Excess K-Ar ages of glauconite from the Upper Marine Molasse and evidence for glauconitization of mica

K-Ar age determinations along with optical investigations were used to examine whether glauconite from the Upper Marine Molasse (OMM) is of authigenic, allogenic or transformed origin. For this purpose 16 glauconite samples from 14 different localities were investigated from the Burdigalian Muschelsandstein collected along a traverse from Lake Constance to west of Geneva.Optical observations on washed grain concentrates reveal the presence of different alteration products of biotite, confirming earlier studies. Moreover, thin-section preparations of sample aliquots showed that the glauconite grains contain biotite-relics, which might account for the elevated absolute ages.The optical evidence is confirmed by individual mineral fractions, which show chlorite with biotite-»nucleii«, chlorite-lamellae, and »layered«-glauconites. All these observations point to glauconite genesis by transformation of biotite. The complete transformation from biotite via chlorite to glauconite apparently results in a chemically more stable state.The K-content of the samples varies from 5.6 to 7.0% K₂O, indicating mature but not highly evolved glauconite. 19 apparent K-Ar dates range from 17.7 to 34.9 Ma. In comparison with the biostratigraphy and the estimated Burdigalian age of about 18 Ma nearly all dates are too high. These strongly scattered dates are thus stratigraphically meaningless and seem to exclude an authigenic formation of these glauconites from faecal pellets. Furthermore, geologic arguments exclude an allogenic (= detrital) origin.Glauconite genesis in the Upper Marine Molasse must therefore be distinguished from both authigenic and allogenic formation mechanisms. A new term »meta-allogenic« is therefore used to describe glauconite growth by transformation of allogenic mica.

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Zusammenfassung Um zu prüfen, ob Glaukonite aus der Oberen Meeresmolasse (OMM) authigen, allothigen oder durch Umwandlung aus anderen Mineralien entstanden sind, wurden sie — nebst mineraloptischen und röntgenographischen Untersuchungen — mit der K-Ar-Methode datiert. Aus 14 verschiedenen Lokalitäten zwischen Bodensee und einigen Kilometern westlich von Genf wurden 16 Glaukonit-Proben aus dem burdigalen Muschelsandstein entnommen.Sedimentpetrologische Studien an Körner-Konzentraten offenbarten verschiedene Umwandlungsprodukte von Biotit. Zudem zeigten Aliquots von Dünnschliff-Präparaten, daß einzelne Körner unterschiedlich große Relikte von Biotit enthalten, die die zu hohen Alterswerte verursachen können.Die verschiedenen Mineralfraktionen bestätigen den Charakter von Übergangsstadien: Chlorit mit Biotit-Kernen, Chloritlamellen und »Schicht«-Glaukonit. Alle diese Beobachtungen deuten auf eine Glaukonitgenese aus der Umwandlung von Biotit. Die vollständige Umwandlung von Biotit über Chlorit zu Glaukonit scheint mit dem End-produkt einen chemisch stabileren Zustand anzustreben.Der K₂O-Gehalt aller Proben variert von 5.6 bis 7.0%. Dies weist auf »reifen«, aber nicht hochentwickelten Glaukonit hin. Die 19 K-Ar-»Alter« liegen zwischen 17.7 und 34.9 Ma. Im Vergleich mit der Biostratigraphie und dem geschätzten burdigalen Alter von ca. 18 Ma, sind diese Daten zu hoch und daher stratigraphisch bedeutungslos. Eine authigene Bildung von Glaukonit aus Kotpillen (faecal pellets) muß somit ausgeschlossen werden. Außerdem kommt aus geologischen Gründen eine detritische (allothigene) Herkunft ebenfalls nicht in Betracht.Für die Glaukonit-Genese in der Oberen Meeresmolasse muß daher ein anderer Bildungsprozess verantwortlich sein. Um die Umwandlung von eingeschwemmtem (= allothigenem) Biotit zu Glaukonit zu beschreiben, wurde der neue Term »meta-allothigen« eingeführt.

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Résumé Afin de rechercher si les glauconites de la OMM (= molasse marine supérieure) sont authigènes, allothigènes ou proviennent de la transformation d'autres minéraux, on les a datées par la méthode K-Ar, conjointement à une étude optique et röntgenographique. 14 localités, situées depuis de lac de Constance jusqu'à quelques kilomètres à l'ouest de Genève, ont fourni 16 échantillons de glauconite du Muschelsandstein burdigalien.L'étude optique des grains, effectuée sur des concentrés, a révélé divers produits de transformation de la biotite. En outre, les examens en coupes minces ont montré, dans les grains de glauconite, des restes de biotite d'importance variable. Ces restes de biotite peuvent être responsables de valeurs trop élevées obtenues dans les mesures d'âge.L'examen des diverses fractions minérales permet de préciser les stades de transformation: chlorite avec noyaux de biotite, lamelles de chlorite et glauconite »stratifiées«. Toutes ces observations indiquent une genèse de la glauconite par transformation de la biotite. La transformation complète de la biotite en chlorite puis en glauconite semble ainsi correspondre à un état chimique plus stable.La teneur en K₂O de tous les échantillons varie entre 5,6 et 7,0%, indiquant une glauconite »mature«, mais pas très évoluée. Les 19 »âges« K-Ar sont compris entre 17,7 et 34,9 Ma. Comparés à la biostratigraphie et à l'âge burdigalien, estimé à environ 18 Ma, ces résultats sont nettement trop élevés et ne présentent donc aucune valeur stratigraphique. Il faut ainsi exclure une formation authigène de la glauconite à partir de pelotes fécales. De plus, une origine détritique (= allothigène) ne peut être envisagée pour des raisons géologiques.En conséquence, c'est bien un processus différent qui est responsable de la genése de la glauconite dans la OMM. Le terme nouveau »méta-allogénique« est proposé pour indiquer la transformation de la biotite détritique en glauconite.

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Mineral equilibria in the six-component seawater system,Na-K-Mg-Ca-SO4-Cl-H2O at 25°C. II: Compositions of the saturated solutions

Using the solubility model developed by Harvie and Weare (1980), the stable mineral-solution assemblages for the six-component system Na-K-Mg-Ca-SO₄-Cl-H₂O and its constituent 5-, 4- and 3-component systems at 25°C have been defined. Invariant point maps have been constructed showing the connections by univariant lines. The solubility volumes for all 20 minerals considered are also illustrated. Of the 37 invariant points, only 3 have solutions which are Ca-rich; the remaining 34 can be plotted in the reciprocal system Na-K-Mg-SO₄-Cl, which is similar to the seawater system, except that the restriction of halite saturation has been removed. Application of these results and implications for the evolution of major brine types are briefly discussed.     

Paleomagnetism of red beds of Early Devonian age from Central Iran

Paleomagnetic results are reported from 13 sites of red beds of Early Devonian age from Central Iran. Detailed paleomagnetic analyses were carried out. Two types of partial progressive demagnetization were applied, one using alternating magnetic fields, the other heating. These procedures resulted in the detection of the characteristic remanences with a mean direction with D = 24.2°, I = 1.3° (α₉₅ = 10.1°). The paleomagnetic pole is located at 51.3°N, 163.7°W. If one shifts the Iranian landmass to its most likely position in the Gondwana configuration, then the position of the paleomagnetic pole coincides with the alternative polar wander path [14,15] which crossed South America in early Middle Paleozoic times.     

Modelling the variability of midlatitude storm activity on decadal to century time scales

The output of several multi-century simulations with a coupled ocean–atmosphere general circulation model is examined with respect to the variability of global storm activity in winter on time scales of decades and longer. The frequency of maximum wind speed events within a grid box, using the lower limits on the Beaufort wind speed scale of 8 and 10 Bft as thresholds, is taken as the characteristic parameter. Two historical climate runs with time-dependent forcing of the last five centuries, one control simulation, and three climate change experiments are considered. The storm frequency shows no trend until recently. Global maps for the industrially influenced period hardly differ from pre-industrial maps, even though significant temperature anomalies temporarily emerge in the historical runs. Two indicators describing the frequency and the regional shift of storm activity are determined. In historical times they are decoupled from temperature. Variations in solar and volcanic forcing in the historical simulations as well as in greenhouse gas concentrations for the industrially influenced period are not related to variations in storm activity. Also, anomalous temperature regimes like the Late Maunder Minimum are not associated with systematic storm conditions. In the climate change experiments, a poleward shift of storm activity is found in all three storm track regions. Over the North Atlantic and Southern Ocean, storm activity increases, while it decreases over the Pacific Ocean. In contrast to the historical runs, and with the exception of the North Pacific storm frequency index, the storm indices parallel the development of temperature, exceeding the 2 σ-range of pre-industrial variations in the early twenty-first century.     

A novel ozone sensor for direct eddy flux measurements

A small, lightweight (1.5 kg) and fast-response ozone sensor for direct eddy flux measurements has been built. The basis for detection is the chemiluminescence of an organic dye adsorbed on dry silica gel in the reaction with ozone. The chemiluminescence is monitored with a cheap and small blue-sensitive photomultiplier. At a flow rate of 100 l min^-1 the ozone sensor has a 90% response time of significantly better than 0.1 s with a detection limit lower than 50 ppt at S/N=3. There are no interferences from other atmospheric trace gases like NO_x, H₂O₂ and PAN. Water vapour and SO₂ enhance the chemiluminescence efficiency of the ozone sensor. Since their response times are 22 seconds and 30 minutes, respectively, no correlation between rapid ozone fluctuations and those of these two trace gases is noticed by the ozone sensor when operating at a frequency of 10 Hz.The ozone sensor was tested for several weeks in continuous measurements of ozone fluxes and deposition velocities over different croplands using the eddy correlation technique. Good agreement was found between ozone dry deposition velocities derived from profile measurements and by eddy correlation.