Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Catalisadores Ni/MgO-SiO2 aplicados na reação de reforma a vapor de glicerol

Catalisadores de Ni (10% em massa) suportado em matrizes mistas MgO-SiO2 foram aplicados na reação de reforma a vapor de glicerol. Os efeitos do teor de MgO como aditivo e do método de preparação foram avaliados frente às propriedades físico-químicas e texturais dos materiais; assim como à atividade, seletividade, estabilidade e formação de carbono na reforma a vapor do glicerol. Os catalisadores foram preparados com diferentes teores mássicos de MgO (10%, 30% e 50%) sobre SiO2 comercial, utilizando processo via seca (mistura física) e via úmida (impregnação sequencial com diferentes solventes: água, etanol e acetona). Foram utilizadas as técnicas de caracterização de espectroscopia de energia dispersiva de raios X, fisissorção de nitrogênio, difratometria de raios X, termogravimetria, difratometria de raios X in situ com O2, redução a temperatura programada com H2, difratometria de raios X in situ com H2, dessorção a temperatura programada com H2 e microscopia eletrônica de varredura. Foi observado que o Ni(II) interage de forma variada com os suportes com diferentes teores de MgO, e que a polaridade do solvente de impregnação utilizado no processo de preparação influencia as propriedades dos catalisadores. A fim de verificar a atividade, seletividade e deposição de carbono; os catalisadores foram testados na reação de reforma a vapor de glicerol a 600oC, por um período de 5h e razão molar água:glicerol de 12:1. Após as reações, os catalisadores foram novamente submetidos às análises de termogravimetria, difratometria de raios X e microscopia eletrônica de varredura, visando a caracterização dos depósitos de carbono obtidos durante o processo catalítico. Os catalisadores de matrizes mistas se mostraram ativos e apresentaram seletividades similares para os produtos gasosos CH4, CO e CO2, além de um alto rendimento em H2. Observou-se que a adição de MgO no suporte, aumentou a dispersão do Ni(II) no material, que por sua vez, influenciou na quantidade de carbono depositado ao longo da reação. A polaridade do solvente de impregnação também teve influência na dispersão metálica, sendo que, quanto menor a polaridade do solvente, maior foi a dispersão obtida no catalisador, e menor a deposição de carbono na reação. O material que apresentou o melhor desempenho catalítico frente ao rendimento de H2 e à deposição de carbono, foi o catalisador preparado com 30% de MgO com etanol como solvente de impregnação.

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.

The prediction and representation of phase equilibria and physicochemical properties in complex slag systems

The development of new experimental techniques for the determination of phase equilibria in complex slag systems, chemical thermodynamic, and viscosity models is reported. The new experimental data, and new thermodynamic and viscosity models, have been combined in a custom-designed computer software package to produce limiting operability diagrams for slag systems. These diagrams are used to describe phase equilibria and physicochemical properties in complex slag systems. The approach is illustrated with calculations on the system FeO-Fe2O3-CaO-SiO-Al2O3 at metallic iron saturation, slags produced in coal slagging gasifiers, and in the reprocessing of nonferrous smelting slags. This article was presented at the Mills Symposium Molten Metals, Slags and Glasses-Characterisation of Properties and Phenomena held in London in August 2000.

Estudo espectroscópico de vidros a base de aluminato de cálcio contendo Nd3+

Multicomponent ( Al2O3, CaO, SiO2, MgO) calcium aluminate-based glasses containing Nd3+ were prepared in order to evaluate their possibilities as laser host materials. The refractive index, UV-visible-near IR absorption spectrum, IR and visible luminescence spectra, and fluorescence decay time were measured. Judd-Ofelt model was used to obtain experimental intensity parameters ( omega2, omega4 and omega6), emission cross-section, radiative lifetimes, emission branching ratios and quantum efficiency.

Condutividade térmica de rochas: uma aplicação para granitos ornamentais

This dissertation focuses on rock thermal conductivity and its correlations with petrographic, textural, and geochemical aspects, especially in granite rocks. It aims at demonstrating the relations of these variables in an attempt to enlighten the behavior of thermal effect on rocks. Results can be useful for several applications, such as understanding and conferring regional thermal flow results, predicting the behavior of thermal effect on rocks based upon macroscopic evaluation (texture and mineralogy), in the building construction field in order to provide more precise information on data refinement on thermal properties emphasizing a rocky material thermal conductivity, and especially in the dimension stone industry in order to open a discussion on the use of these variables as a new technological parameter directly related to thermal comfort. Thermal conductivity data were obtained by using Anter Corporation s QuicklineTM -30 a thermal property measuring equipment. Measurements were conducted at temperatures ranging between 25 to 38 OC in samples with 2cm in length and an area of at least 6cm of diameter. As to petrography data, results demonstrated good correlations with quartz and mafics. Linear correlation between mineralogy and thermal conductivity revealed a positive relation of a quartz percentage increase in relation to a thermal conductivity increase and its decrease with mafic minerals increase. As to feldspates (K-feldspate and plagioclase) they show dispersion. Quartz relation gets more evident when compared to sample sets with >20% and <20%. Sets with more than 20% quartz (sienogranites, monzogranites, granodiorites, etc.), exhibit to a great extent conductivity values which vary from 2,5 W/mK and the set with less than 20% (sienites, monzonites, gabbros, diorites, etc.) have an average thermal conductivity below 2,5 W/mK. As to textures it has been verified that rocks considered thick/porphyry demonstrated in general better correlations when compared to rocks considered thin/medium. In the case of quartz, thick rocks/porphyry showed greater correlation factors when compared to the thin/medium ones. As to feldspates (K-feldspate and plagioclase) again there was dispersion. As to mafics, both thick/porphyry and thin/medium showed negative correlations with correlation factor smaller than those obtained in relation to the quartz. As to rocks related to the Streckeisen s QAP diagram (1976), they tend to fall from alcali-feldspates granites to tonalites, and from sienites to gabbros, diorites, etc. Thermal conductivity data correlation with geochemistry confirmed to a great extent mineralogy results. It has been seen that correlation is linear if there is any. Such behavior could be seen especially with the SiO2. In this case similar correlation can be observed with the quartz, that is, thermal conductivity increases as SiO2 is incremented. Another aspect observed is that basic to intermediate rocks presented values always below 2,5 W/mK, a similar behavior to that observed in rocks with quartz <20%. Acid rocks presented values above 2,5 W/mK, a similar behavior to that observed in rocks with quartz >20% (granites). For all the other cases, correlation factors are always low and present opposite behavior to Fe2O3, CaO, MgO, and TiO2. As to Al2O3, K2O, and Na2O results are not conclusive and are statistically disperse. Thermal property knowledge especially thermal conductivity and its application in the building construction field appeared to be very satisfactory for it involves both technological and thermal comfort aspects, which favored in all cases fast, cheap, and precise results. The relation between thermal conductivity and linear thermal dilatation have also shown satisfactory results especially when it comes to the quartz role as a common, determining phase between the two variables. Thermal conductivity studies together with rocky material density can function as an additional tool for choosing materials when considering structural calculation aspects and thermal comfort, for in the dimension stone case there is a small density variation in relation to a thermal conductivity considerable variation

Geochemical and radioactivity characterization of rocks from the Rio Preto (Go) Project

The Rio Preto Project, developed by the extinct Brazilian nuclear state company, Nuclebrás, during the late 70s and early 80s, consisted of basic geological mapping and radiometric characterization by aerogeophysical gamma-ray spectrometry, without channel discrimination, of a surface area of 650 km2 located to the west of the Chapada dos Veadeiros National Park on the northeastern of Goiás State, Brazil, including the confluence area of Claro and Preto Rivers. Additionally, the natural radioelements U, Th and 40K were determined by gamma-ray spectrometry in 300 rock samples from cores of the Rio Preto Project area. The tests were conducted at LABIDRO-Isotopes and Hydrochemistry Laboratory of the Departament of Petrology and Metallogeny (DPM) of the Institute of Geosciences and Exact Sciences, UNESP, in Rio Claro, SP, Brazil. This paper reports the results of petrographic characterization and chemical analyses of major oxides (SiO2, TiO2, Al2O3, Fe2O3, MgO, MnO, K2O, Na2O, CaO and P2O5) for all samples used to determine the natural radioelements present in the region. The organic matter content results obtained by colorimetry are also reported for selected cores of different lithotypes in order to investigate the possible relationship between graphite and the radioelements uranium and thorium. Finally, uranium content and 234U/238U activity ratio data for selected samples of schists and gneisses of the Lower Member of the Ticunzal Formation suggest the influence of weathering processes in the area. © 2012 Sociedade Brasileira de Geofísica.

Radioelementos naturais na área do Projeto Rio Preto (GO)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desenvolvimento de cerâmicas de mulita a partir de alumina, ácido silícico e aerosil

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A comparative evaluation of the CF:CS and CRS models in Pb-210 chronological studies applied to hydrographic basins in Brazil

The Constant Flux: Constant Sedimentation (CF:CS) and Constant Rate of Supply (CRS) of unsupported/excess Pb-210 models have been applied to a Pb-210 data set providing of eighteen sediments profiles sampled at four riverine systems occurring in Brazil, South America: Corumbatai River basin (S1=Site 1, Sao Paulo State), Atibaia River basin (S2=Site 2, Sao Paulo State), Ribeirao dos Bagres basin (S3=Site 3, Sao Paulo State) and Amazon River mouth. (S4=Site 4, Amapa State). These sites were chosen for a comparative evaluation of the performance of the CF:CS and CRS models due to their pronounced differences on the geographical location, geological context, soil composition, biodiversity, climate, rainfall, and water flow regime, among other variable aspects. However, all sediments cores exhibited a common denominator consisting on a database built from the use of the same techniques for acquiring the sediments major chemical composition (SiO2, Al2O3, Na2O, K2O, CaO, MgO, Fe2O3, MnO, P2O5, TiO2 and LOI-Loss on Ignition) and unsupported/excess 210Pb activity data. In terms of sedimentation rates, the performance of the CRS model was better than that of the CF:CS model as it yielded values more compatible with those expected from field evidences. Under the chronological point of view, the CRS model always provided ages within the permitted range of the Pb-210-method in the studied sites, whereas the CF:CS model predicted some values above 150 years. The SiO2 content decreased in accordance with the LOI increase in all cores analyzed and such inverse relationship was also tracked in the SiO2-LOI curves of historical trends. The SiO2-LOI concentration fluctuations in sites S1 and S3 also coincided with some Cu and Cr inputs in the drainage systems. (C) 2014 Elsevier Ltd. All rights reserved.

Chemistry of gabbroic rocks of ODP Hole 118-735B

We present results of a microprobe investigation of fresh and least-deformed and metamorphosed gabbroic rocks from Leg 118, Hole 735B, drilled on the east side of the Atlantis II Fracture Zone, Southwest Indian Ridge. This rock collection comprises cumulates ranging from troctolites to olivine-gabbro and olivine-gabbronorite to ilmenite-rich ferrogabbros and ferrogabbronorites. As expected, the mineral chemistry is variable and considerably expands the usual oceanic reference spectrum. Olivine, plagioclase, and clinopyroxene are present in all the studied samples. Orthopyroxene and ilmenite, although not rare, are not ubiquitous. Olivine compositions range from Fo85 to Fo30, while plagioclase compositions vary from An70 to An27. Mg/(Mg + Fe2+) of clinopyroxene (mostly diopside to augite) varies from 0.88 to 0.54. Mg/(Mg + Fe2+) of orthopyroxene varies from 0.84 to 0.50. These minerals are not significantly zoned. All mineralogical data indicate that fractional crystallization is an important factor for the formation of cumulates. However, sharp contacts, interpreted as layering boundaries or intrusion margins, suggest polycyclic fractionation of several magma batches of limited volumes. Calculated compositions of magmas in equilibrium with the most magnesian mineral samples at the bottom of the hole represent fractionated liquids through separation of olivine, plagioclase, and clinopyroxene at moderate to low pressures (less than 9 kb). Crystallization of orthopyroxene and ilmenite occurs in the most differentiated liquids. Mixing of magmas having various compositions before entering the cumulate zone is another mechanism necessary to explain extremely differentiated iron-rich gabbros formed in this slow-spreading ridge environment.

Igneous geochemistry of OP Leg 126 samples

Major element, trace element, and radiogenic isotope compositions of samples collected from Ocean Drilling Program Leg 126 in the Izu-Bonin forearc basin are presented. Lavas from the center of the basin (Site 793) are high-MgO, low-Ti, two-pyroxene basaltic andesites, and represent the products of synrift volcanism in the forearc region. These synrift lavas share many of the geochemical and petrographic characteristics of boninites. In terms of their element abundances, ratios, and isotope systematics they are intermediate between low-Ti arc tholeiites from the active arc and boninites of the outer-arc high. These features suggest a systematic geochemical gradation between volcanics related to trench distance and a variably depleted source. A basement high drilled on the western flank of the basin (Site 792) comprises a series of plagioclase-rich two-pyroxene andesites with calc-alkaline affinities. These lavas are similar to calc-alkaline volcanics from Japan, but have lower contents of Ti, Zr, and low-field-strength elements (LFSE). Lavas from Site 793 show inter-element variations between Zr, Ti, Sr, Ni, and Cr that are consistent with those predicted during crystallization and melting processes. In comparison, concentrations of P, Y, LFSE, and the rare-earth elements (REE) are anomalous. These elements have been redistributed within the lava pile, concentrating particularly in sections of massive and pillowed flows. Relative movement of these two-element groupings can be related to the alteration of interstitial basaltic andesite glass to a clay mineral assemblage by a post-eruptive process. Fluid-rock interaction has produced similar effects in the basement lavas of Site 792. In this sequence, andesites and dacites have undergone a volume change related to silica mobility. As a result of this process, some lithologies have the major element characteristics of basaltic andesite and rhyolite, but can be related to andesitic or dacitic precursors by silica removal or addition.