Study of diatoms/aqueous solution interface. I. Acid-base equilibria and spectroscopic observation of freshwater and marine species

This work reports on a concerted study of diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii= TW, Skeletonema costatum= SC) and two freshwater periphytic species (Achnanthidium minutissimum= AMIN, Navicula minima= NMIN). Proton surface adsorption was measured at 25°C, pH of 3 to 11 and ionic strength of 0.001 to 1.0 M via potentiometric titration using a limited residence time reactor. Electrophoretic mobility of living cells and their frustules was measured as a function of pH and ionic strength. Information on the chemical composition and molecular structure of diatoms surfaces was obtained using FT-IR (in situ attenuated total reflectance) and X-ray Photoelectron Spectroscopy (XPS). The surface area of living cells and their frustules in aqueous solutions was quantified using Small Angle X-ray Scattering Spectroscopy (SAXS).These observations allowed us to identify the nature and to determine the concentration of the major surface functional groups (carboxyl, amine and silanol) responsible for the amphoteric behavior of cell surfaces in aqueous solutions. Taking into account the relative proportion of surface sites inferred from XPS and FT-IR measurements, a surface complexation model of diatom-solution interfaces was generated on the basis of surface titration results. The cell-normalized ratios of the three major surface sites {>COOH}: {>NH₃}: {>SiOH} are 1:1:0.1, 1:10:0, 1:1:0.4 and 1:1:0.3 for TW, SC, AMIN and NMIN, respectively. The total amount of proton/hydroxyl active surface sites for investigated species ranges from 1 (NMIN) to 9 (SC) mmol/g dry weight. Normalization of these site densities to the area of siliceous skeleton yields values between 0.3 (NMIN) and 0.9 mmol/m² (SC) which are an order of magnitude higher than corresponding values for organic-free frustules or amorphous silica. This suggests that the amphoteric properties and possibly the affinity for metal adsorption of diatom cultures are essentially controlled by the 3-D organic layers covering the silica frustule.     

Middle Miocene peralkaline ignimbrites in the Hermosillo region (Sonora, Mexico): Geodynamic implications

Scattered ignimbritic mesas crop out in the Hermosillo region (Sonora, Mexico). These rocks that have been dated at 12.5 Ma (Middle Miocene) have the petrography and chemical characteristics of comendites. Such a flare-up of peralkaline acidic volcanism, after a long period of subduction-related arc volcanism, emphasises an important change in the source of volcanism. It corresponds to the latest stage of continental extension prior to the marine invasion and the development of spreading centres in the Gulf of California. To cite this article: J. Vidal Solano et al., C. R. Geoscience 337 (2005).     

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.     

Fundamental processes controlling the first stage of alteration of a basalt glass by seawater: an experimental study between 200° and 320°C

The first stage of alteration of a basalt glass by seawater has been studied experimentally between 200° and 320°C under vapor pressure, following both the chemical evolution of the reacting solutions during the experiments and the chemical and mineralogical transformations of the altered glass surface via microprobe, scanning transmission electron microscope and resonant nuclear reactions.The alteration is controlled by diffusion of dissolved species through an altered layer and not by surface chemical reaction. Selective removal of cations with respect to SiO₂ leads to the formation of a thick, porous protonated surface layer enriched in SiO₂. Aqueous diffusion of dissolved species from the reacting glass and from solution through the pores of this layer results in the formation of an amorphous silicate gel which is the precursor of normal crystalline clays (saponites) appearing in a later stage.Computer simulations of the alteration generated with the EQ3/6 computer software package account for the chemical composition of the rim and the sequence of secondary minerals found in the experiments.     

Fluorapatite surface composition in aqueous solution deduced from potentiometric, electrokinetic, and solubility measurements, and spectroscopic observations

The surface chemistry of fluorapatite in aqueous solution was investigated using electrokinetic techniques, potentiometric titrations, solubility measurements, and attenuated total reflection infrared spectroscopy. All methods indicate the formation of Ca/F depleted, P enriched altered layer via exchange reactions between H⁺ and Ca²⁺, and OH⁻ and F⁻ at the fluorapatite (FAP) surface. Observations suggest that this leached layer has a di-calcium phosphate (CaHPO₄) composition and that it controls the apparent solubility of FAP. Electrokinetic measurements yield an iso-electric point value of 1 ± 0.5 consistent with a negatively charged FAP surface at pH > 1. In contrast, surface titrations give an apparent pH of point of zero charge of ∼7.7, consistent with a positively charged surface at pH < 7.7. These differences are shown to stem from proton consumption by both proton exchange and dissolution reactions at the FAP surface. After taking account for these effects, FAP surface charge is shown to be negative to at least pH 4 by surface titration analysis.     

ESR chronology of the Somme River Terrace system and first human settlements in Northern France

The Somme Valley, Northern France, is famous for its archaeological sequence, where numerous rich Palaeolithic sites, such as Saint-Acheul, the type site of the Acheulian, have been discovered. The archaeological levels are often directly associated with fossil alluvial sediments of the River Somme or with slope deposits, including loess and palaeosols. In the middle reaches of the valley, near Amiens, the system of fossil-stepped fluvial terraces is particularly well developed and preserved, and occurs on 10 alluvial formations. These terraces, from +5 to +55 m above the present-day valley bedrock, allow the study of the environmental changes and the human settlement of this area through the Pleistocene.

Since 1988, ESR dating was systematically applied on bleached quartz extracted from the fossil fluvial deposits, in order to better describe the geological evolution of the stepped system. More recently, U-series/ESR dating has also been performed on teeth collected from the different terrace deposits. Here we present a synthetic review of the main ESR results, and propose an ESR chronology for the geological evolution of the Somme fluvial system and for the Middle Pleistocene human settlement of northern France.     

Apport des marqueurs isotopiques et biogéochimiques dans la reconstitution du paléoenvironnement de la grotte du Lazaret (Nice,Alpes-Maritimes) au cours du Pléistocène supérieur (stade isotopique 5)

The isotopic composition of calcite from the stalagmitic floor E of the Lazaret Cave is interpreted as proxy of atmospheric circulation and vegetal cover changes during IOS 5. The ${\delta }^{18}\mathrm{O}$ variations could indicate change in precipitation sources, which could originate from the Mediterranean Sea during warm periods and from the Atlantic Ocean during colder periods. The ${\delta }^{13}\mathrm{C}$ variations could be related to vegetal cover and soil type. Tree cover appears to be dominant according to pollen spectra, and organic molecules trapped into calcite (sterols, terpenoids, humic acids). To cite this article: L. Rousseau et al., C. R. Geoscience 337 (2005).     

A 12,000-Year Pollen Record from Lake Maliq, Albania

Pollen data from Lake Maliq, the first from Albania, contribute new information to the discussion of the vegetational, hydrological, and climatological history of the Balkans since 12,000 yr B.P. During late-glacial time, a perennial lake expanded at Maliq. It was surrounded by a complex vegetation association composed of steppe and mixed forest elements. The highly diverse forest flora suggest that late-glacial forest refugia were more developed here at middle altitude, rather than at higher altitude as previously suggested. The forest developed after 9800 yr B.P., while the water level remained high in the Korçë basin until 5000 yr B.P. Different environmental conditions, characterized by lower available moisture and warmer winters, progressively took place after this date. Human activity in the Korçë basin ca. 4500 yr B.P. was coeval with conditions characterized by an increase in winter temperatures and a decrease in summer moisture.