Nouvelles données sur le téphra de Sarliève et le téphra CF7, marqueurs chrono-stratigraphiques de Grande Limagne (Massif central,France)

A trachytic tephra, discovered in the ancient lake of Sarliève, ‘Grande Limagne’, has been dated using the thermoluminescence technique. The obtained age, 16±4 ka ($\text{2}\text{σ}$), is older than that of the trachytic volcanoes of the Cha??ne des Puys, the ashes of which have already been locally recognised in the region. Its analysis confirms its originality. In the course of the comparisons made to search for its spring, it appears that the wide-dispersion tephra CF7, beforehand correlated by hypothesis to the Puy de Clierzou, probably originates from the Kilian crater or the Puy de Vasset. To cite this article: D. Miallier et al., C. R. Geoscience 336 (2004).     

Biradical character of D-rich carriers in the insoluble organic matter of carbonaceous chondrites: A relic of the protoplanetary disk chemistry

The insoluble organic matter (IOM) of the Orgueil meteorite contains deuterium-rich radicals detectable by Electron Paramagnetic Resonance (EPR) techniques (Gourier et al., 2008). However the structure of these deuterium carriers remains poorly constrained. In this work, their electronic structure is deduced from the measurement of the spin states S by transient nutation in pulsed-EPR. It is shown that these deuterium-rich radicals are dominated by biradicaloids (species with S = 0 ground state and thermally accessible S = 1 state) and biradicals (species with S = 1 ground state) representing ∼61% and ∼31% of the radicals in the IOM of Orgueil, respectively, while single radicals (S = 1/2) contribute only to ∼8%. This is definitely different from mature terrestrial IOMs, which are known to contain almost exclusively S = 1/2 radicals. A structural model is proposed, whereby the occurrence of dominant biradicaloids and biradicals is the direct consequence of the structure of the IOM, made of a network of small aromatic moieties linked by branched and short aliphatic units. This implies that the formation of stable biradicaloids and biradicals by C-H breaking and their deuterium enrichment are produced after the formation of the IOM in the primitive solar system. These results reinforce the idea that the formation of the IOM and the deuterium-rich hotspots are the product of ion chemistry in the solar disk.     

Formation of U-depleted rhyolite from a basanite at El Hierro, Canary Islands

Phonolite and trachyte are the felsic magmas of the alkaline magma suites, which characterize the Canary Islands. The October 2011 submarine eruption off El Hierro, the westernmost island, nevertheless, produced a small volume of rhyolitic magma. The rhyolite occurred as highly vesicular, white coloured pumices enveloped in and mingled with darker coloured basanitic pumice. The basanitic pumice is relatively crystal poor with a few euhedral olivines (mostly Fo_77–79), clinopyroxenes and Fe-rich spinels, whereas very rare olivine of same composition is found together with equally rare Fe-sulphide and FeTi-rich oxides in the rhyolite. The Fe–Mg exchange equilibrium in the oxides permits to calculate an equilibrium temperature of 970–890 °C for the rhyolite, in agreement with quartz-melt equilibrium at ca. 930 °C. A striking mineralogical feature of the rhyolite is the presence of rounded to contorted grains of milky quartz, which are xenocrysts incorporated and partly dissolved into the magma. Analyses of residual volatile concentrations in the glasses show that the rhyolite melt was highly degassed, whereas the basanitic glass still has important halogen concentrations. Trace element patterns of the mafic glasses and their elevated incompatible element concentrations are typical of the western Canary Island basanites. In contrast, the trace element composition of the rhyolite shows surprisingly low concentrations for all elements except the most incompatible ones (e.g. Rb, Ba, K and Th). All other measured LILE, HFSE and REE have significantly lower concentration than the basanitic counterpart that can be explained by fractionation of accessory phases (1 % apatite, 1 % sphene and 0.1 % zircon). Surprisingly, low U concentration is presumably related to elevated oxygen fugacity in the rhyolite, causing U to be in a hexavalent state, and fluxing of F-rich gas leading to volatilization of UF₆, known to emanate at low temperature. The results suggest that a gas-rich basanitic melt remobilized a small volume of stagnant rhyolitic melt formed by incorporation of approximately 10 % quartz-rich sediment into a late differentiate of trachytic composition. Sediments at the interface of an old oceanic crust adjacent to a continental shield and younger volcanic island are likely to act as magma traps were sediment assimilation may alter the mantle-derived magma composition. Quartz assimilation thus explains the production of rhyolite magma in a volcanic island characterized by an alkaline magma series from primitive basanites to trachytes.     

Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

Extrusion movements of a tunnel head reinforced by finite length bolts—a closed‐form solution using homogenization approach

An analytical model on the general behaviour of a tunnel head, reinforced by finite length bolts is proposed. This model is based on the homogenization method and spherical symmetry assumption. Despite its simplicity, and in consequence its limits of validity, it does allow a quick estimation of the key design parameters: frontal displacement, extension of decompressed zone, ground stresses and bolt tension, and constitutes thereby a very useful and handy tool for design engineers. In particular, the influence of the reinforcement length, as well as other important design parameters, are studied by the proposed model. The charts resulting from the parametric studies are directly applicable. Otherwise, the comparison to a 3D numerical model is also presented in this paper. The first results provide the validation of the analytical solution, at least in terms of average extrusion movements. Copyright © 2000 John Wiley & Sons, Ltd.     

Establishing constraints on groundwater ages with Cl,C, H,and noble gases: A case study in the eastern Paris basin,France

Groundwaters from the Tithonian/Kimmeridgian, Oxfordian and Upper Dogger aquifers, within the eastern part of the Paris basin (France), were characterised using ³H, ¹⁴C and ³⁶Cl, and noble gases tracers, to evaluate their residence times and determine their recharge period. This information is an important prerequisite to evaluating the confinement properties of the Callovo-Oxfordian clay formation sandwiched between the Oxfordian aquifer and the Dogger aquifer, currently being investigated by the French nuclear waste management agency (Andra) for radioactive waste disposal. Data presented in this paper are used to test 4 hypotheses.     

Well placement optimization with the covariance matrix adaptation evolution strategy and meta-models

The amount of hydrocarbon recovered can be considerably increased by finding optimal placement of non-conventional wells. For that purpose, the use of optimization algorithms, where the objective function is evaluated using a reservoir simulator, is needed. Furthermore, for complex reservoir geologies with high heterogeneities, the optimization problem requires algorithms able to cope with the non-regularity of the objective function. In this paper, we propose an optimization methodology for determining optimal well locations and trajectories based on the covariance matrix adaptation evolution strategy (CMA-ES) which is recognized as one of the most powerful derivative-free optimizers for continuous optimization. In addition, to improve the optimization procedure, two new techniques are proposed: (a) adaptive penalization with rejection in order to handle well placement constraints and (b) incorporation of a meta-model, based on locally weighted regression, into CMA-ES, using an approximate stochastic ranking procedure, in order to reduce the number of reservoir simulations required to evaluate the objective function. The approach is applied to the PUNQ-S3 case and compared with a genetic algorithm (GA) incorporating the Genocop III technique for handling constraints. To allow a fair comparison, both algorithms are used without parameter tuning on the problem, and standard settings are used for the GA and default settings for CMA-ES. It is shown that our new approach outperforms the genetic algorithm: It leads in general to both a higher net present value and a significant reduction in the number of reservoir simulations needed to reach a good well configuration. Moreover, coupling CMA-ES with a meta-model leads to further improvement, which was around 20% for the synthetic case in this study.     

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.     

In Situ Determination of Au and Cu in Natural Pyrite by Near‐Infrared Femtosecond Laser Ablation‐Inductively Coupled Plasma‐Quadrupole Mass Spectrometry: No Evidence for Matrix Effects

Gold and copper concentrations were determined in natural pyrite by near‐infrared femtosecond LA‐ICP‐QMS, using both sulfide reference materials (pyrrhotite Po‐726 and in‐house natural chalcopyrite Cpy‐RM) and NIST SRM 610 as external calibrators. Firstly, using NIST SRM 610 as the external calibrator, we calculated the Au concentration in Po‐726 and the Cu concentration in Cpy‐RM. The calculated concentration averages for Au and Cu were similar to the values published for Po‐726 and Cpy‐RM, respectively. Secondly, we calculated Au and Cu concentrations taking NIST SRM 610 as an unknown sample and using Po‐726 and Cpy‐RM as external calibrators. Again, the average values obtained closely reflected the preferred concentrations for NIST SRM 610. Finally, we calculated Au and Cu concentrations in natural pyrite using sulfide and silicate reference materials as external calibrators. In both cases, calculated concentrations were very similar, independent of the external calibrator used. The aforementioned data, plus the fact that we obtained very small differences in relative sensitivity values (percentage differences are between 5% and 17% for ⁵⁷Fe, ⁶³Cu and ¹⁹⁷Au) on analyses of silicate and sulfide RMs, indicate that there were no matrix effects related to the differences in material composition. Thus, it is possible to determine Au and Cu in natural sulfides using NIST silicate glasses as an external calibrator.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.