Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers   总被引：3，自引：0，他引：3  

Claudette Spiteri  Philippe Van Cappellen  Pierre Regnier 《Geochimica et cosmochimica acta》2008,72(14):3431-3445

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.  相似文献   

Magnesium isotope systematics of the lithologically varied Moselle river basin, France   总被引：2，自引：0，他引：2  

Agnès Brenot  Christophe Cloquet  Nathalie Vigier  Jean Carignan  Christian France-Lanord 《Geochimica et cosmochimica acta》2008,72(20):5070-5089

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.  相似文献   

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates     

Philippe E. Raison  Regis Jardin  Daniel Bouëxière  Rudy J. M. Konings  Thorsten Geisler  Claudiu C. Pavel  Jean Rebizant  Karin Popa 《Physics and Chemistry of Minerals》2008,35(10):603-609

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.  相似文献   

DEM analysis of the crack propagation in brittle clays under uniaxial compression tests   总被引：2，自引：0，他引：2  

Luis F. Vesga  Luis E. Vallejo  Sebastian Lobo‐Guerrero 《国际地质力学数值与分析法杂志》2008,32(11):1405-1415

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Numerical estimation of REV and permeability tensor for fractured rock masses by composite element method   总被引：2，自引：0，他引：2  

S.‐H. Chen  X.‐M. Feng  S. Isam 《国际地质力学数值与分析法杂志》2008,32(12):1459-1477

The Monte Carlo method is used to generate parent stochastic discrete fracture network, from which a series of fractured rock samples of different sizes and orientations are extracted. The fracture network combined with a regular grid forms composite element mesh of the fractured rock sample, in which each composite element is composed of sub‐elements incised by fracture segments. The composite element method (CEM) for the seepage is implemented to obtain the nodal hydraulic potential as well as the seepage flow rates through the fractured rock samples. The application of CEM enables a large quantity of stochastic tests for the fractured rock samples because the pre‐process is facilitated greatly. By changing the sizes and orientations of the samples, the analysis of the seepage characteristics is realized to evaluate the variation of the permeability components, the existence of the permeability tensor and the representative element volume. The feasibility and effectiveness are illustrated in a numerical example. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

Biaxial test simulations using a packing of polygonal particles   总被引：1，自引：0，他引：1  

A. A. Peña  A. Lizcano  F. Alonso‐Marroquin  H. J. Herrmann 《国际地质力学数值与分析法杂志》2008,32(2):143-160

The mechanical response of cohesionless granular materials under monotonic loading is studied by performing molecular dynamic simulations. The diversity of shapes of soil grains is modelled by using randomly generated convex polygons as granular particles. Results of the biaxial test obtained for dense and loose media show that samples achieve the same void ratio at large strains independent of their initial density state. This limit state resembles the so‐called critical state of soil mechanics, except for some stress fluctuations, which remain for large deformations. These fluctuations are studied at the micro‐mechanical level, by following the evolution of the co‐ordination number, force chains and the fraction of the sliding contacts of the sample. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

Flexural isostatic response of the Alps to increased Quaternary erosion recorded by foreland basin remnants,SE France     

Jean‐Daniel Champagnac  Peter Van Der Beek  Gaël Diraison  Samuel Dauphin 《地学学报》2008,20(3):213-220

We test the hypothesis that flexural isostatic compensation of the mass removed by enhanced Quaternary erosion is responsible for uplift of the Western European Alps and their forelands. We use two well‐preserved and well‐dated (1.8 Ma) abandonment surfaces of foreland basin remnants in SE France (the Chambaran and Valensole plateaux) as passive benchmarks for tilting of the foreland. Estimating their initial slope from morphometric scaling relationships, we determine bulk post‐depositional tilting of 0.5–0.8% for these surfaces. The calculated isostatic response of the Alpine lithosphere to erosional unloading, using the method recently proposed by Champagnac et al. [Geology 35 (2007) 195–198] , yields a predicted tilting of 0.3–0.4% in the considered areas, explaining approximately half of the determined post‐depositional tilting. Such long‐term deformation being insensitive to cyclic loading/unloading because of glaciations, we suspect the other half to be related to as yet undetermined long‐wavelength and long‐lived tectonic process(es).  相似文献   

Potentiometric determination of calcium and magnesium in seawater     

Jean Lebel  Alain Poisson   《Marine Chemistry》1976,4(4):321-332

Methods are described for the complexometric determination of calcium and magnesium in seawater, using an amalgamated silver electrode for end-point detection. In the presence of a small amount of mercury(II)-chelonate, the amalgamated silver electrode serves as a pM indicator during the complexometric titration, the Hg complex being stronger than Ca, Mg and Sr complexes. Calcium is determined by titration with EGTA, calcium+magnesium+strontium by titration with EDTA and magnesium is obtained by difference. Average values of 0.02120 (standard deviation 0.00004) for Ca:Cl‰ and 0.06671 (standard deviation 0.00014) for Mg:Cl‰ were obtained for samples from tropical North Atlantic Ocean.  相似文献   

An improved multiple-frequency method for measuring in situ target strengths     

Conti  Stephane G.; Demer  David A.; Soule  Michael A.; Conti  Jean H.E. 《ICES Journal of Marine Science》2005,62(8):1636-1646

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Bioaccumulation et elimination du ⁶⁵Zn par Gammarus aequicauda martimov     

Jean Pierre Baudin 《Marine environmental research》1982,7(3):227-233

Uptake of ⁶⁵Zn by Gammarus aequicauda results in a concentration factor of approximately 50 and it is characterised by a maximal accumulation level attained as early as the third day of the experiment. After ingestion by the gammarids of twenty contaminated meals which are distributed over a 45-day period, a transfer of ⁶⁵Zn between the food and the consumer can be observed but there is no sign of the biomagnification phenomenon. The retention rate of the radionuclide is only about 1·5% and the ⁶⁵Zn concentration in the gammarids remains markedly inferior to that of the ingested food.The elimination of the ⁶⁵Zn fixed directly from water takes place according to an exponential model which corresponds to the existence of three biological half-lives of the radionuclide, $\text{Tb}{}_1\text{? 0·5 day, Tb}{}_2\text{? 3·5 days and Tb}{}_3\text{? days}$. The excretion of ⁶⁵Zn accumulated from food is a simple exponential phenomenon which corresponds to only one biological half-life of approximately 17 days.  相似文献