Search Results - (Author, Cooperation:S. C. Kohn)

2016-01-08

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1476-4687

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2011-09-17

American Association for the Advancement of Science (AAAS)

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1476-4687

Nature Archives 1869 - 2009

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Natural Sciences in General

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[Auszug] The proton magic-angle-spinning (MAS) NMR spectrum for sample SIC, an SiO2 glass containing 2.5 wt% water quenched from 1,320°C and 1 kbar (Fig. \b) consists of an asymmetric peak, broadened towards high frequency. Although this could be explained in terms of a distribution of proton ...

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract A number of leucite group materials with the formula X2YSi5O12 where X=K, Rb, Cs and Y=Mg, Zn, Cd have been synthesized by dry and hydrothermal crystallization of glass starting materials. 29Si MASNMR has been used to obtain structural information, such as the number of distinct tetrahedral sites, degree of cation ordering, and estimates of the mean T-O-T bond angles of the tetrahedra. X-ray powder diffraction gave information on cell volumes and degree of distortion from cubic symmetry for all the samples and space group and structural information for some samples. Integration of the different length-scale data obtained using these two complementary techniques allows greater reliance to be placed on the structures deduced for these leucite samples, which are only available as fine-grained powders. Hydrothermally synthesized K2MgSi5O12, K2ZnSi5O12 and Rb2ZnSi5O12 have structures with 12 distinct tetrahedral sites (T-sites) and are monoclinic P21/c while the dry-synthesized equivalents are disordered with single T-sites and are cubic, Ia3d. Most of the other members of the group have structures with 6 tetrahedral sites with Cs2CdSi5O12 being orthorhombic, Pbca. Cs2ZnSi5O12 has an intermediate “5+2” structure. Decreasing the size of the X+ cation for a given Y2+ cation gives more collapsed and distorted frameworks. 133Cs NMR was used to show that samples with 6 T-sites have 2 alkali sites. It is deduced that samples with 12 T-sites will undergo a displacive phase transition to a 6 T-site structure (possibly via a 5+2 intermediate in some cases) with no change in the framework topology or degree of T-site ordering.

Electronic Resource

1432-2021

Springer Online Journal Archives 1860-2000

Chemistry and Pharmacology

Geosciences

Physics

Abstract Phases with the composition K2MgSi5O12, belonging to the leucite structure group were synthesised under dry and hydrothermal conditions and studied using 29Si NMR. The 29Si spectrum for the dry-crystallised material (which is cubic) consists of a single broad line, suggesting a high degree of disorder. The hydrothermally crystallised material (which is probably monoclinic, with a distorted leucite lattice) has a 29Si spectrum which consists of ten lines of equal intensity, two of which have small chemical shift anisotropies and are therefore assigned to Q4(4Si) sites. These data have been interpreted in terms of a structure with 12 distinct tetrahedral sites over which 2 Mg atoms and 10 Si atoms are fully ordered. A 2-dimensional COSY spectrum shows correlations between some Q4(3Si) silicon atoms and two other Q4(3Si) silicon atoms. This fully constrains the topology of the unit cell. Two schemes of Si/Mg ordering over the unit cell can give good fits to the COSY spectrum. Using the tetrahedral (T) site notation defined for natural tetragonal leucite, the first of these arrangements involves Mg and Q4(4Si) silicon atoms each occupying one T1-type site and one T3-type site, and Q4(3Si) silicons occupying the remaining sites, i.e. four T2-type sites, two T1-type sites and two T3-type sites. In the second arrangement, the T2-type sites are occupied by Mg atoms and Q4(4Si) silicon atoms and all the T1-and T3-type sites are occupied by Q4(3Si) atoms.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract Electron and ion-probe microanalysis have been used to obtain zoning profiles for major and trace elements in olivine phenocrysts from a high-magnesian andesite from Shodo-Shima island, southwest Japan. This rock was previously thought to represent undifferentiated, primary magma. Some crystals have unzoned cores, while others show cores which are reversely zoned with respect to Mg/ (Mg+Fe), Ni, Mn and Cr. In addition, some Ni profiles show a normally zoned “hump” at the most central portions of the reversely zoned crystals. All crystals show normally zoned rims. The Li concentrations are constant throughout the cores of all crystals studied, but rise sharply, by a factor of up to at least six, in the rims. The Ca and Co concentrations are essentially constant throughout all the crystals. Mechanisms for producing the observed zoning profiles are discussed, and it is concluded that the reverse zoning was produced by the introduction of crystals into a less differentiated magma than that in which they grew. The reversely zoned crystals could therefore represent xenocrysts which were introduced into an undifferentiated magma, or phenocrysts introduced into a more primitive magma by a magma mixing process. The Ni profiles are used to estimate the residence time of these crystals in the more primitive magma. The following trace element partition co-efficients have been estimated for the olivine-groundmass system in this rock: D Ni=16; D Mn=1.1; D Co=4.2; D Ca =0.02; D Ti=0.005; D V=0.05; D Sc=0.2; D Na=0.0002. Studies of trace element zoning will become increasingly important as the new generation of trace element microprobes become available but a larger database of experimentally determined values for trace element partition coefficients and diffusion coefficients in crystals and magmas, and a better understanding of other disequilibrium processes are required to fully exploit the new data.

Electronic Resource

1432-0967

Springer Online Journal Archives 1860-2000

Geosciences

Abstract The structural environments of Mn2+ and Sr2+ at concentrations of 0.2–0.8 wt% in dry and hydrous silicate glasses have been studied using X-ray absorption spectroscopy (EXAFS and XANES). The environment of Mn in hydrous silica glasses containing 4.5 and 6.0 wt% H2O appears to be close to an undistorted octahedral site, whereas Mn in other compositions, both dry and hydrous, occupies either a distribution of octahedral and tetrahedral sites, or distorted, non-centrosymmetric sites. The fraction of non-centrosymmetric sites (including tetrahedral) or the average degree of distortion of the sites decreases with both increasing dissolved water concentration and number of non-bridging oxygens in the glass. For Sr the changes as a function of polymerisation and water concentration are less clear, but it appears that the average Sr-O distances are shorter than in crystalline silicates and decrease further with decreasing polymerisation. The structural data obtained in this study are not readily integrated with previous partitioning data for Mn, suggesting that changes in the first-shell coordination geometry of Mn do not play a direct role in controlling the melt compositional dependence of trace element partition coefficients. It is tentatively suggested that distortions of the framework resulting from the incorporation of Mn (i.e. a second shell effect) control the partitioning behaviour.

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