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).     

Tetrahedral Plots of the Phase Relations for Basalts

The phase relations of quaternary systems are generally represented by projections onto ternary compositional planes. Such projections often obscure relationships that would only be evident in a three-dimensional tetrahedral plot. The tetrahedral plot requires that compositions of the minerals and melts be transformed into Cartesian coordinates. It is shown here how this transformation is carried out. The application is demonstrated by tetrahedral plots of experimental melt compositions of partially molten lherzolite. Furthermore, the plot can be used to evaluate whether or not a particular basaltic composition represents a primary melt. The methods are applicable to any four-component system.     

Pumpellyite in Low-grade Metamorphism

The regional metamorphism of the Kant? Mountains in Japan producedrocks of the following facies, with rising temperature: chloritefacies, pumpellyite-chlorite facies, glauco-phane-schist facies,and greenschist facies. This relationship is compared with theprogressive metamorphic zones in other regions where pumpellyitehas been found. Almost similar relations appear to hold in manymetamorphic terrains. Pumpellyites in glaucophanitic metamorphicterrains have, generally, low Fe'/R'R ratios. Physical andchemical conditions responsible for the formation of pumpellyiteare also discussed.     

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.     

A Raman spectroscopic study on the structural disorder of monazite–(Ce)

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO₄ stretching near 970?cm^?1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν₁(PO₄) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.     

Fluid inclusion studies of the Abawso gold prospect,near the Ashanti Belt,Ghana

The major Ghanaian lode gold deposits are preferentially aligned along the western and eastern contacts of the Kumasi Basin with the Ashanti and Sefwi Belts, respectively. The investigated area of the Abawso small-scale concession, covering the workings of the old Ettadom mine, is situated 3 km west of the lithological contact of the Birimian metavolcanic rocks of the Akropong Belt in the east with the Birimian metasedimentary rocks of the Kumasi Basin in the west. The rocks of the Abawso concession represent a steeply NW-dipping limb of a SE-verging anticline with an axis plunging to the SW. Quartz veining occurs predominantly in the form of en échelon dilatational veins along NNE–SSW-striking shear zones of a few metres width and shows evidence of brittle and ductile deformation. Also stockwork-style quartz veining occurs in the vicinity of the main shaft of the old Ettadom mine. Hydrothermal alteration includes sericitisation, sulphidation and locally carbonatisation. The auriferous quartz veins mainly follow the trend of brittle to ductile deformed quartz veins; however, some occur in stockwork. Fluid inclusion studies reveal a large number of H₂O inclusions along intragranular trails in auriferous quartz vein samples, as well as an overall dominance of H₂O and H₂O-CO₂ inclusions over CO₂ inclusions. Textural observations and physico-chemical fluid inclusion properties indicate post-entrapment modifications for all quartz vein samples due to grain boundary migration recrystallisation. This process is interpreted to be responsible for the generation of the CO₂ inclusions from a H₂O-CO₂ parent fluid. In comparison with mineralisation at the Ashanti and Prestea deposits, which are characterised by CO₂±N₂ inclusions, the observed inclusion assemblage may be due to a shallower crustal level of mineralisation, or different degrees and styles of recrystallisation, or a less pronounced development of laminated quartz veins due to comparably restricted pressure fluctuations. Furthermore, the microthermometric observations allow the reconstruction of a possible retrograde P-T path, depicting near-isothermal decompression in the P-T range of the brittle/ductile transition.Editorial handling: E. Frimmel     

Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

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.