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.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Nonlinear wave propagation on a sphere: Interaction between Rossby waves and gravity waves; stability of the Rossby waves

Abstract

An analytical spectral model of the barotropic divergent equations on a sphere is developed using the potential-stream function formulation and the normal modes as basic functions. Explicit expressions of the coefficients of nonlinear interaction are obtained in the asymptotic case of a slowly rotating sphere, i.e. when the normal modes can be expressed as single spherical harmonics.     

Orbital imprint on Holocene palaeohydrological variations in west‐central Europe as reflected by lake‐level changes at Cerin (Jura Mountains,eastern France)

This paper presents a lake‐level record for the Holocene at Lake Cerin (Jura Mountains, eastern France). It is based on a range of sedimentological techniques validated in previous studies, with a combination of systematic lithostratigraphic investigations of the infillings accumulated in the lacustrine basin, and sediment analyses of two selected cores. The chronology is based on 10 radiocarbon dates and pollen stratigraphy. On a millennial scale, the Cerin lake‐level record shows three distinct successive phases characterised by higher lake‐level conditions until ca. 9000 cal. a BP, followed by a maximal lowering at ca. 9000–8500 cal. a BP, and a progressive rise until the present. This rise was punctuated by centennial‐scale fluctuations, with major events around 4000, 2800 and after 1500 cal. a BP. Considered on a multimillennial scale, the general pattern of palaeohydrological changes reconstructed at Cerin reflects the impact of orbitally driven summer insolation. This is in agreement with other regional and extra‐regional palaeoclimatic records, although every record shows peculiarities in timing and shape depending on the proxy used for reconstruction. In this general context, centennial to multicentennial oscillations appear to have been second‐order events in comparison with the major influence of the orbital factor. Copyright © 2011 John Wiley & Sons, Ltd.     

Holocene glacier and deep water dynamics,Adélie Land region,East Antarctica

This study presents a high-resolution multi-proxy investigation of sediment core MD03-2601 and documents major glacier oscillations and deep water activity during the Holocene in the Adélie Land region, East Antarctica. A comparison with surface ocean conditions reveals synchronous changes of glaciers, sea ice and deep water formation at Milankovitch and sub-Milankovitch time scales. We report (1) a deglaciation of the Adélie Land continental shelf from 11 to 8.5 cal ka BP, which occurred in two phases of effective glacier grounding-line retreat at 10.6 and 9 cal ka BP, associated with active deep water formation; (2) a rapid glacier and sea ice readvance centred around 7.7 cal ka BP; and (3) five rapid expansions of the glacier–sea ice systems, during the Mid to Late Holocene, associated to a long-term increase of deep water formation. At Milankovich time scales, we show that the precessionnal component of insolation at high and low latitudes explains the major trend of the glacier–sea ice–ocean system throughout the Holocene, in the Adélie Land region. In addition, the orbitally-forced seasonality seems to control the coastal deep water formation via the sea ice–ocean coupling, which could lead to opposite patterns between north and south high latitudes during the Mid to Late Holocene. At sub-Milankovitch time scales, there are eight events of glacier–sea ice retreat and expansion that occurred during atmospheric cooling events over East Antarctica. Comparisons of our results with other peri-Antarctic records and model simulations from high southern latitudes may suggest that our interpretation on glacier–sea ice–ocean interactions and their Holocene evolutions reflect a more global Antarctic Holocene pattern.     

L'évolution magmatique du Complexe de Morin et son apport au problème des anorthosites

The Morin Plutonic Complex, in the southern part of the Grenville tectonic province (Canadian Shield) consists of a rock suite ranging from troctolite to farsundite. The centre of the complex is a large domical anorthosite body. Twenty-six chemical analyses have been carried out in order to compare the Morin Complex with similar complexes in the Grenville and Nain provinces. Variation diagrams constructed by plotting the major oxides vs. the differentiation index Al₂O₃+CaO+MgO show a gap between troctolite and anorthosite in the Morin Complex whereas this gap is absent in the anorogenic complexes of Labrador (Nain province). It is inferred that this gap is the result of intrusion, from the same magma chamber, of two distinct pulses separated by an intervening period of crustal uplift.A second gap occurs between anorthosites and farsundites in all complexes as yet investigated. This gap is an argument for an independent, possibly anatectic, origin of the farsundites.Mineral assemblages in the Morin Complex are compatible with cooling in the lower crust, at a depth of approximately 30 km.     

Links Between Weather Phenomena and Characteristics of Refractivity Measured by Precipitation Radar

Refractivity depends on meteorological parameters such as temperature and water vapour pressure and can be measured using a weather radar. A realistic atmospheric simulation from the Meso-NH numerical model is used in order to describe and establish the relation between refractivity and the dynamic and thermodynamic phenomena responsible for the development and propagation of convection. These investigations lead to discussion of the complementarity between the refractivity and the convective available potential energy. The relation observed between the refractivity signal and the meteorological parameters calls the refractivity measurement into question, since it is based on phase differentiation with time and space and can be degraded by phase aliasing problems. These aliasing problems increase with the radar frequency (perceptible in the S-band, serious in the C-band, and more serious in the X-band) and also with the integration range and sampling time. Thus, a statistical approach permits us to simulate the possibility of measuring the refractivity with operational radar during convective events. A typical case in the south-east region of France is selected to simulate measurements by radar (S-band, C-band, X-band) in convective systems, in order to evaluate the measurement feasibility, particularly in terms of phase ambiguity, related to temporal and spatial sampling, of a future implementation of the refractivity measurement over the French operational radar network. This numerical statistical approach is completed with a similar study using in-situ measurements performed at the Trappes station. The seasonal and diurnal dependencies of aliasing are investigated, leading to clarification of the impact of the turbulent fluxes on the refractivity measurement.     

Quantification of Hydrophone Records of the 2004 Sumatra Tsunami

The 2004 Sumatra-Andaman tsunami was recorded by hydrophones of the International Monitoring System at Site H08 near Diego Garcia, notably in frequency bands extending outside the range of the Shallow Water Approximation. Despite the severe high-pass filtering involved in this instrumentation, we show that the spectral amplitudes recovered around T = 87 s can be successfully explained by generation from the seismic source, in the framework of the normal mode theory of tsunami excitation. At the lower frequencies characteristic of more conventional tsunami waves (800 to 3200 s), the signal is probably present in the hydrophone records, but reliable deconvolution of its spectral amplitude is precluded by the fact that the instrumental filters lowered the tsunami signal to the level of resolution of the instrument digitizer. In the context of distant tsunami warning, hydrophone records could provide useful insight into high-frequency tsunami components, and even at lower, more conventional, frequencies, provided that an unfiltered channel could be recorded routinely.     

Pliensbachian magnetostratigraphy: new data from Paris Basin (France)

Sampling of an industrial drill string from the northeastern Paris Basin (Montcornet, France) provides early Jurassic magnetostratigraphic data coupled with biochronological control. About 375 paleomagnetic samples were obtained from a 145 m thick series of Pliensbachian rocks. A composite demagnetization thermal up to 300°C and an alternating field up to 80 mT were used to separate the magnetic components. A low unblocking temperature component (<250°C) with an inclination of about 64° is interpreted as a present-day field overprint. The characteristic remanent component with both normal and reversed antipodal directions was isolated between 5 and 50 mT. Twenty-nine polarity intervals were recognized. Correlation of these new results from the Paris Basin with data from the Breggia Gorge section (Ticino, southern Alps, Switzerland), which is generally considered as the reference section for Pliensbachian magnetostratigraphy, reveals almost identical patterns of magnetic polarity reversals. However, the correlation implies significant paleontological age discrepancies. Revised age assignments of biostratigraphic data of Breggia as well as an objective evaluation of the uncertainties on zonal boundaries in both Breggia and Moncornet resolve the initial discrepancies between magnetostratigraphic correlations and biostratigraphic ages. Hence, the sequence of magnetic reversals is significantly strengthened and the age calibration is notably improved for the Pliensbachian, a stage for which sections combining adequate magnetic signal and biostratigraphic constraints are still very few.