The H<Subscript>2</Subscript>O solubility of alkali basaltic melts: an experimental study

Experiments were conducted to determine the water solubility of alkali basalts from Etna, Stromboli and Vesuvius volcanoes, Italy. The basaltic melts were equilibrated at 1,200°C with pure water, under oxidized conditions, and at pressures ranging from 163 to 3,842 bars. Our results show that at pressures above 1 kbar, alkali basalts dissolve more water than typical mid-ocean ridge basalts (MORB). Combination of our data with those from previous studies allows the following simple empirical model for the water solubility of basalts of varying alkalinity and fO₂ to be derived: \textH ₂ \textO( \textwt% ) = \text H ₂ \textO_\textMORB ( \textwt% ) + ( 5.84 ×10 ^{- 5} *\textP - 2.29 ×10 ^{- 2} ) ×( \textNa₂ \textO + \textK₂ \textO )( \textwt% ) + 4.67 ×10 ^{- 2} ×\Updelta \textNNO - 2.29 ×10 ^{- 1} {\text{H}}_{ 2} {\text{O}}\left( {{\text{wt}}\% } \right) = {\text{ H}}_{ 2} {\text{O}}_{\text{MORB}} \left( {{\text{wt}}\% } \right) + \left( {5.84 \times 10^{ - 5} *{\text{P}} - 2.29 \times 10^{ - 2} } \right) \times \left( {{\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}}} \right)\left( {{\text{wt}}\% } \right) + 4.67 \times 10^{ - 2} \times \Updelta {\text{NNO}} - 2.29 \times 10^{ - 1} where H₂O_MORB is the water solubility at the calculated P, using the model of Dixon et al. (1995). This equation reproduces the existing database on water solubilities in basaltic melts to within 5%. Interpretation of the speciation data in the context of the glass transition theory shows that water speciation in basalt melts is severely modified during quench. At magmatic temperatures, more than 90% of dissolved water forms hydroxyl groups at all water contents, whilst in natural or synthetic glasses, the amount of molecular water is much larger. A regular solution model with an explicit temperature dependence reproduces well-observed water species. Derivation of the partial molar volume of molecular water using standard thermodynamic considerations yields values close to previous findings if room temperature water species are used. When high temperature species proportions are used, a negative partial molar volume is obtained for molecular water. Calculation of the partial molar volume of total water using H₂O solubility data on basaltic melts at pressures above 1 kbar yields a value of 19 cm³/mol in reasonable agreement with estimates obtained from density measurements.     

ESR,U-series and paleomagnetic dating of Gigantopithecus fauna from Chuifeng Cave,Guangxi, southern China

Several Gigantopithecus faunas associated with taxonomically undetermined hominoid fossils and/or stone artifacts are known from southern China. These faunas are particularly important for the study of the evolution of humans and other mammals in Asia. However, the geochronology of the Gigantopithecus faunas remains uncertain. In order to solve this problem, a program of geochronological studies of Gigantopithecus faunas in Guangxi Province was recently initiated. Chuifeng Cave is the first studied site, which yielded 92 Gigantopithecus blacki teeth associated with numerous other mammalian fossils. We carried out combined ESR/U-series dating of fossil teeth and sediment paleomagnetic studies. Our ESR results suggest that the lower layers at this cave can be dated to 1.92 ± 0.14 Ma and the upper layers can be dated to older than 1.38 ± 0.17 Ma. Correlation of the recognized magnetozones to the geomagnetic polarity timescale was achieved by combining magnetostratigraphic, biostratigraphic and ESR data. The combined chronologies establish an Olduvai subchron (1.945–1.778 Ma) for the lowermost Chuifeng Cave sediments. We also analyzed the enamel δ¹³C values of the Gigantopithecus faunas. Our results show that southern China was dominated by C₃ plants during the early Pleistocene and that the Gigantopithecus faunas lived in a woodland-forest ecosystem.     

Revisiting the thermodynamics of hardening plasticity for unsaturated soils

A thermodynamically consistent extension of the constitutive equations of saturated soils to unsaturated conditions is often worked out through the use of a unique ‘effective’ interstitial pressure, accounting equivalently for the pressures of the saturating fluids acting separately on the internal solid walls of the pore network. The natural candidate for this effective interstitial pressure is the space averaged interstitial pressure. In contrast experimental observations have revealed that, at least, a pair of stress state variables was needed for a suitable framework to describe stress–strain–strength behaviour of unsaturated soils. The thermodynamics analysis presented here shows that the most general approach to the behaviour of unsaturated soils actually requires three stress state variables: the suction, which is required to describe the invasion of the soil by the liquid water phase through the retention curve; two effective stresses, which are required to describe the soil deformation at water saturation held constant. However a simple assumption related to the plastic flow rule leads to the final need of only a Bishop-like effective stress to formulate the stress–strain constitutive equation describing the soil deformation, while the retention properties still involve the suction and possibly the deformation. Commonly accepted models for unsaturated soils, that is the Barcelona Basic Model and any approach based on the use of an effective averaged interstitial pressure, appear as special extreme cases of the thermodynamic formulation proposed here.     

Geophysical characterisation of karstic networks – Application to the Ouysse system (Poumeyssen,France)

In the framework of the management of karstic aquifers, geophysical reconnaissance can be used to locate conduits and caves, and to characterise the surrounding limestone matrix. Suitable characterisation of heterogeneities in the karstic environment is, however, challenging for ground-based geophysical methods. The present article describes the results, and evaluates the response and accuracy of combined geophysical measurements carried out at the Poumeyssen test site in France, involving electrical resistivity imaging (ERI), magnetic resonance sounding (MRS), “mise-à-la-masse” electrical mapping, and seismic tomography. This site provides the opportunity to study a relatively wide, shallow, water-filled conduit whose location and shape are known from topographic work carried out by cave divers. Seismic and MRS provided the exact location and width of the conduit, to within a few meters. The seismic and electrical data suggest that the limestone medium surrounding the conduit is not homogeneous.     

New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

Estimating aquifer thickness using multiple pumping tests

A method to estimate aquifer thickness and hydraulic conductivity has been developed, consisting of multiple pumping tests. The method requires short-duration pumping cycles on an unconfined aquifer with significant seasonal water-table fluctuations. The interpretation of several pumping tests at a site in India under various initial conditions provides information on the change in hydrodynamic parameters in relation to the initial water-table level. The transmissivity linearly decreases compared with the initial water level, suggesting a homogeneous distribution of hydraulic conductivity with depth. The hydraulic conductivity is estimated from the slope of this linear relationship. The extrapolation of the relationship between transmissivity and water level provides an estimate of the aquifer thickness that is in good agreement with geophysical investigations. The hydraulically active part of the aquifer is located in both the shallow weathered and the underlying densely fractured zones of the crystalline basement. However, no significant relationship is found between the aquifer storage coefficient and initial water level. This new method contributes to filling the methodological gap between single pumping tests and hydraulic tomography, in providing information on the variation of the global transmissivity according to depth. It can be applied to any unconfined aquifer experiencing large seasonal water-table fluctuations and short pumping cycles.     

Genesis of the Dordogne (France) high-purity silica placers

This article describes the formation of the principal French high-purity silica placer (source for electrometallurgy of silicon and ferrosilicon), the Boudeau deposit in Dordogne, and of one of its subordinate deposits, the Pays Brûlé deposit. Boudeau has always been considered to be a colluvial deposit, formed in a trap produced by extensional tectonism. The present work suggests a new genetic interpretation, based on a combined study of the deposits and their underlying rocks. It shows that the quartz gravel deposits, laid down by stream flow within braided channels, were reworked by karstic progressive sinking, and that the mechanism responsible for the increase in the thickness of the economic formations is cryptokarstic corrosion. This undercovers weathering process, which involves dissolution of karstifiable rocks (oolitic and bioclastic limestones) at their interface with a permeable, non-karstifiable cover composed of chemically pure quartz gravels in a sandy-argillaceous matrix. A typological study of the gravels provides a basis for tackling the problem of their origin and their purity. They seem to be derived mainly from the synmetamorphic quartz mobilisates of the stripped metamorphic units (the lower and upper gneiss units forming the western edge of the Massif Central). Lastly, a dynamic model is suggested for the genesis of the high-purity silica deposits of Dordogne.