Über die Geschwindigkeit der Krustenverkürzung in den Zentralalpen

Zusammenfassung Die alpine Krustenverkürzung (300–400 km oder mehr im Profil der Westschweiz, 400–500 km oder mehr im Profil der Ostschweiz) erfolgte in diskreten orogenen Phasen, welche durch Zeiten langsamerer Bewegung oder eigentlicher Remission getrennt waren. Während der wichtigsten Phase, an der Eozän-Oligozän-Wende, betrug die Relativgeschwindigkeit der nördlichen Platte und der südlichen Kleinplatte einige cm/a.

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Crustal shortening in the Central Alps (300–400 km or more in western Switzerland, 400–500 km or more in eastern Switzerland) occurrend in discrete orogenic phases, separated by times of slower movement or of complete stop. During the most important phase, at the turn from the Eocene to the Oligocene, the rate of relative movement of the northern plate and the southern microplate was of the order of several cm/y.

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Résumé Le raccourissement de la croûte dans les Alpes Centrales (300–400 km ou davantage en Suisse occidentale, 400–500 km ou davantage en Suisse orientale) se fit par phases orogéniques défines, séparées par des intervalles à mouvement plus lent ou même à arrêt total. Pendant la phase principale, à la fin de l'Eocène ou au début de l'Oligocène, la vitesse relative de la plaque septentrionale et de la microplaque méridionale était de l'ordre de plusieurs cm/a.

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(300–400 , , 400–500 , ) , , . , - , /.

     

Neuere Untersuchungsmethoden der Geophysik und das Problem der Bewegung der Kontinente

Zusammenfassung Die Arbeit gibt eine Übersicht über den gegenwärtigen Stand der geophysikalischen Vorstellungen zur Kontinentalverschiebung. Die grundlegende paläomagnetische Beweisführung für großräumige Kontinentalbewegungen wird als richtig angesehen, und die Daten, die auf laufende Bewegungen in dieser Größenordnung hinweisen, werden kurz besprochen. Die statische und die dynamische Ausdeutung der Gravitation, des Wärmeflusses und der seismologischen Ergebnisse weisen auf eine Abweichung der Erde von der Idealform und auf die Ungleichförmigkeit innerhalb der Erde hin. Als dynamische Deutung bietet die Konvektionshypothese die beste Erklärung für Kontinentalbewegungen, und es wird versucht, mit dieser Hypothese auch die neuesten ozeanographischen Ergebnisse zu interpretieren. Schließlich seien einige geologische Folgerungen aus der Konvektionshypothese, wie z. B. der Verschiebungsmechanismus, betrachtet. Eine mögliche zyklische Theorie für die ozeanische Kruste sowie die Beziehung zwischen abweichenden paläomagnetischen Ergebnissen und Fragen der Großtektonik in orogenen Gebieten werden diskutiert.

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The present state of geophysical ideas with respect to continental drift is reviewed. The basic palaeomagnetic argument for large scale continental displacement outlined is accepted as valid, and the data available indicating current movements of the same order of magnitude briefly discussed. Two interpretations, static and dynamic, of the gravity, heat flow, and seismic data which indicate the departure of the Earth from a hydrostatic state are described.Adopting the dynamic interpretation, the convection hypothesis offers the best available explanation for continental drift. An attempt is made to show how this can also be used to interpret modern oceanographic results. Finally some of the geological implications of the convection hypothesis as the drift mechanism are considered. Reference is made to a possible cycling of the oceanic crust, and to the possible relation of the anomalous palaeomagnetic results to the questions of megatectonics in orogenic areas.

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Résumé Les idées géophysicales modernes en ce qui concerne les déplacements des continents sont décrites. Acceptant les arguments paléomagnétiques comme base, les indications des mouvements actuels de même ordre de grandeur sont indiquées. Il se trouve deux interprétations importantes, statique et dynamique, des résultats gravimétriques, du flux de chaleur et de la séismologie qui indiquent une déviation de la Terre de la forme hydrostatique.Si l'on accepte l'interprétation dynamique, alors c'est la théorie des courants convectifs dans le manteau qui, jusqu'à présent, peut mieux expliquer les déplacements des continents. Cette étude essaye de montrer l'interprétation à l'aide de cette théorie des données océanographiques récentes. Enfin les implications géologiques de convection comme mécanisme de déplacements sont considérées, telle que l'idée d'un mouvement cyclique de la croûte océanique, et les relations possibles entre les résultats paléomagnétiques anomals et les questions mégatectoniques des zones orogéniques.

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Contribution no. 28 W. R. U. Geology Dept.

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For the German translation of this article my most sincere thanks must be recorded to Dipl. Geol. O.Stehn and K.Krumsieck, Geol. Inst. Bonn, and to the editorial staff of Geol. Rundschau.     

Titania precipitation in sapphire containing iron and titanium

Titania, TiO₂, precipitation in natural blue sapphire (Fe, Ti: -Al₂O₃) has been investigated using high resolution and analytical transmission electron microscopy. The structure and habit of the TiO₂ precipitate depends on both the Ti⁴⁺ concentration and the temperature at which the precipitate formed. Tetragonal TiO₂ (Rutile) grows at 1350° C but at 1150° C an orthorhombic non-equilibrium TiO₂ polymorph precipitates. Both TiO₂ polymorphs nucleate in the (0001)s plane as lens shaped discs twinned along their diameter. The crystallographic alignment of each type of TiO₂ precipitate with respect to the -Al₂O₃ host matrix provides a high degree of structural coherency with minimal lattice mismatch. Electron diffraction analysis established the following precipitate/host orientation relationships: tetragonal TiO₂: {011}r {11 07B;100}r(0001)s and 01 r10 0s twinned along the (011)r planeand orthorhombic TiO₂: {021}{11 0}s, {100}(0001)s and 0 2 10 0s twinned along the (021) plane.     

β(Mg0.9, Fe0.1)2SiO4: Single crystal structure,cation distribution,and properties of coordination polyhedra

The synthesis boundaries of the phase transformation; ++ in (Mg_0.9, Fe_0.1)SiO₄, have been clarified at temperatures to 2000° C and pressures up to 20 GPa in order to synthesize single crystals of high quality. A single crystal of (Mg_0.9, Fe_0.1)₂SiO₄ was grown successfully to a size of 500 m. The crystal structure has been refined from single-crystal X-ray intensities. The ferrous ions prefer M1 and M3 sites to over the larger M2 site. The volume change of all the occupied polyhedra does not contribute to the decrease of total volume in the transformation; rather it tends to increase the bulk volume through the expansion of occupied tetrahedra. The volume reduction in the phase transformations is accounted for by unoccupied polyhedra, with the octahedra contributory 60% and the tetrahedra 40% to the V of the transition. The volume change in the transformation is caused also partly by the volume decrease of MO ₆ (25%), partly the unoccupied tetrahedra (45%) and octahedra (30%).     

Correlation of terrigenous and biogenic sediment fluxes in the North Atlantic Ocean during the past 150 my

The depositional history of the North Atlantic Ocean is described on the basis of about 120 deep-sea drill sites. Sediment fluxes were quantified by calculating accumulation rates (g·cm^–2·my^–1) of terrigenous and calcareous biogenic sediment components. They were plotted versus an absolute time scale, into palinspastic maps and into age versus paleodepth diagrams.Dominantly terrigenous deposits fill the deeper parts of the western and eastern subbasins of the North Atlantic Ocean, because of the depth-dependent dissolution of calcium carbonate. Along the continental margins they are mixed with biogenic calcareous and siliceous components. Temporal maxima in the terrigenous sediment input occurred in the Late Jurassic to Early Cretaceous time interval and from Middle Miocene to Recent times.High carbonate fluxes are also found in the Jurassic and Early Cretaceous and in the Neogene. The accumulation rates remained modest over most of the time in between. High fluxes are mainly restricted to the continental margins and to a minor extent to the Mid-Atlantic Ridge. The distribution patterns of calcareous material in the deepsea indicate large-scale sediment displacements.Input rates of terrigenous and biogenic calcareous materials seem to have varied simultaneously for long time intervals suggesting a causal relationship. They indicate a uniform depositional environment until Early Cretaceous. Then the North Atlantic Ocean differentiated into an eastern and western subbasin with their own depositional environments, which varied according to latitude and paleodepth.

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Zusammenfassung Die Ablagerungsgeschichte des Nordatlantischen Ozeans wurde auf der Grundlage von etwa 120 DSDP-Tiefseebohrungen rekonstruiert. Um den Sedimenteintrag zu quantifizieren, wurden Akkumulationsraten (in g·cm^–2· my^–1) für die terrigenen und biogenen kalkigen Sedimentkomponenten berechnet. Sie wurden gegen eine absolute Zeitskala aufgetragen, in palinspastischen Karten und in Alter/Paläotiefen-Diagrammen dargestellt.Ablagerungen hauptsächlich terrigener Zusammensetzung füllen die tieferen Teile der westlichen und östlichen Teilbecken des Nordatlantiks, da die kalkigen Sedimentkomponenten aufgrund einer CCD oberhalb des Beckenbodens aufgelöst wurden. Entlang der Kontmentalränder sind sie mit biogenen kalkigen und kieseligen Komponenten vermischt. Zeitliche Maxima im Eintrag terrigener Sedimentpartikel treten vom Späten Jura bis zur Frühen Kreide und vom Mittelmiozän bis heute auf.Hohe Karbonatsedimentation fand ebenfalls vom Jura bis zur Frühen Kreide und im Neogen statt. In der dazwischenliegenden Zeit blieben die CaCO₃-Akkumulationsraten im allgemeinen gering. Hohe Akkumulationsraten waren vor allem auf die Kontinentalränder und, in geringerem Maße, auf den Mittelatlantischen Rücken beschränkt. Die Verteilungsmuster von Kalziumkarbonat in der Tiefsee weisen auf großräumige Sedimentumlagerungen hin.Akkumulationsraten terrigenen und biogenen kalkigen Materials scheinen sich über lange Zeiträume hinweg gleichzeitig geändert zu haben und deuten auf eine ursächliche Beziehung zwischen den beiden Komponenten hin. Sie belegen ein gleichförmiges Ablagerungsmilieu bis zur Frühen Kreide. Danach differenzierte sich der Nordatlantik in ein östliches und ein westliches Teilbecken, die je nach geographischer Breite und nach Paläotiefenverhältnissen ihr eigenes Ablagerungsmilieu entwickelten.

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Résumé L'histoire sédimentaire de l'Atlantique Nord a été reconstituée à partir de quelque 120 forages en mer profonde. Afin de quantifier l'apport sédimentaire, le taux d'accumulation (en gr·cm^–2·ma^–1) a été calculé pour les composants terrigénes d'une part et biogéniques calcaires d'autre part. Ces taux ont été reportés en fonction d'une échelle d'âges absolus sur des cartes palynspastiques et dans des diagrammes de paléo-profondeur.Les parties les plus profondes des bassins oriental et occidental de l'Atlantique Nord sont remplies par des dépôts de composition terrigéne dominante, en conséquence de la dissolution des carbonates sous la profondeur de compensation. Le long des marges continentales, les dépôts sont mêlés de composants biogéniques carbonatés et siliceux. Des maxima temporaires dans les apports terrigénes se marquent pendant les intervalles Jurassique supérieur -Crétacé inférieur et Miocène moyen-Récent.Une abondante sédimentation carbonatée s'est produite également du Jurassique au Crétacé inférieur ainsi qu'au Néogéne.Pendant la période intermédiaire, les taux d'accumulation du CaCO₃ sont, en général restés faibles, les valeurs élevées restant localisées principalement sur les marges continentales et, dans une moindre mesure, sur la crête médiatlantique. La distribution du matériau calcaire en mer profonde indique des remaniements à grande échelle des sédiments.Les taux d'accumulation des matérieux terrigénes et biogéniques calcaires semblent présenter des variations simultanées au cours de longues périodes, ce qui suggère une cause commune. Ils indiquent un milieu de dépôt uniforme jusqu'au Crétacé inférieur. Ensuite, l'Atlantique Nord s'est différencié en deux bassins — oriental et occidental — possédant chacun ses propres conditions de milieu, variables en fonction de la latitude et de la paléoprofondeur.

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The elasticity of the upper mantle orthosilicates olivine and garnet to 3 GPa

The elastic moduli of single crystals of pyrope-rich garnet and San Carlos olivine have been measured over a 3 GPa pressure range at room temperature. The combination of improved ultrasonic techniques and this large pressure range provide for more reliable characterization of the pressure dependence of acoustic wave velocities than has previously been possible. First and second pressure derivatives of the velocities have been determined within 1 percent and 10 percent respectively. The Hashin-Shtrikman bounds for the pressure dependences of the bulk and shear moduli of the garnet used in this study are; K = 173.6 GPa, K = 4.93, K = –0.28 GPa^–1, G= 94.9 GPa, G = 1.56, G = –0.08 GPa^–1 and the Hashin-Shtrikman least-upper bounds and greatestlower bounds for the pressure dependences of the bulk and shear moduli of the San Carlos olivine are K=129.8 GPa, K = 4.66, K= –0.15 GPa^–1, G = 77.8 GPa, G = 1.93, G = –0.11 GPa^–1 and K = 129.2 GPa, K = 4.63, K= –0.15 GPa^–1 G = 77.3 GPa, G=1.96, G = –0.11 GPa^–1 respectively. The determination of the room-pressure elastic moduli of this pyrope-almandine garnet removes the previously observed anomaly in the predictions of systematic treatments of variations of the elastic moduli of garnets with composition. The determination of the second pressure derivatives of the moduli of garnet and olivine illustrates the importance of these terms in extrapolations to higher pressures — with K/P for these crystals being reduced by 17 percent and 9 percent respectively over the 3 GPa pressure range.     

Formulation of the thermodynamic functions for mantle minerals: MgO as an example

The formulas for thermodynamic functions for minerals are presented, couched in terms of the important thermodynamic variable K_T= (P/T)_v, where is the volume thermal expansivity and K_T is the isothermal bulk modulus. Presenting the formulas in this way leads to simplification since K_T as a product varies only slightly with volume, and is close to being independent of temperature at high temperature. Using our equations, we present as examples some computed data in the form of graphs on the entropy, internal energy, Helmholtz free energy, and Gibbs free energy in the high temperature regime (up to 2000 K) and for high compression (up to 0.7), for MgO. For entropy, knowledge of the V, T dependence of K_T is sufficient. For enthalpy and internal energy, the equation of state is needed in addition.     

Mössbauer study of a California desert celadonite and its pedogenically-related smectite

Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe³⁺ doublet with isomer shift 0.4 mm s^–1 and quadrupole splitting 0.4 mm s^–1, another Fe³⁺ doublet with 0.4, 1.2 mm/s and two Fe²⁺ doublets with 1.1, 1.7, 2.7 mm s^–1 at 300 K were distinguished. The minor Fe³⁺ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M⁺–M²⁺ array. However, about 10% is M1 trans-OH Fe²⁺. Isomer shift vs. T gives Debye temperatures of 570 K for Fe³⁺ in M2 and 380 K for both Fe²⁺ sites, indicating greater vibrational freedom for Fe²⁺. Quadrupole splitting vs. T for Fe²⁺ gives a valence electronic energy splitting of 760 cm^–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe²⁺ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.     

The α-β phase transition in cristobalite,SiO2

Cristobalite, a high temperature phase of silica, SiO₂, undergoes a (metastable) first-order phase transition from a cubic, , to a tetragonal, P4₃2₁2 (or P4₁2₁2), structure at around 220° C. The cubic C9-type structure for -cristobalite (Wyckoff 1925) is improbable because of two stereochemically unfavorable features: a 180° Si-O-Si angle and an Si-O bond length of 1.54 Å, whereas the corresponding values in tetragonal -cristobalite are 146° and 1.609 Å respectively. The structure of the -phase is still controversial. To resolve this problem, a symmetry analysis of the (or P4₁2₁2) transition in cristobalite has been carried out based on the Landau formalism and projection operator methods. The starting point is the ideal cubic ( ) C9-type structure with the unit cell dimension a (7.432 Å) slightly larger than the known a dimension (7.195 Å at 205° C) of -cristobalite, such that the Si-O-Si angle is still 180°, but the Si-O bond length is 1.609 Å. The six-component order parameter driving the phase transition transforms according to the X₄ representation. The transition mechanism essentially involves a simultaneous translation and rotation of the silicate tetrahedra coupled along 110. A Landau free-energy expression is given as well as a listing of the three types of domains expected in -cristobalite from the transition. These domains are: (i) transformation twins from a loss of 3-fold axes, (ii) enantiomorphous twins from a loss of the inversion center, and (iii) antiphase domains from a loss of translation vectors 1/2 110 (FP). These domains are macroscopic and static in -cristobalite, and microscopic and dynamic in -cristobalite. The order parameter , couples with the strain components as ², which initiates the structural fluctuations, thereby causing the domain configurations to dynamically interchange in the -phase. Hence, the - cristobalite transition is a fluctuation-induced first-order transition and the -phase is a dynamic average of -type domains.     

Die Möglichkeit der Entstehung ultrabasischer Magmen bei Gegenwart geringer Alkalimengen

Zusammenfassung Mischungen von Forsterit und Enstatit werden bei Zugabe von wenigen Prozent K₂O in Anwesenheit eines Wasserüberschusses unter Drucken von 1 bis 5 Kilobar bereits bei sehr niedrigen Temperaturen (etwa 550–700° C) teilweise aufgeschmolzen. Da auch in den Gesteinen des Erdmantels die Gegenwart von Alkalien und Wasser zu erwarten ist, können diese Komponenten zur Bildung von Ultrabasit-Schmelzbreien im Oberen Erdmantel führen, welche in höhere Stockwerke, d. h. in die Erdkruste, intrudieren können. Die Anwesenheit von Alkalien in Ultrabasitschmelzen vor und während deren Platznahme kann sich durch Alkalimetasomatosen im Nebengestein äußern, da die Alkalien bei noch niedrigeren Temperaturen vorwiegend in eine leichtflüchtige Gasphase eingehen, welche die Intrusion verläßt.

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Mixtures of forsterite and enstatite show partial melting in the pressure range 1–5 kb at very low temperatures (approximately 550–700° C), if small amounts of K₂O are added in the presence of excess H₂O. Since alkalies and water are also expected to be minor constituents of the material forming the earth's mantle, they may cause, in this region, the formation of ultrabasic crystal mushes that may intrude into higher levels, i. e. the earth's crust. The presence of alkalies in ultrabasic melts before or during their emplacement may result in alkali metasomatism of the adjoining country rocks, because most of these alkalies are being incorporated at still lower temperatures in a gas phase leaving the intrusion.

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Résumé On a trouvé qu'en présence de K₂O et d'un excès d'eau des mélanges de forsterite et d'enstatite peuvent être fondues en partie à des températures très basses (550–700° C), sous une pression d'un à 5 kilobars. La présence des alkalis et de l'eau dans l'enveloppe pierreuse externe est probable. Conséquemment on pourrait supposer la formation de magmas d'ultrabasite par ces components dans l'enveloppe pierreuse externe. Ces magmas pourraient pénétrer dans des étages élevés. La présence des alkalis dans les magmas d'ultrabasite, avant et aussi bien au cours de la formation de ces dernières, pourrait se manifester par des métasomatoses d'alkali dans la roche encaissante, puisque à des températures encore plus basses les alkalis sont présents en phase volatile; cette phase peut quitter l'intrusion.

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Wir danken der Deutschen Forschungsgemeinschaft für die Bereitstellung der Apparaturen zur Durchführung der Experimente.

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Anschrift der Verfasser: Dr. F.Seifert, Prof. W.Schreyer, Institut für Mineralogie der Ruhr-Universität Bochum, Lehrstuhl für Petrologie, z. Z, 23 Kiel. Olshausenstr. 40–60.     

Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

A case of ore deposition associated with paleogeothermal activity: The polymetallic ore veins of Aïn Barbar (NE Constantinois,Algeria)

The Aïn Barbar area was at Langhian times the site of a terrestrleial high energy geothermal field related to acid Langhian magmatic activity. A granite body probably occurs at depth, as evidenced by microgranite and rhyolite dikes. The reservoir is made up of Upper Cretaceous Massylian flyschs, overlain by an impermeable cover of Oligo-Miocene Numidian flysch. Due to erosional unroofing, its thickness, initially on the order of one kilometer, was probably halved towards the termination of activity of the liquid-dominated geothermal field.Geothermal activity, which lasted about 1 Ma, developed in two stages:     

Oxygen isotope geochemistry of pyroclastic clinopyroxene monitors carbonate contributions to Roman-type ultrapotassic magmas

The oxygen isotope geochemistry and chemical composition of clinopyroxene crystals from Alban Hills pyroclastic deposits constrain the petrological evolution of ultrapotassic Roman-type rocks. Volcanic eruptions in the 560–35 ka time interval produced thick pyroclastic deposits bearing clinopyroxene phenocrysts with recurrent chemical characteristics. Clinopyroxenes vary from Si–Mg-rich to Al–Fe-rich with no compositional break, indicating that they were derived from a continuous process of crystal fractionation. Based on the ¹⁸O and trace element data no primitive samples were recovered: monomineralic clinopyroxene cumulates set the oxygen isotope composition of primary magmas in the range of uncontaminated mantle rocks (5.5), but their REE composition resulted from extensive crystal fractionation. Departing from these mantle-like ¹⁸O_Cpx values the effects of crustal contamination of clinopyroxene O-isotope composition were identified and used to monitor chemical variations in the parental magma. ¹⁸O values in Si–Mg-rich clinopyroxene are slightly higher than typical mantle values (5.9–6.2), and the low REE contents are representative of early stages of magmatic differentiation. ¹⁸O values as high as 8.2 are associated with Al–Fe³⁺-rich clinopyroxene showing high REE contents. These ¹⁸O values are characteristic of crystals formed during the late magmatic stages of each main eruptive phase. Geochemical modelling of ¹⁸O values vs. trace element contents indicates that these ultrapotassic magmas were derived from fractional crystallization plus assimilation of limited amounts of carbonate wall rocks starting from a primary melt, and from interaction with CO₂ derived from country rocks during crystal fractionation.     

Stable isotope geochemistry and phase equilibria of coesite-bearing whiteschists,Dora Maira Massif,western Alps

Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The ¹⁸O(smow) values of the quartz (after coesite) (¹⁸O=8.1 to 8.6, n=6), phengite (6.2 to 6.4, n=3), kyanite (6.1, n=2), garnet (5.5 to 5.8, n=9), ellenbergerite (6.3, n=1) and rutile (3.3 to 3.6, n=3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700–750 °C. Minimum pressures are 31–32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc+kyanite=pyrope+coesite+H₂O, the a(H₂O) must be reduced to 0.4–0.75 at 700–750 °C. The reduced a(H₂O) cannot be due to dilution by CO₂, as pyrope is not stable at X(CO₂)>0.02 (T=750 °C; P=30 kb). In the absence of a more exotic fluid diluent (e.g. CH₄ or N₂), a melt phase is required. Granite solidus temperatures are 680 °C/30 kb at a(H₂O)=1.0 and are calculated to be 70°C higher at a(H₂O)=0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H₂O) estimates for the whiteschist are 34±2 kb, 700–750 °C and 0.4–0.75. The oxygen isotope fractionation between quartz (¹⁸O=11.6) and garnet (¹⁸O=8.7) in the surrounding orthognesiss is identical to that in the coesitebearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (D(_SMOW)=-27 to-32), on secondary talc and chlorite rite after pyrope (D=-39 to -44) and on the surrounding biotite (D=-64) and phengite (D=-44) gneiss. All phases appear to be in nearequilibrium. The very high D values for the primary hydrous phases is consistent with an initial oceanicderived/connate fluid source. The fluid source for the retrograde talc+chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar D, but dissimilar ¹⁸O values of the coesite bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.     

Al-O--Al paramagnetic defects in kaolinite

Trapped holes located on Al-O-Al bonds in kaolinite were studied by electron paramagnetic resonance spectroscopy (EPR) at 9.3 and 35 GHz applied to well-crystallized, X-ray irradiated and oriented samples. The Q-band EPR spectrum is characterized by three clearly separated groups of 11 quasi-equidistant superhyperfine lines centered at g_xx=2.040±0.0005, g_yy=2.020±0.0005 and g_zz=2.002±0.001. In each of these groups, the 11 superhyperfine lines exhibit intensities according to the ratios 12345654321. An angular dependence of the Q-band EPR spectrum with respect to the magnetic field is demonstrated by measurements on oriented films of kaolinite. An appropriate numerical treatment of the EPR spectra is described, which allowed extraction of the SuperHyperfine Structures (SHFS). X-and Q-band spectra have also been simulated. It is concluded from these experiments that only one type of center is present. This center, labelled the B-center in the literature, is very probably a hole trapped on oxygen (O^- center) atoms coupled to two octahedral aluminium.     

Mechanisms of the transformations between the α, β and γ polymorphs of Mg2SiO4 at 15 GPa

Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg₂SiO₄ at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg₂GeO₄ and Ni₂SiO₄) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg₂SiO₄ olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.     

The energetics of interaction between oxygen vacancies in sillimanite: A model for the mullite structure

A microscopic model is introduced to discuss the modulated structure of mullite. The oxygen vacancies of this aluminosilicate are known to play a central role. In particular, a single vacancy strongly orders its surrounding Al/Si tetrahedral sites. It is shown in this work that if two oxygen vacancies approach too closely to one another, their Al/Si dressing overlap. This situation results in repulsive interaction. The field of interaction between the vacancies is estimated with the use of an atomistic computer simulation. We use a Bragg-Williams type of theory to dicuss the ordering pattern of the vacancies. Due to frustration between the two dominant repulsive interactions, our model predicts a modulated phase transition in agreement with observation.     

Editorial

Other papers presented at the meeting will be published in 1989 and 1990 in two special issues of Tourism Recreation Research devoted to North American perspectives on international tourism and International tourism in developing countries.     

Nature of the coordination polyhedra around M 2 cations in pigeonite

An understanding of the irregular coordination polyhedra exhibited by the M2 cations in clinopyroxenes is of prime importance in connection with the behaviour of solid solutions and polymorphism in pyroxenes.As shown by unfolding the silica chains in pigeonite, cations with octahedral stereochemistry like Mg⁺⁺and Fe⁺⁺ cause kinking of the silica chains, whereas larger cations like Ca⁺⁺and Na⁺have an opposite namely straightening effect. This is a probable factor causing immiscibility in the Mg⁺⁺-Ca⁺⁺ solid solutions in pyroxenes. In pyroxene structures with kinked silica chains the arrangement of oxygen atoms approaches close packing; consequently different stacking sequences will be energetically possible leading to polymorphism in pyroxenes.When Pauling's electrostatic valence rule is applied to clinopyroxenes, the charge balance will be exceedingly improved if effective coordination number of M2 cation is assigned and if the distortions of M 2 coordination polyhedron is considered.