The structure of the natural stratosphere and the impact of chlorofluoromethanes on the ozone layer investigated in a 2-D time dependent model

two-dimensional time dependent model of the stratosphere incorporating the major interactions between radiative-photochemical and dynamical processes is described. The main prognostic equations considered are the thermodynamic equation and the general conservation equation for the minor chemical constituents representing the odd oxygen (O _x =O+('D)+O₃), odd hydrogen (HO _x =HO+HO₂), N₂O, odd nitrogen (NO _x =NO+NO₂+HNO₃), CF₂Cl₂, CFCl₃ and odd chlorine (Cl _x =Cl+ClO+HCl). The zonal wind and mean meridional circulations are determined diagnostically by the integration of the thermal wind equation and the stream function equation in the meridional plane espectively. The large scale eddy processes are parameterized in terms of zonal mean quantities using the generalized diffusion formulation on a sloping surface. The radiative heating and cooling and the hotochemical sources and sinks are incorporated in a form which allows for the major interactions among the minor trace constituents, temperature and mean circulation.Two integrations consisting of natural stratosphere and a stratosphere contaminated by the chlorofluoromethanes through lower boundary fluxes are carried out for 23 model years by changing the declination of the sun every day and using 6-hour time step. The model simulations of temperature, mean circulation, ozone, HO _x , N₂O and NO _x in the meridional plane for the normal stratosphere, show satisfactory agreement with the available observations. Based on the results of second integration it is found that the injection of chlorofluoromethanes in the atmosphere at the estimated current production rates can lead to significant changes in the meridional distribution of ozone, temperature and NO _x in the middle and upper stratosphere. The results also indicate that the percentage total ozone depletion increases from tropics to high latitudes and from summer to winter high latitudes. Also discussed are the results of additional experiments incorporating the reaction of HO₂ with NO and the reactions involving ClNO₃.     

Melting of Mg2GeO4 under pressure

Melting point of germanate forsterite, Mg₂GeO₄, was raised by compression at the rate of 30°C/GPa. The triple point, at which three phases of olivine- and spinel-type solids and liquid coexisted, was fixed at 1950°C and 3.5GPa. Wen these results are combined with the thermodynamical data of forsterite, Mg₂SiO₄, it is estimated that the triple point of forsterite lies in a region ranging from 2700° to 3000°C in temperature and from 20 to 30GPa in pressure.     

Elastic modulus and internal friction in enstatite,forsterite and peridotite at seismic frequencies and high temperatures

Spectra of internal friction between 2 and 8 Hz were studied in a single crystal of enstatite, in a polycrystal of synthetic forsterite and in several samples of natural peridotite. Measurements of Q^?1 and μ were performed in vacuum (10^?6 torr), from room temperature up to 1100°C. For these experimental conditions no peak was observed in the polycrystalline undeformed forsterite, but the background attenuation irregularly increased from 5 · 10^?3 to 10^?2.A peak Q^?1 = 7 · 10^?2 appears in a deformed peridotite at 930°C. It is reduced of 60% after 5 h of annealing at 1100°C. But the background attenuation persists. In the single crystal of enstatite, a peak is observed at 760°C (Q^?1 = 6 · 10^?2). A mechanism involving dislocations is suggested as a possible explanation for the peak obtained with the peridotite samples. If this hypothesis is right, the observed effect would be diffusion controlled so that one can expect pressure to translate it towards higher temperature. This mechanism could therefore appear in the upper mantle. Background attenuation could be the result of intergranular thermal losses.     

Paléo-bactéries et minéralisations plombo-zincifères du Bled Zelfane (tunisie centrale)

Résumé Le Bled Zelfane est un synclinal mio-pliocène sur la bordure septentriono-orientale de l'ile de Kasserine. L'ile de Kasserine est une plate-forme devenue insulaire à partir du Crétacé supérieur et restée émergée jusqu'au Miocène moyen. Ce môle a été soumis apparemment pendant sa période continentale à un climat oxydant de type méditerranéen relativement sec. On note une certaine diversification dans la nature des dépôts en zones basses (secteur de Kasserine) et en zones hautes (secteur du Bled Zelfane). En zones basses, la sécheresse climatique a favorisé la formation de dépôts de gypse, d'argiles rouges et de calcrêtes. En zones hautes, une érosion par lessivage acide a créé des dépressions karstiques dans les calcaires du Crétacé supérieur (Aïn Khamouda) et dans les calcaires du Maëstrichtien (Sidi Mabrouk et Guémata). Le remplissage des cavités karstiques (poches, crevasses) s'est fait avec de l'argile blanche (halloysite), contenant des micro-cristaux de galène, avec de la calamine et des oxydes de fer. Les conditions climatiques étaient trop oxydantes pour que le zinc se dépose autrement que sous forme de calamine. Elles expliquent aussi la présence de paléo-algobactéries (aérobies) sur la calamine. La présence de micro-cristaux de galène dans l'halloysite serait liée à un sulfuretum et non à des conditions réductrices réelles. Il semble en effet que dans ces karsts du Bled Zelfane une flore bactérienne très riche a joué un rôle essentiel dans le piégeage d'éléments lourds et notamment dans la genèse de galènes supergènes et dans la cristallisation de la calamine. Une minéralisation, elle aussi plombo-zincifère, de type stratiforme, s'observe à la base de Miocène inférieur et montre de même des bactéries fossiles à foison.

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Bled Zelfane is a Mio-Pliocene syncline on the NE edge of the palaeo-island of Kasserine, a platform which became insular at the beginning of the Upper Cretaceous and remained emergent until the Middle Miocene. During its long emergence this platform was affected by an oxidising, relatively dry, Mediterranaean-type climate. There exists a certain diversity in the sedimentary accumulations in both the lower (Kasserine area) and upper (Bled Zelfane area) sectors of this palaeo-relief. In the lower sectors the dry climate has favourised gypsum, red clays and calcrete formation. In the higher sectors erosion and leaching by acid waters has created karstic depressions in the Upper Cretaceous (Aïn Khamouda) and in the limestones of Maestrichtian (Sidi Mabrouk and Guémata). The karst cavities (pockets and fissures) are filled with white, halloysite clays containing micro-crystals of galena associated with calamine (Zn) and iron oxides. The climatic conditions were too oxidising to permit the formation of Zn other than in the form of calamine. The dry climate is also an explanation for the presence of aerobic palaeo-algobacteria on this calamine. The presence of micro-crystals of galena within the halloysite is probably related to a sulfuretum and not to effective reducing conditions. It would seem that the presence of a rich bacterial flora within the karst at Bled Zelfane has played a significant role in the stabilisation of heavy elements, and especially the supergene genesis of the galena. A Lead/Zinc mineralisation also exists at the base of the Miocene. This latter is diffused through the cement in conglomerates and sandstones.

     

Exploration geochemistry—Distribution of elements and recognition of anomalies

The exploration geochemist faces a serious problem in reconciling theoretical statistics with the empirical distribution of elements in materials in the earth's crust. The results of computer-simulation experiments being conducted by the Exploration Geochemistry Group at the University of New Brunswick illustrate some of the problems of the relation between frequency distributions and spatial distributions of elements and raise some interesting questions about sampling patterns and physical size of samples. Most importantly, the simulation experiments and empirical examples support the contention that attempts to make an assumption of normality more efficient by performing log transformations on positively skewed data may defeat the purpose of statistical analysis for exploration work. New developments in computer-data presentation and interpretation, including population sorting and classification, illustrate the increasing use of the computer in exploration geochemistry.     

The petroporphyrins of a Cretaceous oil

The petroporphyrins of a Cretaceous crude oil, La Paz, from western Venezuela are shown to be a mixture of etio and DPEP homologues (C₂₇-C₃₉) maximising at C₃₀ and C₃₁, respectively. Minor amounts of rhodoporphyrins (C₃₀-C₃₉) are also present. Thin-layer chromatography afforded fractions which have been shown by mass spectrometry to contain up to 80% of a single-molecular-weight species. Oxidative degradation of La Paz petroporphyrins to maleimides and mass-spectrometric study of t.l.c. fractions indicate that some of these porphyrins are to a great extent incompletely substituted. Dealkylation reactions have presumably played an important role in their geologic history. Furthermore, the relative simplicity of the alkyl substitution pattern of the La Paz petroporphyrins suggests that transalkylation reactions have not taken place to any significant extent.The fraction of petroporphyrins isolated from the asphaltenes contains a higher proportion of the DPEP homologues than do the total petroporphyrins isolated from the original crude oil.     

A reinterpretation of the entrainment process in some laboratory experiments

Pollard et al. (1973) proposed a closure hypothesis for the entrainment process in the stress-mixed layer of a stratified fluid. Some laboratory experiments suitable for testing the hypothesis were carried out by Kantha et al. (1977) and by Kato and Phillips (1969). In the early period of each experiment, before side-wall friction becomes important, these experiments support the closure hypothesis, with a critical Froude number close to 1, perhaps F = 1.2 ± 0.2.     

Age of the Laschamp paleomagnetic excursion revisited

The reverse paleomagnetism of the lava flows of Laschamp and Olby, already discovered by Bonhommet and Babkine, is confirmed. The ages of these flows, measured by¹⁴C, thermoluminescence and K-Ar dating are respectively36,000 ± 4000 and42,000 ± 5000years. VGP's comparison of the “Laschamp event” with those of the 30,000-year Lake Mungo excursion does not show evidence of coincidence between these two events.     

Cyclic triaxial tests on frozen sand

Strain-controlled cyclic triaxial tests were performed on a one-size silica (Ottawa) sand artificially frozen into 71.1-mm-diameter cylindrical samples. Ice-saturated samples with three different sand contents were tested under the following conditions: axial strains ranging from 3 × 10⁻³ to 3 X 10⁻²%, confining pressures from zero to 1.378 MPa, frequencies of 0.05–5.0 cps and temperatures from −1 to −10 °C.

Test equipment included (1) an MTS electrohydraulic closed-loop testing system which applies the load to the sample, (2) a triaxial cell completely immersed in a low-temperature coolant for temperature control, (3) a refrigeration unit for control of the coolant temperature and constant coolant circulation and (4) measuring devices including an LVDT and load cell, together with recording devices such as a digital multimeter, an oscilloscope, a strip-chart recorder and a minicomputer.

Test results indicate that the dynamic Young's modulus increases with increasing frequency, confining pressure and sand content, but decreases with increasing strain and temperature. The damping ratio decreases with increasing frequency, sand content and lower temperatures. The influence of confining pressures and axial strain on the damping ratio are less explicit for the ranges considered. The experimental results are compared with data from other sources.