Martine Buatier

Smectite-Illite Transition in Barbados Accretionary Wedge Sediments: TEM and AEM Evidence for Dissolution/Crystallization at Low Temperature

Sediments from depths to 670 m in the Barbados accretionary complex and transecting the décollement zone have been studied by transmission and analytical electron microscopy (TEM/AEM). The sediments consist of claystone and mudstone intercalated with layers of volcanic ash. Smectite comprises the bulk of the noncalcareous sediments and forms a continuous matrix enveloping sparse, irregular, large grains of illite, chlorite, kaolinite and mixed-layer illite/chlorite of detrital origin at all depths. The detrital origin of illite is implied by illite-smectite textural relations, well-ordered 2M polytypism, and a muscovite-like composition. K is the dominant interlayer cation in smectite at all depths, in contrast to the Na and Ca that are normally present in similar rocks.Deeper samples associated with the décollement zone contain small (up to 100 Å thick) illite packets included within still-dominant subparallel layers of contiguous smectite. AEM analyses of these packets imply illite-like compositions. Selected area electron diffraction (SAED) patterns show that this illite is the 1Md polytype. Packets display step-like terminations like those seen in illite of hydrothermal origin. The data collectively demonstrate that smectite transforms progressively to illite via a dissolution-re-crystallization process within a depleting matrix of smectite, and not by a mechanism of layer replacement. This illite seems to form at depths as shallow as 500 m and temperatures of 20°-30°C, which is in marked contrast to the much higher temperature conditions normally assumed for this transformation. This implies that the high water/rock ratios associated with the décollement zone are significant in promoting reaction.

Fe-smectite-glauconite transition in hydrothermal green clays from the Galapagos spreading center

X-ray powder diffraction (XRD) and energy-dispersive X-ray analyses (EDX) of individual clay particles from hydrothermal mounds in the Galapagos spreading center (GSC) (Deep Sea Drilling Project, hole 509B) and high-resolution transmission electron microscopy (HRTEM) of the <2-µm size fraction of these sediments were carried out to document the mineralogy, geochemistry, and evolution of their clay horizons. The hydrothermal clay minerals of the GSC mounds were found to be intercalated with pelagic sediments and occurred as irregular interstratified illite/smectite according to X-ray powder diffraction analyses. On the basis of TEM, HRTEM, and EDX data, two types of clays appeared to coexist; these types differed in morphology, potassium content, and mode of stacking sequence. Lath-shaped particles having regular 10-Å, spacings were identified as glauconite, and filmy or veil-like particles, having curly edges and variable 10-13-Å spacings were identified as Fe-smectite (nontronite and Fe-montmorillonite). The absence of lattice fringes between Fe-smectite and glauconite crystallites was observed by HRTEM in clay aggregates. This structural discontinuity between Fe-smectite and glauconite layers suggests that a dissolution-recrystallization mechanism was responsible for the textural and chemical transition from the filmy Fe-smectite to the lath-like glauconite.

Land use change, soil erosion and alluvial dynamic in the lower Doubs Valley over the 1st millenium AD (Neublans, Jura, France)

Abstract Geochemical and particle size analyses, surface scanning magnetic susceptibility, microscopic charcoal counting and pollen analysis, have been carried out on two cores from the lower Doubs valley in order to reconstruct the land use history. The interpretation of anthropogenic pollen indicators and micro-charcoal deposits is discussed in relation to the lithological variation of sedimentary accumulation and evolution of the settlement. The environmental changes which occurred during the 1st and the 6th century AD reflect the impact of human activities on the landscape in the immediate surroundings of the site. Multiproxy indicators indicate that soil erosion as a consequence of agricultural activities including fire practices. A reactivation of hydrologic flow of the river recorded in the sedimentary sequences attests to a larger environmental perturbation between 1st–3rd and 7th–8th century AD.

Fluid–sediment interactions related to hydrothermal circulation in the Eastern Flank of the Juan de Fuca Ridge

Abstract Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east–west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe–Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.

CHARACTERIZATION AND ORIGIN OF Fe3+-MONTMORILLONITE IN DEEP-WATER CALCAREOUS SEDIMENTS (PACIFIC OCEAN, COSTA RICA MARGIN)

Millimetric to centimetric green grains widespread in pelagic calcareous sediments recovered at a water depth of3000 m near the Costa Rica margin were studied by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. Samples were collected, during the Ticoflux II expedition, from the upper bioturbated part of four sedimentary cores (0.13–3.75 m below seafloor). The sediments are calcareous and siliceous nanofossil oozes (coccoliths, diatoms, radiolarians, etc.).Green grains show generally a concentric zoning with a green rim in which smectite largely predominates over pyrite and a black core in which pyrite is prevalent. Observations by SEM indicate that this zoning results from a progressive inward alteration and replacement of the accumulations of pyrites by smectites. The high-resolution TEM observations of the smectite-pyrite interfaces suggest that the replacement of pyrites by smectite occurs through a dissolution-precipitation process with the formation of a gel. The pyrite matrix is composed of a huge number of very small (0.5–22 µm) pyrite octahedra, a typical texture resulting from the pyritization of organic material in early diagenetic environments.The accurate mineralogical and crystal chemical characterization of the smectites indicate that they are Fe3+-montmorillonites (Fe3+-rich smectite with a dominant octahedral charge, rarely recorded in the literature). The formation of such Fe3+-montmorillonites forming green grains could be explained by two successive diagenetic redox stages: (1) reducing stage: early pyritization of the organic matter by microbial reduction within reducing micro-environments; (2) oxidizing stage: Fe3+-montmorillonite crystallized in space liberated after dissolution of pyrite connected with the rebalancing of the redox conditions of the micro-environments with the oxidizing surrounding sediments.

Mineralogical characterization and genesis of hydrothermal Mn oxides from the flank of the Juan the Fuca Ridge

Abstract Several sites of active hydrothermal flow have been found on the eastern flank of the Juan de Fuca Ridge. These sites are typically located along the edge of basaltic outcrops where sediment is thin. We present data on Mn-oxides formed on such outcrops (Zona Bare and Grinin Bare). These oxides are either black-layered crust or soft micro-concretions found in partially altered sediments. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses of Mn crusts indicate the presence of well-crystallized todorokite and birnessite encrusting detrital minerals and replacing siliceous fossil. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) analyses were used to identify amorphous and poorly crystallized Mn-rich phases in partially altered sediments and crusts. TEM of impregnated samples showed textural evidence suggesting that amorphous Mn oxides are incrusting cellular structures that could be bacteria. The valence state of Mn in these oxides was determined by parallel electron energy loss spectroscopy (PEELS). Results indicate that todorokite and birnessite have an average valence state of about 3.7 whereas the poorly crystallized Mn-rich phases have a lower valence state. These data suggest that the formation of hydrothermal Mn concretions occurs in several steps. The initial step is the adsorption or precipitation of Mn, Fe, and Si around cell-wall bacteria, extracellular polymers, and siliceous fossil remains. These mineralizations are poorly crystallized phyllomanganates, which progressively increase in size and crystallinity to give the final birnessite and todorokite products. All of these Mn-rich phases are the result of interactions between hydrothermal fluid and sediments and formed in areas where hydrothermal fluids discharge through the sediment.

TEM-EDX investigation on Zn- and Pb-contaminated soils

Abstract Lead and zinc contaminated soils from a smelter area in the northern part of France have been studied by transmission electron microscopy (TEM). This study was carried out with 4 different soils contaminated by Pb and Zn but with different chemical and physical characteristics. Two soils are tilled and have a neutral or slightly basic pH, one is a wooded soil and the last one is a meadow soil with acidic pH and high total organic content . TEM images of the soil samples have been coupled with focused energy dispersive X-ray (EDX) analyses and chemical mapping on a few micron-sized windows. This study demonstrates that TEM is a particularly efficient method to investigate metal speciation in the fine fractions of the contaminated soils. Zinc could be detected locally in sulphide minerals probably coming from the smelter emissions, but the major phases retaining Zn are Fe-oxyhydroxides and smectites. Lead could be detected in small aggregates which were characterized by EDX and selected area electron diffraction. Their structural formulae correspond to a pyromorphite-like mineral in which Pb is partly substituted by Ca and Na. Pyromorphite is present only in the wooded and meadow soils where it forms partly from amorphous Si-rich phases (slags) coming from the smelter. These results are compared with data previously obtained by spectroscopic methods on the same samples.

Clay diagenesis in the sandstone reservoir of the Ellon Field (Alwyn, North Sea)

The nature, composition, and relative abundance of clay minerals in the sandstones of the Brent Group reservoir were studied between 3200–3300 m in a well of the Ellon Field (Alwyn area, North Sea). The sandstones have a heterogeneous calcite cement which occurred during early-diagenesis. Clay diagenesis of the cemented and uncemented sandstones was investigated using optical microscopy, scanning electron microscopy (SEM), X-ray diffraction analyses (XRD), and infrared spectroscopy (IR). The influence of cementation on clay neoformation is demonstrated in this study. Detrital illite and authigenic kaolinite are present in both the calcite-cemented and uncemented sandstones suggesting that kaolinite precipitated before calcite cementation. In the uncemented sandstones, blocky dickite replaces vermiform kaolinite with increasing depth. At 3205 m, authigenic illite begins to replace kaolinite and shows progressive morphological changes (fibrous to lath-shape transition). At 3260 m, all sandstones are not cemented by calcite. Illite is the only clay mineral and shows a platelet morphology.In the cemented samples, vermiform kaolinite is preserved at all depths, suggesting that dickite transformation was inhibited by the presence of the calcite cement. This observation suggests that calcite cement would prevent fluid circulation and dissolution-precipitation reactions.

Fluid migration during Eocene thrust emplacement in the south Pyrenean foreland basin (Spain): an integrated structural, mineralogical and geochemical approach

Abstract In the frontal part of the south Pyrenean Eocene thrust-fault system, syn-kinematic fluid flow during the early compressional deformation of the foreland basin marls is evidenced macroscopically by the abundance of calcite shear veins within the thrust-fault zones and folds. The geometry and distribution of the veins are indicative of the mechanisms and kinematics of fluid-deformation relationships, and give assessment of the fluid migration paths. The crack-seal mechanism of formation of the shear veins attests to the episodic nature of fault-slip and associated fluid flow in fractures. The distribution of the veins suggests that the main source of fluid was the dewatering of the overpressured, poorly permeable marls from the thrust footwalls, probably related to both (i) vertical compaction due to burial under thrust sheets and (ii) tectonic horizontal shortening. These fluids drained upwards towards the thrust-fault zones, in which they migrated laterally towards the thrust front due to the anisotropy of the fracture permeability in these zones. The geochemistry of the vein-filling minerals and their comparison with the geochemistry and mineralogy of the host marls are indicative of the fluid types, fluid origins, fluid-sediment interactions, and fluid migration paths. The δ34S and 87Sr/86Sr ratio of the host marl calcite and of the calcite and celestite in the veins away from the thrust-fault zones indicate that the original water trapped interstitially in the marls was Eocene seawater. The elemental composition (Ca, Sr, Mg, Mn, and Fe), δ18O, and δ13C of the same samples reveal a change of the pore-water composition from marine to formation water during the early burial stage. Fluid-inclusion analyses of the celestite in the veins reveal the presence of a hot, saline ascending fluid restricted to these discontinuities, where it was mixed with the local formation water. These two types of fluids drained towards the thrust-fault zones where they acquired a higher 87Sr/86Sr ratio, probably related to local fluid-sediment reactions. Indeed, dickite precipitated during cleavage formation in the most intensely strained part of the fault zones, and its formation was probably mainly controlled by stress. δ18O depletion in the calcite from the structurally highest/innermost thrust-fault zones suggests also the influence of meteoric water derived from the emerged part of the belt in these structures. The earlier fluid regime in the Ainsa basin was an intergranular (porous) flow regime (compactional flow) allowing for a pervasive isotopic, and elemental exchange of the marls prior to vein formation. With the onset of compressional deformation, channelized flow along tectonic slip surfaces became dominant.

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.