In situ anaerobic degradation of petroleum alkanes in marine sediments: preliminary results

The degradation of acyclic petroleum hydrocarbons was studied during a 24-month experiment in Mediterranean coastal sediments (Gulf of Fos). Sediment cores entirely contaminated with oil (Arabian Light Crude Oil) were incubated in situ. The use of conservative tracers of sediment's particles reworking (luminophores) allowed the distinction of the reworked layer from the anoxic deeper sediments. Using the 17α,21βC₃₀ hopane (C₃₀H) as an inert internal reference, we could demonstrate that, after 24 months of experiment, acyclic petroleum hydrocarbons can be degraded under natural anaerobic conditions. The reactivity of individual alkanes appeared to depend on their chemical structure. To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).     

Metastable staurolite–cordierite assemblage of the Bossòst dome: Late Variscan decompression and polyphase metamorphism in the Axial Zone of the central Pyrenees

A kilometre-scale shear zone is recognized in the Cambro–Ordovician schist of the Bossòst dome, a Variscan metamorphic and structural dome in the Axial Zone of the central Pyrenees. Non-coaxial deformation is recorded by rotated garnet and staurolite porphyroblasts following regional metamorphism M₁, while coaxial conditions prevailed during later contact metamorphic M₂ growth of andalusite and cordierite. Mineral compositions and bulk rock analyses show that garnet–staurolite–andalusite–cordierite assemblages are significantly enriched in Mg and Mn over the garnet–staurolite assemblage, which lacks sufficient Mg for cordierite to form. The garnet–staurolite assemblage preserves conditions during M₁, estimated by AFM diagrams and P–T pseudosections to be 5.5 kbar and 580 °C, respectively. Pseudosections also indicate that staurolite is not a stable phase in cordierite–andalusite assemblages of M₂, suggesting polyphase metamorphism and decompression along a clockwise P–T path for the staurolite–cordierite–andalusite assemblages. This concurs with proposed extensional tectonics along the regional shear zone. To cite this article: J.E. Mezger et al., C. R. Geoscience 336 (2004).     

Structure cristalline d'une ménéghinite naturelle pauvre en cuivre,Cu0,58Pb12,72(Sb7,04Bi0,24)S24Crystal structure of a Cu-poor natural meneghinite,Cu0.58Pb12.72(Sb7.04Bi0.24)S24

Cu-poor meneghinite from La Lauzière Massif (Savoy, France) has the composition (electron microprobe) (in wt%): Pb 59.50, Sb 20.33, Bi 1.19, Cu 0.87, Ag 0.05, Fe 0.03, S 17.62, Se 0.05, Total 99.64. Its crystal structure (X-ray on a single crystal) was solved with R1=0.0506, wR2=0.1026, with an orthorhombic symmetry, space group Pnma, and a=24.080(5) Å, b=4.1276(8) Å, c=11.369(2) Å, V=1130.0(4) Å³, Z=4. Relatively to the model of Euler and Hellner (1960), this structure shows a significantly lower site occupancy factor for the tetrahedral Cu site (0.146 against 0.25). Among the five other metallic sites, Bi appears in the one with predominant Sb. Developed structural formula: Cu_0.15Pb₂(Pb_0.53Sb_0.47)(Pb_0.46Sb_0.54)(Sb_0.75Pb_0.19Bi_0.06)S₆; the reduced one: Cu_0.58Pb_12.72(Sb_7.04Bi_0.24)S₂₄. The formation of such a Cu-poor variety seems to be related to specific paragenetic conditions (absence of coexisting galena), or to crystallochemical constraints (minor Bi). To cite this article: Y. Moëlo et al., C. R. Geoscience 334 (2002) 529–536.     

Datation par la méthode U/Th d'un travertin quaternaire du Sud-Est marocain : implications paléoclimatiques pendant le Pléistocène moyen et supérieur

A large travertine outcrop south of Errachidia, southern Morocco, was studied and U/Th dated. The carbonate fraction was provided by groundwaters then, as now, from the eastern High Atlas percolating through the regional Infra-Cenomanian aquifer. There were two main periods of accumulation at ca 262 kyr BP and 20–11.5 kyr BP separated by a long discontinuity with some limited weathering and erosion and correlated in part with a period of erosion at 30–20 kyr BP further to the west. The two travertine-deposition periods suggest increased rainfall and/or cooler thermal conditions in the eastern High Atlas source regions. Massive travertine accumulation ceased at the end of the Upper Pleistocene. To cite this article: L. Boudad et al., C. R. Geoscience 335 (2003).To cite this article: L. Boudad et al., C. R. Geoscience 335 (2003).     

Expérimentation et modélisation de la lixiviation de l'azote nitrique dans un sol sableux

We performed two column experiments to study the impact of different levels of irrigation intensity on the leaching of nitric nitrogen. The experiment was run on a soil packed column and using 200 kg?N/ha as fertilization rate for the first column, and none for the second. In parallel, we carried out digital simulations (mechanist model) to study the transfer of nitrogen through the studied columns followed by an application of the model to various amounts of nitrogen. The impact study of successive irrigations showed that these contribute to the transport and the accumulation of nitric nitrogen of the upper layers towards the deeper layers. The quantity of nitric nitrogen N–NO₃ drained by scrubbing was about 191 kg?N/ha for the first column, and 15 kg?N/ha for the second. In addition, the numerical simulations revealed that the precision of the model is satisfactory with an over-estimation of about 20%. To cite this article: M. Ibnoussina et al., C. R. Geoscience 338 (2006).     

Oxydation expérimentale de Fe-tourmalines et corrélation avec une déprotonation des groupes hydroxyleAnnealing in oxidising conditions of Fe-tourmalines and correlated deprotonation of OH groups

Annealing at 400?T?600 °C (40?P?60 MPa and HM buffer-controlled f(O₂)) of tourmalines synthesised at the same T and P with NNO buffer induces an oxidation of Fe²⁺ into Fe³⁺ in some Y sites only (Mössbauer Spectroscopy data). Annealing in the same conditions of natural tourmalines is consistent with these results. FTIR spectroscopy shows that oxidation of Fe²⁺ into Fe³⁺ is charge-balanced by deprotonation of the external OH₍₃₎ groups. To cite this article: Y. Fuchs et al., C. R. Geoscience 334 (2002) 245–249.     

Tectonique transpressive en terre Adélie au Paléoprotérozoı̈que (Est Antarctique)Palaeoproterozoic transpression in Terre Adélie (East Antarctica)

The Palaeoproterozoic units of Terre Adélie show two types of structural domains associated with HT–LP metamorphic conditions: domes and NS–N340° striking vertical shear zones. Shear zones reflect dextral transpressive motions. Domes reflect sub-vertical shortening and principal stretching subparallel to shear zones. They could partly result from longitudinal flow coeval with transpression. Deformations are comparable to those described along the eastern and western boundaries of the Archean Gawler Craton (South-East Australia), which underlines the continuity between these two areas before opening of the Austral Ocean. To cite this article: A. Pelletier et al., C. R. Geoscience 334 (2002) 505–511.     

Water and magmas: clarification of a controversy on applications of the Gibbs-Duhem equation

It is shown mathematically that if the activity coefficient of water in ternary water-magma (aluminosilicate) systems is constant or varies only with the mole fraction of water, it is not necessary that the binary magmas form ideal solutions contrary to the claims by Burnham et al. (1978, Geochim. Cosmochim. Acta42, 275–276). A molecular viewpoint is presented to support this argument. The properties of analytical equations capable of representing the activity coefficients of usual and unusual systems are discussed. The correct form of the Gibbs-Dunhem equation for dissociative dissolution processes is presented to disprove the claims by Burnham (1975, Fortschr. Mineral.52, 101–118; 1975, Geochim. Cosmochim. Acta39, 1077–1084), and by Burnhamet al. (1978, Geochim. Cosmochim. Acta42, 275–276).     

Les concentrations à sillimanite du Sud Velay et l'évolution P–T–t fini-hercynienne dans le Massif central (France)

The Late Hercynian evolution in the French Massif Central corresponds to the transition from a LP–HT (M₃ event at 314 ± 5 Ma) to a higher temperature metamorphism corresponding to the emplacement of the Velay granite dome (M₄ event at 301 ± 5 Ma). This transition is outlined by the development of sillimanite folia, which represent planes of base-cation leaching, associated with ductile deformation. This evolution implies a counterclockwise retrograde $P\text{–}T\text{–}t$ path under subsolidus conditions between M₃ and M₄. To cite this article: P. Barbey et al., C. R. Geoscience 337 (2005).     

Évaluation de la mobilité des métaux dans les sédiments fluviaux du bassin de la Vire (Normandie,France) par extractions simples ou séquentielles

This work compares the quantities of labile metals removed from the Vire River (Normandy) sediments by a sequential extraction procedure to those liberated by single leaches (Mg(NO₃)₂, HCl and EDTA). Compared to the other extractions, Mg(NO₃)₂ underestimated the mobility results. The sequential procedure was the most aggressive, except for Ca and Pb. The hypothetic correlation between quantities of an element removed by single leaches and its fractionation in the sediment according to the sequential procedure was not satisfying. Finally, it should be underlined that enrichments of Cd, Pb and Zn were noticed in the Vire sediments. To cite this article: L. Leleyter, F. Baraud, C. R. Geoscience 337 (2005).     

The ion-pair constant and other thermodynamic properties of HCl up to 350°C

Solubilities of silver chloride in aqueous hydrochloric acid solutions have been determined from 100 up to 350°C. From these measurements, the ionisation constant of HC1 has been evaluated up to 225°C. Evidence is presented to show that a protonated silver species, HAgCl₂⁰, exists at 275°C and above. Available experimental data up to 200°C have been firted to Pitzer's equation to generate an algorithm to calculate stoichiometric activity and osmotic coefficients of HCl up to 350°C and concentrations up to at least 3.0 m. Using the present results and those of Wrightet al. (1961), Pearsonet al. (1963) and Lukashowet al. (1976), the dissociation constant (K_d) of HCl as a function of temperature is described by the equation log₁₀K = 2136.898 + 1.020349T−4.5045 × 10⁻⁴T²−50396.40/T−901.770 10g₁₀T (Tin °K) which is valid in the range 25–350°C. Calculated enthalpy (ΔH⁰), entropy (ΔS⁰) and heat capacity change (ΔC_p⁰) functions for HCl dissociation have been rationalized in terms of changing solute and solvent characteristics as temperature is raised.     

Late Wuchiapingian (Late Dzhulfian,early Late Permian) limestone olistolites within the Tertiary flysch of Glypia Unit (Mount Parnon,central–eastern Peloponnesus,Greece)

Some olistolites reworked in a Tertiary flysch of Mount Parnon (Peloponnesus, Greece) exhibit a Late Permian assemblage, dominated by Paradunbarula (Shindella) shindensis, Hemigordiopsis cf. luquensis and Colaniella aff. minima. This association corresponds to the Late Wuchiapingian (=Late Dzhulfian), a substage whose algae and foraminifera are generally little known. Contemporaneous limestones crop out in the middle part of the Episkopi Formation in Hydra, but they are rather commonly reworked in Mesozoic and Cainozoic sequences. The palaeobiogeographical affinities shared by the foraminiferal markers of Greece, southeastern Pamir, and southern China, are very strong (up to the specific level), and are congruent with the Pangea B reconstructions. To cite this article: E. Skourtsos et al., C. R. Geoscience 334 (2002) 925–931.     

Méthodologie de l'extraction des hydrocarbures aromatiques polycycliques. Application à des sédiments de la lagune de Bizerte (Tunisie)Methodology of extraction of polycyclic aromatic hydrocarbons. Application to sediment from the Bizerte Lagoon (Tunisia)

The marine environment is very complex, with several important chemical, biological, and sedimentological interactions. Sediments constitute a reservoir for numerous pollutants, including polycyclic aromatic hydrocarbons (PAHs). PAHs are known by their mutagenic and/or carcinogenic effect. This study evaluates contamination levels in Bizerte Lagoon with respect to PAHs. The extraction efficiency of PAHs from sediment has been evaluated using Soxhlet or ultrasonic procedures, based on the recovery of an internal standard (9,10-dihydroanthracene). Several PAHs were found, including sixteen that are reported in the priority list of pollutants of the US Environmental Protection Agency (EPA). PAHs analysis was carried out by GC–FID and GC–MS for 16 samples sampled in two seasons: summer and winter. Results permit an assessment of PAHs pollution in the Bizerte Lagoon. To cite this article: N. Mzoughi et al., C. R. Geoscience 334 (2002) 893–901.     

Natural alteration products of sulphide mattes from primary lead smelting

The natural alteration products developed on mattes from lead metallurgy were determined: oxides and hydroxides (HFO, Cu(OH)₂), sulphates (thenardite, gypsum), hydroxysulphates (jarosite, beaverite, brochantite) and carbonates (cerussite, malachite, NaOH·2 PbCO₃). The large range of stability of newly formed phases confirms a significant variety of E_h–pH conditions of natural weathering of matte. Jarosite is stable at pH<3, but some hydroxides and carbonates typically form in neutral and alkaline environments. Consequently, the best dumping conditions for metallurgical mattes are difficult to determine. Such materials can have severe environmental effects and should be dumped in controlled waste-disposal sites. To cite this article: V. Ettler et al., C. R. Geoscience 335 (2003).     

Étude expérimentale de la réactivité du CO2 supercritique vis-à-vis de phases minérales pures. Implications pour la séquestration géologique de CO2

Carbon dioxide sequestration in deep aquifers and depleted oilfields is a potential technical solution for reducing green-house gas release to the atmosphere: the gas containment relies on several trapping mechanisms (supercritical CO₂, CO_2(sc), dissolution together with slow water flows, mineral trapping) and on a low permeability cap-rock to prevent CO_2(sc), which is less dense than the formation water, from leaking upwards. A leakproof cap-rock is thus essential to ensure the sequestration efficiency. It is also crucial for safety assessment to identify and assess potential alteration processes that may damage the cap-rock properties: chemical alteration, fracture reactivation, degradation of injection borehole seals, etc. The reactivity of the host-rock minerals with the supercritical CO₂ fluid is one of the potential mechanisms, but it is altogether unknown. Reactivity tests have been carried out under such conditions, consisting of batch reactions between pure minerals and anhydrous supercritical CO₂, or a two-phase CO₂/H₂O fluid at 200?°C and 105/160 bar. After 45 to 60 days, evidence of appreciable mineral-fluid reactivity was identified, including in the water-free experiments. For the mixed H₂O/CO₂ experiments, portlandite was totally transformed into calcite; anorthite displayed many dissolution patterns associated with calcite, aragonite, tridymite and smectite precipitations. For the anhydrous CO₂ experiments, portlandite was totally carbonated to form calcite and aragonite; anorthite also displayed surface alteration patterns with secondary precipitation of fibrous calcite. To cite this article: O. Regnault et al., C. R. Geoscience 337 (2005).     

Effet de l'agrégation sur le transport de la kaolinite recouverte d'acide humique à travers un sable de quartz d'origine naturelleAggregation effect on the transport of humic-coated kaolinite colloids through a natural quartz sand

To evaluate the risk of contaminant transport by mobile colloids, it is necessary to understand how colloids and associated pollutants behave during their migration through uncontaminated soil or groundwater. In this study, we investigated the influence of aggregation induced by Ca²⁺ and trace metals (Pb²⁺, Cu²⁺) concentrations on the transport of humic-coated kaolinite colloids through a natural quartz sand at pH=4. Adsorbed divalent cations reduce the colloids surface charge and thereby induce aggregation and deposition in porous media. To cite this article: R. Ait Akbour et al., C. R. Geoscience 334 (2002) 981–985.     

États de contraintes et mécanismes d'ouverture et de fermeture des bassins permiens du Maroc hercynien. L'exemple des bassins des Jebilet et des RéhamnaStates of stresses and opening/closing mechanisms of the Permian basins in Hercynian Morocco. The example of the Jebilet and Réhamna Basins

The fracturing analysis in the Permian basins of Jebilet and Rehamna (Hercynian Morocco) and the underlying terranes allowed us to suggest a model for their opening. Three tectonic episodes are distinguished: a transtensional episode NNE–SSW-trending (Permian I), occurring during the opening along sinistral wrench faults N70–110-trending, associated with synsedimentary normal faults; a transpressive episode ESE–WNW-trending (Permian II), initiating the closure, the normal faults playing back reverse faults and the N70 trending faults dextral wrench faults; a compressional episode NNW–SSE (post-Permian, ante-Triassic), accentuating the closure and the deformation and putting an end to the Tardi-Hercynian compressive movements. To cite this article: A. Saidi et al., C. R. Geoscience 334 (2002) 221–226.     

Insights into preservation of fossil plant cuticles using thermally assisted hydrolysis methylation

The chemical composition of Cretaceous leaf remains showing exceptionally well preserved cuticles was investigated using pyrolysis gas chromatography–mass spectrometry (Py-GC–MS) and thermally assisted hydrolysis methylation (THM)-GC–MS. Samples of Coniferales (Frenelopsis) and Ginkgoales (Nehvizdya penalveri) leaf remains were collected from freshwater and coastal marine depositional environments. Material for pyrolysis included (i) untreated leaves and cuticles obtained after extraction from mineral rock matrix and bleaching, (ii) kerogen fraction from both materials, (iii) non-hydrolysable fraction from kerogen. The THM-GC–MS data from untreated leaves and bleached cuticles show that the fossil cuticle geopolymer essentially released aliphatic components upon thermal treatment, with a dominance of fatty acids (FAs) and n-alkanes/n-alkenes. The FAs are essentially resistant to bleaching and remain after solvent extraction. They occur mainly as short chain compounds ranging from C₆ to C₁₆ and with maximum abundance at C₈–C₉. The n-alkanes/n-alkenes from kerogen and the non-hydrolysable residue occur mainly as short chain compounds in the range C₁₀–C₁₆, with the highest abundance at C₉–C₁₂. The THM-GC–MS pyrograms of the fossil cuticles differ from those of cutan from fresh living plants. They support the preservation model via polymerization of monomers derived from cutin or from unsaturated cell FAs.     

Enrichissement en uranium authigène dans les sédiments glaciaires de l'océan AustralEnrichments in authigenic uranium in glacial sediments of the Southern Ocean

Four sediment cores from the Polar frontal zone and the Antarctic zone in the Indian sector of the Southern Ocean present an increase of authigenic uranium during glacial periods. We show that this increase in uranium is due to a combination of (i) an increase in the lateral transport of organic matter, (ii) a decrease in the oxygen in deep waters, and (iii) a process of diagenesis. It appears that uranium concentration cannot be used as a proxy of palaeoproductivity in the Southern Ocean, as previously suggested by Kumar et al. in 1995. To cite this article: L. Dezileau et al., C. R. Geoscience 334 (2002) 1039–1046.