Preliminary data on chemical changes in the Aral Sea during low-level periods from the last 9000 years

The withdrawal of the Aral Sea tributaries (Amu and Syr Daria) for cultures has led to significant falls of its level and an important increase in its salinity. During the Holocene, a succession of low and high water inputs occurred. Silty deposits correspond to the high levels and carbonates to the low levels. This study makes a distinction between the Syr Daria and the Amu Daria water inputs during low-level periods by using mineralogical and chemical compositions of the carbonates deposits. Waters from the Syr Daria are more sulphatic and have a low iron content in comparison with that of the Amu Daria. The Syr Daria was the major tributary around 7500, 4956 and 970 yr?BP, whereas around 6200 and 3610 yr?BP, inflow also from the Amu Daria is observed. To cite this article: L. Le Callonnec et al., C. R. Geoscience 337 (2005).     

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).     

Mise au point d'un milieu de culture pour l'étude de l'altération de silicates en présence de Pseudomonas aeruginosa

The influence of microorganisms on mineral alteration is not easy to determine in environmental conditions, because of the difficulty to raise for comparison purposes an identical but abiotic system. Another problem in this context is the choice of reliable tracers to evaluate the alteration rate of materials during in vitro experiments. To face such difficulties, we elaborated a defined medium allowing both the growth of Pseudomonas aeruginosa and a precise measurement of the elements solubilized from the minerals. Thanks to this medium, we were able to quantitatively determine the amounts of major elements solubilized from the materials in the presence of bacterial growth, compared to a sterile system. Moreover, the analysis by ICP-MS of trace elements was possible after a chromatographic treatment, which selectively eliminated 99% of the sodium content of the medium. To cite this article: G. Aouad et al., C. R. Geoscience 337 (2005).     

Dissolution of calcitic marble and dolomitic rock in high iron concentrated acid mine drainage: application to anoxic limestone drains

Oxidation of sulphide mining waste can generate acid mine drainage (AMD) that has the potential to seriously affect the ecosystems. Acid mine drainage is characterised by a high acidity, high concentrations of sulphates and metals. To reduce the environmental impacts due to AMD, neutralisation using limestone drains is an option proposed in the literature and used around the world. The present study focuses on the influence of the carbonate rock mineralogy and their particle size on the neutralising capacity. The tests were performed in two different anoxic conditions: in batch reactors, and in columns having a hydraulic retention time of 15?h. The results showed that the neutralisation capacity of calcite was more important than for dolomitic rock, and smaller particle size gave higher alkalinity production (fine calcite dissolved faster in contact with AMD). A characterization of metal precipitate in sludge and in limestone coating was performed and demonstrated that gypsum, lepidocrocite and goethite were the predominant secondary minerals to be formed. Finally, this study underlines that anoxic limestone drain cannot be used alone to treat high iron concentrated AMD.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Proximal and distal styles of pegmatite-related metasomatic emerald mineralization at Ianapera,southern Madagascar

The Ianapera emerald deposit is located in the Neoproterozoic Vohibory Block of southern Madagascar. The local geology consists of intercalated migmatitic gneissic units and calcareous metasedimentary rocks, containing boudinaged metamorphosed mafic/ultramafic lenses, all intruded by pegmatite veins. These units occur near the hinge of the tightly folded Ianapera antiform, within a few kilometers of the Ampanihy shear zone. Emerald mineralization is hosted by metasomatic phlogopite veins, and bodies developed within the mafic/ultramafic rocks. Based on field and textural relationships, we distinguish proximal and distal styles of mineralization. Proximal mineralization occurs at the contact of pegmatite veins with mafic/ultramafic units; in the distal style, pegmatites are not observed. Three types of emeralds could be distinguished, mainly on the basis of color and mineral zoning. Some of these emeralds have the most Al-depleted and Cr-rich composition ever recorded. Another characteristic feature to the Ianapera deposit and, to our knowledge, yet unreported, is the association of some emeralds with scapolite in metasomatised mafic rocks. Mineral inclusions are common in most emeralds and include phlogopite, carbonates, barite, K-feldspar, quartz, pyrite, zircon, monazite, bastnaesite, phenakite, plus Fe and Cr oxides. However, feldspar and rare earth element-bearing minerals occur predominantly in proximal emeralds, which also have a more incompatible trace-element signature than distal emeralds. We propose a model related to syn- to post-tectonic magmatic-hydrothermal activity. Pegmatitic bodies intruded units of the Ianapera antiform probably during tectonic relaxation. Exsolution of fluids rich in halogens and incompatible elements from the cooling pegmatites caused hydrothermal metasomatism of Cr-bearing mafic/ultramafic rocks in direct contact with the pegmatites. Local fracturing favored fluid infiltration, permitting the formation of distal mineralization. Emerald composition was controlled by the chemistry of the host rock. The presence of carbonate mineral inclusions in the emeralds and the high F-activity indicated by elevated F-contents in newly formed minerals suggest transport of Be as a fluoride-carbonate complex. It seems likely that beryl formation was triggered by precipitation of F-rich phlogopite, which removed the complexing ligand from the fluid.     

Infrared reflectivity spectra of single crystal cassiterites

The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm^–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO₂ spectra is a dip near 500 cm^–1 understood as the activation of an infrared forbidden E _g mode due to the amount of Fe³⁺ and Ti⁴⁺ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.     

An Overview of Dissolved and Suspended Matter Fluxes in the Loire River Basin: Natural and Anthropogenic Inputs

The spatial and temporal distributions of major elements were investigated in the surface waters and in associated suspended matter at two sites of the upper Loire basin (Orleans and Brehemont) between 1995 and 1998.According to geochemical and isotopic patterns, the dissolved load appears to result from a process of mixing rainwater inputs, weathering processes of carbonate and silicate bedrock, and agricultural and urban inputs. Natural inputs influence 60% of water chemical composition at both sites. Annual dissolved fluxes were estimated to be 1300 10³ t/y at Orleans and 1620 10³ t/y at Brehemont. Major elements are transported mainly in the dissolved fraction. After correcting for atmospheric and anthropogenic inputs, the silicate specific export rate was calculated to be 11 t/y/km² throughout the basin and the carbonate specific export rate to be from 47 t/y/km² at Orleans to 23 t/y/km² at Brehemont.The suspended load appears to result from at least two particle reservoirs: a silicate reservoir and a carbonate reservoir. The silicate reservoir has a detrital origin, mainly during periods of high flow, while the carbonate reservoir has a detrital origin during periods of high flow and an authigenic origin during periods of low flow. Of the total annual flow of suspended matter, this authigenic material represents 16% at Orleans, 25% at Brehemont and 37% in the fluvial part of the estuary. After correcting authigenic inputs, the specific export rate due to mechanical weathering was estimated to be 8 t/y/km² throughout the Loire basin.     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.