Surface chemistry and structural properties of mackinawite prepared by reaction of sulfide ions with metallic iron

Tetragonal FeS_1−x mackinawite, has been synthesized by reacting metallic iron with a sodium sulfide solution and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). Based on XRD and TEM analyses, synthetic mackinawite exhibits crystallization and is identical to the natural mineral. Unit cell parameters derived from XRD data are a = b = 0.3670 nm and c = 0.5049 nm. The bulk Fe:S ratio derived from the quantitative dispersive energy analysis is practically 1. XPS analyses, however, showed that mackinawite surface is composed of both Fe(II) and Fe(III) species bound to monosulfide. Accordingly, monosulfide is the dominant S species observed at the surface with lesser amount of polysulfides and elemental sulfur. TMS analysis revealed the presence of both Fe(II) and Fe(III) in the mackinawite structure, thus supporting the XPS analysis. We propose that the iron monosulfide phase synthesized by reacting metallic iron and dissolved sulfide is composed of Fe(II) and S(-II) atoms with the presence of a weathered thin layer covering the bulk material that consists of both Fe(II) and Fe(III) bound to S(-II) atoms and in a less extent of polysulfide and elemental sulfur.     

Dissolved trace metals in the Western Mediterranean Sea: total concentration and fraction isolated by C18 Sep-Pak technique

An investigation of trace metal distributions in the Western Mediterranean Sea was carried out during the RRS Discovery cruise (July 1993) in which a transect from the Strait of Gibraltar to the Strait of Sicily was conducted. Organically complexed dissolved trace metals and their total concentrations were measured to investigate the end-members and to predict the environmental capacity of the Mediterranean for potential toxic metals. The distribution of trace metals can be accounted for by the mixing of several end-members and by some atmospheric inputs to the surface water. For Pb and Fe, the effects of the atmospheric inputs are more pronounced than for the other metals. Due to the rapid exchange of water masses, the Western Mediterranean may have the ability to assimilate the increased external inputs for some trace metals such as Cu, Cd, Ni and Zn. But the external inputs for Pb and Fe exceed the removal capacity of the Western Mediterranean and these elements may accumulate in the water column of the western basin. The C18 Sep-Pak technique and direct determination by DPASV were used to determine the amount of trace metal–organic complexes. The C18 Sep-Pak column isolates only a small fraction of trace metals except for Cu. The maximum hydrophobic fractions for the studied trace metals, except for Cd and Pb, which are not detectable, were found in the subsurface layer at all stations. This maximum may well be linked to picoplankton activity and the picoplankton, prochlorophytes may have an important role in the speciation of dissolved Cu as well as Synechococcus. These organic ligands for Cu were produced at the maximum of biological activity in the Western Mediterranean basin and seem to be accumulated at halocline level by Mediterranean hydrodynamic characteristics. However, direct determination by DPASV showed that the major part of Cu, Cd and Pb, complexed by organic materials, was not isolated by C18 Sep-Pak technique.     

Magnetic changes observed in the formation of two filaments in a complex active region: TRACE and MSDP observations

This paper is focused on the formation of two filaments in a complex center of decaying active regions (AR 8329 and AR 8326), located in the northern hemisphere. The observations were obtained in Hα by the Multi-channel Subtractive Double Pass spectrograph (MSDP mounted on the German telescope VTT in Tenerife) and EUV lines with TRACE (Transition Region And Corona Explorer). High Doppler shifts are found to be related to the ends of filament segments where canceling magnetic fields are also located (as seen on magnetograms from Big Bear Solar Observatory). At these locations, velocities along the line of sight, derived by using a cloud model method reach −20 km s⁻¹, the segments of filaments merge and frequently a time-related sub-flare is observed by TRACE. The chirality of the filament segments has been determined by different methods: the segments of dextral chirality join together and form a long dextral filament, and a single filament of sinistral chirality forms end to end with the dextral filament but does not merge with it. Assuming a model of twisted flux tube for filament material, we suggest that the dextral filament has negative helicity and a relationship between its formation and the close by sunspot with the same sign of helicity.     

Spectra of accretion discs around white dwarfs

We present the spectra of accretion discs around white dwarfs calculated with an improved and updated version of Shaviv and Wehrse [Shaviv, G., Wehrse, R., 1991. A&A 251, 117] model. The new version includes line opacities and convective energy transport and can be used to calculate the spectra of hot discs in bright systems (nova-like variables or dwarf novae in outburst) as well as the spectra of cold accretion discs in quiescent dwarf novae.     

An experimental study of the dissolution mechanism and rates of muscovite

Steady-state muscovite dissolution rates have been measured at temperatures from 60 to 201 °C and 1 ? pH ? 10.3 as a function of reactive solution K, Si, and Al concentration. The pegmatitic muscovite used in these experiments has a composition consistent with (Na_0.09, K_0.86)Fe_0.05Al_2.92Si_3.05O₁₀(OH_1.95, F_0.06). All experiments were performed in titanium mixed-flow reactors. All experiments were performed at far-from-equilibrium conditions with respect to muscovite. All reactive solutions were undersaturated with respect to secondary product phases other than for some experiments which were supersaturated with respect to bohemite and diaspore; steady-state dissolution was stoichiometric for all experiments that were undersaturated with respect to these phases.The variation of rates with reactive solution composition depends on the solution pH. At pH ? 7 rates were found to decrease significantly with increasing reactive fluid Al activity but be independent of aqueous SiO₂ activity. pH < 7 rates measured in the present study from 60 to 175 °C are consistent with

     

Transport of terrestrial organic matter in the Ogooué deep sea turbidite system (Gabon)

In order to define the nature and distribution of the organic matter (OM) preserved in the modern Ogooué deep sea turbidite system (Gabon), bulk geochemical techniques (Rock-Eval pyrolysis, elemental and isotopic analyses) and palynofacies were applied to three piston cores collected in the Cape Lopez Canyon and lobe and on the continental slope, north of the canyon.The hemipelagic sedimentation in the study area is characterized by high accumulations of well-preserved OM (∼2-3 wt. TOC %). Bulk geochemical and palynofacies analysis indicate both a marine and terrestrial origin of the OM. Contribution of the marine source is higher on the slope than in the canyon and lobe.OM accumulation in turbidites is strongly controlled by the combined influence of the Cape Lopez Canyon and littoral drift. In the canyon and lobe, turbidites show generally low TOC content (0.5 wt. %) and OM is oxidized. The origin of the OM is interpreted as both marine and terrestrial, with a higher contribution of continental source versus marine source. The low TOC contents are due to the large siliciclastic fraction transported by the littoral drift and diverted in the Cape Lopez Canyon during high energy processes (e.g. storms) which tend to dilute the OM in the turbidites. Transport by long-shore currents and/or turbiditic flows leads to oxidation of the OM.On the continental slope located north of the Cape Lopez Canyon, large amounts of OM are deposited in turbidites (up to 14 wt. %). The OM is predominantly derived from terrestrial land plants and has not been subjected to intense oxidation. These deposits are characterized by high hydrocarbon potential (up to 27 kg HC/t rock), indicating a good potential as gas-prone source rock. Because Cape Lopez Canyon captures a significant part of the sediment transported by the littoral drift, the siliciclastic sedimentary flux is reduced north of the canyon; OM is thus concentrated in the turbidites. Variation in TOC content within turbidite laminae can be explained by the burst and sweep deposition process affecting the boundary layer of the turbulent flow.This study confirms that gravity flows play a preponderant role in the accumulation and preservation of OM in deep water and that deep sea turbidite systems could be regarded as an environment where organic sedimentation occurs.     

Geochemical characteristics of an intracontinental shoshonitic association: the example of the Damavand volcano,IranCaractéristiques géochimiques d'une association shoshonitique intracontinentale : exemple du Damavand,Iran

Lavas of the Quaternary Damavand volcano (Central Alborz, Northern Iran) have been analysed for major and trace elements. The shoshonitic character of this magmatic series is definitively confirmed and most samples correspond to banakites. The Nb, Ta and Ti negative anomalies observed in all lavas suggest that they derive from of a sub-continental lithosphere metasomatised in a subduction setting. Their variable trace element enrichments are explained both by mineral fractionation and by crustal contamination in a shallow magmatic chamber. To cite this article: H. Mehdizadeh et al., C. R. Geoscience 334 (2002) 111–117.     

Analyse d'Image pour l'Évaluation de l'Exposition de la Côte à l'Action des Vagues

A method of analysis was developed to estimate wind-induced wave heights in the coastal zone. The analysis is based on a digital bathymetry model in raster format. The model uses wind characteristics such as direction, velocity, and fetch. In addition, underwater terrain slope magnitude and orientation, and water depth are used in the computation of the model to estimate wave heights. Two analyses are shown, taking into account waves built from short fetch wind and indefinite fetch wind. The analysis was applied to Hare Bay in northern Newfoundland. First, we take into account a northerly wind of 6.9 ms⁻¹ where the fetch is 19 km or less. The estimated wave heights vary between 0 and 0.5 m. With the second application, we considered an indefinite ESE fetch wind of 17.8 ms⁻¹. In this case, the wave heights resulting from the application of the model vary between 0 and 11.8 m. We compared the modelling results based on ESE wind and the wave energy derived through visual analysis. Relationships were identified between the wave height classes and the wave energy categories.     

Release of cadmium in the Danube estuary: contribution of physical and chemical processes as determined by an experimental approach

The behavior of dissolved cadmium (Cd) in the Danube estuary was investigated through field sampling and mixing experiments using Danube River water and Black Sea water. The experiments were performed by mixing these two end-member waters in various proportions, with the addition of stable or radioactive Cd to the freshwater Danube end-member prior to the mixing. The release of Cd that resulted in maximum concentrations under field conditions was well simulated by mixing experiments. The experimental results were modeled assuming that the release of Cd was the sum of the contribution of physical effects resulting from dilution effects and the contribution of chemical effects resulting from dissolved Cd-complex formation (and isotopic exchange when concerned). In the absence of dissolved Cd-complexing ligands, the release of Cd due to the dilution of the particulate phase during mixing could explain part of the maximum concentrations observed in field conditions. Kinetic effects were established by comparing the theoretical and measured contribution of chemical effects resulting from dissolved Cd-complex formation. The non-equilibrium state observed during the mixing experiment suggested the presence of particulate labile Cd that was not easily mobilized. All these features supported the hypothesis that Cd released in estuaries is controlled both by the dilution of the particulate phase and by kinetic competitive complexation between particulate ligands (covering a large spectrum of nature and strength) and dissolved ligands.     

Comparison of free-surface and rigid-lid finite element models of barotropic instabilities

The main goal of this work is to appraise the finite element method in the way it represents barotropic instabilities. To that end, three different formulations are employed. The free-surface formulation solves the primitive shallow-water equations and is of predominant use for ocean modeling. The vorticity–stream function and velocity–pressure formulations resort to the rigid-lid approximation and are presented because theoretical results are based on the same approximation. The growth rates for all three formulations are compared for hyperbolic tangent and piecewise linear shear flows. Structured and unstructured meshes are utilized. The investigation is also extended to time scales that allow for instability meanders to unfold, permitting the formation of eddies. We find that all three finite element formulations accurately represent barotropic instablities. In particular, convergence of growth rates toward theoretical ones is observed in all cases. It is also shown that the use of unstructured meshes allows for decreasing the computational cost while achieving greater accuracy. Overall, we find that the finite element method for free-surface models is effective at representing barotropic instabilities when it is combined with an appropriate advection scheme and, most importantly, adapted meshes.