Thermodynamic data from redox reactions at high temperatures. IV. Calibration of the Re-ReO2 oxygen buffer from EMF and NiO+Ni-Pd redox sensor measurements

The chemical potential of oxygen defined by the equilibrium:

Early Cretaceous volcaniclastic and quartzose sandstones from north central Nepal: composition,sedimentology and geotectonic significance

Early Cretaceous sandstones and shales from the Thakkhola region (Chukh and Tangbe Formations) were deposited on the subsiding northern (Tethyan) margin of Gondwana; current directions indicate a source area to the south. Whereas the Berriasian Chukh Formation is dominated by quartz arenites, volcaniclastic sandstones and minor conglomerates dominate the Tangbe Formation of Valanginian to Aptian age. Upsection, the composition of the volcaniclastic components changes from mainly basaltic to dominantly dacitic/rhyolitic. Magmatism was preceded and accompanied by strong uplift in the source area of the Chukh and Tangbe clastics, resulting in the erosion of probably more than several hundred meters of pre-Cretaceous sedimentary, metamorphic and plutonic rocks. A geochemical whole rock analysis of basaltic pebble fragments shows their alkaline character and suggests a within-plate geotectonic setting for the volcanic source. This volcanotectonic event is probably related to rifting between Australia and Greater India, where seafloor spreading began in late Valanginian/Hauterivian times.     

Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.     

Fossil carotenoids and paleolimnology of meromictic Mahoney Lake,British Columbia,Canada

Vertical distribution of fossil carotenoids in a sediment core from meromictic Mahoney Lake was studied. Besides okenone and demethylated okenone, lutein and zeaxanthin and-carotene isomers were identified. No carotenoids typical for purple nonsulfur or green sulfur bacteria were detected. The ratio of zeaxanthin to lutein (above 1:1 in all samples) indicates a dominance of cyanobacteria over green algae in the phytoplankton assemblages of the past. Okenone, which is found exclusively in Chromatiaceae, was the dominating carotenoid in all sediment zones.The oldest sediment layers containing okenone were deposited 11 000 years ago. Between 9000 and 7000 and since 3000 years b.p., Chromatiaceae reached a considerable biomass in the lake. Vertical changes in okenone concentration were not related to changes of paleotemperatures. In contrast, okenone concentrations decreased during periods of volcanic ash input. During most of the lake history, however, mean okenone concentrations were positively correlated with sedimentation rates. This indicates that vertical changes of okenone concentration in the sediment reflect past changes of purple sulfur bacterial biomass in the lake.According to these results, the past limnology of Mahoney Lake resembled that of the present with a sulfide-containing monimolimnion and a well-developed population of okenone-bearing purple sulfur bacteria.     

Synthetic zeolites formed from expanded perlite: Type,formation conditions and properties

Summary The starting material used was expanded perlite with a grain size < 40 m (74.5 wt.% SiO₂; 12.5 wt.% Al₂O₃). This material is a waste product obtained during the production of expanded perlite. The experiments were carried out with KOH solutions, mixtures of KOH and NaOH solutions (1:1) as well as NaOH solutions in the concentration range 0.5 N to 6.0 N at temperatures of between 100° and 140°C and with reaction periods of 2 hours to 13 days in closed system. In the experiments with KOH containing solutions zeolite ZK-19 (phillipsite), W (merlinoite), G (chabazite) and F (edingtonite) formed. Without addition of aluminium high percentages of zeolite ZK-19 (80–100 wt.%) and zeolite W (90–100 wt.%) were obtained. The addition of aluminium rendered possibly the formation of 90 to 100 wt.% of zeolite G and 85 to 100 wt.% of zeolite F, respectively. In the experiments with NaOH solutions analcime, zeolite Na-Pc (gismondine), zeolite HS (sodalite hydrate) and zeolite A formed. High percentages of zeolite Na-Pc (90–100 wt.%), zeolite HS (up to 100 wt.%) and analcime (up to 100 wt.%) were synthesized without addition of aluminium. The formation of high percentages of zeolite A (95–100 wt.%), however, needs the addition of aluminium, NaCI and seed crystals. The temperature stability of the zeolites decreases in the following sequence: K-F > K-W K-ZK-19 (Na), K-W Na, K-F G_si-rich (Na), K-ZK-19 >> Na-Pc G_si-poor. Zeolite A has a very good temperature stability up to temperatures of } 550 °C similar to that of zeolite K-W. At higher temperatures, however, its stability is very poor. The NH₄ ⁺-exchange capacities (meq/g) of the different zeolites amount to the following values: ZK-19:2.8 - 3.2; W:3.0 - 3.2; G:2.3 - 3.6; A:3.1 - 3.2; Na-Pc:3.5 - 3.6; F : 3.9 - 4.8.

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Zeolithsynthese aus Blähperlit—Art, Bildungsbedingungen und Eigenschaften

Zusammenfassung Ausgangsmaterial der experimentellen Untersuchungen war Blähperlit mit einer Korngröße < 40 ,m (74,5 Gew.-% SiO₂; 12,5 Gew.-% Al₂O₃). Dieses Material ist ein Abfallprodukt, das bei der Produktion von Blähperlit anfällt. Die Experimente wurden mit KOH-Lösungen, Lösungsgemischen aus KOH und NaOH (1:1) sowie mit NaOH-Losungen im Konzentrationsbereich 0,5 n-6,0 n bei Temperaturen von 100° – 140°C und über Reaktionszeiten von 2 Stunden bis zu 13 Tagen im geschlossenen System durchgeführt. In den Experimenten mit KOH-hältigen Lösungen bildeten sich die Zeolithe ZK-19 (Phillipsit), W (Merlinoit), G (Chabasit) und F (Edingtonit). Hohe Prozentgehalte an Zeolith ZK-19 (80 – 100 Gew.-%) und Zeolith W (90–100 Gew.-%) entstehen nur ohne Zugabe von Aluminium. Die Bildung von 90–100 Gew.-% Zeolith G bzw. 85–100 Gew. % Zeolith F ist dagegen durch die Zugabe von Aluminium möglich. In den Experimenten mit NaOH-Lösungen bildeten sich die Zeolithe Analcim, Na-Pc (Gismondin), HS (Sodalithhydrat) und Zeolith A. Hohe Prozentanteile an Zeolith Na-Pc (90–100 Gew.-%), HS (bis zu 100 Gew. %) und Analcim (bis zu 100 Gew.-%) wurden ohne Aluminium-Zugabe synthetisiert. Die Bildung von hohen Gehalten an Zeolith A (95–100 Gew. %) ist jedoch nur unter Zugabe von Aluminium, NaCl und Kristallkeimen möglich.Die Temperaturbeständigkeit der Zeolithe nimmt in der folgenden Reihenfolge ab: K-F > K-W - K-ZK-19 (Na), K-W Na, K-F G_si-reich (Na), K-ZK-19 >> Na-Pc G_si-am. Zeolith A weist bis zu Temperaturen von etwa 550°C eine gute Temperaturbeständigkeit auf, die in etwa der von Zeolith K-W entspricht. Bei höheren Temperaturen ist die Beständigkeit jedoch sehr gering.Die NH⁴⁺-Austauschkapazitäten (mÄqu/g) der verschiedenen Zeolithe erreichen folgende Werte: ZK-19:2,8 - 3,2; W:3,0 - 3,2; G:2,3 - 3,6; A:3,1 - 3,2; Na-Pc:3,5 -3,6; F:3,9 - 4,8.

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With 2 Figures     

Die Rheingrabenrandverwerfung im Wattkopftunnel bei Ettlingen (Nordschwarzwald)

The Wattkopftunnel, near Ettlingen (Nordschwarzwald), drives through the eastern margin of the Rheingraben. The tunnel passes cenozoic and mesozoic sediments. Early quarternary and tertiary beds are situated west of the main thrust of the Rheingraben. Fossil record indicates upper Oligocene age (Chatt) for parts of the tertiary sediments. At the eastern border of the Rheingraben, wedges of jurassic and middle triassic series are squeezed. East of the Rheingraben the tunnel drives in the lower triassic Bausandstein. The eastern margin of the Rheingraben was investigated in detail during tunneling. Faults of the Rheingraben margin are distributed in an 130 meter wide fault zone in the tunnel. Total stratigraphic separation by the normal faults reaches more than 2 000 meters. The cenozoic sequence suffered synsedimentary to early diagenetic deformation, while the mesozoic series are characterized by ruptural deformation. The fault- and joint system is directed in the rheinische Richtung (SSW-NNE). East of the Rheingraben a second direction occur, running parallel to the lower Albtal (W-E).

     

Palaeoclimatic studies in South Shetland Islands,Antarctica, based on numerous stratigraphic variables in lake sediments

The hitherto longest found lake sediment sequence on Byers Peninsula, Livingston Island, South Shetland Islands, was analysed with respect to lithology, chronology, diatoms, Pediastrum, pollen and spores, mosses, mineralogy, and sediment chemistry. During the ca. 5000 year long development the sediments were influenced by frequent tephra fall-outs. This volcanic impact played a major role in the lake's history during two periods, 4700–4600 and 2800–2500 BP, but was of importance during the lake's entire history with considerable influence on many of the palaeoenvironmentally significant indicators. The large and complex data set was analysed and zonated with different types of multivariate analysis. This resulted in a subdivision of the sequence into 8 time periods and 21 variables. Redundancy analysis (RDA) of this data set, both without and with the tephra periods, and with 4–6 of the variables as explanatory environmental variables, reveal that climatic/environmental signals are detectable. The palaeoclimatic picture that emerged out of the tephra noise suggests that the first 100 years were characterized by mild, humid conditions. This was followed by a less mild and humid climate until ca. 4000 BP when a gradual warming seems to have started, coupled with increased humidity. These mild and humid conditions seem to have reached an optimum slightly after 3000 BP. At ca. 2500 BP a distinct climatic deterioration occurred with colder and drier conditions and long seasons with ice cover. This arid, cold phase probably reached its optimum conditions at ca. 1500 BP, when slightly warmer conditions might have prevailed for a while. Except for the modern sample with rather mild climate, the last 1400 years seem to have been fairly arid and cold, and the effects of the frequent volcanic activity during this period is only vaguely seen in the records.     

High-resolution sequence stratigraphy of the Lower Triassic ‘Buntsandstein’ in the Netherlands and northwestern Germany

Detailed log correlations of the largely fluvio-lacustrine Lower Triassic Buntsandstein (Late Permian-Early Anisian), carried out on 80 wells in the Dutch onshore and offshore areas, can be linked to northwest-German high-resolution sequence stratigraphy. The correlations show that cyclic sedimentation occurred in large parts of the basin. Seven 1st-order sequences are recognised, namely the Main Claystone, Rogenstein, Volpriehausen, Detfurth, Hardegsen, Solling and Lower Röt Sequences. They are overlain by the lower part of the Upper Röt–Lower Muschelkalk Sequence. Distinct sequence boundaries have been identified at the bases of four sequences: Volpriehausen, Detfurth, Solling and Upper Röt. The higher-order sequences consist of fining-upwards cycles with a thickness of up to tens of metres. The sequences are laterally persistent and have a characteristic expression on gamma-ray and sonic logs. In the Lower Buntsandstein, they display a uniform character throughout most of the area, with only minor differences in thickness or lithology. NNE-oriented lows and swells were formed during deposition of the Volpriehausen, Detfurth and Hardegsen Sequences. Uplift prior to the deposition of the Solling Sequence caused deep erosion on the swells in the basin and minor erosion in the lows. The high-resolution sequences probably represent alternating, relatively wet and dry climatic periods, with a periodicity of about 100 000 years. An analysis of the sequences suggests that their reduced thickness on the swells is mainly the effect of erosion. This is supported by analyses of the accumulation patterns and rates.     

Geochemistry of the Grenville Dyke Swarm: role of plume-source mantle in magma genesis

Major and trace element data of samples from the approximately 590 Ma Grenville dyke swarm, in the southeastern parts of the Canadian Shield, were used to evaluate the extent of crustal contamination of the dyke magma and to model its probable mantle source. The dyke rocks are mostly saturated, quartz tholeiites. A few samples represent transitional basalts. Their overall chemistries are similar to those of continental flood basalts. Their compositions resemble those of liquids initially produced in the garnet peridotite mantle zone and then subjected to polybaric fractionation. However, fractionation models fail to mass-balance Ti, Fe, K, and P. Geochemical and isotopic criteria indicate that crustal contamination was minimal. The incompatible elements Zr, Y, K, Rb, Nb, V, Ta, Hf, and Th show hyperbolic elemental ratio-ratio distributions indicative of mixing between two end-members. One end-member has elemental ratios similar to those of a depleted N-MORB source and the second of a P-MORB i.e. ertile or plume MORB source. The more enriched dyke compositions can be successfully reproduced by mixing models in the ratio of 6:1 between the most depleted MORB-like dyke magma and a liquid composition similar to metasomatic glass veinlets coexisting with mica peridotite mantle xenoliths, and subsequent crystal fractionation. The Grenville dykes are probably a synrift swarm that was emplaced along a rift arm related to an Iapetan rrr triple junction that is thought to have formed over a mantle plume. The chemistry of the dyke swarm is consistent with its derivation from a plume head, in that the minor enriched source can be identified with plume-source mantle and the major depleted source with entrained mantle. The magma probably originated in the upper cooler parts of the plume head.     

Analysis of COMPTEL gamma-ray burst locations and spectra

In its first three years of operation, the COMPTEL instrument on theCompton Gamma-Ray Observatory has measured the locations (mean accuracy 1°) and spectra (0.75-30 MeV) of 18 gamma-ray bursts and continues to observe new events at a rate of 1/month. With good angular resolution and sensitivity at MeV energies, the growing COMPTEL burst catalog is an important new piece of evidence in the on-going GRB mystery. The COMPTEL burst locations are consistent with an isotropic distribution of sources, yet the spatial coincidence of two of the bursts indicates the possibility of repetition. The COMPTEL burst spectra are in most cases consistent with a single power law model with spectral index in the range 2–3. However, two bursts show evidence of a spectral break in the MeV range. Measurement of rapid variability at MeV energies in the stronger bursts provides evidence that either the sources are nearby (within the Galaxy) or the gamma-ray emission is relativistically beamed. We present an overview of analysis results obtained from the COMPTEL burst catalog concentrating on the search for burst repetition and the implications of highly variable MeV emission.