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.     

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.     

The quiet Sun brightness temperature at 127 MHz

A correction and analysis of routine total flux measurements made in Toru at 127 MHz allowed for the determination of the peak brightness temperature of the Sun (above 9 × 10⁵ K) in three periods grouped around the last minimum, and for estimation of the brightness temperature of the coronal holes: (7.3 ± 1.4) × 10⁵ K.     

Assessment of mercury mobility and bioavailability by fractionation method in sediments from coastal zone inundated by the 26 December 2004 tsunami in Thailand

The 26 December 2004 tsunami covered significant portion of a coastal zone with a blanket of potentially contaminated sediments. In this report are presented results on mercury concentrations in sediments deposited by the tsunami in a coastal zone of Thailand. Since the total mercury concentrations are insufficient to assess mercury mobility and bioavailability in sediment, its fractionation was applied. Sediments were sampled within 50 days after the event and analyzed by sequential extraction method. The procedure of sequential extraction involved five subsequent stages performed with solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH, and aqua regia. The mean concentration of total mercury in sediments was 119 ± 50 ng g⁻¹ dry mass (range 66–230). The fractionation revealed that mercury is mainly bound to the least bioavailable sulphides 75 ± 6% (range 62–86), organomercury compounds 14 ± 7% (range 4–26), and humic matter 9 ± 7% (range 1–27). The lowest contributions bring fractions of water-soluble mercury 0.8 ± 1.0% (range 0.1–3.6) and acid soluble mercury 0.9 ± 0.5% (range 0.2–2.1). Although, the total mercury content is similar in a reference sample and in the tsunami sediments, the highly toxic organomercury fraction contribution is higher in the latter. The results were compared with chemical and sedimentological properties of the sediments but no significant correlations were obtained between them.     

Initiation and development of pull-apart basins with Riedel shear mechanism: insights from scaled clay experiments

Typical pull-apart structures were created in scaled clay experiments with a pure strike-slip geometry (Riedel type experiments). A clay slab represents the sedimentary cover above a strike-slip fault in the rigid basement. At an early stage of the development of the deformation zone, synthetic shear fractures (Riedel shears) within the clay slab display dilatational behaviour. With increasing basal displacement the Riedel shears rotate and open further, developing into long, narrow and deep troughs. The shear displacement and the low angle with the prescribed principal basal fault set them apart from tension gashes. At a more evolved stage, synthetic segments (Y-shears) parallel to the basal principal fault develop and accommodate progressive strike-slip deformation. The Y-shears connect the tips of adjacent troughs developed from the earlier Riedel shears, resulting in the typical rhomb-shaped structures characteristic for pull-apart basins. The Strait of Sicily rift zone, with major strike-slip systems being active from the Miocene to the Present, comprises pull-apart basins at different length scales, for which the structural record suggests development by a mechanism similar to that observed in our experiments.     

Redbed-type gold mineralisation, Kupferschiefer, south-west Poland

A new type of gold mineralisation containing minor amounts of platinum and palladium has been found proximal to the secondary redox interface located below the Cu-Ag Kupferschiefer orebody of the Polkowice-Sieroszowice mine in the south-western part of the Lubin-Sieroszowice district, Poland. This deposit can be classified as redbed-type gold. Our study shows that gold, platinum and palladium occur in secondary red-coloured sections of the basal Zechstein sedimentary rocks and in the uppermost Weissliegendes sandstone. Noble metal mineralisation occurs within an average interval of 0.22 m, which lies directly below the copper ores. The average grade of the horizon is 2.25 ppm Au, 0.138 ppm Pt and 0.082 ppm Pd with a metal content of several tens of tonnes of gold. A transition zone has been recognised between the gold-bearing horizon and the copper deposit. This transition zone is characterised by the presence of low grades of copper (<0.2 wt%) and elevated gold contents (>0.5 ppm). Native gold accompanied by electrum, mercury-bearing gold, haematite, covellite, chalcocite, bornite and chalcopyrite has been identified in the gold-bearing horizon. In some sections, Pd-arsenides, tetra-auricupride, Co-arsenides, clausthalite, tennantite, digenite, yarrowite, spionkopite and galena have also been noted.     

Wrench tectonics flip at oblique subduction. A model from New Zealand

In eastern North Island New Zealand, oblique subduction of the Pacific Plate beneath the Australian Plate is associated with strain partitioning. Dextral along-strike component of displacement occurred first at Early Miocene major faults within the eastern fore-arc domain. These faults were active from Early Miocene to Pliocene times. Since Pliocene times, most of the movement occurs at western faults such as the Wellington Fault. The latter joins the back-arc domain to the north. The jump of wrench faulting is related to the oblique opening of the back-arc domain. Both phenomena are impeded southwards by the Hikurangi oceanic plateau entering the subduction zone. To cite this article: J. Delteil et al., C. R. Geoscience 335 (2003).     

Methodical approach to distribution of epilithic and drifting algae communities in a French subalpine river: Inferences on water quality assessment

In a sub-alpine river, the Asse, with an unpredictable discharge regime, chlorophyll, density and taxonomic diversity of both drifting and periphytic communities were studied from a methodical approach. The investigations based on stamping two close cross-sections to know their spatial distributions in a heterogeneous bed substrate showed a heterogeneous pattern of colonization mainly influenced by hydrological variables as the current velocity, the size of the substrata (gravel-pebble-boulder). For the drifting algae, mainly composed with benthic species temporarily unhooked to the substrata, the heterogeneity of the distribution was reduced in fast flow which induced a mixing of the whole mass of water. For the periphyton, some results indicated that the greatest diversity and the highest chlorophyll concentration were found on pebble substratum where the current velocity was moderate. These results have also shown that the classical methods used to day for investigations were inadequate for most Mediterranean rivers. It was really difficult to estimate the water quality from classical index created for use in regular large plain rivers.     

Remote sensing detection of atmospheric pollutants by differential absorption LIDAR 510M/SODAR PA2 mobile system

Summary Air pollution problem in the Czech Republic is very complex due to large number of factors as turbulent dispersion and chemical reactions concurring in the status of the PBL. For this 3D distribution of pollutants is a key information that cannot be given by conventional monitoring stations. Combined use of DIAL lidar and sodar can give access to such information. Case studies of air pollutants transport are presented using 3D concentration fields of NO₂ and ozone measured by lidar and meteorological conditions monitored by Doppler Sodar.