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.     

Compression of α-MnS (alabandite) and a new high-pressure phase

The compressibility of -Mns (alabandite) was determined by x-ray analysis using a Mao-Bell type diamond anvil cell. The zero pressure bulk modulus (K₀) is 74±2 GPa with the pressure derivative of the bulk modulus (K_o) fixed at four. Allowing (K_o) to vary yielded a statistically better fit with K₀ = 88±6 GPa and k₀ = 2.2±0.6. Our data combined with the data of McCammon (1991) gave K_o = 73±1 GPa with k_o fixed at four. A fit with k_o allowed to vary yielded k_o = 75±2 GPa and k_o = 3.7±0.4. Alabandite transformed from the B1 structure (NaCl-type) to an unknown high-pressure phase at 26 GPa. The high-pressure phase has lower than hexagonal symmetry and it is stable to at least 46±4 GPa.Also affiliated with the James Franck Institute, University of Chicago     

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.     

Vorratsberechnung von Erdöl- und Erdgas-Lagerstätten

Zusammenfassung Als Grundlage für die Berechnung des Öl- und Gasinhalts werden die geologischen Faktoren (Petrophysik, Porosität, Permeabilität, Haftwasser, Porenverteilung, Nettomächtigkeit, Strukturfläche) sowie die Eigenschaften des Poreninhalts (Phasenbeziehungen) beschrieben. Neben den daraus abzuleitenden statischen Methoden sind aber auch dynamische Methoden des Druck- und Förderverhaltens für die Inhaltsberechnung geeignet (Material-Balance-Prinzip). Die vom Poreninhalt gewinnbaren Öl- und Gasmengen werden mittels dynamischer Verfahren und Modellstudien mittels Computer berechnet. Beispiele an Ölfeldern und Ölfeldbereichen der Bundesrepublik erläutern die Auswirkungen der verschiedenen Lagerstätten-Eigenschaften und deren Energie-Verhalten auf die gewinnbaren Reserven, die bei hochviskosen Ölen bei etwa 15–25%, bei niedrigviskosen Ölen bei etwa 30–75%, bei Erdgasen bei etwa 50–80% Entölungs- bzw. Entgasungsgrad liegen. Von besonderer Bedeutung sind dabei technischer Fortschritt und wirtschaftliche Bedingungen. Am Beispiel der Welt wird gezeigt, daß von den etwa 420 Mrd. t Ölinhalt in allen bekannten Ölfeldern zur Zeit etwa 140 Mrd. t gewinnbar sind, die sich um weitere 110 Mrd. t erhöhen lassen, wenn die wirtschaftlichen Bedingungen in Zukunft den Einsatz neuer technischer Verfahren erlauben.

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The geological factors (petrophysics, porosity, permeability, connate water, pore configuration, net pay, productive area) as well as the properties of the pore filling (phase relations) used for determination of the OIP and the GIP are described. Apart from static methods to be derived from these factors, dynamic methods based on the pressure and production behavior can be used for this purpose (principle of material balance). The oil and gas volumes to be recovered from the pore space are calculated by means of dynamic methods and model studies. Oil fields and oil provinces of the Federal Republic of Germany serve as examples to illustrate the effects of the different reservoir charcteristics and the respective energy behavior on the recoverable reserves. The oil or gas recovery factor is about 15–25% with highly viscous oils, about 25–65% with oils of low viscosity and about 50–80% with natural gases. Technical progress and economic factors are of special importance in this connection. It is shown that in addition to the about 140 billion t of oil presently recoverable from worldwide reserves of all known oil fields of about 420 billion t, recovery of another 140 billion t would be possible in future if new technical methods could be applied under the given economic conditions.

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Résumé Sont décrit comme base du calcul de l'huile et du gaz en place les facteurs géologiques (pétrophysique, porosité, perméabilité, eau interstitielle, répartition des pores, épaisseur nette, surface du gisement) ainsi que les propriétés du contenu des pores (relations de phases). Outre les méthodes statiques en dérivées, se prêtent au calcul du contenu en huile ou en gaz aussi des méthodes dynamiques du comportement de pression/production (balance volumétrique). Les quantités de l'huile ou de gaz récoupérables du contenu des pores sont déterminées par des méthodes dynamiques et par des études modèle à l'aide de computer. Des exemples concernant des champs pétrolifères dans la République Fédérale d'Allemagne expliquent les effets des divers propriétés de gisements et leur comportement énergétique sur les ressources récoupérables dont le facteur de récupération de l'huile/du gaz est d'environ 15 à 25% dans le cas des huiles très visqueuses d'environ 25 à 65% dans le cas des huiles de basse viscosité, et d'environ 50 à 80% dans le cas des gaz naturels. A ce propos, le progrès technologique et les conditions économiques sont d'une importance particulière. L'exemple du monde entier montre que de la quantité de 420 milliards de tonnes de l'huile en place dans tous les champs pétrolifères connus, 140 milliards de tonnes environ sont récupérables à présent. Cette quantité pourrait être augmentée encore par 140 milliards de tonnes si les conditions économiques à l'avenir permettent l'emploi de nouvelles techniques.

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: , , , , .., - , . , , . , , - . , , , ; 15–25%, 25–65 % — 50–80 %, . , 420 , 140 . , 140 .

     

Rigid unit modes in the molecular dynamics simulation of quartz and the incommensurate phase transition

A molecular dynamics simulation of quartz at different temperatures both in the a and in the phase has been conducted. The - phase transition could be observed. A phonon analysis of the -phase confirms and rounds out in a quantitative way the origin of the incommensurate (ic) modulated phase. In particular it traces the optic soft mode at becoming (to a good approximation) a so-called rigid unit mode (RUM) at q0, and elucidates its coupling to the transverse acoustic mode which precipitates the incommensurate transition. This success underpins and illuminates the concept of RUMs and their role in structural phase transitions.     

Field-induced oscillation and rotation of diamagnetic oxide crystals

The harmonic oscillations of large diamagnetic mineral samples induced by a magnetic field is reported, for single crystals of quartz, corundum, and calcite. It was seen for the first time that the period of oscillation, , was proportional to the reciprocal of the magnetic field, H, where the restoring force of the string suspending the crystal became negligible in the high magnetic field. Accordingly, the value of diamagnetic anisotropy, , could be measured from the — H curve with a sensitivity of 5 × 10^–10 emu/cc. The values were 5.50 × 10^–9 emu/cc for quartz, 4.20 × 10^–9 emu/cc for corundum, 9.9 × 10^–8 emu/cc for calcite, and 8.8 × 10^–8 emu/cc for polycrystalline talc piled with the (001) planes aligned parallel. Significant field-induced rotations were observed for the suspended crystals. When the field was applied along the direction of the diamagnetic hard axis of the stationary crystal, the crystal gradually rotated with increasing field, so that the direction of the hard-axis was perpendicular to the applied field. The field-induced energy has a the maximum value when the field is applied along the diamagnetic hard axis. This reorientation of the crystal occurs because the torque due to the field-induced anisotropic energy exceeds that of the restoring force in high magnetic fields.     

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.     

Thermal expansion,heat capacity,and entropy of MgO at mantle pressures

The pressure dependence of the Raman spectrum of forsterite was measured over its entire frequency range to over 200 kbar. The shifts of the Raman modes were used to calculate the pressure dependence of the heat capacity, C _v, and entropy, S, by using statistical thermodynamics of the lattice vibrations. Using the pressure dependence of C _v and other previously measured thermodynamic parameters, the thermal expansion coefficient, , at room temperature was calculated from = K _S (T/P) _S C _V/TVK _T, which yields a constant value of ( ln / ln V)_T= 6.1(5) for forsterite to 10% compression. This value is in agreement with ( ln / ln V)_T for a large variety of materials.At 91 kbar, the compression mechanism of the forsterite lattice abruptly changes causing a strong decrease of the pressure derivative of 6 Raman modes accompanied by large reductions in the intensities of all of the modes. This observation is in agreement with single crystal x-ray diffraction studies to 150 kbar and is interpreted as a second order phase transition.     

Pressure-volume-temperature behavior of γ-Fe2SiO4 (spinel) based on static compression measurements at 400° C

Thirteen energy-dispersive x-ray diffraction spectra for -Fe₂SiO₄ (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K _{P 0}) and its first pressure derivative (K _{P 0}), respectively. When compared to the room-Tdeterminations of K _{P 0} available in the literature, our 400° C K _{P 0} yields -4.1 (±6.2)×10^-2 GPa/degree for the average value of (K/T) _{P 0} over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe₂SiO₄ based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(² T/P ²) _v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P ²) _v <0]. along=" the=">-Fe₂SiO₄ reaction boundary V_Rvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe₂SiO₄ V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V _R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V _R at ambient conditions.     

Electrical conductivity,thermopower and <Superscript>57</Superscript>Fe Mössbauer spectroscopy of aegirine (NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)

DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi₂O₆) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity _DC was determined by extrapolating AC data to zero frequency. In both directions, the log _DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of E_A 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of _DC [001] with _DC(300 K) 2.0 × 10^{–6 –1}cm^–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to _DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () ^s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to _DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe²⁺ Fe³⁺ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. ⁵⁷Fe Mössbauer spectroscopy was applied to detect Fe²⁺ in addition to the dominating concentration of Fe³⁺.     

Dynamics of the α-β phase transitions in quartz and cristobalite as observed by in-situ high temperature 29Si and 17O NMR

Relaxation times (T₁) and lineshapes were examined as a function of temperature through the - transition for ²⁹Si in a single crystal of amethyst, and for ²⁹Si and ¹⁷O in cristobalite powders. For single crystal quartz, the three ²⁹Si peaks observed at room temperature, representing each of the three differently oriented SiO₄ tetrahedra in the unit cell, coalesce with increasing temperature such that at the - transition only one peak is observed. ²⁹Si T₁'s decrease with increasing temperature up to the transition, above which they remain constant. Although these results are not uniquely interpretable, hopping between the Dauphiné twin related configurations, ₁ and ₂, may be the fluctuations responsible for both effects. This exchange becomes observable up to 150° C below the transition, and persists above the transition, resulting in -quartz being a time and space average of ₁ and ₂. ²⁹Si T₁'s for isotopically enriched powdered cristobalite show much the same behavior as observed for quartz. In addition, ¹⁷O T₁'s decrease slowly up to the - transition at which point there is an abrupt 1.5 order of magnitude drop. Fitting of static powder ¹⁷O spectra for cristobalite gives an asymmetry parameter () of 0.125 at room T, which decreases to <0.040 at=" the=" transition=" temperature.=" the=" electric=" field=" gradient=" (efg)=" and=" chemical=" shift=" anisotropy=" (csa),=" however,=" remain=" the=" same,=" suggesting=" that=" the=" decrease=" in="> is caused by a dynamical rotation of the tetrahedra below the transition. Thus, the mechanisms of the - phase transitions in quartz and cristobalite are similar: there appears to be some fluctuation of the tetrahedra between twin-related orientations below the transition temperature, and the -phase is characterized by a dynamical average of the twin domains on a unit cell scale.     

Compositional variations in calciturbidites due to sea-level fluctuations,late Quaternary,Bahamas

Piston cores in Tongue of the Ocean, Bahamas, revealed an alternating sequence of periplatform ooze and bankderived turbidites of the past 5 glacial and interglacial periods. By using the point-count method we have analyzed the composition of the turbidite sediment. Variations in the bank-derived fraction are clearly linked to the glacial-interglacial cycles. Nonskeletal components (pellets; ooids; grapestones) are most abundant in interglacial turbidites, while skeletal components (calcareous algae; peneroplids and reef builders) dominate in glacial turbidites. We attribute this pattern to the exposure and flooding of the surrounding carbonate platforms during Late Quaternary sea-level cycles. Because nonskeletal sediment is produced in the interior of the platforms, its growth and subsequent export to the flanks are at a maximum when the banks are flooded, i.e. during interglacial periods. During glacials, skeletal grains dominate because the banks are exposed and carbonate production is limited to a narrow belt of skeletal sands and fringing reefs. The resulting compositional signal appeared to have a good correlation with aragonite variations in the periplatform ooze between the turbidites. Further, compositional variation parallels the change in turbidite frequency described earlier (»highstand bundling«). Frequency and composition of turbidites are both unaffected by diagenesis and therefore provide an excellent monitor of sealevel fluctuations.

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Zusammenfassung In Kolbenlotkernen aus der Tongue of the Ocean, Bahamas, bestehen die jüngsten fünf Glaziale und Interglaziale aus einer Wechselfolge von Periplattform-Schlamm und Turbiditen mit Flachwasser-Material. Die Zusammensetzung der neritischen Kornfraktion in den Turbiditen wurde durch Punktzählung ermittelt. Sie schwankt deutlich im Verlauf eines glazialen Zyklus. Abiogene Komponenten (Pellets, Ooide, Traubenklumpen) dominieren in den interglazialen Turbiditen, während Biogene (Kalkalgen, peneroplide Foraminiferen und Riffbildner) in glazialen Turbiditen vorherrschen. Wir erklären diese Schwankungen mit dem Auftauchen und Überfluten der Bahama Bänke während der jungquartären Schwankungen des Meeresspiegels. Die abiogenen Komponenten werden auf der Innenseite der Plattformen gebildet. Ihre Produktion und Export zu den Plattformflanken erreichen daher ein Maximum während der interglazialen Hochstände des Meeres. In den Glazialen dominieren biogene Komponenten, weil die Plattformen trocken liegen und die Karbonat-Produktion auf einen schmalen Streifen von Saumriffen und Biogensanden beschränkt ist.Die Zusammensetzung der Turbidite variiert im gleichen Rhythmus wie der Aragonitgehalt der zwischengeschalteten Periplattform-Schlamme. Überdies korreliert die Zusammensetzung gut mit der Häufigkeitsverteilung der Turbidite. Während der Interglaziale sind Turbidite häufiger als während der Glaziale (»Hochstand-Bündel«). Häufigkeitsverteilung und Zusammensetzung der Turbidite zusammen ergeben ein gutes, durch Diagenese nicht verwischbares Abbild der Schwankungen des Meeresspiegels.

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Résumé Dans le »Tongue of the Ocean« (Bahamas), des sondages à piston effectués dans les sédiments des cinq dernières périodes glaciaires et interglaciaires montrent une alternance de turbidites et de boues déposées en périphérie de plate-forme. La composition de la fraction néritique des turbidites, dé terminée par la méthode du compteur de points, montre une relation claire avec les cycles glaciaires. Les composants abiogènes (pellets, ooïdes, grapestones) dominent dans les turbidites interglaciaires, tandis que les composants biogènes (algues calcaires, foraminifères de type pénéroplide et organismes constructeurs) sont prépondérants dans les turbidites glaciaires. Nous attribuons cette répartition aux émersions et submersions successives du banc des Bahamas, consécutives aux variations du niveau de la mer au Quaternaire récent. Comme les composants abiogènes ont été formés sur la partie interne de la plate-forme, leur développement et leur transport vers les flancs étaient maximaux lorsque le banc était submergé, au cours des périodes interglaci aires. Par contre, les composants biogènes dominaient pendant les épisodes glaciaires, où la plate-forme était exondée et où la production de carbonate était restreinte à une zone étroite de récifs frangeants et de sables biogènes. Ces variations dans la composition des turbidites présentent une bonne corrélation avec la teneur en anhydrite des boues de périphérie de plate-forme intercalées entre les turbidites. Il existe également une bonne corrélation avec la fréquence des turbidites, plus élevée pendant les interglaciaires. La fréquence et la composition des turbidites ne sont pas affectées par la diagenèse et constituent donc un excellent témoin des fluctuations du niveau de la mer.

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, «» , , . . . / , , / , , .. , . - . . . , . , . , . , / «Hochstand-Bndel» /. , .

     

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%).     

Die Thule-Landbrücke als Wanderweg und Faunenscheide zwischen Atlantik und Skandik im Tertiär

Zusammenfassung Die Auffassung, daß die nordatlantischen Inseln mögliche Relikte einer känozoischen Landbrücke zwischen Europa und Amerika darstellen, wird heute durchweg abgelehnt. Dennoch lassen sich von paläontologischer und biogeographischer Seite zahlreiche Belege sammeln, die eine solche Brücke bis ins jüngere Känozoikum bezeugen. So sind beispielsweise sowohl die heutigen Landbiota dieser Inseln als auch die litoralen marinen Faunen paläogäisch orientiert.Anhand tertiärer, quartärer und rezenter mariner Molluskenfaunen, vor allem der detaillierten historischen Analyse einzelner Gruppen, wird gezeigt, daß ihre Entwicklungen im Atlantik und Skandik getrennt abliefen und folglich beide Meeresgebiete während der längsten Zeit des Känozoikums voneinander vollkommen isoliert waren. Vor dem Pleistozän bestanden nur mittelbare Verbindungen über kurzzeitig existierende epikontinentale europäische Meeresstraßen zur Tethys. Wahrscheinlich war eine solche auch im Paläozän über Mittelgrönland zur Baffin-Bucht vorhanden.Bestehende Differenzen zwischen europäisch-nordatlantischen und amerikanischen Landbiota lassen sich durch die frühe Existenz eines Davis-Baffin-Golfes erklären. Die Ellesmere-Nordgrönland-Landbrücke wirkte mindestens seit dem Oligozän als Filter. Es lassen sich Wanderbewegungen im Neogen über diese Route nachweisen.Die Trennung in zwei Ozeanteilbecken und die gegenüber dem heutigen Zustand geänderten Meeresströmungen haben weitreichende paläoklimatische Folgen. Im subpolaren Raum sind neogene Vereisungen bzw. Abkühlungen nachweisbar, die sich auf West- und Mitteleuropa kaum auswirken. Über Meeresströmungen im Skandik lassen sich aufgrund von Schwermineral-Assoziationen im isländischen Raum Aussagen machen. Nach Wanderbewegungen von Meeresmollusken ist ein Zerbrechen der nordatlantischen Thule-Brücke seit der Wende Plio-Pleistozän nachweisbar.Diese Brücke entwickelte sich syngenetisch zur Aufweitung des Ozeanbeckens und überspannte seit dem ausgehenden Mesozoikum die auseinanderstrebenden Ufer. Ihr Zerfall erfolgte wahrscheinlich durch das Zusammenwirken von kontinentnahen Absenkungsvorgängen, Aufweitungsprozessen und erosiven Vorgängen.

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The view that the islands of the North Atlantic are the possible relicts of a Caenozoic land bridge connecting Europe and North America is today ordinarily rejected. In spite of this, however, abundant evidence of a palaeontological and biogeographical nature can be assembled to bear witness to the existence of such a bridge into the younger Caenozoic. As an example may be quoted the palaeogaeic land biota and littoral marine faunas of these islands.The study of Tertiary, Quaternary and recent marine molluscan faunas, and above all the detailed historical analyses of single groups, indicates that faunal development in the Atlantic and Norwegian Sea followed separate courses. From this it follows that the two areas were completely isolated during most of the Caenozoic. Before the Pleistocene only indirect and short-lived channels of epicontinental nature linked the North European and Tethyan seas. It seems not unlikely that similar Palaeocene passage stretched across the middle part of Greenland to connect with Baffin Bay.Existing differences between European, North Atlantic and American land biota can be explained on the assumption of the early existence of a Davis Strait/Baffin Bay gulf. The Ellesmere/North Greenland land-bridge operated from at least the Oligocene, as a filter barrier. In the younger Tertiary (Neogene) the existence of a migration route over this link can be detected.The separation into two basins and the consequent differences in the oceanic current regimes then as compared with now have far-reaching palaeoclimatic implications. In the sub-polar areas evidence for the existence of late Tertiary (Neogene) glacial and cool periods can be satisfactorily demonstrated, but virtually no traces of such changes can be detected in Western and Central Europe. Heavy mineral suites from the Icelandic region have provided indications of oceanic circulations. The migrations of oceanic molluscs support the breaching of the North Atlantic Thulean bridge at the Plio-Pleistocene boundary.This Thulean bridge developed syngenetically with the moving apart of the oceanic basins and spanned the separating shores from the close of the Mesozoic onward to its break-up, probably as the result of a combination of factors — offshore sinking, widening of the sea floor and erosive processes.

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Résumé La théorie faisant des îles de l'Atlantique-Nord des restes d'un pont continental cénozoique entre l'Europe et l'Amerique demeure aujourd'hui généralement rejetée. Cependant, on peut quand même assembler de nombreuses preuves paléontologiques et bio-géographiques démontrant l'existence d'un tel pont jusqu'au cénozoique supérieur. Ainsi la vie continentale et la faune du littoral marin de ces îles sont encore aujourd'hui de caractère paléogéeique.On démontre, surtout grâce à l'analyse détaillée des différents groupes que le développement de la faune mollusque marine du tertiaire, du quaternaire et de l'époque actuelle s'est déroulé séparément dans le Scandique et l'Atlantique et que par conséquent ces deux régions maritimes étaient complètement isolées l'une de l'autre pendant la plus grande partie du Cénozoique. En dehors du pléistocène, il n'y avait que des contacts indirects avec l'Atlantique par des routes maritimes Européennes épicontinentales qui étaient ouvertes seulement à court terme et qui allaient vers le Téthys. Pendant le paléocène une telle route maritime allait probablement par le Groenland moyen vers la baie de Baffin. Les différences entre la vie continentale Européenne-Atlantique et la vie continentale américaine s'expliquent par l'existence précoce du golfe de Davis-Baffin. Le pont continental entre la terre d'Ellesmere et le Groenland du nord jouait un rôle de filtre au moins depuis l'oligocène. Malgré celà, il est possible de prouver qu'il y a eu des mouvements de migration sur cette route pendant le néogène.La séparation en deux bassins océaniques et les courants marins différents de ce qu'ils sont actuellement ont des effets paléoclimatiques étendus. Dans la région subpolaire (actuelle) il y a déjà des traces des glaciations néogènes respectivement des refroidissements, qui n'ont guère d'effet sur l'Europe occidentale et l'Europe centrale. On peut expliquer grâce aux associations de minéraux lourds dans la région de l'Islande les courants marins Scandinaves. En observant la migration des mollusques marins, on peut démontrer la rupture du pont de l'Atlantique-Nord depuis la limite pliocène-pleistocène. Le pont de Thule s'est développé parallèlement à l'élargissement du bassin océanique reliant depuis la fin du mésozoique les côtes qui s'étaient éloignées. Sa destruction se déroula relativement vite, elle fut probablement causée par des affaissements à proximité du continent, et par des processus d'élargissement et d'érosion.

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Erweiterte Fassung eines Vortrages auf der 60. Jahrestagung der Geologischen Vereinigung in Kiel am 26. Februar 1970. Diese Zusammenstellung stellt ein wesentliches Teilergebnis eingehender Untersuchungen an holarktischen känozoischen Meeresmollusken dar, die als Habilitationsschrift vorgelegt worden sind. Es muß auf zahlreiche, noch nicht publizierte Details verzichtet werden, die im Rahmen einer weiteren Veröffentlichung in Druck gegeben werden und dort einzusehen sind. Den zahlreichen Freunden und Kollegen im Ausland wie in der Heimat sei aber bereits hier gedankt für jede mir bisher erwiesene Hilfe. Im Rahmen der vorliegenden Arbeit aber bin ich wegen wertvoller Anregungen und Diskussionen besonders den Herren Prof. Dr. M.Schwarzbach, Köln, und Prof. Dr. K.Rothausen, Mainz, verpflichtet. Die notwendigen Reisen konnten mit Hilfe der Deutschen Forschungsgemeinschaft durchgeführt werden.     

Solid solution of rare earth elements in synthetic titanite: a reconnaissance study

Summary Titanite varieties doped with rare earth elements (REE) have been prepared by ceramic synthesis and quenching in air. Their crystal structure was determined by Rietveld analysis of the powder X-ray diffraction patterns. Two different substitution schemes, Ca_1–xNa_x/2Sm_x/2TiSiO₅ and Ca_1–xDy_xTi_1–x SiO₅, are studied at x=0.2. Both synthetic varieties of titanite adopt space group A2/a. This implies that both single-site and complex multivalent substitutional schemes destroy the coherence of the off-centering of octahedral chains in the titanite structure resulting in a P2₁/aA2/a phase transition. Unit cell dimensions obtained for the REE-bearing titanite varieties are as follows: a=7.0541(1)Å; b=8.7247(1)Å; c=6.5664(1)Å; =113.732(1)° for Ca_0.8Na_0.1Sm_0.1TiSiO₅; and a=7.0021(1)Å; b=8.7256(1)Å; c=6.5427(1)Å; =113.294(1)° for . Both REE-doped titanite samples and a control sample of the pure titanite end member have similar unit cell parameters and consist of polyhedra distorted to a similar extent with the exception of more-distorted SiO₄ tetrahedron in CaSiTiO₅. The structural data suggest that the Ca_1–xNa_x/2Sm_x/2TiSiO₅ and Ca_1–xDy_xTi_1–xFe_xSiO₅ solid solutions adopting the titanite structure might extend to x sufficiently greater than 0.2 and involve both heavier and lighter trivalent rare earth elements.Permanent address: Geological Institute KSC RAS, 14 Fersmana St., Apatity, 184200 Russia     

An early Miocene arc-tholeiitic magmatic dike event from the Alboran Sea — Evidence for precollisional subduction and back-arc crustal extension in the westernmost Mediterranean

A discussion is made on the general significance of an Early Miocene (22–23 Ma, K/Ar dating) basaltic dike swarm that outcrops within large areas of the central and western Betic Zone of the Betic Cordilleras (Southern Spain). This dike swarm is thought to represent the remains of one of the earliest magmatic episodes within the the Neogene volcanic province that is associated with the late orogenic evolution of the Alboran region, and undoubtedly offers the best preserved igneous material related to this early stage that is known at present. The dike rocks (hypabyssal equivalents of andesitic basalts and basaltic andésites) have both major and trace-element abundance patterns that are akin to those of arc-tholeiitic suites. The field relationships and areal distribution of the dike swarm suggest, on the other hand, that a major E-W-trending rifting belt could have been developing within the Alboran Block in oligo-miocene times, previous to its collision with adjacent continental borderlands in the Early-Middle Miocene.Because of their magmatic character and wide distribution, it is proposed that these dike rocks may be regarded as an indication of the existence of roughly contemporaneous (Oligo-Miocene) Benioff-Wadati zone activity under the Alboran Area, which also points towards the previous existence of subductable lithosphere in its surroundings. The main dilatational vector during dike emplacement was already normal to the present E-W stretching of the Alboran Basin proper, which also adds to the possibility that the latter had already started to individualize tectonically in Oligo-Miocene times, and that some of its present crustal features, especially a prominent E-W-trending pattern of magnetic anomalies, had been generated in relation with the dike event. Continued postcollisional Middle Miocene to Pliocene calc-alkaline to ultrapotassic volcanism in the same area could hence have resulted from decompression partial melting of an already contaminated, and still thermally anomalous, mantle wedge, connected with the occurrence of traverse strike-slip and extensional deep faulting within a crustal segment that stretches from southeastern Spain to Morocco.

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Zusammenfassung Über die generelle Bedeutung einer Vielzahl von Gängen (22–23 Ma, K/Ar-Datierung) wird diskutiert, die in einem weiten Gebiet der Betischen Zone aufgeschlossen sind. Diese Vielzahl von Gängen repräsentiert wahrscheinlich eine der ersten magmatischen Episoden innerhalb der vulkanischen neogenen Provinz, welche mit der späten tektonischen Entwicklung der Region des Alboranischen Meeres verbunden ist. Diese Gänge bieten in jedem Fall das besterhaltene magmatische Material, verglichen mit denen, die man bis jetzt kennt. Die Gesteine, die diese Gänge bilden (hypoabyssiche Aequivalente andesitischer Basalte und basaltischer Andesite), besitzen ebenso Hauptelemente wie auch Spurenelemente, die den Tholeiit-Serien der Inselbögen ähnlich sind. Ihre Flächenverteilung und Feldbeziehungen geben auch an, daß ein ausgedehnter Gürtel in der Zone von Alboran in oligo-miozänen Zeiten in Entwicklung war, bevor sich der Zusammenstoß des sogenannten Alboranblocks mit der naheliegenden Kontinentalzone im unteren-mittleren Miozän produzierte.Diese Gesteine geben das gleichzeitige Vorhandensein einer Benioff-Wadati-Zone aktiv unter der Region von Alboran an, sowohl auf Grund ihres magmatischen Aussehens wie auch auf Grund ihrer weiten Flächenverteilung, und deshalb zeigen sie auch die vorige Existenz subduktionsfähiger Lithosphäre in ihrer Nähe. Der Hauptdilatationsvektor war schon während der Intrusion der Gänge normal zur jetzigen Elongation des Alboran-Beckens gerichtet, was auch vermuten läßt, daß jenes Becken schon während des Oligozäns oder des unteren Miozäns begonnen hatte, sich tektonisch zu individualisieren. In diesem Fall könnte die durch die Gänge repräsentierte vulkanische Episode einige der Charakteristika der dem Becken unterliegenden Kruste erklären und speziell das Vorhandensein eines wichtigen Netzes von magnetischen Anomalien, das Ost-West verläuft. Die spätere Entwicklung des Vulkanismus in dieser Provinz konnte sich aus der Partialschmelzung einer vorher kontaminierten und sogar thermisch anomalen Zone des Mantels ergeben haben, verbunden mit dem Wirken von Verwerfungen und zerrenden Brüchen in einem lithosphärischen Gürtel, der sich vom Südosten der Iberischen Halbinsel bis Marokko ausbreitet.

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Resumen Se hace una discusión sobre la significación general de un enjambre de diques (22–23 M.a., datación K/Ar) que aflora en una amplia extensión de la Zona Bética (Cordilleras Béticas, España Meridional). Este enjambre de diques représenta probablemente uno de los primeras episodios magmáticos dentro de la provincia volcánica neógena asociada a la evolución orogénica tardia de la región del Mar de Alborán, y ofrece en todo caso el material igneo mejor preservado en relación con este estadio de los conocidos hasta el presente. Las rocas que constituyen los diques (equivalentes hipoabisales de basaltos andesiticos y andesitas basálticas) poseen caracteres geoquímicos tanto de elementos mayores como de trazas que son afines a los de las series toleáticas de arcos insulares. Su distribución areal y relaciones de campo indican, por otra parte, que una banda dilatacional podría haberse estado desarrollando en el área de Alborán en tiempos oligo-miocenos, con anterioridad a la colisión del Bloque de Alborán con las áreas continentales adyacentes en el Mioceno Inferior-Medio.A causa tanto de su afinidad magmática como de su amplia distribución areal, estas rocas vienen a indicar la existencia, contemporánea, de una zona de Benioff-Wadati activa bajo la región de Alborán y, por ende, la presencia previa de litosfera subducible en sus inmediaciones. El principal vector dilatacional durante la intrusión de los diques era ya normal a la actual elongación de la cuenca de Alborán, lo cual también sugiere la posibilidad de que aquella hubiese comenzado a individualizarse tectónicamente durante el Oligoceno ó Mioceno Inferior. En tal caso el episodio volcico representado por los diques podría explicar algunas de las características de la corteza subyacente a esta cuenca, y en especial la existencia de una prominente red de anomalias magnéticas de dirección E-W, paralela a la red de dikes. El desarrollo posterior del volcanismo en esta provincia podria haber resultado de la fusión partial de una zona del manto previamente contaminada, y aún térmicamente anómala, en conexión con la actuación de desgarres y fracturación distensiva en una banda litosférica que se extiende desde el sureste de la peninsula ibérica hasta Marruecos.

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Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

Les degats radiatifs dans le charbon uranifere du schaentzel

Résumé L'étude minéragraphique et autoradiographique du charbon du Schaentzel montre le caractère surimposé de la minéralisation d'uranium, son mode d'introduction et de fixation. On a observé une très faible activité du charbon dépourvu d'inclusions ou de fissures, ainsi qu'une relation entre l'augmentation locale de la réflectivité et la quantité d'uranium.

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Mineragraphic and autoradiographic study of the Schaentzel coal shows the superposed character of the uranium mineralization and its mode of introduction and fixation. One observes a very low activity of coal, devoid of inclusions or fractures, and a relationship between the local increase of reflectivity and quantity of uranium.

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Zusammenfassung Eine erzmikroskopische und Kernemulsionsplatte Untersuchung der Schaentzel Kohle zeigt den sekundären Charakter der Uranvererzung, die Art ihrer Zufuhr und Ablagerung. Es konnte eine sehr schwache Aktivität der Einschluß- bzw. spaltfreien Kohle, sowie eine Beziehung zwischen den örtlichen Ansteigen des Reflexionsvermögen und der Uranmenge beobachtet werden.

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