Showing papers by "Bruno Lanson published in 2006"

Structural model for the biogenic Mn oxide produced by Pseudomonas putida

Abstract: X-ray diffraction (XRD) and Mn K-edge extended X-ray absorption Þ ne structure (EXAFS) spectroscopy were combined to elaborate a structural model for phyllomanganates (layer-type Mn oxides) lacking 3D ordering (turbostratic stacking). These techniques were applied to a sample produced by a common soil and freshwater bacterium (Pseudomonas putida), and to two synthetic analogs, δ-MnO2 and acid birnessite, obtained by the reduction of potassium permanganate with MnCl2 and HCl, respectively. To interpret the diffraction and spectroscopic data, we applied an XRD simulation technique utilized previously for well-crystallized birnessite varieties, complementing this approach with single-scattering-path simulations of the Mn K-edge EXAFS spectra. Our structural analyses revealed that all three Mn oxides have an hexagonal layer symmetry with layers comprising edgesharing Mn 4+ O6 octahedra and cation vacancies, but no layer Mn 3+ O6 octahedra. The proportion of cation vacancies in the layers ranged from 6 to 17%, these vacancies being charge-compensated in the interlayer by protons, alkali metals, and Mn atoms, in amounts that vary with the phyllomanganate species and synthesis medium. Both vacancies and interlayer Mn were most abundant in the biogenic oxide. The diffracting crystallites contained three to six randomly stacked layers and have coherent scattering domains of 19–42 A in the c* direction, and of 60–85 A in the a-b plane. Thus, the Mn oxides investigated here are nanoparticles that bear signiÞ cant permanent structural charge resulting from cation layer vacancies and variable surface charge from unsaturated O atoms at layer edges.

The fate of smectite in KOH solutions

Abstract: The aim of the present study was to investigate the detailed evolution of the SAz-1 smectite in 1 M KOH at 80°C at a solid/liquid ratio of 1/80. AFM observations indicated no change in crystal size or shape. XRD measurements at 40% relative humidity revealed changes in expandability of the smectite. The 001 reflection profile of smectite was modelled using the trial-and-error approach of Sakharov et al., 1999b. The results indicate that with increasing run time the number of non expandable layers with zero or one water layer increases and that the coherent scattering domain size of the smectite decreases. Infrared spectroscopy of the reacted smectite suggests that there is no change from the initial clay products. The dehydroxylation temperature showed a slight decrease from 619° to 605°C. STA measurements demonstrated that the cis-vacant character of the octahedral sheet remained nearly unchanged throughout the experiment. Determination of the average layer charge showed a continuous increase from 0.32 to 0.42 eq/Si (Si/Al)4O10 whereas the layer charge distribution indicated the appearance of high charged smectite layers with a charge of ~ 0.6 eq/Si (Si/Al)4O10 and the disappearance of the low charged layers. XPS and SEM measurements indicate an increase of the aluminium in the smectite samples. Isotope data support the theory of a internal diffusion mechanism by gradual changes in δ 18O values. From these data it appears that KOH solutions provoke a mineralogical change in the 2:1 layer of the smectite minerals which increases the layer charge by increasing the Al content. This mineralogical change does not involve dissolution/crystallization processes and then must show solid state transformation of the clays at 80°C.

Chemical signature of two Permian volcanic ash deposits within a bentonite bed from Melo, Uruguay

Abstract: A Permian bentonite deposit at Melo, Uruguay is composed of a calcite-cemented sandstone containing clay pseudomorphs of glass shards (0–0.50 m) overlying a pink massive clay deposit (0.50–2.10m). The massive bed is composed of two layers containing quartz and smectite or pure smectite respectively. The smectite is remarkably homogeneous throughout the profile: it is a complex mixed layer composed of three layer types whose expandability with ethylene glycol (2EG 1EG or 0EG sheets in the interlayer zone which correspond to low-, medium- and high-charge layers respectively) varies with the cation saturating the interlayer zone. The smectite homogeneity through the profile is the signature of an early alteration process in a lagoonal water which was over saturated with respect to calcite. Compaction during burial has made the bentonite bed a K-depleted closed system in which diagenetic illitization was inhibited. Variations in major, REE and minor element abundances throughout the massive clay deposit suggest that it originated from two successive ash falls. The incompatible element abundances are consistent with that of a volcanic glass fractionated from a rhyolite magma formed in a subduction/collision geological context.

Structure of the {001} talc surface as seen by atomic force microscopy: comparison with X-ray and electron diffraction results

Abstract: In this study the surface structure of a centimetre sized crystal of talc from the Trimouns deposit (Ariege, France) was imaged by atomic force microscopy. The direct image shows detailed characteristics of clay tetrahedral surfaces. The unit-cell dimensions obtained 30 using atomic force microscopy (aor = 5.47±0.28 and bor = 9.48±0.28 A) are found to be slightly higher, with an increased uncertainty, than those obtained using X-ray diffraction (aor = 5.288±0.007 and bor = 9.159±0.010 A) and selected-area electron diffraction (aor = 5.32±0.03 and bor = 9.22±0.05 A). Talc has a quasi-ideal surface, clean of strong 34 structural distortion as compared to most of other clay minerals and unlikely surface 35 relaxation. The observation on the obtained image of apparent cell dimension enlargement is 36 then more likely attributed to instrumental artefacts, also responsible for scattered values of unit-cell parameters rather than related to any surface structural features.