Ab initio quantum-mechanical modeling of pyrophyllite [Al2Si4O10(OH)2] and talc [Mg3Si4O10(OH)2] surfaces

Bulk and slab geometry optimizations and calculations of the electrostatic potential at the surface of both pyrophyllite [Al₂Si₄O₁₀(OH)₂] and talc [Mg₃Si₄O₁₀(OH)₂] were performed at Hartree–Fock and DFT level. In both pyrophyllite and talc cases, a modest (001) surface relaxation was observed, and the surface preserves the structural features of the crystal: in the case of pyrophyllite the tetrahedral and octahedral sheets are strongly distorted with respect to the ideal hexagonal symmetry (and basal oxygen are located at different heights along the direction normal to the basal plane), whereas the structure of talc deviates slightly from the ideal hexagonal symmetry (almost co-planar basal oxygen). The calculated distortions are fully consistent with those experimentally observed. Although the potentials at the surface of pyrophyllite and talc are of the same order of magnitude, large topological differences were observed, which could possibly be ascribed to the differences between the surface structures of the two minerals. Negative values of the potential are located above the basal oxygen and at the center of the tetrahedral ring; above silicon the potential is always positive. The value of the potential minimum above the center of the tetrahedral ring of pyrophyllite is ?0.05 V (at 2 Å from the surface), whereas in the case of talc the minimum is ?0.01 V, at 2.7 Å. In the case of pyrophyllite the minimum of potential above the higher basal oxygen is located at 1.1 Å and it has a value of ?1.25 V, whereas above the lower oxygen the value of the potential at the minimum is ?0.2 V, at 1.25 Å; the talc exhibits a minimum of ?0.75 V at 1.2 Å, above the basal oxygen.     

Unusual variations of dissolved As, Sb and Ni in the Rhône River during flood events

Dissolved major and trace element concentrations were determined from November 2000 to December 2003 in the lower Rhône River (France). Subsurface water samples were collected about twice a month and more regularly during flood events. An unusual trend was observed for As, Sb, Ni and Ba concentrations which increased with river discharge at the beginning of the floods, in contrast with other elements. Variations of Sb/Na and As/Na molar ratios show that it is related to higher contributions of waters from western tributaries of the Rhône River enriched in As, Sb, Ni and Ba due to ancient mining activities. These unusual variations of dissolved element concentrations are thus interpreted as mark of a water mass origin within the watershed.     

Determination of the orbit of a natural satellite with hyperbolic flybys

We show that, when a natural satellite like Titan is invisible (e.g., due to an opaque atmosphere) its planetary orbit and its mass can be determined by tracking a spacecraft in close flybys. This is an important problem in the Cassini mission to the Saturnian system, which will be greatly improved by a good astrometric model for all its main components; in particular, an accuracy of a few hundred meters for the orbit of Titan is necessary to allow a measurement of its moment of inertia. The orbit of the spacecraft is the union of elliptical arcs, joined by short hyperbolic transitions: a problem of singular perturbation theory, whose solution leads to a matching condition between the inner hyperbolic orbit and the elliptical orbital elements. Since the inner elements are given in terms of the relative position and velocity of the spacecraft, accurate Doppler measurements in both regions can provide a satisfactory determination of Titan's position and velocity, hence of its Keplerian elements. The errors in this determination are discussed on the basis of the expected Allan deviation of the Doppler method; it is found that the driving errors are those in the elliptical arcs; the fractional errors in Titan's orbital elements are expected to be 10^–7. It is also possible to measure the mass of the satellite; however, when the eccentricity e of the flybys is large, the mass and a scaling transformation are highly correlated and the fractional error in the mass is expected to be e times worse.     

Carbon and oxygen diffusion in calcite: Effects of Mn content and P H2O

The diffusion rates of carbon and oxygen in two calcite crystals of different Mn contents have been studied between 500° and 800° C in a CO₂-H₂O atmosphere (P _{CO 2}=1?5 bars, P _H2_O=0.02?24 bars) labeled with ¹³C and ¹⁸O. Isotope concentration gradients within annealed specimens were measured using a secondary ion microprobe by depth profiling parallel and perpendicular to the c axis. Despite the anisotropic structure of calcite, the diffusion of carbon and oxygen are both very nearly isotropic. Least-squares fitting of the carbon data to an Arrhenius relation gives an activation energy of 87±2 kcal/mole, with D ₀ terms dependent only slightly upon direction: 1 $$D_{\text{0}} {\text{(}}\parallel c{\text{) = }}\left( {9\frac{{ + 12}}{{ - 5}}} \right){\text{x10}}^{\text{2}} cm^2 /s$$ , 2 $$D_{\text{0}} {\text{(}} \bot c{\text{) = }}\left( {5\frac{{ + 6}}{{ - 3}}} \right){\text{x10}}^{\text{2}} cm^2 /s$$ . These results are in close agreement with previous determinations. Results for oxygen diffusion, however, give D values much larger than those previously reported for dry conditions; at 650° to 800° C the D values are two orders of magnitude larger. The diffusion of oxygen, unlike carbon, is strongly dependent on water pressure, as well as Mn content, and does not fit an Arrhenius relation over the entire temperature range. On the basis of these observations and considerations of the defect chemistry of calcite, it is proposed that carbon migrates as a Frenkel pair. The diffusion of oxygen, however, appears to be more complicated and may depend upon several simultaneous mechanisms.     

Systematique U-Pb et Evolution du Gisement d'Uranium de Lodève (France)

Résumé Considérée comme syngénétique ou diagénétique précoce, la minéralisation uranifère de la couche 0 de l'Autunien du bassin de Lodève a été étudiée par la méthode U-Pb sur roches totales. Les données U-Pb démontrent l'existence de perte en radon, principalement dans la chaine de désintégration de ²³⁸U, et l'intérêt de l'utilisation du couple ²⁰⁷Pb-²³⁵U pour la détermination des âges de cristallisation des concentrations uranifères. Pour la couche 0, deux phases de remobilisation de l'uranium et du plomb ont pu être déterminées respectivement à 173±6 Ma et 108±5 Ma. La plus ancienne de ces deux phases est la plus marquée dans les échantillons étudiés, dont les systèmes U-Pb ne montrent pas la mémoire d'une concentration uranifère permienne. La première mobilisation de l'uranium et du plomb s'est faite lors d'une phase de distension à 160–170 Ma, affectant la croûte continentale du Sud du Massif Central. Cette phase a provoqué la circulation de fluides minéralisés et est marquée par une recristallisation des illites des pélites permiennes entre 100 et 200 °C (du fait de l'élévation du gradient géothermique) et par la mise en place d'un volcanisme d'origine mantellique daté à 155±6 Ma. La composition isotopique en plomb d'une galène de l'Autunien du Lodévois, est analogue à celles des feldspaths des granitoïdes du Massif Central français et à celles des galènes des minéralisations stratiformes de Pb-Zn des Causses, ce qui fournit un argument pour faire dériver au moins une partie des métaux en traces dans les pélites autuniennes de l'altération de la croûte continentale hercynienne environnante.

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In the Lodeve basin, the uraniferous mineralization associated with the autunian pelitic layer 0 is usually considered as syngenetic or early diagenetic. U-Pb isotopic data performed on U bearing whole rocks demonstrate occurrence of radon losses, mainly in the ²³⁸U decay series; the ²⁰⁷Pb-²³⁵U geochronometer is particularly suitable to date U-Pb systems disturbed by such radon losses. For the autunian layer 0, two U-Pb mobilization phases have been respectively recognized at 173±6 Ma and 108±5 Ma. The oldest phase is the most clearly expressed in the studied samples, no memory of a permian age could be recognized in the U-Pb systems. The first U-Pb mobilization occurred 170 Ma ago, during a distension phase of the continental crust. This phase induced circulations of mineralized fluids, illite recristallization in the permian pelites at temperatures ranging from 100 to 200 °C and emplacement of a mantellic volcanism recently dated at 155±6 Ma. A galena from the Autunian of the Lodeve basin, the feldspars of the surrounding variscan granitoïds and galenas of mesozoïc stratiform deposits in the Causses, present similar Pb isotopic composition, which is in agreement with the hypothesis that some metals of the autunian pelites originated in the surrounding weathered variscan continental crust.

     

On the advection of turdidity in the saint lawrence middle estuary

The suspension transport away from the extensive turbidity zone of the St. Lawrence estuary is largely determined by the channel topography. The suspended sediments are advected downstream by a 40 km long turbid plume which takes its source in a turbidity maximum at the head of the estuary and flows downstream partly confined by the South Channel. During the ebbing phase of tidal cycles, the turbid waters of the plume are forced downstream through narrow converging sections of the channel, and slowed down through more opened diverging regions, particularly down-stream of the St. Roch Traverse. These, large fluctuations in stratification modulate the vertical transport of suspended material from the bottom to the surface layer. Midway down the estuary, dispersion of the plume occurs along a frontal zone which seasonally migrates 30 km or more in response to changes in fresh water discharge. The plume is reinforced and the turbidity gradient is intensified by local injections of inshore waters from Ste. Anne Bay, a subtidal platform highly enriched in suspended material by intertidal exchanges with large mudllats. Lateral erosion of the plume and cross-channel transport of suspended matter from the South into the North Channel is made possible by large horizontal shears developing in the central part of the middle estuary during the early flood. These are created by a one-hour tidal phase difference between the North and the South Channel.     

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted.We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both ¹³C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26°C than at 11.5°C. The change in δD relative to the change in δ¹³C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway.The change in the δD value for the residual methane was from 8 to 14 times greater than the change in the δ¹³C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria.     

High-pressure synthesis and properties of magnesiocarpholite,MgAl2[Si2O6] (OH)4

Magnesiocarpholite has been synthesized on its own composition between 15 and 25 kb water pressure and 415°–600° C. Best conditions are 25 kb-550° C, starting from a mixture of oxides and synthetic cordierite. Within the MgO-Al₂O₃-SiO₂-H₂O system, possible substitutions appear to be very limited in magnesiocarpholite. Cell-parameters are a=13.706(3), b= 20.075(3), c=5.107(l) Å, space group Ccca. The larger cell, as compared with the most magnesian natural carpholites, is tentatively ascribed to structural disorder. Preliminary stability data confirm the low-temperature character of this mineral which is shown to be a high-pressure equivalent of sudoite+quartz.     

Influence of frozen conditions on the oxygen diffusion coefficient in unsaturated porous materials

The efficiency of soil covers used as oxygen barriers to control the generation of acid drainage from sulfidic mine wastes can be evaluated in terms of the diffusive oxygen flux reaching the underlying wastes. Oxygen diffusion has been extensively investigated over the last few decades for unsaturated porous materials that are not frozen. However, little attention has been paid to materials that are fully or partially frozen, and thus, the diffusion of oxygen through soil covers during the winter freezing period has been generally neglected. This paper presents a laboratory method developed to evaluate the effective diffusion coefficient of oxygen (D_e) in frozen, inert materials. The method is a modified version of the conventional double-chamber cell in which the temperature and unfrozen volumetric water content of the sample are measured in addition to the more commonly monitored change in oxygen concentration. Several tests were conducted on non-reactive materials: that is, a sand at multiple degrees of saturation (S_r?=?20, 30, 39, and 42%), a silt (S_r?=?47%), and a mixture of the two (S_r?=?90%). Experimental data were interpreted using the POLLUTE code. Values of D_e for frozen materials were slightly lower than those obtained at ambient laboratory temperatures. In addition to the development of an empirical method for determining D_e, a preliminary model based on the model proposed by Aachib et al. (Water Air Soil Pollut 156:163–193, 2004) was created for the prediction of D_e in frozen materials by defining the involved parameters as temperature-dependent. The results indicate that predicated values of D_e are slightly higher than experimental values, suggesting that there remains room for improvement in the model.