Occurence of abundant diradicaloid moieties in the insoluble organic matter from the Orgueil and Murchison meteorites: a fingerprint of its extraterrestrial origin?

The highly aromatic structure of the macromolecular organic matter (OM) of the Murchison and Orgueil meteorites was recently shown to contain free organic radicals which are concentrated in micro-regions in contrast with terrestrial samples which always show an homogeneous distribution of radicals. An additional signature is revealed, in the present study, by the evolution of the radical concentration with temperature. Whereas in terrestrial samples, this concentration is independent of temperature (Curie magnetism), a significant increase is observed above 150 K in the two meteorites. Based on the electronic structure of organic radicals, calculated by Extended Hückel and Density Functional methods, this behavior was assigned to the occurrence of diradicaloid moieties hosted by aromatic structures of 10 to 15 rings and having a quinoidal structure. They represent 40 and 25% of the total radicals in Orgueil and Murchison, respectively. The search for the cosmochemical interpretation of this unique observation should open a new field of experimental investigations.     

Comparison of dissolved and particulate arsenic distributions in shallow aquifers of Chakdaha, India, and Araihazar, Bangladesh

Background  

The origin of the spatial variability of dissolved As concentrations in shallow aquifers of the Bengal Basin remains poorly understood. To address this, we compare here transects of simultaneously-collected groundwater and aquifer solids perpendicular to the banks of the Hooghly River in Chakdaha, India, and the Old Brahmaputra River in Araihazar, Bangladesh.     

Microstructural Inhomogeneity and Mechanical Anisotropy Associated with Bedding in Rothbach Sandstone

This study present the result of conventional triaxial tests conducted on samples of Rothbach sandstone cored parallel, oblique (at 45 degrees) and perpendicular to the bedding at effective pressures ranging from 5 to 250 MPa. Mechanical and microstructural data were used to determine the role of the bedding on mechanical strength and failure mode. We find that samples cored at 45 degrees to the bedding yield at intermediate level of differential stress between the ones for parallel and perpendicular samples at all effective pressures. Strain localization at high confining pressure (i.e., in the compactive domain) is observed in samples perpendicular and oblique to the bedding but not in samples cored parallel to the bedding. However, porosity reduction is comparable whether compactive shear bands, compaction bands or homogeneous cataclastic flow develop. Microstructural data suggest that (1) mechanical anisotropy is controlled by a preferred intergranular contact alignment parallel to the bedding and that (2) localization of compaction is controlled by bedding laminations and grain scale heterogeneity, which both prevent the development of well localized compaction features.     

Quality assessment of GPS reprocessed terrestrial reference frame

The International GNSS Service (IGS) contributes to the construction of the International Terrestrial Reference Frame (ITRF) by submitting time series of station positions and Earth Rotation Parameters (ERP). For the first time, its submission to the ITRF2008 construction is based on a combination of entirely reprocessed GPS solutions delivered by 11 Analysis Centers (ACs). We analyze the IGS submission and four of the individual AC contributions in terms of the GNSS frame origin and scale, station position repeatability and time series seasonal variations. We show here that the GPS Terrestrial Reference Frame (TRF) origin is consistent with Satellite laser Ranging (SLR) at the centimeter level with a drift lower than 1 mm/year. Although the scale drift compared to Very Long baseline Interferometry (VLBI) and SLR mean scale is smaller than 0.4 mm/year, we think that it would be premature to use that information in the ITRF scale definition due to its strong dependence on the GPS satellite and ground antenna phase center variations. The new position time series also show a better repeatability compared to past IGS combined products and their annual variations are shown to be more consistent with loading models. The comparison of GPS station positions and velocities to those of VLBI via local ties in co-located sites demonstrates that the IGS reprocessed solution submitted to the ITRF2008 is more reliable and precise than any of the past submissions. However, we show that some of the remaining inconsistencies between GPS and VLBI positioning may be caused by uncalibrated GNSS radomes.     

The LMDZ4 general circulation model: climate performance and sensitivity to parametrized physics with emphasis on tropical convection

The LMDZ4 general circulation model is the atmospheric component of the IPSL–CM4 coupled model which has been used to perform climate change simulations for the 4th IPCC assessment report. The main aspects of the model climatology (forced by observed sea surface temperature) are documented here, as well as the major improvements with respect to the previous versions, which mainly come form the parametrization of tropical convection. A methodology is proposed to help analyse the sensitivity of the tropical Hadley–Walker circulation to the parametrization of cumulus convection and clouds. The tropical circulation is characterized using scalar potentials associated with the horizontal wind and horizontal transport of geopotential (the Laplacian of which is proportional to the total vertical momentum in the atmospheric column). The effect of parametrized physics is analysed in a regime sorted framework using the vertical velocity at 500 hPa as a proxy for large scale vertical motion. Compared to Tiedtke’s convection scheme, used in previous versions, the Emanuel’s scheme improves the representation of the Hadley–Walker circulation, with a relatively stronger and deeper large scale vertical ascent over tropical continents, and suppresses the marked patterns of concentrated rainfall over oceans. Thanks to the regime sorted analyses, these differences are attributed to intrinsic differences in the vertical distribution of convective heating, and to the lack of self-inhibition by precipitating downdraughts in Tiedtke’s parametrization. Both the convection and cloud schemes are shown to control the relative importance of large scale convection over land and ocean, an important point for the behaviour of the coupled model.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

Magnitude of latent heat in thermally loaded clays

Temperature changes are known to induce specific couplings in clay, in particular, an anomalously high thermal pressurization in undrained conditions or a thermal compaction in drained conditions, both of which are potential threats for the mechanical stability and sealing capacity of the geomaterials. Thermodynamical analysis of those peculiar thermomechanical couplings points to a potentially important latent energy, which in turn could limit the temperature change upon heating or cooling. The direct measurement of latent energy developed during a laboratory geomechanical test is challenging. Instead, proper identification of thermal hardening in conventional experiments with temperature changes provides an alternative route to estimate latent energy. In this work, existing laboratory thermomechanical tests of clays are analyzed with a rigorous thermodynamic framework to quantify the magnitude of latent energy in thermomechanically loaded clays. A thermodynamically consistent constitutive model for fully saturated clays that combines two key features, (a) the temperature dependence of the blocked energy and (b) the framework of bounding plasticity, is proposed. The performance of the model is validated by reproducing results obtained in laboratory tests for Boom and Opalinus clays. The thermomechanical loads considered to validate the model performance were then used to estimate the percentage of work that remains latent in the clayey material during plastic yielding. We find that the magnitude of latent energy is quite significant, typically a few tens of percent of the total dissipated energy, and increases significantly with temperature. Accordingly, it is expected to play an important role in the thermomechanical response of clays.     

Provenance discrimination of fine sediments by mid-infrared spectroscopy: Calibration and application to fluvial palaeo-environmental reconstruction

Determining sediment provenance allows a better understanding of fluvial palaeo-dynamics, and identifying involved watersheds, at broad spatio-temporal scales. Conventional approaches for source identification are usually based on the physical, mineralogical, geochemical, magnetic or isotopic properties of sediments. Rapid, non-destructive and, in well-established contexts, highly accurate, mid-infrared spectroscopy is an alternative method for investigating sediment sources. The present research objectives are: (i) to use the mid-infrared spectroscopy method to discriminate the provenance of fine sediments, by applying discriminant analysis on a large set of reference samples from three different watersheds in the Upper Rhine area (associated with the Rhine, Ill and Vosges tributaries); (ii) to clarify whether the provenance spectra signatures are influenced by riverine depositional contexts (bars versus banks) and, to some extent, by grain size and/or high organic matter content; and (iii) to apply the mid-infrared spectroscopy – discriminant analysis method to a study of fluvial palaeo-dynamics and determine the provenance of palaeo-channel infillings. Three main sedimentary sources, divided into eight sub-categories, have been characterized by 196 modern reference samples from 78 collecting sites. Discriminant analysis displayed a strong separating power by classifying correctly the origin of samples without any inter-group overlap, independently from the geomorphological context (bar or bank) and associated slight changes in organic matter contents or grain size. Mid-infrared spectroscopy – discriminant analysis investigations of the palaeo-channel infill, complemented by radiocarbon dates and mineralogical data, allowed reconstructing general trends for the local morpho-sedimentary dynamics over the last ca 12 millennia.