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.     

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.     

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.     

Manganese olivine I: Electrical conductivity

To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn₂SiO₄, electrical conductivity () of single crystals was measured along either the [100] or the [010] direction. The experiments were carried out at temperatures T=850–1200 °C and oxygen fugacities atm under both Mn oxide (MO) buffered and MnSiO₃ (MS) buffered conditions. Under the same thermodynamic conditions, charge transport along [100] is 2.5–3.0 times faster than along [010]. At high oxygen fugacities, the electrical conductivity of samples buffered against MS is 1.6 times larger than that of samples buffered against MO; while at low oxygen fugacities, the electrical conductivity is nearly identical for the two buffer cases. The dependencies of electrical conductivity on oxygen fugacity and temperature are essentially the same for conduction along the [100] and [010] directions, as well as for samples coexisting with a solid-state buffer of either MO or MS. Hence, it is proposed that the same conduction mechanisms operate for samples of either orientation in contact with either solid-state buffer.The electrical conductivity data lie on concave upward curves on a log-log plot of vs , giving rise to two regimes with different oxygen fugacity exponents. In the low- regime , the exponent, m, is 0, the MnSiO₃-activity exponent, q, is 0, and the activation energy, Q, is 45 kJ/mol. In the high regime 10^{ - 7} {\text{atm}}} \right)$$ " align="middle" border="0"> , m=1/6, q=1/4–1/3, and Q=45 and 200 kJ/mol for T<1100 °c=" and=">T>1100 °C, respectively.     

31P solid-state nuclear magnetic resonance spectroscopy of aluminum phosphate minerals

This study examines the links between ³¹P solidstate NMR studies of aluminum phosphate minerals and their crystallographic structures. We found that ³¹P isotropic chemical shift values, _iso, carry little information about mineral structures. There seems to be no relation between the chemical shift anisotropy, =₃₃–₁₁ (₃₃>₂₂> ₁₁), and indicies of phosphate-tetrahedra distortion. ³¹P¹H heteronuclear magnetic dipole interactions, on the other hand, carry important information about hydrous phosphate mineral structures, information that should prove to be quite valuable in studies of phosphate adsorbed on mineral surfaces. This interaction can be measured through a variety of qualitative and quantitative experiments. It appears that spin diffusion is so rapid that subtle differences in hydrogen-bonding environments cannot be resolved.     

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.     

Temperature dependence of the magnetic rotation process of kaolinite microcrystals containing paramagnetic impurity ions dispersed in liquid medium

Temperature dependencies of magnetic rotation were measured in micron-sized silicates dispersed in ethanol for two different samples of kaolinite. Magnetic rotation proceeded by balance between thermal agitation energy and magnetic anisotropy energy. Measurements were performed between 195 and 343 K. The field intensity required to achieve magnetic alignment of microcrystals increases with temperature, because of the temperature dependence of paramagnetic anisotropy, and the temperature dependence of thermal agitation energy. The results indicate that the values of magnetic anisotropy of nonmagnetic materials might partially derive from the paramagnetic moments, which derive from paramagnetic impurity ions. The present experiment provides a technical basis for determining the precise values of diamagnetic anisotropy ()_DIA from minerals which have a concentration of paramagnetic ions and do not form a single crystal large enough to allow bulk measurements. The values of ()_DIA can be obtained by extrapolating the –T relations, which follow the Curie law, to the temperature limits.     

Al-Si ordering in Sr-feldspar SrAl2Si2O8: IR,TEM and single-crystal XRD evidences

Al-Si ordering in Sr-feldspar has been followed by isothermal annealing, starting from a disordered metastable configuration. Ordering could not be followed by changes in the spontaneous strain as cell parameters did not show significant changes with thermal treatment from 0.016 h to 452 h at T=1350° C, while, on the contrary, significant changes in IR spectra are observed. A single crystal obtained from melt (Q _od 0) has been progressively heated up to 678 h at T=1350° C and the relevant structural refinements enabled to monitor changes in degree of Al-Si order up to Q_od = 0.86. In isothermal treatment for Sr-feldspar it is observed a significantly lower Q _od than in anorthite after the same annealing time. TEM observation has shown in Sr-feldspar, also for shortest annealing, b type reflections, while in anorthite, in the same conditions, e type reflections have been observed (Carpenter 1991a). In the first stages of ordering b APDs sized 100 Å (at T=1350° C, 0.33 h) have been observed in Sr-feldspar; APD coarsening occurs with an activation energy of 120±7 kcal mol^-1, not significantly different from anorthite. The ordering process seems to be a slower process in Sr-feldspar than in anorthite, even though data from longer annealing suggest that the Q _od close to the equilibrium is the same in Sr and Ca-feldspar (Q _od = 0.86 at T=1350° C).     

Hydrostatic compression of γ-(Mg0.6, Fe0.4)2SiO4 to 50.0 GPa

The bulk modulus, K ₀, and its pressure derivative K₀, of -(Mg_0.6, Fe_0.4)₂SiO₄ have been accurately determined to 50.0 GPa under hydrostatic conditions at room temperature in a diamond cell using synchrotron radiation. Our results agree with Brillouin and ultrasonic measurements on -Mg₂SiO₄ at low pressure, indicating normal elastic behaviour in the metastable pressure range of this high pressure mineral. Our values of K ₀ and k₀ are 183.0 GPa and 5.4, respectively.     

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%).     

Structural relaxation in silicate melts and non-Newtonian melt rheology in geologic processes

The timescale of structural relaxation in a silicate melt defines the transition from liquid (relaxed) to glassy (unrelaxed) behavior. Structural relaxation in silicate melts can be described by a relaxation time, , consistent with the observation that the timescales of both volume and shear relaxation are of the same order of magnitude. The onset of significantly unrelaxed behavior occurs 2 log₁₀ units of time above . In the case of shear relaxation, the relaxation time can be quantified using the Maxwell relationship for a viscoelastic material; _S = _S/G (where _S is the shear relaxation time, G is the shear modulus at infinite frequency and _S is the zero frequency shear viscosity). The value of G known for SiO₂ and several other silicate glasses. The shear modulus, G , and the bulk modulus, K , are similar in magnitude for every glass, with both moduli being relatively insensitive to changes in temperature and composition. In contrast, the shear viscosity of silicate melts ranges over at least ten orders of magnitude, with composition at fixed temperature, and with temperature at fixed composition. Therefore, relative to _S, G may be considered a constant (independent of composition and temperature) and the value of _S, the relaxation time, may be estimated directly for the large number of silicate melts for which the shear viscosity is known.For silicate melts, the relaxation times calculated from the Maxwell relationship agree well with available data for the onset of the frequency-dependence (dispersion) of acoustic velocities, the onset of non-Newtonian viscosities, the scan-rate dependence of the calorimetric glass transition, with the timescale of an oxygen diffusive jump and with the Si-O bond exchange frequency obtained from ²⁹Si NMR studies.     

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.     

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 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.     

The precambrian evolution of South America

Zusammenfassung Mit Hilfe von ca. 1500 radiometrischen Zeitmessungen wird eine Synthese der prÄkambrischen Entwicklung Südamerikas aufgestellt. In Abb. 1 wird versucht, die Lage der spÄtprÄkambrischen orogenen Gürtel sowie ihre Plattformen darzustellen.Der grö\te alte Kern des Kontinents umfa\t den Guyana-Schild, das Basement des Amazonas-Sedimentbeckens und den Guaporé-Kraton im Süden, einen Raum von ungefÄhr 4,5 Mio. qkm. Die meisten Gesteine wurden von dem transamazonischen orogenen Zyklus erfa\t, dessen radiometrisches Alter etwa 2000 M. J. betrÄgt. Der etwa gleichaltrige SÃo-Francisco-Kraton in Ostbrasilien umfa\t ungefÄhr 1 Mio. qkm. Kleinere Kerne, die ebenfalls die Ereignisse des transamazonischen Zyklus' widerspiegeln, wurden nahe der Atlantikküste, östlich der Mündung des Amazonasflusses (SÃo-Luis-Kraton-Gebiet) und in der Umgebung des La-Plata-Flusses (Rio de la Plata-Kraton-Gebiet) gefunden.Die Kratone sind getrennt durch metamorphe Gürtel, die zum brasilianischen orogenen Zyklus spÄtprÄkambrischen Alters gehören. Der Caririan-Gürtel und die Sergipe-Geosynklinale liegen in der Nordostecke von Brasilien, und der Ribeira-Gürtel erstreckt sich entlang der Atlantikküste im Süden. Zwei symmetrische geosynklinale Einheiten wurden im zentralen Teil des Kontinents erkannt: der Brasilia- und der Paraguay-Araguaia-Gürtel.In den brasilianischen orogenen Gürteln treten an vielen Stellen transamazonische oder sogar Ältere Serien auf, Anzeichen für aufgearbeitetes altes Basement. Dies scheint zu zeigen, da\ die Sialkruste des südamerikanischen Kontinents vor 2000 M. J. schon eine rÄumliche Ausdehnung von mehr als 10 Mio. qkm hatte.

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A general synthesis of the precambrian evolution of South America has been made with the aid of about 1500 radiometric age determinations. In Fig. 1, the position of the late precambrian orogenic belts, as well as their platforms, is tentatively outlined.The largest ancient core of the continent includes the Guyana Shield, the basement of the Amazon sedimentary basin, and the Guaporé craton, to the south, covering an area of about 4.5 million square kilometers. Most of the rocks were affected by the Trans-Amazonian orogenic cycle, whose radiometric ages are close to 2000 m. y. The SÃo Francisco craton of similar age outcrops over an area of about one million square kilometers, in eastern Brazil. Smaller ancient nucleii, also reflecting the events of the Tranz-Amazonian cycle, were found near the Atlantic coast, east of the mouth of the Amazon river (SÃo Luis cratonic area), and surrounding the La Plata river (Rio de la Plata cratonic area).The old cratonic areas are separated from each other by metamorphic belts which belong to the Brazilian orogenic cycle of late precambrian age. The Caririan belt, and the Sergipe geosyncline, occur at the northeastern corner of Brazil, and the Ribeira belt along the Atlantic coast, to the south. Two symmetrical geosynclinal units were recognized in the central part of the continent: the Brasilia and the Paraguay-Araguaia belts.Within the areas of the Brazilian orogenic belts, in many places Trans-Amazonian or even older ages occur, indicating remobilized ancient basement. This seems to demonstrate that the sialic crust of the South American continent, 2000 m. y. ago, already exhibited an areal extent of more than 10 million square kilometers.

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Résumé Une synthèse générale de l'évolution précambrienne de l'Amérique du Sud a été faite à l'aide de 1500 déterminations d'âge radiométrique. La fig. 1 présente un essai sur la répartition des zones orogéniques du Précambrien supérieur et de leurs platesformes.Le noyau ancien du continent, qui est le plus vaste, comprend le bouclier de la Guyane, le socle du bassin sédimentaire de l'Amazone et le Craton de Guaporé, au Sud, couvrant une aire d'environ 4,5 millions de Km². La plupart des roches ont été affectées par le cycle orogénique Trans-Amazonien dont l'âge radiométrique est d'environ 2000 millions. Le craton de SÃo Francisco d'âge semblable, affleure sur une étendue d'environ 1 million de Km², dans l'Est du Brésil. Des noyaux anciens plus petits, affectés également par le cycle Trans-Amazonien, ont été trouvés près de la cÔte Atlantique, à l'Est de l'embouchure de l'Amazone (région cratonique de SÃo Luis), et aux environs du fleuve la Plata (région cratonique du Rio de la Plata).Les régions cratoniques anciennes sont séparées les unes des autres par des zones métamorphiques appartenant au cycle orogénique brésilien, d'âge Précambrien supérieur. La zone caririenne et le géosynclinal de Sergipe affleurent dans l'extrémité NE du Brésil, et la zone de Ribeira, le long de la cÔte Atlantique au S. Deux unités géosynclinales symétriques ont été reconnues dans la partie centrale du continent: les zones de Brasilia et de Paraguay-Araguaia.Dans les régions occupées par les ceintures orogéniques Brésiliennes, il existe en beaucoup d'endroits des roches d'âge Trans-Amazonien et mÊme plus ancien, indices d'un socle ancien remobilisé. Ceci semble démontrer que la croûte sialique du continent Sud Américain montrait déjà, il y a environ 2000 millions d'années, une étendue de plus de 10 millions de Km².

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1500 . . 1 , , . , Guaporé , . . 4,5 . , 2000 . Sao Francisco 1 . . , , , ( Sao Luis) la Plata ( (Rio de la Plata). , . Caririan Sergipe , Paraiba . : Brasilia Paraguay-Araguaia. , . , , , - , 10 . 2000 .

     

The Triassic of the southern margin of the Tethys in the Levant and its correlation across the Jordan Rift Valley

The Triassic of the Levantine region consists of four sedimentary cycles: I. Scythian — Lower Anisian; II. Early Upper Anisian; III. Late Upper Anisian — Carnian; IV. Late Carnian — Norian.Regional biofacial affinities point to the existance of a western Tethyan Werfen facies (cycle I), a sephardic biofacies (cycles II and III) and a rather alpinotype platform facies (cycle IV). A correlation across the Jordan Rift Valley is suggested, primarily based on bio- and lithostratigraphic evidence of the Permo-Triassic rocks. The stratigraphic implications of this correlation support the existance of a left lateral strike slip along the Jordan Rift Valley.

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Zusammenfassung Die Trias im Levant ist in vier Sedimentationszyklen gegliedert: I. Skythian — Unteres Anisian; II. Oberes Anisian; III. Oberes Anisian — Karnian; IV. Oberes Karman — Norian.Die regionalen Faziesbeziehungen deuten auf das Vorhandensein einer Westtethyalen Werfener Fazies (Zyklus I), einer West- und Südtethyalen Sephardischen Fazies (Zyklen II und III) und einer eher alpinotypischen Plattformfazies (Zyklus IV).Eine Korrelation der permisehen und untertriadischen Gesteine auf beiden Seiten des Jordantales wird vorgeschlagen. Die stratigraphischen Folgerungen dieser Korrelation unterstützen die Existenz einer linken Transversalverschiebung entlang des Jordantal Rifts.

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Résumé Le Trias du Levant comprend quatre cycles sédimentaires: I. Scythien-Anisien inférieur; II. Anisien supérieur; III. Anisien supérieur — Carnien; IV. Carnien supérieur — Norien.La succession des biofaciès débute par le faciès Werfénien, qui englobait pratiquement la Téthys occidentale éotriasique toute entière (cycle I). Dans le courant du Mésotrias, le faciès Sépharade s'étend aux marges méridionales et occidentales de la Téthys (cycles II et III), tandis qu'un faciès de plateforme d'affinité plutôt alpine représente le Trias terminal (cycle IV).Une corrélation des séries Permo-Eotriasiques du Néguev et de Transjordanie est proposée. Les implications stratigraphiques de cette corrélation appuient l'existence d'un coulissage sénestre tout au long du Rift de la vallée du Jourdain.

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4 : 1. — ; 2. ; 3. — ; 4. — . — 1, — 2 3 — 4. - , .

     

Die wachsende Bedeutung der Ingenieurgeologie im Zeitalter der Umweltzerstörung

Zusammenfassung Die Entwicklung der Technik führt zu immer größeren Bauprojekten im Bereich des Talsperrenbaus, Verkehrswegebaus, Untertagebaus, Bergbaus und Grundbaus. Diese großen Bauprojekte stellen in vielfacher Hinsicht eine erhebliche Belastung der Natur sowie eine Beeinträchtigung ihres Gleichgewichts dar und rufen teilweise unvorhergesehene Wechselwirkungen von Bauwerk und Baugrund hervor. Die technische Entwicklung überrollte die Natur so stürmisch, daß ihre ökologischen Folgen weder von den Wissenschaftlern noch von den Praktikern erkannt und bedacht wurden. Die Aufgaben, die sich in diesem Rahmen dem Ingenieurgeologen stellen, bestehen nicht nur in der möglichst genauen Erfassung der geologischen Parameter zur Gewährleistung der Sicherheit des Bauwerks, wirtschaftlich vertretbarer Baukosten unter optimaler Berücksichtigung geologischer Gegebenheiten, sondern sie haben auch die Vorhersage der Wechselwirkungen von Bauwerk und Baugrund sowie von Störungen des oft erstaunlich labilen Gleichgewichts von Geo-, Bio- und Atmosphäre einzubeziehen. Dabei spielen oft rezente geologische Vorgänge eine bisher in der Ingenieurgeologie viel zu wenig gewürdigte Rolle. Die Notwendigkeit, die Ingenieurgeologie schon bei der allerersten Planung, beim Entwurf und der Bauwerksüberwachung mitbestimmen zu lassen, wird an einzelnen Projekten erläutert.

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Summary Technical development leads to dams, roads, tunnels, mines and foundations of always larger dimensions. Various aspects of these projects represent a serious encumbrance of nature and an impairment of her equilibrium and can cause unforeseen interactions between structure and the earth. Development has taken place so quickly, that the ecological consequences have not been recognised or considered in many cases — neither by the scientists nor by the practitioners. The tasks, confronting the engineering geologists in this regard, consist not only in an exact investigation of the geological parameters to guarantee the safety of the construction project and to achieve project costs by taking into consideration the geological conditions, but must encompass the recognition of the interactions of construction and the earth as well as the disturbance of the often astonishingly fragile equilibrium of the geo-, bio- and atmosphere. Specifically recent geological processes are often not accounted for, despite their possibly disadvantageous effects. The necessity, that the engineering geologist contributes in all project stages from the first planning, to the design upto the surveillance of the construction, is stressed by giving examples.

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Résumé Le développement technique a conduit à des projets de construction toujour plus grands dans le domain des barrages, des routes, des tunnels, des mines et des fondations. Ces grands projets représentent sous beaucoup d'aspects une immense contreinte pour l'environnement naturel, un préjudice pour son équilibre et conduisent parfois à une interaction imprévue entre la construction et le sol. Le développement fut si rapide que les conséquences écologiques ne furent pas reconnues et prises en compte, ni par la science ni par la pratique. Les taches, qui se présentent au géologue ingénieur sur le terrain, comprennent non seulement l'investigation exacte des paramètres géologiques dans le but d'assurer la securité de la construction pour des frais raisonnables tout en prenant en compte d'une façon optimale les conditions géologiques, mais aussi la prévision de ces interactions entre l'ouvrage et le sol, ainsi que les perturbations de l'équilibre de l'environnement géologique, biologique et atmosphérique, équilibre qui est souvent éxtrêmement fragile.Les phénomènes géologiques récents ne sont que très peu considérés dans ces études. La necessité de la participation du géologue ingénieur dès le début des études pendant la conception et la surveillance de l'ouvrage est illustrée à l'aide de projets particuliers.

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Comparative organic petrology of interlayered sandstones,siltstones, mudstones and coals in the Upper Carboniferous Ruhr basin,Northwest Germany,and their thermal history and methane generation

In the coal-mining Ruhr-area, Upper Carboniferous rocks (ca. 4000 m) consist of interlayered sandstones, siltstones, mudstones and coals. They were deposited in a tropical, paralic environment where alternating fluvial sedimentation, occasional marine ingressions, and swamp growth resulted in an irregular cyclic succession. The total sedimentary package contains on an average 6 Vol.-% of organic matter. About 70 Vol.-% of the organic matter occurs in coal seams, the rest as dispersed organic matter in clastic rocks. The organic matter is autochthonous in the coals and allochthonous in associated sandstones and siltstones. It consists of about 70% vitrinite, 20% inertinite, and 10% liptinite. The overall maceral group composition is the same for coals and dispersed organic matter. This surprising similarity is caused by a nearly exclusive input of land-plant derived organic matter to swamps and fluvial systems and a similar degree of preservation. Highest average liptinite contents (% of total macerals) were found in unrooted mudstones, highest average inertinite contents in coarse-grained siltstones and highest average vitrinite percentages in sandstones.Maturities of the sediments studied are well within the hydrocarbon generation window, e. g. vitrinite reflectivities range from 0.6% to 1.6%. Reflectivities measured on dispersed particles in clastic rocks are similar to those measured in coal seams. Calculations of the amount of methane generated indicate that coal seams contributed more to the total hydrocarbon generation than dispersed organic matter.

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Zusammenfassung Das Oberkarbon des Ruhrgebietes besteht aus ca. 4000 Metern wechsellagernder Sandsteine, Siltsteine und Kohleflöze. Der Ablagerungsraum der Sedimente war eine Region mit tropischem Klima, genauer ein paralisches Environment mit unregelmäßig alternierenden Folgen von fluviatilen Sedimenten, marinen Transgressionen und verbreiteten Sumpfablagerungen. Der Anteil organischer Substanzen an der gesamten Sedimentmenge beträgt durchschnittlich 6%. 70% dieser organischen Masse ist in Kohleflözen angereichert, der Rest liegt verteilt in den klastischen Gesteinen vor. Die Herkunft der organischen Substanz in den Kohleflözen ist autochthon, die in den benachbarten Sand- und Siltsteinen allochton. Die Zusammensetzung des organischen Materials ist 70% Vitrinit, 20% Inertinit und 10% Liptinit. Die allgemeine Zusammensetzung nach Mazeral-Gruppen ist für die Kohleflöze und das verteilte Material in den Nachbargesteinen identisch. Diese Ähnlichkeit beruht auf der gemeinsamen Herkunft der organischen Substanz in Sümpfen und Flußsystemen, die fast ausschließlich von Landpflanzen bestimmt wird, und einer sich entsprechenden Konservierung.Der Reifegrad der analysierten Sedimente liegt innerhalb des Kohlenwasserstoff-Bildungsbereiches (die Vitrinit-Reflexionen reichen von 0,6–1,6%). Dabei entsprechen die in den klastischen Gesteinen beobachteten Reflexionswerte weitgehend denen der Kohleflöze. Anhand der Menge des erzeugten Methans läßt sich erkennen, daß der Anteil der Kohleflöze an der Kohlenwasserstoff-Produktion höher ist als der Anteil, den disperse organische Substanzen der Klastika beisteuern.

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Résumé Dans la région minière de la Ruhr, le Carbonifère supérieur constitue une succession, épaisse de 4.000 m environ, de grès, de siltites et de charbon. Leur dépôt, dans un milieu paralique tropical, a été marqué par des alternances de sédimentation fluiviale, de transgressions marines occasionnelles, et d'épisodes marécageux; il en résulte une disposition cyclique irrégulière. La série sédimentaire contient dans l'ensemble 6% de matière organique en moyenne. Environ 70% de cette matière organique se trouve dans les couches de charbon où elle est autochtone; le reste est allochtone et dispersé dans les grès et siltites. La matière organique se répartit approximativement en 70% de vitrinite, 20% d'inertinite et 10% de liptinite. La composition moyenne du groupe «macéral» est la même pour les charbons et la matière organique dispersée. Cette identité surprenante est l'expression d'une alimentation provenant exclusivement de plantes terrestres et d'un même degré de conservation.La maturité des sédiments étudiés se situe à l'intérieur du domaine de genèse des hydrocarbures: le pouvoir réflecteur de la vitrinite s'échelonne entre 0,6% et 1,6%. Les gradients du pouvoir réflecteur observés dans les roches détritiques et dans les couches de charbon sont analogues. Le calcul de la quantité de méthane engendré indique que la contribution des couches de charbon à la production totale d'hydrocarbure est supérieur à celle de la matière organique dispersée.

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SiO2-Diagenese in Tiefseesedimenten

Zusammenfassung Im SiO₂-Kreislauf des Weltozeans ist Kieselsäure biogener Herkunft (Skelettopal) der wichtigste SiO₂-Lieferant, während vulkanogene und andere Quellen zurücktreten. Die Erhaltung von biogenem Opal und seine spätere Umbildung in authigenen Opal-CT und Klinoptilolith wird durch hohe Kieselplankton-Produktivität und Sedimentationsraten (z. B. in Auftriebsgebieten) begünstigt. Vulkanglas wird langsamer gelöst und führt zur Ausfällung von authigenem Smektit und Phillipsit, aber nicht zur Hornsteinbildung.Im allgemeinen verläuft die SiO₂-Diagense als ein diskontinuierlicher zeit-, teufen-, temperatur- und faziesabhängiger Reifungsprozeß von instabilem biogenem Opal (Opal-A) über metastabilen Opal-CT (fehlgeordneter Tief-Cristobalit/Tridymit) zu stabilem Quarz. Opal-CT ist also immer die erste (10–65 Ma nach der Ablagerung gefällte) SiO₂-Phase, aus der dann erst später (50–140 Ma nach Ablagerung der ursprünglichen Kieselsedimente) echte Quarzhornsteine entstehen. Unabhängig davon wird akzessorischer Quarz schon frühdiagenetisch in Porzellaniten ausgefällt, wo er Hohlräume füllt oder den Calcit von Fossilien verdrängt.Während die Opal-AOpal-CT-Umwandlung meist über einen Lösungsschritt geht, können Kieselskelette auchin-situ in Opal-CT umgewandelt werden. Das Opal-CT-Gitter erfährt einen teufen- und temperaturabhängige, röntgenographisch nachweisbare strukturelle Reifung. Diese führt später zur Opal-CTQuarz-Umwandlung, die möglicherweise ohne generelle Lösung und Wiederausfällung abläuft.Obwohl Alter/Versenkungstiefen-Diagramme ein weit überlappendes Vorkommen von Opal-A, Opal-CT und Quarz zeigen, läßt sich im allgemeinen eine positive Korrelation der Reife der SiO₂-Phasen mit diesen Parametern feststellen. Die Umwandlung von biogenem Opal in authigenen Opal-CT verläuft allerdings etwas rascher in karbonatischem als in tonigem Milieu, während tonige Fazies die Opal-CTQuarz-Umbildung beträchtlich verlangsamt. Die SiO₂-Transformationen werden allerdings nicht nur durch die Faktoren Zeit, Teufe (Temperatur) und Gastsedimentfazies gesteuert. Weitere, noch weitgehend unbekannte Parameter spielen vermutlich eine bedeutende Rolle.

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Biogenic silica is the most important source for the global oceanic SiO₂ cycle, whereas volcanogenic and other sources are less significant. High silica plankton fertility and sedimentation rates (e. g. in upwelling areas) favour the preservation of skeletal opal and its later transformation into authigenic opal-CT and clinoptilolite. Volcanic glass is less easily dissolved and leads to the precipitation of authigenic smectite and phillipsite, but not to the formation of porcellanites and cherts.In general, silica diagenesis proceeds as a discontinuous age-, burial- and facies-dependant maturation from instable biogenic opal (opal-A) via metastable opal-CT (disordered low-temperature cristobalite/tridymite) to stable quartz. Opal-CT is always the precursor silica phase (precipitated 10–65 m.y. after deposition), followed by the formation of genuine quartz cherts (about 50–140 m.y. after deposition of the original siliceous oozes). Already during early diagenesis, accessory quartz is directly precipitated in porcellanites and fills voids or replaces calcitic fossils.Whereas the opal-Aopal-CT transformation usually involves a solution step, opaline skeletons can also be transformedin situ into opal-CT. A maturation of the opal-CT structure takes place with increasing burial depth, which later leads to an opal-CT quartz transformation, possibly without any major silica mobilization.Altough age/burial depth diagrams show a wide overlap for the distribution of opal-A, opal-CT, and quartz, a general positive correlation of the maturity of the silica phases with these parameters is evident. On the other hand, the rate of the opal-Aopal-CT transformation is slightly faster in calcareous than in clayey sediments, whereas clayey facies retards the opal-CTquartz transformation considerably. However, the silica transformations are not only controlled by the factors time, burial depth (temperature) and host rock facies, but also by additional, largely unknown parameters.

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Résumé Dans le cycle SiO₂ des océans les organismes siliceux sont les fournisseurs principaux de SiO₂. Les autres sources de silice, volcanogénes ou autres, sont de moindre importance. Une haute productivité de plancton siliceux alliée à un taux d'accumulation élevé (par exemple, dans les zones des upwellings) favorisent la conservation de l'opale biogène et sa transformation subséquente en opale-CT et en clinoptilolite. Les verres volcaniques se dissolvent plus lentement et donnent des smectites authigènes et des phillipsites, mais pas de cherts.En général, la diagénèse de la silice se poursuit comme un processus des maturation discontinu, dépendant des facteurs temps, profondeur, température et faciès: au cours de ce cycle, l'opale biogène instable (»opale-A«) se transforme en opale-CT métastable (-cristobalite/tridymite avec désordre unidimensionnel), puis en quartz stable. L'opale-CT est donc toujours la première phase SiO₂ (précipité 10–65 Ma après le dépÔt du sédiment), suivi plus tard (50–140 Ma après le dépÔt des sédiments biosiliceux originaux) par des cherts à quartz. Indépendamment, du quartz accessoire peut Être précipité au cours d'un stade précoce de la diagénèse dans les porcellanites, ou il remplit les vacoules ou remplace la calcite des fossiles.Alors que la transformation de l'opale-A en opale-CT s'opère, de manière générale, par l'intermédiaire d'une phase de dissolution, les restes des organismes siliceux peuvent Être transformésin situ en opale-CT. La grille de l'opale-CT subit un processus de maturation structurale en relation avec la profondeur et la température, visible par l'analyse aux rayons X. C'est cette maturation de la grille qui conduira plus tard à la transformation de l'opale-CT en quartz, cette étape pouvant avoir lieu sans dissolution totale ni reprécipitation.Bien que les diagrammes âges-profondeurs montrent des recouvrements importants de l'opale-A, de l'opale-CT et du quartz, on peut remarquer souvent une corrélation positive entre la maturité des phases de silice et ces paramètres. La transformation de l'opale biogène en opale-CT authigène se poursuit toutefois un peu plus rapidement en milieu carbonatique qu'en milieu argileux, alors que les faciès argileux freinent considérablement la transformation d'opale-CT en quartz. Cependant les transformations de SiO₂ ne sont pas uniquement dirigées par les facteurs temps, profondeur (température) et faciès du sédiment-hÔte. D'autres paramètres encore mal connus semblent jouer un rÔle important au cours de ces phénomènes.

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Geringfügig erweiterte Fassung eines auf der 69. Jahrestagung der Geologischen Vereinigung in Heidelberg gehaltenen übersichtsreferates.