Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides     

Laura E. Wasylenki  Bryan A. Rolfe  Thomas G. Spiro 《Geochimica et cosmochimica acta》2008,72(24):5997-6005

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.  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

  相似文献   

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   

Vibrations of a simply supported plate carrying an elastically mounted concentrated mass     

D. R. Avalos  H. Larrondo  P. A. A. Laura 《Ocean Engineering》1993,20(2)

A large number of papers and technical reports are available on the technically important problem of structural elements executing transverse vibrations and carrying concentrated masses. In general it is assumed that the attachment is perfectly rigid. On the other hand, a rather limited amount of published work is available when the mass is elastically connected to the structure. The system then exhibits a more complex behavior than in the case of rigid attachment. The present study deals with the solution of the title problem using the well-known normal mode, sinusoidal eigenfunction expansions.  相似文献   

Analytical and experimental investigation on vibrating rectangular plates with two opposite free edges and internal supports while the remaining are elastically restrained against rotation     

P.A.A. Laura  L. Ercoli 《Ocean Engineering》1986,13(3)

This paper deals with the determination of an approximate fundamental frequency equation for a rectangular plate with two edges (y = 0, b) elastically restrained against rotation while the edges x=0, a are free but internal supports parallel to the free edges are present in the structural system. The algorithmic procedure can be easily implemented on a micro computer or even a hand, programmable calculator.Good engineering agreement with experimental results is shown to exist in the case of a plate with edges y=0,b rigidly clamped.  相似文献   

A unified, polynomial approach for the approximate solution of thermoelastic problems in rectangular plates     

C.A. Rossit  P.A.A. Laura 《Ocean Engineering》1997,24(6):543-549

The present paper, of a tutorial nature, solves two different thermoelastic problems using a unified approach: (a) thermoelastic stresses and deflections in thin, rectangular plates with edges elastically restrained against rotation when small-deflection theory is used and stress resultants in the middle plane of the plates are neglected; and (b) thermoelastic plane stress situations in rectangular plates with stress-free edges subjected to a two-dimensional temperature distribution.The first problem is attacked using polynomial coordinate functions which identically satisfy the governing boundary conditions, and the Ritz method is used to determine the plate response. When the flexibility coefficients approach zero (clamped edge conditions) the calculated results practically coincide with the exact solution for the test case treated in this paper. On the other hand this degenerate solution turns out to be a very convenient approximation for obtaining a solution to Airy's problem described in the second place and which is also solved in a straightforward manner using a variational approach.  相似文献   

Dynamic response of the leg of a tension leg platform subjected to an axial, suddenly applied load at one end     

C.A. Rossit  P.A.A. Laura  D.V. Bambill 《Ocean Engineering》1996,23(3):219-224

This paper deals with the solution of the problem of the dynamic response of the leg of a tension leg platform subjected to an axial, suddenly applied load at one end, considering a highly simplified model but taking into account several complicating factors. The problem is solved by means of a non-harmonic Fourier expansion in terms of eigenfunctions obtained from a non-regular Sturm-Liouville system.  相似文献   

In Situ Measurement of Pinna nobilis Shells for Age and Growth Studies:
A New Device     

Jos Rafael García‐March  Antonio Manuel García‐Carrascosa  lvaro Luís Pea 《Marine Ecology》2002,23(3):207-217

Abstract. Pinna nobilis Linnaeus 1758 is an endemic bivalve mollusc in the Mediterranean Sea, where it inhabits seagrass meadows, especially Posidonia oceanica (L.) Delile. It is the largest bivalve in the Mediterranean, reaching lengths up to 120 cm. In its natural habitat, P. nobilis lives with the anterior part of the valve buried in the seabed, attached to Posidonia rhizomes by byssus threads.
This habit makes it impossible to measure its total length directly in situ. As the only way to determine the individual age is the relationship between age and total length, several equations have been proposed to estimate total length by relating it to the unburied parts of the shell. Such measurements are essential to ecological studies that consider age, growth, and population dynamics, and that evaluate the environmental factors that affect this species.
Accurately estimating total length depends on the accuracy and precision of the method employed to measure the unburied shell parts. In this paper, we point out the lack of precision of the instruments and methods used until now; we also demonstrate the reason for this imprecision. A new device to measure unburied parts of Pinna nobilis with a precision comparable to that obtained when measuring extracted valves is described. This device is unaffected by substratum type and reduces measurement time. The latter is a very important feature, because these procedures are usually performed whilst SCUBA diving. Finally, a growth equation has been fitted to the measurements obtained with the new device from a population located in Moraira (Alicante, western Mediterranean).  相似文献