Lippmann Diagrams: Theory and Application to Carbonate Systems

Since 1980 when F. Lippmann's seminal paper appeared, ourunderstanding of solubility equilibria involving ionic solidsolutions has been advanced by theoretical considerations as wellas careful experimental studies designed to determine excess Gibbsfunctions. A unified theory of solid-solution aqueous-solutionequilibria as well as the thermodynamic background of thephenomenon of ``stoichiometric saturation' are reviewed.It is shown that Lippmann diagrams effectively summarize thethermodynamic basis of solid-solute aqueous-solution equilibria ofsparingly soluble metal carbonate systems. Clearly, the predictivepower of these diagrams may be limited due to kineticrestrictions. Only when dissolution and precipitation areessentially reversible, favourable conditions to synthesizehomogeneous solid phases can be derived from studies of equilibria.     

Multistage Variscan magmatism in the central Tauern Window (Austria) unveiled by U/Pb SHRIMP zircon data

U/Pb SHRIMP ages of nine Variscan leucocratic orthogneisses from the central Tauern Window (Austria) reveal three distinct pulses of magmatism in Early Carboniferous (Visean), Late Carboniferous (Stephanian) and Early Permian, each involving granitoid intrusions and a contemporaneous opening of volcano-sedimentary basins. A similar relationship has been reported for the Carboniferous parts of the basement of the Alps further to the west, e.g. the “External massifs” in Switzerland. After the intrusion of subduction-related, volcanic-arc granitoids (374?±?10?Ma; Zwölferkogel gneiss), collisional intrusive-granitic, anatectic and extrusive-rhyolitic/dacitic rocks were produced over a short interval at ca. 340?Ma (Augengneiss of Felbertauern: 340?±?4?Ma, Hochweißenfeld gneiss: 342?± 5?Ma, Falkenbachlappen gneiss: 343?±?6?Ma). This Early Carboniferous magmatism, which produced relatively small volumes of melt, can be attributed to the amalgamation of the Gondwana-derived “Tauern Window” terrane with Laurussia–Avalonia. Probably due to the oblique nature of the collision, transtensional phenomena (i.e. volcano-sedimentary troughs and high-level intrusives) and transpressional regimes (i.e. regional metamorphism and stacked nappes with anatexis next to thrust planes) evolved contemporaneously. The magmas are mainly of the high-K I-type and may have been generated during a short phase of decompressional melting of lithospheric mantle and lower crustal sources. In the Late Carboniferous, a second pulse of magmatism occurred, producing batholiths of calc-alkaline I-type granitoids (e.g. Venediger tonalite: 296?±?4?Ma) and minor coeval bodies of felsic and intermediate volcanics (Heuschartenkopf gneiss: 299?±?4?Ma, Peitingalm gneiss: 300?±?5?Ma). Prior to this magmatism, several kilometres of upper crust must have been eroded, because volcano-sedimentary sequences hosting the Heu- schartenkopf and Peitingalm gneisses rest unconformably on 340-Ma-old granitoids. The youngest (Permian) period of magma generation contains the intrusion of the S-type Granatspitz Central Gneiss at 271?±?4?Ma and the extrusion of the rhyolitic Schönbachwald gneiss protolith at 279?±?9?Ma. These magmatic rocks may have been associated with local extension along continental wrench zones through the Variscan orogenic crust or with a Permian rifting event. The Permian and the above-mentioned Late Carboniferous volcano-sedimentary sequences were probably deposited in intra-continental graben structures, which survived post-Variscan uplift and Alpine compressional tectonics.     

Zur Geologie der Danakil-Senke

Geological and geophysical investigations in the Northern part of Afar-Region were carried out by a group of scientists in 1967 and 1968. The Afar-structure is framed by the Ethiopian Highland in the West, the Somali Plateau in the South and the Danakil horst in the E. Its northern part is occupied by the NNW trending Danakil Depression (Danakil Graben), a branch of the NW trending Red Sea-Graben. The block mosaic border land in the West as well as the Danakil Alps consist of basement overlain by unfolded Mesozoic strata. Within the Afar Depression the pre-Tertiary formations are covered by limnic-fluviatile — in upper portions marine — sediments, Miocene and Pliocene in age, thickening towards the centre of the Depression. These basin fillings indicate a major phase of rift faulting prior to and during their deposition. Marginal extensions of these “Danakil-Formation” on both flanks of the Depression accompany the structural borders of the Danakil Graben, coinciding with the “outer rift structural margin” (Mohr 1967). Evaporites occupy the deepest part of the structure, “the inner Danakil Graben”, downfaulted or opened by major rift movements during Pliocene. A NW trending fault zone cutting through the flat plain north of Dallol covered by gypsum beds, seems to form the Eastern margin of the inner Danakil Graben. In its southeastern prolongation the fault and fissure system of the Amarti Volcanic Range is situated. Still active rift faulting during Quaternary caused the present topographic form of the region. These movements were followed by a marine ingression. Its sediments (Zariga-Formation, 14 C Modell ages 25 000–34 000 y) ring the depression and pass into gypsum beds towards the centre of the basin. The deepest parts of the Depression are hidden beneath the Afrera-Formation (14 C Modell ages 5800 y) framing the Lake Assale/Bakili and the Lake Afrera (soft limestones, clay and gypsum beds). The rift-forming movements in the northern Afar were accompanied by strong volcanic activity. Besides different igneous rocks intruding the pre-Tertiary and Tertiary strata of the rift margin, extensive basaltic lava flows intercalate and locally underly the Danakil-Formation. Potassium-argon age determinations on these “Afar Basalts” yielded Miocene to Pliocene age. In the southern area of the Danakil Graben the Upper Tertiary sedimentary basin fillings are replaced by “Afar Basalts” (plateau-forming flood basalt) flows. They are succeeded by scoriaceous fissure alkali-olivine-basalts and their differentiated lavas forming huge volcanoes aligned parallel to the rift structures. The Central Volcanic Range (Erta Ale volcanic chain) marking the central part of the Danakil Graben, remains active today. Besides the basaltic activity, numerous huge volcanoes display rhyolitic rocks with strong alkaline affinity.     

A dynamic deterministic model of hydrocarbon generation in the Midgard Field drainage area offshore Mid-Norway

The Midgard Field offshore mid-Norway is a gas-condensate accumulation with a thin oil leg reservoired in Early and Middle Jurassic sandstones. There are two potential source rocks in the area; the Late Jurassic Spekk Formation is a marine shale with type II kerogen and a rich potential for oil, and the Åre Formation of Early Jurassic age which is a thick coal-bearing sequence with type III kerogen and potential mainly for gas. Geochemical analyses indicate that both the condensate and the oil leg are sourced mainly from the coal-bearing Åre Formation. Any contribution from the Spekk Formation appears to be of minor importance. Computer simulation of hydrocarbon generation in the drainage area for the Midgard Field indicates that huge volumes are formed, and confirms that hydrocarbon generation from the Åre Formation is volumetrically far more important than from the Spekk Formation. The simulation results also exclude any contribution to the reservoired gas from the Spekk Formation.

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Zusammenfassung Das Midgard Feld vor der Küste Mittelnorwegens ist eine Gas-Kondensat-Akkumulation mit einem nur geringen Ölanteil innerhalb unter- und mitteljurassischer Sandsteine. In diesem Gebiet gibt es zwei mögliche Muttergesteine: Einmal die oberjurassische Spekk-Formation, bei der es sich um einen marinen Schiefer mit Typ II Kerogen handelt und die ein hohes Ölpotential darstellt. Zum anderen gibt es die unterjurassische Åre-Formation, eine mächtige Kohle-führende Folge mit Typ III Kerogen und ein möglicher Gaslieferant. Geochemische Analysen deuten darauf hin, daß sowohl das Gas-Kondensat als auch das Öl des Midgard Feldes auf diese Kohle-führende Åre-Formation zurückzuführen sind. Jede Zufuhr aus der Spekk-Formation scheint von geringer Bedeutung zu sein. Eine durch Computersimulation rekonstruierte Kohlenwasserstofferzeugung im Einzugsgebiet des Midgard Feldes spricht für eine hohe Bildungsrate und bestätigt die Annahme, daß die Kohlenwasserstoff-produktion der Spekk-Formation gegenüber der Åre-Formation zu vernachlässigen ist. Die Simulation ergab ferner, daß keinerlei Gas von der Spekk-Formation dem Reservoir zugeführt wurde.

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Résumé Le champ off-shore de Midgard (Norvège moyenne) est une accumulation de gaz condensé accompagnée d'un mince corps d'huile, accumulation renfermée dans des grès d'âge jurassique inférieur et moyen. Il existe dans le secteur deux sources possibles: la formation de Spekk (shale marins du Jurassique tardif, à kérogène de type II, possédant un riche potentiel en huile) et la formation d'Åre (série épaisse jurassique inférieure, à couches de charbon, à kérogène de type III et potentiel essentiellement en gaz). Les analyses géochimiques montrent que le gaz condensé et l'huile ont tous deux comme origine la formation charbonneuse de Åre. La formation de Spekk ne semble être intervenue que de manière subordonnée. Une simulation par ordinateur de la genèse de l'hydrocarbure dans l'aire d'alimentation du champ de Midgard fait apparaître que des volumes importants ont été formés et confirme la large prépondérance de la formation de Åre parmi les roches-mères. De plus, cette simulation exclut toute expèce de contribution de la formation de Spekk dans la genèse du gaz.

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Midgard / / . : Spekk — , 2, , Are , 3 . . . , Are. Spekk, , . Midgard , Are . , , Spekk .

     

New Universities and their cities, the case of Vaasa, Finland

University activities began in Finland in 1640 when the University of Turku was founded. Later it was transferred to Helsinki, the new capital of Finland. The turn of the century saw the emergence of new university level institutions in Helsinki and Turku. The explosion of the Finnish university system took place after the Second World War. Now there are 20 university level institutes. Consequently the access to university studies and other services has improved greatly. The university centre of Vaasa belongs to the new wave of universities founded from 1960 on. In the city there are now 4 units, one Finnish speaking, two Swedish speaking and one bilingual. This reflects the language structure of the area. All of the universities have had their individual development features. The Finnish speaking University of Vaasa is the biggest one. The main impact of the Vaasa universities is the participation in the rising of the level of education in Finland and its effect on economy and other development. The research institute of Vaasa University has served the surrounding areas and nation through applied research projects. The continuing education centre has served the areas firms with many kinds of tailored courses for the management. In the humanistics influence has been through specialised language courses and multilingual immersion. A newspaper university is one of the new forms of impact. The city has an Academic axis going through the innermost part of the city. It is divided clearly into two Finnish and one Swedish speaking area.     

Rubidium-Strontium-Altersbestimmungen an Biotit-Muskowit-Granitgneisen (Typus Augen- und Flasergneise) aus dem nördlichen Großvenedigerbereich (Hohe Tauern)

Zusammenfassung An vier Proben aus dem Augen- und Flasergneiskomplex in Großvenedigergebiet (Hohe Tauern) wurden Rb–Sr-Altersbestimmungen durchgeführt. Die Biotit-Alterswerte lagen bei zirka 20 M. J. Sie sind der alpidischen Tauernkristallisation zuzuordnen. Eine Gesamtgesteinsisochrone von drei typischen Augen- und Flasergranitgneisen ergab 246 M. J. und wird als Bildungsalter eines magmatischen Granitkörpers interpretiert. Es muß daher zur Perm-Zeit in den westlichen Hohen Tauern ein ausgedehnter Granitmagmatismus angenommen werden. Auf die Schwierigkeiten, dieses Ereignis in das derzeitige geologische-Entstehungsbild einzuordnen, wurde hingewiesen.

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Rubidium-strontium age determinations on biotite-muscovite-gneisses (Augen-and Flaser-gneisses) from the Northern Grossvenediger region (Tauern, Austrian Alps)

Summary Rb–Sr ages were determined for 4 samples from the Augen- and Flaser-gneiss complex of the Grossvenediger region, Hohe Tauern, Austria. The biotite ages of 20 m. y. may be attributed to the Tauern-crystallization of Alpidic age. A total rock isochrone of 246 m. y. based on 3 typical Augen- and Flaser-granite gneisses is interpreted as the age of a granite body. Thus extensive granite magmatism is assumed to have prevailed in the western part of the Hohe Tauern during the Permian. There are, however, difficulties in correlating this event with the present picture of the geologic evolution in this region.

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Mit 2 Abbildungen     

Complex formation in the ternary system Mg(II)-CO2-H2O

The carbonato and hydrogencarbonato complexes of Mg²⁺ were investigated at 25 and 50° in solutions of the constant ClO₄^? molality (3 M) consisting preponderantly of NaClO₄. The experimental data could be explained assuming the following equilibria: Mg²⁺ + CO_2B + H₂O ag MgHCO⁺₃ + H⁺, $\text{log}{}^1\text{β}{}_1\text{= ?7.64}{}_4\text{± 0.01}{}_7\text{(25°), ?7.46}{}_2\text{± 0.01}{}_1\text{(50°)}$, Mg²⁺ + 2 CO_2g + 2 H₂Oag Mg(HCO₃)⁰₂ ± 2 H⁺, $\text{log}{}^1\text{β}{}_2\text{= ?15.00 ± 0.14 (25°)}$, ?15.37 ± 0.39 (50°), Mg²⁺ + CO_2g + H₂Oag MgCO⁰₃ + 2 H⁺, $\text{log}{}^1\text{k}{}_1\text{= ?15.64 ± 0.06 (25°)}$,?15.23 ± 0.02 (50°), with the assumption γ_MgCO3⁰ = γ_Mg(HCO3)⁰2, ΔG⁰(I = 0) for the reaction MgCO⁰₃ + CO_2g + H₂O = Mg(HCO₃)⁰₂ was estimated to be ?3.9₁ ± 0.8₆ and 0.6 ± 2.4 kJ/mol at 25 and 50°C, respectively. The abundance of carbonate linked Mg(II) species in fresh water systems is discussed.     

Numerical simulation of a stratigraphic model

A multi-lithology diffusive stratigraphic model is considered, which simulates at large scales in space and time the infill of sedimentary basins governed by the interaction between tectonics displacements, eustatic variations, sediment supply, and sediment transport laws. The model accounts for the mass conservation of each sediment lithology resulting in a mixed parabolic, hyperbolic system of partial differential equations (PDEs) for the lithology concentrations and the sediment thickness. It also takes into account a limit on the rock alteration velocity modeled as a unilaterality constraint. To obtain a robust, fast, and accurate simulation, fully and semi-implicit finite volume discre tization schemes are derived for which the existence of stable solutions is proved. Then, the set of nonlinear equations is solved using a Newton algorithm adapted to the unilaterality constraint, and preconditioning strategies are defined for the solution of the linear system at each Newton iteration. They are based on an algebraic approximate decoupling of the sediment thickness and the concentration variables as well as on a proper preconditioning of each variable. These algorithms are studied and compared in terms of robustness, scalability, and efficiency on two real basin test cases.     

Ambient pressure thermal desorption spectroscopy (AP-TDS) of NiO/SiO2 catalysts

The Sabatier reaction is a key process in the “power-to-gas” application which is considered to contribute to future chemical energy storage systems. In this contribution we focus on the catalytic active sites of a NiO catalyst supported on SiO₂ (NiO/SiO₂) which is commonly used in the Sabatier reaction. A novel technique for the characterization of the active sites is presented and discussed using thermal desorption spectroscopy at ambient pressure. This analytical tool is operated under reaction conditions and allows element specific measurements during the catalytic process of CO₂ reforming towards methane. Beside the desorption experiments, XPS and XAS measurements of pristine and catalytically used samples are performed to determine the influence of the Sabatier reaction conditions on the surface structure of the catalyst.