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).     

Intra-interstadial environmental changes in Last Glacial loess revealed by molluscan assemblages from the Upper Palaeolithic site of Amiens-Renancourt 1 (Somme,France)

The Amiens-Renancourt 1 site recently yielded one of the most important Upper Palaeolithic human occupations of northern France by the number of flint artefacts and especially by the presence of Venus figurines. All the material comes from a single archaeological layer located in a tundra gley bracketed by loess units. A multi-proxy study combining a detailed stratigraphy, luminescence and radiocarbon datings and high-resolution (5 cm per sample) grain size and molluscan analyses was therefore carried out to reconstruct and date the associated environmental changes and to determine the exact context of the human occupation. The chronological frame thus established supports the correlations of the archaeology-bearing tundra gley and of an underlying arctic brown soil with Greenland interstadials GI-4 and GI-3. Composition changes in the molluscan population enabled the identification of transitional and optimum phases and sub-phases within these two pedogenetic horizons. A conceptual correlation model linking molluscan phases with millennial-scale variations of Greenland ice-core and Sieben Hengste speleothem climate records is proposed. The Human occupation appears contemporaneous to the end of the stadial–interstadial transition of GI-3. Synchronous in Amiens-Renancourt 1 and Nussloch, subsequent micro-gleys may also result from a regional/global forcing. Such a level of detail is unprecedented in a loess sequence.     

An automated salt‐tracing gauge for flow‐velocity measurement

This article introduces the SVG (salt‐velocity gauge), a novel automated technique for measuring flow velocity by means of salt tracing. SVG allows a high measuring rate (up to one every 2 seconds), short control section length (down to 10 cm), high accuracy (+[sol ]?1·5 cm s^?1), and unbiased calculation of the mean velocity in experimental conditions with turbulent, supercritical flow. A few cubic centimetres of saturated salt solution (NaCl) are injected into the flow at regular time intervals using a programmable solenoid valve. The tracer successively passes two conductivity probes placed a short distance downstream. The transformation of the signal between the two probes is modelled as a one‐dimensional diffusion wave equation. Model calibration gives an estimation of the mean velocity and the diffusion for each salt plume. Two implementations of the SVG technique are described. The first was an outdoors simulated rainfall experiment in Senegal (conductivity probes at 40 cm apart, 8 Hz measurement rate, salt injections at 10 second intervals). Mean velocity was estimated to range between 0·1 and 0·3 m s^?1. The second was a laboratory‐based flume experiment (conductivity probes at 10 cm apart, 32 Hz, salt injections at 2 second intervals). Another SVG with probes at 34 cm apart was used for comparison. An acoustic Doppler velocimeter (ADV) was also used to give an independent assessment of velocity. Using the 10 cm salt gauge, estimated mean velocity ranged from 0·6 to 0·9 m s^?1 with a standard deviation of 1·5 cm s^?1. Comparisons between ADV, 10 cm SVG and 34 cm SVG were consistent and demonstrated that the salt‐tracing results were unbiased and independent of distance between probes. Most peaks were modelled with r² > 90 per cent. The SVG technology offers an alternative to the dye‐tracing technique, which has been severely criticized in the literature because of the wide interval of recommended values for the correction factor α to be applied to the timings. This article demonstrates that a fixed value of α is inappropriate, since the correction factor varies with velocity, diffusion and the length of the control section. Copyright © 2005 John Wiley & Sons, Ltd.     

Trace element geochemistry of CR chondrite metal

We report trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) of metal grains from nine different CR chondrites, distinguishing grains from chondrule interior (“interior grains”), chondrule surficial shells (“margin grains”), and the matrix (“isolated grains”). Save for a few anomalous grains, Ni‐normalized trace element patterns are similar for all three petrographic settings, with largely unfractionated refractory siderophile elements and depleted volatile Au, Cu, Ag, S. All three types of grains are interpreted to derive from a common precursor approximated by the least‐melted, fine‐grained objects in CR chondrites. This also excludes recondensation of metal vapor as the origin of the bulk of margin grains. The metal precursors were presumably formed by incomplete condensation, with evidence for high‐temperature isolation of refractory platinum‐group‐element (PGE)‐rich condensates before mixing with lower temperature PGE‐depleted condensates. The rounded shape of the Ni‐rich, interior grains shows that they were molten and that they equilibrated with silicates upon slow cooling (1–100 K h^?1), largely by oxidation/evaporation of Fe, hence their high Pd content, for example. We propose that Ni‐poorer, amoeboid margin grains, often included in the pyroxene‐rich periphery common to type I chondrules, result from less intense processing of a rim accreted onto the chondrule subsequent to the melting event recorded by the interior grains. This means either that there were two separate heating events, which formed olivine/interior grains and pyroxene/margin grains, respectively, between which dust was accreted around the chondrule, or that there was a single high‐temperature event, of which the chondrule margin records a late “quenching phase,” in which case dust accreted onto chondrules while they were molten. In the latter case, high dust concentrations in the chondrule‐forming region (at least three orders of magnitude above minimum mass solar nebula models) are indicated.     

Constraints in 3D gravity inversion

A three-dimensional (3D) inversion program is developed to interpret gravity data using a selection of constraints. This selection includes minimum distance, flatness, smoothness and compactness constraints, which can be combined using a Lagrangian formulation. A multigrid technique is also implemented to resolve separately large and short gravity wavelengths. The subsurface in the survey area is divided into rectangular prismatic blocks and the problem is solved by calculating the model parameters, i.e. the densities of each block. Weights are given to each block depending on depth, a priori information on density and the density range allowed for the region under investigation. The present computer code is tested on modelled data for a dipping dike and multiple bodies. Results combining different constraints and a weight depending on depth are shown for the dipping dike. The advantages and behaviour of each method are compared in the 3D reconstruction. Recovery of geometry (depth, size) and density distribution of the original model is dependent on the set of constraints used. From experimentation, the best combination of constraints for multiple bodies seems to be flatness and a minimum volume for the multiple bodies. The inversion method is tested on real gravity data from the Rouyn-Noranda (Quebec) mining camp. The 3D inversion model for the first 10 km is in agreement with the known major lithological contacts at the surface; it enables the determination of the geometry of plutons and intrusive rocks at depth.     

Volcanic edifice stability during cryptodome intrusion

Limit equilibrium analyses were applied to the 1980 Mount St. Helens and 1956 Bezymianny failures in order to examine the influence on stability of structural deformation produced by cryptodome emplacement. Weakening structures associated with the cryptodome include outward-dipping normal faults bounding a summit graben and a flat shear zone at the base of the bulged flank generated by lateral push of the magma. Together with the head of the magmatic body itself, these structures serve directly to localize failure along a critical surface with low stability deep within the interior of the edifice. This critical surface, with the safety coefficient reduced by 25-30%, is then very sensitive to stability condition variation, in particular to the pore-pressure ratio (r_u) and seismicity coefficient (n). For r_u=0.3, or n=0.2, the deep surface suffers catastrophic failure, removing a large volume of the edifice flank. In the case of Mount St. Helens, failure occurred within a material with angle of friction ~40°, cohesion in the range 10⁵-10⁶ Pa, and probably significant water pore pressure. On 18 May 1980, detachment of slide block I occurred along a newly formed rupture surface passing through the crest of the bulge. Although sliding of block I may have been helped by the basal shear zone, significant pore pressure and a triggering earthquake were required (r_u=0.3 and n=0.2). Detachment of the second block was guided by the summit normal fault, the front of the cryptodome, and the basal shear zone. This occurred along a deep critical surface, which was on the verge of failure even before the 18 May 1980 earthquake. The stability of equivalent surfaces at Bezymianny Volcano appears significantly higher. Thus, although magma had already reached the surface, weaker materials, or higher pore pressure and/or seismic conditions were probably required to reach the rupture threshold. From our analysis, we find that deep-seated sector collapses formed by removing the edifice summit cannot generally result from a single slide. Cryptodome-induced deformation does, however, provide a deep potential slip surface. As previously thought, it may assist deep-seated sector collapse because it favors multiple retrogressive slides. This leads to explosive depressurization of the magmatic and hydrothermal systems, which undermines the edifice summit and produces secondary collapses and explosive blasts.     

Hydrothermal calderas

The standard model of caldera formation is related to the emptying of a magma chamber and ensuing roof collapse during large eruptions or subsurface withdrawal. Although this model works well for numerous volcanoes, it is inappropriate for many basaltic volcanoes (with the notable exception of Hawaii), as these have eruptions that involve volumes of magma that are small compared to the collapse. Many arc volcanoes also have similar oversized depressions, such as Poas (Costa Rica) and Aoba (Vanuatu). In this article, we propose an alternative caldera model based on deep hydrothermal alteration of volcanic rocks in the central part of the edifice. Under certain conditions, the clay-rich altered and pressurized core may flow under its own weight, spread laterally, and trigger very large caldera-like collapse. Several specific mechanisms can generate the formation of such hydrothermal calderas. Among them, we identify two principal modes: mode 1: ripening with summit loading and flank spreading and mode II: unbuttressing with flank subsidence and flank sliding. Processes such as summit loading or flank subsidence may act simultaneously in hybrid mechanisms. Natural examples are shown to illustrate the different modes of formation. For ripening, we give Aoba (Vanuatu) as an example of probable summit loading, while Casita (Nicaragua) is the type example of flank spreading. For unbuttressing, Nuku Hiva Island (Marquesas) is our example for flank subsidence and Piton de la Fournaise (La Réunion) is our example of flank sliding. The whole process is slow and probably needs (a) at least a few tens of thousands of years to deeply alter the edifice and reach conditions suitable for ductile flow and (b) a few hundred years to achieve the caldera collapse. The size and the shape of the caldera strictly mimic that of the underlying weak core. Thus, the size of the caldera is not controlled by the dimensions of the underlying magma reservoir. A collapsing hydrothermal caldera could generate significant phreatic activity and trigger major eruptions from a coexisting magmatic complex. As the buildup to collapse is slow, such caldera-forming events could be detected long before their onset.