Paléoenvironnements et caractérisation des roches mères pétrolières des séries pré-salifères du bassin intérieur du Gabon

The Interior Basin of Gabon, created during the break-up between South America and Africa, displays thick Neoproterozoic to Aptian p.p. fluvio-lacustrine deposits overlain by Aptian to Albian marine facies. Rock–Eval analyses from outcrop and drillhole samples show high content in organic matter (up to 25%) related to types I and II. These intervals are encountered within Permian, Neocomian–Barremian as well as Aptian siliciclastic succession. They constitute fairly good to excellent potential petroleum source rocks, which are most probably at the origin of oil indices recognized both in drillholes and in surface.     

Fluid inclusions in granulites, granulitized eclogites and garnet clinopyroxenites from the Dabie–Sulu terranes, eastern China

Minor granulites (believed to be pre-Triassic), surrounded by abundant amphibolite-facies orthogneiss, occur in the same region as the well-documented Triassic high- and ultrahigh-pressure (HP and UHP) eclogites in the Dabie–Sulu terranes, eastern China. Moreover, some eclogites and garnet clinopyroxenites have been metamorphosed at granulite- to amphibolite-facies conditions during exhumation. Granulitized HP eclogites/garnet clinopyroxenites at Huangweihe and Baizhangyan record estimated eclogite-facies metamorphic conditions of 775–805 °C and ≥15 kbar, followed by granulite- to amphibolite-facies overprint of ca. 750–800 °C and 6–11 kbar. The presence of (Na, Ca, Ba, Sr)-feldspars in garnet and omphacite corresponds to amphibolite-facies conditions. Metamorphic mineral assemblages and P–T estimates for felsic granulite at Huangtuling and mafic granulite at Huilanshan indicate peak conditions of 850 °C and 12 kbar for the granulite-facies metamorphism and 700 °C and 6 kbar for amphibolite-facies retrograde metamorphism. Cordierite–orthopyroxene and ferropargasite–plagioclase coronas and symplectites around garnet record a strong, rapid decompression, possibly contemporaneous with the uplift of neighbouring HP/UHP eclogites.

Carbonic fluid (CO₂-rich) inclusions are predominant in both HP granulites and granulitized HP/UHP eclogites/garnet clinopyroxenites. They have low densities, having been reset during decompression. Minor amounts of CH₄ and/or N₂ as well as carbonate are present. In the granulitized HP/UHP eclogites/garnet clinopyroxenites, early fluids are high-salinity brines with minor N₂, whereas low-salinity fluids formed during retrogression. Syn-granulite-facies carbonic fluid inclusions occur either in quartz rods in clinopyroxene (granulitized HP garnet clinopyxeronite) or in quartz blebs in garnet and quartz matrices (UHP eclogite). For HP granulites, a limited number of primary CO₂ and mixed H₂O–CO₂(liquid) inclusions have also been observed in undeformed quartz inclusions within garnet, orthopyroxene, and plagioclase which contain abundant, low-density CO₂±carbonate inclusions. It is suggested that the primary fluid in the HP granulites was high-density CO₂, mixed with a significant quantity of water. The water was consumed by retrograde metamorphic mineral reactions and may also have been responsible for metasomatic reactions (“giant myrmekites”) occurring at quartz–feldspar boundaries. Compared with the UHP eclogites in this region, the granulites were exhumed in the presence of massive, externally derived carbonic fluids and subsequently limited low-salinity aqueous fluids, probably derived from the surrounding gneisses.     

Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy

The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (m_Fe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H₂O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (N_edge = 1-2; N_corner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Fe_edge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe₂Si_1-2 and Fe₃Si_2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO₆-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (R_Fe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.     

Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

On Some Simplifications of Cokriging Neighborhood

Choosing the cokriging neighborhood is often difficult. A poor choice, ignoring influent data, can result in a loss of information as well as in artifacts in simulations based on cokriging. Then it is convenient to use if possible, or to refer to models that lead to simplified cokriging neighborhood. We essentially consider the case of two stationary variables, a target variable and an auxiliary one. By examining possible simplifications, we set up a list of models (essentially models with residuals) that, in general or under specific configurations, lead to simplifications of cokriging neighborhood. Collocated, dislocated, and other types of neighborhood are identified, that are optimal in some models and configurations. Possible extensions to cokriging with unknown means, and to more variables, are included.     

Environmental impact of an urban landfill on a coastal aquifer (El Jadida, Morocco)

The El Jadida landfill is one among many uncontrolled dumping sites in Morocco with no bottom liner. About 150 tons/day of solid wastes from mixed urban and industrial origins are placed directly on the ground. At the site of this landfill, the groundwaters circulate deeply (10–15 m) in the Cenomanian rock (calcareous–marl), which is characterised by an important permeability from cracks. The soil is sand–clay characterized by a weak coefficient of retention.The phreatic water ascends to the bottom of three quarries, which are located within the landfill. These circumstances, along with the lack of a leachate collection system, worsen the risks for a potential deterioration of the aquifer.To evaluate groundwater pollution due to this urban landfill, piezometric level and geochemical analyses have been monitored since 1999 on 60 wells. The landfill leachate has been collected from the three quarries that are located within the landfill. The average results of geochemical analyses show an important polluant charge vehiculed by landfill leachate (chloride = 5680 mg l⁻¹, chemical oxygen demand = 1000 mg l⁻¹, iron = 23 000 μg l⁻¹). They show also an important qualitative degradation of the groundwater, especially in the parts situated in the down gradient area and in direct proximity to the landfill. In these polluted zones, we have observed the following values: higher than 4.5 mS cm⁻¹ in electric conductivity, 1620 and 1000 mg l⁻¹ respectively in chlorides and sulfate (), 15–25 μg l⁻¹ in cadmium, and 60–100 μg l⁻¹ in chromium. These concentrations widely exceed the standard values for potable water.Several determining factors in the evolution of groundwater contamination have been highlighted, such as (1) depth of the water table, (2) permeability of soil and unsaturated zone, (3) effective infiltration, (4) humidity and (5) absence of a system for leachate drainage. So, to reduce the pollution risks of the groundwater, it is necessary to set a system of collection, drainage and treatment of landfill leachates and to emplace an impermeable surface at the site of landfill, in order to limit the infiltration of leachate.     

Effet de la teneur en eau d'un sol sur la réduction bactérienne d'oxydes de fer

Iron-reducing activity of autochthonous bacteria from two temporary hydromorphic soils is evaluated by the study of iron reductive dissolution, as a function of water content. The release of ferrous iron in solution is coupled to the mineralization of soil organic carbon. Water soil saturation is not necessary for iron reductive dissolution, since the highest dissolution is obtained for a wet, but not water-saturated soil (100% of water holding capacity WHC), and dissolution is also very high in a soil at 75% WHC. To cite this article: S.J. Stemmler et al., C. R. Geoscience 336 (2004).     

Delayed geochemical hazard: Concept, digital model and case study

Delayed Geochemical Hazard (DGH briefly) presents the whole process of a kind of serious ecological and environmental hazard caused by sudden reactivation and sharp release of long-term accumulated pollutant from stable species to active ones in soil or sediment system due to the change of physical-chemical conditions (such as temperature, pH, Eh, moisture, the concentrations of organic matters, etc.) or the decrease of environment capacity. The characteristics of DGH are discussed. The process of a typical DGH can be expressed as a nonlinear polynomial. The points where the derivative functions of the first and second orders of the polynomial reach zero, minimum and maximum are keys for risk assessment and harzard pridication.The process and mechanism of the hazard is due to the transform of pollutant among different species principally. The concepts of "total releasable content of pollutant", TRCP, and "total concentration of active specie", TCAS, are necessarily defined to describe the mechanism of DGH. The possibility of the temporal and spatial propagation is discussed. Case study shows that there exists a transform mechanism of "gradual release" and "chain reaction" among the species of the exchangeable and the bounds to carbonate, iron and manganese oxides and organic matter, thus causing the delayed geochemical hazard.