Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.

The effect of the CaO/SiO2 ratio on the phase equilibria in the ZnO-“Fe2O3”-(PbO + CaO + SiO2) system in air: CaO/SiO2 = 0.1, PbO/(CaO + SiO2) = 6.2, and CaO/SiO2 = 0.6, PbO/(CaO + SiO2) = 4.3

Experimental studies on phase equilibria in the multi-component system PbO-ZnO-CaO-SiO2-FeO-Fe2O3 in air have been conducted to characterize the phase relations of a complex slag system used in the oxidation smelting of lead and in typical lead blast furnace sinters. The liquidus in two pseudoternary sections ZnO-Fe2O3-(PbO + CaO + SiO2) with the CaO/SiO2 weight ratio of 0.1 and the PbO/(CaO + SiO2) weight ratio of 6.2, and with CaO/SiO2 weight ratio of 0.6 and the PbO/(CaO + SiO2) weight ratio of 4.3, have been constructed.

Probing crystallisation of a fluoro-apatite - mullite system using neutron diffraction

Real-time small angle neutron scattering and wide angle neutron scattering studies were undertaken concurrently on a glass ionomer of nominal composition 4.5(SiO2)-3(Al2O3)-1.5(P2O5)-3(CaO)-2(CaF2). Neutron studies were conducted as a function of temperature to investigate the crystallisation process. No amorphous phase separation was observed at room temperature and the onset of crystallisation was found to occur at 650°C, which is 90°C lower than previously reported. The first crystalline phase observed corresponded to fluorapatite; it was only upon further heating was the mullite phase became present. The crystallite size at 650°C was found to be ~115Å and the result was consistent across all measurements.

Application of staged O2 feeding in the oxidative dehydrogenation of ethylbenzene to styrene over Al2O3 and P2O5/SiO2 catalysts

Drastic improvements in styrene yield and selectivity were achieved in the oxidative dehydrogenation of ethylbenzene by staged feeding of O2. Six isothermal packed bed reactors were used in series with intermediate feeding of O2, while all EB was fed to the first reactor, diluted with helium or CO2 (1:5 molar ratio), resulting in total O2:EB molar feed ratios of 0.2-0.6. The two catalyst samples, γ-Al 2O3 and 5P/SiO2, that were applied both benefitted from this operation mode. The ethylbenzene conversion per stage and the selectivity to styrene were significantly improved. The production of COX was effectively reduced, while the selectivity to other side products remained unchanged. Compared with co-feeding at a total O 2:EB molar feed ratio of 0.6, by staged feeding the EB conversion (+15% points for both catalysts), ST selectivity (+4% points for both samples) and O2 (ST) selectivity (+9% points for γ-Al2O 3 and +17% points for 5P/SiO2) all improved. The ethylbenzene conversion over 5P/SiO2 can be increased from 18% to 70% by increasing the number of reactors from 1 to 6 with each reactor a total amount of O2 of 0.1 without the loss of ST selectivity (93%). For 5P/SiO2 a higher temperature (500 C vs. 450 C for Al 2O3) is required. Essentially more catalyst (5P/SiO 2) was required to achieve full O2 conversion in each reactor. Staged feeding of O2 does not eliminate the existing issues of the catalyst stability both in time-on stream and as a function of the number of catalyst regenerations (5P/SiO2), or the relatively moderate performance (relatively low styrene selectivity for γ-Al2O 3). © 2014 Elsevier B.V.

Azul de metileno imobilizado na celulose/TiO2 e SiO2/TiO2: propriedades eletroquímicas e planejamento fatorial

The electrochemical properties of methylene blue immobilized on cellulose/TiO2 and mixed oxide SiO2/TiO2 matrices were investigated by means of cyclic voltammetry. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of four factors in two levels. The experimental observations and data analyses on the system indicate that the lowest peak separation occurs for Sil/TiOAM, 1.0 mol L-1 KCl solution and 20 mV s-1 scan rate, while values of current ratio closest to unity were found for Cel/TiOAM independent of electrolyte concentration, 0.2 or 1.0 mol L-1, and scan rate, 20 mV s-1 or 60 mV s-1.

Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y(2)O(3))(0.2)-(Al(2)O(3))(x)-(B(2)O(3))(0.8-x)

The structure of laser glasses in the system (Y(2)O(3))(0.2){(Al(2)O(3))(x))(B(2)O(3))(0.8-x)} (0.15 <= x <= 0.40) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. (11)B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as (11)B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO(2/2)O(-)), doubly charged pyroborate (BO(1/2)(O(-))(2)), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. (27)Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three-and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. (89)Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly ""aluminate-like'' with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.

Thermodynamic modelling of an Al(2)O(3)-MnO system using the ionic model

The thermodynamic assessment of an Al(2)O(3)-MnO pseudo-binary system has been carried out with the use of an ionic model. The use of the electro-neutrality principles in addition to the constitutive relations, between site fractions of the species on each sub-lattice, the thermodynamics descriptions of each solid phase has been determined to make possible the solubility description. Based on the thermodynamics descriptions of each phase in addition to thermo-chemical data obtained from the literature, the Gibbs energy functions were optimized for each phase of the Al(2)O(3)-MnO system with the support of PARROT(R) module from ThemoCalc(R) package. A thermodynamic database was obtained, in agreement with the thermo-chemical data extracted from the literature, to describe the Al(2)O(3)-MnO system including the solubility description of solid phases. (C) 2009 Elsevier Ltd. All rights reserved.

Reforming of methane with carbon dioxide over Ni/Al2O3 catalysts: Effect of nickel precursor

The catalytic activities of Ni/gamma-Al2O3 catalysts prepared using different nickel precursor compounds were studied for the reaction of methane reforming with CO2. It is found that the nickel precursor employed in the catalyst preparation plays an important role. The catalyst based on nickel nitrate exhibited higher catalytic activity and stability over a 24-h test period than the other two catalysts derived from nickel chloride and nickel acetylacetonate. A comprehensive characterisation of the catalysts showed that the weak interaction between Ni particles and gamma-Al2O3 resulted in more active sites on Ni nitrate-derived Ni/gamma-Al2O3 catalyst. Coking studies showed that carbon deposition on Ni catalysts derived from inorganic precursors (nitrate and chloride) were more severe than on the organic precursor-derived catalyst. However, the Ni nitrate-derived catalyst was found to have the highest stability (or lowest deactivation rate) mainly due to the active carbon species (-C-C-) of the resulting graphitic structure and their close contact with the metal particles. In contrast, the carbon formed on Ni-AA catalyst (from Ni acetylacetonate) is dominated by inactive -CO-C- species, thus leading to a rapid accumulation of carbon in this catalyst and more severe deactivation. (C) 1998 Elsevier Science B.V.

The effect of Al2O3 on liquidus temperatures of fayalite slags

The effect of alumina on the liquidus temperatures of fayalite slags at iron saturation has been investigated experimentally. Equilibrated synthetic slags were quenched, and the samples were subsequently examined using optical microscopy and electron probe microanalysis (EPMA). The isotherms in the fayalite primary field and boundary lines were determined, and the results were presented in the form of pseudo-ternary phase diagrams of FeO-CaO-SiO2 with 0, 2, 4, and 6 wt pet Al2O3 in the slag. The experimental results show that the alumina addition expands the fayalite primary phase field and decreases the liquidus temperatures in the fayalite primary phase field.