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.     

Contribution to a geodynamic reconstruction of the Anti-Atlas (Morocco) during Pan-African times with the emphasis on inversion tectonics and metallogenic activity at the Precambrian–Cambrian transition

New geochronological analyses (U–Pb SIMS zircon ages) have yielded ages of 552 ± 5 Ma for the Bou Madine rhyolitic dome (Ougnat, eastern Anti-Atlas), 543 ± 9 Ma for the Tachkakacht rhyolitic dyke (Saghro–Imiter, eastern Anti-Atlas), and 531 ± 5 Ma for the Aghbar trachytic sill (Bou Azzer, central Anti-Atlas). Inherited zircon cores from the Aghbar trachytic sill and from the Bou Madine rhyolitic dome have been shown to be of Statherian age (ca. 1600–1800 Ma) and Palæoproterozoic (>2100 Ma) age, respectively, suggesting that a significantly older protolith underlies the Pan-African rocks in the Central and Eastern Anti-Atlas. Granodiorites and rhyolites from the Saghro–Imiter area have similar low ⁸⁷Sr/⁸⁶Sr (0.702–0.706) and ¹⁴³Nd/¹⁴⁴Nd (0.5116–0.5119) initial ratios, suggesting a mixture of mantle and lower crust sources. This can also be inferred from the low ¹⁸⁷Os/¹⁸⁸Os ratios obtained on pyrite crystals from the rhyolites.A recently published lithostratigraphic framework has been combined with these new geochemical and geochronological data, and those from the literature to produce a new reconstruction of the complex orogenic front that developed at the northern edge of the Eburnian West African craton during Pan-African times. Three Neoproterozoic magmatic series can be distinguished in the Anti-Atlas belt, i.e., high-K calc-alkaline granites, high-K calc-alkaline to shoshonitic rhyolites and andesites, and alkaline-shoshonitic trachytes and syenites, which have been dated at 595–570, 570–545 and 530 Ma, respectively.The accretion of the Pan-African Anti-Atlas belt to the West African super continent (WAC) was a four-stage event, involving extension, subduction, moderate collision and extension. The calc-alkaline magmatism of the subduction stage was associated with large-scale base metal and gold mineralisation. Metallogenic activity was greatest during the final extensional stage, at the Precambrian–Cambrian boundary. It is characterised by world-class precious metal deposits, base–metal porphyry and SEDEX-type occurrences.     

Two cation exchange models for direct and inverse modelling of solution major cation composition in equilibrium with illite surfaces

Na/K, Na/Ca and Na/Mg exchange isotherms were performed on the fine fraction (<2 μm) of Imt-2 illite samples at a total normality of about 0.005 mol/L in anionic chloride medium. The derived selectivity coefficients for Na/K, Na/Ca and Na/Mg were found to vary as a function of the exchanger composition and compared well with the data collected in the literature for similar experimental conditions. Two models were built to reproduce the data: the first was a multi(2)-site model with constant Gaines and Thomas selectivity coefficients; the second was a one-site model taking into account surface species activity coefficients. The results of the models were in rather good agreement with both our data and literature data. The multi-site model proved to be efficient in predicting the exchanger composition as a function of the Na/Ca/Mg/K concentrations in solution, whereas the one-site model proved to be a better approach to derive the Na/Ca/Mg/K concentrations in solution based on the knowledge of the exchanger composition and the total normality of the solution. The interest of this approach is illustrated by the need for major cation solute concentration predictions in compacted clay for the characterization of nuclear deep disposal host rock repositories.     

Draa Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcanogenic massive sulphide deposit in a Hercynian sediment-dominant terrane

Draa Sfar is a Visean, stratabound, volcanogenic massive sulphide ore deposit hosted by a Hercynian carbonaceous, black shale-rich succession of the Jebilet terrane, Morocco. The ore deposit contains 10 Mt grading 5.3 wt.% Zn, 2 wt.% Pb, and 0.3 wt.% Cu within two main massive sulphides orebodies, Tazakourt (Zn-rich) and Sidi M'Barek (Zn–Cu rich). Pyrrhotite is by far the dominant sulphide (70 to 95% of total sulphides), sphalerite is fairly abundant, chalcopyrite and galena are accessory, pyrite, arsenopyrite and bismuth minerals are rare. Pyrrhotite is monoclinic and mineralogical criteria indicate that it is of primary origin and not formed during metamorphism. Its composition is very homogeneous, close to Fe₇S₈, and its absolute magnetic susceptibility is 2.10^− 3 SI/g. Ar–Ar dating of hydrothermal sericites from a coherent rhyolite flow or dome within the immediate deposit footwall indicates an age of 331.7 ± 7.9 Ma for the Draa Sfar deposit and rhyolite volcanism.The Draa Sfar deposit has undergone a low-grade regional metamorphic event that caused pervasive recrystallization, followed by a ductile–brittle deformation event that has locally imparted a mylonitic texture to the sulphides and, in part, is responsible for the elongated and sheet-like morphology of the sulphide orebodies. Lead isotope data fall into two compositional end-members. The least radiogenic end-member, (²⁰⁶Pb/²⁰⁴Pb = 18.28), is characteristic of the Tazakourt orebody, whereas the more radiogenic end-member (²⁰⁶Pb/²⁰⁴Pb  18.80) is associated with the Sidi M'Barek orebody, giving a mixing trend between the two end-members. Lead isotope compositions at Draa Sfar testify to a significant continental crust source for the base metals, but are different than those of the Hajar and South Iberian Pyrite Belt VMS deposits.The abundance of pyrrhotite versus pyrite in the orebodies is attributed to low fO₂ conditions and neither a high temperature nor a low aH₂S (below 10^− 3) is required. The highly anoxic conditions required to stabilize pyrrhotite over pyrite are consistent with formation of the deposit within a restricted, sediment-starved, anoxic basin characterized by the deposition of carbonaceous, pelagic sediments along the flank of a rhyolitic flow-dome complex that was buried by pelitic sediments. Deposition of sulphides likely occurred at and below the seafloor within anoxic and carbonaceous muds.Draa Sfar and other Moroccan volcanogenic massive sulphide deposits occur in an epicontinental volcanic domain within the outer zone of the Hercynian belt and formed within a sedimentary environment that has a high pelagic component. In spite of the diachronous emplacement between the IPB deposits (late Devonian to Visean) and Moroccan deposits (Dinantian), all were formed around 340 ± 10 Ma following a major phase of the Devonian compression.     

Disproportionation of Fe<Superscript>2+</Superscript> in Al-free silicate perovskite in the laser heated diamond anvil cell as recorded by electron probe microanalysis of oxygen

Experimental evidence is reported for Fe²⁺ disproportionation in Al-free perovskite (Pv), when submitted to large temperature gradients (i.e., under off-equilibrium conditions) in a laser heated diamond anvil cell (LHDAC). To enable this effect, the experimental procedure was designed to produce large radial and axial temperature gradients. In the Pv and ferropericlase (Fp) assemblage synthesized after dissociation of natural olivine, the three chemical states of iron (i.e., Fe⁰, Fe²⁺ and Fe³⁺) could be evidenced by electron probe microanalysis (EPMA), through variations of oxygen contents attached to the Fe cations. Despite inherent difficulties for determination of O-contents and Fe³⁺/ΣFe ratios using EPMA, we recorded significant changes in iron oxidation state across the laser-heated strip. These changes are correlated with variations in composition for the major elements (Fe, Mg, and Si), which evidences that the Pv/Fp assemblage experienced large segregation under the strong temperature gradients. Grains of metallic iron were detected in parts of the laser-heated strip coexisting with a Pv phase with Fe/(Mg + Fe) = 6 at% and most of its iron as Fe³⁺. This Fe²⁺-disproportionation reaction involves insertion of Fe³⁺-defects in the Pv lattice. This Fe³⁺-bearing Pv phase is presumably unstable and decomposes into a mineral assemblage including magnesioferrite, which is detected at the border of the laser-heated strip.     

Thermal Conductivity of Argillaceous Rocks: Determination Methodology Using In Situ Heating Tests

This study focuses on the characterisation of thermal conductivity for three potential host rocks for radioactive waste disposal. First, the heat conduction process is reviewed on the basis of an analytical solution and key aspects related to anisotropic conduction are discussed. Then the existing information on the three rocks is summarised and a broad uncertainty range of thermal conductivity is estimated based on the mineralogical composition. Procedures to backanalyse the thermal conductivity on the basis of in situ heating tests are assessed and a methodology is put forward. Finally, this methodology is used to estimate the impact of experimental uncertainties and applied to the four in situ heating tests. In the three potential host rocks, a clear influence of the bedding planes was identified and anisotropic heat conduction was shown to be necessary to interpret the observed temperature field. Experimental uncertainties were also shown to induce a larger uncertainty on the anisotropy ratio than on the equivalent thermal conductivity defined as the geometric mean of the thermal conductivity in the three principal directions.     

Does sediment resuspension by storms affect the fate of polychlorobiphenyls (PCBs) in the benthic food chain? Interactions between changes in POM characteristics, adsorption and absorption by the mussel Mytilus galloprovincialis

Environmental parameters and gross sedimentation rates (GSR) were monitored at a fixed site located in the Bay of Banyuls-sur-Mer (NW Mediterranean), between March 1997 and April 1998, together with the main biochemical characteristics of both sedimenting and sedimented particulate organic matter (POM). Three storms which occurred during this time period resulted in natural sediment resuspension. This is indicated by the corresponding increase in GSR and a decrease in the enzymatically hydrolysable amino acids/totally hydrolysable amino acids ratio (EHAA/THAA), within the sedimenting POM. Only the strongest storm resulted in (1) a transitory increase in fine-grained particles, (2) concomitant increases in organic carbon, carbohydrates, lipids and THAA, and (3) a decrease in the EHAA/THAA ratio in surficial sediments. For most of the assayed parameters, the values recorded after the December 1997 storm corresponded to extremes for the whole period under study. This emphasises the role of storms in controlling the characteristics of sedimented and sedimenting POM.Ten sediment types, with contrasting biochemical characteristics, were selected for experiments; these were based on the results of the monitoring survey and were used during adsorption and absorption experiments involving ¹⁴C tetrachlorobiphenyl (TCB). Adsorption rates differed significantly between the sediment types, but did not correlate with any of the assayed biochemical parameters. Absorption efficiency by the mussel Mytilus galloprovincialis also differed between the sediment types; it correlated positively with all the assayed biochemical parameters, except lipids. Comparison between the magnitudes of the increase in GSR, together with the decrease in absorption efficiency during resuspension events, suggests that resuspension tends to enhance the transfer of organic pollutants in the benthic food chain.     

Characterizing and Locating Very Weak (−2.2 ≥ M L ≥ −3.4) Induced Seismicity in Unstable Sandstone Cliffs by Nanoseismic Monitoring

Unloaded natural rock masses are known to generate seismic signals (Green et al., 2006; Hainzl et al., 2006; Husen et al., 2007; Kraft et al., 2006). Following a 1,000 m³ mass failure into the Mediterranean Sea, centimeter-wide tensile cracks were observed to have developed on top of an unstable segment of the coastal cliff. Nanoseismic monitoring techniques (Wust-Bloch and Joswig, 2006; Joswig, 2008), which function as a seismic microscope for extremely weak seismic events, were applied to verify whether brittle failure is still generated within this unconsolidated sandstone mass and to determine whether it can be detected. Sixteen days after the initial mass failure, three small-aperture sparse arrays (Seismic Navigation Systems-SNS) were deployed on top of this 40-m high shoreline cliff. This paper analyzes dozens of spiky nanoseismic (?2.2 ≥ M _L ≥ ?3.4) signals recorded over one night in continuous mode (at 200 Hz) at very short slant distances (3–67 m). Waveform characterization by sonogram analysis (Joswig, 2008) shows that these spiky signals are all short in duration (>0.5 s). Most of their signal energy is concentrated in the 10–75 Hz frequency range and the waveforms display high signal similarity. The detection threshold of the data set reaches M _L ?3.4 at 15 m and M _L ?2.7 at 67 m. The spatial distribution of source signals shows 3-D clustering within 10 m from the cliff edge. The time distribution of M _L magnitude does not display any decay pattern of M _L over time. This corroborates an unusual event decay over time (modified Omori’s law), whereby an initial quiet period is followed by regained activity, which then fades again. The polarization of maximal waveform amplitude was used to estimate spatial stress distribution. The orientation of ellipses displaying maximal signal energy is consistent with that of tensile cracks observed in the field and agrees with rock mechanics predictions. The M _L– surface rupture length relationship displayed by our data fits a constant-slope extrapolation of empirical data collected by Wells and Coppersmith (1994) for normal fault features at much larger scale. Signal characterization and location as well as the absence of direct anthropogenic noise sources near the monitoring site, all indicate that these nanoseismic signals are generated by brittle failure within the top section of the cliff. The atypical event decay over time that was observed suggests that the cliff material is undergoing post-collapse bulk strain accommodation. This feasibility study demonstrates the potential of nanoseismic monitoring in rapidly detecting, locating and analyzing brittle failure generated within unconsolidated material before total collapse occurs.     

Sismique marine haute résolution 3D : un nouvel outil de reconnaissance à destination de la communauté scientifique

This note presents the first results of the development of 3D high-resolution marine seismic method designed for scientific application. A particular attention was paid to the realisation of an operational system to be in agreement with the expected goals in term of acquisition and processing. To cite this article: Y. Thomas et al., C. R. Geoscience 336 (2004).     

Climates of the Earth and Cryosphere Evolution

The interrelationship between the cryosphere and the climate is not always operating on Earth over a scale of billions or millions of years. Indeed, most of the time, the Earth is regulated at temperatures such that no ice sheet exists. Nevertheless, it is very fruitful to understand the conditions where and when ice sheets were triggered during the Earth??s history. This paper deals with the paleoclimate and the cryosphere in the last 4.6 Ga and explains the different processes that make the climate of the first 4 billion years warm despite the weaker solar luminosity. We also describe the more recent evolution in the last 65 million years when a global decrease in atmospheric CO₂ from around 4 PAL to 1 PAL was associated with a global cooling (1 PAL present atmospheric level = 280 ppm). It is in this context that the Quaternary occurred characterized by low atmospheric CO₂ and the presence of two perennial ice sheets in Greenland and Antarctica. The last million years are certainly the most documented since direct and reliable CO₂ measurements are available. They are characterized by a complex climate/cryosphere dynamics leading to oscillations between long glacial periods with four ice sheets and shorter ones with only two ice sheets (interglacial). We are currently living in one of those interglacials, generally associated with a CO₂ level of 280 ppm. Presently, anthropogenic activities are seriously perturbing the carbon cycle and the atmospheric CO₂ content and therefore the climate. The last but not least question raised in this paper is to investigate whether the anthropogenic perturbation may lead to a melting of the ice sheets.