4He diffusion in specular hematite

In order to test the chronometer qualities of speculante for the (U + Th)/He dating method, ⁴He release experiments by stepwise heating of two specularites from the Rimbach mineralization locality in the southern Vosgues (France) have been carried out. The diffusion coefficients define linear Arrhenius plots within a temperature interval of 250 to 830 °C, which is suggestive of volume diffusion. Extrapolation of the diffusion behavior to 20° C yields diffusion coefficients (D₂₀ values) smaller than 10^?26 [cm² s^?1] for both hematites with activation energies at 116 [kJ/mole]. The results of our study suggest that specularite is a very helium retentive hematite variety which is capable of quantitatively retaining radiogenic helium over geologic periods of time.     

The fall and rise of metropolitan government in Copenhagen

In this paper it is argued that the re-establishment of a metropolitan government in the Greater Copenhagen Area in 2000 (Greater Copenhagen Authority) is not to be seen as a return to the kind of regional, coordinative authority (Greater Copenhagen Council) that was abolished in the Thatcherite climate of the 1980s. Throughout the 1980s and 1990s new forms of urban governance, entrepreneurialism and a higher national priority to the capital region were introduced, which changed the conditions under which the new metropolitan government is operating. This `contextualization' of the analysis of the two generations of metropolitan government points to the fact that typologies of metropolitan government, such as the one put forward by Sharpe (1995), often lacks analytical cogency. This revised version was published online in August 2006 with corrections to the Cover Date.     

New major element analyses of proximal tephras from the Azores and suggested correlations with cryptotephras in North-West Europe

The Azores Archipelago is one of the most active volcanic areas in the North Atlantic region. Approximately 30 eruptions have been reported over the last 600 years with some major VEI 5 (Volcanic Explosivity Index) eruptions further back in time. The geochemical composition of associated tephra-derived glass, however, is not well characterized. An Azorean origin of cryptotephras found in distal areas such as North Africa, the British Isles and Greenland has been suggested, but proximal data from the Azores are scarce and the correlations have only been tentative. These tephras have a traychtic composition, which excludes an Icelandic origin. In a previous study, we presented major element analyses of proximal tephra-derived glass from five Holocene eruptions on the Azores Islands. There is a striking geochemical similarity between tephras from volcanoes on São Miguel and Irish cryptotephras, and especially with eruptives from the Furnas volcano. Here we present new analyses of proximal tephras that confirm and strengthen a link between Furnas and cryptotephras found in south-west Ireland. We also suggest a correlation between a previously unsourced tephra found in a Swedish bog with an eruption of the Sete Cidades volcano c. 3880 a cal BP.     

Water solubility in orthopyroxene

The solubility of water in pure enstatite was measured on samples synthesized at 1,100 °C and pressures to 100 kbar. Enstatite crystals were grown under water-saturated conditions from a stoichiometric mixture of high-purity SiO₂ and Mg(OH)₂. Water contents were calculated from polarized FTIR spectra measured on oriented single crystals. The water solubility in orthoenstatite increases with pressure to 867ᆷ ppm H₂O by weight at 75 kbar. At 100 kbar, in the stability field of high-clinoenstatite, a water solubility of 714ᆷ ppm was observed. The water solubility in enstatite at 1,100 °C can be described by the equation c_H2O=Af_H2O exp(-P(V/RT), where f_H2O is water fugacity, A=0.0204 ppm/bar and (V=12.3 cm³/mol. The infrared spectra of the hydrous enstatite crystals show a sharp, intense band at 3,363 cm^-1 and a broad, weaker band at 3,064 cm^-1. Both bands are strongly polarized parallel c. Most likely, pairs of protons attached to non-bridging oxygen atoms substitute for Mg²⁺. In order to investigate the effect of chemical impurities on water solubility in enstatite, an additional series of experiments was carried out with gels doped with Al, B, or Li as starting material. Whereas, the presence of Li and B had no detectable effect on water solubility, the addition of about 1 wt% Al₂O₃ increased water solubility in enstatite from 199 to 1,100 ppm at 1,100°C and 15 kbar. In the infrared spectra of these aluminous samples, additional bands occur in the range from 3,450 to 3,650 cm^-1. Similar bands are also observed in natural, aluminous orthopyroxenes and are most likely caused by protons coupled with Al according to the substitution of Al³⁺+H⁺ for Si⁴⁺. A series of hydrous annealing experiments on a natural, gem-quality aluminous enstatite from Tanzania yielded water solubilities generally consistent with the results from the synthetic model systems. The results presented here imply that pure enstatite has a similar storage capacity for water as olivine; however, aluminous orthopyroxenes in the mantle may dissolve much larger amounts of water comparable with the entire mass of the present hydrosphere. Moreover, the mechanism of aluminum substitution in orthopyroxenes, i.e., the distribution of Al between tetrahedral and octahedral sites, may be a potential probe of water fugacity.     

Zircon fission‐track ages from Newfoundland—A proxy for high geothermal gradients and exhumation before opening of the Central Atlantic Ocean

Following Appalachian orogenesis, metamorphic rocks in central Newfoundland were exhumed and reburied under Tournaisian strata. New zircon fission‐track (ZFT) ages of metamorphic rocks below the Tournaisian unconformity yield post‐depositionally reset ages of 212–235 Ma indicating regional fluid‐absent reheating to at least ≥220°C. Post‐Tournaisian sedimentary thicknesses in surrounding basins show that burial alone cannot explain such temperatures, thus requiring that palaeo‐geothermal gradients increased to ≥30–40°C/km before final late Triassic accelerated cooling. We attribute these elevated palaeo‐geothermal gradients to localized thermal blanketing by insulating sediments overlying radiogenic high‐heat‐producing granitoids. Late Triassic rifting and magmatism before break up of Pangaea likely also contributed to elevated heat flow, as well as uplift, triggering late Triassic accelerated cooling and exhumation. Thermochronological ages of 240–200 Ma are seen throughout Atlantic Canada, and record rifting and basaltic magmatism on the conjugate margins of the Central Atlantic Ocean preceding the onset of oceanic spreading at ~190 Ma.     

Electrical conductivity of orthopyroxene and plagioclase in the lower crust

The electrical conductivities of lower crustal orthopyroxene and plagioclase, as well as their dependence on water content, were measured at 6–12 kbar and 300–1,000°C on both natural and pre-annealed samples prepared from fresh mafic xenolith granulites. The complex impedance was determined in an end-loaded piston cylinder apparatus by a Solarton-1260 Impedance/Gain Phase analyzer in the frequency range of 0.1–10⁶ Hz. The spectra usually show an arc over the whole frequency range at low temperature and an arc plus a tail in the high and low frequency range, respectively, at high temperature. The arc is due to conduction in the sample interior, while the tails are probably due to electrode effects. Different conduction mechanisms have been identified under dry and hydrous conditions. For the dry orthopyroxene, the activation enthalpy is ~105 kJ/mol, and the conduction is likely due to small polarons, e.g., electrons hopping between Fe²⁺ and Fe³⁺. For the dry plagioclase, the activation enthalpy is ~161 kJ/mol, and the conduction may be related to the mobility of Na⁺. For the hydrous samples, the activation enthalpy is ~81 kJ/mol for orthopyroxene and ~77 kJ/mol for plagioclase, and the electrical conductivity is markedly enhanced, probably due to proton conduction. For each mineral, the conductivity increases with increasing water content, with an exponent of ~1, and the activation enthalpies are nearly independent of water content. Combining these data with our previous work on the conductivity of lower crustal clinopyroxene, the bulk conductivity of lower crustal granulites is modeled, which is usually >~10⁻⁴ S/m in the range of 600–1,000°C. We suggest that the high electrical conductivity in most regions of the lower crust, especially where it consists mostly of granulites, can be explained by the main constitutive minerals, particularly if they contain some water. Contributions from other highly conducting materials such as hydrous fluids, melts, or graphite films are not strictly necessary to explain the observed conductivities.     

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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