Delphine Charpentier

EFFECTS OF TEMPERATURE, pH, AND IRON/CLAY AND LIQUID/CLAY RATIOS ON EXPERIMENTAL CONVERSION OF DIOCTAHEDRAL SMECTITE TO BERTHIERINE, CHLORITE, VERMICULITE, OR SAPONITE

AbstractIn deep geological repositories for high-level nuclear wastes, interactions between steel canisters and clay-rich materials may lead to mineralogical transformations with a loss of the confining properties of the clays. Experiments simulating the conversion of smectite to Fe-rich clay phases in contact with Fe metal have been carried out to evaluate such a possibility by taking into account the effects of a series of critical parameters, including temperature, pH, and Fe/clay (Fe/C) and liquid/clay (L/C) ratios. The mineralogical and chemical transformations observed in these experiments have been compared with data from the literature, and subsequently used to propose a conceptual model for the main mineralogical transformations which can be expected in clay formations surrounding high-level nuclear waste repositories. In the presence of Fe metal and under low oxygen fugacity (<-40) the main mineralogical sequences are as follows: (1)up to 150°C, under neutral pH, and L/C > 5: dioctahedral smectite (di-sm) → 7 Å Fe-rich phase (berthierine, odinite-cronstedtite) for large Fe/C ratios (>0.5), or di-sm → Fe-rich di-sm + Fe-rich trioctahedral smectite (tri-sm) for small Fe/C ratios (0.1)(2)up to 150°C, under alkaline pH (10–12), and L/C > 5: di-sm → Fe di-sm (±palygorskite) for a small Fe/C ratio (0.1)(3)at 300°C, Fe/C = 0.1, and L/C > 5: di-sm → Fe-rich saponite → trioctahedral chlorite + feldspar + zeolite (near-neutral pH); di-sm → Fe-rich vermiculite + mordenite (pH 10–12). Low temperatures (<150°C) and large L/C and Fe/C ratios seem to favor the crystallization of the serpentine group minerals instead of Fe-rich trioctahedral smectites or chlorites, the latter being favored by higher temperatures. The role of L/C and Fe/C ratios and the competition between them at different temperatures is a crucial point in understanding the transformation of smectite in contact with Fe metal.

EFFECTS OF ETHYLENE GLYCOL SATURATION PROTOCOLS ON XRD PATTERNS: A CRITICAL REVIEW AND DISCUSSION

Study of the transformation of smectite to illite, chlorite or vermiculite via interstratified clay minerals needs precise qualitative and quantitative determinations of the different layers in the mixed-layer clays and is generally based on X-ray diffraction (XRD) patterns after specific treatments of the clay samples. Saturation with K or Mg followed by ethylene glycol (EG) solvation are classical methods used to identify high-charge smectite and vermiculite. These procedures have been applied to two experimental clays, one composed of smectite layers and the second, a mixture of vermiculite and smectite layers. Different methods of glycolation (EG vapor or liquid EG) produce significant differences in the XRD patterns. Comparison with literature data indicates that K-saturated, high-charge smectite (≈0.8 < total charge <1/unit-cell) and Mg-vermiculite (whatever its charge) do not expand in ethylene glycol vapor (d values ≈14–15 Å). Expansion to 17 Å in liquid ethylene glycol occurs for Mg-vermiculite with a total charge of <~1.2/unit-cell and for K-saturated, high-charge smectite, when the tetrahedral charge is <≈0.7/unit-cell. This study shows that: (1) glycolation procedures need to be standardized; (2) the use of saturation protocols using both liquid ethylene glycol and ethylene glycol vapor yields useful additional information about the distribution of charges in clay minerals.

Oxidation of mudstone in a tunnel (Tournemire, France): consequences for the mineralogy and crystal chemistry of clay minerals

Abstract The excavation of a tunnel through a mudstone formation provides an opportunity to examine the effects of the modification of the physical and chemical environment on the rock. The mineralogical and chemical consequences of hydration-dehydration cycles and of oxidation have been evaluated in the case of the Toarcian mudstone formation at the Tournemire experimental site (France). Studies by X-ray diffraction and tansmission electron microscopy of both altered and preserved samples show that the introduction of air and condensed water causes the oxidation of pyrite and the subsequent generation of acid and sulphate-rich waters at the micron scale, in the local environment of pyrites. The fluid-clay particle interactions around the oxidized pyrites induce: (1) a statistical enrichment in Si of the I-S clay minerals; (2) an increase in the Fe(III)/Fe total ratio in some of the I-S particles; and (3) the dissolution of illite layers in mixed-layer I-S. These evolutions are consistent with the results of numerical modelling which reproduced the interaction between the clay particles and the acid water.

Évolution minéralogique des argilites en zone sous-saturée oxydée : exemple des parois du tunnel de Tournemire (Aveyron, France)

Abstract Digging of underground work such as that of the Tournemire tunnel in a Toarcian argillite formation, has an impact on the surface mineralogy of the rock blocks. In spite of its very low water content, the argillite is reactive as a consequence of the modification of the redox conditions. Thus, atmospheric oxygen in presence of adsorbed water induces pyrite corrosion and formation of secondary mineral phases such as gypsum, celestite, jarosite and Fe-hydroxides, which play a significant role on the water–rock equilibria of the mechanically disturbed zone.

Influence of fault rock foliation on fault zone permeability: The case of deeply buried arkosic sandstones (Gres d'Annot, southeastern France)

We describe the structure, microstructure, and petrophysical properties of fault rocks from two normal fault zones formed in low-porosity turbiditic arkosic sandstones, in deep diagenesis conditions similar to those of deeply buried reservoirs. These fault rocks are characterized by a foliated fabric and quartz-calcite sealed veins, which formation resulted from the combination of the (1) pressure solution of quartz, (2) intense fracturing sealed by quartz and calcite cements, and (3) neoformation of synkinematic white micas derived from the alteration of feldspars and chlorite. Fluid inclusion microthermometry in quartz and calcite cements demonstrates fault activity at temperatures of 195C to 268C. Permeability measurements on plugs oriented parallel with the principal axes of the finite strain ellipsoid show that the Y axis (parallel with the foliation and veins) is the direction of highest permeability in the foliated sandstone (10–2 md for Y against 10–3 md for X, Z, and the protolith, measured at a confining pressure of 20 bars). Microstructural observations document the localization of the preferential fluid path between the phyllosilicate particles forming the foliation. Hence, the direction of highest permeability in these fault rocks would be parallel with the fault and subhorizontal, that is, perpendicular to the slickenlines representing the local slip direction on the fault surface. We suggest that a similar relationship between kinematic markers and fault rock permeability anisotropy may be found in other fault zone types (reverse or strike-slip) affecting feldspar-rich lithologies in deep diagenesis conditions.

Temperature micro-mapping in oscillatory-zoned chlorite: Application to study of a green-schist facies fault zone in the Pyrenean Axial Zone (Spain)

Abstract Oscillatory compositional zoning in minerals has been observed in hydrothermal, magmatic, and metamorphic environments and is commonly attributed to chemical or physical cyclical changes during crystal growth. Chemical zoning is a common feature of solid solutions, which has been rarely reported in phyllosilicates. In this study, oscillatory zoning in chlorite is described in samples from the Pic-de-Port- Vieux thrust, a minor thrust fault associated to the major Gavarnie thrust fault zone (Central Pyrenees, Spain). The Pic-de-Port-Vieux thrust sheet comprises a 1-20 m thick layer of Triassic red pelite and sandstone thrust over mylonitized Cretaceous dolomitic limestone. The thrust fault zone deformation comprises secondary faults and cleavage affecting the Triassic pelite and sandstone. An important feature responsible to this deformation is a set of veins filled by quartz and chlorite. Chlorite is present in crack-seal extension veins and in shear veins; both structures opened under the same stress conditions. In some shear veins, chlorite occurs as pseudo-uniaxial plates arranged in rosette-shaped aggregates. These aggregates appear to have developed as a result of radial growth of the chlorite platelets. Oscillatory zoning has been imaged by backscattered scanning electron microscopy and by X‑ray quantitative micro-mapping. These oscillations correspond to chemical zoning with alternating iron-rich and magnesium-rich bands. The chlorite composition ranges from a Fe-rich pole to a Mg-rich pole. Fe3+/ΣFe values were measured in chlorite using μ-XANES spot analyses and vary from 0.23 to 0.44. The highest values are in the Ferich area. Temperature maps, built from standardized microprobe X‑ray images and redox state using the program XMapTools, indicate oscillatory variations from about 310 to 400 ± 50 °C during chlorite crystallization. These temperature variations are correlated with a Fe3+/ΣFe variation by Al3+Fe3+-1 and ditrioctahedral substitutions highlighted by Mg and FeTot contents (Fe-Mg zoning). Chemical variations could be then explained by alternation of cooling times and cyclical pulses of a fluid hotter than the host rock. It is however not excluded that kinetic effects influence the incorporation of Mg or Fe during chlorite crystallization.

Clays and zeolite authigenesis in sediments from the flank of the Juan de Fuca Ridge

Abstract This study focuses on the mineralogical and chemical analysis of sediments overlying basaltic basement through which seawater circulates (ODP Leg 168, flank of the Juan de Fuca Ridge). A SEM and TEM-EDX study of the authigenic clays and zeolites allowed the characterization of the hydrothermal phases and the determination of their mechanism of formation. Silicate authigenesis related to hydrothermal alteration of sediment was observed in the sediment layer just above basement at sites located >30 km from the ridge axis. This sediment alteration is particularly intense at Site 1031 where authigenic formation of Fe-Mg- rich smectites (montmorillonite and saponite) and zeolites occur, linked to the dissolution of biogenic calcite. Vertical advection of basement fluid through the sediment column is required to produce this alteration. This process is still active at Site 1031, based on systematic variations in porewater profiles and temperatures obtained from stable isotopic data on calcium carbonates, and the nature of authigenic minerals.

Fluid–rock interactions related to metamorphic reducing fluid flow in meta-sediments: example of the Pic-de-Port-Vieux thrust (Pyrenees, Spain)

In orogens, shortening is mainly accommodated by thrusts, which constitute preferential zones for fluid–rock interactions. Fluid flow, mass transfer, and mineralogical reactions taking place along thrusts have been intensely investigated, especially in sedimentary basins for petroleum and uranium research. This study combines petrological investigations, mineralogical quantifications, and geochemical characterizations with a wide range of analytical tools with the aim of defining the fluid properties (nature, origin, temperature, and redox) and fluid–host rock interactions (mass transfers, recrystallization mechanisms, and newly formed synkinematic mineralization) in the Pic-de-Port-Vieux thrust fault zone (Pyrenees, Spain). We demonstrate that two geochemically contrasted rocks have been transformed by fluid flow under low-grade metamorphism conditions during thrusting. The hanging-wall Triassic red pelite was locally bleached, while the footwall Cretaceous dolomitic limestone was mylonitized. The results suggest that thrusting was accompanied by a dynamic calcite recrystallization in the dolomitic limestone as well as by leaching of iron via destabilization of iron oxides and phyllosilicate crystallization in the pelite. Geochemical and physical changes highlighted in this study have strong implications on the understanding of the thrust behavior (tectonic and hydraulic), and improve our knowledge of fluid–rock interactions in open fluid systems in the crust.

Frictional Properties of Subduction Input Sediments at an Erosive Convergent Continental Margin and Related Controls on Décollement Slip Modes: The Costa Rica Seismogenesis Project

The spectrum of slip modes occurring along shallow portions of the plate boundary decollement in subduction zones includes aseismic slip, slow slip, and seismogenic slip. The factors that control slip modes directly influence the hazard potential of subduction zones for generating large magnitude earthquakes and tsunamis. We conducted an experimental study of the frictional behaviour of subduction input sediments, recovered from two IODP expeditions to the erosive subduction margin offshore Costa Rica (Exp. 334, 344),employing rotary shear under hydrothermal conditions. The velocity dependence of friction was explored, using simulated gouges prepared from all major lithologies, covering a wide range of conditions representative for the initial stages of subduction. Temperature, effective normal stress, and pore fluid pressure were varied systematically up to 140 °C, 110 MPa and 120 MPa respectively. Sliding velocities up to 100 μm/s, relevant for earthquake rupture nucleation and slow slip, were investigated. The only sediment type that produced frictional instabilities (i.e. laboratory earthquakes) was the calcareous ooze carried by the incoming Cocos Plate, which by virtue of its slip weakening behaviour is also a likely candidate for triggering slow slip events. We evaluate this mechanism of producing unstable slip and consider alternatives. Therefore, locking and unlocking of plate boundary megathrusts are not only related to variations in pore fluid pressure, but may also depend on the presence of pelagic carbonate‐rich lithologies. Subduction systems containing such input are likely low‐latitude, where extensive deposition of carbonates takes place above the CCD.