Structure of heavy metal sorbed birnessite. Part III: Results from powder and polarized extended X-ray absorption fine structure spectroscopy

The local structures of divalent Zn, Cu, and Pb sorbed on the phyllomanganate birnessite (Bi) have been studied by powder and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy. Metal-sorbed birnessites (MeBi) were prepared at different surface coverages by equilibrating at pH 4 a Na-exchanged buserite (NaBu) suspension with the desired aqueous metal. Me/Mn atomic ratios were varied from 0.2% to 12.8% in ZnBi and 0.1 to 5.8% in PbBi. The ratio was equal to 15.6% in CuBi. All cations sorbed in interlayers on well-defined crystallographic sites, without evidence for sorption on layer edges or surface precipitation. Zn sorbed on the face of vacant layer octahedral sites (□), and shared three layer oxygens (O_layer) with three-layer Mn atoms (Mn_layer), thereby forming a tridentate corner-sharing (TC) interlayer complex (Zn-3O_layer-□-3Mn_layer). ^TCZn complexes replace interlayer Mn²⁺ (Mn_inter²⁺) and protons. ^TCZn and ^TCMn_inter³⁺ together balance the layer charge deficit originating from Mn_layer⁴⁺ vacancies, which amounts to 0.67 charge per total Mn according to the structural formula of hexagonal birnessite (HBi) at pH 4. At low surface coverage, zinc is tetrahedrally coordinated to three O_layer and one water molecule (^[IV]TC complex: (H₂O)-^[IV]Zn-3O_layer). At high loading, zinc is predominantly octahedrally coordinated to three O_layer and to three interlayer water molecules (^[VI]TC complex: 3(H₂O)-^[VI]Zn-3O_layer), as in chalcophanite (^[VI]ZnMn₃⁴⁺O₇·3H₂O). Sorbed Zn induces the translation of octahedral layers from −a/3 to +a/3, and this new stacking mode allows strong H bonds to form between the ^[IV]Zn complex on one side of the interlayer and oxygen atoms of the next Mn layer (O_next): O_next…(H₂O)-^[IV]Zn-3O_layer. Empirical bond valence calculations show that O_layer and O_next are strongly undersaturated, and that ^[IV]Zn provides better local charge compensation than ^[VI]Zn. The strong undersaturation of O_layer and O_next results not only from Mn_layer⁴⁺ vacancies, but also from Mn³⁺ for Mn⁴⁺ layer substitutions amounting to 0.11 charge per total Mn in HBi. As a consequence, ^[IV]Zn,Mn_layer³⁺, and Mn_next³⁺ form three-dimensional (3D) domains, which coexist with chalcophanite-like particles detected by electron diffraction. Cu²⁺ forms a Jahn-Teller distorted ^[VI]TC interlayer complex formed of two oxygen atoms and two water molecules in the equatorial plane, and one oxygen and one water molecule in the axial direction. Sorbed Pb²⁺ is not oxidized to Pb⁴⁺ and forms predominantly ^[VI]TC interlayer complexes. EXAFS spectroscopy is also consistent with the formation of tridentate edge-sharing (^[VI]TE) interlayer complexes (Pb-3O_layer-3Mn), as in quenselite (Pb²⁺Mn³⁺O₂OH). Although metal cations mainly sorb to vacant sites in birnessite, similar to Zn in chalcophanite, EXAFS spectra of MeBi systematically have a noticeably reduced amplitude. This higher short-range structural disorder of interlayer Me species primarily originates from the presence of Mn_layer³⁺, which is responsible for the formation of less abundant interlayer complexes, such as ^[IV]Zn TC in ZnBi and ^[VI]Pb TE in PbBi.     

Analyse multirésolution croisée de pluies et débits de sources karstiquesMultiresolution cross-analysis of rainfall rates and karstic spring runoffs

In order to quantify the quality of the rainfall/discharge relationship across time-scales, we propose the use of both orthogonal wavelet multiresolution analysis and cross-correlation analysis. By using the two techniques together, it is possible to show, scale-by-scale, the influence of the input to the system (rainfall) on the response (discharge) of the aquifer and also to relate these results to the internal structure of the aquifer and to the degree of organisation of the karst drainage. An application of this method to three Pyrenean karsts is also shown. To cite this article: D. Labat et al., C. R. Geoscience 334 (2002) 551–556.     

Signification des ferruginisations des formations néoprotérozoı̈ques du Nord-Burkina Faso (Afrique de l'Ouest)Meaning of ironstones in the sedimentary Neoproterozoic formations of the northern Burkina Faso (western Africa)

There are many small ferruginous outcrops of different facies, often breccia-like, in the Neoproterozoic sedimentary formations in northern Burkina. These outcrops are made up of goethite and quartz, and are often along with high grades of various elements. It could be a question of gossans. Their large distribution in this part of the Taoudéni Basin offers it prospects as a province geochemically rich in Cu, Pb, Zn, Mo, As, Cd, Co... This basin would be a geochemical bin for ancient formations, which would have been evacuated before the Neoproterozoic. The ironstones would be the mark of further concentrations. To cite this article: A. Blot, C. R. Geoscience 334 (2002) 909–915.     

Preliminary results on a high east–west gradient in the macrozoobenthic community structure of the macrotidal Mont Saint-Michel bay

Environmental conditions in terms of river inputs, salt marsh development, shellfish cultures, hydrodynamics and sediment characteristics are very different from the western and the eastern part of the Mont Saint-Michel bay. A large scale study on the spatial structure of the intertidal macrozoobenthic community was then performed at the bay scale in order to determinate how these various conditions may modify the community composition and species density. In terms of density, the community was globally dominated by suspension/deposit filter-feeding bivalves, as well as amphipods in the eastern high levels of the intertidal zone. Several biocoenotic assemblage of the Macoma balthica community were described and large differences in the species composition and density were observed between the eastern and the western sectors of the bay. Total density for all species and recruitment were much higher in the eastern sector than in the west. We discussed about these east–west variations in terms of hydrodynamics, sedimentation processes and trophic conditions. Indeed, the large salt marsh extension and river inputs, as well as the lack of shellfish cultures in the east, may favour high food availability for benthic invertebrates of the area whereas the low river inputs and salt marsh development, the high sedimentation process and the intensification of mussel and oyster cultures in the west may create less favourable environments.     

Dissolved organic carbon, nitrogen and phosphorus in the N-E Atlantic and the N-W Mediterranean with particular reference to non-refractory fractions and degradation

Dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) measured in deep profiles in the N-E Atlantic and in the N-W Mediterranean in the period 1984–2002 are described. After accurate validation, they show close agreement with those previously published.Classic profiles were obtained, with concentrations decreasing in deep waters. In the Mediterranean and in the Atlantic comparable concentrations were found in the 1500–2000 m waters, 44–46 μmol l⁻¹ DOC, 2.6–2.8 μmol l⁻¹ DON and 0.02–0.03 μmol l⁻¹ DOP. In the surface layers, DOC concentrations were higher, but DON and DOP concentrations lower, in the Mediterranean than in the Atlantic, leading to higher element ratios in the Mediterranean. In autumn, values were, respectively, DOC:DON 17 vs. 14, DOC:DOP 950 vs. 500 and DON:DOP 55 vs. 35. The data suggest an increase in DOC and DON in the North Atlantic Central Water over 15 years, which may be linked to the North Atlantic climatic oscillations.Refractory DOM found in the 1500–2000 m layer exhibited C:N:P ratios of 1570:100:1. The labile+semi-labile (=non-refractory) DOM (nrDOM) pool was computed as DOM in excess of the refractory pool. Its contribution to total DOM above the thermocline in the open sea amounted to 25–35% of DOC, 30–35% of DON, and 60–80% of DOP. Element ratios of the nrDOM varied among stations and were lower than those of refractory DOM, except for C:N in the Mediterranean: nrDOC:nrDON 10–19, nrDOC:nrDOP 160–530 and nrDON:nrDOP 15–38. The specific stoichiometry of DOM in the Mediterranean led us to postulate that overconsumption of carbon is probably a main process in that oligotrophic sea.By coupling non-refractory DOM stoichiometry and relationships between the main DOM elements in the water column, the relative mineralization of C, N and P from DOM was studied. Below the thermocline, the preferential removal of phosphorus with regard to carbon from the semi-labile DOM can be confirmed, but not the preferential removal of nitrogen. In the ocean surface layers, processes depend on the oceanic area and can differ from deep waters, so preferential carbon removal seems more frequent. Bacterial growth efficiency data indicate that bacteria are directly responsible for mineralization of a high proportion of DON and DOP in the deep water.     

Magnetostratigraphic dating of an intensification of glacial activity in the southern Italian Alps during Marine Isotope Stage 22

We applied magnetostratigraphy and mammal biostratigraphy to date climate-sensitive pollen cycles and lithostratigraphic units of the Pliocene-Pleistocene Leffe sedimentary succession from the Southern Alps, Italy. The Leffe section was correlated to additional sections (Casnigo, Fornaci di Ranica, and Pianengo) to construct a stratigraphic network along a common fluviatile system (the Serio River) sourced in the Southern Alps and flowing southward into the Po River Basin. We obtained a coherent scenario of climate variability for the last ∼ 2 Myr. At Leffe, lacustrine deposition commenced during the Olduvai Normal Subchron (1.94-1.78 Ma) and lasted up to a chronologic level compatible with Marine Isotope Stage (MIS) 22 (0.87 Ma). Pollen analysis revealed that climate varied cyclically from warm-temperate to cool during this time interval, but never as cold as during glacial intervals. At around MIS 22, climate cooled globally. Gravels, attributed to high-energy braided river systems fed locally by alluvial fans, prograded from the Serio River catchment area over the Leffe Basin and toward the Po Plain in response to a generalized event of vegetation withdrawal and enhanced physical erosion. At this time, Alpine valley glaciers reached their first maximum southward expansion with glacier fronts located at only ∼ 5 km upstream from Leffe.     

The glauconite–Fe‐illite–Fe‐smectite problem: a critical review

Iron silicate minerals are a significant component of sedimentary systems but their modes of formation remain controversial. Our analysis of published data identifies end‐member compositions and mixtures and allows us to recognize controls of formation of different mineral species. The compositional fields of glaucony, Fe‐illite, Fe–Al smectites are determined in the M⁺/4Si vs. Fe/Sum of octahedral cations (M⁺ = interlayer charge). Solid solutions could exist between these phases. The Fe–Al and Fe‐rich clay minerals form two distinct solid solutions. The earliest phases to be formed are Fe–Al smectites or berthierine depending on the sedimentation rate. Reductive microsystems appear in the vicinity of organic debris in unconsolidated sediments. The Fe is incorporated first in pyrite and then in silicates after oxidation. Potassium ions diffuse from the sea‐water–sediment interface. If not interrupted, the diffusion process is active until reaction completion is reached, i.e. formation of Fe‐illite or glauconite or a mineral assemblage (berthierine–nontronite) according to the available Al ion amounts in the microsystem. Mixed‐layer minerals are formed when the diffusion process is interrupted because of sedimentation, compaction or cementation. Despite the common belief of their value as palaeoenvironment indicators, these minerals can form in a variety of environments and over a period of millions of years during sediment burial.     

Comparison of several BHT correction methods: a case study on an Australian data set

Bottom-hole temperatures (BHT) from oil exploration provide useful constraints on the subsurface thermal regime, but they need to be corrected to obtain the equilibrium temperature. In this work, we introduce several BHT correction methods and compare them using a large Australian data set of more than 650 groups of multiple BHT measurements in about 300 oil exploration boreholes. Existing and suggested corrections are classified within a coherent framework, in which methods are divided into: line/cylinder source; instantaneous/continuous heat extraction; one/two component(s). Comparisons with reservoir test temperatures show that most of the corrections lead to reliable estimates of the formation equilibrium temperature within ±10 °C, but too few data exist to perform an intercomparison of the models based on this criterion. As expected, the Horner method diverges from its parent models for small elapsed times (or equivalently large radii). The mathematical expression of line source models suffers from an unphysical delay time that also restrains their domain of applicability. The model that takes into account the difference of thermal properties between circulating mud and surrounding rocks—that is the two-component model—is delicate to use because of its high complexity. For these reasons, our preferred correction methods are the cylindrical source models. We show that mud circulation time below 10 hr has a negligible effect. The cylindrical source models rely on one parameter depending on the thermal diffusivity and the borehole radius, which are poorly constrained, but the induced uncertainty on the extrapolations remains reasonably low.     

Analysis of central western Europe deformation using GPS and seismic data

The kinematic field of central western Europe is characterized by relatively small movements (around 1–2 mm/year) and diffuse seismicity with earthquakes occurring mostly in the shallow crust (within 15 km), prevalently concentrated along the Alps and the European Cenozoic Rift System (ECRIS). In order to study and constrain the current crustal kinematic field we reconstructed the velocity and the strain field using permanent GPS stations, belonging to different networks (AGNES, EUREF, REGAL, RGP). The 2D strain rate tensor has been calculated using the method of least-squares collocation. Our results show that the area of maximum compression is located along the Alpine chain, where maximum values of 7 ± 2 nstrain/year are found, while maximum extension is measured between the Armorican Massif and the Massif Central, where values of 4 ± 2 nstrain/year are reached.The earthquakes with M > 3.0, have been used to estimate the seismic strain rates, while the style of the seismic deformation was reconstructed from the fault plane solutions (FPS) available from the literature. Relatively high values of seismic strain rates (around 10 nstrain/year) are measured along the Alpine Chain and the ECRIS. Results obtained by geodetic and seismic data are quite in agreement and reflect the different tectonic evolution of the geological features characterizing the area of study. The orientation of the compressional geodetic and seismic strain axes are NW-SE in most of the area of study, on account of the action of plate boundary forces. A rotation of the same axes to N-S direction along the eastern Alps, possibly related to the Adria convergence, is found.