathway to deliver the amine product in a single step can be invoked and, on the other, a stepwise σ-insertive pathway that comprises a rapid, reversible migratory olefin insertion step linked to a less facile, irreversible Ae-C alkyl bond aminolysis. The results of the study presented herein, which employed a heavily benchmarked and reliable DFT methodology, supports a stepwise σ-insertive pathway that involves fast and reversible migratory C=C bond insertion into the polar Ae-N pyrrolido σ bond. This proceeds with strict 2,1 regioselectivity via a highly polarised four-centre transition state (TS) structure, linked to irreversible intramolecular Ae-C bond aminolysis of the alkaline-earth alkyl intermediate as the energetically favourable mechanism. Turnover-limiting aminolysis is consistent with the significant KIE measured; the DFT-derived effective barrier matches the Eyring parameter empirically determined for the best-performing {N^N}Ba(NR2) catalyst gratifyingly well. It also predicts the observed trend in reactivity (Ca

  16. Theoretical investigation of the structures, stabilities, and NLO responses of calcium-doped pyridazine: alkaline-earth-based alkaline salt electrides.

    PubMed

    Wang, Yin-Feng; Huang, Jiangen; Jia, Li; Zhou, Guangpei

    2014-02-01

    Currently, whether alkaline-earth-doped compounds with electride characteristics are novel candidates for high-performance nonlinear optical (NLO) materials is unknown. In this paper, using quantum chemical computations, we show that: when doping calcium atoms into a family of alkaline-substituted pyridazines, alkaline-earth-based alkaline salt electrides M-H₃C₄N₂⋯Ca (M=H, Li, and K) with distended excess electron clouds are formed. Interestingly, from the triplet to the singlet state, the chemical valence of calcium atom changes from +1 to 0, and the dipole moment direction (μ₀) of the molecule reverses for each M-H₃C₄N₂⋯Ca. Changing pyridazine from without (H₄C₄N₂⋯Ca) to with one alkaline substituent (M-H₃C₄N₂⋯Ca, M=Li and K), the ground state changes from the triplet to the singlet state. The alkaline earth metal doping effect (electride effect) and alkaline salt effect on the static first hyperpolarizabilities (β₀) demonstrates that (1) the β₀ value is increased approximately 1371-fold from 2 (pyridazine, H₄C₄N₂) to 2745au (Ca-doped pyridazine, H₄C₄N₂⋯Ca), (2) the β₀ value is increased approximately 1146-fold from 2 in pyridazine (H₄C₄N₂) to 2294au in an Li-substituted pyridazine (Li-H₃C₄N₂), and (3) the β₀ value is increased 324-(M=Li) and 106-(M=K) fold from 826 (MLi) and 2294au (MK) to 268,679 (M=Li) and 245,878au (M=K), respectively, from the alkalized pyridazine (M-H₃C₄N₂) to the Ca-doped pyridazine (M-H₃C₄N₂⋯Ca). These results may provide a new means for designing high-performance NLO materials.

  17. Method of determining pH by the alkaline absorption of carbon dioxide

    DOEpatents

    Hobbs, David T.

    1992-01-01

    A method for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction.

  18. Quantum phase transition of alkaline-earth fermionic atoms confined in an optical superlattice

    NASA Astrophysics Data System (ADS)

    Silva-Valencia, J.; Franco, R.; Figueira, M. S.

    2013-03-01

    Using the density matrix renormalization group method, we evaluate the spin and charge gaps of alkaline-earth fermionic atoms in a periodic one-dimensional optical superlattice. The number of delocalized atoms is equal to the lattice size and we consider an antiferromagnetic coupling between delocalized and localized atoms. We found a quantum phase transition from a Kondo insulator spin liquid state without confining potential to a charge-gapped antiferromagnetic state with nonzero potential. For each on-site coupling, there is a critical potential point for which the spin gap vanishes and its value increases linearly with the local interaction.

  19. Single-stage sub-Doppler cooling of alkaline earth atoms.

    PubMed

    Xu, Xinye; Loftus, Thomas H; Dunn, Josh W; Greene, Chris H; Hall, John L; Gallagher, Alan; Ye, Jun

    2003-05-16

    We report the first experimental study of sub-Doppler cooling in alkaline earth atoms (87Sr) enabled by the presence of nuclear spin-originated magnetic degeneracy in the atomic ground state. Sub-Doppler cooling in a sigma(+)-sigma(-) configuration is achieved despite the presence of multiple, closely spaced excited states. This surprising result is confirmed by an expanded multilevel theory of the radiative cooling force. Detailed investigations of system performance have shed new insights into (sigma(+)-sigma(-)) cooling dynamics and will likely play an important role in the future development of neutral atom-based optical frequency standards.

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

    DOEpatents

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

    1981-01-01

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

  1. Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates

    DOEpatents

    Epperly, William R.; Deane, Barry C.; Brunson, Roy J.

    1982-01-01

    An improved liquefaction process wherein wall scale and particulate agglomeration during the liquefaction of solid carbonaceous materials containing alkaline earth metal humates is reduced and/or eliminated by subjecting the solid carbonaceous materials to controlled cyclic cavitation during liquefaction. It is important that the solid carbonaceous material be slurried in a suitable solvent or diluent during liquefaction. The cyclic cavitation may be imparted via pressure cycling, cyclic agitation and the like. When pressure cycling or the like is employed an amplitude equivalent to at least 25 psia is required to effectively remove scale from the liquefaction vessel walls.

  2. Studies on the interactions between purified bovine caseins and alkaline-earth-metalions

    PubMed Central

    Dickson, I. R.; Perkins, D. J.

    1971-01-01

    1. Alkaline-earth-metal cations at low concentrations form soluble complexes with bovine caseins. The relative order of binding capacities is: Mg2+>Ca2+>Ba2+>Sr2+. 2. The cations interact with both free ionized carboxyl groups of aspartic acid and glutamic acid and with monoester phosphate groups covalently bound to serine and threonine; at low concentrations of the cations interactions are predominantly with the phosphate groups. 3. The order of binding capacities for purified components of the casein complex is: αs1-casein>β-casein>κ-casein. PMID:5166590

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  4. Measurements of the mobility of alkaline earth ions in liquid xenon

    NASA Astrophysics Data System (ADS)

    Jeng, S.-C.; Fairbank, W. M., Jr.; Miyajima, M.

    2009-02-01

    The mobility of alkaline earth ions, Mg+, Ca+, Sr+ and Ba+, in liquid xenon is measured for the first time. The mobility of Tl+ is also determined for comparison with a measurement by other researchers. The Atkins cluster model for positive ions in non-polar liquids, based on the electrostriction effect, gives general agreement with the magnitude of the mobility values. This is some evidence that the positive ions form a snowball rather than a bubble structure in liquid xenon. However, the temperature dependence of the mobility does not match well with the Atkins theory, so there are still open theoretical questions on the nature of the environment of alkaline earth ions in liquid xenon. The lower mobility of Mg+ and Ba+ may be explained by a better size match to interstitial and substitutional sites, respectively, in solid Xe. These measurements are motivated by the development of a new technique to search for neutrino masses through 0νββ decay of 136Xe. A key component of one version of the proposed experiment is tagging of 136Ba+ daughter ions in liquid 136Xe by laser-induced fluorescence.

  5. Atomic hydrogen in. gamma. -irradiated hydroxides of alkaline-earth elements

    SciTech Connect

    Spitsyn, V.I.; Yurik, T.K.; Barsova, L.I.

    1982-04-01

    Atomic hydrogen is an important intermediate product formed in the radiolysis of compounds containing X-H bonds. H atoms have been detected in irradiated matrices of H/sub 2/ and inert gases at 4/sup 0/K, in irradiated ice and frozen solutions of acids in irradiated salts and in other systems. Here results are presented from a study of the ESR spectra of H atoms generated in polycrystalline hydroxides of alkaline-earth elements that have been ..gamma..-irradiated at 77/sup 0/K, after preliminary treatment at various temperatures. For the first time stabilization of atomic hydrogen in ..gamma..-irradiated polycrystalline alkaline-earth element hydroxides has been detected. Depending on the degree of dehydroxylation, several types of hydrogen atoms may be stabilized in the hydroxides, these hydrogen atoms having different radiospectroscopic parameters. In the magnesium-calcium-strontium-barium hydroxide series, a regular decrease has been found in the hfi constants for H atoms with the cations in the immediate surroundings. A direct proportionality has been found between the parameters ..delta..A/A/sub 0/ and the polarizability of the cation.

  6. Temperature-induced collapse of alkaline Earth cation-polyacrylate anion complexes.

    PubMed

    Lages, Sebastian; Schweins, Ralf; Huber, Klaus

    2007-09-06

    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

  7. Tungstate-ferrates of some alkali and alkaline-earth metals

    SciTech Connect

    Gruba, A.I.; Danileiko, L.A.; Moroz, Ya.A.; Zyats, M.N.

    1988-02-01

    Tungstate-ferrates of some alkali and alkaline-earth metals with the ratio Fe:W = 2:11, the iron ions in which are found in two types of coordination, tetrahedral and octahedral, were synthesized. The similarity of the IR spectra of the compounds obtained and known compounds with the anion structure of the Keggin type with the composition M/sub X/(XZW/sub 11/O/sub 40/H/sub m/) x nH/sub 2/O indicates that their heteropolyanions are isostructural. The thermal stability of the compounds studied and the structure of the products of thermolysis depend on the charge and radius of the extrasphere cation. When the ratio of the radii of the extrasphere cation of the alkali or alkaline-earth metal to the radius of the ion of the central 3d element, appearing in the coordination sphere of the heteropolytungstates, exceeds 1.6, the most likely products of thermolysis of heteropolycompounds are the compounds of the pyrochlore family and tungsten bronzes.

  8. Matrix diffusion of some alkali- and alkaline earth-metals in granitic rock

    SciTech Connect

    Johansson, H.; Byegaard, J.; Skarnemark, G.; Skaalberg, M.

    1997-12-31

    Static through-diffusion experiments were performed to study the diffusion of alkali- and alkaline earth-metals in fine-grained granite and medium-grained Aespoe-diorite. Tritiated water was used as an inert reference tracer. Radionuclides of the alkali- and alkaline earth-metals (mono- and divalent elements which are not influenced by hydrolysis in the pH-range studied) were used as tracers, i.e., {sup 22}Na{sup +}, {sup 45}Ca{sup 2+} and {sup 85}Sr{sup 2+}. The effective diffusivity and the rock capacity factor were calculated by fitting the breakthrough curve to the one-dimensional solution of the diffusion equation. Sorption coefficients, K{sub d}, that were derived from the rock capacity factor (diffusion experiments) were compared with K{sub d} determined in batch experiments using crushed material of different size fractions. The results show that the tracers were retarded in the same order as was expected from the measured batch K{sub d}. Furthermore, the largest size fraction was the most representative when comparing batch K{sub d} with K{sub d} evaluated from the diffusion experiments. The observed effective diffusivities tended to decrease with increasing cell lengths, indicating that the transport porosity decreases with increasing sample lengths used in the diffusion experiments.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  12. Solid / solution interaction: The effect of carbonate alkalinity on adsorbed thorium

    NASA Astrophysics Data System (ADS)

    LaFlamme, Brian D.; Murray, James W.

    1987-02-01

    Elevated activities of dissolved Th have been found in Soap Lake, an alkaline lake in Eastern Washington. Dissolved 232Th ranges from less than 0.001 to 4.9 dpm/L compared to about 1.3 × 10 -5 dpm/ L in sea water. The enhanced activity in the lake coincides with an increase in carbonate alkalinity. Experiments were conducted to evaluate the effect of pH, ionic strength and carbonate alkalinity on Th adsorption on goethite. Thorium (10 -13 M total) in the presence of 5.22 mg/L α-FeOOH and 0.1 M NaNO 3 has an adsorption edge from pH 2-5. At pH 9.0 ± 0.6 the percent Th absorbed on the solid began to decrease from 100% at 100 meq/L carbonate alkalinity and exhibited no adsorption above 300 meq/L. The experimental data were modeled to obtain the intrinsic adsorption equilibrium constants for Th hydrolysis species. These adsorption constants were incorporated in the model to interpret the observed effect of carbonate alkalinity on Th adsorption. There are two main effects of the alkalinity. To a significant degree the decrease in Th adsorption is due to competition of HCO -3 and CO 2-3 ions for surface sites. Dissolved Th carbonate complexes also contribute to the increase of Th in solution.

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

    PubMed Central

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-01-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: [3]Li+, [3]Na+, [4]K+, [4]Rb+, [6]Cs+, [3]Be2+, [4]Mg2+, [6]Ca2+, [6]Sr2+ and [6]Ba2+, 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 U eq(Na)/U eq(bonded anions) is partially correlated with 〈[6]Na+—O2−〉 (R 2 = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li+ in [4]- and [6]-coordination, Na+ in [4]- and [6

  14. Competition between humic acid and carbonates for rare earth elements complexation.

    PubMed

    Pourret, Olivier; Davranche, Mélanie; Gruau, Gérard; Dia, Aline

    2007-01-01

    The competitive binding of rare earth elements (REE) to humic acid (HA) and carbonates was studied experimentally at various pH and alkalinity values by combining ultrafiltration and inductively coupled plasma mass spectrometry techniques. The results show that the REE species occur as binary humate or carbonate complexes but not as ternary REE-carbonate-humate as previously proposed. The results also reveal the strong pH and alkalinity dependence of the competition as well as the existence of a systematic fractionation across the REE series. Specifically, carbonate complexation is at a maximum at pH 10 and increase with increasing alkalinity and with the atomic number of the REE (LuCO(3)>LaCO(3)). Modeling of the data using Model VI and recently published stability constants for complexation of REE by humic acid well reproduced the experimental data, confirming the ability of Model VI to accurately determine REE speciation in natural waters. This modeling also confirms the reliability of recently published stability constants. This work shed more light not only on the competition between carbonates and HA for REE complexation but also on the reliability of WHAM 6 and Model VI for calculating the speciation of REE with organic matter in alkaline organic-rich water.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    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.

  17. Prolonged QT Syndrome and Seizure Secondary to Alkaline Earth Metal Deficiency: A Case Report.

    PubMed

    McKinney, A; Keegan, B C

    2011-01-01

    Introduction. Alkaline earth metal deficiency is recognized as a cause of both seizure and long QT syndrome. Their deficiency can have significant repercussions on the function of cells, tissues, and organs of the body. An understanding of the role of electrolytes allows an appreciation of the significance of depleted levels on cell function. Case Report. A 65-year-old lady was admitted with symptoms of chest discomfort, vomiting, increased stoma output, and dizziness. Two days following admission she suffered a tonic-clonic seizure. ECG review demonstrated a prolonged QTc interval, raising the possibility of an underlying Torsades de Pointes as the precipitant. This was attributed to electrolyte disturbance arising as a result of multiple aetiologies. Discussion. This paper highlights the multisystem effects of electrolyte disturbance, with emphasis upon its role in precipitating cardiac arrhythmia and neurological symptoms.

  18. Alkaline earth metal cation exchange: effect of mobile counterion and dissolved organic matter.

    PubMed

    Indarawis, Katrina; Boyer, Treavor H

    2012-04-17

    The goal of this research was to provide an improved understanding of the interactions between alkaline earth metals and DOM under conditions that are encountered during drinking water treatment with particular focus on cation exchange. Both magnetically enhanced and nonmagnetic cation exchange resins were converted to Na, Mg, Ca, Sr, and Ba mobile counterion forms as a novel approach to investigate the exchange behavior between the cations and the interactions between the cations and DOM. The results show that cation exchange is a robust process for removal of Ca(2+) and Mg(2+) considering competition with cations on the resin surface and presence of DOM. DOM was actively involved during the cation exchange process through complexation, adsorption, and coprecipitation reactions. In addition to advancing the understanding of ion exchange processes for water treatment, the results of this work are applicable to membrane pretreatment to minimize fouling, treatment of membrane concentrate, and precipitative softening.

  19. Hydration process of alkaline-earth metal atoms in water clusters

    NASA Astrophysics Data System (ADS)

    Okai, Nobuhiro; Ishikawa, Haruki; Fuke, Kiyokazu

    2005-10-01

    Ionization potentials (IPs) of water clusters containing alkaline-earth metal atoms are measured by a photoionization threshold method to examine the hydration process of the metal atoms in clusters. IPs of Mg(H 2O) n and Ca(H 2O) n are found to decrease with increasing n and become constant at 3.18 eV for n ⩾ 9 and n ⩾ 8, respectively. The observed constant IP agrees with an estimated photoelectric threshold (3.2 eV) of bulk ice. From the comparison with the results on the theoretical calculations as well as the IPs for alkali atom-water clusters, the anomalous size dependence of IPs is ascribed to the formation of an ion-pair state.

  20. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    PubMed

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

    2014-06-01

    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.

  1. Magnetic crystals and helical liquids in alkaline-earth fermionic gases

    PubMed Central

    Barbarino, Simone; Taddia, Luca; Rossini, Davide; Mazza, Leonardo; Fazio, Rosario

    2015-01-01

    The joint action of a magnetic field and of interactions is crucial for the appearance of exotic quantum phenomena, such as the quantum Hall effect. Owing to their rich nuclear structure, equivalent to an additional synthetic dimension, one-dimensional alkaline-earth(-like) fermionic gases with synthetic gauge potential and atomic contact repulsion may display similar related properties. Here we show the existence and the features of a hierarchy of fractional insulating and conducting states by means of analytical and numerical methods. We demonstrate that the gapped states are characterized by density and magnetic order emerging solely for gases with effective nuclear spin larger than 1/2, whereas the gapless phases can support helical modes. We finally argue that these states are related to an unconventional fractional quantum Hall effect in the thin-torus limit and that their properties can be studied in state-of-the-art laboratories. PMID:26350624

  2. Quantum Degenerate Mixtures of Alkali and Alkaline-Earth-Like Atoms

    SciTech Connect

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

    2011-05-20

    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 {sup 6}Li with evaporatively cooled bosonic {sup 174}Yb and, separately, fermionic {sup 173}Yb. Using cross-thermalization studies, we also measure the elastic s-wave scattering lengths of both Li-Yb combinations, |a{sub {sup 6}Li-{sup 174}Yb}|=1.0{+-}0.2 nm and |a{sub {sup 6}Li-{sup 173}Yb}|=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.

  3. First hyperpolarizability of cyclooctatetraene modulated by alkali and alkaline earth metals.

    PubMed

    Roy, Ria Sinha; Mondal, Avijit; Nandi, Prasanta K

    2017-03-01

    In the present investigation, the first hyperpolarizability of alkali and alkaline earth metal derivatives of cyclooctatetraene (COT) has been calculated using BHHLYP and CAM-B3LYP functional for 6-311++G(d,p), 6-311++G(3df,3pd), and aug-pc 2 basis sets. Introduction of Na/K atoms at the axial position of COT and Li, Na, K/Be, Mg, Ca metal atoms and cyanide groups at the equatorial sites leads to lager enhancement of first hyperpolarizability. The ring charge density can account for the variation of first hyperpolarizability. The two state model has been invoked to explain the variation of first hyperpolarizability.

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

    PubMed

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

    2011-07-04

    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.

  5. Relationship between microstructure and efficiency of lithium silicate scintillating glasses: The effect of alkaline earths

    SciTech Connect

    Bliss, M.; Craig, R.A.; Sunberg, D.S.; Weber, M.J.

    1996-12-31

    Lithium silicate glasses containing Ce{sup 3+} are known to be scintillators. Glasses in this family in which the Li is enriched ({sup 6}Li) are used as neutron detectors. The addition of Mg to this glass is known to increase the scintillation efficiency. We have found that substituting other alkaline earths results in a monotonic decrease of the scintillation efficiency with increasing atomic number. The total variation in scintillation efficiency from Mg to Ba is nearly a factor of 3. Prior experiments with this glass family show small differences in Raman and fluorescence spectra; evidence from thermoluminescence experiments indicates that the scintillation efficiency is most strongly correlated with structural effects in the neighborhood of the Ce{sup 3+} activator ion. The results of low-temperature studies of fluorescence and thermoluminescence of these glasses will be reported.

  6. Alkaline solution absorption of carbon dioxide method and apparatus

    DOEpatents

    Hobbs, D.T.

    1991-01-01

    Disclosed is a method for measuring the concentration of hydroxides (or pH) in alkaline solutions, using the tendency of hydroxides to adsorb CO{sub 2}. The method comprises passing CO{sub 2} over the surface of an alkaline solution in a remote tank before and after measurements of the CO{sub 2} concentration. Comparison of the measurements yields the adsorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to adsorption fraction. A schematic is given of a process system according to a preferred embodiment of the invention. 2 figs.

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

    PubMed Central

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  9. Method of determining pH by the alkaline absorption of carbon dioxide

    DOEpatents

    Hobbs, D.T.

    1992-10-06

    A method is described for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction. 2 figs.

  10. Soil carbon cycle of different saline and alkaline soils under cotton fields in Tarim River Basin

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaoning; Zhao, Chengyi; Stahr, Karl; Kuzyakov, Yakov

    2015-04-01

    Calcium carbonate is the most common form of carbon (C) in semiarid and arid soils. Depending on pH and salinity changes, soils can act as sink or source of atmospheric CO2 as well as contribute to C exchange between CO2 and CaCO3 leading to formation of pedogenic carbonates. However, the rates of these processes and the effects of environmental factors remains unknown. 14CO2 was used to assess carbonate recrystallization in 4 saline and alkaline soils (Aksu alkaline, Aksu saline, Yingbazar alkaline, Yingbazar saline) (EC = 0.32, 1.35, 1.72, 3.67 (1:20) mS cm-1, pH = 8.5, 8.2, 8.9, 7.9 respectively) and to trace the C exchange in the soils of the Tarim River basin depending on CO2 concentrations in soils (0.02%, 0.04%, 0.2%, 0.4% and 4%). 14C was traced in soil water and air as well as in carbonates. The highest 14C in 14CO2 (95% of the 14C input) was observed in Aksu alkaline soil and the highest 14C incorporation in CaCO3 (54%) was observed in Yingbazar saline soil. There were close negative linear relationships between initial CO2 concentrations (0.04%, 0.4% and 4%) and the 14C in Ca14CO3 and in 14CO2. The carbonate recrystallization rate increased with the CO2 concentration and were depended on the recrystalliztion period. The average carbonate recrystallization rate was highest at 4% CO2 concentration for Yingbazar saline soil (6.59×10-4 % per day) and the lowest at 0.04% CO2 concentration for Aksu alkaline soil (0.03×10-4 % per day). The carbonate recrystallization rate linearly increased with the soil EC and with 0.04% and 0.4% CO2 concentration , whereas the carbonate recrystallization rate decreased with pH. The highest CO2 concentration of 4% can 10 to 100 times shorten the full carbonate recrystallization of the remaining primary carbonates compared to lower CO2 concentrations 0.4% and 0.04% for complete (95%) recrystallization of soil carbonate. We conclude that microbial and root respiration affecting CO2 concentration in soil is the most important

  11. Mineral Carbonation Potential of CO2 from Natural and Industrial-based Alkalinity Sources

    NASA Astrophysics Data System (ADS)

    Wilcox, J.; Kirchofer, A.

    2014-12-01

    Mineral carbonation is a Carbon Capture and Storage (CSS) technology where gaseous CO2 is reacted with alkaline materials (such as silicate minerals and alkaline industrial wastes) and converted into stable and environmentally benign carbonate minerals (Metz et al., 2005). Here, we present a holistic, transparent life cycle assessment model of aqueous mineral carbonation built using a hybrid process model and economic input-output life cycle assessment approach. We compared the energy efficiency and the net CO2 storage potential of various mineral carbonation processes based on different feedstock material and process schemes on a consistent basis by determining the energy and material balance of each implementation (Kirchofer et al., 2011). In particular, we evaluated the net CO2 storage potential of aqueous mineral carbonation for serpentine, olivine, cement kiln dust, fly ash, and steel slag across a range of reaction conditions and process parameters. A preliminary systematic investigation of the tradeoffs inherent in mineral carbonation processes was conducted and guidelines for the optimization of the life-cycle energy efficiency are provided. The life-cycle assessment of aqueous mineral carbonation suggests that a variety of alkalinity sources and process configurations are capable of net CO2 reductions. The maximum carbonation efficiency, defined as mass percent of CO2 mitigated per CO2 input, was 83% for CKD at ambient temperature and pressure conditions. In order of decreasing efficiency, the maximum carbonation efficiencies for the other alkalinity sources investigated were: olivine, 66%; SS, 64%; FA, 36%; and serpentine, 13%. For natural alkalinity sources, availability is estimated based on U.S. production rates of a) lime (18 Mt/yr) or b) sand and gravel (760 Mt/yr) (USGS, 2011). The low estimate assumes the maximum sequestration efficiency of the alkalinity source obtained in the current work and the high estimate assumes a sequestration efficiency

  12. Optical and electronic properties of conductive ternary nitrides with rare- or alkaline-earth elements

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    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.

  13. Carbon dioxide warming of the early Earth.

    PubMed

    Arrhenius, G

    1997-02-01

    Svante Arrhenius' research in atmospheric physics extended beyond the recent past and the near future states of the Earth, which today are at the center of sociopolitical attention. His plan encompassed all of the physical phenomena known at the time to relate to the formation and evolution of stars and planets. His two-volume textbook on cosmic physics is a comprehensive synopsis of the field. The inquiry into the possible cause of the ice ages and the theory of selective wavelength filter control led Arrhenius to consider the surface states of the other terrestrial planets, and of the ancient Earth before it had been modified by the emergence of life. The rapid escape of hydrogen and the equilibration with igneous rocks required that carbon in the early atmosphere prevailed mainly in oxidized form as carbon dioxide, together with other photoactive gases exerting a greenhouse effect orders of magnitude larger than in our present atmosphere. This effect, together with the ensuing chemical processes, would have set the conditions for life to evolve on our planet, seeded from spores spreading through an infinite Universe, and propelled, as Arrhenius thought, by stellar radiation pressure.

  14. Carbon dioxide warming of the early Earth

    NASA Technical Reports Server (NTRS)

    Arrhenius, G.

    1997-01-01

    Svante Arrhenius' research in atmospheric physics extended beyond the recent past and the near future states of the Earth, which today are at the center of sociopolitical attention. His plan encompassed all of the physical phenomena known at the time to relate to the formation and evolution of stars and planets. His two-volume textbook on cosmic physics is a comprehensive synopsis of the field. The inquiry into the possible cause of the ice ages and the theory of selective wavelength filter control led Arrhenius to consider the surface states of the other terrestrial planets, and of the ancient Earth before it had been modified by the emergence of life. The rapid escape of hydrogen and the equilibration with igneous rocks required that carbon in the early atmosphere prevailed mainly in oxidized form as carbon dioxide, together with other photoactive gases exerting a greenhouse effect orders of magnitude larger than in our present atmosphere. This effect, together with the ensuing chemical processes, would have set the conditions for life to evolve on our planet, seeded from spores spreading through an infinite Universe, and propelled, as Arrhenius thought, by stellar radiation pressure.

  15. Predicting Carbonate Ion Transport in Alkaline Anion Exchange Materials

    DTIC Science & Technology

    2012-01-01

    Schematic of the permeation cell experiment used to measure transient CO2 flux across the polymer electrolyte membrane. Experimental result vs. model trend...Microstructure on Charge Transfer, Mass Transfer, and Electrochemical Reactions in Solid Oxide Fuel Cells ; Part 2. Ion and Water Transport in Alkaline Anion...through the use of the Fuel Cell Technologies Test Station such as the relative humidity and flow rate of the feed gases, the cell temperature, and the

  16. The Disordered Kinetics of Earth's Carbon Cycle

    NASA Astrophysics Data System (ADS)

    Rothman, Daniel

    2008-03-01

    The carbon cycle describes the transformations of carbon as it cycles through living organisms and the physical environment. In its simplest form, the cycle amounts to a loop between photosynthesis and respiration. Photosynthesis produces organic carbon and molecular oxygen from carbon dioxide and water. Respiration reverses the process by oxidation of organic carbon. The duration of the cycle spans a vast range of time scales: from days or less for fast-growing plankton in the oceans, to hundreds of millions of years or more for the small fraction of organic matter that is buried as rock. The rates at which the cycle is closed set atmospheric carbon dioxide levels at short time scales and oxygen levels at geologic time scales. Respiration rates thereby influence not only climate---by the determination of equilibrium carbon dioxide concentrations---but also biological evolution---because the oxygenation of Earth's atmosphere must have preceded the advent of aerobic metabolism. We review recent advances in the understanding of the rates that control the carbon cycle, with emphasis on the respiratory back-reaction. Given considerable biological, chemical, and environmental variation, it comes as no surprise that measurements of rates vary greatly. Observations suggest, however, some surprising simplicity: for example, the rates of microbial consumption of organic matter in sediments and soils slow down systematically like the inverse of the age of the organic matter. This aging effect can be quantitatively understood as the macroscopic observation of microscopically disordered kinetics. The disorder can arise purely physically as the consequence of a reaction-diffusion process in porous media, but any combination of physical, chemical, and biological parameters that yield a wide range of rates suffices. A predicted practical consequence is a slow, logarithmic decay of organic matter in sediments and soils, which compares well with measurements. Further observations

  17. CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.

    PubMed

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-09-01

    This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char.

  18. Evaluating Carbonate System Algorithms in a Nearshore System: Does Total Alkalinity Matter?

    PubMed Central

    Sweet, Julia; Brzezinski, Mark A.; McNair, Heather M.; Passow, Uta

    2016-01-01

    Ocean acidification is a threat to many marine organisms, especially those that use calcium carbonate to form their shells and skeletons. The ability to accurately measure the carbonate system is the first step in characterizing the drivers behind this threat. Due to logistical realities, regular carbonate system sampling is not possible in many nearshore ocean habitats, particularly in remote, difficult-to-access locations. The ability to autonomously measure the carbonate system in situ relieves many of the logistical challenges; however, it is not always possible to measure the two required carbonate parameters autonomously. Observed relationships between sea surface salinity and total alkalinity can frequently provide a second carbonate parameter thus allowing for the calculation of the entire carbonate system. Here, we assessed the rigor of estimating total alkalinity from salinity at a depth <15 m by routinely sampling water from a pier in southern California for several carbonate system parameters. Carbonate system parameters based on measured values were compared with those based on estimated TA values. Total alkalinity was not predictable from salinity or from a combination of salinity and temperature at this site. However, dissolved inorganic carbon and the calcium carbonate saturation state of these nearshore surface waters could both be estimated within on average 5% of measured values using measured pH and salinity-derived or regionally averaged total alkalinity. Thus we find that the autonomous measurement of pH and salinity can be used to monitor trends in coastal changes in DIC and saturation state and be a useful method for high-frequency, long-term monitoring of ocean acidification. PMID:27893739

  19. Molten metal reactor and method of forming hydrogen, carbon monoxide and carbon dioxide using the molten alkaline metal reactor

    DOEpatents

    Bingham, Dennis N.; Klingler, Kerry M.; Turner, Terry D.; Wilding, Bruce M.

    2012-11-13

    A molten metal reactor for converting a carbon material and steam into a gas comprising hydrogen, carbon monoxide, and carbon dioxide is disclosed. The reactor includes an interior crucible having a portion contained within an exterior crucible. The interior crucible includes an inlet and an outlet; the outlet leads to the exterior crucible and may comprise a diffuser. The exterior crucible may contain a molten alkaline metal compound. Contained between the exterior crucible and the interior crucible is at least one baffle.

  20. Alkaline earth metal fluxes for the growth of single crystal oxides

    NASA Astrophysics Data System (ADS)

    Ramirez, Daniel

    Oxide ceramics are materials with a wide range of properties. Insulators are most common, however semiconductors, strongly correlated electron materials, and even superconductors are all relevant oxide materials. Here we seek to synthesize novel oxide single crystal phases and study their properties using an alkaline earth metal flux technique. The specific flux techniques are new, and we will seek to understand the capabilities of these fluxes as a novel synthesis tool. The use of a barium metal flux to grow single crystal oxides is rather counterintuitive, but is exemplified further with the growth of europium monoxide (Fm3¯m #225, Z = 4). Eu1-xBaxO single crystals (x = 0.01 - 0.25) are grown and studied for their ferromagnetic properties. A new oxide phase Ba2Eu2P2O (P4/mbm #127, Z = 2) has also been synthesized from the same method, and may potentially be studied as a ferromagnetic semiconductor based on preliminary observations. Other examples of single crystal oxide phases grown from barium metal flux includes Ba2TeO (P4/nmm #129, Z = 2), BaLn2O4 (Ln = La - Lu) (Pnma #62, Z = 4), and Ba3Yb2O 5Te (P4/mmm #123 Z = 1). The new crystal phases Ba3Ln2O5Cl 2 (Ln = Sm - Lu, Y) are synthesized using a reactive barium metal flux. Single crystal x-ray diffraction is used to determine their structures with space group (I4/mmm #139, Z = 2) related to the Ruddlesden-Popper structure type. The unit cell dimensions range from a = 4.46(6) A and c = 24.87(6) A for Ba3Gd2O5Cl2 to a = 4.35(6) A and c = 24.57(6) A for Ba3Lu2O 5Cl2 with the dimensions following the expected lanthanide contraction trends. The magnetic properties of these materials are studied and related to their structures. The use of alkaline earth fluxes such as magnesium or calcium based fluxes are also briefly considered for their capabilities to produce novel mixed anion phases. A calcium flux is shown to produce the novel semimetals Ca 4TeOH4 and Ca3Ca1-xEuxTeOH 4 (I4/mmm #139, Z = 2), and highly reducing

  1. Facile synthesis of water-soluble carbon nano-onions under alkaline conditions.

    PubMed

    Ahmed, Gaber Hashem Gaber; Laíño, Rosana Badía; Calzón, Josefa Angela García; García, Marta Elena Díaz

    2016-01-01

    Carbonization of tomatoes at 240 °C using 30% (w/v) NaOH as catalyst produced carbon onions (C-onions), while solely carbon dots (C-dots) were obtained at the same temperature in the absence of the catalyst. Other natural materials, such as carrots and tree leaves (acer saccharum), under the same temperature and alkaline conditions did not produce carbon onions. XRD, FTIR, HRTEM, UV-vis spectroscopy, and photoluminescence analyses were performed to characterize the as-synthesized carbon nanomaterials. Preliminary tests demonstrate a capability of the versatile materials for chemical sensing of metal ions. The high content of lycopene in tomatoes may explain the formation of C-onions in alkaline media and a possible formation mechanism for such structures was outlined.

  2. Facile synthesis of water-soluble carbon nano-onions under alkaline conditions

    PubMed Central

    Ahmed, Gaber Hashem Gaber; Laíño, Rosana Badía; Calzón, Josefa Angela García

    2016-01-01

    Summary Carbonization of tomatoes at 240 °C using 30% (w/v) NaOH as catalyst produced carbon onions (C-onions), while solely carbon dots (C-dots) were obtained at the same temperature in the absence of the catalyst. Other natural materials, such as carrots and tree leaves (acer saccharum), under the same temperature and alkaline conditions did not produce carbon onions. XRD, FTIR, HRTEM, UV–vis spectroscopy, and photoluminescence analyses were performed to characterize the as-synthesized carbon nanomaterials. Preliminary tests demonstrate a capability of the versatile materials for chemical sensing of metal ions. The high content of lycopene in tomatoes may explain the formation of C-onions in alkaline media and a possible formation mechanism for such structures was outlined. PMID:27335764

  3. Predicting Carbonate Species Ionic Conductivity in Alkaline Anion Exchange Membranes

    DTIC Science & Technology

    2012-06-01

    anion exchange membranes. Andrew M. Kiss, Timothy D . Myles, Kyle N. Grew, Aldo A. Peracchio, George J. Nelson, and Wilson K. S. Chiu University of...Alkaline Anion Exchange Membranes Andrew M. Kiss1, Timothy D . Myles1, Kyle N. Grew2, Aldo A. Peracchio1, George J. Nelson1, and Wilson K. S. Chiu1* 1...Vol. 301, 93-106, 2007. 16. Satterfleld,M.B., Benziger,J.B., J. Phys. Chem. B, Vol. 112,12, 3693 -3704, 2008. 17. Motupally,S., Becker,A.J

  4. Quantification of carbon dioxide poisoning in air breathing alkaline fuel cells

    NASA Astrophysics Data System (ADS)

    Tewari, A.; Sambhy, V.; Urquidi Macdonald, M.; Sen, A.

    Carbon dioxide intolerance has impeded the development of alkaline fuel cells as an alternate source of power supply. The CO 2, in a fuel cell system, could come from the anode side (if "dirty" H 2 is used as fuel), from the cathode side (if air instead of pure O 2 is used as an oxidant) or from inside the electrolyte (if methanol is used as a fuel). In this work, an novel analytical approach is proposed to study and quantify the carbon dioxide poisoning problem. Accelerated tests were carried out in an alkaline fuel cell using methanol as a fuel with different electrical loads and varying the concentration of carbon dioxide in a mixture CO 2/O 2 used as oxidant. Two characteristic quantities, t max and R max, were specified which were shown to comprehensively define the nature and extent of carbon dioxide poisoning in alkaline fuel cells. The poisoning phenomenon was successfully quantified by determining the dependence of these characteristic quantities on the operating parameters, viz. atmospheric carbon dioxide concentration and applied electrical load. Such quantification enabled the prediction of the output of a fuel cell operating in a carbon dioxide enriched atmosphere. In addition, static and dynamic analyses of electrolytes were carried out to determine the dependence of cell current on the electrolyte composition in a fuel cell undergoing poisoning. It was observed that there is a critical concentration of KOH in the electrolyte only below which the effect of carbon dioxide poisoning is reflected on the cell performance. Potentiostatic polarization tests confirmed that the underlying reason for the decreased cell performance because of carbon dioxide poisoning is the sluggish kinetics of methanol oxidation in the presence of potassium carbonate in the electrolyte. Moreover, the decreased conductivity of the electrolyte resulting from hydroxide to carbonate conversion was also shown to increase the ohmic loses in an alkaline fuel cell leading to lower

  5. Bond ionicity of alkaline-earth oxides studied by low-energy D+ scattering

    NASA Astrophysics Data System (ADS)

    Souda, R.; Yamamoto, K.; Hayami, W.; Aizawa, T.; Ishizawa, Y.

    1994-08-01

    Low-energy D+ scattering is employed to explore the nature of the bonding of polycrystalline alkaline-earth oxides MgO, CaO, SrO, and BaO, with particular emphasis on the investigation of the ionicity of the topmost-layer atoms. Increasing ionicity as one goes to the heavier cations is concluded from the probability of the resonance neutraliztion of the D+ ions, which is consistent with the conventional chemical arguments based on electronegativity scales but is in apparent contradiction to the results of recent ab initio cluster-model calculations. It is also concluded that the metallic Ba layer is formed rather patchily on the BaO surface after the heat treatment up to 1000 °C. This is probably because free Ba atoms, being supplied by the reaction of BaO with the Ta substrate, are precipitated at the BaO surface. Another example is concerned with the interactions of the Ba adatoms with Si(001) and Pt(111) surfaces; Ba is found to have marked covalency with the substrate atoms.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  7. Crystal and defect chemistry influences on band gap trends in alkaline earth perovskites

    SciTech Connect

    Lee, Soonil; Woodford, William H.; Randall, Clive A.

    2008-05-19

    A number of perovskites with A-site alkaline earth chemistries being Ca, Sr, and Ba, and tetravalent cations including Ce, Zr, and Ti are measured for optical band gap and found to vary systematically with tolerance factor and lattice volume within limits defined by the chemistry of the octahedral site. This paper also focuses on the BaTiO{sub 3} system, considering equilibrated nonstoichiometries, and determines the changes in band gap with respect to Ba/Ti ratios. It was found that the optical band gap changes in the solid solution regime and is invariant in the second phase regions, as would be expected. In the cases of Ba/Ti<1.0, the variation in band gap scales with lattice volume, but in the Ba/Ti>1.0 stoichiometries, there is a distinct Urbach tail and the trend with lattice volume no longer holds. It is inferred that the V{sub Ti}{sup q}prime-2V{sub O} partial Schottky complex controls the band gap trend with Ba-rich nonstoichiometries.

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

    NASA Astrophysics Data System (ADS)

    Acevedo, Oscar Leonardo; Rey, Ana Maria

    2016-05-01

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

  9. Process for depositing epitaxial alkaline earth oxide onto a substrate and structures prepared with the process

    DOEpatents

    McKee, Rodney A.; Walker, Frederick J.

    1996-01-01

    A process and structure involving a silicon substrate utilize molecular beam epitaxy (MBE) and/or electron beam evaporation methods and an ultra-high vacuum facility to grow a layup of epitaxial alkaline earth oxide films upon the substrate surface. By selecting metal constituents for the oxides and in the appropriate proportions so that the lattice parameter of each oxide grown closely approximates that of the substrate or base layer upon which oxide is grown, lattice strain at the film/film or film/substrate interface of adjacent films is appreciably reduced or relieved. Moreover, by selecting constituents for the oxides so that the lattice parameters of the materials of adjacent oxide films either increase or decrease in size from one parameter to another parameter, a graded layup of films can be grown (with reduced strain levels therebetween) so that the outer film has a lattice parameter which closely approximates that of, and thus accomodates the epitaxial growth of, a pervoskite chosen to be grown upon the outer film.

  10. The Characterization of Eu2+-Doped Mixed Alkaline-Earth Iodide Scintillator Crystals

    SciTech Connect

    Neal, John S; Boatner, Lynn A; Ramey, Joanne Oxendine; Wisniewski, D.; Kolopus, James A; Cherepy, Nerine; Payne, Stephen A.

    2011-01-01

    The high-performance inorganic scintillator, SrI2:Eu2+, when activated with divalent europium in the concentration range of 3 to 6%, has shown great promise for use in applications that require high-energy-resolution gamma-ray detection. We have recently grown and tested crystals in which other alkaline-earth ions have been partially substituted for Sr ions. Specifically, europium-doped single crystals have been grown in which up to 30 at % of the strontium ions have been substituted for either by barium, magnesium, or calcium ions. In the case of the strontium iodide scintillator host, a material that is characterized by an orthorhombic crystal structure, there are three other column IIA elements that are obvious choices for investigations whose purpose is to realize potential improvements in the performance of SrI2:Eu2+-based scintillators via the replacement of strontium ions with either Mg2+, Ca2+, or Ba2+. Light yields of up to 81,400 photons/MeV with an associated energy resolution of 3.7% (fwhm for 662 keV gamma-rays) have been observed in the case of a partial substitution of Ba2+ for Sr2+. The measured decay times ranged from 1.1 to 2.0 s, while the peak emission wavelengths ranged from 432 to 438 nm.

  11. Alkaline earth silicate wools - A new generation of high temperature insulation.

    PubMed

    Brown, Robert C; Harrison, Paul T C

    2012-11-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α02-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α02-), and (Λ) increases with increasing of K2O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K2O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  13. Heavy water reactions with alkaline-earth metal dications in the gas phase

    NASA Astrophysics Data System (ADS)

    Feil, Stefan; Koyanagi, Greg K.; Bohme, Diethard K.

    2009-02-01

    Room temperature rate coefficients and product distributions are reported for the reactions initiated in D2O with dications of the alkaline-earth metals Mg, Ca, Sr and Ba. The measurements were performed with a selected-ion flow tube (SIFT) tandem mass spectrometer and electrospray ionization (ESI). Mg2+ reacts with water by a fast electron transfer leading to charge separation with a rate coefficient of 1.4 × 10-9 cm3 molecule-1 s-1. Ca2+ reacts with D2O in a first step to form the adduct Ca2+(D2O), with an effective bimolecular rate coefficient of 2.3 × 10-11 cm3 molecule-1 s-1, which then undergoes rapid charge separation by deuteron transfer to form CaOD+ and D3O+ in a second step with k = 7.9 × 10-10 cm3 molecule-1 s-1. The CaOD+ ion reacts further by clustering up to five more D2O molecules. Sr2+ clusters up to eight D2O molecules and Ba2+ up to seven D2O molecules, with the first addition of D2O being rate determining in each case and the last addition being distinctly slower, as might be expected from a transition in the occupation of the added water molecules from an inner to an outer hydration shell.

  14. CO2 mitigation potential of mineral carbonation with industrial alkalinity sources in the United States.

    PubMed

    Kirchofer, Abby; Becker, Austin; Brandt, Adam; Wilcox, Jennifer

    2013-07-02

    The availability of industrial alkalinity sources is investigated to determine their potential for the simultaneous capture and sequestration of CO2 from point-source emissions in the United States. Industrial alkalinity sources investigated include fly ash, cement kiln dust, and iron and steel slag. Their feasibility for mineral carbonation is determined by their relative abundance for CO2 reactivity and their proximity to point-source CO2 emissions. In addition, the available aggregate markets are investigated as possible sinks for mineral carbonation products. We show that in the U.S., industrial alkaline byproducts have the potential to mitigate approximately 7.6 Mt CO2/yr, of which 7.0 Mt CO2/yr are CO2 captured through mineral carbonation and 0.6 Mt CO2/yr are CO2 emissions avoided through reuse as synthetic aggregate (replacing sand and gravel). The emission reductions represent a small share (i.e., 0.1%) of total U.S. CO2 emissions; however, industrial byproducts may represent comparatively low-cost methods for the advancement of mineral carbonation technologies, which may be extended to more abundant yet expensive natural alkalinity sources.

  15. Discrete divalent rare-earth cationic ROP catalysts: ligand-dependent redox behavior and discrepancies with alkaline-earth analogues in a ligand-assisted activated monomer mechanism.

    PubMed

    Liu, Bo; Roisnel, Thierry; Maron, Laurent; Carpentier, Jean-François; Sarazin, Yann

    2013-03-18

    The first solvent-free cationic complexes of the divalent rare-earth metals, [{RO}RE(II) ](+) [A](-) (RE(II) =Yb(II) , 1; Eu(II) , 2) and [{LO}RE(II) ](+) [A](-) ([A](-) =[H2 N{B(C6 F5 )3 }2 ](-) ; RE(II) =Yb(II) , 3; Eu(II) , 4), have been prepared by using highly chelating monoanionic aminoether-fluoroalkoxide ({RO}(-) ) and aminoether-phenolate ({LO}(-) ) ligands. Complexes 1 and 2 are structurally related to their alkaline-earth analogues [{RO}AE](+) [A](-) (AE=Ca, 5; Sr, 6). Yet, the two families behave very differently during catalysis of the ring-opening polymerization (ROP) of L-lactide (L-LA) and trimethylene carbonate (TMC) performed under immortal conditions with excess BnOH as an exogenous chain-transfer agent. The ligand was found to strongly influence the behavior of the RE(II) complexes during ROP catalysis. The fluoroalkoxide RE(II) catalysts 1 and 2 are not oxidized under ROP conditions, and compare very favorably with their Ca and Sr congeners 5 and 6 in terms of activity (turnover frequency (TOF) in the range 200-400 molL-LA (molEu  h(-1) )) and control over the parameters during the immortal ROP of L-LA (Mn,theor ≈Mn,SEC , Mw /Mn <1.05). The Eu(II) -phenolate 4 provided one of the most effective ROP cationic systems known to date for L-LA polymerization, exhibiting high activity (TOF up to 1 880 molL-LA ⋅(molEu  h)(-1) ) and good control (Mw /Mn =1.05). By contrast, upon addition of L-LA the Yb(II) -phenolate 3 immediately oxidizes to inactive RE(III) species. Yet, the cyclic carbonate TMC was rapidly polymerized by combinations of 3 (or even 1) and BnOH, revealing excellent activities (TOF=5000-7000 molTMC ⋅(molEu  h)(-1) ) and unusually high control (Mn,theor ≈Mn,SEC , Mw /Mn <1.09); under identical conditions, the calcium derivative 5 was entirely inert toward TMC. Based on experimental and kinetic data, a new ligand-assisted activated monomer ROP mechanism is suggested, in which the so-called ancillary ligand plays a

  16. Optimizing the performance of bandpass photon detectors for inverse photoemission: Transmission of alkaline earth fluoride window crystals

    SciTech Connect

    Thiede, Christian Schmidt, Anke B.; Donath, Markus

    2015-08-15

    Bandpass photon detectors are widely used in inverse photoemission in the isochromat mode at energies in the vacuum-ultraviolet spectral range. The energy bandpass of gas-filled counters is usually formed by the ionization threshold of the counting gas as high-pass filter and the transmission cutoff of an alkaline earth fluoride window as low-pass filter. The transmission characteristics of the window have, therefore, a crucial impact on the detector performance. We present transmission measurements in the vacuum-ultraviolet spectral range for alkaline earth fluoride window crystals in the vicinity of the transmission cutoff as a function of crystal purity, surface finish, surface contamination, temperature, and thickness. Our findings reveal that the transmission characteristics of the window crystal and, thus, the detector performance depend critically on these window parameters.

  17. The contents of alkali and alkaline earth metals in soils of the southern Cis-Ural region

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    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.

  18. Spin-Orbit-Coupled Correlated Metal Phase in Kondo Lattices: An Implementation with Alkaline-Earth Atoms

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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.

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

    SciTech Connect

    Guo, W.; Ma, H.A.; Jia, X.

    2014-03-01

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

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

    NASA Astrophysics Data System (ADS)

    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 < 0.2 L/(mol*cm). Prompt gamma activation analysis (PGAA) measurements conducted at the National Institute of Standards and Technology (NIST) found OH concentrations in the glasses in the range from 10 to 27.5 ppm. The alkaline earth-doped fibers exhibited lower OH absorption at 1.39 mum) than germanium and aluminum-doped reference fibers. Fibers doped with either magnesium, calcium or strontium displayed up

  1. 5 d-4 f luminescence of Nd3+, Gd3+, Er3+, Tm3+, and Ho3+ ions in crystals of alkaline earth fluorides

    NASA Astrophysics Data System (ADS)

    Radzhabov, E. A.; Prosekina, E. A.

    2011-09-01

    The vacuum ultraviolet emission spectra of alkaline-earth fluoride (CaF2, SrF2, BaF2) crystals with rare earth impurity ions (Nd, Gd, Er, Tm, Ho) have been investigated. The main luminescence bands are described well by the transitions from the lowest excited 5 d state to different 4 f levels of rare earth ions.

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

    PubMed

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

    2016-09-21

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

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

    SciTech Connect

    Brandao, Paula; Reis, Mario S; Gai, Zheng; Moreira Dos Santos, Antonio F

    2013-01-01

    Two new alkaline earth copper(II) germanates were hydrothermally synthesized: CaCuGeO4 center dot H2O (1) and BaCu2Ge3O9 center dot H2O (2), and their structures determined by single crystal X-ray diffraction. Compound (1) crystallizes in space group P2(1)/c with a=5.1320(2) angstrom, b=16.1637(5) angstrom, c=5.4818(2) angstrom, beta=102.609(2)degrees, V=443.76(3) angstrom(3) and Z=4. This copper germanate contains layers of composition [CuGeO4](infinity)(2-) comprising CuO4 square planes and GeO4 tetrahedra with calcium and water molecules in the inter-layer space. Compound (2) crystallizes in the Cmcm space group with a=5.5593(3) angstrom, b=10.8606(9) angstrom, c=13.5409(8) angstrom, V=817.56(9) angstrom(3) and Z=4. This structure contains GeO6 and CuO6 octahedra as well as GeO4 tetrahedra, forming a three-dimensional network of interconnecting six-membered ring channels. The magnetic susceptibility for both samples can be interpreted as S=1/2 chains, in agreement with the copper topology observed in the crystal structure. The susceptibility of (1) exhibits a Bonner-Fisher type behavior, resulting from antiferromagnetic intra-chain interactions without three-dimensional ordering down to 5 K-the lowest measured temperature. This observation, together with the absence of super-exchange paths between the copper chains, make this system particularly promising for the study of low dimensional magnetism. The magnetic properties of (2) show a very weak ferromagnetic near-neighbor interaction along the chain. In this compound a peak the chi T plot seems to indicate the onset of interchain antiferromagentic correlations. However, no ordering temperature is detected in the susceptibility data.

  4. Accumulation of alkaline earth metals by the green macroalga Bryopsis maxima.

    PubMed

    Takahashi, Shigekazu; Aizawa, Kyoko; Nakamura, Saki; Nakayama, Katsumi; Fujisaki, Shingo; Watanabe, Soichiro; Satoh, Hiroyuki

    2015-04-01

    Twenty-five days after the disaster at the Fukushima Daiichi nuclear power plant in 2011, we collected samples of the green macroalga Bryopsis maxima from the Pacific coast of Japan. Bryopsis maxima is a unicellular, multinuclear, siphonous green macroalga. Radiation analysis revealed that B. maxima emitted remarkably high gamma radiation of (131)I, (134)Cs, (137)Cs, and (140)Ba as fission products of (235)U. Interestingly, B. maxima contained naturally occurring radionuclides derived from (226)Ra and (228)Ra. Analysis of element content revealed that B. maxima accumulates many ocean elements, especially high quantities of the alkaline earth metals Sr (15.9 g per dry-kg) and Ba (3.79 g per dry-kg), whereas Ca content (12.5 g per dry-kg) was lower than that of Sr and only 61 % of the mean content of 70 Japanese seaweed species. Time-course analysis determined the rate of radioactive (85)Sr incorporation into thalli to be approximately 0.13 g Sr per dry-kg of thallus per day. Subcellular fractionation of B. maxima cells showed that most of the (85)Sr was localized in the soluble fraction, predominantly in the vacuole or cytosol. Given that (85)Sr radioactivity was permeable through a dialysis membrane, the (85)Sr was considered to be a form of inorganic ion and/or bound with a small molecule. Precipitation analysis with sodium sulfate showed that more than 70% of the Sr did not precipitate as SrSO4, indicating that a proportion of the Sr may bind with small molecules in B. maxima.

  5. LEACHING OF URANIUM ORES USING ALKALINE CARBONATES AND BICARBONATES AT ATMOSPHERIC PRESSURE

    DOEpatents

    Thunaes, A.; Brown, E.A.; Rabbits, A.T.; Simard, R.; Herbst, H.J.

    1961-07-18

    A method of leaching uranium ores containing sulfides is described. The method consists of adding a leach solution containing alkaline carbonate and alkaline bicarbonate to the ore to form a slurry, passing the slurry through a series of agitators, passing an oxygen containing gas through the slurry in the last agitator in the series, passing the same gas enriched with carbon dioxide formed by the decomposition of bicarbonates in the slurry through the penultimate agitator and in the same manner passing the same gas increasingly enriched with carbon dioxide through the other agitators in the series. The conditions of agitation is such that the extraction of the uranium content will be substantially complete before the slurry reaches the last agitator.

  6. Inhibitive effects of palm kernel oil on carbon steel corrosion by alkaline solution

    NASA Astrophysics Data System (ADS)

    Zulkafli, M. Y.; Othman, N. K.; Lazim, A. M.; Jalar, A.

    2013-11-01

    The behavior of carbon steel SAE 1045 in 1 M NaOH solution containing different concentrations of palm kernel oil (PKO) has been studied by weight loss and polarization measurement. Results showed that the corrosion of carbon steel in NaOH solution was considerably reduced in presence of such inhibitors. The inhibition efficiency increases when concentration of inhibitor increase. Maximum inhibition efficiency (≈ 96.67%) is obtained at PKO concentration 8 v/v %. This result revealed that palm kernel oil can act as a corrosion inhibitor in an alkaline medium. Corrosion rates of carbon steel decrease as the concentration of inhibitor is increased.

  7. Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents.

    PubMed

    Fromm, Katharina M

    2006-11-21

    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

  8. ION EXCHANGE IN FUSED SALTS. II. THE DISTRIBUTION OF ALKALI METAL AND ALKALINE EARTH IONS BETWEEN CHABAZITE AND FUSED LINO3, NANO3, AND KNO3,

    DTIC Science & Technology

    ION EXCHANGE, SALTS ), (*ALKALI METALS, ION EXCHANGE), (*ALKALINE EARTH METALS, ION EXCHANGE), (*NITRATES, ION EXCHANGE), SODIUM , CALCIUM, POTASSIUM...BARIUM, RUBIDIUM, CESIUM, LITHIUM COMPOUNDS, SODIUM COMPOUNDS, POTASSIUM COMPOUNDS, DISTRIBUTION, MINERALS, IONS

  9. [Effect of bivalent alkaline earth fluorides introduction on thermal stability and spectroscopic properties of Er3+/Tm3+ /Yb3+ co-doped oxyfluorogermanate glasses].

    PubMed

    Hu, Yue-bo; Zhang, Xin-na; Zhou, Da-li; Jiao, Qing; Wang, Rong-fei; Huang, Jin-feng; Long, Xiao-bo; Qiu, Jian-bei

    2012-01-01

    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.

  10. Co-composting solid biowastes with alkaline materials to enhance carbon stabilization and revegetation potential.

    PubMed

    Chowdhury, Saikat; Bolan, Nanthi S; Seshadri, Balaji; Kunhikrishnan, Anitha; Wijesekara, Hasintha; Xu, Yilu; Yang, Jianjun; Kim, Geon-Ha; Sparks, Donald; Rumpel, Cornelia

    2016-04-01

    Co-composting biowastes such as manures and biosolids can be used to stabilize carbon (C) without impacting the quality of these biowastes. This study investigated the effect of co-composting biowastes with alkaline materials on C stabilization and monitored the fertilization and revegetation values of these co-composts. The stabilization of C in biowastes (poultry manure and biosolids) was examined by their composting in the presence of various alkaline amendments (lime, fluidized bed boiler ash, flue gas desulphurization gypsum, and red mud) for 6 months in a controlled environment. The effects of co-composting on the biowastes' properties were assessed for different physical C fractions, microbial biomass C, priming effect, potentially mineralizable nitrogen, bioavailable phosphorus, and revegetation of an urban landfill soil. Co-composting biowastes with alkaline materials increased C stabilization, attributed to interaction with alkaline materials, thereby protecting it from microbial decomposition. The co-composted biowastes also increased the fertility of the landfill soil, thereby enhancing its revegetation potential. Stabilization of biowastes using alkaline materials through co-composting maintains their fertilization value in terms of improving plant growth. The co-composted biowastes also contribute to long-term soil C sequestration and reduction of bioavailability of heavy metals.

  11. Ammonium carbonate and/or bicarbonate plus alkaline chlorate oxidant for recovery of uranium values

    SciTech Connect

    Stapp, P.R.

    1983-09-06

    In accordance with the present invention, uranium values are extracted from materials containing uranium in valence states lower than its hexavalent state by contacting the materials containing uranium with an aqueous alkaline leach solution containing an alkaline chlorate in an amount sufficient to oxidize at least a portion of the uranium in valence states lower than its hexavalent state to its hexavalent state. In a further embodiment of the present invention, the alkaline leach solution is an aqueous solution of a carbonate selected from the group consisting of ammonium carbonate, ammonium bicarbonate and mixtures thereof. In yet another embodiment of the present invention, at least one catalytic compound of a metal selected from the group consisting of copper, cobalt, iron, nickel, chromium and mixtures thereof adapted to assure the presence of the ionic species Cu/sup + +/, Co/sup + +/, Fe/sup + + +/, Ni/sup + +/, Cr/sup + + +/ and mixtures thereof, respectively, during the contacting of the material containing uranium with the alkaline leach solution and in an amount sufficient to catalyze the oxidation of at least a portion of the uranium in its lower valence states to its hexavalent state, is present.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  14. Overview of the crystal chemistry of the actinide chalcogenides: incorporation of the alkaline-earth elements.

    PubMed

    Mesbah, Adel; Prakash, Jai; Ibers, James A

    2016-10-18

    This review focuses on the results of exploratory syntheses of alkaline-earth-metal actinide chalcogenides Ak-An-Q (Ak = Ba, Sr; An = Th, U; Q = S, Se, and Te). About thirty new compounds are described. Although the basic building blocks of their structures are usually AnQ6 octahedra and AkQ8 bicapped trigonal prisms, these are combined in diverse ways to afford eleven new structure types. The structures reconfirm the prevailing presence of An(4+) in chalcogenides, although some of the compounds discovered are mixed An(4+)/An(5+) systems, and a few contain only An(5+). The tendency of the chalcogens to form Q-Q bonds is again evident from the presence of S-S single bonds and infinite Te-Te-Te linear chains. The latter possess interatomic distances of lengths greater than that of a Te-Te single bond but less than that of a Te-Te van der Waals interaction. Assignment of formal oxidation states in compounds containing these chains is arbitrary at best. Addition of metal atoms (M) affords quaternary structures, some of which show remarkable flexibility in the positions of the An and M atoms, and in such compounds the nature of the M elements influences directly the dimensionality of the resultant structure. The presence of adventitious oxygen, often from etching of the fused-silica tubes by oxyphilic An elements, results in new quintary compounds that show remarkable structural variations with change of M. The compounds discussed have shown transport and electronic structures that range from metallic-like to semiconducting. We find, with the exception of BaUSe3, when comparisons can be made that the values of the calculated band gaps are reasonably close but usually lower than the experimentally derived values. Thus the method used, in particular the HSE functional, has been generally successful on these 5f actinides. This is an important result because in the absence of suitable crystals, and hence experimental measurements, it still may be possible to offer credible

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

    SciTech Connect

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

    2012-07-01

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

  16. The effect of glycine on the growth of calcium carbonate in alkaline silica gel

    NASA Astrophysics Data System (ADS)

    Gan, Xiong; He, Kunhuan; Qian, Baosong; Deng, Qin; Lu, Laixian; Wang, Yun

    2017-01-01

    Calcium carbonate was crystallized in alkaline silica gel with the presence of glycine. The crystallization proceeded with a counterdiffusion method by the reaction of calcium chloride and sodium carbonate. Optical microscopy observation showed a significant effect of glycine on the morphology control of calcite crystals. When the initial concentration of glycine was high enough (10 mg/mL, 20 mg/mL), spherical vaterite particles formed in alkaline silica gel concomitantly together with dumbbell shaped calcite particles. The in situ study by micro-Raman spectroscopy demonstrated that both vaterite and the concomitant calcite were stable phases during their growth processes since the initial appearance. A possible mechanism has been discussed to emphasize the effect of glycine on the nucleation of vaterite and the morphological control of calcite.

  17. Ca12InC13-x and Ba12InC18H4: alkaline-earth indium allenylides synthesized in AE/Li flux (AE = Ca, Ba).

    PubMed

    Blankenship, Trevor V; Dickman, Matthew J; van de Burgt, Lambertus J; Latturner, Susan E

    2015-02-02

    Two new complex main-group metal carbides were synthesized from reactions of indium, carbon, and a metal hydride in metal flux mixtures of an alkaline earth (AE = Ca, Ba) and lithium. Ca(12)InC(13-x) and Ba(12)InC(18)H(4) both crystallize in cubic space group Im3̅ [a = 9.6055(8) and 11.1447(7) Å, respectively]. Their related structures are both built on a body-centered-cubic array of icosahedral clusters comprised of an indium atom and 12 surrounding alkaline-earth cations; these clusters are connected by bridging monatomic anions (either H(-) or C(4-)) and allenylide anions, C(3)(4-). The allenylide anions were characterized by Raman spectroscopy and hydrolysis studies. Density of states and crystal orbital Hamilton population calculations confirm that both compounds are metallic.

  18. An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

    NASA Technical Reports Server (NTRS)

    Reid, M. A.

    1978-01-01

    A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9 - 8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

  19. An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

    NASA Technical Reports Server (NTRS)

    Reid, M. A.

    1978-01-01

    A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9-8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

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

    PubMed

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

    2014-08-14

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

  1. Comparing Soil Organic Carbon Dynamics in Perennial Grasses and Shrubs in a Saline-Alkaline Arid Region, Northwestern China

    PubMed Central

    Su, Jiaqi; Zhang, Jingli; Zheng, Yuanrun; Ni, Jian; Xiao, Chunwang; Wang, Renzhong

    2012-01-01

    Background Although semi-arid and arid regions account for about 40% of terrestrial surface of the Earth and contain approximately 10% of the global soil organic carbon stock, our understanding of soil organic carbon dynamics in these regions is limited. Methodology/Principal Findings A field experiment was conducted to compare soil organic carbon dynamics between a perennial grass community dominated by Cleistogenes squarrosa and an adjacent shrub community co-dominated by Reaumuria soongorica and Haloxylon ammodendron, two typical plant life forms in arid ecosystems of saline-alkaline arid regions in northwestern China during the growing season 2010. We found that both fine root biomass and necromass in two life forms varied greatly during the growing season. Annual fine root production in the perennial grasses was 45.6% significantly higher than in the shrubs, and fine root turnover rates were 2.52 and 2.17 yr−1 for the perennial grasses and the shrubs, respectively. Floor mass was significantly higher in the perennial grasses than in the shrubs due to the decomposition rate of leaf litter in the perennial grasses was 61.8% lower than in the shrubs even though no significance was detected in litterfall production. Soil microbial biomass and activity demonstrated a strong seasonal variation with larger values in May and September and minimum values in the dry month of July. Observed higher soil organic carbon stocks in the perennial grasses (1.32 Kg C m−2) than in the shrubs (1.12 Kg C m−2) might be attributed to both greater inputs of poor quality litter that is relatively resistant to decay and the lower ability of microorganism to decompose these organic matter. Conclusions/Significance Our results suggest that the perennial grasses might accumulate more soil organic carbon with time than the shrubs because of larger amounts of inputs from litter and slower return of carbon through decomposition. PMID:22900067

  2. Tris(pyrazolyl)methanides of the alkaline earth metals: influence of the substitution pattern on stability and degradation.

    PubMed

    Müller, Christoph; Koch, Alexander; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias

    2015-01-20

    Trispyrazolylmethanides commonly act as strong tridentate bases toward metal ions. This expected coordination behavior has been observed for tris(3,4,5-trimethylpyrazolyl)methane (1a), which yields the alkaline-earth-metal bis[tris(3,4,5-trimethylpyrazolyl)methanides] of magnesium (1b), calcium (1c), strontium (1d), and barium (1e) via deprotonation of 1a with dibutylmagnesium and [Ae{N(SiMe3)2}2] (Ae = Mg, Ca, Sr, and Ba, respectively). Barium complex 1e degrades during recrystallization that was attempted from aromatic hydrocarbons and ethers. In these scorpionate complexes, the metal ions are embedded in distorted octahedral coordination spheres. Contrarily, tris(3-thienylpyrazolyl)methane (2a) exhibits a strikingly different reactivity. Dibutylmagnesium is unable to deprotonate 2a, whereas [Ae{N(SiMe3)2}2] (Ae = Ca, Sr, and Ba) smoothly metalates 2a. However, the primary alkaline-earth-metal bis[tris(3-thienylpyrazolyl)methanides] of Ca (2c), Sr (2d), and Ba (2e) represent intermediates and degrade under the formation of the alkaline-earth-metal bis(3-thienylpyrazolates) of calcium (3c), strontium (3d), and barium (3e) and the elimination of tetrakis(3-thienylpyrazolyl)ethene (4). To isolate crystalline compounds, 3-thienylpyrazole has been metalated, and the corresponding derivatives [(HPz(Tp))4Mg(Pz(Tp))2] (3b), dinuclear [(tmeda)Ca(Pz(Tp))2]2 (3c), mononuclear [(pmdeta)Sr(Pz(Tp))2] (3d), and [(hmteta)Ba(Pz(Tp))2] (3e) have been structurally characterized. Regardless of the applied stoichiometry, magnesiation of thienylpyrazole 3a with dibutylmagnesium yields [(HPz(Tp))4Mg(Pz(Tp))2] (3b), which is stabilized in the solid state by intramolecular N-H···N···H-N hydrogen bridges. The degradation of [Ae{C(Pz(R))3}2] (R = Ph and Tp) has been studied by quantum chemical methods, the results of which propose an intermediate complex of the nature [{(Pz(R))2C}2Ca{Pz(R)}2]; thereafter, the singlet carbenes ([:C(Pz(R))2]) dimerize in the vicinity of the alkaline

  3. The effect of alkaline earth metal ion dopants on photocatalytic water splitting by NaTaO(3) powder.

    PubMed

    Iwase, Akihide; Kato, Hideki; Kudo, Akihiko

    2009-01-01

    Alkaline earth metal ions (Ca, Sr, and Ba) are doped into a NaTaO(3) photocatalyst, yielding fine particles and surface structures with nanometer-scale "steps." The formation of the surface nanostep structure depends on the amount of doped Sr and Ba. The photocatalytic water splitting over NaTaO(3) is enhanced: NaTaO(3) doped with 0.5 and 1.0 mol % of Sr shows high activities for photocatalytic water splitting without loading of a co-catalyst, and the photocatalytic activity is further improved by loading with a NiO co-catalyst.

  4. Luminescence properties of Eu-activated alkaline and alkaline-earth silicate Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}

    SciTech Connect

    Wang, Jing; Huang, Yanlin; Wang, Xigang; Qin, Lin; Seo, Hyo Jin

    2014-07-01

    Highlights: • A novel yellow-emitting alkaline and alkaline-earth silicate Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} was first developed. • Under excitation with UV or near UV light the silicate presents broad emission band centered at 580 nm. - Abstract: Yellow-emitting phosphors of Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} was prepared by wet chemistry sol–gel method. X-ray powder diffraction and SEM measurements were applied to characterize the structure and morphology, respectively. The luminescence properties were investigated by the photoluminescence excitation and emission spectra, decay curve (lifetimes), CIE coordinates and the internal quantum efficiencies. The excitation spectra can match well with the emission light of near UV-LED chips (360–400 nm). Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} presents a symmetric emission band from 4f{sup 6}5d{sup 1} ⟶ 4f{sup 7}({sup 8}S{sub 7/2}) transitions of Eu{sup 2+} ions on doping below 3.0 mol%. On increasing Eu-doping levels, the sample contains two kinds of emission centers, i.e., Eu{sup 2+} and Eu{sup 3+} ions, which present the characteristic broad band (5d ⟶ 4f) and narrower (4f ⟶ 4f) luminescence lines, respectively. The energy transfer, the luminescence thermal stability (activation energy ΔE for thermal quenching) and luminescence mechanism of Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} phosphors were discussed by analyzing the relationship between the luminescence characteristics and the crystal structure.

  5. Carbon segregation-induced highly metallic ni nanoparticles for electrocatalytic oxidation of hydrazine in alkaline media.

    PubMed

    Jeon, Tae-Yeol; Watanabe, Masahiro; Miyatake, Kenji

    2014-11-12

    The important roles of Ni in electrocatalytic reactions such as hydrazine oxidation are limited largely by high oxidation states because of its intrinsically high oxophilicity. Here, we report the synthesis and properties of highly metallic Ni nanoparticles (NPs) on carbon black supports. We discovered that the heat treatment of as-prepared Ni NPs with an average particle size of 5.8 nm produced highly metallic Ni NPs covered with thin carbon shells, with negligible particle coarsening. The carbon shells were formed by the segregation of carbons in the Ni lattice to the surface of the Ni NPs, leaving highly metallic Ni NPs. X-ray photoelectron spectroscopic analyses revealed that the atomic ratio of metallic Ni increased from 19.2 to 71.7% as a result of the heat treatment. The NPs exhibited higher electrocatalytic activities toward the hydrazine oxidation reaction in alkaline solution, as compared to those of the as-prepared Ni NPs and commercial Ni powders.

  6. The carbon cycle on early Earth--and on Mars?

    PubMed

    Grady, Monica M; Wright, Ian

    2006-10-29

    One of the goals of the present Martian exploration is to search for evidence of extinct (or even extant) life. This could be redefined as a search for carbon. The carbon cycle (or, more properly, cycles) on Earth is a complex interaction among three reservoirs: the atmosphere; the hydrosphere; and the lithosphere. Superimposed on this is the biosphere, and its presence influences the fixing and release of carbon in these reservoirs over different time-scales. The overall carbon balance is kept at equilibrium on the surface by a combination of tectonic processes (which bury carbon), volcanism (which releases it) and biology (which mediates it). In contrast to Earth, Mars presently has no active tectonic system; neither does it possess a significant biosphere. However, these observations might not necessarily have held in the past. By looking at how Earth's carbon cycles have changed with time, as both the Earth's tectonic structure and a more sophisticated biology have evolved, and also by constructing a carbon cycle for Mars based on the carbon chemistry of Martian meteorites, we investigate whether or not there is evidence for a Martian biosphere.

  7. Geochemical modeling of the influence of silicate mineral alteration on alkalinity production and carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Herda, Gerhard; Kraemer, Stephan M.; Gier, Susanne; Meister, Patrick

    2016-04-01

    High CO2 partial pressure (pCO2) in deep rock reservoirs causes acidification of the porefluid. Such conditions occur during injection and subsurface storage of CO2 (to prevent the release of greenhouse gas) but also naturally in zones of strong methanogenic microbial activity in organic matter-rich ocean margin sediments. The acidic fluids are corrosive to carbonates and bear the risk of leakage of CO2 gas to the surface. Porefluid acidification may be moderated by processes that increase the alkalinity, i.e. that produce weak acid anions capable of buffering the acidification imposed by the CO2. Often, alkalinity increases as a result of anaerobic microbial activity, such as anaerobic oxidation of methane. However, on a long term the alteration of silicates, in particular, clay minerals, may be a more efficient mechanism of alkalinity production. Under altered temperature, pressure and porefluid composition at depth, clay minerals may change to thermodynamically more stable states, thereby increasing the alkalinity of the porefluid by partial leaching of Mg-(OH)2 and Ca-(OH)2 (e.g. Wallmann et al., 2008; Mavromatis et al., 2014). This alteration may even be enhanced by a high pCO2. Thus, silicate alteration can be essential for a long-term stabilization of volatile CO2 in the form of bicarbonate or may even induce precipitation of carbonate minerals, but these processes are not fully understood yet. The goal of this study is to simulate the alkalinity effect of silicate alteration under diagenetic conditions and high pCO2 by geochemical modeling. We are using the program PHREEQC (Parkhurst and Appelo, 2013) to generate high rock/fluid ratio characteristics for deep subsurface rock reservoirs. Since we are interested in the long-term evolution of diagenetic processes, over millions of years, we do not consider kinetics but calculate the theoretically possible equilibrium conditions. In a first step we are calculating the saturation state of different clay minerals

  8. Synthesis and Characterization of Alkaline-Earth Metal (Ca, Sr, and Ba) Doped Nanodimensional LaMnO3 Rare-Earth Manganites

    NASA Astrophysics Data System (ADS)

    Asma, Khalid; Saadat, Anwar Siddiqi; Affia, Aslam

    2013-07-01

    The substitution of divalent cations of alkaline-earth elements in nanodimensional structures of rare-earth manganites produces advanced materials with potential electrical and magnetic functionalities. A systematic investigation of La0.65A0.35MnO3 (A = Ca, Sr, Ba) materials synthesized with a modified citrate route adopting ethanol dehydration has been undertaken. The structural and morphological analyses are carried out by using x-ray diffraction and scanning electron microscopy, respectively. Resistivity measurements are performed in variation with temperature to study the electrical transport properties which are found to vary with the size of the A-site cationic radius. Room temperature magnetic measurements are carried out to investigate the type of magnetic phase present in materials. The stability of the magnetic phase and coercivity are found to be dependent on the size of nanocrystallites.

  9. Carbonic anhydrase 2-like and Na⁺-K⁺-ATPase α gene expression in medaka (Oryzias latipes) under carbonate alkalinity stress.

    PubMed

    Yao, Zongli; Lai, Qifang; Hao, Zhuoran; Chen, Ling; Lin, Tingting; Zhou, Kai; Wang, Hui

    2015-12-01

    High carbonate alkalinity is one of the major stress factors for living organisms in saline-alkaline water areas. Acute and chronic effects of carbonate alkalinity on expression of two genes, carbonic anhydrase 2-like (CA2-like) and Na(+)-K(+)-ATPase α subunit (NKA-α) mRNA in medaka (Oryzias latipes) were evaluated to better understand the responses important for coping with a carbonate alkalinity stress. In the acute exposure experiment, the expression of CA2-like and NKA-α mRNA in the gill and kidney of medaka were examined from 0 h to 7 days exposed to 30.4 mM carbonate alkalinity water. Exposure to high carbonate alkalinity resulted in a transitory alkalosis, followed by a transient increase in gill and kidney CA2-like and NKA-α mRNA expression. In the chronic exposure experiment, the expression of these two genes was examined in the gill and kidney at 50 days post-exposure to six different carbonate alkalinity concentrations ranging from 1.5 to 30.4 mM. Gill and kidney CA2-like mRNA levels in 30.4 mM were approximately 10 and 30 times higher than that of the control (1.5 mM), respectively. Less differences were found in NKA-α expression in the 50-days exposure. The results indicate that when transferred to high carbonate alkalinity water, a transitory alkalosis may occur in medaka, followed by compensatory acid-base and ion regulatory responses. Thus, CA2-like and NKA-α are at least two of the important factors that contribute to the regulation of alkalinity stress.

  10. Thermodynamic stability of perovskites and related compounds in some alkaline earth-transition metal-oxygen systems

    NASA Astrophysics Data System (ADS)

    Yokokawa, Harumi; Sakai, Natsuko; Kawada, Tatsuya; Dokiya, Masayuki

    1991-09-01

    The thermodynamic properties of some alkaline earth ( A)-transition metal ( M) perovskites and K 2NiF 4 compounds have been collected, analyzed, and utilized to examine their stabilities by constructing the chemical potential diagrams of a log [ {a(A)}/{a(M)}] vs log P(O 2) plot. A thermodynamic analysis was performed on the dissociation reaction of K 2NiF 4 compounds ( A2MO 4) into perovskites ( AMO 3) and alkaline earth oxides ( AO) using empirical correlations between stabilization energy and tolerance factor. It has been found that the softness of calcium ions, which shrink markedly with decreasing coordination number from 12 to 9, makes the calcium K 2NiF 4 compounds (Ca 2MO 4) relatively less stable with increasing radius of the transition metal ions, r( M4+). This destabilization related to the coordination-number-dependent radii implies that when compared with the strontium perovskites, the calcium analogous perovskites may have a smaller number of oxygen vacancies, because the formation of oxygen vacancies should be accompanied with a decrease in coordination number of A-site ions.

  11. Binding and selectivity of phenazino-18-crown-6-ether with alkali, alkaline earth and toxic metal species: A DFT study

    NASA Astrophysics Data System (ADS)

    Islam, Nasarul; Chimni, Swapandeep Singh

    2017-02-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Zhou, Qiang; Qian, Jun; Zhang, Chi

    2016-09-01

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

  13. Basalt as a solid source of calcium and alkalinity for the sequestration of carbon dioxide in building materials

    NASA Astrophysics Data System (ADS)

    Johnson, N. C.; Westfield, I.; Lu, P.; Bourcier, W. L.; Kendall, T.; Constantz, B. R.

    2010-12-01

    Motivated by the idea of converting waste carbon dioxide into usable building products, Calera Corporation has developed a multi-step process that sequesters CO2 as carbonate minerals in cementitious materials. Process inputs include dissolved divalent cations and alkalinity, both of which can be extracted from basalt. In one mode of the Calera process, the electrochemical production of alkalinity generates large volumes of hydrochloric acid as a by-product, which has been shown to effectively leach divalent cations from basalt while being neutralized by the basalt dissolution reaction. Using a 10:1 1M HCl solution to rock ratio, 3500 ppm Ca was extracted while the initial solution was neutralized to a pH of 2.60 in two weeks at a temperature of 80oC in an anoxic batch reactor. In this scenario, mineral carbonation occurs via three steps: electrochemical production of alkalinity, CO2 absorption by the alkaline stream, then precipitation by mixing the basalt-derived divalent cation stream and the CO2-containing alkaline stream. In a second scenario, alkalinity is extracted from basalt using an alkalinity capacitor, a weak acid. This solution may contain a proton source, such as ammonium chloride, or a hydroxyl acceptor, such as boric acid, but the main design constraint is that the pKa of the capacitor be high enough to deprontonate carbonic acid. The weak acid solution is mixed with basalt in an anoxic batch reactor and the dissolving rock consumes protons from the weak acid, generating the conjugate base. The solution rich in conjugate base then absorbs CO2 and the carbonate-rich solution is mixed with a calcium-rich stream to precipitate carbonate minerals. We have extracted up to 1100 mmol alkalinity per kg rock using an alkalinity capacitor, versus no more than 50 mmol alkalinity per kg rock using DI water as a solvent. Again, carbon sequestration occurs via three steps: alkalinity extraction from basalt, CO2 absorption, and finally carbonate precipitation

  14. Carbon monoxide and the burning earth

    SciTech Connect

    Newell, R.E.; Reichle, H.G. Jr.; Seiler, W.

    1989-10-01

    Carbon monoxide is one of many gases whose presence in the atmosphere is blamed largely on industrial activity in the Northern Hemisphere. Data collected by the authors show that the gas is also abundant in the Southern Hemisphere, where it comes mainly from the burning of tropical rain forests and savannas. The high levels of carbon monoxide confirm other evidence that the rain forests are being diminished rapidly, which may affect the climates of these regions as well as globally. Increases in carbon monoxide could also encourage the accumulation of pollutant gases such as ozone and methane. The first is highly toxic to plants and the second would add to the greenhouse effect.

  15. Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

    PubMed

    Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

    2014-10-01

    Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques.

  16. Palladium and palladium-tin supported on multi wall carbon nanotubes or carbon for alkaline direct ethanol fuel cell

    NASA Astrophysics Data System (ADS)

    Geraldes, Adriana Napoleão; Furtunato da Silva, Dionisio; Martins da Silva, Júlio César; Antonio de Sá, Osvaldo; Spinacé, Estevam Vitório; Neto, Almir Oliveira; Coelho dos Santos, Mauro

    2015-02-01

    Pd and PdSn (Pd:Sn atomic ratios of 90:10), supported on Multi Wall Carbon Nanotubes (MWCNT) or Carbon (C), are prepared by an electron beam irradiation reduction method. The obtained materials are characterized by X-Ray diffraction (XRD), Energy dispersive X-ray analysis (EDX), Transmission electron Microscopy (TEM) and Cyclic Voltammetry (CV). The activity for ethanol electro-oxidation is tested in alkaline medium, at room temperature, using Cyclic Voltammetry and Chronoamperometry (CA) and in a single alkaline direct ethanol fuel cell (ADEFC), in the temperature range of 60-90 °C. CV analysis finds that Pd/MWCNT and PdSn/MWCNT presents onset potentials changing to negative values and high current values, compared to Pd/C and PdSn/C electrocatalysts. ATR-FTIR analysis, performed during the CV, identifies acetate and acetaldehyde as principal products formed during the ethanol electro-oxidation, with low conversion to CO2. In single fuel cell tests, at 85 °C, using 2.0 mol L-1 ethanol in 2.0 mol L-1 KOH solutions, the electrocatalysts supported on MWCNT, also, show higher power densities, compared to the materials supported on carbon: PdSn/MWCNT, presents the best result (36 mW cm-2). The results show that the use of MWCNT, instead of carbon, as support, plus the addition of small amounts of Sn to Pd, improves the electrocatalytic activity for Ethanol Oxidation Reaction (EOR).

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

  18. Snowball Earth prevention by dissolved organic carbon remineralization.

    PubMed

    Peltier, W Richard; Liu, Yonggang; Crowley, John W

    2007-12-06

    The 'snowball Earth' hypothesis posits the occurrence of a sequence of glaciations in the Earth's history sufficiently deep that photosynthetic activity was essentially arrested. Because the time interval during which these events are believed to have occurred immediately preceded the Cambrian explosion of life, the issue as to whether such snowball states actually developed has important implications for our understanding of evolutionary biology. Here we couple an explicit model of the Neoproterozoic carbon cycle to a model of the physical climate system. We show that the drawdown of atmospheric oxygen into the ocean, as surface temperatures decline, operates so as to increase the rate of remineralization of a massive pool of dissolved organic carbon. This leads directly to an increase of atmospheric carbon dioxide, enhanced greenhouse warming of the surface of the Earth, and the prevention of a snowball state.

  19. Carbon and nitrogen in the deep Earth

    NASA Technical Reports Server (NTRS)

    Mattey, D. P.; Carr, L. P.; Carr, R. H.; Wright, I. P.; Pillinger, C. T.

    1985-01-01

    High sensitivity mass spectrometric techniques were utilized to study the C-N isotope systematics in basic igneous rocks and mantle materials in an attempt to ultimately constrain the primordial isotopic compositions of these elements and their subsequent fate during the early history of the Earth. Preliminary results obtained for a selection of submarine basaltic glasses and diamonds are summarized concentrating on: (1) the problem of whether isotopes are significantly fractionated during igneous processes; and on (2) the effects of crustal recycling.

  20. New host for carbon in the deep Earth.

    PubMed

    Boulard, Eglantine; Gloter, Alexandre; Corgne, Alexandre; Antonangeli, Daniele; Auzende, Anne-Line; Perrillat, Jean-Philippe; Guyot, François; Fiquet, Guillaume

    2011-03-29

    The global geochemical carbon cycle involves exchanges between the Earth's interior and the surface. Carbon is recycled into the mantle via subduction mainly as carbonates and is released to the atmosphere via volcanism mostly as CO(2). The stability of carbonates versus decarbonation and melting is therefore of great interest for understanding the global carbon cycle. For all these reasons, the thermodynamic properties and phase diagrams of these minerals are needed up to core mantle boundary conditions. However, the nature of C-bearing minerals at these conditions remains unclear. Here we show the existence of a new Mg-Fe carbon-bearing compound at depths greater than 1,800 km. Its structure, based on three-membered rings of corner-sharing (CO(4))(4-) tetrahedra, is in close agreement with predictions by first principles quantum calculations [Oganov AR, et al. (2008) Novel high-pressure structures of MgCO(3), CaCO(3) and CO(2) and their role in Earth's lower mantle. Earth Planet Sci Lett 273:38-47]. This high-pressure polymorph of carbonates concentrates a large amount of Fe((III)) as a result of intracrystalline reaction between Fe((II)) and (CO(3))(2-) groups schematically written as 4FeO + CO(2) → 2Fe(2)O(3) + C. This results in an assemblage of the new high-pressure phase, magnetite and nanodiamonds.

  1. Storage/Turnover rate of inorganic carbon and its dissolvable part in the profile of saline/alkaline soils.

    PubMed

    Wang, Yugang; Wang, Zhongyuan; Li, Yan

    2013-01-01

    Soil inorganic carbon is the most common form of carbon in arid and semiarid regions, and has a very long turnover time. However, little is known about dissolved inorganic carbon storage and its turnover time in these soils. With 81 soil samples taken from 6 profiles in the southern Gurbantongute Desert, China, we investigated the soil inorganic carbon (SIC) and the soil dissolved inorganic carbon (SDIC) in whole profiles of saline and alkaline soils by analyzing their contents and ages with radiocarbon dating. The results showed that there is considerable SDIC content in SIC, and the variations of SDIC and SIC contents in the saline soil profile were much larger than that in the alkaline profile. SDIC storage accounted for more than 20% of SIC storage, indicating that more than 1/5 of the inorganic carbon in both saline and alkaline soil is not in non-leachable forms. Deep layer soil contains considerable inorganic carbon, with more than 80% of the soil carbon stored below 1 m, whether for SDIC or SIC. More importantly, SDIC ages were much younger than SIC in both saline soil and alkaline soil. The input rate of SDIC and SIC ranged from 7.58 to 29.54 g C m(-2) yr(-1) and 1.34 to 5.33 g C m(-2) yr(-1) respectively for saline soil, and from 1.43 to 4.9 g C m(-2) yr(-1) and 0.79 to 1.27 g C m(-2) yr(-1)respectively for alkaline soil. The comparison of SDIC and SIC residence time showed that using soil inorganic carbon to estimate soil carbon turnover would obscure an important fraction that contributes to the modern carbon cycle: namely the shorter residence and higher input rate of SDIC. This is especially true for SDIC in deep layers of the soil profile.

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

    PubMed

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

    2016-02-01

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

  3. Mantle to surface degassing of carbon- and sulphur-rich alkaline magma at El Hierro, Canary Islands

    NASA Astrophysics Data System (ADS)

    Longpré, Marc-Antoine; Stix, John; Klügel, Andreas; Shimizu, Nobumichi

    2017-02-01

    Basaltic volcanoes transfer volatiles from the mantle to the surface of the Earth. The quantification of deep volatile fluxes relies heavily on estimates of the volatile content of primitive magmas, the best archive of which is provided by melt inclusions. Available data from volcanoes producing mafic alkaline lavas in a range of tectonic settings suggest high volatile fluxes, but information remains sparse, particularly for intraplate ocean islands. Here we present measurements of volatile and trace element concentrations, as well as sulphur speciation, in olivine-hosted melt inclusions and matrix glasses from quenched basanite lava balloon samples from the 2011-2012 submarine eruption at El Hierro, Canary Islands. The results reveal remarkably high concentrations of dissolved volatiles and incompatible trace elements in this magma, with ∼80 ppm Nb and up to 3420 ppm CO2, 3.0 wt.% H2O and 5080 ppm S. Reconstructed primitive CO2 contents, considering CO2/Nb systematics and possible CO2 sequestration in shrinkage bubbles, reach weight percent levels, indicating that carbon is a major constituent of Canary Island magmas at depth and that exsolution of a CO2-rich fluid begins in the mantle at pressures in excess of 1 GPa. Correlations between sulphur concentration, sulphur speciation and water content suggest strong reduction of an initially oxidised mantle magma, likely controlled by coupled H2O and S degassing. This late-stage redox change may have triggered sulphide saturation, recorded by globular sulphide inclusions in clinopyroxene and ulvöspinel. The El Hierro basanite thus had a particularly high volatile-carrying capacity and released a minimum of 1.3-2.1 Tg CO2 and 1.8-2.9 Tg S to the environment, causing substantial stress on the local submarine ecosystem. These results highlight the important contribution of alkaline ocean island volcanoes, such as the Canary Islands, to volatile fluxes from the mantle.

  4. Process for the recycling of alkaline and zinc-carbon spent batteries

    NASA Astrophysics Data System (ADS)

    Ferella, Francesco; De Michelis, Ida; Vegliò, Francesco

    In this paper a recycling process for the recovery of zinc and manganese from spent alkaline and zinc-carbon batteries is proposed. Laboratory tests are performed to obtain a purified pregnant solution from which metallic zinc (purity 99.6%) can be recovered by electrolysis; manganese is recovered as a mixture of oxides by roasting of solid residue coming from the leaching stage. Nearly 99% of zinc and 20% of manganese are extracted after 3 h, at 80 °C with 10% w/v pulp density and 1.5 M sulphuric acid concentration. The leach liquor is purified by a selective precipitation of iron, whereas metallic impurities, such as copper, nickel and cadmium are removed by cementation with zinc powder. The solid residue of leaching is roasted for 30 min at 900 °C, removing graphite completely and obtaining a mixture of Mn 3O 4 and Mn 2O 3 with 70% grade of Mn. After that a technical-economic assessment is carried out for a recycling plant with a feed capacity of 5000 t y -1 of only alkaline and zinc-carbon batteries. This analysis shows the economic feasibility of that plant, supposing a battery price surcharge of 0.5 € kg -1, with a return on investment of 34.5%, gross margin of 35.8% and around 3 years payback time.

  5. Effect of CO2 on crystallization and properties of diamond from ultra-alkaline carbonate melt

    NASA Astrophysics Data System (ADS)

    Palyanov, Yuri N.; Kupriyanov, Igor N.; Sokol, Alexander G.; Borzdov, Yuri M.; Khokhryakov, Alexander F.

    2016-11-01

    An experimental study on diamond crystallization in CO2-rich sodium-carbonate melts has been undertaken at a pressure of 6.3 GPa in the temperature range of 1250-1570 °C and at 7.5 GPa in the temperature range of 1300-1700 °C. Sodium oxalate (Na2C2O4) was used as the starting material, which over the course of the experiment decomposed to form sodium carbonate, carbon dioxide and elemental carbon. The effects of pressure, temperature and dissolved CO2 in the ultra-alkaline carbonate melt on diamond crystallization, morphology, internal structure and defect-and-impurity content of diamond crystals are established. Diamond growth is found to proceed with formation of vicinal structures on the {100} and {111} faces, resulting eventually in the formation of rounded polyhedrons, whose shape is determined by the combination tetragon-trioctahedron, trigon-trioctahedron and cube faces. Spectroscopic studies reveal that the crystallized diamonds are characterized by specific infrared absorption and photoluminescence spectra. The defects responsible for the 1065 cm- 1 band dominating in the IR spectra and the 566 nm optical system dominating in the PL spectra are tentatively assigned to oxygen impurities in diamond.

  6. Half metallic ferromagnetism in alkaline-earth metal nitrides XN (X=Ca, Sr and Ba): A first principles study

    NASA Astrophysics Data System (ADS)

    Palanichamy, R. Rajeswara; Priyanga, G. Sudha; Cinthia, A. Jemmy; Murugan, A.; Meenaatci, A. T. Asvini; Iyakutti, K.

    2013-11-01

    The structural, electronic, mechanical and magnetic properties of 3 alkaline-earth metal nitrides (XN: X=Ca, Sr, and Ba) are investigated by the first principles calculations based on density functional theory using the Vienna ab-initio simulation code. At ambient pressure all the 3 nitrides are stable in the ferromagnetic state with a cubic NaCl structure. The calculated lattice parameters are in good agreement with the available results. The electronic structure reveals that these materials are half metallic ferromagnets at normal pressure. A pressure-induced structural phase transition from NaCl (B1) to CsCl (B2) phase is observed in CaN, SrN and BaN. On further increasing the pressure, a half metallic to metallic transition is also observed in these nitrides. Ferromagnetism is quenched in all the 3 nitrides at high pressures.

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

    NASA Astrophysics Data System (ADS)

    Iskin, M.

    2016-07-01

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

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

    SciTech Connect

    Sobolewski, R.; Gierlowski, P.; Kula, W.; Zarembinski, S.; Lewandowski, S.J.; Berkowski, M.; Pajaczkowska, A. ); Gorshunov, B.P.; Lyudmirsky, D.B.; Sirotinsky, O.I. )

    1991-03-01

    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.

  9. Cyclotron dynamics of a Kondo singlet in a spin-orbit-coupled alkaline-earth-metal atomic gas

    NASA Astrophysics Data System (ADS)

    Jiang, Bo-Nan; Lv, Hao; Wang, Wen-Li; Du, Juan; Qian, Jun; Wang, Yu-Zhu

    2014-11-01

    We propose a scheme to investigate the interplay between the Kondo-exchange interaction and the quantum spin Hall effect with ultracold fermionic alkaline-earth-metal atoms trapped in two-dimensional optical lattices using ultracold collision and laser-assisted tunneling. In the strong Kondo-coupling regime, although the loop trajectory of the mobile atom disappears, collective dynamics of an atom pair in two clock states can exhibit an unexpected spin-dependent cyclotron orbit in a plaquette, realizing the quantum spin Hall effect of the Kondo singlet. We demonstrate that the collective cyclotron dynamics of the spin-zero Kondo singlet is governed by an effective Harper-Hofstadter model in addition to second-order diagonal tunneling.

  10. Physical and optical absorption studies of Fe3+ - ions doped lithium borate glasses containing certain alkaline earths

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

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

    PubMed

    Parker, David; Singh, David J

    2013-10-01

    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.

  12. Dispersion coefficients for H and He interactions with alkali-metal and alkaline-earth-metal atoms

    SciTech Connect

    Mitroy, J.; Bromley, M.W.J.

    2003-12-01

    The van der Waals coefficients C{sub 6}, C{sub 8}, and C{sub 10} for H and He interactions with the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are determined from oscillator strength sum rules. The oscillator strengths were computed using a combination of ab initio and semiempirical methods. The dispersion parameters generally agree with close to exact variational calculations for Li-H and Li-He at the 0.1% level of accuracy. For larger systems, there is agreement with relativistic many-body perturbation theory estimates of C{sub 6} at the 1% level. These validations for selected systems attest to the reliability of the present dispersion parameters. About half the present parameters lie within the recommended bounds of the Standard and Certain compilation [J. Chem. Phys. 83, 3002 (1985)].

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

    SciTech Connect

    Parker, David S; Singh, David J

    2013-01-01

    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 Ca2 Sn, Sr2 Sn and Ba2 Sn. 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.

  14. Heteroleptic alkyl and amide iminoanilide alkaline earth and divalent rare earth complexes for the catalysis of hydrophosphination and (cyclo)hydroamination reactions.

    PubMed

    Liu, Bo; Roisnel, Thierry; Carpentier, Jean-François; Sarazin, Yann

    2013-09-27

    [{N^N}M(X)(thf)n] alkyl (X=CH(SiMe3)2) and amide (X=N(SiMe3)2) complexes of alkaline earths (M=Ca, Sr, Ba) and divalent rare earths (Yb(II) and Eu(II) ) bearing an iminoanilide ligand ({N^N}(-)) are presented. Remarkably, these complexes proved to be kinetically stable in solution. X-ray diffraction studies allowed us to establish size-structure trends. Except for one case of oxidation with [{N^N}Yb(II){N(SiMe3)2}(thf)], all these complexes are stable under the catalytic conditions and constitute effective precatalysts for the cyclohydroamination of terminal aminoalkenes and the intermolecular hydroamination and intermolecular hydrophosphination of activated alkenes. Metals with equal sizes across alkaline earth and rare earth families display almost identical apparent catalytic activity and selectivity. Hydrocarbyl complexes are much better catalyst precursors than their amido analogues. In the case of cyclohydroamination, the apparent activity decreases with metal size: Ca>Sr>Ba, and the kinetic rate law agrees with R(CHA) =k[precatalyst](1)[aminoalkene](1). The intermolecular hydroamination and hydrophosphination of styrene are anti-Markovnikov regiospecific. In both cases, the apparent activity increases with the ionic radius (Ca

  15. EPR and optical absorption studies of Cu{sup 2+} ions in alkaline earth alumino borate glasses

    SciTech Connect

    Ramesh Kumar, V.; Rao, J.L. . E-mail: jlrao46@yahoo.co.in; Gopal, N.O.

    2005-08-11

    Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu{sup 2+} ions in alkaline earth alumino borate glasses doped with different concentrations of CuO have been studied. The EPR spectra of all the glasses exhibit the resonance signals, characteristic of Cu{sup 2+} ions present in axially elongated octahedral sites. The number of spins participating in the resonance has been calculated as a function of temperature for calcium alumino borate (CaAB) glass doped with 0.1 mol% of CuO. From the EPR data, the paramagnetic susceptibility ({chi}) was calculated at different temperatures (T) and from the 1/{chi}-T graph, the Curie temperature of the glass has been evaluated. The optical absorption spectra of all the glasses show a single broad band, which has been assigned to the {sup 2}B{sub 1g} {yields} {sup 2}B{sub 2g} transition of the Cu{sup 2+} ions. The variation in the intensity of optical absorption with the ionic radius of the alkaline earth ion has been explained based on the Coulombic forces. By correlating the EPR and optical absorption spectral data, the nature of the in-plane {sigma} bonding between Cu{sup 2+} ion and the ligands is estimated. From the fundamental ultraviolet absorption edges of the glasses, the optical energy gap (E {sub opt}) and the Urbach energy ({delta}E) are evaluated. The variation in E {sub opt} and {delta}E is explained based on the number of defect centers in the glass.

  16. Structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Cinthia, A. Jemmy; Priyanga, G. Sudha; Rajeswarapalanichamy, R.; Iyakutti, K.

    2015-04-01

    The structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba) in the cubic (B1, B2 and B3) phases and in the wurtzite (B4) phase are investigated using density functional theory calculations as implemented in VASP code. The lattice constants, cohesive energy, bulk modulus, band structures and the density of states are computed. The calculated lattice parameters are in good agreement with the experimental and the other available theoretical results. Electronic structure reveals that all the five alkaline earth metal oxides exhibit semiconducting behavior at zero pressure. The estimated band gaps for the stable wurtzite phase of BeO is 7.2 eV and for the stable cubic NaCl phases of MgO, CaO, SrO and BaO are 4.436 eV, 4.166 eV, 4.013 eV, and 2.274 eV respectively. A pressure induced structural phase transition occurs from wurtzite (B4) to NaCl (B1) phase in BeO at 112.1 GPa and from NaCl (B1) to CsCl (B2) phase in MgO at 514.9 GPa, in CaO at 61.3 GPa, in SrO at 42 GPa and in BaO at 14.5 GPa. The elastic constants are computed at zero and elevated pressures for the B4 and B1 phases for BeO and for the B1 and B2 phases in the case of the other oxides in order to investigate their mechanical stability, anisotropy and hardness. The sound velocities and the Debye temperatures are calculated for all the oxides using the computed elastic constants.

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

    SciTech Connect

    Du, Mao -Hua; Singh, David J.; Zhang, Lijun; Li, Yuwei; Xu, Qiaoling; Ma, Yanming; Zheng, Weitao

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    DOE PAGES

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

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can bemore » stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.« less

  20. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

    PubMed

    Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

  1. Above-belowground Carbon Allocation in Earth System Models

    NASA Astrophysics Data System (ADS)

    Song, X.; Hoffman, F. M.; Xu, X.; Iversen, C. M.; Kumar, J.

    2014-12-01

    Above-belowground carbon allocation is a critical mechanism for vegetation growth and its adaptation to the changing environment. The model representation of carbon allocation mechanisms significantly influence the simulated carbon stock and land-atmosphere exchange in Earth System Models (ESMs). Few previous studies, however, have investigated and evaluated the above-belowground carbon allocation in ESMs. In this study, we analyzed carbon density in belowground, total vegetation (above + belowground), and belowground:vegetation ratios of eleven ESMs from the Coupled Model Inter-comparison Project Phase 5 (CMIP5), which were used for the latest IPCC Assessment Report (AR5). Overall, results of ESMs are not consistent with observational data; both the belowground and total vegetation carbon density are underestimated in tropical/subtropical and temperate regions, while overestimated in arctic/subarctic regions. Moreover, the ratios of belowground:total vegetation carbon are underestimated in all three climate zones. The model-data discrepancies in carbon density vary substantially among biomes, while the ratios of belowground:total vegetation carbon are consistently underestimated across all major biomes expect tropical moist forests. This study indicates that the carbon allocation algorithms in current ESMs need to be improved to better simulate vegetation growth and its responses to global change.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  3. Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

    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).

  4. Defective Multilayer Carbon Nanotubes Increase Alkaline Phosphatase Activity and Bone-Like Nodules in Osteoblast Cultures.

    PubMed

    Zancanela, Daniela Cervelle; Simaã, Ana Maria Sper; Matsubara, Elaine Yoshiko; Rosolen, José Maurício; Ciancaglini, Pietro

    2016-02-01

    Carbon nanotubes (CNT) is one of the most studied biomaterials, and issues about its cytotoxicity remain. The objective of our study was to investigate the in vitro influence of defective CNT on culture growth and on the formation of mineralized matrix nodules by primary osteoblastic cells grown in plastic or titanium (Ti) surfaces. Cellular viability, alkaline phosphatase activity and formation of mineral nodules were evaluated, besides the CNT characterization tests. The CNT studies showed better cell viability for osteoblasts incubated at stationary phase of culture in the presence of Ti (about 70%), but for the other phases, the cells suffered a significant reduction in viability. A peak of maximum alkaline phosphatase activity in the intermediate stage of growth (14 days of culture), which is characteristic for osteoblasts, was not affected, regardless of the presence of Ti or combination of CNT and Ti. Mineralized matrix nodules grew much more when the cells were incubated with CNT in the last 2 phases than when incubated in the first week, mainly when the cultures were grown on Ti discs. This study provides information for the application of CNT associated or not with Ti in processes of mineralization biostimulation.

  5. Efficiency of non-optimized direct carbon fuel cell with molten alkaline electrolyte fueled by carbonized biomass

    NASA Astrophysics Data System (ADS)

    Kacprzak, A.; Kobyłecki, R.; Włodarczyk, R.; Bis, Z.

    2016-07-01

    The direct carbon fuel cells (DCFCs) belong to new generation of energy conversion devices that are characterized by much higher efficiencies and lower emission of pollutants than conventional coal-fired power plants. In this paper the DCFC with molten hydroxide electrolyte is considered as the most promising type of the direct carbon fuel cells. Binary alkali hydroxide mixture (NaOH-LiOH, 90-10 mol%) is used as electrolyte and the biochar of apple tree origin carbonized at 873 K is applied as fuel. The performance of a lab-scale DCFC with molten alkaline electrolyte is investigated and theoretical, practical, voltage, and fuel utilization efficiencies of the cell are calculated and discussed. The practical efficiency is assessed on the basis of fuel HHV and LHV and the values are estimated at 40% and 41%, respectively. The average voltage efficiency is calculated as roughly 59% (at 0.65 V) and it is in a relatively good agreement with the values obtained by other researchers. The calculated efficiency of fuel utilization exceeds 95% thus indicating a high degree of carbon conversion into the electric power.

  6. The fabrication of a bifunctional oxygen electrode without carbon components for alkaline secondary batteries

    NASA Astrophysics Data System (ADS)

    Price, Stephen W. T.; Thompson, Stephen J.; Li, Xiaohong; Gorman, Scott F.; Pletcher, Derek; Russell, Andrea E.; Walsh, Frank C.; Wills, Richard G. A.

    2014-08-01

    The fabrication of a gas diffusion electrode (GDE) without carbon components is described. It is therefore suitable for use as a bifunctional oxygen electrode in alkaline secondary batteries. The electrode is fabricated in two stages (a) the formation of a PTFE-bonded nickel powder layer on a nickel foam substrate and (b) the deposition of a NiCo2O4 spinel electrocatalyst layer by dip coating in a nitrate solution and thermal decomposition. The influence of modifications to the procedure on the performance of the GDEs in 8 M NaOH at 333 K is described. The GDEs can support current densities up to 100 mA cm-2 with state-of-the-art overpotentials for both oxygen evolution and oxygen reduction. Stable performance during >50 successive, 1 h oxygen reduction/evolution cycles at a current density of 50 mA cm-2 has been achieved.

  7. Evaluation studies on carbon supported catalysts for oxygen reduction in alkaline medium

    NASA Technical Reports Server (NTRS)

    Srinivasan, Vakula S.; Singer, Joseph

    1986-01-01

    This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.

  8. A New Carbonate Chemistry in the Earth's Lower Mantle

    NASA Astrophysics Data System (ADS)

    Boulard, E.; Gloter, A.; Corgne, A.; Antonangeli, D.; Auzende, A.; Perrillat, J.; Guyot, F. J.; Fiquet, G.

    2010-12-01

    The global geochemical carbon cycle involves exchange between the Earth’s mantle and the surface. Carbon (C) is recycled into the mantle via subduction and released to the atmosphere via volcanic outgassing. Carbonates are the main C-bearing minerals that are transported deep in the Earth’s mantle via subduction of the oceanic lithosphere [1]. The way C is recycled and its contribution to the lower mantle reservoir is however largely unknown [ e.g 2, 3]. In this respect, it is important to assess if carbonates can be preserved in the deep mantle, or if decarbonatation, melting or reduction play a role in the deep carbon cycle. To clarify the fate of carbonates in the deep mantle, we carried out high-pressure and high-temperature experiments up to 105 GPa and 2850 K. Natural Fe-Mg carbonates or oxide mixtures of (Mg,Fe)O + CO2 were loaded into laser heated diamond anvil cells. In situ characterizations were done by X-ray Diffraction (XRD) using synchrotron radiation at the high-pressure beamline ID27 of the European Synchrotron Radiation Facility. A focused ion beam technique was then used to prepare the recovered samples for electron energy loss spectroscopy in a dedicated scanning transmission electron microscope (EELS-STEM) and scanning transmission X-ray microscopy (STXM). In situ XRD clearly shows the transformation of the initial carbonate phase into a new Mg-Fe high pressure carbonate phase at lower mantle conditions. We also provide direct evidence for recombination of CO2 with (Mg,Fe)O to form this new carbonate structure. In addition, subsequent EELS-STEM and STXM spectroscopies carried out on recovered samples yields C K-edge and stoechiometry characteristic to this new carbonate structure. This new high pressure phase concentrates a large amount of Fe(III), as a result of redox reactions within the siderite-rich carbonate. The oxidation of iron is balanced by partial reduction of carbon into CO groups and/or diamond. These reactions may provide an

  9. Recent progress on earth abundant hydrogen evolution reaction and oxygen evolution reaction bifunctional electrocatalyst for overall water splitting in alkaline media

    NASA Astrophysics Data System (ADS)

    Jamesh, Mohammed Ibrahim

    2016-11-01

    Electrochemical water-splitting is one of the promising ways for producing clean chemical fuel (Hydrogen) while cheap-earth-abundant-bifunctional-electrocatalyst is one of the possible way for improving the overall cost efficiency of water-splitting. This paper reviews the chemical state, hydrogen and oxygen evolution reaction activity in alkaline media, overall water-splitting performance in alkaline media, stability, and possible-factors for improving its efficiency of various kinds of recently reported electrocatalyst such as Ni-P, Co-P, Ni-Co-P, graphene-Co-P, O/N/C-Co/Ni, Ni-S, B-Ni/Co, Ni-Co, Mo, Se, Fe, Mn/Zn/Ti, and metal-free based earth-abundant-bifunctional-electrocatalyst. This paper also reviews and highlights the remarkable water splitting performance of the earth-abundant-bifunctional-electrocatalyst those exhibit better or well comparable with Pt/C//RuO2.

  10. A carbon isotope challenge to the snowball Earth.

    PubMed

    Sansjofre, P; Ader, M; Trindade, R I F; Elie, M; Lyons, J; Cartigny, P; Nogueira, A C R

    2011-10-05

    The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation. High partial pressures of atmospheric CO(2) (pCO2; from 20,000 to 90,000 p.p.m.v.) in the aftermath of the Marinoan glaciation (∼635 Myr ago) have been inferred from both boron and triple oxygen isotopes. These pCO2 values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise. The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units, provide estimates lower than 3,200 p.p.m.v.--and possibly as low as the current value of ∼400 p.p.m.v. Our new constraint, and our re-interpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.

  11. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol

    NASA Astrophysics Data System (ADS)

    Hicks, Raea K.; Day, Douglas A.; Jimenez, Jose L.; Tolbert, Margaret A.

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres.

  12. Cometary origin of carbon, nitrogen, and water on the earth

    NASA Technical Reports Server (NTRS)

    Delsemme, A. H.

    1992-01-01

    In this paper, two assumptions on the origin of the earth are substantiated: (1) that the earth accreted from fine hot degassed dust particles containing no volatiles; and (2) that, after the accretion was finished, all the volatiles of the biosphere, including the atmosphere and the oceans, were brought to the earth by cometary bombardment. A temperature of more than 1000 K is deduced at the time when the dust that was going to form the earth was separated from the gas phase. This implies grains of anhydrous silicates and of reduced iron, without either water, carbon, or any labile elements, which remained in gas phase; thus, the minor bodies could not produce atmosphere or oceans. The second assumption is based on the evidence that cometary nuclei are formed in the outer space, by accumulation of frosty particles containing large amounts of ice and volatile molecules. It is shown that the icy bodies which hit the earth are more than enough to explain the whole biosphere.

  13. Thermal treatment for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries

    SciTech Connect

    Belardi, G.; Lavecchia, R.; Medici, F.; Piga, L.

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer We separated Zn from Mn in zinc-carbon and alkaline batteries after removal of Hg. Black-Right-Pointing-Pointer Almost total removal of Hg is achieved at low temperature in air. Black-Right-Pointing-Pointer Nitrogen atmosphere is needed to reduce zinc and to permit its volatilization. Black-Right-Pointing-Pointer A high grade Zn concentrate was obtained with a high recovery at 1000-1200 Degree-Sign C. Black-Right-Pointing-Pointer The grade of Mn in the residue was enhanced with complete recovery. - Abstract: The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357 Degree-Sign C and 906 Degree-Sign C the boiling point of mercury and zinc and 1564 Degree-Sign C the melting point of Mn{sub 2}O{sub 3}. Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400 Degree-Sign C and 10 min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000 Degree-Sign C and 30 min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at

  14. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    SciTech Connect

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  15. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    DOE PAGES

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

  16. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte.

    PubMed

    Zhuang, Zhongbin; Giles, Stephen A; Zheng, Jie; Jenness, Glen R; Caratzoulas, Stavros; Vlachos, Dionisios G; Yan, Yushan

    2016-01-14

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.

  17. Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

    PubMed Central

    Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

    2016-01-01

    The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

  18. Experimental evidence for carbonate stability in the Earth's lower mantle

    NASA Astrophysics Data System (ADS)

    Biellmann, Claudine; Gillet, Philippe; Guyot, Francois; Peyronneau, Jean; Reynard, Bruno

    1993-07-01

    We present experimental results on the stability of carbonates up to 50 GPa and at high temperatures (1500-2500 K). The experiments were conducted in a laser-heated diamond anvil cell, and the run products were characterized by analytical TEM. Dolomite is shown to break down to a CaCO3 + MgCO3 assemblage at pressures between 20 and 50 GPa. No decarbonation was evident, suggesting that carbonates remain stable under these conditions with respect to rocksalt oxide + CO2 assemblages. Equimolar mixed powders of dolomite + enstatite and dolomite + olivine were transformed into magnesite + calcic perovskite and into magnesite + calcic and magnesian perovskites + magnesiowustite, respectively. The very strong partitioning of Ca in silicates suggests that magnesite is the stable carbonate in the presence of silicates in the Earth's lower mantle down to at least 1500 km. Finally, eutectoid or eutectic intergrowth of magnesiowustite and magnesite is observed, suggesting a possible mutual solubility between these two phases at high pressures and high temperatures. Lower mantle magnesiowustite may provide an alternative host for carbon in the Earth's lower mantle.

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

    PubMed

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

    2013-12-20

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

  20. Modelling the carbon cycle though Neoproterozoic Earth system changes

    NASA Astrophysics Data System (ADS)

    Bjerrum, C. J.; Canfield, D. E.

    2011-12-01

    The Neoproterozoic-Cambrian records major changes in geochemical proxies as a result of a profound reorganization of the Earth system. Extensive glaciations and the first oxygenation of the deep ocean with a shift from sulfidic/ferruginous conditions to more oxic conditions was accompanied by the radiation of the first animals. The reorganization was also recorded in enigmatic large-amplitude fluctuations in the isotopic composition of marine carbonate carbon (δ13CIC ), were only some are associated with major known glaciations. The carbon isotope events seem to grow in amplitude through the Neoproterozoic culminating in the Shuram anomaly - the largest in Earth history. The δ13CIC events are also accompanied by changes in the isotope composition of marine organic carbon (δ13COC), where the co-variation of δ13CIC and δ13COC seems to evolve from markedly positive relationship over a subdued δ13COC variation and an almost inverse pattern. There is limited understanding as to why or how the structure of these isotope events evolved over time and how these events may tie to the reorganization of the Earth system. We use our published quantitative model of the Shuram anomaly to explore carbon cycle dynamics during the Neoproterozoic. By changing in pre-event atmosphere-ocean chemistry we explore which factors contribute to the observed patterns of the large Neoproterozoic carbon isotope events. In particular, decreasing atmospheric CO2 and a slight increase of oxygen together with an increasing CO source from rising DOC concentrations results in progressively larger event amplitudes with changing co-variation between δ13CIC and δ13COC , culminating with the structure observed for the Shurum-Wonaka anomaly in the Ediacaran. In our model, the carbon isotope excursions were driven by methane from sediment-hosted clathrate hydrate deposits. Being a powerful greenhouse gas, methane increased temperature and melted icecaps. These combined to produce a negative 18O

  1. Structures and stabilities of alkaline earth metal peroxides XO2 (X=Ca, Be, Mg) studied by a genetic algorithm

    SciTech Connect

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

    2013-09-17

    The structures and stabilities of alkaline earth metal peroxides XO2 (X = Ca, Be, Mg) were studied using an adaptive genetic algorithm (GA) for global structure optimization in combination with first-principles calculations. From the adaptive GA search, we obtained an orthorhombic structure for CaO2 with 12 atoms in the unit cell, which is energetically more favorable than the previously proposed structures. Reaction energy of the decomposition CaO2 → CaO + 1/2O2 determined by density functional theory (DFT) calculation shows that this orthorhombic calcium peroxide structure is thermodynamically stable. The simulated X-ray diffraction (XRD) pattern using our predicted structure is in excellent agreement with experimental data. We also show that crystal phase BeO2 is unlikely to exist under normal conditions. MgO2 has a cubic pyrite structure, but it is not stable against decomposition: MgO2 → MgO + 1/2O2.

  2. X-ray Diffraction Studies of the Structure and Thermochemistry of Alkaline-Earth Oxide-Coated Thermionic Cathodes

    NASA Technical Reports Server (NTRS)

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

    1998-01-01

    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.

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

    PubMed

    Hereijgers, Bart P C; Weckhuysen, Bert M

    2009-01-01

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

  4. Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

    PubMed

    Su, Guijin; Liu, Yexuan; Huang, Linyan; Shi, Yali; Zhang, Aiqian; Zhang, Lixia; Liu, Wenbin; Gao, Lirong; Zheng, Minghui

    2013-01-01

    The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO.

  5. Cardiac ryanodine receptor: Selectivity for alkaline earth metal cations points to the EF-hand nature of luminal binding sites.

    PubMed

    Gaburjakova, Jana; Gaburjakova, Marta

    2016-06-01

    A growing body of evidence suggests that the regulation of cardiac ryanodine receptor (RYR2) by luminal Ca(2+) is mediated by luminal binding sites located on the RYR2 channel itself and/or its auxiliary protein, calsequestrin. The localization and structure of RYR2-resident binding sites are not known because of the lack of a high-resolution structure of RYR2 luminal regions. To obtain the first structural insight, we probed the RYR2 luminal face stripped of calsequestrin by alkaline earth metal divalents (M(2+): Mg(2+), Ca(2+), Sr(2+) or Ba(2+)). We show that the RYR2 response to caffeine at the single-channel level is significantly modified by the nature of luminal M(2+). Moreover, we performed competition experiments by varying the concentration of luminal M(2+) (Mg(2+), Sr(2+) or Ba(2+)) from 8 mM to 53 mM and investigated its ability to compete with 1mM luminal Ca(2+). We demonstrate that all tested M(2+) bind to exactly the same RYR2 luminal binding sites. Their affinities decrease in the order: Ca(2+)>Sr(2+)>Mg(2+)~Ba(2+), showing a strong correlation with the M(2+) affinity of the EF-hand motif. This indicates that the RYR2 luminal binding regions and the EF-hand motif likely share some structural similarities because the structure ties directly to the function.

  6. Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers.

    PubMed

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

    2014-10-01

    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.

  7. First-Principles Calculation of Solution Energy of Alkaline-Earth Metal Elements to BaTiO3

    NASA Astrophysics Data System (ADS)

    Moriwake, Hiroki; Hirayama, Tsukasa; Ikuhara, Yuichi; Tanaka, Isao

    2007-10-01

    Quantitative analysis of the solution energy of alkaline-earth metal elements to perovskite-type BaTiO3 was carried out by a first-principles calculation combined with thermodynamics theory. The solution energies of neutral solute and a compensated solute with an oxygen vacancy were systematically calculated. They were obtained for two cation sites and four thermodynamical conditions with different chemical potentials of constituent atoms. Both Ca and Sr preferably occupy the Ba site of BaTiO3. On the other hand, Mg occupies the Ti site. This corresponds well to the widely accepted experimental findings regarding site preference. Moreover, under the condition of coexising BaO, CaO and BaTiO3, energy difference between the Ba-site solution and O-vacancy compensated Ti-site solution of Ca ions has been found to be smaller than that of Sr. Under this condition, the O-vacancy compensated Ti-site solution of Ca should be favorable compared with that of Sr. The same number of oxygen vacancies as Ca ions occupying Ti sites can be introduced. This also explains well experimental feature of the Ca-doped BaTiO3-based nonreducible multilayer ceramics capacitor (MLCC) materials regarding solution site of the Ca ion and abundance of O-vacancy.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  9. Carbon trading, climate change, environmental sustainability and saving planet Earth

    NASA Astrophysics Data System (ADS)

    Yim, W. W.

    2009-12-01

    Carbon trading namely the reduction of future carbon dioxide levels has been widely touted as a solution needed to counter the problem of climate change. However, there are enormous risks involved as the measure tackles only one of the causes of climate change and may prove to be ineffective. This presentation highlights ten points relevant to the discussion on carbon trading, climate change, environmental sustainability and saving planet Earth for increasing public awareness. They include: (1) Climate has changed throughout Earth’s history. (2) The present level of about 388 parts per million level of carbon dioxide in the atmosphere has already exceeded the maximum level of the past 800,000 years. This value is obtained from air bubbles trapped within the ice in Antarctica but the consequence of further increases remains uncertain. (3) Earth scientists do not have an overwhelming consensus on whether carbon trading alone is an effective measure in mitigating climate change. (4) The present state of the Earth’s demise is largely the result of human actions including population growth and the mismanagement of the Earth. (5) The latest evidence on sea-level changes in the South China Sea a far-field region unaffected by glacial isostatic readjustment is not in support of a ‘rapid’ rate of future sea-level rise through global warming. (6) Volcanic eruptions have an important role in driving the Earth’s climate. Examples of temperature lowering as well as abnormally wet and dry years can both be found in the instrumental record. (7) Humans have drastically modified the ‘natural’ water cycle. This is however not a well recognized cause of climate change compared to the emission of greenhouse gases through fossil fuel consumption. (8) The bulk (~75%) of the rise in mean annual temperature of about 1oC observed at the Hong Kong Observatory Station since record began in 1884 is best explained by the thermal heat island effect. (9) No evidence has been found

  10. NiP₂ nanosheet arrays supported on carbon cloth: an efficient 3D hydrogen evolution cathode in both acidic and alkaline solutions.

    PubMed

    Jiang, Ping; Liu, Qian; Sun, Xuping

    2014-11-21

    Designing efficient and stable hydrogen evolution catalysts made from earth-abundant elements is essential to the development of solar-driven water-splitting devices. In this communication, we develop a two-step strategy for constructing NiP2 nanosheet arrays on carbon cloth (NiP2 NS/CC). As a novel 3D hydrogen evolution cathode, the NiP2 NS/CC electrode is highly active in acidic solutions and needs an overpotential of 75 and 204 mV to achieve current densities of 10 and 100 mA cm(-2), respectively, and it preserves its catalytic activity for at least 57 h. Moreover, it also operates efficiently under alkaline conditions.

  11. Diarylsulfonamides and their bioisosteres as dual inhibitors of alkaline phosphatase and carbonic anhydrase: Structure activity relationship and molecular modelling studies.

    PubMed

    Al-Rashida, Mariya; Ejaz, Syeda Abida; Ali, Sharafat; Shaukat, Aisha; Hamayoun, Mehwish; Ahmed, Maqsood; Iqbal, Jamshed

    2015-05-15

    The effect of bioisosteric replacement of carboxamide linking group with sulfonamide linking group, on alkaline phosphatase (AP) and carbonic anhydrase (CA) inhibition activity of aromatic benzenesulfonamides was investigated. A series of carboxamide linked aromatic benzenesulfonamides 1a-1c, 2a-2d and their sulfonamide linked bioisosteres 3a-3d, 4a-4d was synthesized and evaluated for inhibitory activity against bovine tissue non-specific alkaline phosphatase (TNAP), intestinal alkaline phosphatase (IAP) and bCA II. A significant increase in CA inhibition activity was observed upon bioisosteric replacement of carboxamide linking group with a sulfonamide group. Some of these compounds were identified as highly potent and selective AP inhibitors. Compounds 1b, 2b, 3d, 4d 5b and 5c were found to be selective bTNAP inhibitors, whereas compounds 1a, 1c, 2a, 2c, 2d, 3a, 3c, 4a, 4b, 4c, 5a were found to be selective bIAP inhibitors. For most active AP inhibitor 3b, detailed kinetic studies indicated a competitive mode of inhibition against tissue non-specific alkaline phosphatase (TNAP) and non-competitive mode of inhibition against intestinal alkaline phosphatase (IAP). Molecular docking studies were carried out to rationalize important binding site interactions.

  12. Carbon-bearing iron phases and the carbon isotope composition of the deep Earth.

    PubMed

    Horita, Juske; Polyakov, Veniamin B

    2015-01-06

    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.

  13. Amido-based potassium-alkaline earth metallates--synthesis and structures of heterobimetallic complexes of heavy s-block elements.

    PubMed

    Glock, Carsten; Görls, Helmar; Westerhausen, Matthias

    2011-08-28

    The metathesis reaction of potassium N-isopropylanilide with alkaline earth metal diiodides of calcium, strontium and barium in a molar ratio of 4:1 yields the corresponding alkaline earth metalates of the type [(THF)(n)K(μ-NPhiPr)(2)Ae(μ-NPhiPr)(2)K(THF)(n)] (1: Ae = Ca, n = 2). Stabilization and crystallization of such derivatives succeeds after exchange of the THF ligands by multidentate amino bases such as tetramethylethylenediamine (TMEDA) or pentamethyldiethylenetriamine (PMDETA). The influence of the size and hardness of the alkaline earth metal center on the molecular structures is studied with [(L)K(μ-NPhiPr)(2)Ae(μ-NPhiPr)(2)K(L)] (2: Ae = Ca, L = TMEDA; 3: Ae = Sr, L = TMEDA; 4: Ae = Sr, L = PMDETA; and 5: Ae = Ba, L = PMDETA). The molecular structures are dominated by (attractive and repulsive) electrostatic and steric factors leading to a shortening of the non-bonding AeK distances from calcium to barium.

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

    PubMed

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

    2014-05-01

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

  15. Measurement of thermophysical properties of molten salts: Mixtures of alkaline carbonate salts

    SciTech Connect

    Araki, N.; Matsuura, M.; Makino, A.; Hirata, T.; Kato, Y.

    1988-11-01

    The purpose of this study is to develop measuring methods for the thermal diffusivity, the specific heat capacity, and the density of molten salts, as well as to measure these properties of mixtures of alkaline carbonate salts. The thermal diffusivity is measured by the stepwise heating method. The sample salt is poured into a thin container, and as a result, a three-layered cell is formed. The thermal diffusivity is obtained from the ratio of temperature rises at different times measured at the rear surface of the cell when the front surface is heated by the stepwise energy from an iodine lamp. The specific heat capacity is measured using an adiabatic scanning calorimeter. The density is measured by Archimedes' principle. Thermal conductivity is determined from the above properties. Measured samples are Li/sub 2/CO/sub 3/-K/sub 2/CO/sub 3/ (42.7-57.3, 50.0-50.0, and 62.0-38.0 mol%).

  16. In situ spectroscopic ellipsometry during electrochemical treatment of zinc in alkaline carbonate electrolyte

    NASA Astrophysics Data System (ADS)

    Chen, Ying; Erbe, Andreas

    2013-01-01

    In situ spectroscopic ellipsometry (SE, 297-820 nm, 4.4-1.5 eV) during electrochemical oxidation/reduction of zinc in alkaline carbonate electrolyte was performed using a specially designed optical-electrochemical cell. The growth and shrinkage of the interfacial layer on Zn was analysed on the basis of Lekner's first order perturbation theory. For non-absorbing thin films on metal surfaces, an algorithm has been derived to extract the thickness of a surface film directly from ellipsometric data without the need of optical modelling. During cyclic voltammetry (CV), a rapid decrease/increase in the layer thickness in the reduction/oxidation peak has been found. In the potential regime where the surface is oxide-covered, the layer thickness increases/decreases linearly with potential in anodic/cathodic scans. The density of the interfacial region in this regime is constant. During chronoamperometric experiments, a fast correlating jump in thickness was found after potential jumps. An ageing of the films is observed in the absorption spectrum (from the ellipsometric parameter Ψ), which shows changes until ≈ 30 min after potential jumps. Analysis of the current transients points to continuous dissolution of Zn.

  17. Quaternary structure of partially liganded intermediates of sheep carbon monoxide hemoglobin at alkaline pH.

    PubMed

    Gray, R D

    1975-01-25

    A rapid change in absorbance was observed in the Soret region during the interval between photolysis of sheep carbon monoxide hemoglobin and the subsequent reassociation of CO in the dark. The rate constant for this spectral change was about 4000 s--1 at 20 degrees in 0.05 M solium borate, pH 9.3. The wavelength dependence of the amplitude of the absorbance change is similar to that observed when deoxygenated alpha and theta chains are allowed to recombine (Brunori, M., Antonini, E., Wyman, J., and Anderson, S. R. (1968) J. Mol. Biol. 34, 357-359), and therefore reflects changes in the quanternary structure of the hemoglobin tetramer induced by ligand displacement. The amplitude of this conformation-dependent spectral change was not a linear function of the fraction of bound CO removed by photolysis. The results suggest that of the possible intermediate species present after partial photolysis, only Hb4 and Hb4(CO) change from the ligand-bound to the ligand-free sturcture prior to CO reassociation under these alkaline conditions.

  18. Diamond crystallization in a CO2-rich alkaline carbonate melt with a nitrogen additive

    NASA Astrophysics Data System (ADS)

    Khokhryakov, Alexander F.; Palyanov, Yuri N.; Kupriyanov, Igor N.; Nechaev, Denis V.

    2016-09-01

    Diamond crystallization was experimentally studied in a CO2-bearing alkaline carbonate melt with an increased content of nitrogen at pressure of 6.3 GPa and temperature of 1500 °C. The growth rate, morphology, internal structure of overgrown layers, and defect-impurity composition of newly formed diamond were investigated. The type of growth patterns on faces, internal structure, and nitrogen content were found to be controlled by both the crystallographic orientation of the growth surfaces and the structure of the original faces of diamond seed crystals. An overgrown layer has a uniform structure on the {100} plane faces of synthetic diamond and a fibrillar (fibrous) structure on the faceted surfaces of a natural diamond cube. The {111} faces have a polycentric vicinal relief with numerous twin intergrowths and micro twin lamellae. The stable form of diamond growth under experimental conditions is a curved-face hexoctahedron with small cube faces. The nitrogen impurity concentration in overgrown layers varies depending on the growth direction and surface type, from 100 to 1100 ppm.

  19. Thermal treatment for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries.

    PubMed

    Belardi, G; Lavecchia, R; Medici, F; Piga, L

    2012-10-01

    The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn(2)O(3). Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10 min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30 min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30 min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.

  20. Multidimensional (0D to 3D) Alkaline-Earth Metal Diphosphonates: Synthesis, Structural Diversity, and Luminescence Properties.

    PubMed

    Senthil Raja, Duraisamy; Lin, Pin-Chun; Liu, Wei-Ren; Zhan, Jun-Xiang; Fu, Xin-Yi; Lin, Chia-Her

    2015-05-04

    A series of new alkaline-earth metal diphosphonate frameworks were successfully synthesized under solvothermal reaction condition (160 °C, 3 d) using 1-hydroxyethylidene-1,1-diphosphonic acid (CH3C(OH)(H2PO3)2, hedpH4) as a diphosphonate building block and Mg(II), Ca(II), Sr(II), or Ba(II) ions as alkaline-earth metal ion centers in water, dimethylformamide, and/or EtOH media. These diphosphonate frameworks, (H2NMe2)4[Mg(hedpH2)3]·3H2O (1), (H2NMe2)2[Ca(hedpH2)2] (2), (H2NMe2)2[Sr3(hedpH2)4(H2O)2] (3), and [Ba3(hedpH2)3]·H2O (4) exhibited interesting structural topologies (zero-, one-, two-, and three-dimensional (0D, 1D, 2D, and 3D, respectively)), which are mainly depending on the metal ions and the solvents used in the synthesis. The single-crystal analysis of these newly synthesized compounds revealed that 1 was a 0D molecule, 2 has 1D chains, 3 was a 3D molecule, and 4 has 2D layers. All compounds were further characterized using thermogravimetric analysis, solid-state (31)P NMR, powder X-ray diffraction analysis, UV-vis spectra, and infrared spectroscopy. In addition, Eu(III)- and Tb(III)-doped compounds of 1-4, namely, (H2NMe2)4[Ln(x)Mg(1-x)(hedpH2)2(hedpH(2-x))]·3H2O (1Ln), (H2NMe2)2[Ln(x)Ca(1-x)(hedpH2)(hedpH(2-x))] (2Ln), (H2NMe2)2[Ln(x)Sr(3-x)(hedpH2)3(hedpH(2-x))(H2O)2] (3Ln), and [Ln(x)Ba(3-x)(hedpH2)2(hedpH(2-x))]·H2O (4Ln) (where Ln = Eu, Tb), were synthesized, and their photoluminescence properties were studied. The quantum yield of 1Eu-4Eu was measured with reference to commercial red phosphor, Y2O2S:Eu(3+) (YE), and the quantum yield of terbium-doped compounds 1Tb-4Tb was measured with reference to commercial green-emitting phosphor CeMgAl10O17:Tb(3+). Interestingly, the compound 2Eu showed very high quantum yield of 92.2%, which is better than that of the reference commercial red phosphor, YE (90.8%).

  1. Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Third progress report, September 1, 1980-April 1, 1981

    SciTech Connect

    Christensen, J.J.

    1981-04-15

    The overall objective of this project is to study the use of liquid membrane systems employing macrocyclic ligand carriers in making separations among metal cations. During the third year of the project, work continued in the development of a mathematical model to describe cation transport. The model was originally developed to describe the relationship between cation transport rate (J/sub M/) and the cation-macrocycle stability constant (K). The model was tested by determining the rates of transport of alkali and alkaline earth cations through chloroform membranes containing carrier ligands where the stability constants for their reaction with cations in methanol were known. From the results, it is clear that the model correctly describes the dependence of J/sub M/ on log K. The model also correctly describes the effect of cation concentration and carrier concentration on cation transport rates, as detailed in the previous progress report. During the third year of the project, the transport model was expanded so as to apply to competitive transport of cations from mixtures of two cations in the source aqueous phase. Data were collected under these conditions and the ability of the model to predict the flux of each cation was tested. Representative data of this type are presented along with corresponding data which were obtained when each cation was transported by the same carrier from a source phase containing only that cation. Comparison of transport rates determined under the two experimental conditions indicates that the relationship between the two sets of data is complex. To date, a few of these data involving transport from binary cation mixtures have been tested against the transport model. It was found that the model correctly predicts the cation fluxes from cation mixtures. These preliminary results indicate that the transport model can successfully predict separation factors when cation mixtures are used.

  2. DEVELOPMENT OF GLASS COMPOSITIONS TO IMMOBILIZE ALKALI, ALKALINE EARTH, LANTHANIDE AND TRANSITION METAL FISSION PRODUCTS FROM NUCLEAR FUEL REPROCESSING

    SciTech Connect

    Marra, J.; Billings, A.

    2009-06-24

    The Advanced Fuel Cycle Initiative (AFCI) waste management strategy revolves around specific treatment of individual or groups of separated waste streams. A goal for the separations processes is to efficiently manage the waste to be dispositioned as high level radioactive waste. The Advanced Fuel Cycle Initiative (AFCI) baseline technology for immobilization of the lanthanide (Ln) and transition metal fission product (TM) wastes is vitrification into a borosilicate glass. A current interest is to evaluate the feasibility of vitrifying combined waste streams to most cost effectively immobilize the wastes resulting from aqueous fuel reprocessing. Studies showed that high waste loadings are achievable for the Ln only (Option 1) stream. Waste loadings in excess of 60 wt % (on a calcined oxide basis) were demonstrated via a lanthanide borosilicate (LaBS) glass. The resulting glasses had excellent relative durability as determined by the Product Consistency Test (PCT). For a combined Ln and TM waste stream glass (Option 2), noble metal solubility was found to limit waste loading. However, the measured PCT normalized elemental releases for this glass were at least an order of magnitude below that of Environmental Assessment (EA) glass. Current efforts to evaluate the feasibility of vitrifying combined Ln, TM, alkali (Cs is the primary radionuclide of concern) and alkaline earth (Sr is the primary radionuclide of concern) wastes (Option 3) have shown that these approaches are feasible. However, waste loading limitations with respect to heat load (Cs/Sr loading), molybdenum solubility and/or noble metal solubility will likely be realized and must be considered in determining the cost effectiveness of these approaches.

  3. Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

    SciTech Connect

    Lian, Chen; Liu, Liu; Guo, Xu; Long, Yinshuang; Jia, Shanshan; Li, Huanhuan; Yang, Lirong

    2016-01-15

    Two novel coordination polymers, namely, [Ca(NCP){sub 2}]{sub ∞} (I) and [Sr(NCP){sub 2}]{sub ∞} (II) were synthesized under hydrothermal conditions based on 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (HNCP) and characterized by elemental analysis, infrared spectrometry, X-ray powder diffraction and single crystal X-ray diffraction. Findings indicate that I and II are isomorphous and isostructural, containing the unit of M(NCP{sup −}){sub 4} (M=Ca(II) and Sr(II)), based on which to assemble into three-dimensional (3D) porous 4-fold interpenetration honeycomb-shaped neutral coordination polymers (CPs). Between the adjacent lamellar structures in I and II, there exist π–π interactions between the pyridine rings belonging to phenanthroline of NCP{sup −} which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability. - Graphical abstract: One-dimensional nanotubular channels with the cross dimension of 37.1959(20)×23.6141(11)Å{sup 2} in the three-dimensional honeycomb-shaped coordination network of II are observed. The topological analysis of II indicates that there exists a typical diamond framework possessing large adamantanoid cages, which containing four cyclohexane-shaped patterns in chair conformations. - Highlights: • Two isomorphous and isostructural coordination polymers based on flexible ligand and two alkaline-earth metal salts have been synthesized and characterized. • Structural analysis indicates that I and II are assembled into 3D porous honeycomb-shaped metal-organic frameworks. • Both I and II display stronger fluorescence emissions and higher thermal stability.

  4. Carbon in the Galaxy: Studies from Earth and Space

    NASA Technical Reports Server (NTRS)

    Tarter, Jill C. (Editor); Chang, Sherwood (Editor); Defrees, Doug J. (Editor)

    1990-01-01

    Presented here is the text of the invited papers presented during a meeting entitled, Carbon in the Galaxy: Studies from Earth and Space, that was held at NASA Ames Research Center on November 5 and 6, 1987. For completeness, abstracts from all of the poster papers and the text of a paper summarizing what was learned during the course of the meeting are also included. The underlying premise for the meeting was that there is much to be gained by bringing together scientists from very different disciplines, all of whom study carbon in different ways for different reasons. The interchanges took place during the meeting and the contents of the enclosed papers validate that premise.

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

    PubMed

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

    2014-12-07

    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.

  6. The Earth System Science Pathfinder Orbiting Carbon Observatory (OCO) Mission

    NASA Technical Reports Server (NTRS)

    Crisp, David

    2003-01-01

    A viewgraph presentation describing the Earth System Science Pathfinder Orbiting Carbon Observatory (OCO) Mission is shown. The contents include: 1) Why CO2?; 2) What Processes Control CO2 Sinks?; 3) OCO Science Team; 4) Space-Based Measurements of CO2; 5) Driving Requirement: Precise, Bias-Free Global Measurements; 6) Making Precise CO2 Measurements from Space; 7) OCO Spatial Sampling Strategy; 8) OCO Observing Modes; 9) Implementation Approach; 10) The OCO Instrument; 11) The OCO Spacecraft; 12) OCO Will Fly in the A-Train; 13) Validation Program Ensures Accuracy and Minimizes Spatially Coherent Biases; 14) Can OCO Provide the Required Precision?; 15) O2 Column Retrievals with Ground-based FTS; 16) X(sub CO2) Retrieval Simulations; 17) Impact of Albedo and Aerosol Uncertainty on X(sub CO2) Retrievals; 18) Carbon Cycle Modeling Studies: Seasonal Cycle; 19) Carbon Cycle Modeling Studies: The North-South Gradient in CO2; 20) Carbon Cycle Modeling Studies: Effect of Diurnal Biases; 21) Project Status and Schedule; and 22) Summary.

  7. Carbon-bearing iron phases and the carbon isotope composition of the deep Earth

    PubMed Central

    Horita, Juske; Polyakov, Veniamin B.

    2015-01-01

    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 δ13C ≈ −5 ± 3‰ with a very broad distribution to lower values (∼−40‰). The processes that have produced the wide δ13C distributions to the observed low δ13C 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 13C 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 δ13C values. The sharp contrast in the δ13C 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 δ13C values and that an average δ13C value of the bulk Earth could be much lower than ∼−5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted δ13C 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. PMID:25512520

  8. Carbon solubility in olivine and the mode of carbon storage in the Earth's mantle.

    PubMed

    Keppler, Hans; Wiedenbeck, Michael; Shcheka, Svyatoslav S

    2003-07-24

    The total amount of carbon in the atmosphere, oceans and other near-surface reservoirs is thought to be negligible compared to that stored in the Earth's mantle. Although the mode of carbon storage in the mantle is largely unknown, observations of microbubbles on dislocations in minerals from mantle xenoliths has led to the suggestion that carbon may be soluble in silicates at high pressure. Here we report measurements of carbon solubility in olivine, the major constituent of the upper mantle, at pressures up to 3.5 GPa. We have found that, contrary to previous expectations, carbon solubility in olivine is exceedingly low--of the order of 0.1 to 1 parts per million by weight. Together with similar data for pyroxenes, garnet and spinel, we interpret this to imply that most carbon must be present as a separate phase in the deeper parts of the upper mantle, probably as a carbonate phase. Large-scale volcanic eruptions tapping such a carbonate-bearing mantle reservoir might therefore rapidly transfer large amounts of carbon dioxide into the atmosphere, consistent with models that link global mass extinctions to flood basalt eruptions via a sudden increase in atmospheric carbon dioxide levels.

  9. Multi-decadal increases in dissolved organic carbon and alkalinity flux from the Mackenzie drainage basin to the Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Tank, Suzanne E.; Striegl, Robert G.; McClelland, James W.; Kokelj, Steven V.

    2016-05-01

    Riverine exports of organic and inorganic carbon (OC, IC) to oceans are intricately linked to processes occurring on land. Across high latitudes, thawing permafrost, alteration of hydrologic flow paths, and changes in vegetation may all affect this flux, with subsequent implications for regional and global carbon (C) budgets. Using a unique, multi-decadal dataset of continuous discharge coupled with water chemistry measurements for the Mackenzie River, we show major increases in dissolved OC (DOC) and IC (as alkalinity) fluxes since the early 1970s, for a watershed that covers 1.8 M km2 of northwestern Canada, and provides substantial inputs of freshwater and biogeochemical constituents to the Arctic Ocean. Over a 39-year period of record, DOC flux at the Mackenzie mouth increased by 39.3% (44.5 ± 22.6 Gmol), while alkalinity flux increased by 12.5% (61.5 ± 60.1 Gmol). Isotopic analyses and substantial increases in sulfate flux indicate that increases in alkalinity are driven by accelerating sulfide oxidation, a process that liberates IC from rock and soils in the absence of CO2 consumption. Seasonal and sub-catchment trends suggest that permafrost thaw plays an important role in the observed increases in DOC and alkalinity: sub-catchment increases for all constituents are confined to northern, permafrost-affected regions, while observed increases in autumn to winter are consistent with documented landscape-scale changes that have resulted from changing thaw dynamics. This increase in DOC and sulfide-derived alkalinity represents a substantial intensification of land-to-ocean C mobilization, at a level that is significant within the regional C budget. The change we observe, for example, is similar to current and projected future rates of CO2 consumption by weathering in the Mackenzie basin.

  10. Multi-decadal increases in dissolved organic carbon and alkalinity flux from the Mackenzie drainage basin to the Arctic Ocean

    USGS Publications Warehouse

    Tank, Suzanne E.; Striegl, Robert G.; McClelland, James W.; Kokelj, Steven V.

    2016-01-01

    Riverine exports of organic and inorganic carbon (OC, IC) to oceans are intricately linked to processes occurring on land. Across high latitudes, thawing permafrost, alteration of hydrologic flow paths, and changes in vegetation may all affect this flux, with subsequent implications for regional and global carbon (C) budgets. Using a unique, multi-decadal dataset of continuous discharge coupled with water chemistry measurements for the Mackenzie River, we show major increases in dissolved OC (DOC) and IC (as alkalinity) fluxes since the early 1970s, for a watershed that covers 1.8 M km2 of northwestern Canada, and provides substantial inputs of freshwater and biogeochemical constituents to the Arctic Ocean. Over a 39-year period of record, DOC flux at the Mackenzie mouth increased by 39.3% (44.5 ± 22.6 Gmol), while alkalinity flux increased by 12.5% (61.5 ± 60.1 Gmol). Isotopic analyses and substantial increases in sulfate flux indicate that increases in alkalinity are driven by accelerating sulfide oxidation, a process that liberates IC from rock and soils in the absence of CO2 consumption. Seasonal and sub-catchment trends suggest that permafrost thaw plays an important role in the observed increases in DOC and alkalinity: sub-catchment increases for all constituents are confined to northern, permafrost-affected regions, while observed increases in autumn to winter are consistent with documented landscape-scale changes that have resulted from changing thaw dynamics. This increase in DOC and sulfide-derived alkalinity represents a substantial intensification of land-to-ocean C mobilization, at a level that is significant within the regional C budget. The change we observe, for example, is similar to current and projected future rates of CO2 consumption by weathering in the Mackenzie basin.

  11. No One's Home: the Fate of Carbon on Lifeless Earths

    NASA Astrophysics Data System (ADS)

    Neveu, Marc

    Although several thousands of exoplanets are now known, including many terrestrial planets, their possible geology and climates remain poorly understood and understudied. Yet, understanding how elements such as carbon are cycled between a planet's interior, surface, and atmosphere is crucial to predict how lifeless planets operate and, by contrast, be able to detect deviations from abiotic backgrounds due to biology, the holy grail of exoplanet science. As a first, feasible step towards the difficult, long-term goal of understanding how key reactive elements (H, C, N, O, S) are cycled in the atmospheres, surfaces, and interiors of terrestrial exoplanets through time, we propose to carry out a self-consistent theoretical study of the fate of carbon in the atmospheres and at the surfaces of Earth-like, lifeless exoplanets. We will: 1. Model the near-surface geochemistry and geophysics of the carbon cycle to determine net carbon gas fluxes as a function of terrestrial planet size and redox conditions; 2. Model the atmospheric fate of carbon species as a function of stellar input; 3. Perform simulations that self-consistently combine geological and atmospheric processes; 4. Convert resulting atmospheric compositions to spectra to be archived as a public database for use by observers. We will track the abiotic fate of carbon and its atmospheric expression on Earth-like planets as a function of three key parameters: planet size, surface and atmospheric redox conditions, and stellar irradiation. To do so, we will further develop and use state-of-theart planetary geological ("Geo") and atmospheric ("Atmos") models. We have previously developed a code that couples geophysical evolution and water-rock geochemistry (Neveu et al. 2015, GRL 42, 10197). Using this code, we will calculate the speciation of carbon species versus depth in subaerial oceans, their possible incorporation into the crust by water-rock interaction at the seafloor or by subduction of sediments, and

  12. The synthesis and crystal structures of the first rare-earth alkaline-earth selenite chlorides MNd 10(SeO 3) 12Cl 8 ( M=Ca and Sr)

    NASA Astrophysics Data System (ADS)

    Berdonosov, P. S.; Olenev, A. V.; Dolgikh, V. A.; Lightfoot, P.

    2007-11-01

    Two new alkaline-earth Nd selenite chlorides MNd 10(SeO 3) 12Cl 8 ( M=Ca, Sr) were obtained using crystal growth from alkaline-earth chloride melts in quartz tubes. These new compounds crystallize in the orthorhombic system in space group C cca (#68). The compounds were studied by energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction. It was shown that both compounds adopt the same structure type, constructed by complex [M 11(SeO 3) 12] 8+ slabs separated by chloride anion layers perpendicular to the longest cell parameter. The SeO 3 groups show a pyramidal shape and may be described as SeO 3E tetrahedra. Such SeO 3 groups decorate the Nd-O skeletons forming the [M 11(SeO 3) 12] 8+ slabs.

  13. Climatological variations of total alkalinity and total dissolved inorganic carbon in the Mediterranean Sea surface waters

    NASA Astrophysics Data System (ADS)

    Gemayel, E.; Hassoun, A. E. R.; Benallal, M. A.; Goyet, C.; Rivaro, P.; Abboud-Abi Saab, M.; Krasakopoulou, E.; Touratier, F.; Ziveri, P.

    2015-12-01

    A compilation of data from several cruises between 1998 and 2013 was used to derive polynomial fits that estimate total alkalinity (AT) and total dissolved inorganic carbon (CT) from measurements of salinity and temperature in the Mediterranean Sea surface waters. The optimal equations were chosen based on the 10-fold cross-validation results and revealed that second- and third-order polynomials fit the AT and CT data respectively. The AT surface fit yielded a root mean square error (RMSE) of ± 10.6 μmol kg-1, and salinity and temperature contribute to 96 % of the variability. Furthermore, we present the first annual mean CT parameterization for the Mediterranean Sea surface waters with a RMSE of ± 14.3 μmol kg-1. Excluding the marginal seas of the Adriatic and the Aegean, these equations can be used to estimate AT and CT in case of the lack of measurements. The identified empirical equations were applied on the 0.25° climatologies of temperature and salinity, available from the World Ocean Atlas 2013. The 7-year averages (2005-2012) showed that AT and CT have similar patterns with an increasing eastward gradient. The variability is influenced by the inflow of cold Atlantic waters through the Strait of Gibraltar and by the oligotrophic and thermohaline gradient that characterize the Mediterranean Sea. The summer-winter seasonality was also mapped and showed different patterns for AT and CT. During the winter, the AT and CT concentrations were higher in the western than in the eastern basin. The opposite was observed in the summer where the eastern basin was marked by higher AT and CT concentrations than in winter. The strong evaporation that takes place in this season along with the ultra-oligotrophy of the eastern basin determines the increase of both AT and CT concentrations.

  14. CarbonSat: ESA's Earth Explorer 8 Candidate Mission

    NASA Astrophysics Data System (ADS)

    Meijer, Y. J.; Ingmann, P.; Löscher, A.

    2012-04-01

    The CarbonSat candidate mission is part of ESA's Earth Explorer Programme. In 2010, two candidate opportunity missions had been selected for feasibility and preliminary definition studies. The missions, called FLEX and CarbonSat, are now in competition to become ESA's eighth Earth Explorer, both addressing key climate and environmental change issues. In this presentation we will provide a mission overview of CarbonSat with a focus on science. CarbonSat's primary mission objective is the quantification and monitoring of CO2 and CH4 sources and sinks from the local to the regional scale for i) a better understanding of the processes that control carbon cycle dynamics and ii) an independent estimate of local greenhouse gas emissions (fossil fuel, geological CO2 and CH4, etc.) in the context of international treaties. A second priority objective is the monitoring/derivation of CO2 and CH4 fluxes on regional to global scale. These objectives will be achieved by a unique combination of frequent, high spatial resolution (2 x 2 km2) observations of XCO2 and XCH4 coupled to inverse modelling schemes. The required random error of a single measurement at ground-pixel resolution is of the order of between 1 and 3 ppm for XCO2 and between 9 and 17 ppb for XCH4. High spatial resolution is essential in order to maximize the probability for clear-sky observations and to identify flux hot spots. Ideally, CarbonSat shall have a wide swath allowing a 6-day global repeat cycle. The CarbonSat observations will enable CO2 emissions from coal-fired power plants, localized industrial complexes, cities, and other large emitters to be objectively assessed at a global scale. Similarly, the monitoring of natural gas pipelines and compressor station leakage will become feasible. The detection and quantification of the substantial geological greenhouse gas emission sources such as seeps, volcanoes and mud volcanoes will be achieved for the first time. CarbonSat's Greenhouse Gas instrument will

  15. Carbon Dioxide Cycling and the Climate of Ancient Earth

    NASA Technical Reports Server (NTRS)

    Zahnle, Kevin; Sleep, Norman H.

    2001-01-01

    The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early Sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

  16. Carbon Dioxide Cycling And The Climate of Ancient Earth

    NASA Technical Reports Server (NTRS)

    Zahnle, Kevin; Sleep, Norman H.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

  17. Accretion and differentiation of carbon in the early Earth.

    PubMed

    Tingle, T N

    1998-05-15

    The abundance of C in carbonaceous and ordinary chondrites decreases exponentially with increasing shock pressure as inferred from the petrologic shock classification of Scott et al. [Scott, E.R.D., Keil, K., Stoffler, D., 1992. Shock metamorphism of carbonaceous chondrites. Geochim. Cosmochim. Acta 56, 4281-4293] and Stoffler et al. [Stoffler, D., Keil, K., Scott, E.R.D., 1991. Shock metamorphism of ordinary chondrites. Geochim. Cosmochim. Acta 55, 3845-3867]. This confirms the experimental results of Tyburczy et al. [Tyburczy, J.A., Frisch, B., Ahrens, T.J., 1986. Shock-induced volatile loss from a carbonaceous chondrite: implications for planetary accretion. Earth Planet. Sci. Lett. 80, 201-207] on shock-induced devolatization of the Murchison meteorite showing that carbonaceous chondrites appear to be completely devolatilized at impact velocities greater than 2 km s-1. Both of these results suggest that C incorporation would have been most efficient in the early stages of accretion, and that the primordial C content of the Earth was between 10(24) and 10(25) g C (1-10% efficiency of incorporation). This estimate agrees well with the value of 3-7 x 10(24) g C based on the atmospheric abundance of 36Ar and the chondritic C/36Ar (Marty and Jambon, 1987). Several observations suggest that C likely was incorporated into the Earth's core during accretion. (1) Graphite and carbides are commonly present in iron meteorites, and those iron meteorites with Widmanstatten patterns reflecting the slowest cooling rates (mostly Group I and IIIb) contain the highest C abundances. The C abundance-cooling rate correlation is consistent with dissolution of C into Fe-Ni liquids that segregated to form the cores of the iron meteorite parent bodies. (2) The carbon isotopic composition of graphite in iron meteorites exhibits a uniform value of -5% [Deines, P., Wickman, F.E. 1973. The isotopic composition of 'graphitic' carbon from iron meteorites and some remarks on the troilitic

  18. Electrolytic recycling of a carbonate salt in a process with a dissolution of spent nuclear fuel in a strong alkaline carbonate media

    SciTech Connect

    Kwang-Wook Kim; In-Tae Kim; Seong-Min Kim; Yeon-Hwa Kim; Eil-Hee Lee; Kwang-Yong Jee

    2007-07-01

    A removal of only uranium from spent nuclear fuel with the concepts of a high proliferation-resistance and a minimal generation of waste is helpful for a spent fuel management in view of a volume reduction of the high level radioactive waste generated from the spent fuel treatment. That can be accomplished by a process using a selective oxidative dissolution of the spent fuel in a carbonate solution of high alkalinity. In this work, an electrolytic method for a de-carbonation and a recovery of CO{sub 2} for recycling the used carbonate solution contaminated with some impurity metal ions generated in such a process with a concept of zero-release of waste solution was studied. A carbonate solution generated from such a system was confirmed to be completely recycled within the system, while the impurity ions being separated from the carbonate solution. (authors)

  19. High-pressure densified solid solutions of alkaline earth hexaborides (Ca/Sr, Ca/Ba, Sr/Ba) and their high-temperature thermoelectric properties

    SciTech Connect

    Gürsoy, M.; Takeda, M.; Albert, B.

    2015-01-15

    Solid solutions of alkaline earth hexaborides were synthesized and densified by spark plasma sintering at 100 MPa. The high-temperature thermoelectric properties (Seebeck coefficients, electrical and thermal diffusivities, heat capacities) were measured between room temperature and 1073 K. CaB{sub 6}, SrB{sub 6}, BaB{sub 6} and the ternary hexaborides Ca{sub x}Sr{sub 1−x}B{sub 6}, Ca{sub x}Ba{sub 1−x}B{sub 6}, Sr{sub x}Ba{sub 1−x}B{sub 6} (x = 0.25, 0.5, 0.75) are n-type conducting compounds over the whole compositional and thermal ranges. The values of the figure of merit ZT for CaB{sub 6} (ca. 0.3 at 1073 K) were found to be significantly increased compared to earlier investigations which is attributed to the densification process. - Highlights: • Solid solutions of alkaline earth hexaborides were synthesized. • High-temperature thermoelectric properties of mixed calcium borides are excellent. • Spark plasma source densification results in high ZT values. • Borides are rare-earth free and refractory materials.

  20. Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China.

    PubMed

    Yu, Jie; Qiao, Yu; Jin, Limei; Ma, Chuan; Paterson, Nigel; Sun, Lushi

    2015-12-01

    This study aims to vaporize heavy metals and alkali/alkaline earth metals from two different types of fly ashes by thermal treatment method. Fly ash from a fluidized bed incinerator (HK fly ash) was mixed with one from a grate incinerator (HS fly ash) in various proportions and thermally treated under different temperatures. The melting of HS fly ash was avoided when treated with HK fly ash. Alkali/alkaline earth metals in HS fly ash served as Cl-donors to promote the vaporization of heavy metals during thermal treatment. With temperature increasing from 800 to 900°C, significant amounts of Cl, Na and K were vaporized. Up to 1000°C in air, less than 3% of Cl and Na and less than 5% of K were retained in ash. Under all conditions, Cd can be vaporized effectively. The vaporization of Pb was mildly improved when treated with HS fly ash, while the effect became less pronounced above 900°C. Alkali/alkaline earth metals can promote Cu vaporization by forming copper chlorides. Comparatively, Zn vaporization was low and only slightly improved by HS fly ash. The low vaporization of Zn could be caused by the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4. Under all conditions, less than 20% of Cr was vaporized. In a reductive atmosphere, the vaporization of Cd and Pb were as high as that in oxidative atmosphere. However, the vaporization of Zn was accelerated and that of Cu was hindered because the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4 and copper chloride was depressed in reductive atmosphere.

  1. Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

    USGS Publications Warehouse

    Bullen, T.D.; Bailey, S.W.

    2005-01-01

    Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87Sr/86Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87Sr/86Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87Sr/86Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible

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

    SciTech Connect

    Yedukondalu, N.; Babu, K. Ramesh; Bheemalingam, Ch.; Singh, David J; Vaitheeswaran, G.; Kanchana, V.

    2011-01-01

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

  3. Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

    SciTech Connect

    Gallegos, María V.; Falco, Lorena R.; Peluso, Miguel A.; Sambeth, Jorge E.; Thomas, Horacio J.

    2013-06-15

    Highlights: • Manganese oxides were synthesized using spent batteries as raw materials. • Spent alkaline and zinc–carbon size AA batteries were used. • A biohydrometallurgical process was employed to bio-lixiviate batteries. • Manganese oxides were active in the oxidation of VOCs (ethanol and heptane). - Abstract: Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO{sub 4} solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO{sub x} synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn{sub 2}O{sub 3} in the EMO and the CMO samples, together with some Mn{sup 4+} cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn{sub 3}O{sub 4}. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO{sub 2}. The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  4. Upper ocean carbon cycling inferred from direct pH observations made by profiling floats and estimated alkalinity

    NASA Astrophysics Data System (ADS)

    Johnson, K. S.; Plant, J. N.; Jannasch, H. W.; Coletti, L. J.; Elrod, V.; Sakamoto, C.; Riser, S.

    2015-12-01

    The annual cycle of dissolved inorganic carbon (DIC) is a key tracer of net community production and carbon export in the upper ocean. In particular, the DIC concentration is much less sensitive to air-sea gas exchange, when compared to oxygen, another key tracer of upper ocean metabolism. However, the annual DIC cycle is observed with a seasonal resolution at only a few time-series stations in the open ocean. Here, we consider the annual carbon cycle that has been observed using profiling floats equipped with pH sensors. Deep-Sea DuraFET pH sensors have been deployed on profiling floats for over three years and they can provide temporal and spatial resolution of 5 to 10 days and 5 to 10 m in the upper ocean over multi-year periods. In addition to pH, a second carbon system parameter is required to compute DIC. Total alkalinity can be derived from the float observations of temperature, salinity and oxygen using equations in these variables that are fitted to shipboard observations of alkalinity obtained in the global repeat hydrography programs (e.g., Juranek et al., GRL, doi:10.1029/2011GL048580, 2011), as the relationships should be stable in time in the open ocean. Profiling floats with pH have been deployed from Hawaii Ocean Time-series (HOT) cruises since late 2012 and an array of floats with pH have been deployed since early 2014 in the Southern Ocean as part of the SOCCOM program. The SOCCOM array should grow to nearly 200 floats over the next 5 years. The sensor data was quality controlled and adjusted by comparing observations at 1500 m depth to the deep climatology of pH (derived from DIC and alkalinity) computed with the GLODAP data set. After adjustment, the surface DIC concentrations were calculated from pH and alkalinity. This yields a data set that is used to examine annual net community production in the oligotrophic North Pacific and in the South Pacific near 150 West from 40 South to 65 South.

  5. Sewage sludge pretreatment by microwave irradiation combined with activated carbon fibre at alkaline pH for anaerobic digestion.

    PubMed

    Sun, Dedong; Guo, Sixiao; Ma, Nina; Wang, Guowen; Ma, Chun; Hao, Jun; Xue, Mang; Zhang, Xinxin

    2016-01-01

    This research focuses on the effects of microwave-assisted activated carbon fibre (ACF) (MW-ACF) treatment on sewage sludge at alkaline pH. The disintegration and biodegradability of sewage sludge were studied. It was found that the MW-ACF process at alkaline pH provided a rapid and efficient process to disrupt the microbial cells in the sludge. The results suggested that when irradiated at 800 W MW for 110 s with a dose of 1.0 g ACF/g solid concentration (SS) at pH 10.5, the MW-ACF pretreatment achieved 55% SS disintegration, 23% greater than the value of MW alone (32%). The concentration of total nitrogen, total phosphorus, supernatant soluble chemical oxygen demand, protein, and polysaccharide increased by 60%, 144%, 145%, 74%, and 77%, respectively. An increase in biogas production by 63.7% was achieved after 20 days of anaerobic digestion (AD), compared to the control. The results indicated that the MW-ACF pretreatment process at alkaline pH provides novel sludge management options in disintegration of sewage sludge for further AD.

  6. Alkaline direct ethanol fuel cell performance using alkali-impregnated polyvinyl alcohol/functionalized carbon nano-tube solid electrolytes

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Yi; Lin, Jia-Shiun; Pan, Wen-Han; Shih, Chao-Ming; Liu, Ying-Ling; Lue, Shingjiang Jessie

    2016-01-01

    This study investigates the application of a polyvinyl alcohol (PVA)/functionalized carbon nano-tubes (m-CNTs) composite in alkaline direct ethanol fuel cells (ADEFC). The m-CNTs are functionalized with PVA using the ozone mediation method, and the PVA composite containing the modified CNTs is prepared. Adding m-CNT into the PVA matrix enhances the alkaline uptake and the ionic conductivity of the KOH-doped electrolyte. Meanwhile, the m-CNT-containing membrane exhibited a lower swelling ratio and suppressed ethanol permeability compared to the pristine PVA film. The optimal condition for the ADEFC is determined to be under operation at an anode feed of 3 M ethanol in a 5 M KOH solution (at a flow rate of 5 cm3 min-1) with a cathode feed of moisturized oxygen (with a flow rate of 100 cm3 min-1) and the KOH-doped PVA/m-CNT electrolyte. We achieved a peak power density value of 65 mW cm-2 at 60 °C, which is the highest among the ADEFC literature data and several times higher than the proton-exchange direct ethanol fuel cells using sulfonated membrane electrolytes. Therefore, the KOH-doped PVA/m-CNT electrolyte is a suitable solid electrolyte for ADEFCs and has potential for commercialization in alkaline fuel cell applications.

  7. Molybdenum Carbide-Embedded Nitrogen-Doped Porous Carbon Nanosheets as Electrocatalysts for Water Splitting in Alkaline Media.

    PubMed

    Lu, Chenbao; Tranca, Diana; Zhang, Jian; Rodrı Guez Hernández, Fermı N; Su, Yuezeng; Zhuang, Xiaodong; Zhang, Fan; Seifert, Gotthard; Feng, Xinliang

    2017-03-20

    Molybdenum carbide (Mo2C) based catalysts were found to be one of the most promising electrocatalysts for hydrogen evolution reaction (HER) in acid media in comparison with Pt-based catalysts but were seldom investigated in alkaline media, probably due to the limited active sites, poor conductivity, and high energy barrier for water dissociation. In this work, Mo2C-embedded nitrogen-doped porous carbon nanosheets (Mo2C@2D-NPCs) were successfully achieved with the help of a convenient interfacial strategy. As a HER electrocatalyst in alkaline solution, Mo2C@2D-NPC exhibited an extremely low onset potential of ∼0 mV and a current density of 10 mA cm(-2) at an overpotential of ∼45 mV, which is much lower than the values of most reported HER electrocatalysts and comparable to the noble metal catalyst Pt. In addition, the Tafel slope and the exchange current density of Mo2C@2D-NPC were 46 mV decade(-1) and 1.14 × 10(-3) A cm(-2), respectively, outperforming the state-of-the-art metal-carbide-based electrocatalysts in alkaline media. Such excellent HER activity was attributed to the rich Mo2C/NPC heterostructures and synergistic contribution of nitrogen doping, outstanding conductivity of graphene, and abundant active sites at the heterostructures.

  8. The sulphate-reduction alkalinity pump tested

    NASA Astrophysics Data System (ADS)

    Meister, Patrick; Petrishcheva, Elena

    2016-04-01

    Carbonate precipitation has been suggested to be induced by alkalinity increase during sulphate reduction under anoxic conditions. This mechanism may explain the formation of carbonate deposits in shallow marine environments, either within a redox stratified sediment inhabited by phototrophic microbial mats or in shallow water within the photic zone where sulphidic water is upwelling onto the shelf. The alkalinity pump may work as long as the sulphide is not reoxidized to sulphate, a process that would acidify the surrounding. The alkalinity effect of sulphate reduction was recently tested by Aloisi (2008) for microbial mats using a model approach. He found that sulphate reduction does not significantly increase or even decrease carbonate saturation and is unlikely to have played a significant role through Earth history. The model considers many environmental factors, including the effect of carbonate precipitation itself on the carbonate equilbrium and on the alkalinity. We used a modified version of Aloisi's (2008) model to simulate the saturation states of aragonite, calcite and dolomite without the effects of carbonate precipitation. This is necessary to evaluate the effect of microbial metabolisms exclusively on carbonate saturation, since carbonate precipitation is only the consequence, but not the cause of oversaturation. First results show that the saturation state is increased in the zone of phototrophic CO2 uptake. In contrast, the saturation state is strongly decreased in the zone where dissolved oxygen overlaps with dissolved sulphide. Aerobic sulphide oxidation consumes most of the HS- and dissipates most of the alkalinity produced in the sulphate reduction zone below. Hence, our results are consistent with the findings of Aloisi (2008), and they even more clearly show that sulphate reduction does not induce carbonate precipitation nor contributes to carbonate precipitation in combination with phototrophic CO2 uptake. The alkalinity effect of sulphate

  9. Determination of hydroxide and carbonate contents of alkaline electrolytes containing zinc

    NASA Technical Reports Server (NTRS)

    Otterson, D. A.

    1975-01-01

    A method to prevent zinc interference with the titration of OH- and CO3-2 ions in alkaline electrolytes with standard acid is presented. The Ba-EDTA complex was tested and shown to prevent zinc interference with acid-base titrations without introducing other types of interference. Theoretical considerations indicate that this method can be used to prevent interference by other metals.

  10. 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.

    PubMed

    Kim, Hugh I; Beauchamp, J L

    2008-01-30

    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.

  11. Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

    PubMed

    Liu, Yong-Qiang; Yu, Hong

    2017-02-20

    A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg(2+) , Ca(2+) , and Sr(2+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg(2+) , Ca(2+) , and Sr(2+) were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg(2+) , Ca(2+) , and Sr(2+) within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded.

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

    PubMed

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

    2016-04-05

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  14. The adsorption of rare earth ions using carbonized polydopamine nano shells

    SciTech Connect

    Sun, Xiaoqi; Luo, Huimin; Mahurin, Shannon Mark; Dai, Sheng; Liu, Rui; Hou, Xisen; Dai, Sheng

    2016-01-07

    Herein we report the structure effects of nano carbon shells prepared by carbonized polydopamine for rare earth elements (REEs) adsorption for the first time. The solid carbon sphere, 60 nm carbon shell and 500 nm carbon shell were prepared and investigated for adsorption and desorption of REEs. The adsorption of carbon shells for REEs was found to be better than the solid carbon sphere. The effect of acidities on the adsorption and desorption properties was discussed in this study. The good adsorption performance of carbon shells can be attributed to their porous structure, large specific surface area, amine group and carbonyl group of dopamine.

  15. The adsorption of rare earth ions using carbonized polydopamine nano shells

    DOE PAGES

    Sun, Xiaoqi; Luo, Huimin; Mahurin, Shannon Mark; ...

    2016-01-07

    Herein we report the structure effects of nano carbon shells prepared by carbonized polydopamine for rare earth elements (REEs) adsorption for the first time. The solid carbon sphere, 60 nm carbon shell and 500 nm carbon shell were prepared and investigated for adsorption and desorption of REEs. The adsorption of carbon shells for REEs was found to be better than the solid carbon sphere. The effect of acidities on the adsorption and desorption properties was discussed in this study. The good adsorption performance of carbon shells can be attributed to their porous structure, large specific surface area, amine group andmore » carbonyl group of dopamine.« less

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  17. Speciation of dissolved silicates in natural waters containing alkaline and alkaline-earth ions. A case study--waters from arid lands (North West China).

    PubMed

    Tanaka, Miho; Takahashi, Kazuya; Sahoo, Yu Vin

    2004-02-01

    The concentration of silica in water samples from the desert area of Xinjiang, N. W. China, has been measured by colorimetry with ammonium molybdate. The observed pattern of dependence of the concentration of silica on the concentration of sodium ion (Na(+)) in the water samples is consistent with the pattern obtained by experiments on in-vitro dissolution of silica gel in sodium chloride (NaCl) solution. This indicates that the dissolution of silica in the hydrologic system in this area depends on the concentration of Na(+). Calcium ion (Ca(2+)), which is known to play an important role on the dissolution of silica on the basis of in-vitro experiments, was observed to take little part in the dissolution of silica in actual natural water samples. This implies that the Ca(2+) is bound to the hydrogen carbonate anion or that the Ca(2+) content of natural water containing salts is very low, owing to precipitation. In these samples silicate-Na(+) was identified as the dissolution species of silica; it was also ascertained that Ca(2+) did not form complexes with silicate species. These observations resulted from direct identification of dissolved chemical species by use of FAB-MS (fast atom bombardment mass spectrometry). The research indicates that in water samples in this critically arid region the concentration of "dissolved" silica is basically determined by the concentration of Na(+), indicative of pure inorganic conditions in the desert area of Xinjiang, N.W. China.

  18. The CarbonSat Earth Explorer 8 candidate mission: Error analysis for carbon dioxide and methane

    NASA Astrophysics Data System (ADS)

    Buchwitz, Michael; Bovensmann, Heinrich; Reuter, Maximilian; Gerilowski, Konstantin; Meijer, Yasjka; Sierk, Bernd; Caron, Jerome; Loescher, Armin; Ingmann, Paul; Burrows, John P.

    2015-04-01

    CarbonSat is one of two candidate missions for ESA's Earth Explorer 8 (EE8) satellite to be launched around 2022. The main goal of CarbonSat is to advance our knowledge on the natural and man-made sources and sinks of the two most important anthropogenic greenhouse gases (GHGs) carbon dioxide (CO2) and methane (CH4) on various temporal and spatial scales (e.g., regional, city and point source scale), as well as related climate feedbacks. CarbonSat will be the first satellite mission optimised to detect emission hot spots of CO2 (e.g., cities, industrialised areas, power plants) and CH4 (e.g., oil and gas fields) and to quantify their emissions. Furthermore, CarbonSat will deliver a number of important by-products such as Vegetation Chlorophyll Fluorescence (VCF, also called Solar Induced Fluorescence (SIF)) at 755 nm. These applications require appropriate retrieval algorithms which are currently being optimized and used for error analysis. The status of this error analysis will be presented based on the latest version of the CO2 and CH4 retrieval algorithm and taking the current instrument specification into account. An overview will be presented focusing on nadir observations over land. Focus will be on specific issues such as errors of the CO2 and CH4 products due to residual polarization related errors and errors related to inhomogeneous ground scenes.

  19. Effect of different carbon sources on decolourisation of an industrial textile dye under alkaline-saline conditions.

    PubMed

    Ottoni, Cristiane; Lima, Luis; Santos, Cledir; Lima, Nelson

    2014-01-01

    White-rot fungal strains of Trametes versicolor and Phanerochaete chrysosporium were selected to study the decolourisation of the textile dye, Reactive Black 5, under alkaline-saline conditions. Free and immobilised T. versicolor cells showed 100 % decolourisation in the growth medium supplemented with 15 g l(-1) NaCl, pH 9.5 at 30 °C in liquid batch culture. Continuous culture experiments were performed in a fixed-bed reactor using free and immobilised T. versicolor cells and allowed 85-100 % dye decolourisation. The immobilisation conditions for the biomass and the additional supply of carbon sources improved the decolourisation performance during a long-term trial of 40 days. Lignin peroxidase, laccase and glyoxal oxidase activities were detected during the experiments. The laccase activity varied depending on carbon source utilized and glycerol-enhanced laccase activity compared to sucrose during extended growth.

  20. Recovery of manganese oxides from spent alkaline and zinc-carbon batteries. An application as catalysts for VOCs elimination.

    PubMed

    Gallegos, María V; Falco, Lorena R; Peluso, Miguel A; Sambeth, Jorge E; Thomas, Horacio J

    2013-06-01

    Manganese, in the form of oxide, was recovered from spent alkaline and zinc-carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO4 solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnOx synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn2O3 in the EMO and the CMO samples, together with some Mn(4+) cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn3O4. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200°C, while heptane requires more than 400°C. The CMO has the highest oxide selectivity to CO2. The results show that manganese oxides obtained using spent alkaline and zinc-carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  1. Alkaline earth imidazolate coordination polymers by solvent free melt synthesis as potential host lattices for rare earth photoluminescence: (x)(∞)[AE(Im)2(ImH)(2-3)], Mg, Ca, Sr, Ba, x = 1-2.

    PubMed

    Zurawski, Alexander; Rybak, J-Christoph; Meyer, Larissa V; Matthes, Philipp R; Stepanenko, Vladimir; Dannenbauer, Nicole; Würthner, Frank; Müller-Buschbaum, Klaus

    2012-04-14

    The series of alkaline earth elements magnesium, calcium, strontium and barium yields single crystalline imidazolate coordination polymers by reactions of the metals with a melt of 1H-imidazole: (1)(∞)[Mg(Im)(2)(ImH)(3)] (1), (2)(∞)[AE(Im)(2)(ImH)(2)], AE = Ca (2), Sr (3), and (1)(∞)[Ba(Im)(2)(ImH)(2)] (4). No additional solvents were used for the reactions. Co-doping experiments by addition of the rare earth elements cerium, europium and terbium were carried out. They indicate (2)(∞)[Sr(Im)(2)(ImH)(2)] as a possible host lattice for cerium(III) photoluminescence showing a blue emission and thus a novel blue emitting hybrid material phosphor 3:Ce(3+). Co-doping with europium and terbium is also possible but resulted in formation of (3)(∞)[Sr(Im)(2)]:Ln, Ln = Eu and Tb (5), with both exhibiting green emission of either Eu(2+) or Tb(3+). The other alkaline earth elements do not show acceptance of the rare earth ions investigated and a different structural chemistry. For magnesium and barium one-dimensional strand structures are observed whereas calcium and strontium give two-dimensional network structures. Combined with an increase of the ionic radii of AE(2+) the coordinative demand is also increasing from Mg(2+) to Ba(2+), reflected by four different crystal structures for the four elements Mg, Ca, Sr, Ba in 1-4. Different linkages of the imidazolate ligands result in a change from complete σ-N coordination in 1 to additional η(5)-π coordination in 4. The success of co-doping with different lanthanide ions is based on a match in the chemical behaviour and cationic radii. The use of strontium for host lattices with imidazole is a rare example in coordination chemistry of co-doping with small amounts of luminescence centers and successfully reduces the amount of high price rare earth elements in hybrid materials while maintaining the properties. All compounds are examples of pure N-coordinated coordination polymers of the alkaline earth metals and were

  2. Global Distribution of Total Inorganic Carbon and Total Alkalinity below the Deepest Winter Mixed Layer Depths

    SciTech Connect

    Goyet, C.; Healy, R.; Ryan, J.; Kozyr, A.

    2000-05-01

    Modeling the global ocean-atmosphere carbon dioxide system is becoming increasingly important to greenhouse gas policy. These models require initialization with realistic three-dimensional (3-D) oceanic carbon fields. This report presents an approach to establishing these initial conditions from an extensive global database of ocean carbon dioxide (CO{sub 2}) system measurements and well-developed interpolation methods.

  3. Earth's Early Biosphere and the Biogeochemical Carbon Cycle

    NASA Technical Reports Server (NTRS)

    DesMarais, David

    2004-01-01

    Our biosphere has altered the global environment principally by influencing the chemistry of those elements most important for life, e g., C, N, S, O, P and transition metals (e.g., Fe and Mn). The coupling of oxygenic photosynthesis with the burial in sediments of photosynthetic organic matter, and with the escape of H2 to space, has increased the state of oxidation of the Oceans and atmosphere. It has also created highly reduced conditions within sedimentary rocks that have also extensively affected the geochemistry of several elements. The decline of volcanism during Earth's history reduced the flow of reduced chemical species that reacted with photosynthetically produced O2. The long-term net accumulation of photosynthetic O2 via biogeochemical processes has profoundly influenced our atmosphere and biosphere, as evidenced by the O2 levels required for algae, multicellular life and certain modem aerobic bacteria to exist. When our biosphere developed photosynthesis, it tapped into an energy resource that was much larger than the energy available from oxidation-reduction reactions associated with weathering and hydrothermal activity. Today, hydrothermal sources deliver globally (0.13-1.1)x10(exp l2) mol yr(sup -1) of reduced S, Fe(2+), Mn(2+), H2 and CH4; this is estimated to sustain at most about (0.2-2)xl0(exp 12)mol C yr(sup -1) of organic carbon production by chemautotrophic microorganisms. In contrast, global photosynthetic productivity is estimated to be 9000x10(exp 12) mol C yr(sup -1). Thus, even though global thermal fluxes were greater in the distant geologic past than today, the onset of oxygenic photosynthesis probably increased global organic productivity by some two or more orders of magnitude. This enormous productivity materialized principally because oxygenic photosynthesizers unleashed a virtually unlimited supply of reduced H that forever freed life from its sole dependence upon abiotic sources of reducing power such as hydrothermal emanations

  4. Carbon and sulfur budget of the silicate Earth explained by accretion of differentiated planetary embryos

    NASA Astrophysics Data System (ADS)

    Li, Yuan; Dasgupta, Rajdeep; Tsuno, Kyusei; Monteleone, Brian; Shimizu, Nobumichi

    2016-10-01

    The abundances of volatile elements in the Earth's mantle have been attributed to the delivery of volatile-rich material after the main phase of accretion. However, no known meteorites could deliver the volatile elements, such as carbon, nitrogen, hydrogen and sulfur, at the relative abundances observed for the silicate Earth. Alternatively, Earth could have acquired its volatile inventory during accretion and differentiation, but the fate of volatile elements during core formation is known only for a limited set of conditions. Here we present constraints from laboratory experiments on the partitioning of carbon and sulfur between metallic cores and silicate mantles under conditions relevant for rocky planetary bodies. We find that carbon remains more siderophile than sulfur over a range of oxygen fugacities; however, our experiments suggest that in reduced or sulfur-rich bodies, carbon is expelled from the segregating core. Combined with previous constraints, we propose that the ratio of carbon to sulfur in the silicate Earth could have been established by differentiation of a planetary embryo that was then accreted to the proto-Earth. We suggest that the accretion of a Mercury-like (reduced) or a sulfur-rich (oxidized) differentiated body--in which carbon has been preferentially partitioned into the mantle--may explain the Earth's carbon and sulfur budgets.

  5. Carbon dioxide capture process with regenerable sorbents

    DOEpatents

    Pennline, Henry W.; Hoffman, James S.

    2002-05-14

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

  6. Carbon Dioxide Earth Degassing and Structural Setting in Italy

    NASA Astrophysics Data System (ADS)

    Chiodini, G.

    2005-12-01

    A modelling of the water-rock-gas interaction in the groundwaters circulating in the aquifers of central southern Italy has shown that most of the dissolved inorganic carbon (DIC) derives from deep carbon sources with an isotopic composition in the range of the CO2 emitted in Italy from active volcanoes, geothermal fields, and the many cold gas emissions located in the region. This suggests that a common, deep and inorganic source of CO2 is active in Italy as highlighted by the regional map of CO2 degassing that has been elaborated on the base of the deeply derived carbon dissolved in the groundwater. The map shows that two large degassing structures affect the Tyrrhenian side of the Italian peninsula. The northern degassing structure (TRDS, Tuscan Roman degassing structure) includes Tuscany, Latium and part of Umbria regions (~30000 km2) and releases ~ 1.4 × 1011 mol/year of deeply derived CO2. The southern degassing structure (CDS, Campanian degassing structure) occupies the Campania region (~ 10000 km2) and releases ~ 0.7 × 1011 mol/year of deeply derived CO2. The total CO2 released by TRDS and CDS (~ 2.1 × 1011) is globally significant, being ~ 10 % of the estimated present-day total CO2 discharge from sub aerial volcanoes of the Earth. The central parts of both TRDS and CDS coincide with the quaternary volcanism of Italy and with regions of high heat flow where were drilled many geothermal systems containing fluids saturated in CO2, i.e. with dissolved CO2 concentrations correspondent to the saturation values at the pressures (depths) of the geothermal reservoirs. These geothermal reservoirs represent the shallowest storage zone of the CO2 of deep provenance before the expulsion of the gas either directly in the atmosphere trough the numerous natural gas emissions of the area, or as dissolved gas species in the main aquifers. It is our opinion that the two degassing structures are the surface expression of two large plumes of mantle fluids which intrude

  7. The Formation of Sodium Stannate from Mineral Cassiterite by the Alkaline Decomposition Process with Sodium Carbonate (Na2CO3)

    NASA Astrophysics Data System (ADS)

    Andriyah, L.; Lalasari, L. H.; Manaf, A.

    2017-02-01

    Extraction of cassiterite using alkaline decomposition of sodium carbonate (Na2CO3) has been studied. Cassiterite (SnO2) is a mineral ore that contains tin (Sn) about 57.82 wt% and impurities like quartz, ilmenite, monazite, rutile and zircon. The initial step for the process was to remove the impurities in cassiterite through washing and separation by a high magnetic separator (HTS). The aim of this research is to increase the added value of cassiterite from local area Indonesia that using alkaline decomposition to form sodium stannate (Na2SnO3). The result shows that cassiterite from Indonesia can form sodium stannate (Na2SnO3) which soluble with water in the leaching process. The longer the time for decomposition, the more phases of sodium stannate that will be formed. Optimum result reached when the decomposition process was done in 850 °C for 4 hours with a mole ratio Na2CO3 to cassiterite 3:2. High Score Plus (HSP) was used in this research to analyze the mass of sodium stannate (Na2SnO3). HSP analysis showed that mass of sodium stannate (Na2SnO3) is 70.3 wt%.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  9. Low pressure ion chromatography with a low cost paired emitter-detector diode based detector for the determination of alkaline earth metals in water samples.

    PubMed

    Barron, Leon; Nesterenko, Pavel N; Diamond, Dermot; O'Toole, Martina; Lau, King Tong; Paull, Brett

    2006-09-01

    The use of a low pressure ion chromatograph based upon short (25 mm x 4.6 mm) surfactant coated monolithic columns and a low cost paired emitter-detector diode (PEDD) based detector, for the determination of alkaline earth metals in aqueous matrices is presented. The system was applied to the separation of magnesium, calcium, strontium and barium in less than 7min using a 0.15M KCl mobile phase at pH 3, with post-column reaction detection at 570 nm using o-cresolphthalein complexone. A comparison of the performance of the PEDD detector with a standard laboratory absorbance detector is shown, with limits of detection for magnesium and calcium using the low cost PEDD detector equal to 0.16 and 0.23 mg L(-1), respectively. Finally, the developed system was used for the determination of calcium and magnesium in a commercial spring water sample.

  10. Alkaline earth metal-based metal-organic framework: hydrothermal synthesis, X-ray structure and heterogeneously catalyzed Claisen-Schmidt reaction.

    PubMed

    Saha, Debraj; Maity, Tanmoy; Koner, Subratanath

    2014-09-14

    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.

  11. Calculation of thermodynamic potentials with the inclusion of fractional occupation numbers and investigation of FCC-BCC structural phase transitions in alkaline-earth metals

    NASA Astrophysics Data System (ADS)

    Pozhivatenko, V. V.

    2013-10-01

    The smearing near the Fermi level has been taken into account in the calculations of the thermodynamic characteristics of metals in order to improve the convergence of the performed calculations and to increase the quality of the obtained results. The choice of the smearing parameter usually has not been explained, although the results of the calculations differ significantly for different values of this parameter. Possible schemes for calculating the thermodynamic potentials with the inclusion of the smearing parameter and additional parameters of the volume and energy shifts have been considered. The influence of these parameters on the calculations of the thermodynamic properties of alkaline-earth metals under pressure and on the description of the structural phase transition has been analyzed.

  12. The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-aminophenyl)arsonic acid.

    PubMed

    Smith, Graham; Wermuth, Urs D

    2017-01-01

    (4-Aminophenyl)arsonic acid (p-arsanilic acid) is used as an antihelminth in veterinary applications and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl. Examples of complexes with this acid are rare. The structures of the alkaline earth metal (Mg, Ca, Sr and Ba) complexes with (4-aminophenyl)arsonic acid (p-arsanilic acid) have been determined, viz. hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate, [Mg(H2O)6](C6H7AsNO3)·4H2O, (I), catena-poly[[[diaquacalcium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ(2)O:O']-[diaquacalcium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ(2)O:O

  13. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS{sub 2}

    SciTech Connect

    Li, X. D.; Fang, Y. M.; Wu, S. Q. E-mail: wsq@xmu.edu.cn; Zhu, Z. Z. E-mail: wsq@xmu.edu.cn

    2015-05-15

    Single adsorption of different atoms on pristine two-dimensional monolayer MoS{sub 2} 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 MoS{sub 2}. Additionally, local or long-range magnetic moments of two-dimensional MoS{sub 2} sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS{sub 2} monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  15. Determining How Atmospheric Carbon Dioxide Concentrations Have Changed during the History of the Earth

    ERIC Educational Resources Information Center

    Badger, Marcus P. S.; Pancost, Richard D.; Harrison, Timothy G.

    2011-01-01

    The reconstruction of ancient atmospheric carbon dioxide concentrations is essential to understanding the history of the Earth and life. It is also an important guide to identifying the sensitivity of the Earth system to this greenhouse gas and, therefore, constraining its future impact on climate. However, determining the concentration of…

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

    SciTech Connect

    Xia Zhengqiang; Chen Sanping; Wei Qing; Qiao Chengfang

    2011-07-15

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

  17. Carbon supported Pd-Ni-P nanoalloy as an efficient catalyst for ethanol electro-oxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Ye; Shi, Fei-Fei; Yang, Yao-Yue; Cai, Wen-Bin

    2013-12-01

    Carbon-supported well-dispersed Pd-Ni-P ternary catalyst targeted for ethanol oxidation reaction (EOR) in alkaline media is synthesized in a simple aqueous bath containing Pd(II) and Ni(II) salts with sodium hypophosphite as the reducing agent and the source for P and sodium citrate as the complexing agent. XRD analysis on the as-prepared Pd-Ni-P/C reveals that Ni shrinks while P expands the Pd lattice structure, and XPS measurement suggests different electronic effects of the two alloying elements on Pd. Cyclic voltammetry and chronoamperometry indicate that the Pd-Ni-P/C presents a remarkably higher electrocatalytic activity than the state-of-the-art Pd/C, Pd-P/C and Pd-Ni/C catalysts. This may be ascribed to the unique electronic, geometric and bifunctional effects involved in this ternary nanoalloy.

  18. High electrocatalytic performance of nitrogen-doped carbon nanofiber-supported nickel oxide nanocomposite for methanol oxidation in alkaline medium

    NASA Astrophysics Data System (ADS)

    Al-Enizi, Abdullah M.; Elzatahry, Ahmed A.; Abdullah, Aboubakr M.; Vinu, Ajayan; Iwai, Hideo; Al-Deyab, Salem S.

    2017-04-01

    Nitrogen-Doped Carbon Nanofiber (N-CNF)-supported NiO composite was prepared by electrospinning a sol-gel mixture of graphene and polyaniline (PANi) with aqueous solutions of Polyvinylpyrrolidone (PVP) followed by a high-temperature annealing process. The electrospun was stabilized for 2 h at 280 °C, carbonized for 5 h at 1200 °C then loaded by 10% NiO. The electrocatalytic activities of the produced nanocomposite have been studied using cyclic voltammetry, and chronoamperometry. Also, N-CNF was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and scanning-electron microscopy (SEM). The obtained N-doped carbon nanofiber was found to have a nitrogen content of 2.6 atomic% with a diameter range of (140-160) nm, and a surface area (393.3 m2 g-1). In addition, it showed a high electrocatalytic behavior towards methanol oxidation reaction in alkaline medium and high stability and resistivity to the adsorption of intermediates.

  19. Evaluation of metal oxide and carbonate nanoparticle stability in soybean oil: Implications for controlled release of alkalinity during subsurface remediation

    NASA Astrophysics Data System (ADS)

    Ramsburg, C. A.; Leach, O. I.; Sebik, J.; Muller, K.

    2011-12-01

    Traditional methods for adjusting groundwater pH rely on injection of aqueous solutes and therefore, amendment distribution is reliant upon aqueous phase flow and transport. This reliance can limit mixing and sustention of amendments within the treatment zone. Oil-in-water emulsions offer an alternative for amendment delivery - one that has potential to enhance control of the distribution and release of buffering agents within the subsurface. Focus here is placed on using metal oxide and carbonate nanoparticles to release alkalinity from soybean oil, a common dispersed phase within emulsions designed to support remediation activities. Batch reactor systems were employed to examine the influence of dispersed phase composition on particle stability and solubility. The stability of uncoated MgO and CaCO3 particles in unmodified soybean oil was explored in a series of sedimentation studies conducted at solid loadings of 0.05, 0.1, and 0.2% mass. Three nominal sizes of MgO particles were examined (20, 50, and 100 nm) and one CaCO3 particle size (60 nm). Results from sedimentation studies conducted over four hours suggest that the viscosity of the soybean oil imparts a kinetic stability, for all sizes of the uncoated MgO and CaCO3 nanoparticles, which is sufficient time for particle encapsulation within oil-in-water emulsions. Based upon these results, the sedimentation of the 50 nm and 100 nm MgO, and 60 nm CaCO3 particles was assessed over longer durations (≥72 hr). Results from these stability tests suggest that the 50 nm and 100 nm MgO particles have greater kinetic stability than the 60 nm CaCO3. Batch studies were also used to assess the influence of n-butanol, a co-solvent hypothesized to aid in controlling the rate of alkalinity release, on phase behavior and metal (Mg2+ and Ca2+) solubility. Phase behavior studies suggest that n-butanol has a limited region of miscibility within the soybean oil-water system. Use of n-butanol and water within this region of

  20. Calcium Carbonate Nucleation in an Alkaline Lake Surface Water, Pyramid Lake, Nevada, USA

    USGS Publications Warehouse

    Reddy, M.M.; Hoch, A.

    2012-01-01

    Calcium concentration and calcite supersaturation (??) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has ?? values of 10-16. Notwithstanding high ??, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM (n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean ?? at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water ??. Calcium concentration and ?? regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower ?? than filtered samples. Calcium concentration and ?? at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (??) + B. The best fit rate equation "Rate (?? mM/?? min) = -0.0026 ?? + 0.0175 (r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, ?? at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors. ?? 2011 U.S. Government.

  1. Calcium carbonate nucleation in an alkaline lake surface water, Pyramid Lake, Nevada, USA

    USGS Publications Warehouse

    Reddy, Michael M.; Hoch, Anthony

    2012-01-01

    Calcium concentration and calcite supersaturation (Ω) needed for calcium carbonate nucleation and crystal growth in Pyramid Lake (PL) surface water were determined during August of 1997, 2000, and 2001. PL surface water has Ω values of 10-16. Notwithstanding high Ω, calcium carbonate growth did not occur on aragonite single crystals suspended PL surface water for several months. However, calcium solution addition to PL surface-water samples caused reproducible calcium carbonate mineral nucleation and crystal growth. Mean PL surface-water calcium concentration at nucleation was 2.33 mM (n = 10), a value about nine times higher than the ambient PL surface-water calcium concentration (0.26 mM); mean Ω at nucleation (109 with a standard deviation of 8) is about eight times the PL surface-water Ω. Calcium concentration and Ω regulated the calcium carbonate formation in PL nucleation experiments and surface water. Unfiltered samples nucleated at lower Ω than filtered samples. Calcium concentration and Ω at nucleation for experiments in the presence of added particles were within one standard deviation of the mean for all samples. Calcium carbonate formation rates followed a simple rate expression of the form, rate (mM/min) = A (Ω) + B. The best fit rate equation "Rate (Δ mM/Δ min) = -0.0026 Ω + 0.0175 (r = 0.904, n = 10)" was statistically significant at greater than the 0.01 confidence level and gives, after rearrangement, Ω at zero rate of 6.7. Nucleation in PL surface water and morphology of calcium carbonate particles formed in PL nucleation experiments and in PL surface-water samples suggest crystal growth inhibition by multiple substances present in PL surface water mediates PL calcium carbonate formation, but there is insufficient information to determine the chemical nature of all inhibitors.

  2. Rapid hydrolysis of model phosphate diesters by alkaline-earth cations in aqueous DMSO: speciation and kinetics.

    PubMed

    Taran, Olga; Medrano, Felipe; Yatsimirsky, Anatoly K

    2008-12-14

    Kinetics of the cleavage of two phosphate diesters, bis(4-nitrophenyl) phosphate and 2-hydroxypropyl 4-nitrophenyl phosphate and a triester, 4-nitrophenyl diphenyl phosphate, in the presence of Mg(II), Ca(II) and Sr(II) were studied in 90% vol. DMSO at 37 degrees C. The alkaline hydrolysis of the triester was inhibited by all cations, but with both phosphodiesters strong catalytic effects were observed. Potentiometric titrations of metal perchlorates by Bu4N(OH) revealed formation of M2(OH)3+, M(OH)+, M(OH)2 and M2(OH)5- species. Rate constants for phosphodiester cleavage by individual species were obtained from analysis of rate-concentration profiles. Observed first-order rate constants in the presence of 1-2 mM Mg(II) or Ca(II) in neutral and weakly basic solutions were 10(8)-10(11) times higher than those for background hydrolysis at the same pH while in water additions of up to 50 mM metal produced <100-fold accelerations. Possible structures of DMSO solvated catalyst-substrate complexes were modeled by DFT calculations with Mg(II). The increased catalytic activity in 90% DMSO is attributed to stronger association of hydroxide ions and anionic phosphodiesters with metal ions and to preferable solvation of cations by DMSO, which creates favorable for reaction anhydrous microenvironment in the coordination sphere of the catalyst.

  3. Microbial fouling and corrosion of carbon steel in deep anoxic alkaline groundwater.

    PubMed

    Rajala, Pauliina; Bomberg, Malin; Vepsäläinen, Mikko; Carpén, Leena

    2017-02-01

    Understanding the corrosion of carbon steel materials of low and intermediate level radioactive waste under repository conditions is crucial to ensure the safe storage of radioactive contaminated materials. The waste will be in contact with the concrete of repository silos and storage containers, and eventually with groundwater. In this study, the corrosion of carbon steel under repository conditions as well as the microbial community forming biofilm on the carbon steel samples, consisting of bacteria, archaea, and fungi, was studied over a period of three years in a groundwater environment with and without inserted concrete. The number of biofilm forming bacteria and archaea was 1,000-fold lower, with corrosion rates 620-times lower in the presence of concrete compared to the natural groundwater environment. However, localized corrosion was detected in the concrete-groundwater environment indicating the presence of local microenvironments where the conditions for pitting corrosion were favorable.

  4. Climatic consequences of very high carbon dioxide levels in the earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, James F.; Ackerman, Thomas P.

    1986-01-01

    The possible consequences of very high carbon dioxide concentrations in the earth's early atmosphere have been investigated with a radiative-convective climate model. The early atmosphere would apparently have been stable against the onset of a runaway greenhouse (that is, the complete evaporation of the oceans) for carbon dioxide pressures up to at least 100 bars. A 10- to 20-bar carbon dioxide atmosphere, such as may have existed during the first several hundred million years of the earth's history, would have had a surface temperature of approximately 85 to 110 C. The early stratosphere should have been dry, thereby precluding the possibility of an oxygenic prebiotic atmosphere caused by photodissociation of water vapor followed by escape of hydrogen to space. Earth's present atmosphere also appears to be stable against a carbon dioxide-induced runaway greenhouse.

  5. Climatic consequences of very high carbon dioxide levels in the earth's early atmosphere.

    PubMed

    Kasting, J F; Ackerman, T P

    1986-12-12

    The possible consequences of very high carbon dioxide concentrations in the earth's early atmosphere have been investigated with a radiative-convective climate model. The early atmosphere would apparently have been stable against the onset of a runaway greenhouse (that is, the complete evaporation of the oceans) for carbon dioxide pressures up to at least 100 bars. A 10- to 20-bar carbon dioxide atmosphere, such as may have existed during the first several hundred million years of the earth's history, would have had a surface temperature of approximately 85 degrees to 110 degrees C. The early stratosphere should have been dry, thereby precluding the possibility of an oxygenic prebiotic atmosphere caused by photodissociation of water vapor followed by escape of hydrogen to space. Earth's present atmosphere also appears to be stable against a carbon dioxide-induced runaway greenhouse.

  6. Ni/Pd-Decorated Carbon NFs as an Efficient Electrocatalyst for Methanol Oxidation in Alkaline Medium

    NASA Astrophysics Data System (ADS)

    Mohamed, Ibrahim M. A.; Khalil, Khalil Abdelrazek; Mousa, Hamouda M.; Barakat, Nasser A. M.

    2017-01-01

    In this study, Ni/Pd-decorated carbon nanofibers (NFs) were fabricated as an electrocatalyst for methanol oxidation. These NFs were synthesized based on carbonization of poly(vinyl alcohol), which has high carbon content compared to many polymers used to prepare carbon NFs. Typically, calcination of an electrospun mat composed of nickel acetate, palladium acetate, and poly(vinyl alcohol) can produce Ni/Pd-doped carbon NFs. The introduced NFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy, line TEM energy dispersive x-ray spectrometry, field emission scanning electron microscopy, and x-ray powder diffraction. These physicochemical characterizations are acceptable tools to investigate the crystallinity and chemistry of the fabricated Ni/Pd-carbon NFs. Accordingly, the prepared NFs were tested to enhance the economic and catalytic behavior of methanol electrooxidation. Experimentally, the obtained onset potential was small compared to many reported materials; 0.32 V (versus Ag/AgCl as a reference electrode). At the same time, the current density changed from 5.08 mA/cm2 in free methanol at 0.6 V to 12.68 mA/cm2 in 0.1 mol/L methanol, which can be attributed to the MeOH oxidation. Compared to nanoparticles, the NFs have a distinct effect on the electrocatalytic performance of material due to the effect of the one-dimensional structure, which facilitates the electron transfer. Overall, the presented work opens a new way for non-precious one-dimensional nanostructured catalysts for direct methanol fuel cell technology.

  7. Crystallization behavior and kinetics of calcium carbonate in highly alkaline and supersaturated system

    NASA Astrophysics Data System (ADS)

    Zhu, Ganyu; Li, Huiquan; Li, Shaopeng; Hou, Xinjuan; Xu, Dehua; Lin, Rongyi; Tang, Qing

    2015-10-01

    In causticization process of Na2CO3-Ca(OH)2, which is a liquid-solid system with high alkalinity and supersaturation, agglomeration and morphology instability of CaCO3 crystal have greatly limited its application. To deeply investigate the internal relations between crystallization process and condition control in this system, crystallization kinetics was conducted in a continuously operated crystallizer. The kinetic equations of growth rate, nucleation rate and agglomeration kernel were correlated in terms of power law kinetic expressions based on the agglomeration population balance equation. Magma density and mean residence time exert a considerable effect on crystal growth, nucleation, and agglomeration. Crystal growth and nucleation are surface-integration-limited and size-limited, respectively. Agglomeration increases with increasing mean residence time, but the increase in magma density break down the agglomerates by frequent and energetic collisions. Through the study, crystallization behavior of CaCO3 in causticization system was revealed, and the particle size and morphology were efficiently predicted and controlled. These results can provide a basis for understanding the design of the reactor.

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

    SciTech Connect

    Nadeau, S.L.; Epstein, S.; Stolper, E.

    1999-06-01

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

  9. Effect of alkaline earth oxides on the formation of surface microphases that protect strontium titanate from reduction

    SciTech Connect

    Aksenova, L.A.; Kostikov, Yu.P.; Leonov, A.I.; Rotenberg, B.A.; Strykanov, V.S.

    1986-08-20

    The authors studied the effect of addition of strontium oxide, barium oxide, and calcium oxide on the formation of surface microphases and the reduction of strontium titanate. The materials were strontium carbonate, barium carbonate, and calcium carbonate (analytical grade) and titanium dioxide (pure grade). X-ray diffraction analysis was carried out on a DRON-2.0 diffractometer (CuK/sub ..cap alpha../, Ni filter). The surface layers were studies in an electron spectrometer by ESCA (exciting irradiation Al/sub K..cap alpha../; bond energy in standard gold sample Au/sub 4/f/sub 1/2/ = 84.1 eV; depth of layer 8 nm). Samplers were prepared according to the usual ceramic technology. It was found that protection from reduction of strontium titanate that is doped with calcium, strontium, or barium oxide is related to the formation of surface microphases that are close to M/sub 2/TiO/sub 4/ in composition and do not undergo reduction when calcined in a medium at low partial pressure of oxygen.

  10. Down-to-earth studies of carbon clusters

    NASA Technical Reports Server (NTRS)

    Smalley, R. E.

    1990-01-01

    Recent advances in supersonic beam experiments with laser-vaporization sources of clusters have provided some interesting new insights into the nature of the small clusters of carbon, and the processes through which carbon condenses. One cluster in particular, C(sub 60), appears to play a central role. It is argued that this cluster takes the shape of a soccerball: a hollow sphere composed of a shell of 60 carbon atoms connected by a lattice of hexagonal and pentagonal rings, in a pattern of overall icosahedral symmetry. Although C(sub 60) appears to be uniquely stable due to its perfect symmetry, all other even-numbered carbon clusters in the 32 to 100+ atom size range seem to favor similar closed spheroidal forms. These species are interpreted as relatively unreactive side products in condensation reactions of carbon vapor involving spiraling graphitic sheets. The prevalence of C(sub 60) in laser-vaporized carbon vapors and sooting flames suggests that it may be formed readily whenever carbon condenses. Such ready formation and extraordinary stability may have substantial astrophysical implications.

  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.

    PubMed

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

    2014-02-01

    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. Control of carbonate alkalinity on Mg incorporation in calcite: Insights on the occurrence of high Mg calcites in diagenetic environments

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Dietzel, Martin

    2015-04-01

    High Mg calcites (HMC), with up to 25 mol % of Mg, are common features in early diagenetic environments and are frequently associated with bio-induced anaerobic oxidation of methane (AOM). Such archives hold valuable information about the biogeochemical processes occurring in sedimentary environments in the geological past. Despite the frequency AOM-induced HMC observed in marine diagenetic settings and their potential role in dolomitization, only a minor number of experimental studies has been devoted on deciphering their formation conditions. Thus, in order to improve our understanding on the formation mechanism of HMC induced by elevated carbonate ion concentrations, we precipitated HMC by computer controlled titration of a (Mg,Ca)Cl2 solution at different Mg/Ca ratios into a NaHCO3 solution under precisely defined physicochemical conditions (T = 25.00 ±0.03°C; pH = 8.3 ±0.1). The formation of carbonates was monitored at a high temporal resolution using in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. We identified two distinct mechanisms of HMC formation. In solutions with molar Mg/Ca ratios ≤ 1/8 calcium carbonate was precipitated as crystalline phases directly from homogeneous solution. In contrast, higher Mg/Ca ratios induced the formation of Mg-rich ACC (up to 10 mol % of Mg), which was subsequently transformed to HMC with up 20 mol % of Mg. Our experimental results highlight that the finally formed HMC has a higher Mg content than the ACC precursor phase. Considering experimental data for Mg containing ACC transformation to crystalline calcium carbonate from literature, the continuous enrichment of Mg in the precipitate throughout transformation of amorphous to crystalline CaCO3 most likely occurs due to the high carbonate alkalinity (DIC about 0.1 M) of our reactive solutions. The Mg incorporation into calcite lattice seems to be favored by intensive supply of carbonate ions as

  13. Methylene blue adsorption from aqueous solution by activated carbon: effect of acidic and alkaline solution treatments.

    PubMed

    Ijagbemi, Christianah O; Chun, Ji I; Han, Da H; Cho, Hye Y; O, Se J; Kim, Dong S

    2010-01-01

    The removal of Methylene Blue (MB) from aqueous solution using activated carbon (AC) has been investigated. Adsorption experiments were conducted and the maximum adsorption capacity was determined. The effect of experimental parameters such as pH, dye concentration and temperature were studied on the adsorption process. Equilibrium data were mathematically modeled using the Langmuir and Freundlich adsorption models to describe the equilibrium isotherms at different dye concentrations and temperature. Parameters of best-fit model were calculated and discussed. To understand the mechanism of adsorption, kinetic models were employed to follow the adsorption processes; the pseudo-first-order best described the adsorption of MB onto AC. It was found that pH plays a major role in the adsorption process; adsorption capacity was influenced by the physical and surface chemical properties of carbon and the pH of the solution. 99.0% MB removal was achieved at equilibrium.

  14. The oxygen and carbon dioxide balance in the earth's atmosphere

    NASA Technical Reports Server (NTRS)

    Johnson, F. S.

    1975-01-01

    The oxygen-carbon dioxide cycle is described in detail, and steps which are sensitive to perturbation or instability are identified. About half of the carbon dioxide consumption each year in photosynthesis occurs in the oceans. Phytoplankton, which are the primary producers, have been shown to assimilate insecticides and herbicides. The impact of such materials on phytoplankton photosynthesis, both direct and as the indirect result of detrimental effects higher up in the food chain, cannot be assessed. Net oxygen production is very small in comparison with the total production and occurs almost exclusively in a few ocean areas with anoxic bottom conditions and in peat-forming marshes which are sensitive to anthropogenic disturbances. The carbon dioxide content of the atmosphere is increasing at a relatively rapid rate as the result of fossil fuel combustion. Increases in photosynthesis as the result of the hothouse effect may in turn reduce the carbon dioxide content of the atmosphere, leading to global cooling.

  15. Toward more realistic projections of soil carbon dynamics by Earth system models: SOIL CARBON MODELING

    SciTech Connect

    Luo, Yiqi; Ahlström, Anders; Allison, Steven D.; Batjes, Niels H.; Brovkin, Victor; Carvalhais, Nuno; Chappell, Adrian; Ciais, Philippe; Davidson, Eric A.; Finzi, Adien; Georgiou, Katerina; Guenet, Bertrand; Hararuk, Oleksandra; Harden, Jennifer W.; He, Yujie; Hopkins, Francesca; Jiang, Lifen; Koven, Charlie; Jackson, Robert B.; Jones, Chris D.; Lara, Mark J.; Liang, Junyi; McGuire, A. David; Parton, William; Peng, Changhui; Randerson, James T.; Salazar, Alejandro; Sierra, Carlos A.; Smith, Matthew J.; Tian, Hanqin; Todd-Brown, Katherine E. O.; Torn, Margaret; van Groenigen, Kees Jan; Wang, Ying Ping; West, Tristram O.; Wei, Yaxing; Wieder, William R.; Xia, Jianyang; Xu, Xia; Xu, Xiaofeng; Zhou, Tao

    2016-01-21

    Soil carbon (C) is a critical component of Earth system models (ESMs) and its diverse representations are a major source of the large spread across models in the terrestrial C sink from the 3rd to 5th assessment reports of the Intergovernmental Panel on Climate Change (IPCC). Improving soil C projections is of a high priority for Earth system modeling in the future IPCC and other assessments. To achieve this goal, we suggest that (1) model structures should reflect real-world processes, (2) parameters should be calibrated to match model outputs with observations, and (3) external forcing variables should accurately prescribe the environmental conditions that soils experience. Firstly, most soil C cycle models simulate C input from litter production and C release through decomposition. The latter process has traditionally been represented by 1st-order decay functions, regulated primarily by temperature, moisture, litter quality, and soil texture. While this formulation well captures macroscopic SOC dynamics, better understanding is needed of their underlying mechanisms as related to microbial processes, depth-dependent environmental controls, and other processes that strongly affect soil C dynamics. Secondly, incomplete use of observations in model parameterization is a major cause of bias in soil C projections from ESMs. Optimal parameter calibration with both pool- and flux-based datasets through data assimilation is among the highest priorities for near-term research to reduce biases among ESMs. Thirdly, external variables are represented inconsistently among ESMs, leading to differences in modeled soil C dynamics. We recommend the implementation of traceability analyses to identify how external variables and model parameterizations influence SOC dynamics in different ESMs. Overall, projections of the terrestrial C sink can be substantially improved when reliable datasets are available to select the most representative model structure, constrain parameters, and

  16. Carbon nanotubes/heteroatom-doped carbon core-sheath nanostructures as highly active, metal-free oxygen reduction electrocatalysts for alkaline fuel cells.

    PubMed

    Sa, Young Jin; Park, Chiyoung; Jeong, Hu Young; Park, Seok-Hee; Lee, Zonghoon; Kim, Kyoung Taek; Park, Gu-Gon; Joo, Sang Hoon

    2014-04-14

    A facile, scalable route to new nanocomposites that are based on carbon nanotubes/heteroatom-doped carbon (CNT/HDC) core-sheath nanostructures is reported. These nanostructures were prepared by the adsorption of heteroatom-containing ionic liquids on the walls of CNTs, followed by carbonization. The design of the CNT/HDC composite allows for combining the electrical conductivity of the CNTs with the catalytic activity of the heteroatom-containing HDC sheath layers. The CNT/HDC nanostructures are highly active electrocatalysts for the oxygen reduction reaction and displayed one of the best performances among heteroatom-doped nanocarbon catalysts in terms of half-wave potential and kinetic current density. The four-electron selectivity and the exchange current density of the CNT/HDC nanostructures are comparable with those of a Pt/C catalyst, and the CNT/HDC composites were superior to Pt/C in terms of long-term durability and poison tolerance. Furthermore, an alkaline fuel cell that employs a CNT/HDC nanostructure as the cathode catalyst shows very high current and power densities, which sheds light on the practical applicability of these new nanocomposites.

  17. Coordination chemistry of the alkaline earth metal ions with Zwitterionic forms of the Schift bases. X-Ray studies and other spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Tajmir-Riahi, H. A.; Lotfipoor, M.

    The non-ionized forms of tetradentate Schiff bases NN'-ethylenebis(salicylideneimine), H 2L and NN'-propane-1,3-diylbis(salicylideneimine), H 2L' react with hydrated alkaline earth halide and nitrate to give complexes of the type: M(H 2L)Cl 2· nH 2O [M = Mg(II), Ca(II), Sr(II); n = 0-4], M(H 2L) 2Cl 2 [M = Ca(II), Sr(II), M(H 2L) nBr 2 [M = Ca(II), Sr(II); n = 2, 3 and Mg 2(H 2L) 3Br 4], M(H 2L) nI 2 [M = Mg(II), Ca(II), Sr(II), Ba(II); n = 2, 3)], M(H 2L) n(NO 3) 2 and M(H 2L') n(NO 1) 2[M = Mg(II), Ca(II); n = 1, 2)]. Because of distinct spectral similarities with structurally known Ca(H 2L')(NO 3) 2 compound, the Schiff bases are coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms of the azomethine groups, which carry the protons transferred from phenolic groups on complexation. Halide and nitrate are coordinated to the central metal ion except in 2:1 nitrato complexes where the presence of both ionic and coordinated nitrate groups are evident and also in 3:1 halide complexes where the presence of non-coordinated halide cannot be excluded. X-Ray powder photographs showed no marked similarities between Ca(H 2L')(NO 3) 2 and Mg(H 2L')(NO 3) 2 while there are some isomorphic features between the same types of halide complexes. Infrared spectra and other structural information revealed the polymeric nature of the complexes. Therefore the coordination numbers exhibited by the alkaline earth metal cations would be 4, 6 or 8 in these series of Schiff base complexes.

  18. Dissolution stoichiometry and adsorption of alkali and alkaline earth elements to the acid-reacted wollastonite surface at 25°C

    NASA Astrophysics Data System (ADS)

    Xie, Zhixin; Walther, John V.

    1994-06-01

    The Ca 2+/H + exchange reaction on the wollastonite surface was investigated at 25°C with both short-term (<2.5 h) and long-term (>48 h) dissolution studies. In acidic solutions, the dissolution of wollastonite is nonstoichiometric with a greater release of Ca than Si relative to the wollastonite stoichiometry. Both short-term and long-term Ca 2+/H + exchange reaction stoichiometries are 0.5. Rapid desorption of Ca 2+ from the surface of untreated wollastonite caused a rise of the suspension pH to about 10 in a couple of minutes. Therefore, potentiometric titrations were performed with an acidreacted wollastonite where most surface detachable Ca 2+ had been removed. Addition of alkali and alkaline earth metal chloride solutions to the acid-reacted wollastonite suspension results in a pH decrease with K +> Na + > Ba 2+ > Mg 2+ > Ca 2+ in equal molal solutions. This suggests that the cations in these solutions are adsorbed to the wollastonite surface. Surface protonation properties of the acid-reacted wollastonite are found to be similar to those of microporous silica but with the point of zero salt effect (pzse) of 4.5-5.5 rather than the 3.0 of microporous silica. The surface protonation-deprotonation as a function of pH is modeled with a one-site double layer model which includes Na adsorption from the background electrolyte to reasonable accuracy. The adsorption of CrO 42-, MoO 42-, Ca 2+, Mg 2+, Ba 2+, and Na + from aqueous solutions to the acidreacted wollastonite/water interface was determined as a function of the pH and ionic strength of the solution. CrO 42- and MoO 42- were not adsorbed to the wollastonite surface at pH above 3. The extent of cation adsorption increases with increasing pH and decreases with increasing ionic strength. Ca 2+ adsorption depends on both the surface area of wollastonite and total amount of Ca 2+ in the suspension. For alkaline earth metals at the same concentration, the adsorption sequence is Ba 2+> Ca 2+> Mg 2+. At pH 8.5, the

  19. Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells.

    PubMed

    Wang, Xin; Gao, Ningshengjie; Zhou, Qixing; Dong, Heng; Yu, Hongbing; Feng, Yujie

    2013-09-01

    Activated carbon (AC) is a high performing and cost effective catalyst for oxygen reduction reactions (ORRs) of air-cathodes in microbial fuel cells (MFCs). Acidic (HNO3) and alkaline (KOH) pretreatments on AC at low temperature (85°C) are conducted to enhance the performance of MFCs. The alkaline pretreatment increased the power density by 16% from 804±70 to 957±31 mW m(-2), possibly due to the decrease of ohmic resistance (from 20.58 to 19.20 Ω) and the increase of ORR activities provided by the adsorbed hydroxide ion and extra micropore area/volume after alkaline pretreatment. However, acidic pretreatment decreased the power output to 537±36 mW m(-2), which can be mainly attributed to the corrosion by adsorbed proton at the interface of AC powder and stainless steel mesh and the decreased pore area.

  20. Novel As-doped, As and N-codoped carbon nanotubes as highly active and durable electrocatalysts for O2 reduction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Liu, Ziwu; Li, Meng; Wang, Fang; Wang, Quan-De

    2016-02-01

    To develop more efficient metal-free cathode electrocatalysts for fuel cells, novel arsenic (As)-doped, As and N-codoped carbon nanotubes are synthesized by chemical vapor deposition in this work. The as-prepared As-containing carbon nanotubes exhibit significantly enhanced activity and long-term durability for the oxygen reduction reaction (ORR) in alkaline medium, indicating that the doping of As or codoping As with other heteroatoms into carbon matrix could improve the ORR activity of carbon materials due to the changes in electronic and physical properties of carbon nanotubes evidenced by density functional theory calculations. Moreover, As-containing carbon nanotubes also display much better methanol tolerance, showing a good potential application for future fuel cells.

  1. Batch and column adsorption of herbicide fluroxypyr on different types of activated carbons from water with varied degrees of hardness and alkalinity.

    PubMed

    Pastrana-Martínez, L M; López-Ramón, M V; Fontecha-Cámara, M A; Moreno-Castilla, C

    2010-02-01

    There has been little research into the effects of the water hardness and alkalinity of surface waters on the adsorption of herbicides on activated carbons. The aim of this study was to determine the influence of these water characteristics on fluroxypyr adsorption on different activated carbons. At low fluroxypyr surface concentrations, the amount adsorbed from distilled water was related to the surface hydrophobicity. Surface area of carbons covered by fluroxypyr molecules ranged from 60 to 65%. Variations in fluroxypyr solubility with water hardness and alkalinity showed a salting-in effect. Calcium, magnesium and bicarbonate ions were adsorbed to a varied extent on the activated carbons. The presence of fluroxypyr in solution decreased their adsorption due to a competition effect. K(F) from the Freundlich equation linearly increased with water hardness due to salt-screened electrostatic repulsions between charged fluroxypyr molecules. The amount adsorbed from distilled water was largest at high fluroxypyr solution concentrations, because there was no competition between inorganic ions and fluroxypyr molecules. The column breakthrough volume and the amount adsorbed at breakthrough were smaller in tap versus distilled water. Carbon consumption was lower with activated carbon cloth than with the use of granular activated carbon.

  2. Adsorption of crystal violet with diatomite earth&carbon by a modification of hydrothermal carbonization process.

    PubMed

    Zhang, Yanzhuo; Li, Jun; Chen, Guanghui; Bian, Wei; Lu, Yun; Li, Wenjing; Zheng, Zhaoming; Cheng, Xiaojie

    2016-01-01

    The high colority and difficulty of decolorization are the most important tasks on printing and dyeing wastewater. This study investigates the ability of diatomite earth&carbon (DE&C) as an adsorbent to removal crystal violet (CV) from aqueous solutions. Fourier transform infrared spectroscopy results indicate the importance of functional groups during the adsorption of CV. The obtained N2 adsorption-desorption isotherm values accord with well IUPAC type II. Our calculations determined a surface area of 73.15 m(2) g(-1) for DE&C and an average pore diameter of 10.56 nm. Equilibrium data of the adsorption process fitted very well to the Langmuir model (R(2) > 0.99). The results of kinetics study showed that the pseudo-second-order model fitted to the experimental data well. The thermodynamic parameters were also evaluated. ΔH° <0, ΔS° > 0 and ΔG° < 0 demonstrated that the adsorption process was spontaneous and exothermic for dye. Furthermore the positive value of ΔS° reflected good affinity of the CV dye.

  3. Hydrazines and carbohydrazides produced from oxidized carbon in earth's primitive environment

    NASA Technical Reports Server (NTRS)

    Folsome, C. E.; Brittain, A.; Smith, A.; Chang, S.

    1981-01-01

    Whether abiological organic compounds can be formed from the interactions of energy sources with nitrogen, oxidized carbon and water is held to be of importance in geochemical models of the primordial earth atmosphere. It is reported that experiments using quenched spark discharges through molecular nitrogen on aqueous suspensions of CaCO3 and other reactants to simulate the hydrosphere/atmosphere interface yield hydrazine and carbohydrazine in significant but low yields. Such reactions in primitive aquatic environments may have supplied a pathway for chemical evolution and the origin of life, on a primitive earth in which fully oxidized states of carbon were available for the primary synthesis of organic matter.

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

    PubMed

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

    2012-03-14

    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.

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

    NASA Astrophysics Data System (ADS)

    Duan, Yuhua; Sorescu, Dan C.

    2010-08-01

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

  6. Heating temperature dependence of Cr(III) oxidation in the presence of alkali and alkaline earth salts and subsequent Cr(VI) leaching behavior.

    PubMed

    Verbinnen, Bram; Billen, Pieter; Van Coninckxloo, Michiel; Vandecasteele, Carlo

    2013-06-04

    In this paper, the temperature dependence of Cr(III) oxidation in high temperature processes and the subsequent Cr(VI) leaching was studied using synthetic mixtures. It was experimentally shown that in the presence of alkali and alkaline earth salts, oxidation of Cr(III) takes place, consistent with thermodynamic calculations. Heating of synthetic mixtures of Cr2O3 and Na, K, or Ca salts led to elevated leaching of Cr(VI); in the presence of Na, more than 80% of the initial Cr(III) amount was converted to Cr(VI) at 600-800 °C. Kinetic experiments allowed explanation of the increase in Cr(VI) leaching for increasing temperatures up to 600-800 °C. After reaching a maximum in Cr(VI) leaching at temperatures around 600-800 °C, the leaching decreased again, which could be explained by the formation of a glassy phase that prevents leaching of the formed Cr(VI). By way of illustration, Cr(VI) formation and leaching was evaluated for a case study, the fabrication of ceramic material from contaminated sludge. Based on the proposed reaction mechanisms, countermeasures to prevent Cr oxidation (addition of NH4H2PO4, heating under inert atmosphere) were proposed and successfully tested for synthetic mixtures and for the case study.

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

    PubMed

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

    2005-09-01

    Sugar cane bagasse and cane trash were pyrolysed in a novel quartz fluidised-bed/fixed-bed reactor. Quantification of the Na, K, Mg and Ca in chars revealed that pyrolysis temperature, heating rate, valence and biomass type were important factors influencing the volatilisation of these alkali and alkaline earth metallic (AAEM) species. Pyrolysis at a slow heating rate (approximately 10 K min(-1)) led to minimal (often <20%) volatilisation of AAEM species from these 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  9. Optimized electrospinning synthesis of iron-nitrogen-carbon nanofibers for high electrocatalysis of oxygen reduction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Yan, Xingxu; Liu, Kexi; Wang, Xiangqing; Wang, Tuo; Luo, Jun; Zhu, Jing

    2015-04-01

    To achieve iron-nitrogen-carbon (Fe-N-C) nanofibers with excellent electrocatalysis for replacing high-cost Pt-based catalysts in the cathodes of fuel cells and metal-air batteries, we have investigated and evaluated the effects of polyacrylonitrile (PAN) concentration and the proportion of iron to PAN, along with voltage and flow rate during the electrospinning process, and thus proposed three criteria to optimize these parameters for ideal nanofiber catalysts. The best half-wave potential of an optimized catalysts is 0.82 V versus reversible hydrogen electrode in an alkaline medium, which reaches the best range of the non-precious-metal catalysts reported and is very close to that of commercial Pt/C catalysts. Furthermore, the electron-transfer number of our catalysts is superior to that of the Pt/C, indicating the catalysts undergo a four-electron process. The durability of the optimized Fe-N-C nanofibers is also better than that of the Pt/C, which is attributed to the homogeneous distribution of the active sites in our catalysts.

  10. Electrochemical sandwich-type biosensors for α-1 antitrypsin with carbon nanotubes and alkaline phosphatase labeled antibody-silver nanoparticles.

    PubMed

    Zhu, Gangbing; Lee, Hye Jin

    2017-03-15

    A novel sandwich-type biosensor was developed for the electrochemical detection of α-1 antitrypsin (AAT, a recognized biomarker for Alzheimer's disease). The biosensor was composed of 3, 4, 9, 10-perylene tetracarboxylic acid/carbon nanotubes (PTCA-CNTs) as a sensing platform and alkaline phosphatase-labeled AAT antibody functionalized silver nanoparticles (ALP-AAT Ab-Ag NPs) as a signal enhancer. CNTs offer high surface area and good electrical conductivity. Importantly, Ag NPs could increase the amount of ALP on the sensing surface and the ALP could dephosphorylate 4-amino phenyl phosphate (APP) enzymatically to produce electroactive species 4-aminophenol (AP). For detecting AAT based on the sandwich-type biosensor, the results show that the peak current value of AP using ALP-AAT Ab-Ag NPs as signal enhancer is much higher than that by using ALP-AAT Ab bioconjugate (without Ag NPs), the biosensor exhibited desirable performance for AAT determination with a wide linearity in the range from 0.05 to 20.0pM and a low detection limit of 0.01pM. Finally, the developed sensor was successfully applied to the analysis of AAT concentration in serum samples.

  11. Amperometric nitric oxide sensors with enhanced selectivity over carbon monoxide via platinum oxide formation under alkaline conditions.

    PubMed

    Jensen, Gary C; Zheng, Zheng; Meyerhoff, Mark E

    2013-11-05

    An improved planar amperometric nitric oxide (NO) sensor with enhanced selectivity over carbon monoxide (CO), which represents a volatile interfering species for NO sensors that has been largely overlooked until recently, is described. Formation of an oxide film on the inner platinum working electrode via anodic polarization using an inner alkaline electrolyte solution provides the basis for improved selectivity. Cyclic voltammetry reveals that formation of an oxidized Pt film inhibits adsorption of CO to the electrode surface, which is a necessary initial step in the electrocatalytic oxidation of CO on Pt. Previous NO gas sensors that employ internal electrolyte solutions have been assembled using acidic internal solutions that inhibit the formation of a dense platinum oxide film on the working electrode surface. It is demonstrated herein that increasing the internal electrolyte pH promotes oxidized platinum film formation, resulting in improved selectivity over CO. Selectivity coefficients (log KNO,j) for sensors assembled with internal solutions at various pH values range from -0.08 at pH 2.0 to -2.06 at pH 11.7, with average NO sensitivities of 1.24 nA/μM and a limit of detection (LOD) of <1 nM.

  12. Carbon quantum dots-based recyclable real-time fluorescence assay for alkaline phosphatase with adenosine triphosphate as substrate.

    PubMed

    Qian, Zhaosheng; Chai, Lujing; Tang, Cong; Huang, Yuanyuan; Chen, Jianrong; Feng, Hui

    2015-03-03

    A convenient, reliable, and highly sensitive real-time assay for alkaline phosphatase (ALP) activity in the continuous and recyclable way is established on the basis of aggregation and disaggregation of carbon quantum dots (CQDs) through the competitive assay approach. CQDs and adenosine triphosphate (ATP) were used as the fluorescent indicator and substrate for ALP activity assessment, respectively. Richness of carboxyl groups on the surface of CQDs enables their severe aggregation triggered by cerium ions, which results in effective fluorescence quenching. Under the catalytic hydrolysis of ALP, ATP can be rapidly transformed to phosphate ions. Stronger affinity of phosphate ions to cerium ions than carboxyl groups is taken advantage of to achieve fluorescence recovery induced by redispersion of CQDs in the presence of ALP and ATP. Quantitative evaluation of ALP activity in a broad range from 4.6 to 383.3 U/L with the detection limit of 1.4 U/L can be realized in this way, which endows the assay with high enough sensitivity for practical detection in human serum. The assay can be used in a recyclable way for more than three times since the generated product CePO4 as a precipitate can be easily removed from the standard assay system. This strategy broadens the sensing application of fluorescent CQDs with excellent biocompatibility and provides an example based on disaggregation in optical probe development.

  13. New insights into the burial history of organic carbon on the early Earth

    NASA Astrophysics Data System (ADS)

    Bjerrum, Christian J.; Canfield, Donald E.

    2004-08-01

    The isotope record of organic matter and calcium carbonate is often used to infer the burial history of organic carbon through time. As organic carbon burial is widely held to control long-term oxygen production, the isotope record also relates to the production rates of oxygen on Earth. Current interpretations of the record suggest a long-term consistency in the proportion of total carbon buried as organic carbon (f ratio), with some important periods of much higher burial proportions. The isotope record is analyzed here with a new carbon isotope mass balance model, which considers submarine hydrothermal weathering of ocean crust as a significant removal pathway of inorganic carbon. With this model the f ratio is considerably reduced if isotopically depleted inorganic carbon is precipitated during hydrothermal weathering and if hydrothermal weathering dominates inorganic carbon removal from the surface environment. In contrast to previous calculations, our analysis of the carbon isotope record shows that organic carbon burial in the Archean accounted for only between 0% and 10% of the total carbon burial. These low burial proportions would have contributed to a slow accumulation of atmospheric oxygen in the Archean.

  14. Molybdenum Carbide Nanoparticles on Carbon Nanotubes and Carbon Xerogel: Low-Cost Cathodes for Hydrogen Production by Alkaline Water Electrolysis.

    PubMed

    Šljukić, Biljana; Santos, Diogo M F; Vujković, Milica; Amaral, Luís; Rocha, Raquel P; Sequeira, César A C; Figueiredo, José L

    2016-05-23

    Low-cost molybdenum carbide (Mo2 C) nanoparticles supported on carbon nanotubes (CNTs) and on carbon xerogel (CXG) were prepared and their activity for the hydrogen evolution reaction (HER) was evaluated in 8 m KOH aqueous electrolyte at 25-85 °C. Measurements of the HER by linear scan voltammetry allowed us to determine Tafel slopes of 71 and 74 mV dec(-1) at 25 °C for Mo2 C/CNT and Mo2 C/CXG, respectively. Stability tests were also performed, which showed the steady performance of the two electrocatalysts. Moreover, the HER kinetics at Mo2 C/CNT was enhanced significantly after the long-term stability tests. The specific activity of both materials was high, and a higher stability was obtained for the activated Mo2 C/CNT (40 A g(-1) at -0.40 V vs. the reversible hydrogen electrode).

  15. Enhanced oxygen reduction reaction activity of iron-containing nitrogen-doped carbon nanotubes for alkaline direct methanol fuel cell application

    NASA Astrophysics Data System (ADS)

    Ratso, Sander; Kruusenberg, Ivar; Sarapuu, Ave; Rauwel, Protima; Saar, Rando; Joost, Urmas; Aruväli, Jaan; Kanninen, Petri; Kallio, Tanja; Tammeveski, Kaido

    2016-11-01

    Non-precious metal catalysts for electrochemical oxygen reduction reaction are synthesised by pyrolysis of multi-walled carbon nanotubes in the presence of nitrogen and iron precursors. For the physico-chemical characterisation of the catalysts transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction are used. The electrocatalytic activity of the catalysts for oxygen reduction is studied in 0.1 M KOH solution using the rotating disk electrode method. The Fe-containing nitrogen-doped carbon nanotubes exhibit an enhanced electrocatalytic performance as compared to metal-free counterparts and their electrocatalytic activity is comparable to that of commercial Pt/C catalyst. Alkaline direct methanol fuel cell tests also show performance close to Pt/C. Thus, these materials can be considered as promising cathode catalysts for application in alkaline fuel cells.

  16. Introduction of carbonate in the rare earth-containing oxyapatite

    NASA Astrophysics Data System (ADS)

    Lacout, J. L.; Mikou, M.; Bonel, G.

    1990-06-01

    The lanthanum-containing oxyapatite, Ca10-xLax(PO 4) 6O 1+ {x}/{2}□ 1- {x}/{2}, treated in a CO 2 atmosphere at 950°C can be partially carbonated if x < 2; it remains uncarbonated when x = 2. The general formula of the carbonated apatites is Ca10-xLax(PO 4) 6O x( CO3) 1- {x}/{2}□ 1- {x}/{2}O ≤ x ≤ 2 . The number of La 3+ and O 2- ions on the one hand and the number of CO 2-3 ions and vacancies on the other hand are equal; each O 2- ion is joined to a close La 3+ ion, and each CO 2-3 ion is next to a vacancy.

  17. Advanced technology for extended endurance alkaline fuel cells

    NASA Astrophysics Data System (ADS)

    Sheibley, D. W.; Martin, R. A.

    Advanced components have been developed for alkaline fuel cells with a view to the satisfaction of NASA Space Station design requirements for extended endurance. The components include a platinum-on-carbon catalyst anode, a potassium titanate-bonded electrolyte matrix, a lightweight graphite electrolyte reservoir plate, a gold-plated nickel-perforated foil electrode substrate, a polyphenylene sulfide cell edge frame material, and a nonmagnesium cooler concept. When incorporated into the alkaline fuel cell unit, these components are expected to yield regenerative operation in a low earth orbit Space Station with a design life greater than 5 years.

  18. Advanced technology for extended endurance alkaline fuel cells

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Martin, R. A.

    1987-01-01

    Advanced components have been developed for alkaline fuel cells with a view to the satisfaction of NASA Space Station design requirements for extended endurance. The components include a platinum-on-carbon catalyst anode, a potassium titanate-bonded electrolyte matrix, a lightweight graphite electrolyte reservoir plate, a gold-plated nickel-perforated foil electrode substrate, a polyphenylene sulfide cell edge frame material, and a nonmagnesium cooler concept. When incorporated into the alkaline fuel cell unit, these components are expected to yield regenerative operation in a low earth orbit Space Station with a design life greater than 5 years.

  19. Are mangroves drivers or buffers of coastal acidification? Insights from alkalinity and dissolved inorganic carbon export estimates across a latitudinal transect

    NASA Astrophysics Data System (ADS)

    Sippo, James Z.; Maher, Damien T.; Tait, Douglas R.; Holloway, Ceylena; Santos, Isaac R.

    2016-05-01

    Mangrove forests are hot spots in the global carbon cycle, yet the fate for a majority of mangrove net primary production remains unaccounted for. The relative proportions of alkalinity and dissolved CO2 [CO2*] within the dissolved inorganic carbon (DIC) exported from mangroves is unknown, and therefore, the effect of mangrove DIC exports on coastal acidification remains unconstrained. Here we measured dissolved inorganic carbon parameters over complete tidal and diel cycles in six pristine mangrove tidal creeks covering a 26° latitudinal gradient in Australia and calculated the exchange of DIC, alkalinity, and [CO2*] between mangroves and the coastal ocean. We found a mean DIC export of 59 mmol m-2 d-1 across the six systems, ranging from import of 97 mmol m-2 d-1 to an export of 85 mmol m-2 d-1. If the Australian transect is representative of global mangroves, upscaling our estimates would result in global DIC exports of 3.6 ± 1.1 Tmol C yr-1, which accounts for approximately one third of the previously unaccounted for mangrove carbon sink. Alkalinity exchange ranged between an import of 1.2 mmol m-2 d-1 and an export of 117 mmol m-2 d-1 with an estimated global export of 4.2 ± 1.3 Tmol yr-1. A net import of free CO2 was estimated (-11.4 ± 14.8 mmol m-2 d-1) and was equivalent to approximately one third of the air-water CO2 flux (33.1 ± 6.3 mmol m-2 d-1). Overall, the effect of DIC and alkalinity exports created a measurable localized increase in coastal ocean pH. Therefore, mangroves may partially counteract coastal acidification in adjacent tropical waters.

  20. Redox freezing and melting in the Earth's deep mantle resulting from carbon-iron redox coupling.

    PubMed

    Rohrbach, Arno; Schmidt, Max W

    2011-04-14

    Very low seismic velocity anomalies in the Earth's mantle may reflect small amounts of melt present in the peridotite matrix, and the onset of melting in the Earth's upper mantle is likely to be triggered by the presence of small amounts of carbonate. Such carbonates stem from subducted oceanic lithosphere in part buried to depths below the 660-kilometre discontinuity and remixed into the mantle. Here we demonstrate that carbonate-induced melting may occur in deeply subducted lithosphere at near-adiabatic temperatures in the Earth's transition zone and lower mantle. We show experimentally that these carbonatite melts are unstable when infiltrating ambient mantle and are reduced to immobile diamond when recycled at depths greater than ∼250 kilometres, where mantle redox conditions are determined by the presence of an (Fe,Ni) metal phase. This 'redox freezing' process leads to diamond-enriched mantle domains in which the Fe(0), resulting from Fe(2+) disproportionation in perovskites and garnet, is consumed but the Fe(3+) preserved. When such carbon-enriched mantle heterogeneities become part of the upwelling mantle, diamond will inevitably react with the Fe(3+) leading to true carbonatite redox melting at ∼660 and ∼250 kilometres depth to form deep-seated melts in the Earth's mantle.

  1. Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth.

    PubMed

    Pan, Ding; Spanu, Leonardo; Harrison, Brandon; Sverjensky, Dimitri A; Galli, Giulia

    2013-04-23

    Water is a major component of fluids in the Earth's mantle, where its properties are substantially different from those at ambient conditions. At the pressures and temperatures of the mantle, experiments on aqueous fluids are challenging, and several fundamental properties of water are poorly known; e.g., its dielectric constant has not been measured. This lack of knowledge of water dielectric properties greatly limits our ability to model water-rock interactions and, in general, our understanding of aqueous fluids below the Earth's crust. Using ab initio molecular dynamics, we computed the dielectric constant of water under the conditions of the Earth's upper mantle, and we predicted the solubility products of carbonate minerals. We found that MgCO3 (magnesite)--insoluble in water under ambient conditions--becomes at least slightly soluble at the bottom of the upper mantle, suggesting that water may transport significant quantities of oxidized carbon. Our results suggest that aqueous carbonates could leave the subducting lithosphere during dehydration reactions and could be injected into the overlying lithosphere. The Earth's deep carbon could possibly be recycled through aqueous transport on a large scale through subduction zones.

  2. Application of a fluidized bed reactor charged with aragonite for control of alkalinity, pH and carbon dioxide in marine recirculating aquaculture systems

    USGS Publications Warehouse

    Paul S Wills, PhD; Pfeiffer, Timothy; Baptiste, Richard; Watten, Barnaby J.

    2016-01-01

    Control of alkalinity, dissolved carbon dioxide (dCO2), and pH are critical in marine recirculating aquaculture systems (RAS) in order to maintain health and maximize growth. A small-scale prototype aragonite sand filled fluidized bed reactor was tested under varying conditions of alkalinity and dCO2 to develop and model the response of dCO2 across the reactor. A large-scale reactor was then incorporated into an operating marine recirculating aquaculture system to observe the reactor as the system moved toward equilibrium. The relationship between alkalinity dCO2, and pH across the reactor are described by multiple regression equations. The change in dCO2 across the small-scale reactor indicated a strong likelihood that an equilibrium alkalinity would be maintained by using a fluidized bed aragonite reactor. The large-scale reactor verified this observation and established equilibrium at an alkalinity of approximately 135 mg/L as CaCO3, dCO2 of 9 mg/L, and a pH of 7.0 within 4 days that was stable during a 14 day test period. The fluidized bed aragonite reactor has the potential to simplify alkalinity and pH control, and aid in dCO2 control in RAS design and operation. Aragonite sand, purchased in bulk, is less expensive than sodium bicarbonate and could reduce overall operating production costs.

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

    PubMed

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

    2014-01-01

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

  4. The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media

    DOE PAGES

    John, Samuel St.; Atkinson, Robert W.; Roy, Asa; ...

    2016-01-11

    In this paper, we investigated the performance of several carbon-supported RuxPty electrocatalysts for their alkaline hydrogen oxidation and oxygen reduction performance in the presence of carbonate and compared their performance with monometallic, carbon-supported Pt. Our results indicate a strong dependence of HOR upon pH for the monometallic Pt catalysts (22 mV/pH) and a weak dependence upon pH for the Ru-containing electrocatalysts (3.7, 2.5, and 4.7 mV/pH on Ru0.2Pt0.8, Ru0.4Pt0.6, and Ru0.8Pt0.2, respectively). These results are consistent with our previous findings that illustrate a change in rds from electron transfer (on monometallic Pt) to dissociative hydrogen adsorption (on RuxPty catalysts). Analysismore » of the kinetic currents to determine the rate-determining step via Tafel slope analysis provides additional data supporting this conclusion. There is no difference in the performance at comparable pH values in the presence or absence of carbonate on monometallic Pt indicating that water/hydroxide is the primary proton acceptor for alkaline HOR in 0.1 M KOH aqueous electrolyte. Finally, we observe no pH or carbonate dependence for the ORR on monometallic Pt.« less

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

    SciTech Connect

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

    2015-11-15

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

  6. Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    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.

  7. Unimolecular and hydrolysis channels for the detachment of water from microsolvated alkaline earth dication (Mg2+, Ca2+, Sr2+, Ba2+) clusters

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2014-02-07

    We examine theoretically the three channels that are associated with the detachment of a single water molecule from the aqueous clusters of the alkaline earth dications, [M(H2O)n]2+, M = Mg, Ca, Sr, Ba, n ≤ 6. These are the unimolecular water loss (M2+(H2O)n-1 + H2O) and the two hydrolysis channels resulting to the loss of hydronium ([MOH(H2O)n-2]+ + H3O+) and Zundel ([MOH(H2O)n-3]+ + H3O+(H2O)) cations. The Potential Energy Curves (PECs) corresponding to those three channels were constructed at the Møller-Plesset second order perturbation (MP2) level of theory with basis sets of double- and triple-ζ quality. We furthermore investigated the water and hydronium loss channels from the mono-hydroxide water clusters with up to four water molecules, [MOH(H2O)n]+, 1 ≤ n ≤ 4. Our results indicate the preference of the hydronium loss and possibly the Zundel cation loss channels for the smallest size clusters, whereas the unimolecular water loss channel is preferred for the larger ones as well as the mono-hydroxide clusters. Although the charge separation (hydronium and Zundel cation loss) channels produce more stable products when compared to the ones for the unimolecular water loss, they also require the surmounting of high energy barriers, a fact that makes the experimental observation of fragments related to these hydrolysis channels difficult.

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

    SciTech Connect

    Davis, Barry M.; McCaffrey, John G.

    2016-01-28

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

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

    PubMed

    Davis, Barry M; McCaffrey, John G

    2016-01-28

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y(1)P ← a(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(-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 Sr2 while this transition is quenched in Ba2. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba2 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.

  10. Characterization of Surface and Bulk Nitrates of γ-Al2O3-Supported Alkaline Earth Oxides using Density Functional Theory

    SciTech Connect

    Mei, Donghai; Ge, Qingfeng; Kwak, Ja Hun; Kim, Do Heui; Verrier, Christelle M.; Szanyi, Janos; Peden, Charles HF

    2009-05-14

    “Surface" and "bulk" nitrates formed on a series of alkaline earth oxides (AEOs), AE(NO3)2, were investigated using first-principles density functional theory calculations. The formation of these surface and bulk nitrates was modeled by the adsorption of NO2+NO3 pairs on gamma-Al2O3-supported monomeric AEOs (MgO, CaO, SrO, and BaO) and on the extended AEO(001) surfaces, respectively. The calculated vibrational frequencies of the surface and bulk nitrates based on our proposed models are in good agreement with experimental measurements of AEO/gamma-Al2O3 materials after prolonged NO2 exposure. This indicates that experimentally observed "surface" nitrates are most likely formed with isolated two dimensional (including monomeric) AEO clusters on the gamma-Al2O3 substrate, while the "bulk" nitrates are formed on exposed (including (001)) surfaces (and likely in the bulk as well) of large three dimensional AEO particles supported on the gamma-Al2O3 substrate. Also in line with the experiments, our calculations show that the low and high frequency components of the vibrations for both surface and bulk nitrates are systematically red shifted with the increasing basicity and cationic size of the AEOs. The adsorption strengths of NO2+NO3 pairs are nearly the same for the series of alumina-supported monomeric AEOs, while the adsorption strengths of NO2+NO3 pairs on the AEO surfaces increase in the order of MgO < CaO < SrO ~ BaO. Compared to the NO2+NO3 pair that only interacts with monomeric AEOs, the stability of NO2+NO3 pairs that interact with both the monomeric AEO and the gamma-Al2O3 substrate is enhanced by about 0.5 eV. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

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

    PubMed

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

    2016-03-24

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

  12. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions.

    PubMed

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

    2014-01-28

    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.

  13. Substrate and environmental controls on microbial assimilation of soil organic carbon: a framework for Earth system models.

    PubMed

    Xu, Xiaofeng; Schimel, Joshua P; Thornton, Peter E; Song, Xia; Yuan, Fengming; Goswami, Santonu

    2014-05-01

    A mechanistic understanding of microbial assimilation of soil organic carbon is important to improve Earth system models' ability to simulate carbon-climate feedbacks. A simple modelling framework was developed to investigate how substrate quality and environmental controls over microbial activity regulate microbial assimilation of soil organic carbon and on the size of the microbial biomass. Substrate quality has a positive effect on microbial assimilation of soil organic carbon: higher substrate quality leads to higher ratio of microbial carbon to soil organic carbon. Microbial biomass carbon peaks and then declines as cumulative activity increases. The simulated ratios of soil microbial biomass to soil organic carbon are reasonably consistent with a recently compiled global data set at the biome level. The modelling framework developed in this study offers a simple approach to incorporate microbial contributions to the carbon cycling into Earth system models to simulate carbon-climate feedbacks and explain global patterns of microbial biomass.

  14. Climate-induced tree mortality: earth system consequences for carbon, energy, and water exchanges

    NASA Astrophysics Data System (ADS)

    Adams, H. D.; Macalady, A.; Breshears, D. D.; Allen, C. D.; Luce, C.; Royer, P. D.; Huxman, T. E.

    2010-12-01

    One of the greatest uncertainties in global environmental change is predicting changes in feedbacks between the biosphere and atmosphere that could present hazards to current earth system function. Terrestrial ecosystems, and in particular forests, exert strong controls on the global carbon cycle and influence regional hydrology and climatology directly through water and surface energy budgets. Widespread, rapid, drought- and infestation-triggered tree mortality is now emerging as a phenomenon affecting forests globally and may be linked to increasing temperatures and drought frequency and severity. We demonstrate the link between climate-sensitive tree mortality and risks of altered earth system function though carbon, water, and energy exchange. Tree mortality causes a loss of carbon stocks from an ecosystem and a reduction sequestration capacity. Recent research has shown that the 2000s pinyon pine die-off in the southwest US caused the loss of 4.6 Tg of aboveground carbon stocks from the region in 5 years, far exceeding carbon loss from other disturbances. Widespread tree mortality in British Columbia resulted in the loss of 270 Tg of carbon, shifting affected forestland from a carbon sink to a source, and influenced Canadian forest policy on carbon stocks. Tree mortality, as an immediate loss of live tree cover, directly alters albedo, near-ground solar radiation, and the relative contributions of evaporation and transpiration to total evapotranspiration. Near-ground solar radiation, an important ecosystem trait affecting soil heating and water availability, increased regionally following the pinyon pine die-off. Conversely, forest canopy loss with tree mortality, is expected to increase regional albedo, especially for forests which experience winter snow cover, potentially offsetting the climate forcing of terrestrial carbon releases to the atmosphere. Initial hydrological response to die-off is likely a reduction in evapotranspiration, which can increase

  15. Electrocatalysis of carbon black- or poly(diallyldimethylammonium chloride)-functionalized activated carbon nanotubes-supported Pd-Tb towards methanol oxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Li; Wang, Yi; Li, An; Yang, Yunshang; Tang, Qinghu; Cao, Hongbin; Qi, Tao; Li, Changming

    2014-07-01

    The Pd-Tb/C catalysts with different Pd/Tb ratios were synthesized by a simple simultaneous reduction reaction with sodium borohydride in aqueous solution. The structure and morphology of those catalysts had been characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrocatalytic performance of those catalysts for methanol oxidation in alkaline media was investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and CO stripping experiments. It is found that the 20%Pd-1%Tb/C catalyst has a higher catalytic activity than the 20%Pd/C catalyst, but the effect of Tb cannot be explained by a bi-functional mechanism. According to the X-Ray photoelectron spectroscopy (XPS) analyses, it is suggested that the higher content of metallic Pd caused by the addition of Tb contributes to the better catalytic activity of 20%Pd-1%Tb/C. Based on the good electrocatalytic performance of 20%Pd-1%Tb/C, the 20%Pd-1%Tb catalyst supported on poly(diallyldimethylammonium chloride) (PDDA)-functionalized activated carbon nanotubes was prepared, and it exhibits a better catalytic activity. The improvement mainly results from the further increase of metallic Pd due to the presence of PDDA.

  16. Toward an improved understanding of tropical forest carbon cycle feedbacks in the Earth's climate system

    NASA Astrophysics Data System (ADS)

    Chambers, J. Q.

    2015-12-01

    There are large uncertainties regarding the response of tropical forest carbon cycling to expected global changes over the 21st Century. Whether tropical forests continue to act as large carbon sinks, or shift to become significant carbon sources, plays a major role in determining the rate and intensity of climate change impacts. Most terrestrial models predict a large current tropical forest carbon sink due to the effects of rising atmospheric CO2 on plant productivity. Yet the strength of this sink is likely limited by multiple factors, and the magnitudes of these constraints remain in question. As atmospheric CO2 levels continue to rise, nutrient limitations are likely to become more prominent, yet the current suite of Earth system models (ESMs) have inadequate representations of nutrient constraints on tropical forest productivity. Concurrently, the negative effects of rising temperatures and shifting precipitation patterns on plant production are expected to become more pronounced, likely driving reductions in tropical forest carbon assimilation and storage. In addition to these carbon-climate feedbacks, human land-use activities in the tropics result in both carbon sources from deforestation, and carbon sinks in secondary forests, both of which are also inadequately represented in ESMs. This talk will focus on recent advances in our understanding of these key carbon cycle processes, and explore several field research activities needed to advance ESM treatment of the underlying mechanisms.

  17. A General Silica-Templating Synthesis of Alkaline Mesoporous Carbon Catalysts for Highly Efficient H2S Oxidation at Room Temperature.

    PubMed

    Zhang, Zixiao; Jiang, Wuyou; Long, Donghui; Wang, Jitong; Qiao, Wenming; Ling, Licheng

    2017-01-25

    A general synthesis of alkaline mesoporous carbons (AMCs) is developed based on a simplified silica-templating method for room-temperature catalytic oxidation of H2S. The key to the success relies on dissolving the silica templates to create the interconnected mesoporous structure as well as leaving parts of the alkaline products in the pores; both of them are prerequisites for H2S oxidation. By adjusting the alkaline etching degree and organic/inorganic ratio, the porosity and basicity of the AMC could be simultaneously tuned, allowing the AMCs direct use for H2S catalytic oxidation with an unprecedented removal capacities of 4.49 ± 0.12 g/g. Such excellent catalytic performance should be attributed to the developed pore structure that stores the product sulfur and the strong basicity that promotes the dissociation of H2S into HS(-) ions. Moreover, this simplified silica-templating method could be easily extended to the preparation of various silica templated mesoporous carbon catalysts. All these AMCs demonstrate a successful combination of low cost with high performance, which may well be the answer for the technical development of industrial H2S removal.

  18. The active outer shell of Earth: What remains to be explored in carbon and life interactions?

    NASA Astrophysics Data System (ADS)

    Boetius, Antje

    2016-04-01

    Recent advances in methods and technologies have allowed us to explore the interaction between life and abiotic resources from nano to megascales in space and time, and this has set new challenges to the geosciences. This lecture aims at discussing key biological factors in the question of the dynamics of carbon reservoirs and fluxes on Earth, and the challenges to the geosciences to incorporate and further this knowledge. Humans themselves as one such biological factor have considerably changed the dynamics of carbon and other elements, with repercussions to most other life forms on Earth. Which other life forms shape carbon fluxes and reservoirs, and what do we know about their key traits in catalyzing geochemical reactions, their past and their future? I will use case studies from my own research field - geobiology of the oceans and the cryosphere - and from other geoscience areas to highlight the considerable non-linearity introduced by life to element fluxes and the environment; and discuss advances but also gaps in knowledge and research approaches concerning assessing and predicting carbon transformations in the active outer shell of Earth.

  19. Low-cost, acid/alkaline-resistant, and fluorine-free superhydrophobic fabric coating from onionlike carbon microspheres converted from waste polyethylene terephthalate.

    PubMed

    Hu, Haibo; Gao, Lei; Chen, Changle; Chen, Qianwang

    2014-01-01

    Onionlike carbon microspheres composed of many nanoflakes have been prepared by pyrolyzing waste polyethylene terephthalate in supercritical carbon dioxide at 650 °C for 3 h followed by subsequent vacuum annealing at 1500 °C for 0.5 h. The obtained onionlike carbon microspheres have very high surface roughness and exhibit unique hydrophobic properties. Considering their structural similarities with a lotus leaf, we further developed a low-cost, acid/alkaline-resistant, and fluorine-free superhydrophobic coating strategy on fabrics by employing the onionlike carbon microspheres and polydimethylsiloxane as raw materials. This provides a novel technique to convert waste polyethylene terephthalate to valuable carbon materials. At the same time, we demonstrate a novel application direction of carbon materials by taking advantage of their unique structural properties. The combination of recycling waste solid materials as carbon feedstock for valuable carbon material production, with the generation of highly value-added products such as superhydrophobic fabrics, may provide a feasible solution for sustainable solid waste treatment.

  20. 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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

    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 trends with different Ba

  1. ESA Earth Explorer 8 Candidate Mission CarbonSat: Error Budget for Atmospheric Carbon Dioxide and Methane Retrievals

    NASA Astrophysics Data System (ADS)

    Buchwitz, M.; Bovensmann, H.; Reuter, M.; Krings, T.; Heymann, J.; Schneising, O.; Burrows, J. P.; Boesch, H.; Meijer, Y.; Sierk, B.; Loscher, A.; Caron, J.; Ingmann, P.

    2015-11-01

    CarbonSat is one of two candidate missions for ESA's Earth Explorer 8 (EE8) satellite; one of them will be selected for implementation in November 2015 for a targeted launch date around 2023. The main goal of CarbonSat is to advance our knowledge of the sources and sinks, both natural and man-made, of the two most important anthropogenic greenhouse gases; carbon dioxide (CO2) and methane (CH4) from the global via the sub-continental to the local scale. CarbonSat will be the first satellite mission to image local scale emission hot spots of CO2 (e.g., cities, volcanoes, industrial areas) and CH4 (e.g., fossil fuel production, landfills, seeps) and to quantify their emissions and discriminate them from surrounding biospheric fluxes. The primary geophysical data products of CarbonSat are atmospheric column- averaged dry air mole fractions of CO2 and CH4, i.e., XCO2 (in ppm) and XCH4 (in ppb), respectively. In addition, CarbonSat will deliver a number of secondary data products, which will also be of good quality, such as vegetation chlorophyll Sun-Induced Fluorescence (SIF) as retrieved from clear solar Fraunhofer lines located at 755 nm; SIF will be retrieved simultaneously with the primary products. Here we present an updated error budget using the latest retrieval algorithm and instrument/mission specification focusing on nadir observations over land.

  2. Long-term legacy of massive carbon input to the Earth system: Anthropocene versus Eocene.

    PubMed

    Zeebe, Richard E; Zachos, James C

    2013-10-28

    Over the next few centuries, with unabated emissions of anthropogenic carbon dioxide (CO2), a total of 5000 Pg C may enter the atmosphere, causing CO2 concentrations to rise to approximately 2000 ppmv, global temperature to warm by more than 8(°)C and surface ocean pH to decline by approximately 0.7 units. A carbon release of this magnitude is unprecedented during the past 56 million years-and the outcome accordingly difficult to predict. In this regard, the geological record may provide foresight to how the Earth system will respond in the future. Here, we discuss the long-term legacy of massive carbon release into the Earth's surface reservoirs, comparing the Anthropocene with a past analogue, the Palaeocene-Eocene Thermal Maximum (PETM, approx. 56 Ma). We examine the natural processes and time scales of CO2 neutralization that determine the atmospheric lifetime of CO2 in response to carbon release. We compare the duration of carbon release during the Anthropocene versus PETM and the ensuing effects on ocean acidification and marine calcifying organisms. We also discuss the conundrum that the observed duration of the PETM appears to be much longer than predicted by models that use first-order assumptions. Finally, we comment on past and future mass extinctions and recovery times of biotic diversity.

  3. New alkaline earth-zirconium oxalates M2Zr(C 2O 4) 4· nH 2O ( M=Ba, Sr, Ca) synthesis, crystal structure and thermal behavior

    NASA Astrophysics Data System (ADS)

    Chapelet-Arab, B.; Nowogrocki, G.; Abraham, F.; Grandjean, S.

    2004-11-01

    Three new alkaline earth-zirconium oxalates M2Zr(C 2O 4) 4· nH 2O have been synthesized by precipitation methods for M=Ba, Sr, Ca. For each compound the crystal structure was determined from single crystals obtained by controlled diffusion of M 2+ and Zr 4+ ions through silica gel containing oxalic acid. Ba 2Zr(C 2O 4) 4·7H 2O, monoclinic, space group C2/c, a=9.830(2), b=29.019(6), c=9.178(2) Å, β=122.248(4) °, V=2214.2(8) Å, Z=4, R=0.0427; Sr 2Zr(C 2O 4) 4·11H 2O, tetragonal, space group I41/acd, a=16.139(4), c=18.247(6) Å, V=4753(2) Å,Z=8, R=0.0403; Ca 2Zr(C 2O 4) 4·5H 2O, orthorhombic, space group Pna2 1, a=8.4181(5), b=15.8885(8), c=15.8885(8) Å, V=2125(2) Å, Z=4, R=0.0622. The structures of the three compounds consist of chains of edge-shared MO 6(H 2O) x ( x=2 or 3) polyhedra connected to ZrO 8 polyhedra through oxalate groups. Depending on the arrangement of chains, the ZrO 8 polyhedron geometry (dodecahedron or square antiprism) and the connectivity, two types of three-dimensional frameworks are obtained. For the smallest M2+ cations (Sr 2+, Ca 2+), large tunnels are obtained, running down the c direction of the unit cell, which can accommodate zeolitic water molecules. For the largest Ba 2+ cation, the second framework is formed and is closely related to that of Pb 2Zr(C 2O 4) 4· nH 2O. The decomposition at 800°C into strontium carbonate, barium carbonate or calcium oxide and MZrO 3 ( M=Sr, Ba, Ca) perovskite is reported from thermal analyses studies and high temperature X-ray powder diffraction.

  4. New alkaline earth-zirconium oxalates M{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.nH{sub 2}O (M=Ba, Sr, Ca) synthesis, crystal structure and thermal behavior

    SciTech Connect

    Chapelet-Arab, B.; Abraham, F. . E-mail: francis.abraham@ensc-lille.fr; Grandjean, S.

    2004-11-01

    Three new alkaline earth-zirconium oxalates M{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.nH{sub 2}O have been synthesized by precipitation methods for M=Ba, Sr, Ca. For each compound the crystal structure was determined from single crystals obtained by controlled diffusion of M{sup 2+} and Zr{sup 4+} ions through silica gel containing oxalic acid. Ba{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.7H{sub 2}O, monoclinic, space group C2/c, a=9.830(2), b=29.019(6), c=9.178(2)A, {beta}=122.248(4){sup o}, V=2214.2(8)A3, Z=4, R=0.0427; Sr{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.11H{sub 2}O, tetragonal, space group I41/acd, a=16.139(4), c=18.247(6)A, V=4753(2)A3, Z=8, R=0.0403; Ca{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.5H{sub 2}O, orthorhombic, space group Pna2{sub 1}, a=8.4181(5), b=15.8885(8), c=15.8885(8)A, V=2125(2)A3, Z=4, R=0.0622. The structures of the three compounds consist of chains of edge-shared MO{sub 6}(H{sub 2}O){sub x} (x=2 or 3) polyhedra connected to ZrO{sub 8} polyhedra through oxalate groups. Depending on the arrangement of chains, the ZrO{sub 8} polyhedron geometry (dodecahedron or square antiprism) and the connectivity, two types of three-dimensional frameworks are obtained. For the smallest M{sup 2+} cations (Sr{sup 2+}, Ca{sup 2+}), large tunnels are obtained, running down the c direction of the unit cell, which can accommodate zeolitic water molecules. For the largest Ba{sup 2+} cation, the second framework is formed and is closely related to that of Pb{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.nH{sub 2}O. The decomposition at 800{sup o}C into strontium carbonate, barium carbonate or calcium oxide and MZrO{sub 3} (M=Sr, Ba, Ca) perovskite is reported from thermal analyses studies and high temperature X-ray powder diffraction.

  5. On the abundances of carbon dioxide isotopologues in the atmospheres of mars and earth

    NASA Astrophysics Data System (ADS)

    Shved, G. M.

    2016-03-01

    The isotopic composition of carbon dioxide in the Martian atmosphere from the measurements of Mars Science Laboratory have been used to estimate the relative abundances of CO2 isotopologues in the Martian atmosphere. Concurrently, this study has revealed long-standing errors in the amounts of some of low-abundance CO2 isotopologues in the Earth's atmosphere in the databases of spectroscopic parameters of gases (HITRAN, etc.).

  6. Chemical composition of modern and fossil hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation - Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

    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

  7. Metal-free N-doped carbon nanofibers as an efficient catalyst for oxygen reduction reactions in alkaline and acid media.

    PubMed

    Li, Ruchun; Shao, Xiaofeng; Li, Shuoshuo; Cheng, Pengpeng; Hu, Zhaoxia; Yuan, Dingsheng

    2016-12-16

    The development of metal-free catalysts to replace the use of Pt has played an important role in relation to its application to fuel cells. We report N-doped carbon nanofibers as the catalyst of an oxygen reduction reaction, which were synthesized via carbonizing bacterial cellulose-polypyrrole composites. The as-prepared material exhibited remarkable catalytic activity toward the oxygen reduction reaction with comparable onset potential and the ability to limit the current density of commercial Pt/C catalysts in both alkaline and acid media due to the unique porous three-dimensional network structure and the doped nitrogen atoms. The effect of N functionalities on catalytic behavior was systematically investigated. The results demonstrated that pyridinic-N was the dominating factor for catalytic performance toward the oxygen reduction reaction. Additionally, N-doped carbon nanofibers also demonstrated excellent cycling stability (93.2% and 89.4% retention of current density after chronoamperometry 20 000 s in alkaline and media, respectively), obviously superior to Pt/C.

  8. Metal-free N-doped carbon nanofibers as an efficient catalyst for oxygen reduction reactions in alkaline and acid media

    NASA Astrophysics Data System (ADS)

    Li, Ruchun; Shao, Xiaofeng; Li, Shuoshuo; Cheng, Pengpeng; Hu, Zhaoxia; Yuan, Dingsheng

    2016-12-01

    The development of metal-free catalysts to replace the use of Pt has played an important role in relation to its application to fuel cells. We report N-doped carbon nanofibers as the catalyst of an oxygen reduction reaction, which were synthesized via carbonizing bacterial cellulose-polypyrrole composites. The as-prepared material exhibited remarkable catalytic activity toward the oxygen reduction reaction with comparable onset potential and the ability to limit the current density of commercial Pt/C catalysts in both alkaline and acid media due to the unique porous three-dimensional network structure and the doped nitrogen atoms. The effect of N functionalities on catalytic behavior was systematically investigated. The results demonstrated that pyridinic-N was the dominating factor for catalytic performance toward the oxygen reduction reaction. Additionally, N-doped carbon nanofibers also demonstrated excellent cycling stability (93.2% and 89.4% retention of current density after chronoamperometry 20 000 s in alkaline and media, respectively), obviously superior to Pt/C.

  9. Storage and recycling of water and carbon dioxide in the earth

    NASA Technical Reports Server (NTRS)

    Wood, Bernard J.

    1994-01-01

    The stabilities and properties of water- and carbon-bearing phases in the earth have been determined from phase equilibrium measurements, combined with new data on the equations of state of water, carbon dioxide, carbonates and hydrates. The data have then been used to predict the fate of calcite and hydrous phases in subducting oceanic lithosphere. From the compositions of MORB's one can estimate concentrations of water and carbon of around 200 ppm and 80 ppm respectively in the upper mantle. Lower mantle estimates are very uncertain, but 1900 ppm water and 2000 ppm C are plausible concentrations. Measurements of the density of supercritical water to 3 GPa demonstrate that this phase is less compressible than anticipated from the equations of state of Haar et al. or Saul and Wagner and is closer to predictions based on molecular dynamics simulations. Conversely, fugacity measurements on carbon dioxide to 7 GPa show that this fluid is more compressible than predicted from the MRK equation of state. The results imply that hydrates are relatively more stable and carbonates less stable at pressures greater than 5 GPa than would be predicted from simple extrapolation of the low pressure data. Nevertheless, carbonates remain extremely refractory phases within both the upper and lower mantle.

  10. The Carbon Cycle and the Earth Systems--Studying the Carbon Cycle in Multidisciplinary Environmental Context.

    ERIC Educational Resources Information Center

    Gudovitch, Yossi; Orion, Nir

    This paper describes a method that attempts to confront the challenges of developing an environmentally-based earth sciences program. The research scheme includes five stages: (1) predevelopment study; (2) curriculum development; (3) implementation; (4) formative evaluation; and (5) curriculum modification. The research results indicate that the…

  11. Assessment of DNA damage of Lewis lung carcinoma cells irradiated by carbon ions and X-rays using alkaline comet assay

    NASA Astrophysics Data System (ADS)

    Li, Ping; Zhou, Li-Bin; Jin, Xiao-Dong; He, Jing; Dai, Zhong-Ying; Zhou, Guang-Ming; Gao, Qing-Xiang; Li, Sha; Li, Qiang

    2008-01-01

    DNA damage and cell reproductive death determined by alkaline comet and clonogenic survival assays were examined in Lewis lung carcinoma cells after exposure to 89.63 MeV/u carbon ion and 6 MV X-ray irradiations, respectively. Based on the survival data, Lewis lung carcinoma cells were verified to be more radiosensitive to the carbon ion beam than to the X-ray irradiation. The relative biological effectiveness (RBE) value, which was up to 1.77 at 10% survival level, showed that the DNA damage induced by the high-LET carbon ion beam was more remarkable than that induced by the low-LET X-ray irradiation. The dose response curves of “Tail DNA (%)” (TD) and “Olive tail moment” (OTM) for the carbon ion irradiation showed saturation beyond about 8 Gy. This behavior was not found in the X-ray curves. Additionally, the carbon ion beam produced a lower survival fraction at 2 Gy (SF2) value and a higher initial Olive tail moment 2 Gy (OTM2) than those for the X-ray irradiation. These results suggest that carbon ion beams having high-LET values produced more severe cell reproductive death and DNA damage in Lewis lung carcinoma cells in comparison with X-rays and comet assay might be an effective predictive test even combining with clonogenic assay to assess cellular radiosensitivity.

  12. The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media

    SciTech Connect

    John, Samuel St.; Atkinson, Robert W.; Roy, Asa; Unocic, Raymond R.; Papandrew, Alexander B.; Zawodzinski, Thomas A.

    2016-01-11

    In this paper, we investigated the performance of several carbon-supported RuxPty electrocatalysts for their alkaline hydrogen oxidation and oxygen reduction performance in the presence of carbonate and compared their performance with monometallic, carbon-supported Pt. Our results indicate a strong dependence of HOR upon pH for the monometallic Pt catalysts (22 mV/pH) and a weak dependence upon pH for the Ru-containing electrocatalysts (3.7, 2.5, and 4.7 mV/pH on Ru0.2Pt0.8, Ru0.4Pt0.6, and Ru0.8Pt0.2, respectively). These results are consistent with our previous findings that illustrate a change in rds from electron transfer (on monometallic Pt) to dissociative hydrogen adsorption (on RuxPty catalysts). Analysis of the kinetic currents to determine the rate-determining step via Tafel slope analysis provides additional data supporting this conclusion. There is no difference in the performance at comparable pH values in the presence or absence of carbonate on monometallic Pt indicating that water/hydroxide is the primary proton acceptor for alkaline HOR in 0.1 M KOH aqueous electrolyte. Finally, we observe no pH or carbonate dependence for the ORR on monometallic Pt.

  13. A Possible Carbon-rich Interior in Super-Earth 55 Cancri e

    NASA Astrophysics Data System (ADS)

    Madhusudhan, Nikku; Lee, Kanani K. M.; Mousis, Olivier

    2012-11-01

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

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

    SciTech Connect

    Madhusudhan, Nikku; Lee, Kanani K. M.; Mousis, Olivier

    2012-11-10

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  17. The oxidation state of the mantle and the extraction of carbon from Earth's interior.

    PubMed

    Stagno, Vincenzo; Ojwang, Dickson O; McCammon, Catherine A; Frost, Daniel J

    2013-01-03

    Determining the oxygen fugacity of Earth's silicate mantle is of prime importance because it affects the speciation and mobility of volatile elements in the interior and has controlled the character of degassing species from the Earth since the planet's formation. Oxygen fugacities recorded by garnet-bearing peridotite xenoliths from Archaean lithosphere are of particular interest, because they provide constraints on the nature of volatile-bearing metasomatic fluids and melts active in the oldest mantle samples, including those in which diamonds are found. Here we report the results of experiments to test garnet oxythermobarometry equilibria under high-pressure conditions relevant to the deepest mantle xenoliths. We present a formulation for the most successful equilibrium and use it to determine an accurate picture of the oxygen fugacity through cratonic lithosphere. The oxygen fugacity of the deepest rocks is found to be at least one order of magnitude more oxidized than previously estimated. At depths where diamonds can form, the oxygen fugacity is not compatible with the stability of either carbonate- or methane-rich liquid but is instead compatible with a metasomatic liquid poor in carbonate and dominated by either water or silicate melt. The equilibrium also indicates that the relative oxygen fugacity of garnet-bearing rocks will increase with decreasing depth during adiabatic decompression. This implies that carbon in the asthenospheric mantle will be hosted as graphite or diamond but will be oxidized to produce carbonate melt through the reduction of Fe(3+) in silicate minerals during upwelling. The depth of carbonate melt formation will depend on the ratio of Fe(3+) to total iron in the bulk rock. This 'redox melting' relationship has important implications for the onset of geophysically detectable incipient melting and for the extraction of carbon dioxide from the mantle through decompressive melting.

  18. Charge Compensation in RE3+ (RE = Eu, Gd) and M+ (M = Li, Na, K) Co-Doped Alkaline Earth Nanofluorides Obtained by Microwave Reaction with Reactive Ionic Liquids Leading to Improved Optical Properties

    SciTech Connect

    Lorbeer, C; Behrends, F; Cybinska, J; Eckert, H; Mudring, Anja -V

    2014-01-01

    Alkaline earth fluorides are extraordinarily promising host matrices for phosphor materials with regard to rare earth doping. In particular, quantum cutting materials, which might considerably enhance the efficiency of mercury-free fluorescent lamps or SC solar cells, are often based on rare earth containing crystalline fluorides such as NaGdF4, GdF3 or LaF3. Substituting most of the precious rare earth ions and simultaneously retaining the efficiency of the phosphor is a major goal. Alkaline earth fluoride nanoparticles doped with trivalent lanthanide ions (which are required for the quantum cutting phenomenon) were prepared via a microwave assisted method in ionic liquids. As doping trivalent ions into a host with divalent cations requires charge compensation, this effect was thoroughly studied by powder X-ray and electron diffraction, luminescence spectroscopy and 23Na, 139La and 19F solid state NMR spectroscopy. Monovalent alkali ions were codoped with the trivalent lanthanide ions to relieve stress and achieve a better crystallinity and higher quantum cutting abilities of the prepared material. 19F-magic angle spinning (MAS)-NMR-spectra, assisted by 19F{23Na} rotational echo double resonance (REDOR) studies, reveal distinct local fluoride environments, the populations of which are discussed in relation to spatial distribution and clustering models. In the co-doped samples, fluoride species having both Na+ and La3+ ions within their coordination sphere can be identified and quantified. This interplay of mono- and trivalent ions in the CaF2 lattice appears to be an efficient charge compensation mechanism that allows for improved performance characteristics of such co-doped phosphor materials.

  19. {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

    SciTech Connect

    Arevalo-Hidalgo, Ana G.; Dugar, Sneha; Fu, Riqiang; Hernandez-Maldonado, Arturo J.

    2012-07-15

    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.

  20. Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Pengcheng; Zhou, Yingke; Hu, Min; Chen, Jian

    2017-01-01

    Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

  1. Application of response surface methodology for optimization of parameters for microwave heating of rare earth carbonates

    NASA Astrophysics Data System (ADS)

    Yin, Shaohua; Lin, Guo; Li, Shiwei; Peng, Jinhui; Zhang, Libo

    2016-09-01

    Microwave heating has been applied in the field of drying rare earth carbonates to improve drying efficiency and reduce energy consumption. The effects of power density, material thickness and drying time on the weight reduction (WR) are studied using response surface methodology (RSM). The results show that RSM is feasible to describe the relationship between the independent variables and weight reduction. Based on the analysis of variance (ANOVA), the model is in accordance with the experimental data. The optimum experiment conditions are power density 6 w/g, material thickness 15 mm and drying time 15 min, resulting in an experimental weight reduction of 73%. Comparative experiments show that microwave drying has the advantages of rapid dehydration and energy conservation. Particle analysis shows that the size distribution of rare earth carbonates after microwave drying is more even than those in an oven. Based on these findings, microwave heating technology has an important meaning to energy-saving and improvement of production efficiency for rare earth smelting enterprises and is a green heating process.

  2. Expression and characterization of a codon-optimized alkaline-stable carbonic anhydrase from Aliivibrio salmonicida for CO2 sequestration applications.

    PubMed

    Jun, So-Young; Kim, Sung Ho; Kanth, Bashista Kumar; Lee, Jinwon; Pack, Seung Pil

    2017-03-01

    The CO2 mineralization process, accelerated by carbonic anhydrase (CA) was proposed for the efficient capture and storage of CO2, the accumulation of which in the atmosphere is the main cause of global warming. Here, we characterize a highly stable form of the cloned CA from the Gram-negative marine bacterium Aliivibrio salmonicida, named ASCA that can promote CO2 absorption in an alkaline solvent required for efficient carbon capture. We designed a mature form of ASCA (mASCA) using a codon optimization of ASCA gene and removal of ASCA signal peptide. mASCA was highly expressed (255 mg/L) with a molecular weight of approximately 26 kDa. The mASCA enzyme exhibited stable esterase activity within a temperature range of 10-60 °C and a pH range of 6-11. mASCA activity remained stable for 48 h at pH 10. We also investigated its inhibition profiles using inorganic anions, such as acetazolamide, sulfanilamide, iodide, nitrate, and azide. We also demonstrate that mASCA is capable of catalyzing the conversion of CO2 to CaCO3 (calcite form) in the presence of Ca(2+). It should be noted that mASCA enzyme exhibits high production yield and sufficient stabilities against relatively high temperature and alkaline pH, which are required conditions for the development of more efficient enzymatic CCS systems.

  3. Control of nitrification/denitrification in an onsite two-chamber intermittently aerated membrane bioreactor with alkalinity and carbon addition: Model and experiment.

    PubMed

    Perera, Mahamalage Kusumitha; Englehardt, James D; Tchobanoglous, George; Shamskhorzani, Reza

    2017-02-20

    Denitrifying membrane bioreactors (MBRs) are being found useful in water reuse treatment systems, including net-zero water (nearly closed-loop), non-reverse osmosis-based, direct potable reuse (DPR) systems. In such systems nitrogen may need to be controlled in the MBR to meet the nitrate drinking water standard in the finished water. To achieve efficient nitrification and denitrification, the addition of alkalinity and external carbon may be required, and control of the carbon feed rate is then important. In this work, an onsite, two-chamber aerobic nitrifying/denitrifying MBR, representing one unit process of a net-zero water, non-reverse osmosis-based DPR system, was modeled as a basis for control of the MBR internal recycling rate, aeration rate, and external carbon feed rate. Specifically, a modification of the activated sludge model ASM2dSMP was modified further to represent the rate of recycling between separate aerobic and anoxic chambers, rates of carbon and alkalinity feed, and variable aeration schedule, and was demonstrated versus field data. The optimal aeration pattern for the modeled reactor configuration and influent matrix was found to be 30 min of aeration in a 2 h cycle (104 m(3) air/d per 1 m(3)/d average influent), to ultimately meet the nitrate drinking water standard. Optimal recycling ratios (inter-chamber flow to average daily flow) were found to be 1.5 and 3 during rest and mixing periods, respectively. The model can be used to optimize aeration pattern and recycling ratio in such MBRs, with slight modifications to reflect reactor configuration, influent matrix, and target nitrogen species concentrations, though some recalibration may be required.

  4. Susceptibility of the early Earth to irreversible glaciation caused by carbon dioxide clouds.

    PubMed

    Caldeira, K; Kasting, J F

    1992-09-17

    Simple energy-balance climate models of the Budyko/Sellers type predict that a small (2-5%) decrease in solar output could result in runaway glaciation on the Earth. But solar fluxes 25-30% lower early in the Earth's history apparently did not lead to this result. One currently favoured explanation is that high partial pressures of carbon dioxide, caused by higher volcanic outgassing rates and/or slower rates of silicate weathering, created a large enough greenhouse effect to keep the planet warm. This does not resolve the problem of climate stability, however, because as we argue here, the oceans can freeze much more quickly than CO2 can accumulate in the atmosphere. Had such a transient global glaciation occurred in the distant past when solar luminosity was low, it might have been irreversible because of the formation of highly reflective CO2 clouds, similar to those encountered in climate simulations of early Mars. Our simulations of the early Earth, incorporating the possible formation of such clouds, suggest that the Earth might not be habitable today had it not been warm during the first part of its history.

  5. Hidden carbon in Earth's inner core revealed by shear softening in dense Fe7C3.

    PubMed

    Chen, Bin; Li, Zeyu; Zhang, Dongzhou; Liu, Jiachao; Hu, Michael Y; Zhao, Jiyong; Bi, Wenli; Alp, E Ercan; Xiao, Yuming; Chow, Paul; Li, Jie

    2014-12-16

    Earth's inner core is known to consist of crystalline iron alloyed with a small amount of nickel and lighter elements, but the shear wave (S wave) travels through the inner core at about half the speed expected for most iron-rich alloys under relevant pressures. The anomalously low S-wave velocity (vS) has been attributed to the presence of liquid, hence questioning the solidity of the inner core. Here we report new experimental data up to core pressures on iron carbide Fe7C3, a candidate component of the inner core, showing that its sound velocities dropped significantly near the end of a pressure-induced spin-pairing transition, which took place gradually between 10 GPa and 53 GPa. Following the transition, the sound velocities increased with density at an exceptionally low rate. Extrapolating the data to the inner core pressure and accounting for the temperature effect, we found that low-spin Fe7C3 can reproduce the observed vS of the inner core, thus eliminating the need to invoke partial melting or a postulated large temperature effect. The model of a carbon-rich inner core may be consistent with existing constraints on the Earth's carbon budget and would imply that as much as two thirds of the planet's carbon is hidden in its center sphere.

  6. When can ocean acidification impacts be detected from decadal alkalinity measurements?

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    We use a large initial condition suite of simulations (30 runs) with an Earth system model to assess the detectability of biogeochemical impacts of ocean acidification (OA) on the marine alkalinity distribution from decadally repeated hydrographic measurements such as those produced by the Global Ship-Based Hydrographic Investigations Program (GO-SHIP). Detection of these impacts is complicated by alkalinity changes from variability and long-term trends in freshwater and organic matter cycling and ocean circulation. In our ensemble simulation, variability in freshwater cycling generates large changes in alkalinity that obscure the changes of interest and prevent the attribution of observed alkalinity redistribution to OA. These complications from freshwater cycling can be mostly avoided through salinity normalization of alkalinity. With the salinity-normalized alkalinity, modeled OA impacts are broadly detectable in the surface of the subtropical gyres by 2030. Discrepancies between this finding and the finding of an earlier analysis suggest that these estimates are strongly sensitive to the patterns of calcium carbonate export simulated by the model. OA impacts are detectable later in the subpolar and equatorial regions due to slower responses of alkalinity to OA in these regions and greater seasonal equatorial alkalinity variability. OA impacts are detectable later at depth despite lower variability due to smaller rates of change and consistent measurement uncertainty.

  7. Catalytic enantioselective construction of tetrasubstituted carbons by self-assembled poly rare earth metal complexes.

    PubMed

    Shibasaki, Masakatsu; Kanai, Motomu

    2007-07-07

    Rare earth metal-based enantioselective catalysts that can promote practical cyanation reactions of ketones and ketoimines were developed. These catalytic enantioselective tetrasubstituted carbon-forming reactions are useful platforms for the synthesis of biologically active compounds. ESI-MS and crystallographic studies of the asymmetric catalysts revealed that the active catalysts are polymetallic complexes produced through the assembly of modules. The higher-order structure of the polymetallic complexes has strong effects on catalyst activity and enantioselectivity. Controlling the higher-order structure of artificial polymetallic asymmetric catalysts is a new strategy for optimizing asymmetric catalysts. Recent progress in this approach is also described.

  8. First-principles study of fission product (Xe, Cs, Sr) incorporation and segregation in alkaline earth metal oxides, HfO2, and MgO-HfO2 interface

    SciTech Connect

    Liu, Xiang-yang; Uberuaga, Blas P; Sickafus, Kurt E

    2008-01-01

    In order to close the nuclear fuel cycle, advanced concepts for separating out fission products are necessary. One approach is to use a dispersion fuel form in which a fissile core is surrounded by an inert matrix that captures and immobilizes the fission products from the core. If this inert matrix can be easily separated from the fuel, via e.g. solution chemistry, the fission products can be separated from the fissile material. We examine a surrogate dispersion fuel composition, in which hafnia (HfO{sub 2}) is a surrogate for the fissile core and alkaline earth metal oxides are used as the inert matrix. The questions of fission product incorporation in these oxides and possible segregation behavior at interfaces are considered. Density functional theory based calculations for fission product elements (Xe, Sr, and Cs) in these oxides are carried out. We find smaller incorporation energy in hafnia than in MgO for Cs and Sr, and Xe if variation of charge state is allowed. We also find that this trend is reversed or reduced for alkaline earth metal oxides with large cation sizes. Model interfacial calculations show a strong tendency of segregation from bulk MgO to MgO-HfO{sub 2} interfaces.

  9. Influences of alkaline earth metal substitution on the crystal structure and physical properties of magnetic RuSr1.9A0.1GdCu2O8 (A = Ca, Sr, and Ba) superconductors.

    PubMed

    Hur, Su Gil; Park, Dae Hoon; Hwang, Seong-Ju; Kim, Seung Joo; Lee, J H; Lee, Sang Young

    2005-11-24

    We have investigated the effect of alkaline earth metal substitution on the crystal structure and physical properties of magnetic superconductors RuSr(1.9)A(0.1)GdCu(2)O(8) (A = Ca, Sr, and Ba) in order to probe an interaction between the magnetic coupling of the RuO(2) layer and the superconductivity of the CuO(2) layer. X-ray diffraction and X-ray absorption spectroscopic analyses demonstrate that the isovalent substitution of Sr ions with Ca or Ba ions makes it possible to tune the interlayer distance between the CuO(2) and the RuO(2) layers. From the measurements of electrical resistance and magnetic susceptibility, it was found that, in contrast to negligible change of magnetization, both of the alkaline earth metal substitutions lead to a notable depression of zero-resistance temperature T(c) (DeltaT(c) approximately 17-19 K). On the basis of the absence of a systematic correlation between the T(c) and the interlayer distance/magnetization, we have concluded that the internal magnetic field of the RuO(2) layer has insignificant influence on the superconducting property of the CuO(2) layer in the ruthenocuprate.

  10. The Mauna Loa carbon dioxide record: lessons for long-term Earth observations

    USGS Publications Warehouse

    Sundquist, Eric T.; Keeling, Ralph F.

    2009-01-01

    The Mauna Loa carbon dioxide record is an iconic symbol of the human capacity to alter the planet. Yet this record would not have been possible without the remarkable work of one man, Charles David Keeling. We describe three emergent themes that characterized his work: (1) his desire to study and understand the processes that control atmospheric CO2 and the global carbon cycle, (2) his campaign to identify and minimize systematic measurement error, and (3) his tenacious efforts to maintain continuous funding despite changing government priorities and institutions. In many ways, the story of the Mauna Loa record demonstrates that distinctions between research and “routine” measurements are not very useful in long-term monitoring of Earth properties and processes.

  11. Carbon-dioxide-rich silicate melt in the Earth's upper mantle.

    PubMed

    Dasgupta, Rajdeep; Mallik, Ananya; Tsuno, Kyusei; Withers, Anthony C; Hirth, Greg; Hirschmann, Marc M

    2013-01-10

    The onset of melting in the Earth's upper mantle influences the thermal evolution of the planet, fluxes of key volatiles to the exosphere, and geochemical and geophysical properties of the mantle. Although carbonatitic melt could be stable 250 km or less beneath mid-oceanic ridges, owing to the small fraction (∼0.03 wt%) its effects on the mantle properties are unclear. Geophysical measurements, however, suggest that melts of greater volume may be present at ∼200 km (refs 3-5) but large melt fractions are thought to be restricted to shallower depths. Here we present experiments on carbonated peridotites over 2-5 GPa that constrain the location and the slope of the onset of silicate melting in the mantle. We find that the pressure-temperature slope of carbonated silicate melting is steeper than the solidus of volatile-free peridotite and that silicate melting of dry peridotite + CO(2) beneath ridges commences at ∼180 km. Accounting for the effect of 50-200 p.p.m. H(2)O on freezing point depression, the onset of silicate melting for a sub-ridge mantle with ∼100 p.p.m. CO(2) becomes as deep as ∼220-300 km. We suggest that, on a global scale, carbonated silicate melt generation at a redox front ∼250-200 km deep, with destabilization of metal and majorite in the upwelling mantle, explains the oceanic low-velocity zone and the electrical conductivity structure of the mantle. In locally oxidized domains, deeper carbonated silicate melt may contribute to the seismic X-discontinuity. Furthermore, our results, along with the electrical conductivity of molten carbonated peridotite and that of the oceanic upper mantle, suggest that mantle at depth is CO(2)-rich but H(2)O-poor. Finally, carbonated silicate melts restrict the stability of carbonatite in the Earth's deep upper mantle, and the inventory of carbon, H(2)O and other highly incompatible elements at ridges becomes controlled by the flux of the former.

  12. The role of continents in modulating the whole Earth carbon and oxygen cycles

    NASA Astrophysics Data System (ADS)

    Lee, C. T.

    2015-12-01

    That Earth owes its oxygenated atmosphere to its presently unique claim on life is clear, but how its atmosphere evolved from an initially oxygen-free state remains unresolved. Here, we show that continents underwent a transformation from mafic to felsic compositions at about 2.7-2.5 Ga. We show that the generation of large amounts of felsic magmas requires hydrous parental magmas, which can only be generated by introduction of water into the mantle source of the hydrous parents. This suggests that this compositional shift in crust marked a switch from stagnant lid to a mobile lid (plate tectonics) convective regime. This compositional transformation resulted in a decrease in the oxidative weathering efficiency of the Earth's surface, which allowed atmospheric O2 to rise rapidly to a new steady state after ~2 Ga. Over the next billion years, steady accumulation of carbon deposited on continental shelves resulted in a gradual increase in the total CO2 inputs into the ocean and atmosphere system as metamorphic and magmatically induced degassing of the growing continental carbon reservoir amplified that from the mantle. Because oxygen production is formed by net organic carbon burial, which scales with total CO2 production, the increasing CO2 inputs to the ocean and atmosphere results in increasing O2 production. This causes slow build-up of atmospheric O2 until a threshold is reached at which atmospheric O2 levels run away, culminating in the oxygenated atmospheric conditions of the Phanerozoic. A two-step rise in atmospheric O2 is thus a necessary consequence of plate tectonics, continent formation and the growth of a crustal carbon reservoir. A provocative prediction of this work is that atmospheric CO2 concentrations may not have been as high in the Archean and Proterozoic as seems required to compensate for the faint young sun.

  13. Tracing Earth's O2 Evolution Using Zn/Fe Systematics in Carbonates

    NASA Astrophysics Data System (ADS)

    Liu, X. M.; Hazen, R. M.; Kah, L. C.; Sverjensky, D. A.; Cui, H.; Kaufmann, A. J.

    2014-12-01

    Redox-sensitive major and trace elements in iron formations and black shales have been developed as proxies to reconstruct paleoenvironmental history in deep time [1, 2]. Many Proterozoic successions, however, contain abundant limestone and dolomite, and so carbonate-based redox proxies could help greatly to expand the paleoredox record in time and space. Most paleoenvironmental research on sedimentary rocks focuses on individual stratigraphic successions; here, however, we adopt a complementary strategy, analyzing a large suite of Mesozoic, Paleozoic, and Precambrian samples that enables us to make global statistical statements about elemental abundances through time. Here we explore the use of Zn/Fe ratios as proxies to trace the evolution of redox profiles in marine basins, based on analysis of major and trace element concentrations in micro-drilled carbonate rocks that are well characterized in terms of stratigraphy, environmental setting, and petrology. Consistent with previous studies, we observed a two step increase of mean Zn/Fe ratios in carbonates through Earth history: at the Paleoproterozoic Great Oxidation Event and during the later Neoproterozoic Oxidation Event. Diagenetic alteration is always an issue for carbonate rocks, and so we carefully screened these carbonates for possible late diagenetic effects and hydrothermal alteration. Individual samples may still bear a trace element signature of early diagenesis, but our statistical approach indicates that despite diagenetic issues, meaningful trends can be discerned in the data. It is unlikely that changes in depositional environment, secular evolution of the mantle, and/or directional change in continental inputs greatly influenced the observed trace element behavior. Therefore, Zn/Fe ratios in shallow marine carbonates have the potential to provide a useful tracer for the redox evolution of the oceans and the rise of atmospheric O2. References:[1] Sahoo et al. (2012) Ocean oxygenation in the wake

  14. Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

    PubMed

    Amosa, Mutiu K

    2016-08-01

    Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process.

  15. Alkaline quinone flow battery.

    PubMed

    Lin, Kaixiang; Chen, Qing; Gerhardt, Michael R; Tong, Liuchuan; Kim, Sang Bok; Eisenach, Louise; Valle, Alvaro W; Hardee, David; Gordon, Roy G; Aziz, Michael J; Marshak, Michael P

    2015-09-25

    Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy.

  16. Infrared and Raman spectroscopic characterization of the carbonate mineral huanghoite - And in comparison with selected rare earth carbonates

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; López, Andrés; Scholz, Ricardo; Xi, Yunfei; Belotti, Fernanda Maria

    2013-11-01

    Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral huanghoite with possible formula given as BaCe(CO3)2F and compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of huanghoite displays three bands are at 1072, 1084 and 1091 cm-1 attributed to the CO32- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of CO32- symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 cm-1. No Raman bands of huanghoite were observed in these positions. Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm-1 assigned to the ν3 (CO3)2- antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands for huanghoite are observed at 687, 704, 718 and 730 cm-1and assigned to the (CO3)2- ν2 bending modes. Raman bands are observed for huanghoite at around 627 cm-1 and are assigned to the (CO3)2- ν4 bending modes. Raman bands are observed for the carbonate ν4 in phase bending modes at 722 cm-1 for bastnasite, 736 and 684 cm-1 for parisite, 714 cm-1 for northupite. Raman bands for huanghoite observed at 3259, 3484 and 3589 cm-1 are attributed to water stretching bands. Multiple bands are observed in the OH stretching region for bastnasite and parisite indicating the presence of water and OH units in their mineral structure. Vibrational spectroscopy enables new information on the structure of huanghoite to be assessed.

  17. Carbon fuel particles used in direct carbon conversion fuel cells

    DOEpatents

    Cooper, John F [Oakland, CA; Cherepy, Nerine [Oakland, CA

    2012-01-24

    A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

  18. Carbon Fuel Particles Used in Direct Carbon Conversion Fuel Cells

    DOEpatents

    Cooper, John F.; Cherepy, Nerine

    2008-10-21

    A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

  19. Carbon fuel particles used in direct carbon conversion fuel cells

    DOEpatents

    Cooper, John F.; Cherepy, Nerine

    2012-10-09

    A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

  20. Carbon fuel particles used in direct carbon conversion fuel cells

    DOEpatents

    Cooper, John F.; Cherepy, Nerine

    2011-08-16

    A system for preparing particulate carbon fuel and using the particulate carbon fuel in a fuel cell. Carbon particles are finely divided. The finely dividing carbon particles are introduced into the fuel cell. A gas containing oxygen is introduced into the fuel cell. The finely divided carbon particles are exposed to carbonate salts, or to molten NaOH or KOH or LiOH or mixtures of NaOH or KOH or LiOH, or to mixed hydroxides, or to alkali and alkaline earth nitrates.

  1. Towards the bulk carbon content of Earth; new metal carbide geobarometer in high pressure diamond.

    NASA Astrophysics Data System (ADS)

    Jones, A. P.; Dobson, D.; Milledge, H. J.

    2009-04-01

    Formation of the metallic core in Earth (and other terrestrial planets) is not thought to have completely removed metallic iron from the lower mantle, where metallic iron might therefore be expected to occur as a widespread minor component [1]. We provide a new interpretation of metallic carbide inclusions in some diamond, which support a very high pressure origin from the lower mantle. Unlike rare carbides reported from diamonds previously without silicon [2], some diamonds from Jagersfontein coexist with iron-rich carbides which do contain significant silicon and oxygen, including in some cases their partial exsolution products. Based on an experimental calibration for liquid iron coexisting with lower mantle perovskite [3], we are able to show that some carbides were likely derived from pressures of approximately 45 GPa, or depths of >1100 km. This potential geobarometer has not been corrected for the behaviour of carbon in the liquid iron system, which might be an important experimental goal. The recognition of this independent carbide geobarometer offers an important new tool to confirm the superdeep origin of some diamond. The carbide-bearing diamonds are from a group whose charcteristics have recently been described [5]. Their distinctive light carbon isotopic signature (13^C ~ 17 ) coupled with evidence for very low contents nitrogen which is nonetheless highly aggregated, might be interpreted as indicative of subducted carbon. However, we are also open to the possibility that the bulk carbon isotopic composition of the Earth might also be different from the normal mantle value (13^C ~ 6 ), in which case the potential 0.4 wt% C in the Earth's core could also be isotopically very light, as suggested by Grady et al [6]. References [1] Frost D et al, Nature 428, 409-412 (2004) [2] Jacob D E et al, Contrib. Mineral. Petrol., 146, 566-576 (2004) [3] Lin et al, Science, 295, 313-315 (2002) [4] Dubrovinsky L. et al, Nature 422, 58-61 (2003) [5] Jones A P et al, 9

  2. Facile synthesis of nitrogen-doped carbon nanotubes encapsulating nickel cobalt alloys 3D networks for oxygen evolution reaction in an alkaline solution

    NASA Astrophysics Data System (ADS)

    Yu, Jie; Zhong, Yijun; Zhou, Wei; Shao, Zongping

    2017-01-01

    Efficient oxygen evolution reaction (OER) catalysts are required to facilitate the large-scale exploitation of renewable energy resources and applications in electrochemical energy conversion technologies. Here, we show that metal alloy-based hybrids can provide higher electrocatalytic activity than their individual metal-based hybrids. In particular, NiCo alloys encapsulated within nitrogen-doped carbon nanotubes (NiCo@NCNTs) showed higher OER activities in an alkaline solution than the individual metal hybrids (Ni@NCNTs and Co@NCNTs), highlighting a synergy between the Ni and Co components. NiCo@NCNTs pyrolyzed at 800 °C displayed an overpotential of ∼41 mV at a current density of 10 mA cm-2 and were more stable than IrO2 during 1000-cycle accelerated durability testing at a scan rate of 100 mV s-1.

  3. The relationship between the surface composition and electrical properties of corrosion films formed on carbon steel in alkaline sour medium: an XPS and EIS study.

    PubMed

    Galicia, Policarpo; Batina, Nikola; González, Ignacio

    2006-07-27

    This work studies the evolution of 1018 carbon steel surfaces during 3-15 day immersion in alkaline sour medium 0.1 M (NH4)2S and 10 ppm CN(-) as (NaCN). During this period of time, surfaces were jointly characterized by electrochemical techniques in situ (electrochemical impedance spectroscopy, EIS) and spectroscopic techniques ex situ (X-ray photoelectron spectroscopy, XPS). The results obtained by these techniques allowed for a description of electrical and chemical properties of the films of corrosion products formed at the 1018 steel surface. There is an interconversion cycle of chemical species that form films of corrosion products whose conversion reactions favor two different types of diffusions inside the films: a chemical diffusion of iron cations and a typical diffusion of atomic hydrogen. These phenomena jointly control the passivity of the interface attacked by the corrosive medium.

  4. Ultrasonic-assisted synthesis of Pd-Pt/carbon nanotubes nanocomposites for enhanced electro-oxidation of ethanol and methanol in alkaline medium.

    PubMed

    Yang, Guohai; Zhou, Yazhou; Pan, Horng-Bin; Zhu, Chengzhou; Fu, Shaofang; Wai, Chien M; Du, Dan; Zhu, Jun-Jie; Lin, Yuehe

    2016-01-01

    Herein, a facile ultrasonic-assisted strategy was proposed to fabricate the Pd-Pt alloy/multi-walled carbon nanotubes (Pd-Pt/CNTs) nanocomposites. A good number of Pd-Pt alloy nanoparticles with an average of 3.4 ± 0.5 nm were supported on sidewalls of CNTs with uniform distribution. The composition of the Pd-Pt/CNTs nanocomposites could also be easily controlled, which provided a possible approach for the preparation of other architectures with anticipated properties. The Pd-Pt/CNTs nanocomposites were extensively studied by electron microscopy, induced coupled plasma atomic emission spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and applied for the ethanol and methanol electro-oxidation reaction in alkaline medium. The electrochemical results indicated that the nanocomposites had better electrocatalytic activities and stabilities, showing promising applications for fuel cells.

  5. Quantification of the dissolved inorganic carbon species and of the pH of alkaline solutions exposed to CO2 under pressure: a novel approach by Raman scattering.

    PubMed

    Beuvier, Thomas; Calvignac, Brice; Bardeau, Jean-François; Bulou, Alain; Boury, Frank; Gibaud, Alain

    2014-10-07

    Dissolved inorganic carbon (DIC) content of aqueous systems is a key function of the pH, of the total alkanility (TA), and of the partial pressure of CO2. However, common analytical techniques used to determine the DIC content in water are unable to operate under high CO2 pressure. Here, we propose to use Raman spectroscopy as a novel alternative to discriminate and quantitatively monitor the three dissolved inorganic carbon species CO2(aq), HCO3(-), and CO3(2-) of alkaline solutions under high CO2 pressure (from P = 0 to 250 bar at T = 40 °C). In addition, we demonstrate that the pH values can be extracted from the molalities of CO2(aq) and HCO3(-). The results are in very good agreement with those obtained from direct spectrophotometric measurements using colored indicators. This novel method presents the great advantage over high pressure conventional techniques of not using breakable electrodes or reference additives and appears of great interest especially in marine biogeochemistry, in carbon capture and storage and in material engineering under high CO2 pressure.

  6. Prokaryotic Responses to Ammonium and Organic Carbon Reveal Alternative CO2 Fixation Pathways and Importance of Alkaline Phosphatase in the Mesopelagic North Atlantic

    PubMed Central

    Baltar, Federico; Lundin, Daniel; Palovaara, Joakim; Lekunberri, Itziar; Reinthaler, Thomas; Herndl, Gerhard J.; Pinhassi, Jarone

    2016-01-01

    To decipher the response of mesopelagic prokaryotic communities to input of nutrients, we tracked changes in prokaryotic abundance, extracellular enzymatic activities, heterotrophic production, dark dissolved inorganic carbon (DIC) fixation, community composition (16S rRNA sequencing) and community gene expression (metatranscriptomics) in 3 microcosm experiments with water from the mesopelagic North Atlantic. Responses in 3 different treatments amended with thiosulfate, ammonium or organic matter (i.e., pyruvate plus acetate) were compared to unamended controls. The strongest stimulation was found in the organic matter enrichments, where all measured rates increased >10-fold. Strikingly, in the organic matter treatment, the dark DIC fixation rates—assumed to be related to autotrophic metabolisms—were equally stimulated as all the other heterotrophic-related parameters. This increase in DIC fixation rates was paralleled by an up-regulation of genes involved in DIC assimilation via anaplerotic pathways. Alkaline phosphatase was the metabolic rate most strongly stimulated and its activity seemed to be related to cross-activation by nonpartner histidine kinases, and/or the activation of genes involved in the regulation of elemental balance during catabolic processes. These findings suggest that episodic events such as strong sedimentation of organic matter into the mesopelagic might trigger rapid increases of originally rare members of the prokaryotic community, enhancing heterotrophic and autotrophic carbon uptake rates, ultimately affecting carbon cycling. Our experiments highlight a number of fairly unstudied microbial processes of potential importance in mesopelagic waters that require future attention. PMID:27818655

  7. Substrate and environmental controls on microbial assimilation of soil organic carbon: a framework for Earth System Models

    SciTech Connect

    Xu, Xiaofeng; Schimel, Joshua; Thornton, Peter E; Song, Xia; Yuan, Fengming; Goswami, Santonu

    2014-01-01

    Microbial assimilation of soil organic carbon is one of the fundamental processes of global carbon cycling and it determines the magnitude of microbial biomass in soils. Mechanistic understanding of microbial assimilation of soil organic carbon and its controls is important for to improve Earth system models ability to simulate carbon-climate feedbacks. Although microbial assimilation of soil organic carbon is broadly considered to be an important parameter, it really comprises two separate physiological processes: one-time assimilation efficiency and time-dependent microbial maintenance energy. Representing of these two mechanisms is crucial to more accurately simulate carbon cycling in soils. In this study, a simple modeling framework was developed to evaluate the substrate and environmental controls on microbial assimilation of soil organic carbon using a new term: microbial annual active period (the length of microbes remaining active in one year). Substrate quality has a positive effect on microbial assimilation of soil organic carbon: higher substrate quality (lower C:N ratio) leads to higher ratio of microbial carbon to soil organic carbon and vice versa. Increases in microbial annual active period from zero stimulate microbial assimilation of soil organic carbon; however, when microbial annual active period is longer than an optimal threshold, increasing this period decreases microbial biomass. The simulated ratios of soil microbial biomass to soil organic carbon are reasonably consistent with a recently compiled global dataset at the biome-level. The modeling framework of microbial assimilation of soil organic carbon and its controls developed in this study offers an applicable ways to incorporate microbial contributions to the carbon cycling into Earth system models for simulating carbon-climate feedbacks and to explain global patterns of microbial biomass.

  8. Using rare earth elements to constrain particulate organic carbon flux in the East China Sea.

    PubMed

    Hung, Chin-Chang; Chen, Ya-Feng; Hsu, Shih-Chieh; Wang, Kui; Chen, Jian Feng; Burdige, David J

    2016-09-27

    Fluxes of particulate organic carbon (POC) in the East China Sea (ECS) have been reported to decrease from the inner continental shelf towards the outer continental shelf. Recent research has shown that POC fluxes in the ECS may be overestimated due to active sediment resuspension. To better characterize the effect of sediment resuspension on particle fluxes in the ECS, rare earth elements (REEs) and organic carbon (OC) were used in separate two-member mixing models to evaluate trap-collected POC fluxes. The ratio of resuspended particles from sediments to total trap-collected particles in the ECS ranged from 82-94% using the OC mixing model, and 30-80% using the REEs mixing model, respectively. These results suggest that REEs may be better proxies for sediment resuspension than OC in high turbidity marginal seas because REEs do not appear to undergo degradation during particle sinking as compared to organic carbon. Our results suggest that REEs can be used as tracers to provide quantitative estimates of POC fluxes in marginal seas.

  9. Friction and wear of rare earths modified carbon fibers filled PTFE composite under dry sliding condition

    NASA Astrophysics Data System (ADS)

    Qian-qian, Shangguan; Xian-hua, Cheng

    2007-09-01

    Carbon fibers (CF) were surface treated with air-oxidation and rare earths (RE), respectively. The friction and wear properties of polytetrafluoroethylene (PTFE) composites filled with differently surface treated carbon fibers, sliding against GCr15 steel under dry sliding condition, were investigated on a block-on-ring M-2000 tribometer. Experimental results revealed that RE treatment largely reduced the friction and wear of CF reinforced PTFE (CF/PTFE) composites. The RE treated composite exhibited the lowest friction and wear under dry sliding. Scanning electron microscopy (SEM) investigation of worn surfaces and transfer films of CF/PTFE composites showed that RE treated CF/PTFE composites had the smoothest worn surface under given load and sliding speed, and a continuous and uniform transfer film formed on the counterface. X-ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that the oxygen concentration was obviously increased after RE treatment, and more carboxyl groups were introduced onto CF surfaces after RE treatment. The increase in the amount of oxygen-containing groups increased the interfacial adhesion between CF and PTFE matrix, and accordingly increased the tribological properties of the composite.

  10. Using rare earth elements to constrain particulate organic carbon flux in the East China Sea

    PubMed Central

    Hung, Chin-Chang; Chen, Ya-Feng; Hsu, Shih-Chieh; Wang, Kui; Chen, Jian Feng; Burdige, David J.

    2016-01-01

    Fluxes of particulate organic carbon (POC) in the East China Sea (ECS) have been reported to decrease from the inner continental shelf towards the outer continental shelf. Recent research has shown that POC fluxes in the ECS may be overestimated due to active sediment resuspension. To better characterize the effect of sediment resuspension on particle fluxes in the ECS, rare earth elements (REEs) and organic carbon (OC) were used in separate two-member mixing models to evaluate trap-collected POC fluxes. The ratio of resuspended particles from sediments to total trap-collected particles in the ECS ranged from 82–94% using the OC mixing model, and 30–80% using the REEs mixing model, respectively. These results suggest that REEs may be better proxies for sediment resuspension than OC in high turbidity marginal seas because REEs do not appear to undergo degradation during particle sinking as compared to organic carbon. Our results suggest that REEs can be used as tracers to provide quantitative estimates of POC fluxes in marginal seas. PMID:27670426

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

    SciTech Connect

    Wang, Jin-Hua; Tang, Gui-Mei; Qin, Ting-Xiao; Yan, Shi-Chen; Wang, Yong-Tao; Cui, Yue-Zhi; Weng Ng, Seik

    2014-11-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  13. Effects of alkalinity on ammonia removal, carbon dioxide stripping, and system pH in semi-commercial scale water recirculating aquaculture systems operated with moving bed bioreactors

    Technology Transfer Automated Retrieval System (TEKTRAN)

    When operating water recirculating systems (RAS) with high make-up water flushing rates in locations that have low alkalinity in the raw water, such as Norway, knowledge about the required RAS alkalinity concentration is important. Flushing RAS with make-up water containing low alkalinity washes out...

  14. 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).

    PubMed

    Gilson, Denis F R; Moyer, Ralph O

    2012-02-06

    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.

  15. Determination of calcium carbonate and sodium carbonate melting curves up to Earth's transition zone pressures with implications for the deep carbon cycle

    NASA Astrophysics Data System (ADS)

    Li, Zeyu; Li, Jie; Lange, Rebecca; Liu, Jiachao; Militzer, Burkhard

    2017-01-01

    Melting of carbonated eclogite or peridotite in the mantle influences the Earth's deep volatile cycles and bears on the long-term evolution of the atmosphere. Existing data on the melting curves of calcium carbonate (CaCO3) and sodium carbonate (Na2CO3) are limited to 7 GPa and therefore do not allow a full understanding of carbon storage and cycling in deep Earth. We determined the melting curves of CaCO3 and Na2CO3 to the pressures of Earth's transition zone using a multi-anvil apparatus. Melting was detected in situ by monitoring a steep and large increase in ionic conductivity, or inferred from sunken platinum markers in recovered samples. The melting point of CaCO3 rises from 1870 K at 3 GPa to ∼2000 K at 6 GPa and then stays within 50 K of 2000 K between 6 and 21 GPa. In contrast, the melting point of Na2CO3 increases continuously from ∼1123 K at 3 GPa to ∼1950 K at 17 GPa. A pre-melting peak in the alternating current through solid CaCO3 is attributed to the transition from aragonite to calcite V. Accordingly the calcite V-aragonite-liquid invariant point is placed at 13 ± 1 GPa and 1970 ± 40 K, with the Clapeyron slope of the calcite V to aragonite transition constrained at ∼70 K/GPa. The experiments on CaCO3 suggest a slight decrease in the melting temperature from 8 to 13 GPa, followed by a slight increase from 14 to 21 GPa. The negative melting slope is consistent with the prediction from our ab initio simulations that the liquid may be more compressible and become denser than calcite V at sufficiently high pressure. The positive melting slope at higher pressures is supported by the ab initio prediction that aragonite is denser than the liquid at pressures up to 30 GPa. At transition zone pressures the melting points of CaCO3 are comparable to that of Na2CO3 but nearly 400 K and 500 K lower than that of MgCO3. The fusible nature of compressed CaCO3 may be partially responsible for the majority of carbonatitic melts found on Earth's surface

  16. Bolide impacts and the oxidation state of carbon in the Earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.

    1992-01-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of Earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the Moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of Earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean. Specifically, high atmospheric CO/CO2 ratios are possible if either: (1) the climate was cool (like today's climate), so that hydration of dissolved CO to formate was slow, or (2) the formate formed from CO was efficiently converted into volatile, reduced carbon compounds, such as methane. A high atmospheric CO/CO2 ratio may have helped to facilitate prebiotic synthesis by enhancing the production rates of hydrogen cyanide and formaldehyde. Formaldehyde may have been produced even more efficiently by photochemical reduction of bicarbonate and formate in Fe(++)-rich surface waters.

  17. Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, James F.

    1990-01-01

    A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    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.

  19. The Alkaline Dissolution Rate of Calcite.

    PubMed

    Colombani, Jean

    2016-07-07

    Due to the widespread presence of calcium carbonate on Earth, several geochemical systems, among which is the global CO2 cycle, are controlled to a large extent by the dissolution and precipitation of this mineral. For this reason, the dissolution of calcite has been thoroughly investigated for decades. Despite this intense activity, a consensual value of the dissolution rate of calcite has not been found yet. We show here that the inconsistency between the reported values stems mainly from the variability of the chemical and hydrodynamic conditions of measurement. The spreading of the values, when compared in identical conditions, is much less than expected and is interpreted in terms of sample surface topography. This analysis leads us to propose benchmark values of the alkaline dissolution rate of calcite compatible with all the published values, and a method to use them in various chemical and hydrodynamic contexts.

  20. Environmentally friendly chemical recycling of poly(bisphenol-A carbonate) through phase transfer-catalysed alkaline hydrolysis under microwave irradiation.

    PubMed

    Tsintzou, Georgia P; Antonakou, Eleni V; Achilias, Dimitris S

    2012-11-30

    The various and widespread uses of polycarbonate (PC) polymers require a meaningful and environmentally friendly disposal method. In this study, depolymerisation of polycarbonate with water in a microwave reactor is suggested as a recycling method. Hydrolysis was investigated in an alkaline (NaOH) solution using a phase-transfer catalyst. All of the experiments were carried out in a sealed microwave reactor, in which the reaction pressure, temperature and microwave power were continuously controlled and recorded. In the hydrolysis products, bisphenol-A monomer was obtained and identified by FTIR measurements. PC degradation higher than 80% can be obtained at 160°C after a microwave irradiation time of either 40 min or 10 min using either a 5 or 10% (w/v) NaOH solution, respectively. GPC, TGA and DSC measurements of the PC residues revealed that surface erosion is the degradation mechanism. First-order reaction kinetics were estimated by implementing a simple kinetic model. Finally, greater than 85% degradation was achieved when waste CDs were treated with the same method. The results confirm the importance of the microwave power technique as a promising recycling method for PC-based waste plastics, resulting in monomer recovery in addition to substantial energy savings.

  1. Utilization of automotive shredder residues in a thermal process for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries.

    PubMed

    Ippolito, N M; Belardi, G; Medici, F; Piga, L

    2016-05-01

    The aim of the study is the recovery by thermal treatment of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, on the basis of the different phase change temperatures of the two metal-bearing phases. ASR (Automotive Shredder Residue), containing 68% of carbon, was added to the mixture to act as a reductant to metallic Zn of the zinc-bearing phases. The mixture was subsequently heated in different atmospheres (air, CO2 and N2) and at different temperatures (900°C, 1000°C and 1200°C) and stoichiometric excess of ASR (300%, 600% and 900%). Characterization of the mixture and of the residues of thermal treatment was carried out by chemical analysis, TGA/DTA, SEM and XRD. The results show that recovery of 99% of zinc (grade 97%) is achieved at 1000°C in N2 with a stoichiometric excess of car-fluff of 900%. This product could be suitable for production of new batteries after refining by hydrometallurgical way. Recovery of Mn around 98% in the residue of the treatment is achieved at any temperature and atmosphere tested with a grade of 57% at 900% excess of car-fluff. This residue is enriched in manganese oxide and could be used in the production of iron-manganese alloys.

  2. The soil carbon/nitrogen ratio and moisture affect microbial community structures in alkaline permafrost-affected soils with different vegetation types on the Tibetan plateau.

    PubMed

    Zhang, Xinfang; Xu, Shijian; Li, Changming; Zhao, Lin; Feng, Huyuan; Yue, Guangyang; Ren, Zhengwei; Cheng, Guogdong

    2014-01-01

    In the Tibetan permafrost region, vegetation types and soil properties have been affected by permafrost degradation, but little is known about the corresponding patterns of their soil microbial communities. Thus, we analyzed the effects of vegetation types and their covariant soil properties on bacterial and fungal community structure and membership and bacterial community-level physiological patterns. Pyrosequencing and Biolog EcoPlates were used to analyze 19 permafrost-affected soil samples from four principal vegetation types: swamp meadow (SM), meadow (M), steppe (S) and desert steppe (DS). Proteobacteria, Acidobacteria, Bacteroidetes and Actinobacteria dominated bacterial communities and the main fungal phyla were Ascomycota, Basidiomycota and Mucoromycotina. The ratios of Proteobacteria/Acidobacteria decreased in the order: SM>M>S>DS, whereas the Ascomycota/Basidiomycota ratios increased. The distributions of carbon and nitrogen cycling bacterial genera detected were related to soil properties. The bacterial communities in SM/M soils degraded amines/amino acids very rapidly, while polymers were degraded rapidly by S/DS communities. UniFrac analysis of bacterial communities detected differences among vegetation types. The fungal UniFrac community patterns of SM differed from the others. Redundancy analysis showed that the carbon/nitrogen ratio had the main effect on bacteria community structures and their diversity in alkaline soil, whereas soil moisture was mainly responsible for structuring fungal communities. Thus, microbial communities and their functioning are probably affected by soil environmental change in response to permafrost degradation.

  3. A fluorometric assay for alkaline phosphatase activity based on β-cyclodextrin-modified carbon quantum dots through host-guest recognition.

    PubMed

    Tang, Cong; Qian, Zhaosheng; Huang, Yuanyuan; Xu, Jiamin; Ao, Hang; Zhao, Meizhi; Zhou, Jin; Chen, Jianrong; Feng, Hui

    2016-09-15

    A convenient, reliable and highly sensitive assay for alkaline phosphatase (ALP) activity in the real-time manner is developed based on β-cyclodextrin-modified carbon quantum dots (β-CD-CQDs) nanoprobe through specific host-guest recognition. Carbon quantum dots were first functionalized with 3-aminophenyl boronic acid to produce boronic acid-functionalized CQDs, and then further modified with hydropropyl β-cyclodextrins (β-CD) through B-O bonds to form β-CD-CQDs nanoprobe. p-Nitrophenol phosphate disodium salt is used as the substrate of ALP, and can hydrolyze to p-nitrophenol under the catalysis of ALP. The resulting p-nitrophenol can enter the cavity of β-CD moiety in the nanoprobe due to their specific host-guest recognition, where photoinduced electron transfer process between p-nitrophenol and CQDs takes place to efficiently quench the fluorescence of the probe. The correlation between quenched fluorescence and ALP level can be used to establish quantitative evaluation of ALP activity in a broad range from 3.4 to 100.0U/L with the detection limit of 0.9U/L. This assay shows a high sensitivity to ALP even in the presence of a very high concentration of glucose. This study demonstrates a good electron donor/acceptor pair, which can be used to design general detection strategy through PET process, and also broadens the application of host-guest recognition for enzymes detection in clinical practice.

  4. Combined effects of carbonate alkalinity and pH on survival, growth and haemocyte parameters of the Venus clam Cyclina sinensis.

    PubMed

    Lin, Tingting; Lai, Qifang; Yao, Zongli; Lu, Jianxue; Zhou, Kai; Wang, Hui

    2013-08-01

    Carbonate alkalinity (CA) and pH are considered to be two important stress factors that determine the response of aquatic animals to sudden transfers into saline-alkaline water. To evaluate the potential for aquaculture production of Venus clams (Cyclina sinensis) farmed in saline-alkaline water, the combined effects of CA (2.5 (control), 10.0, 20.0 and 40.0 meq/l) and pH (8.0 (control), 8.5, 9.0 and 9.5) on survival rate was monitored every day for 10 days. Length gain rate (LGR) and weight gain rate (WGR) were also monitored for two months, and total haemocyte count (THC), phagocytic rate (PR) and haemocyte mortality (HM) were measured for 3, 6, 12 and 24 days under the same water temperature (20 °C) and salinity (15‰) conditions. The results showed that survival rates in treatments of CA ≤ 20.0, combined with pH ≤ 9.0, were 100%. LGR and WGR in treatments of CA 2.5 & pH 8.0 (control), CA 2.5 & pH 8.5 and CA 10.0 & pH 8.0 exhibited the largest values (P > 0.05), while in other treatments, they showed a decreasing trend with an increase in either CA or pH or both (P < 0.05). Similarly, for THC, PR and HM, no significant differences were observed among the fast growth treatments during the entire experimental period (P > 0.05), however, in other treatments, they presented significant differences, especially on day 3 and 6 (P < 0.05), most notably with increases in CA or pH, but returned to control levels on day 12. In conclusion, in this study, a strong interaction between CA and pH was observed. Additionally, it was ascertained that the Venus clam C. sinensis can withstand the stress of CA 20.0 combined pH 9.0, although individuals grows slowly and may take approximately 12 days to recover to the unstressed condition.

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  6. Carbon Offsets in California: What Role for Earth Scientists in the Policy Process? (Invited)

    NASA Astrophysics Data System (ADS)

    Cullenward, D.; Strong, A. L.

    2013-12-01

    This talk addresses the policy structure in California for developing and approving carbon offset protocols, which rely on findings from the environmental and earth sciences communities. In addition to providing an overview of the legal requirements of carbon offsets, we describe a series of case studies of how scientists can engage with policymakers. Based on those experiences, we suggest ways for the earth sciences community to become more involved in climate policy development. California's climate law, known as AB 32, requires that major sectors of the state's economy reduce their emissions to 1990 levels by 2020. As part of AB 32, the California Air Resources Board created a cap-and-trade market to ensure compliance with the statutory target. Under this system, regulated companies have to acquire tradable emissions permits (called 'compliance instruments') for the greenhouse gas emissions they release. The State allocates a certain number of allowances to regulated entities through a mixture of auctions and free transfers, with the total number equal to the overall emissions target; these allowances, along with approved offsets credits, are the compliance instruments that regulated entities are required to obtain by law. One of the key policy design issues in California's cap-and-trade market concerns the use of carbon offsets. Under AB 32, the Air Resources Board can issue offset credits to project developers who reduce emissions outside of the capped sectors (electricity, industry, and transportation)--or even outside of California--pursuant to approved offset protocols. Project developers then sell the credits to regulated companies in California. Essentially, offsets allow regulated entities in California to earn credit for emissions reductions that take place outside the scope of AB 32. Many regulated entities and economists are in favor of offsets because they view them as a source of low-cost compliance instruments. On the other hand, critics argue that

  7. Evaluating carbon dioxide variability in the Community Earth System Model against atmospheric observations

    NASA Astrophysics Data System (ADS)

    Keppel-Aleks, G.; Randerson, J. T.; Lindsay, K. T.; Stephens, B. B.; Moore, J. K.; Doney, S. C.; Thornton, P. E.; Mahowald, N. M.; Hoffman, F. M.; Sweeney, C.; Tans, P. P.; Wennberg, P. O.; Wofsy, S. C.

    2012-12-01

    Changes in atmospheric CO_2 variability during the 21st century may provide insight on ecosystem responses to climate change and have implications for the design of carbon monitoring programs. We analyzed results from a fully coupled climate-carbon simulation using the Community Earth System Model (CESM1-BGC). We evaluated CO2 simulated for the historical period against surface, aircraft, and column observations. The mean annual cycle in total column atmospheric CO2 was underestimated throughout the northern hemisphere relative to TCCON observations, suggesting that the growing season net flux in the land component of CESM was too weak by 50%. Sampling CESM along HIPPO transects confirmed low growing season uptake, but also showed that spring drawdown in the Northern Hemisphere began too early. The vertical gradients in CESM generally agreed with HIPPO data and with NOAA aircraft profiles outside the growing season, but were too weak during the summer. The seasonal bias suggests that vertical transport in CAM4 (the atmospheric component of CESM) was too weak year round. Model evaluation and improvement based on atmospheric observations is crucial. The simulation of surface exchange and atmospheric transport of CO2 in coupled models such as CESM may help with the design of optimal detection strategies. For example, in the simulations of the 21st century, CESM predicted increases in the mean annual cycle of atmospheric CO2 and larger horizontal gradients. Both north-south and east-west contrasts in CO2 strengthened due to changing patterns in fossil fuel emissions and terrestrial carbon exchange, and northern hemisphere interannual variability increased as well. Our results suggest that using atmospheric observations to gain insight about changing terrestrial and ocean processes over the next several decades may become more challenging as anthropogenic contributions to variability on multiple temporal and spatial scales continue to grow.

  8. Carbon Observations from Geostationary Earth Orbit as Part of an Integrated Observing System for Atmospheric Composition

    NASA Astrophysics Data System (ADS)

    Edwards, D. P.

    2015-12-01

    This presentation describes proposed satellite carbon measurements from the CHRONOS mission. The primary goal of this experiment is to measure the atmospheric pollutants carbon monoxide (CO) and methane (CH4) from geostationary orbit, with hourly observations of North America at high spatial resolution. CHRONOS observations would provide measurements not currently available or planned as part of a surface, suborbital and satellite integrated observing system for atmospheric composition over North America. Carbon monoxide is produced by combustion processes such as urban activity and wildfires, and serves as a proxy for other combustion pollutants that are not easily measured. Methane has diverse anthropogenic sources ranging from fossil fuel production, animal husbandry, agriculture and waste management. The impact of gas exploration in the Western States of the USA and oil extraction from the Canadian tar sands will be particular foci of the mission, as will the poorly-quantified natural CH4 emissions from wetlands and thawing permafrost. In addition to characterizing pollutant sources, improved understanding of the domestic CH4 budget is a priority for policy decisions related to short-lived climate forcers. A primary motivation for targeting CO is its value as a tracer of atmospheric pollution, and CHRONOS measurements will provide insight into local and long-range transport across the North American continent, as well as the processes governing the entrainment and venting of pollution in and out of the planetary boundary layer. As a result of significantly improved characterization of diurnal changes in atmospheric composition, CHRONOS observations will find direct societal applications for air quality regulation and forecasting. We present a quantification of this expected improvement in the prediction of near-surface concentrations when CHRONOS measurements are used in Observation System Simulation Experiments (OSSEs). If CHRONOS and the planned NASA Earth

  9. Enhanced alkalinity and dissolved inorganic carbon release in intertidal sands from the Oosterschelde (The Netherlands) induced by a natural macrofaunal community

    NASA Astrophysics Data System (ADS)

    Brenner, Heiko; Montserrat, Francesc; Meysman, Filip

    2014-05-01

    The influence of bioturbation and bioirrigation in intertidal sandflat sediments from the Oosterschelde (The Netherlands) on the rates and sources of benthic alkalinity (TA) and dissolved inorganic carbon (DIC) generation was examined using measurements of sediment-water fluxes of bromide, oxygen, nutrients, TA and DIC. Sediments from the Oosterschelde typically contain the deep-burrowing polychaete Arenicola marina, the sub-surface bioturbator Macoma balthica and the surface bioturbator Cerastoderma edule. Measurements were carried out in six tanks (106 cm x 87 cm x 20 cm). The sediment was collected in November 2012. Measurements were started in June 2013. Each tank was sampled twice for benthic fluxes over the course of one month. Prior measurements three tanks were defaunated by covering the sediment surface with a black plastic sheet. Benthic flux measurements were carried out in closed plastic chambers (diameter 66 cm). These chambers typically contained about 10 cm sediment and 20 cm overlying water. The tank was completely covered with opaque a black plastic sheet during measurements. The incubation time ranged from 6 to 8 hours. Here we present preliminary results from both experimental runs. High benthic fluxes of TA (10 - 70 mmol m-2 d-1) and DIC (35 - 150 mmol m-2 d-1) were observed in all tanks. Whereas benthic TA and DIC fluxes were significantly higher in faunated tanks, total oxygen uptake (TOU: 30 - 75 mmol m-2 d-1) did not show any meaningful trend between the two treatments. Therefore, the apparent community respiratory quotient (CRQ = DIC/TOU) varied between 0.9 and 3.3, with significant higher values in faunated tanks, suggesting enhanced flushing of DIC produced in deeper layers and released by bioirrigation. This DIC was either produced by anaerobic respiration or carbonate dissolution. To unravel the contribution of carbonate dissolution and anaerobic respiration on the observed TA and DIC fluxes, we further present estimations for relevant

  10. Megaripples, multiple cap carbonates, and apparently conformable sections: observations that normalize some interpretations of Snowball Earth stratigraphy while complicating others

    NASA Astrophysics Data System (ADS)

    Raub, T.; Lamb, M. P.; Fischer, W. W.; Myrow, P.; Perron, T.; Kunzmann, M.; Liu, C.; Prave, A. R.

    2012-12-01

    Neoproterozoic Snowball Earth is intellectually alluring in part because its remarkable sedimentary and geochemical record challenges uniformitarian description and demands multiple working hypotheses. Apparently exceptional features in that record may represent the end-products of truly nonuniformitarian processes acting on a fundamentally different Earth than the modern world: an Earth which is oxygen-poor, lacking terrestrial macrobiota, and of uncertain (or arguably bizarre) geomagnetic and geodynamic character. But many features in this remarkable rock record might be explained by perfectly ordinary processes acting on anomalous materials, or in systems bounded by conditions that are rare, but not mysterious, on modern Earth. I will present emerging examples of both interpretive modes. Exceptional bedforms known as cap carbonate megaripples can be explained under normal wave climates by aggradation of unusually large carbonate grains anomalously widespread in a shallow shelfal setting. Bedform topography may be inherited or else migrate laterally through discrete, episodic depositional events if cementation is fast. Trace metal isotopes excurse most prominently at the very base of conformable cap carbonate sections, and in the terminal stages of deglaciation, at times when the seawater saturation state is most dynamic. In the end, basic field geology without genetic presumption, and the interpretive context it lends specific geochemical analyses, remains most likely to successfully evaluate the likelihoods of both existing and new Snowball Earth scenarios. The most fundamental unanswered question remains one of stratigraphic architecture: what is the climatic phase, the timing, and the duration for both diamictite and cap carbonate deposition? End-member solutions remain viable: diamictite and cap carbonate may both be of prolonged duration and globally diachronous, with diamictite representing syn-glacial and interstadial cycles and cap carbonate spanning

  11. Carbon footprint assessment of recycling technologies for rare earth elements: A case study of recycling yttrium and europium from phosphor.

    PubMed

    Hu, Allen H; Kuo, Chien-Hung; Huang, Lance H; Su, Chao-Chin

    2017-02-01

    Rare earth elements are key raw materials in high-technology industries. Mining activities and manufacturing processes of such industries have caused considerable environmental impacts, such as soil erosion, vegetation destruction, and various forms of pollution. Sustaining the long-term supply of rare earth elements is difficult because of the global shortage of rare earth resources. The diminishing supply of rare earth elements has attracted considerable concern because many industrialized countries regarded such elements as important strategic resources for economic growth. This study aims to explore the carbon footprints of yttrium and europium recovery techniques from phosphor. Two extraction recovery methods, namely, acid extraction and solvent extraction, were selected for the analysis and comparison of carbon footprints. The two following functional units were used: (1) the same phosphor amounts for specific Y and Eu recovery concentrations, and (2) the same phosphor amounts for extraction. For acid extraction method, two acidic solutions (H2SO4 and HCl) were used at two different temperatures (60 and 90°C). For solvent extraction method, acid leaching was performed followed by ionic liquid extraction. Carbon footprints from acid and solvent extraction methods were estimated to be 10.1 and 10.6kgCO2eq, respectively. Comparison of the carbon emissions of the two extraction methods shows that the solvent extraction method has significantly higher extraction efficiency, even though acid extraction method has a lower carbon footprint. These results may be used to develop strategies for life cycle management of rare earth resources to realize sustainable usage.

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

    USGS Publications Warehouse

    Oremland, R.S.; Des Marais, D.J.

    1983-01-01

    Distribution and isotopic composition (??13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20-35 m), reached uniform concentrations (55 ??M/l) in the monimolimnion (35-64 m) and again increased with depth in monimolimnion bottom sediments (>400 ??M/kg below 1 m sub-bottom depth). The ??13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<-70 per mil) increased with vertical distance up the core (??13C[CH4] = -55 per mil at sediment surface). Monimolimnion ??13C[CH4] values (-55 to -61 per mil) were greater than most ??13C[CH4] values found in the anoxic mixolimnion (92% of samples had ??13C[CH4] values between -20 and -48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50-60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4 [C2H6 + C3H8] were high (250-620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in ??13C[CH4] and CH4 (C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms. ?? 1983.

  13. CoxC encased in carbon nanotubes: an efficient oxygen reduction catalyst under both acidic and alkaline conditions.

    PubMed

    Chen, Lisong; Cui, Xiangzhi; Wang, Qingsong; Zhang, Xiaohua; Wan, Gang; Cui, Fangming; Wei, Chenyang; Shi, Jianlin

    2015-12-21

    The design of a non-precious metal oxygen reduction reaction (ORR) catalyst of high activity and long durability in acidic electrolyte is of great importance for the development and commercialization of low-temperature fuel cells, which remains a great challenge to date. Here, we demonstrate a facile, scalable protocol for the controlled synthesis of CoxC encapsulated in carbon nanotubes as a novel kind of efficient electrochemical oxygen reduction reaction (ORR) catalyst. The synthesized CoxC/carbon nanotube features a high BET surface area, large pore volume and high graphitic content, which greatly favors enhanced ORR properties. The resultant composite electro-catalyst shows high ORR activity which is comparable with that of 20 wt% Pt/C in 0.1 M KOH electrolyte. More importantly, it also exhibits a high ORR activity in 0.1 M HClO4 with a near-complete 4e pathway. More attractively, compared to the most investigated FexC, CoxC as the proposed main catalytically active center shows much enhanced activity in acidic electrolyte, which will pave the way towards the rational design of an advanced electro-catalyst for an efficient ORR process especially under acidic conditions. Moreover, a fuel cell using the synthesized CoxC/carbon nanotube as a cathode catalyst showed a large open-circuit potential, high output power density and long durability, which make it a promising alternative to Pt/C as a non-precious metal ORR catalyst in proton exchange membrane fuel cells.

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

    PubMed

    Ivlev, A A

    2010-01-01

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

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

    SciTech Connect

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

    2000-01-01

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

  16. Sodium carbonate treatment induces scoparone accumulation, structural changes, and alkalinization in the albedo of wounded citrus fruits.

    PubMed

    Venditti, Tullio; Molinu, Maria Giovanna; Dore, Antonio; Agabbio, Mario; D'hallewin, Guy

    2005-05-04

    Following sodium carbonate treatment, accumulation of scoparone (6,7-dimethoxycoumarin) but not scopoletin (6-methoxy-7-hydroxycoumarin) was found in the albedo of wounded fruit from different Citrus sp. and cultivars. Treating wounded mandarin fruit cv. Fairchild with 5% Na(2)CO(3) (SC) lead to a scoparone accumulation in the albedo of 310, 361, and 382 microg g(-1) fresh weight after 7, 10, and 15 days, respectively. Scoparone accumulation was associated with a decrease in decay severity. When oranges cv. Biondo comune wounded and treated with 5% SC were inoculated with Penicillium digitatum or Penicillium italicum conidia 3 days posttreatment, the decay percentage as compared to untreated wounds was reduced by 97.2 and 93.9%, respectively. Observations by scanning electron microscopy of wounded Citrus fruits treated at 20 degrees C with 2, 3, 4, or 5% (w/v) solutions of sodium carbonate showed structural modifications to the albedo as well as damage to 24-48 h old mycelia of P. digitatum, the cause of citrus green mold. Modifications were more evident in orange, lemon, and grapefruit as compared to mandarin fruit. The efficacy of the treatment was strictly related to the SC interaction with the albedo tissue that, in addition to structural changes, significantly increased tissue pH, affecting P. digitatum pathogenicity. The SC remaining as a film on unwounded flavedo had no effect in preventing contact infection by the Penicillia.

  17. Toward more realistic projections of soil carbon dynamics by Earth system models

    USGS Publications Warehouse

    Luo, Y.; Ahlström, Anders; Allison, Steven D.; Batjes, Niels H.; Brovkin, V.; Carvalhais, Nuno; Chappell, Adrian; Ciais, Philippe; Davidson, Eric A.; Finzi, Adien; Georgiou, Katerina; Guenet, Bertrand; Hararuk, Oleksandra; Harden, Jennifer; He, Yujie; Hopkins, Francesca; Jiang, L.; Koven, Charles; Jackson, Robert B.; Jones, Chris D.; Lara, M.; Liang, J.; McGuire, Anthony; Parton, William; Peng, Changhui; Randerson, J.; Salazar, Alejandro; Sierra, Carlos A.; Smith, Matthew J.; Tian, Hanqin; Todd-Brown, Katherine E. O; Torn, Margaret S.; van Groenigen, Kees Jan; Wang, Ying; West, Tristram O.; Wei, Yaxing; Wieder, William R.; Xia, Jianyang; Xu, Xia; Xu, Xiaofeng; Zhou, T.

    2016-01-01

    Soil carbon (C) is a critical component of Earth system models (ESMs), and its diverse representations are a major source of the large spread across models in the terrestrial C sink from the third to fifth assessment reports of the Intergovernmental Panel on Climate Change (IPCC). Improving soil C projections is of a high priority for Earth system modeling in the future IPCC and other assessments. To achieve this goal, we suggest that (1) model structures should reflect real-world processes, (2) parameters should be calibrated to match model outputs with observations, and (3) external forcing variables should accurately prescribe the environmental conditions that soils experience. First, most soil C cycle models simulate C input from litter production and C release through decomposition. The latter process has traditionally been represented by first-order decay functions, regulated primarily by temperature, moisture, litter quality, and soil texture. While this formulation well captures macroscopic soil organic C (SOC) dynamics, better understanding is needed of their underlying mechanisms as related to microbial processes, depth-dependent environmental controls, and other processes that strongly affect soil C dynamics. Second, incomplete use of observations in model parameterization is a major cause of bias in soil C projections from ESMs. Optimal parameter calibration with both pool- and flux-based data sets through data assimilation is among the highest priorities for near-term research to reduce biases among ESMs. Third, external variables are represented inconsistently among ESMs, leading to differences in modeled soil C dynamics. We recommend the implementation of traceability analyses to identify how external variables and model parameterizations influence SOC dynamics in different ESMs. Overall, projections of the terrestrial C sink can be substantially improved when reliable data sets are available to select the most representative model structure

  18. Toward more realistic projections of soil carbon dynamics by Earth system models

    DOE PAGES

    Luo, Yiqi; Ahlstrom, Anders; Allison, Steven D.; ...

    2016-01-21

    Soil carbon (C) is a critical component of Earth system models (ESMs), and its diverse representations are a major source of the large spread across models in the terrestrial C sink from the third to fifth assessment reports of the Intergovernmental Panel on Climate Change (IPCC). Improving soil C projections is of a high priority for Earth system modeling in the future IPCC and other assessments. To achieve this goal, we suggest that (1) model structures should reflect real-world processes, (2) parameters should be calibrated to match model outputs with observations, and (3) external forcing variables should accurately prescribe themore » environmental conditions that soils experience. First, most soil C cycle models simulate C input from litter production and C release through decomposition. The latter process has traditionally been represented by first-order decay functions, regulated primarily by temperature, moisture, litter quality, and soil texture. While this formulation well captures macroscopic soil organic C (SOC) dynamics, better understanding is needed of their underlying mechanisms as related to microbial processes, depth-dependent environmental controls, and other processes that strongly affect soil C dynamics. Second, incomplete use of observations in model parameterization is a major cause of bias in soil C projections from ESMs. Optimal parameter calibration with both pool-and flux-based data sets through data assimilation is among the highest priorities for near-term research to reduce biases among ESMs. Third, external variables are represented inconsistently among ESMs, leading to differences in modeled soil C dynamics. Furthermore, we recommend the implementation of traceability analyses to identify how external variables and model parameterizations influence SOC dynamics in different ESMs. Overall, projections of the terrestrial C sink can be substantially improved when reliable data sets are available to select the most representative

  19. Toward more realistic projections of soil carbon dynamics by Earth system models

    SciTech Connect

    Luo, Yiqi; Ahlstrom, Anders; Allison, Steven D.; Batjes, Niels H.; Brovkin, Victor; Carvalhais, Nuno; Chappell, Adrian; Ciais, Philippe; Davidson, Eric A.; Finzi, Adien; Georgiou, Katerina; Guenet, Bertrand; Hararuk, Oleksandra; Harden, Jennifer W.; He, Yujie; Hopkins, Francesca; Jiang, Lifen; Koven, Charlie; Jackson, Robert B.; Jones, Chris D.; Lara, Mark J.; Liang, Junyi; McGuire, A. David; Parton, William; Peng, Changhui; Randerson, James T.; Salazar, Alejandro; Sierra, Carlos A.; Smith, Matthew J.; Tian, Hanqin; Todd-Brown, Katherine E. O.; Torn, Margaret; van Groenigen, Kees Jan; Wang, Ying Ping; West, Tristram O.; Wei, Yaxing; Wieder, William R.; Xia, Jianyang; Xu, Xia; Xu, Xiaofeng; Zhou, Tao

    2016-01-21

    Soil carbon (C) is a critical component of Earth system models (ESMs), and its diverse representations are a major source of the large spread across models in the terrestrial C sink from the third to fifth assessment reports of the Intergovernmental Panel on Climate Change (IPCC). Improving soil C projections is of a high priority for Earth system modeling in the future IPCC and other assessments. To achieve this goal, we suggest that (1) model structures should reflect real-world processes, (2) parameters should be calibrated to match model outputs with observations, and (3) external forcing variables should accurately prescribe the environmental conditions that soils experience. First, most soil C cycle models simulate C input from litter production and C release through decomposition. The latter process has traditionally been represented by first-order decay functions, regulated primarily by temperature, moisture, litter quality, and soil texture. While this formulation well captures macroscopic soil organic C (SOC) dynamics, better understanding is needed of their underlying mechanisms as related to microbial processes, depth-dependent environmental controls, and other processes that strongly affect soil C dynamics. Second, incomplete use of observations in model parameterization is a major cause of bias in soil C projections from ESMs. Optimal parameter calibration with both pool-and flux-based data sets through data assimilation is among the highest priorities for near-term research to reduce biases among ESMs. Third, external variables are represented inconsistently among ESMs, leading to differences in modeled soil C dynamics. Furthermore, we recommend the implementation of traceability analyses to identify how external variables and model parameterizations influence SOC dynamics in different ESMs. Overall, projections of the terrestrial C sink can be substantially improved when reliable data sets are available to select the most representative model

  20. Causes and Implications of Persistent Atmospheric Carbon Dioxide Biases in Earth System Models

    SciTech Connect

    Hoffman, Forrest M; Randerson, James T.; Arora, Vivek K.; Bao, Qing; Cadule, Patricia; Ji, Duoying; Jones, Chris D.; Kawamiya, Michio; Khatiwala, Samar; Lindsay, Keith; Obata, Atsushi; Shevliakova, Elena; Six, Katharina D.; Tjiputra, Jerry F.; Volodin, Evgeny M.; Wu, Tongwen

    2014-01-01

    The strength of feedbacks between a changing climate and future CO2 concentrations are uncertain and difficult to predict using Earth System Models (ESMs). We analyzed emission-driven simulations--in which atmospheric CO2 levels were computed prognostically--for historical (1850-2005) and future periods (RCP 8.5 for 2006-2100) produced by 15 ESMs for the Fifth Phase of the Coupled Model Intercomparison Project (CMIP5). Comparison of ESM prognostic atmospheric CO2 over the historical period with observations indicated that ESMs, on average, had a small positive bias in predictions of contemporary atmospheric CO2. Weak ocean carbon uptake in many ESMs contributed to this bias, based on comparisons with observations of ocean and atmospheric anthropogenic carbon inventories. We found a significant linear relationship between contemporary atmospheric CO2 biases and future CO2 levels for the multi-model ensemble. We used this relationship to create a contemporary CO2 tuned model (CCTM) estimate of the atmospheric CO2 trajectory for the 21st century. The CCTM yielded CO2 estimates of 600 {plus minus} 14 ppm at 2060 and 947 {plus minus} 35 ppm at 2100, which were 21 ppm and 32 ppm below the multi-model mean during these two time periods. Using this emergent constraint approach, the likely ranges of future atmospheric CO2, CO2-induced radiative forcing, and CO2-induced temperature increases for the RCP 8.5 scenario were considerably narrowed compared to estimates from the full ESM ensemble. Our analysis provided evidence that much of the model-to-model variation in projected CO2 during the 21st century was tied to biases that existed during the observational era, and that model differences in the representation of concentration-carbon feedbacks and other slowly changing carbon cycle processes appear to be the primary driver of this variability. By improving models to more closely match the long-term time series of CO2 from Mauna Loa, our analysis suggests uncertainties in

  1. Development of a system emulating the global carbon cycle in Earth system models

    NASA Astrophysics Data System (ADS)

    Tachiiri, K.; Hargreaves, J. C.; Annan, J. D.; Oka, A.; Abe-Ouchi, A.; Kawamiya, M.

    2010-08-01

    Recent studies have indicated that the uncertainty in the global carbon cycle may have a significant impact on the climate. Since state of the art models are too computationally expensive for it to be possible to explore their parametric uncertainty in anything approaching a comprehensive fashion, we have developed a simplified system for investigating this problem. By combining the strong points of general circulation models (GCMs), which contain detailed and complex processes, and Earth system models of intermediate complexity (EMICs), which are quick and capable of large ensembles, we have developed a loosely coupled model (LCM) which can represent the outputs of a GCM-based Earth system model, using much smaller computational resources. We address the problem of relatively poor representation of precipitation within our EMIC, which prevents us from directly coupling it to a vegetation model, by coupling it to a precomputed transient simulation using a full GCM. The LCM consists of three components: an EMIC (MIROC-lite) which consists of a 2-D energy balance atmosphere coupled to a low resolution 3-D GCM ocean (COCO) including an ocean carbon cycle (an NPZD-type marine ecosystem model); a state of the art vegetation model (Sim-CYCLE); and a database of daily temperature, precipitation, and other necessary climatic fields to drive Sim-CYCLE from a precomputed transient simulation from a state of the art AOGCM. The transient warming of the climate system is calculated from MIROC-lite, with the global temperature anomaly used to select the most appropriate annual climatic field from the pre-computed AOGCM simulation which, in this case, is a 1% pa increasing CO2 concentration scenario. By adjusting the effective climate sensitivity (equivalent to the equilibrium climate sensitivity for an energy balance model) of MIROC-lite, the transient warming of the LCM could be adjusted to closely follow the low sensitivity (with an equilibrium climate sensitivity of 4.0 K

  2. Ex-situ and in-situ spectroscopic studies of the passive film on alkali and alkaline earth metals in nonaqueous solvents

    SciTech Connect

    Wang, K.; Chottiner, G.S.; Herrera-Fierro, P.; Scherson, D.A. . Dept. of Physics and Chemistry)

    1992-03-01

    The adsorption of carbon dioxide on potassium-dosed Ag(111) has been investigated with temperature-programmed desorption (TPD), work function measurements, and Auger electron (AES), X-ray photoelectron (XPS), and high resolution electron energy loss (HREELS), spectroscopies. Unlike the behavior observed for other K-modified single-crystal metal surfaces, the TPD spectra of near-saturation coverages of CO{sub 2} on K/Ag(111) for K coverages in the range 0.13 < {Theta}{sub K} < 0.47 exhibit a sharply defined m/e = 44 peak at 796 +/{minus} 6 K with no evidence for the desorption of CO at any temperature. Similar TPD experiments involving mixtures of natural and {sup 18}0-labelled CO{sub 2} indicate that the oxygen atoms undergo partial scrambling, suggesting that the overall process cannot be represented in terms of a simple adsorption/desorption of CO{sub 2}. The HREELS spectra of CO{sub 2}-saturated K/Ag(111) show, in addition to very minor features, a sharp peak at about 1480 cm{sup {minus}1}, and XPS spectra of the same interface display a C(ls) peak with a binding energy characteristic of an electron-rich carbon species. This information is consistent with the presence of a carbon-bound CO species on the surface. Evidence against the complete dissociation of CO{sub 2} was obtained from TPD which failed to reveal features associated with carbonate (decomposition) expected to be formed via the reaction of CO{sub 2} and adsorbed O. It is proposed that CO{sub 2} on K/Ag(111) binds through the carbon to the surface leading to the partial'' dissociation (or activation) of each CO{sub 2} molecule into adsorbed CO and O. Within this model, such adsorbed O would serve as a bridge between the carbon atoms of neighboring activated'' CO{sub 2} molecules, and therefore undergo exchange prior to or during thermal desorption.

  3. Ex-situ and in-situ spectroscopic studies of the passive film on alkali and alkaline earth metals in nonaqueous solvents. Final report

    SciTech Connect

    Wang, K.; Chottiner, G.S.; Herrera-Fierro, P.; Scherson, D.A.

    1992-03-01

    The adsorption of carbon dioxide on potassium-dosed Ag(111) has been investigated with temperature-programmed desorption (TPD), work function measurements, and Auger electron (AES), X-ray photoelectron (XPS), and high resolution electron energy loss (HREELS), spectroscopies. Unlike the behavior observed for other K-modified single-crystal metal surfaces, the TPD spectra of near-saturation coverages of CO{sub 2} on K/Ag(111) for K coverages in the range 0.13 < {Theta}{sub K} < 0.47 exhibit a sharply defined m/e = 44 peak at 796 +/{minus} 6 K with no evidence for the desorption of CO at any temperature. Similar TPD experiments involving mixtures of natural and {sup 18}0-labelled CO{sub 2} indicate that the oxygen atoms undergo partial scrambling, suggesting that the overall process cannot be represented in terms of a simple adsorption/desorption of CO{sub 2}. The HREELS spectra of CO{sub 2}-saturated K/Ag(111) show, in addition to very minor features, a sharp peak at about 1480 cm{sup {minus}1}, and XPS spectra of the same interface display a C(ls) peak with a binding energy characteristic of an electron-rich carbon species. This information is consistent with the presence of a carbon-bound CO species on the surface. Evidence against the complete dissociation of CO{sub 2} was obtained from TPD which failed to reveal features associated with carbonate (decomposition) expected to be formed via the reaction of CO{sub 2} and adsorbed O. It is proposed that CO{sub 2} on K/Ag(111) binds through the carbon to the surface leading to the ``partial`` dissociation (or activation) of each CO{sub 2} molecule into adsorbed CO and O. Within this model, such adsorbed O would serve as a bridge between the carbon atoms of neighboring ``activated`` CO{sub 2} molecules, and therefore undergo exchange prior to or during thermal desorption.

  4. N-doped carbon@Ni-Al2O3 nanosheet array@graphene oxide composite as an electrocatalyst for hydrogen evolution reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Wang, Juan; Qiu, Tian; Chen, Xu; Lu, Yanluo; Yang, Wensheng

    2015-10-01

    An NiAl-layered double-hydroxide (NiAl-LDH) nanosheet array is grown on a graphene oxide (GO) substrate (NiAl-LDH@GO) by the hydrothermal method. The NiAl-LDH@GO is used as the precursor to synthetize an N-doped carbon@Ni-Al2O3 nanosheet array@GO composite (N-C@Ni-Al2O3@GO) by coating with dopamine followed by calcination. The N-C@Ni-Al2O3@GO is used as a non-noble metal electrocatalyst for hydrogen evolution reaction in alkaline medium, and exhibits high electrocatalytic activity with low onset overpotential (-75 mV). The improved electrocatalytic performance of N-C@Ni-Al2O3@GO arises from its intrinsic features. First, it has a high specific surface area with the Ni nanoparticles in the composite dispersed well and the sizes of Ni nanoparticles are small, which lead to the exposure of more active sites for electrocatalysis. Second, there is a synergistic effect between the Ni nanoparticles and the N-C coating layer, which is beneficial to reduce the activation energy of the Volmer step and improve the electrocatalytic activity. Third, the N-C coating layer and the XC-72 additive can form an electrically conductive network, which serves as a bridge for the transfer of electrons from the electrode to the Ni nanoparticles.

  5. Electro-oxidation of methanol in alkaline conditions using Pd-Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

    NASA Astrophysics Data System (ADS)

    Manzo-Robledo, A.; Costa, Natália J. S.; Philippot, K.; Rossi, Liane M.; Ramírez-Meneses, E.; Guerrero-Ortega, L. P. A.; Ezquerra-Quiroga, S.

    2015-12-01

    Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd90Ni10, Pd50Ni50, Pd10Ni90, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd2(dba)3, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod)2. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i- E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i- E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions' interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

  6. Method for Extracting and Sequestering Carbon Dioxide

    SciTech Connect

    Rau, Gregory H.; Caldeira, Kenneth G.

    2005-05-10

    A method and apparatus to extract and sequester carbon dioxide (CO2) from a stream or volume of gas wherein said method and apparatus hydrates CO2, and reacts the resulting carbonic acid with carbonate. Suitable carbonates include, but are not limited to, carbonates of alkali metals and alkaline earth metals, preferably carbonates of calcium and magnesium. Waste products are metal cations and bicarbonate in solution or dehydrated metal salts, which when disposed of in a large body of water provide an effective way of sequestering CO2 from a gaseous environment.

  7. Method for extracting and sequestering carbon dioxide

    DOEpatents

    Rau, Gregory H.; Caldeira, Kenneth G.

    2005-05-10

    A method and apparatus to extract and sequester carbon dioxide (CO.sub.2) from a stream or volume of gas wherein said method and apparatus hydrates CO.sub.2, and reacts the resulting carbonic acid with carbonate. Suitable carbonates include, but are not limited to, carbonates of alkali metals and alkaline earth metals, preferably carbonates of calcium and magnesium. Waste products are metal cations and bicarbonate in solution or dehydrated metal salts, which when disposed of in a large body of water provide an effective way of sequestering CO.sub.2 from a gaseous environment.

  8. Apparatus for extracting and sequestering carbon dioxide

    DOEpatents

    Rau, Gregory H.; Caldeira, Kenneth G.

    2010-02-02

    An apparatus and method associated therewith to extract and sequester carbon dioxide (CO.sub.2) from a stream or volume of gas wherein said apparatus hydrates CO.sub.2 and reacts the resulting carbonic acid with carbonate. Suitable carbonates include, but are not limited to, carbonates of alkali metals and alkaline earth metals, preferably carbonates of calcium and magnesium. Waste products are metal cations and bicarbonate in solution or dehydrated metal salts, which when disposed of in a large body of water provide an effective way of sequestering CO.sub.2 from a gaseous environment.

  9. Sodalite-like rare-earth carbonates: a study of structural transformation and diluted magnetism.

    PubMed

    Wang, Yanyan; Han, Tian; Ding, You-Song; Zheng, Zhiping; Zheng, Yan-Zhen

    2016-01-21

    A series of novel rare earth carbonates, RE3(OH)6(CO3)Cl (RE = Dy, Er, Y), with sodalite-like (SOD-like) zeolite topologies have been successfully synthesized by introducing an appropriate amount of CO3(2-) from NaCO3 or atmospheric carbon dioxide as a template. Single-crystal X-ray diffraction reveals that the structure consists of the RE3(OH)6(3+) cationic framework with a SOD-like topology built from vertex-sharing [RE4(μ3-OH)4] cubes. The CO3(2-) anions seal the 6-ring opening and Cl(-) anions situated in the channels to achieve charge balance. After calcination at 370 °C, the compound RE3(OH)6(CO3)Cl in situ transforms into a new phase formulated as RE3O4Cl. Interestingly, the structure of RE3O4Cl represents a new SOD-like open framework, associated with the removal of the CO3(2-) from RE3(OH)6(CO3)Cl. The samples are characterized by thermogravimetric analysis (TGA), elemental analysis, X-ray photoelectron spectroscopy and magnetic studies. Furthermore, single-molecule magnet behaviours can be observed for the diluted samples of Dy0.0068Y2.9932(OH)6(CO3)Cl and Dy0.0068Y2.9932O4Cl with a Dy/Y molar ratio of up to 1/440 as well as Er0.19Y2.81(OH)6(CO3)Cl with an Er/Y ratio of 1/15, showing dominant single-ion effects.

  10. Carbon dioxide addition to microbial fuel cell cathodes maintains sustainable catholyte pH and improves anolyte pH, alkalinity, and conductivity.

    PubMed

    Fornero, Jeffrey J; Rosenbaum, Miriam; Cotta, Michael A; Angenent, Largus T

    2010-04-01

    Bioelectrochemical system (BES) pH imbalances develop due to anodic proton-generating oxidation reactions and cathodic hydroxide-ion-generating reduction reactions. Until now, workers added unsustainable buffers to reduce the pH difference between the anode and cathode because the pH imbalance contributes to BES potential losses and, therefore, power losses. Here, we report that adding carbon dioxide (CO(2)) gas to the cathode, which creates a CO(2)/bicarbonate buffered catholyte system, can diminish microbial fuel cell (MFC) pH imbalances in contrast to the CO(2)/carbonate buffered catholyte system by Torres, Lee, and Rittmann [Environ. Sci. Technol. 2008, 42, 8773]. We operated an air-cathode and liquid-cathode MFC side-by-side. For the air-cathode MFC, CO(2) addition resulted in a stable catholyte film pH of 6.61 +/- 0.12 and a 152% increase in steady-state power density. By adding CO(2) to the liquid-cathode system, we sustained a steady catholyte pH (pH = 5.94 +/- 0.02) and a low pH imbalance (DeltapH = 0.65 +/- 0.18) over a 2-week period without external salt buffer addition. By migrating bicarbonate ions from the cathode to the anode (with an anion-exchange membrane), we increased the anolyte pH (DeltapH = 0.39 +/- 0.31), total alkalinity (494 +/- 6 to 582 +/- 6 as mg CaCO(3)/L), and conductivity (1.53 +/- 0.49 to 2.16 +/- 0.03 mS/cm) relative to the feed properties. We also verified with a phosphate-buffered MFC that our reaction rates were limited mainly by the reactor configuration rather than limitations due to the bicarbonate buffer.

  11. Generation of methane in the Earth's mantle: In situ high pressure–temperature measurements of carbonate reduction

    PubMed Central

    Scott, Henry P.; Hemley, Russell J.; Mao, Ho-kwang; Herschbach, Dudley R.; Fried, Laurence E.; Howard, W. Michael; Bastea, Sorin

    2004-01-01

    We present in situ observations of hydrocarbon formation via carbonate reduction at upper mantle pressures and temperatures. Methane was formed from FeO, CaCO3-calcite, and water at pressures between 5 and 11 GPa and temperatures ranging from 500°C to 1,500°C. The results are shown to be consistent with multiphase thermodynamic calculations based on the statistical mechanics of soft particle mixtures. The study demonstrates the existence of abiogenic pathways for the formation of hydrocarbons in the Earth's interior and suggests that the hydrocarbon budget of the bulk Earth may be larger than conventionally assumed. PMID:15381767

  12. Generation of Methane in the Earth's Mantle: In situ High P-T Measurements of Carbonate Reduction

    SciTech Connect

    Scott, H P; Hemley, R J; Mao, H; Herschbach, D R; Fried, L E; Howard, W M; Bastea, S

    2004-09-10

    We present in situ observations of hydrocarbon formation via carbonate reduction at upper mantle pressures and temperatures. Methane was formed from FeO, CaCO{sub 3}-calcite and water at pressures between 5 and 11 GPa and temperatures ranging from 500 to 1500 C. The results are shown to be consistent with thermodynamic calculations of the relevant chemical reactions based on the thermochemical models and ab initio theory. The study demonstrates the existence of abiogenic pathways for the formation of hydrocarbons in the Earth's interior and suggests that the hydrocarbon budget of the bulk Earth may be larger than conventionally assumed.

  13. Synthesis and characterization of 3D Ni nanoparticle/carbon nanotube cathodes for hydrogen evolution in alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    McArthur, M. A.; Jorge, L.; Coulombe, S.; Omanovic, S.

    2014-11-01

    Renewable alternative energy sources are required to decrease or eliminate the use of environmentally unfriendly fossil fuels. Hydrogen produced by electrolysis has been identified as one such renewable energy carrier. In the current work, Ni nanoparticle (NP)-decorated multiwall carbon nanotube (MWCNT) electrocatalyst cathodes are prepared by a simple two-step procedure. MWCNTs are grown on stainless steel meshes by thermal-chemical vapour deposition (t-CVD) and then decorated with Ni NPs by pulsed laser ablation (PLA). The morphological and electrochemical properties of the produced Ni NP/MWCNT cathodes were characterized through electron microscopy and linear Tafel polarization (LTP)/electrochemical impedance spectroscopy (EIS), respectively. SEM and TEM imaging revealed that the Ni NPs deposited by PLA are on the order of 4 nm in diameter with a narrow size distribution. The LTP measurements showed that the electrocatalytic activity of the Ni NP/MWCNT cathodes towards the hydrogen evolution reaction (HER) is dependent on PLA time and shows a maximum at tPLA = 40 min. EIS measurements revealed that the HER response is characterized by a two time constants process representing HER kinetics and adsorption of hydrogen.

  14. A flexible alkaline rechargeable Ni/Fe battery based on graphene foam/carbon nanotubes hybrid film.

    PubMed

    Liu, Jilei; Chen, Minghua; Zhang, Lili; Jiang, Jian; Yan, Jiaxu; Huang, Yizhong; Lin, Jianyi; Fan, Hong Jin; Shen, Ze Xiang

    2014-12-10

    The development of portable and wearable electronics has promoted increasing demand for high-performance power sources with high energy/power density, low cost, lightweight, as well as ultrathin and flexible features. Here, a new type of flexible Ni/Fe cell is designed and fabricated by employing Ni(OH)2 nanosheets and porous Fe2O3 nanorods grown on lightweight graphene foam (GF)/carbon nanotubes (CNTs) hybrid films as electrodes. The assembled f-Ni/Fe cells are able to deliver high energy/power densities (100.7 Wh/kg at 287 W/kg and 70.9 Wh/kg at 1.4 kW/kg, based on the total mass of active materials) and outstanding cycling stabilities (retention 89.1% after 1000 charge/discharge cycles). Benefiting from the use of ultralight and thin GF/CNTs hybrid films as current collectors, our f-Ni/Fe cell can exhibit a volumetric energy density of 16.6 Wh/l (based on the total volume of full cell), which is comparable to that of thin film battery and better than that of typical commercial supercapacitors. Moreover, the f-Ni/Fe cells can retain the electrochemical performance with repeated bendings. These features endow our f-Ni/Fe cells a highly promising candidate for next generation flexible energy storage systems.

  15. Enhanced supercapacitive performance of delaminated two-dimensional titanium carbide/carbon nanotube composites in alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Yan, Pengtao; Zhang, Ruijun; Jia, Jin; Wu, Chao; Zhou, Aiguo; Xu, Jiang; Zhang, Xuesha

    2015-06-01

    MXenes, a new family of two-dimensional materials, are terminated by O, OH and F groups. The existence of the oxygen-containing functional groups indicates a potential application in supercapacitor based on a redox mechanism. However, the irreversible stacking of MXenes will lead to an insufficient utilization of these functional groups and thus a decrease in the supercapacitive performance. To solve the problem, we synthesized a composite material comprised of carbon nanotube (CNT) and Ti3C2 sheets (d-Ti3C2) delaminated from MXenes by ultrasonic stirring. The FTIR result suggests that the ultrasonication has no significant effect on the oxygen-containing functional groups. The resultant composites exhibit significantly higher volumetric capacitance and better capacitance retention (during 5-100 mv s-1) than d-Ti3C2. A highest volumetric capacitance of 393 F cm-3 at 5 mv s-1 in KOH electrolyte can be obtained when the weight ratio of d-Ti3C2 to CNT is 2:1. In addition, the volumetric capacitance has no significant degradation even after 10000 cycles in cycling stability test, showing an excellent cycling stability compared with metal oxides. These enhanced electrochemical performances can be ascribed to the introduction of CNTs, which impede the stacking of Ti3C2, enlarge the distance between Ti3C2 sheets and improve the electrical conductivity.

  16. Changes in soil organic carbon storage predicted by Earth system models during the 21st century

    NASA Astrophysics Data System (ADS)

    Todd-Brown, K. E. O.; Randerson, J. T.; Hopkins, F.; Arora, V.; Hajima, T.; Jones, C.; Shevliakova, E.; Tjiputra, J.; Volodin, E.; Wu, T.; Zhang, Q.; Allison, S. D.

    2014-04-01

    Soil is currently thought to be a sink for carbon; however, the response of this sink to increasing levels of atmospheric carbon dioxide and climate change is uncertain. In this study, we analyzed soil organic carbon (SOC) changes from 11 Earth system models (ESMs) contributing simulations to the Coupled Model Intercomparison Project Phase 5 (CMIP5). We used a reduced complexity model based on temperature and moisture sensitivities to analyze the drivers of SOC change for the historical and high radiative forcing (RCP 8.5) scenarios between 1850 and 2100. ESM estimates of SOC changed over the 21st century (2090-2099 minus 1997-2006) ranging from a loss of 72 Pg C to a gain of 253 Pg C with a multi-model mean gain of 65 Pg C. Many ESMs simulated large changes in high-latitude SOC that ranged from losses of 37 Pg C to gains of 146 Pg C with a multi-model mean gain of 39 Pg C across tundra and boreal biomes. All ESMs showed cumulative increases in global NPP (11 to 59%) and decreases in SOC turnover times (15 to 28%) over the 21st century. Most of the model-to-model variation in SOC change was explained by initial SOC stocks combined with the relative changes in soil inputs and decomposition rates (R2 = 0.89, p < 0.01). Between models, increases in decomposition rate were well explained by a combination of initial decomposition rate, ESM-specific Q10-factors, and changes in soil temperature (R2 = 0.80, p < 0.01). All SOC changes depended on sustained increases in NPP with global change (primarily driven by increasing CO2). Many ESMs simulated large accumulations of SOC in high-latitude biomes that are not consistent with empirical studies. Most ESMs poorly represented permafrost dynamics and omitted potential constraints on SOC storage, such as priming effects, nutrient availability, mineral surface stabilization, and aggregate formation. Future models that represent these constraints are likely to estimate smaller increases in SOC storage over the 21st century.

  17. Vapor-liquid partitioning of alkaline earth and transition metals in NaCl-dominated hydrothermal fluids: An experimental study from 360 to 465 °C, near-critical to halite saturated conditions

    NASA Astrophysics Data System (ADS)

    Pester, Nicholas J.; Ding, Kang; Seyfried, William E.

    2015-11-01

    Multi-phase fluid flow is a common occurrence in magmatic hydrothermal systems; and extensive modeling efforts using currently established P-V-T-x properties of the NaCl-H2O system are impending. We have therefore performed hydrothermal flow experiments (360-465 °C) to observe vapor-liquid partitioning of alkaline earth and first row transition metals in NaCl-dominated source solutions. The data allow extraction of partition coefficients related to the intrinsic changes in both chlorinity and density along the two-phase solvus. The coefficients yield an overall decrease in vapor affinity in the order Cu(I) > Na > Fe(II) > Zn > Ni(II) ⩾ Mg ⩾ Mn(II) > Co(II) > Ca > Sr > Ba, distinguished with 95% confidence for vapor densities greater than ∼0.2 g/cm3. The alkaline earth metals are limited to purely electrostatic interactions with Cl ligands, resulting in an excellent linear correlation (R2 > 0.99) between their partition coefficients and respective ionic radii. Though broadly consistent with this relationship, relative behavior of the transition metals is not well resolved, being likely obscured by complex bonding processes and the potential participation of Na in the formation of tetra-chloro species. At lower densities (at/near halite saturation) partitioning behavior of all metals becomes highly non-linear, where M/Cl ratios in the vapor begin to increase despite continued decreases in chlorinity and density. We refer to this phenomenon as "volatility", which is broadly associated with substantial increases in the HCl/NaCl ratio (eventually to >1) due to hydrolysis of NaCl. Some transition metals (e.g., Fe, Zn) exhibit volatility prior to halite stability, suggesting a potential shift in vapor speciation relative to nearer critical regions of the vapor-liquid solvus. The chemistry of deep-sea hydrothermal fluids appears affected by this process during magmatic events, however, our results do not support suggestions of subseafloor halite precipitation

  18. Kinetic study of the α-tocopherol-regeneration reaction of ubiquinol-10 in methanol and acetonitrile solutions: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    PubMed

    Mukai, Kazuo; Oi, Masanori; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-03-01

    A kinetic study of regeneration reaction of α-tocopherol (α-TocH) by ubiquinol-10 has been performed in the presence of four kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), NaI, and Mg(ClO(4))(2)) in methanol and acetonitrile solutions, using double-mixing stopped-flow spectrophotometry. The second-order rate constants (k(r)'s) for the reaction of α-tocopheroxyl (α-Toc•) radical with ubiquinol-10 increased and decreased notably with increasing concentrations of metal salts in methanol and acetonitrile, respectively. The k(r) values increased in the order of no metal salt < NaClO(4) ~ NaI < LiClO(4) < Mg(ClO(4))(2) at the same concentration of metal salts in methanol. On the other hand, in acetonitrile, the k(r) values decreased in the order of no metal salt > NaClO(4) ~ NaI > LiClO(4) > Mg(ClO(4))(2) at the same concentration of metal salts. The metal salts having a smaller ionic radius of cation and a larger charge of cation gave a larger k(r) value in methanol, and a smaller k(r) value in acetonitrile. The effect of anion was almost negligible in both the solvents. Notable effects of metal cations on the UV-vis absorption spectrum of α-Toc• radical were observed in aprotic acetonitrile solution, suggesting complex formation between α-Toc• and metal cations. On the other hand, effects of metal cations were negligible in protic methanol, suggesting that the complex formation between α-Toc• and metal cations is hindered by the hydrogen bond between α-Toc• and methanol molecules. The difference between the reaction mechanisms in methanol and acetonitrile solutions was discussed on the basis of the results obtained. High concentrations of alkali and alkaline earth metal salts coexist with α-TocH and ubiquinol-10 in plasma, blood, and many tissues, suggesting the contribution of the metal salts to the above regeneration reaction in biological systems.

  19. Synthesis, crystal and band structures, and optical properties of a new lanthanide-alkaline earth tellurium(IV) oxide: La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2}

    SciTech Connect

    Jiang Hailong; Kong Fang; Mao Jianggao

    2007-05-15

    A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2}, has been prepared by the solid-state reaction and structurally characterized. The compound crystallizes in monoclinic space group C2/c with a=19.119(3), b=5.9923(5), c=13.2970(19) A, {beta}=107.646(8){sup o}, V=1451.7(3) A{sup 3} and Z=4. La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} features a 3D network structure in which the cationic [La{sub 2}Ba(TeO{sub 3}){sub 2}]{sup 4+} layers are cross-linked by Te{sub 3}O{sub 8} {sup 4-} anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} is a wide band-gap semiconductor. - Graphical abstract: A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2}, has been prepared by the solid-state reaction and structurally characterized. The structure of La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} is 3D network in which the cationic [La{sub 2}Ba(TeO{sub 3}){sub 2}]{sup 4+} layers are cross-linked by Te{sub 3}O{sub 8} {sup 4-} anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} is a wide band-gap semiconductor.

  20. The carbon reduction research of teaching staff commuting aided by Google Earth: taking Guangzhou University as an example

    NASA Astrophysics Data System (ADS)

    Xie, Hongyu; Wang, Xixiang; Zhao, Meichan; Zhao, Huaqing; Lin, Zhien

    2008-10-01

    In this paper, taking Guangzhou University as an example, carbon reduction of teaching staff commuting was researched. Firstly, considering carbon emission of teaching staff commuting is come from the fuel consumption of vehicle used to trip, the routes, schedule, vehicle type, fuel type and fuel consumption per 100 km of service express bus, public bus and private car were investigated from relevant department and web questionnaire in office automation system. Secondly, the routes of service express bus, public bus and private car were drawn in Google earth browser to measure distance. Thirdly, combined the bus schedule, school calendar, curriculum timetable of teacher and fuel consumption per 100 km of all kinds of vehicle, the fuel consumption of service express bus, public bus and private car were computed. Fourthly, carbon emission was calculated according to net calorific factor and calorie carbon emission factors of fuel. Finally, the measures of carbon reduction were discussed. The research results show that teaching staff commuting emitted 455.433 tons carbon in 2005-2006 academic year. And reducing usage rate of private car and adding new service express bus line are efficient measure of carbon reduction. Former measure can reduce 33.6891 tons carbon and about 7.4% of original emission. The latter can reduce 7.6317 tons and about 1.68% of original emission.

  1. Rare Earth Element Speciation Along Groundwater Flow Paths in Two Different Aquifer Types (i.e., Sand vs. Carbonate)

    NASA Astrophysics Data System (ADS)

    Tang, J.; Johannesson, K. H.

    2003-12-01

    Groundwater samples were collected in two different types of aquifer (i.e., Carrizo sand aquifer, Texas and Upper Floridan carbonate aquifer, west-central Florida) to study the concentrations, fractionation, and speciation of rare earth elements (REE) along groundwater flow paths in each aquifer. The solution complexation of REEs in these two aquifers was modeled using Humic Ion-Binding Model V. The results of the REE speciation modeling indicate that the solution complexation of REEs is controlled by pH, alkalinity, and DOC concentration. Because DOC is low (less than 0.65 mg/L) in Carrizo aquifer, organic complexation of REEs is not significant in these groundwaters. For LREEs, LnCO3+ and/or Ln(CO3)2- are the dominant species when pH is above 7.0, but when pH is below 7.0, besides LnCO3+, Ln3+ and LnSO4+ are also significant and their importance increases with decreasing pH. For HREEs, LnCO3+ and/or Ln(CO3)2- are always the dominant species, however, LnPO4o is important in some groundwaters. The similar general patterns of inorganic solution complexation of the REEs are also observed in groundwaters from the Upper Floridan aquifer. However, because of the relatively high DOC concentrations measured in the Floridan groundwaters, organic complexation of REEs, especially LREEs, is also predicted to be significant in some groundwaters. Linear correlation coefficients for total REE, Nd, Gd, and Yb concentrations, and (Yb/Nd)SN vs. pH, CO3, DOC, SO4, Fe, and Mn indicate that for the Carrizo groundwaters, REE concentrations are not correlatd to any of these factors. However, (Yb/Nd)SN is inversely related to pH and the [CO32-] concentration of these groundwaters. Because REE speciation is strongly related to pH and the [CO32-] concentration, it is reasonable to expect that REE solution complexation plays a greater role in fractionating REE than controlling absolute concentrations in the Carrizo Sand aquifer. In Upper Floridan aquifer, LREE concentrations are positively

  2. Evaluation of NorESM-OC (versions 1 and 1.2), the ocean carbon-cycle stand-alone configuration of the Norwegian Earth System Model (NorESM1)

    NASA Astrophysics Data System (ADS)

    Schwinger, Jörg; Goris, Nadine; Tjiputra, Jerry F.; Kriest, Iris; Bentsen, Mats; Bethke, Ingo; Ilicak, Mehmet; Assmann, Karen M.; Heinze, Christoph

    2016-08-01

    Idealised and hindcast simulations performed with the stand-alone ocean carbon-cycle configuration of the Norwegian Earth System Model (NorESM-OC) are described and evaluated. We present simulation results of three different model configurations (two different model versions at different grid resolutions) using two different atmospheric forcing data sets. Model version NorESM-OC1 corresponds to the version that is included in the NorESM-ME1 fully coupled model, which participated in CMIP5. The main update between NorESM-OC1 and NorESM-OC1.2 is the addition of two new options for the treatment of sinking particles. We find that using a constant sinking speed, which has been the standard in NorESM's ocean carbon cycle module HAMOCC (HAMburg Ocean Carbon Cycle model), does not transport enough particulate organic carbon (POC) into the deep ocean below approximately 2000 m depth. The two newly implemented parameterisations, a particle aggregation scheme with prognostic sinking speed, and a simpler scheme that uses a linear increase in the sinking speed with depth, provide better agreement with observed POC fluxes. Additionally, reduced deep ocean biases of oxygen and remineralised phosphate indicate a better performance of the new parameterisations. For model version 1.2, a re-tuning of the ecosystem parameterisation has been performed, which (i) reduces previously too high primary production at high latitudes, (ii) consequently improves model results for surface nutrients, and (iii) reduces alkalinity and dissolved inorganic carbon biases at low latitudes. We use hindcast simulations with prescribed observed and constant (pre-industrial) atmospheric CO2 concentrations to derive the past and contemporary ocean carbon sink. For the period 1990-1999 we find an average ocean carbon uptake ranging from 2.01 to 2.58 Pg C yr-1 depending on model version, grid resolution, and atmospheric forcing data set.

  3. Rare-earth oxides of manganese and cobalt rival platinum for the treatment of carbon monoxide in auto exhaust.

    PubMed

    Voorhoeve, R J; Remeika, J P; Freeland, P E; Matthias, B T

    1972-07-28

    The perovskite-like compounds RE(1-X)Pb(5)MnO(3) and RECoO(3), where RE (rare earth) is lanthanum, praseodymium, or neodymium, are active catalysts for the oxidation of carbon monoxide. Crushed single crystals of these compounds compare favorably with commercial platinum catalysts in initial activity and lifetime. Therefore, these compounds are promising substitutes for platinum in devices for the catalytic treatment of auto exhaust.

  4. Carbon and other light element contents in the Earth's core based on first-principles molecular dynamics.

    PubMed

    Zhang, Yigang; Yin, Qing-Zhu

    2012-11-27

    Carbon (C) is one of the candidate light elements proposed to account for the density deficit of the Earth's core. In addition, C significantly affects siderophile and chalcophile element partitioning between metal and silicate and thus the distribution of these elements in the Earth's core and mantle. Derivation of the accretion and core-mantle segregation history of the Earth requires, therefore, an accurate knowledge of the C abundance in the Earth's core. Previous estimates of the C content of the core differ by a factor of ∼20 due to differences in assumptions and methods, and because the metal-silicate partition coefficient of C was previously unknown. Here we use two-phase first-principles molecular dynamics to derive this partition coefficient of C between liquid iron and silicate melt. We calculate a value of 9 ± 3 at 3,200 K and 40 GPa. Using this partition coefficient and the most recent estimates of bulk Earth or mantle C contents, we infer that the Earth's core contains 0.1-0.7 wt% of C. Carbon thus plays a moderate role in the density deficit of the core and in the distribution of siderophile and chalcophile elements during core-mantle segregation processes. The partition coefficients of nitrogen (N), hydrogen, helium, phosphorus, magnesium, oxygen, and silicon are also inferred and found to be in close agreement with experiments and other geochemical constraints. Contents of these elements in the core derived from applying these partition coefficients match those derived by using the cosmochemical volatility curve and geochemical mass balance arguments. N is an exception, indicating its retention in a mantle phase instead of in the core.

  5. 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.

    PubMed

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

    2016-09-06

    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.

  6. Hydrothermal synthesis and crystal structure of two new hydrated alkaline earth metal borates Sr3B6O11(OH)2 and Ba3B6O11(OH)2.

    PubMed

    Heyward, Carla; McMillen, Colin; Kolis, Joseph

    2012-04-02

    Two new hydrated borates Sr(3)B(6)O(11)(OH)(2) (1) and Ba(3)B(6)O(11)(OH)(2) (2) were hydrothermally synthesized. Their structures were determined by single-crystal X-ray diffraction and further characterized by IR, powder XRD, and DSC/TGA. Compound 1 crystallizes in the triclinic space group P-1 with unit cell parameters of a = 6.6275(13) Å, b = 6.6706(13) Å, c = 11.393(2) Å, α = 91.06(3)°, β = 94.50(3)°, and γ = 93.12(3)°, while compound 2 crystallizes in the noncentrosymmetric monoclinic space group Pc with a = 6.958(14) Å, b = 7.024(14) Å, c = 11.346(2) Å, and β = 90.10(3)°. In spite of the differences in symmetry and packing of the borate chains, both structures consist of the same fundamental building block (FBB) of a [B(6)O(11)(OH)(2)](-6) unit and three unique alkaline earth metal atoms.

  7. Spin-Spin Interactions in the Oxides A(3)M'MO(6) (M = Rh, Ir; A = Ca, Sr; M' = Alkaline Earth, Zn, Cd, Na) of the K(4)CdCl(6) Structure Type Examined by Electronic Structure Calculations.

    PubMed

    Lee, K.-S.; Koo, H.-J.; Whangbo, M.-H.

    1999-05-03

    The oxides A(3)M'MO(6) (M = Rh, Ir; A = Ca, Sr; M' = alkaline earth, Zn, Cd) of the K(4)CdCl(6) structure type consist of isolated (MO(6))(8)(-) octahedral anions and exhibit an antiferromagnetic ordering at low temperatures. The spin-spin interactions in these oxides, Ca(3)NaMO(6) (M = Ir, Ru), and Sr(3)NaRuO(6) were examined by calculating how strongly the t(2g)-block levels of adjacent (MO(6))((6+)(n)()())(-) (n = 1, 2) anions interact in the presence and absence of the intervening cations A(2+) and M' (n)()(+) (n = 1, 2). Our calculations show that the spin-spin interactions in these oxides are three-dimensional, and the superexchange interactions occur mainly through the short intrachain and interchain M-O.O-M linkages. When the M(n)()(+) cation is very small compared with the A(2+) cation, the intrachain interaction is substantially stronger than the interchain interaction. The opposite is found when the sizes of the M(n)()(+) and A(2+) cations become similar.

  8. 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.

    PubMed

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

    2015-09-18

    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.

  9. Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF2, SrF2, and BaF2)

    NASA Astrophysics Data System (ADS)

    Nikolaichik, V. I.; Sobolev, B. P.; Zaporozhets, M. A.; Avilov, A. S.

    2012-03-01

    The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF2, SrF2, and BaF2 is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF2 crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of ˜2 × 103 pA/cm2). In BaF2 samples, the transformation of BaO into Ba(OH)2 was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH)2 into BaO. In the initial stage of irradiation of all MF2 compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF2 matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF2 destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of ˜20 nm in the sample.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  11. Carbon sequestration potential and climatic effects of reforestation in an Earth system model

    NASA Astrophysics Data System (ADS)

    Sonntag, Sebastian; Pongratz, Julia; Reick, Christian; Schmidt, Hauke

    2015-04-01

    Studies on the global climatic effects of afforestation have mainly focused on the carbon sequestration potential of plausible scenarios while neglecting biogeophysical effects or were based on highly idealised afforestation scenarios. Here we assess the reduction potential for the atmospheric CO2 concentration and possible consequences for the global climate of following a strong reforestation scenario during this century taking into account both biogeochemical and biogeophysical effects. We perform simulations using the Max Planck Institute for Meteorology Earth System Model (MPI-ESM), forced by anthropogenic emissions according to the Representative Concentration Pathway (RCP) 8.5, but using land use transitions according to RCP 4.5. Thereby we are able to isolate the effects of land use changes in this scenario in which agricultural intensification leads to abandonment of agricultural areas and a regrowth of forest of about 8 million km2 in our model. We find that this reforestation reduces the atmospheric CO2 concentration by about 85 ppm by the end of the century as compared to RCP 8.5. This value is higher than previous estimates for plausible reforestation scenarios, mostly because the CO2 fertilisation effect on the terrestrial vegetation has not been accounted for in previous studies. Due to the lower CO2 concentration the global mean temperature increase is reduced by about 0.27 K. Regionally the simulated effect may exceed 2 K, but the largest annual mean cooling signal occurs in only sparsely populated regions. Concerning temperature extremes, however, the effect can also be large in densely populated areas, mostly caused by local biogeophysical effects of the vegetation changes. Thus, we conclude that the mitigation potential of reforestation is higher than previously thought, the need for adaptation in many regions of the world is still strong, but temperature extremes may be reduced.

  12. V-H+ -ATPase translocation during blood alkalosis in dogfish gills: interaction with carbonic anhydrase and involvement in the postfeeding alkaline tide.

    PubMed

    Tresguerres, Martin; Parks, Scott K; Wood, Chris M; Goss, Greg G

    2007-05-01

    We investigated the involvement of carbonic anhydrase (CA) in mediating V-H(+)-ATPase translocation into the basolateral membrane in gills of alkalotic Squalus acanthias. Immunolabeling revealed that CA is localized in the same cells as V-H(+)-ATPase. Blood plasma from dogfish injected with acetazolamide [30 mg/kg at time (t) = 0 and 6 h] and infused with NaHCO(3) for 12 h (1,000 microeq.kg(-1).h(-1)) had significantly higher plasma HCO(3)(-) concentration than fish that were infused with NaHCO(3) alone (28.72 +/- 0.41 vs. 6.57 +/- 2.47 mmol/l, n = 3), whereas blood pH was similar in both treatments (8.03 +/- 0.11 vs. 8.04 +/- 0.11 pH units at t = 12 h). CA inhibition impaired V-H(+)-ATPase translocation into the basolateral membrane, as estimated from immunolabeled gill sections and Western blotting on gill cell membranes (0.24 +/- 0.08 vs. 1.00 +/- 0.28 arbitrary units, n = 3; P < 0.05). We investigated V-H(+)-ATPase translocation during a postfeeding alkalosis ("alkaline tide"). Gill samples were taken 24-26 h after dogfish were fed to satiety in a natural-like feeding regime. Immunolabeled gill sections revealed that V-H(+)-ATPase translocated to the basolateral membrane in the postfed fish. Confirming this result, V-H(+)-ATPase abundance was twofold higher in gill cell membranes of the postfed fish than in fasted fish (n = 4-5; P < 0.05). These results indicate that 1) intracellular H(+) or HCO(3)(-) produced by CA (and not blood pH or HCO(3)(-)) is likely the stimulus that triggers the V-H(+)-ATPase translocation into the basolateral membrane in alkalotic fish and 2) V-H(+)-ATPase translocation is important for enhanced HCO(3)(-) secretion during a naturally occurring postfeeding alkalosis.

  13. A new phosphorimetry for the determination of trace alkaline phosphatase using multi-wall carbon nanotubes and its diagnosis of human diseases.

    PubMed

    Liu, Jia-Ming; Rao, Ying; Chen, Li; Wang, Xin-Xing; Lin, Li-Ping; Lin, Chang-Qing; Zhang, Li-Hong; Ou-Yang, Ying

    2010-07-01

    Multi-wall carbon nanotubes (MWNTs) could be modified as water soluble MWNTs (it was called as MWNTs-A and MWNTs-B) by chemical methods. MWNTs-A and MWNTs-B could emit room temperature phosphorescence (RTP) signal on the surface of nitrocellulose membrane (NCM). A new solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace alkaline phosphatase (ALP) was established based on the signal magnification effect of tween-80 and ALP on MWNTs-B's RTP intensity and the linear relationship between the content of ALP and the DeltaI(P) of the system. The linear range of this method was 0.0020-0.80 (fg spot(-1), sample volume: 0.40 microl spot(-1)), the regression equation of working curve was DeltaI(P) = 0.8170 + 96.84m(ALP) (fg spot(-1)), correlation coefficient (r) was 0.9986. This method had high sensitivity (detection limit (LD): 1.4 ag spot(-1)), good selectivity (Er < or = +/- 5 in-care-of, coexistence species were of no interference), high precision (RSDs were 4.4%-1.2%) and accuracy. It was applied to the determination of trace ALP in human serum and the diagnosis of human diseases. The results were tallied with those of enzyme-linked immunosorbent assay (ELISA). The mechanism of new SS-RTP for the determination of trace ALP was discussed, which laid the theory foundation for the analytical application of MWNTs in life science.

  14. Impact of internal and external Alkalinity fluxes on the carbonate system in the German Bight / SE North Sea - A model study for the years 2001 - 2009

    NASA Astrophysics Data System (ADS)

    Schwichtenberg, Fabian; Pätsch, Johannes; Amann, Thorben; Schartau, Markus; Thomas, Helmuth; Winde, Vera; Dellwig, Olaf; van Beusekom, Justus; Böttcher, Michael; Grashorn, Sebastian; Salt, Lesley

    2013-04-01

    Rising atmospheric CO2 concentrations may cause enhanced oceanic CO2 concentrations and thus ongoing acidification of the marine environment. Effects of acidification on the coastal ocean exhibit large variabilities due to shallow water column, tight benthic-pelagic coupling, nutrient cycling, and discharge from land. As a result of enhanced biogeochemical processes, seasonal pH variations in coastal and shelf regions can be up to an order of magnitude higher than in the open ocean and may potentially mask the decadal trend of decreasing pH. Total Alkalinity (TA) is an essential part of the carbonate system as it regulates the oceanic CO2 buffer capacity. Variations in TA are vital to understand observed pH variations. In the coastal zone variations in TA are particularly pronounced because of diverse external sources like river discharge, anaerobic degradation of organic material or methane fluxes in tidal flats in association with pore water exchange across the sediment-water interface. Beside these external fluxes TA also changes due to physical, chemical and biological processes. To better understand and quantify the effect of acidification in the southern North Sea as part of the northwest European Shelf we applied the ecosystem model ECOHAM with a prognostic treatment of TA. For the first step we included monthly varying TA and DIC concentrations of the main continental rivers draining to the North Sea. For the Dutch rivers we calculated these data from other parameters of the carbonate system (bicarbonate and pH) that have been measured in the respective estuaries. For the river Elbe we used data of TA and DIC concentrations that have been measured in the estuary. Simulation results reveal that the river contribution to TA flux is insufficient to explain the seasonal variations observed in the German Bight. As high summer concentrations remain unresolved in this model setup, elevated TA concentrations during summer in that area must originate from sources

  15. Alkaline sorbent injection for mercury control

    DOEpatents

    Madden, Deborah A.; Holmes, Michael J.

    2002-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  16. Alkaline sorbent injection for mercury control

    DOEpatents

    Madden, Deborah A.; Holmes, Michael J.

    2003-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  17. Rare earth elements of seep carbonates: Indication for redox variations and microbiological processes at modern seep sites

    NASA Astrophysics Data System (ADS)

    Feng, Dong; Lin, Zhijia; Bian, Youyan; Chen, Duofu; Peckmann, Jörn; Bohrmann, Gerhard; Roberts, Harry H.

    2013-03-01

    At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (ΣREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the ΣREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that ΣREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

  18. Imidazol-2-ylidene-N'-phenylureate ligands in alkali and alkaline earth metal coordination spheres--heterocubane core to polymeric structural motif formation.

    PubMed

    Naktode, Kishor; Bhattacharjee, Jayeeta; Nayek, Hari Pada; Panda, Tarun K

    2015-04-28

    elongated carbon-nitrogen bond distances indicate substantial electron delocalisation from the imidazole ring to the ureate group present in ligand 1.

  19. Massive impact-induced release of carbon and sulfur gases in the early Earth's atmosphere

    NASA Astrophysics Data System (ADS)

    Marchi, S.; Black, B. A.; Elkins-Tanton, L. T.; Bottke, W. F.

    2016-09-01

    Recent revisions to our understanding of the collisional history of the Hadean and early-Archean Earth indicate that large collisions may have been an important geophysical process. In this work we show that the early bombardment flux of large impactors (>100 km) facilitated the atmospheric release of greenhouse gases (particularly CO2) from Earth's mantle. Depending on the timescale for the drawdown of atmospheric CO2, the Earth's surface could have been subject to prolonged clement surface conditions or multiple freeze-thaw cycles. The bombardment also delivered and redistributed to the surface large quantities of sulfur, one of the most important elements