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  • Artikel  (5)
  • 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics
  • Computational biology and bioinformatics
  • Strong Interactions
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  • 1
    Publikationsdatum: 2019-11-04
    Beschreibung: Thermodynamic modelling of magmatic gases shows that SiF4 may be an important F-bearing species at the high pressures typical of magma reservoirs. Upon decompression during degassing, SiF4 will react with water vapour to form HF and silica. Common magmatic gases of high-T fumaroles seem to contain too little SiF4 to be a significant source of silica, except if extremely large amounts of gas percolate through a small volume of rock, as is the case in lava domes. Only if fluorine contents of the gases exceed 1 mol% detectable amounts of silica may be formed, but such high fluorine contents have not yet been observed in natural gases. Alternatively, silica may be formed by heating of cool SiF4-rich gases circulating in cooling lava bodies. We suggest that these mechanisms may be responsible for the deposition of crystalline silica, most probably cristobalite, observed in vesicles in lavas from Lewotolo volcano (Eastern Sunda Arc, Indonesia). Silica occurs as vapour-crystallised patches in vesicles, and is sometimes associated with F-phlogopite, which further supports F-rich conditions during deposition. Because of the connection between F-rich conditions and high-K volcanism, we propose that late-stage gaseous transport and deposition of silica may be more widespread in K-rich volcanoes than elsewhere, and long-term exposure to ash from eruptions of such volcanoes could therefore carry an increased risk for respiratory diseases. The dependence of SiF4/HF on temperature reported here differs from the current calibration used for temperature measurements of fumarolic gases by remote sensing techniques, and we suggest an updated calibration.
    Beschreibung: Published
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): SiF4 ; vapour crystallisation ; silica ; degassing ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 2
    Publikationsdatum: 2019-11-04
    Beschreibung: Phase equilibrium relationships in igneous systems can be estimated using empirical mathematical models based on multi-component regular solution formulae. Although these provide useable results within the fitted region, they can give very misleading values outside the compositional range of curve fitting. Moreover, they usually give poor estimates of the well-characterized melting relations of simple systems and do not relate to the large body of thermodynamic activity data available in the metallurgical literature, nor to spectroscopic, diffraction or computational models of silicate melt properties. The aim of this paper is to extend previous acid-base models of silicate melts and to use a quasi-chemical model to calculate the activities of quasi-chemical silicate mixing units, or structons, from combinations of the oxo-species used in quasi-chemical and polymer models to calculate oxide activities in metallurgy.
    Beschreibung: Published
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): silicate melt ; acid-base ; oxide melt ; thermodynamic properties ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 3
    Publikationsdatum: 2019-11-04
    Beschreibung: The Thermodynamics of quasi-chemical and polymeric models are briefly reviewed. It is shown that the two classes are mutually consistent, and that opportune conversion of the existing quasi-chemical parameterization of binary interactions in MO-SiO2 joins to polymeric models may be afforded without substantial loss of precision. It is then shown that polymeric models are extremely useful in deciphering the structural and reactive properties of silicate melts and glasses. They not only allow the Lux-Flood character of the dissolved oxides to be established, but also discriminate subordinate strain energy contributions to the Gibbs free energy of mixing from the dominant chemical interaction terms. This discrimination means that important information on the short-, medium- and long-range periodicity of this class of substances can be retrieved from thermodynamic analysis. Lastly, it is suggested that an important step forward in deciphering the complex topology of the inhomogeneity ranges observed at high SiO2 content can be performed by applying SCMF theory and, particularly, Matsen-Schick spectral analysis, hitherto applied only to rubberlike materials.
    Beschreibung: Published
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): silicate melts ; structure ; entropy ; unmixing ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
    Format: 1253221 bytes
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  • 4
    Publikationsdatum: 2019-11-04
    Beschreibung: In order to describe and quantify the reactivity of silicate melts, the ionic notation provided by the Temkin formalism has been historically accepted, giving rise to the study of melt chemical equilibria in terms of completely dissociated ionic species. Indeed, ionic modelling of melts works properly as long as the true extension of the anionic matrix is known. This information may be attained in the framework of the Toop-Samis (1962a,b) model, through a parameterisation of the acid-base properties of the dissolved oxides. Moreover, by combining the polymeric model of Toop and Samis with the «group basicity» concept of Duffy and Ingram (1973, 1974a,b, 1976) the bulk optical basicity (Duffy and Ingram, 1971; Duffy, 1992) of molten silicates and glasses can be split into two distinct contributions, i.e. the basicity of the dissolved basic oxides and the basicity of the polymeric units. Application to practical cases, such as the assessment of the oxidation state of iron, require bridging of the energetic gap between the standard state of completely dissociated component (Temkin standard state) and the standard state of pure melt component at P and T of interest. On this basis it is possible to set up a preliminary model for iron speciation in both anhydrous and hydrous aluminosilicate melts. In the case of hydrous melts, I introduce both acidic and basic dissociation of the water component, requiring the combined occurrence of H+ cations, OH- free anions and, to a very minor extent, of T-OH groups. The amphoteric behaviour of water revealed by this study is therefore in line with the earlier prediction of Fraser (1975).
    Beschreibung: Published
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): polymerisation ; basicity ; oxidationstate ; water speciation ; Temkin model ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 5
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    INGV
    Publikationsdatum: 2019-11-04
    Beschreibung: The strong influence of physical conditions during magma formation on Fe equilibria offers a large variety of possibilities to deduce these conditions from Fe-bearing phases and phase assemblages found in magmatic rocks. Conditions of magma genesis and their evolution are of major interest for the understanding of volcanic eruptions. A brief overview on the most common methods used is given together with potential problems and limitations. Fe equilibria are not only sensitive to changes in intensive parameters (especially T and fO2) and extensive parameters like composition also have major effects, so that direct application of experimentally calibrated equilibria to natural systems is not always possible. Best estimates for pre-eruptive conditions are certainly achieved by studies that relate field observations directly to experimental observations for the composition of interest using as many constraints as possible (phase stability relations, Fe-Ti oxides, Fe partitioning between phases, Fe oxidation state in glass etc.). Local structural environment of Fe in silicate melts is an important parameter that is needed to understand the relationship between melt transport properties and melt structure. Assignment of Fe co-ordination and its relationship to the oxidation state seems not to be straightforward. In addition, there is considerable evidence that the co-ordination of Fe in glass differs from that in the melt, which has to be taken into account when linking melt structure to physical properties of silicate melts at T and P.
    Beschreibung: Published
    Beschreibung: JCR Journal
    Beschreibung: open
    Schlagwort(e): iron ; silicate melt ; redox conditions ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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