Sylvain Grangeon

Structure of nanocrystalline phyllomanganates produced by freshwater fungi

Abstract The crystal structures of biogenic Mn oxides produced by three fungal strains isolated from stream pebbles were determined using chemical analyses, XANES and EXAFS spectroscopy, and powder X-ray diffraction. The fungi-mediated oxidation of aqueous Mn2+ produces layered Mn oxides analogous to vernadite, a natural nanostructured and turbostratic variety of birnessite. The crystallites have domain dimensions of ~10 nm in the layer plane (equivalent to ~35 MnO6 octahedra), and ~1.5-2.2 nm perpendicularly (equivalent to ~2-3 layers), on average. The layers have hexagonal symmetry and from 22 to 30% vacant octahedral sites. This proportion likely includes edge sites, given the extremely small lateral size of the layers. The layer charge deficit, resulting from the missing layer Mn4+ cations, is balanced mainly by interlayer Mn3+ cations in triple-corner sharing position above and/or below vacant layer octahedra. The high surface area, defective crystal structure, and mixed Mn valence confer to these bio-minerals an extremely high chemical reactivity. They serve in the environment as sorption substrate for trace elements and possess catalytic redox properties.

Crystal structure of Ni-sorbed synthetic vernadite: a powder X-ray diffraction study

Abstract Vernadite is a nanocrystalline turbostratic phyllomanganate containing Ni, and is widespread in surface environments and oceanic sediments. To improve our understanding of Ni uptake in this mineral, two series of analogues of vernadite (δ-MnO2) were prepared with Ni/Mn atomic ratios of 0.002-0.105 at pH4 and 0.002-0.177 at pH 7. Their structures were characterized using X-ray powder diffraction (XRD). The δ-MnO2 nano-crystals are essentially monolayers with coherent scattering domains sizes of ~10 Å perpendicular to the layering and ~55 Å within the layer plane. For Ni/Mn < 0.01, the layer charge deficit is apparently balanced entirely by interlayer Mn, Na and protons. At higher Ni/Mn, Ni occupies the same site as interlayer Mn above and below vacant sites within the MnO2 layer and at sites along the edges of the layer. However, the layer charge is balanced differently at the two pH values. At pH 4, Ni uptake is accompanied by a reduction in structural Na and protons, whereas interlayer Mn remains strongly bound to the layers. At pH 7, interlayer Mn is less strongly bound and is partially replaced by Ni. The results of this study also suggest that the number of vacant octahedral sites and multi-valent charge-copmpensating interlayer species are underestimated by the currently used structure models of δ-MnO2.

X-ray diffraction: a powerful tool to probe and understand the structure of nanocrystalline calcium silicate hydrates.

The structure of nanocrystalline calcium silicate hydrates (C-S-H) was studied using X-ray diffraction and literature data. It is proposed that C-S-H of Ca/Si ratio ranging between ∼ 0.6 and ∼ 1.7 can be described as nanocrystalline tobermorite affected by turbostratic disorder. The broadening and shift of the basal reflection positioned between ∼ 13.5 and ∼ 11.2 Å (depending on the Ca/Si ratio) arises from nanocrystallinity and possibly from an interstratification phenomenon.

Diurnal production of gaseous mercury in the alpine snowpack before snowmelt

In March 2005, an extensive mercury study was performed just before snowmelt at Col de Porte, an alpine site close to Grenoble, France. Total mercury concentration in the snowpack ranged from 80 +/- 08 to 160 +/- 15 ng l(-1), while reactive mercury was below detection limit (0.2 ng l(-1)). We observed simultaneously a production of gaseous elemental mercury (GEM) in the top layer of the snowpack and an emission flux from the snow surface to the atmosphere. Both phenomena were well correlated with solar irradiation, indicating photo-induced reactions in the snow interstitial air (SIA). The mean daily flux of GEM from the snowpack was estimated at similar to 9 ng m(-2) d(-1). No depletion of GEM concentrations was observed in the SIA, suggesting no occurrence of oxidation processes. The presence of liquid water in the snowpack clearly enhanced GEM production in the SIA. Laboratory flux chamber measurements enabled us to confirm that GEM production from this alpine snowpack was first driven by solar radiation (especially UVA and UVB radiation), and then by liquid water in the snowpack. Finally, a large GEM emission from the snow surface occurred during snowmelt, and we report total mercury concentrations in meltwater of about 72 ng l(-1).

Modeling specific pH dependent sorption of divalent metals on montmorillonite surfaces. A review of pitfalls, recent achievements and current challenges

Within the context of the clay barrier concept for underground nuclear waste disposal, montmorillonite and bentonite have been widely used as reference materials for sorption. In some cases, accompanying modeling work aims at understanding and predicting sorption in complex natural systems where clays are assumed to be representative of the most reactive phases. This bottom-up approach relies heavily on good confidence in the mechanistic understanding of sorption phenomena. The present study aims at reviewing experimental and modeling work on montmorillonite with a focus on divalent metals experiencing pH dependent specific sorption. Current knowledge points out distinct sorption mechanisms on three types of sites: cation exchange on basal planes and surface complexation on edge surfaces with two types of sites: high energy (or strong) sites (HES) with high affinity for metals but low site density and low energy (or weak) sites (LES) with lower affinity for metals but high site density. Based on this current knowledge, criteria are given to select data relevant for surface complexation model calibration (especially ionic strength, pH, clay preparation and characterization, metal to clay ratio and solubility limits), with an emphasis on data uncertainties and reproducibility. Problematic experimental features are highlighted, especially those related to the reversibility of sorption and to the effect of the solid to liquid ratio (RSL) on sorption distribution coefficients. Guidelines for data acquisition and selection are proposed. Surface complexation models available in the literature are then tested in terms of efficiency (data fit) and mechanistic likelihood. None of the currently available models is able to satisfy both aspects. Models directly adapted from oxide surface complexation models fail in both aspects. The most efficient model (in terms of simplicity and accuracy) is a non-electrostatic model. It is the only one that reproduces pH dependent specific sorption data at a low metal clay ratio (<0.001 mol/kgclay; HES) in all selected experimental conditions, as well as data obtained at medium metal to clay ratio (∼0.01-0.05 mol/kgclay; low energy sites). To account for physical mechanisms, an electrostatic surface complexation model has been developed. It takes into account the spill-over effect of negatively charged basal surfaces over edge surfaces, a typical feature of montmorillonite, and is able to reproduce sorption data for LES but not for HES. The reasons for this failure are explained through the mathematical derivations of model equations. This approach shows that it is impossible to reconcile HES properties with an oxide-like surface complexation electrostatic model. Amongst other alternatives, a successful electrostatic surface substitution model, which is compatible with current knowledge on HES structural properties, is proposed.

Atmospheric mercury incorporation in soils of an area impacted by a chlor-alkali plant (Grenoble, France): Contribution of canopy uptake

This study focused on the fluxes of mercury (Hg) and mechanisms of incorporation into soils surrounding a chlor-alkali plant suspected to have emitted up to ~600 kg Hg year(-1) for decades into the atmosphere. Comparison of vertical Hg soil profiles with As, Cu, Ni and Zn (which were not emitted by the plant) support Hg enrichment in surface horizons due to atmospheric Hg inputs from the chlor-alkali plant. Based on chemical extractions and elemental correlations, Hg was found to be weakly leachable and bio-available for plants, and most probably strongly bound to organic matter. In contrast, other trace elements were probably associated with phyllosilicates, iron oxides or with primary minerals. Hg stocks in the surface horizon of a forested soil (1255 mg Hg m(-3)) were two-fold higher than in an agricultural soil (636 mg Hg m(-3)) at a similar distance to the plant. The difference was attributed to the interception of atmospheric Hg by the canopy (most likely gaseous elemental Hg and reactive gaseous Hg) and subsequent litterfall incorporation. Some differences in the ability to trap atmospheric Hg were observed between tree species. The characterization of the litter showed an increasing Hg concentration in the plant material proportional to their degradation stage. In agricultural soils, very low Hg concentrations found in corn leaves and grains suggested a limited uptake via both the foliar and root pathways. Thus, the short-term risk of Hg transfer to agricultural crops and higher levels of the trophic chain appeared limited. A possible risk which remains to be evaluated is the possible transfer of Hg-rich particles from the forest topsoil to downstream aquatic ecosystems during rain and snowmelt events.

Distribution of Water in Synthetic Calcium Silicate Hydrates

Understanding calcium silicate hydrates (CSHs) is of paramount importance for understanding the behavior of cement materials because they control most of the properties of these man-made materials. The atomic scale water content and structure have a major influence on their properties, as is analogous with clay minerals, and we should assess these. Here, we used a multiple analytical approach to quantify water distribution in CSH samples and to determine the relative proportions of water sorbed on external and internal (interlayer) surfaces. Water vapor isotherms were used to explain the water distribution in the CSH microstructure. As with many layered compounds, CSHs have external and internal (interlayer) surfaces displaying multilayer adsorption of water molecules on external surfaces owing to the hydrophilic surfaces. Interlayer water was also quantified from water vapor isotherm, X-ray diffraction (XRD), and thermal gravimetric analyses (TGA) data, displaying nonreversible swelling/shrinkage behavior in response to drying/rewetting cycles. From this quantification and balance of water distribution, we were able to explain most of the widely dispersed data already published according to the various relative humidity (RH) conditions and measurement techniques. Stoichiometric formulas were proposed for the different CSH samples analyzed (0.6 < Ca/Si < 1.6), considering the interlayer water contribution.

Structure of nanocrystalline calcium silicate hydrates: insights from X-ray diffraction, synchrotron X-ray absorption and nuclear magnetic resonance

The structure of nanocrystalline calcium silicates hydrates (C–S–H) having Ca/Si ratios ranging between 0.57 ± 0.05 and 1.47 ± 0.04 was studied. All samples are nanocrystalline and defective tobermorite. An increase of the Ca/Si ratio resulting from omission of bridging Si in the Si chains and incorporation of interlayer Ca was observed.

Quantitative X-ray pair distribution function analysis of nanocrystalline calcium silicate hydrates: a contribution to the understanding of cement chemistry

Quantitative analysis of the X-ray pair distribution function collected on calcium silicate hydrates having Ca/Si ratios ranging between 0.57 and 1.47 was applied. With increasing Ca/Si ratio, Si bridging tetrahedra are omitted and Ca(OH)2 is detected at the highest ratios.

MINERALOGICAL AND ISOTOPIC RECORD OF DIAGENESIS FROM THE OPALINUS CLAY FORMATION AT BENKEN, SWITZERLAND: IMPLICATIONS FOR THE MODELING OF PORE-WATER CHEMISTRY IN A CLAY FORMATION

Argillaceous rocks are considered to be a suitable geological barrier for the long-term containment of wastes. Their efficiency at retarding contaminant migration is assessed using reactive-transport experiments and modeling, the latter requiring a sound understanding of pore-water chemistry. The building of a pore-water model, which is mandatory for laboratory experiments mimicking in situ conditions, requires a detailed knowledge of the rock mineralogy and of minerals at equilibrium with present-day pore waters. Using a combination of petrological, mineralogical, and isotopic studies, the present study focused on the reduced Opalinus Clay formation (Fm) of the Benken borehole (30 km north of Zurich) which is intended for nuclear-waste disposal in Switzerland. A diagenetic sequence is proposed, which serves as a basis for determining the minerals stable in the formation and their textural relationships. Early cementation of dominant calcite, rare dolomite, and pyrite formed by bacterial sulfate reduction, was followed by formation of iron-rich calcite, ankerite, siderite, glauconite, (Ba, Sr) sulfates, and traces of sphalerite and galena. The distribution and abundance of siderite depends heavily on the depositional environment (and consequently on the water column). Benken sediment deposition during Aalenian times corresponds to an offshore environment with the early formation of siderite concretions at the water/sediment interface at the fluctuating boundary between the suboxic iron reduction and the sulfate reduction zones. Diagenetic minerals (carbonates except dolomite, sulfates, silicates) remained stable from their formation to the present. Based on these mineralogical and geochemical data, the mineral assemblage previously used for the geochemical model of the pore waters at Mont Terri may be applied to Benken without significant changes. These further investigations demonstrate the need for detailed mineralogical and geochemical study to refine the model of pore-water chemistry in a clay formation.