Surface complexation of U(VI) on goethite (α-FeOOH)     

David M. Sherman  Caroline L. Peacock  Christopher G. Hubbard 《Geochimica et cosmochimica acta》2008,72(2):298-310

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.  相似文献   

The composition and crystallinity of the near-surface regions of weathered alkali feldspars     

Martin R. Lee  Mark E. Hodson  Maureen MacKenzie  Caroline L. Smith 《Geochimica et cosmochimica acta》2008,72(20):4962-4975

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.  相似文献   

An evaluation of temperature scales for silica diagenesis in diatomaceous sequences including a new approach based on the Miocene Monterey Formation,California     

Margaret A. Keller  Caroline M. Isaacs 《Geo-Marine Letters》1985,5(1):31-35

Geologic relations indicate that silica phases transformed in the Monterey Formation in two zones that persist over a narrow depth/temperature range and do not stratigraphically overlap. The wide and overlapping range of reported temperatures of these transformations is mainly a result of the many uncertainties inherent in the different methods used to estimate temperature and does not indicate that phases transform throughout these ranges. Our approach to a reliable temperature scale for silica diagenesis combines as empirical zonation of silica phases with temperature calibration from a sequence at maximum temperature and depth of burial.  相似文献   

Calibration of visual observations of wave period     

C.Guedes Soares 《Ocean Engineering》1986,13(6)

Visual observations of wave properties are an important source of statistical information needed for the prediction of design and operational conditions of ocean structures. In particular, mean wave periods are important parameters for predicting the response of ocean structures. The existing calibration studies were based on data sets with a poor correlation between observations and measurements. The data set analysed here show a good correlation indicating the feasibility of collecting further good data sets to provide an adequate calibration to the existing statistical compilations of wave data.  相似文献   

Validation of a time-domain strip method to calculate the motions and loads on a fast monohull     

N. Fonseca  C. Guedes Soares   《Applied Ocean Research》2004,26(6):256-273

The paper presents a comparison between experimental data and numerical results of the hydrodynamic coefficients and also of the wave induced motions and loads on a fast monohull model. The model with 4.52 m length was constructed in Fibre Reinforced Plastic (FRP), and made up of 4 segments connected by a backbone in order to measure sectional loads. The objective of the investigation was to assess the capability of a nonlinear time domain strip method to represent the nonlinear and also the forward speed effects on a displacement high speed vessel advancing in large amplitude waves. With this objective in mind the experimental program included forced oscillation tests in heaving and pitching, for a range of periods, three different amplitudes and several speeds of advance. In head regular waves comprehensive ranges of wave periods, wave steepness and speeds, were tested in order to measure heave, pitch and loads in three cross sections.

The numerical method assumes that the radiation and diffraction hydrodynamic forces are linear and the nonlinear contributions arise from the hydrostatics and Froude–Krilov forces and the effects of green water on deck. The assumption of linearity of the radiation forces is validated by comparing calculated hydrodynamic coefficients with experimental data for three different amplitudes of the forced oscillations. Both global coefficients and sectional coefficients are compared. The motions and loads in waves are compared in terms of first and higher harmonic amplitudes and also in terms of sagging and hogging peaks.  相似文献   

Computational study of sail performance in upwind condition     

C. Ciortan  C. Guedes Soares   《Ocean Engineering》2007,34(16):2198-2206

Airflow around yacht sails with imposed final geometry is simulated using a CFD code, reproducing experimental tests carried in a wind tunnel. Two configurations are considered: one, mast–main sail and the other, mast–jib–main sail. Both configurations were studied in the same flow conditions of air velocity and incidence angle. The grid is structured-like next to the sails and unstructured in the rest of the domain. The turbulence model used is Shear Stress Transport. The results are compared against experimental and numerical results.  相似文献   

On the adequacy of second-order models to predict abnormal waves     

P. Petrova  Z. Cherneva  C. Guedes Soares   《Ocean Engineering》2007,34(7):956-961

The paper is intended to extend the investigations about the nature of abnormal waves that have been reported in the work of Guedes Soares et al. (Characteristics of abnormal waves in North Sea states. Applied Ocean Research 25, [337–344]). The same dataset gathered at the oil platform North Alwyn in the North Sea during the November storm in 1997 is used along with the time series from the Draupner platform, in which an abnormal wave occurred. The data are reanalyzed from the viewpoint of the applicability of second-order models to fit large waves. The observed results confirm that the second-order approximation is not adequate to describe highly asymmetric and abnormal waves.  相似文献   

Long term prediction of non-linear vertical bending moments on a fast monohull     

C. Guedes Soares  N. Fonseca  R. Pascoal 《Applied Ocean Research》2004,26(6):288-297

An assessment is made of the maximum wave induced bending moment expected to occur during the operational lifetime of a fast monohull, based on long term distribution calculations of the non-linear vertical bending moment at mid-ship. The ship is assumed to operate in the Northern North Sea, with an operational life of 25 years. A succession of short-term stationary ship responses represented by Rayleigh distributions of peaks results in the long-term distribution of the structural loads. Non-linear pseudo transfer functions are used in the procedure to calculate the variances of the short-term responses. The amplitudes of these transfer functions are calculated by a non-linear time domain seakeeping program. The results are compared with rules minimum required values and also with results from simpler calculation procedures such as adopting design sea states.  相似文献   

Uncertainty in predictions of oil spill trajectories in open sea     

P. Sebastio  C. Guedes Soares 《Ocean Engineering》2007,34(3-4):576-584

A method is introduced to calculate and to account for the uncertainties in the predictions of oil spill trajectories using a classic oil spill model. The method considers the output of the oil spill model as a function of random variables, which are the input parameters, and calculates the standard deviation of the output results which gives a measure of the uncertainty of the model given the uncertainties of the input parameters.Instead of a single trajectory that is calculated by the oil spill model using the mean values of the parameters, a band of trajectories can be defined when various simulations are done taking into account the uncertainties of the input parameters. This band of trajectories defines envelopes of the trajectories that are likely to be followed by the spill given the uncertainties of the input.The method is applied to an oil spill that occurred in open sea near Madeira Islands, in the Atlantic Ocean, in December 1989. The simulations allow the understanding of how a change in the wind direction drove the spill towards the Islands.The envelope of likely trajectories that is obtained with the uncertainty modelling shows a band of trajectories that is in better agreement with the observations than the single trajectory simulated by the oil spill model, based on mean parameters.  相似文献   

Path following control system for a tanker ship model     

Lúcia Moreira  Thor I. Fossen  C. Guedes Soares   《Ocean Engineering》2007,34(14-15):2074-2085

A two-dimensional path following control system for autonomous marine surface vessels is presented. The guidance system is obtained through a way-point guidance scheme based on line-of-sight projection algorithm and the speed controller is achieved through state feedback linearization. A new approach concerning the calculation of a dynamic line-of-sight vector norm is presented which main idea is to improve the speed of the convergence of the vehicle to the desired path. The results obtained are compared with the traditional line-of-sight scheme. It is intended that the complete system will be tested and implemented in a model of the “Esso Osaka” tanker. The results of simulations are presented here showing the effectiveness of the system aiming in to be robust enough to perform tests either in tanks or lakes.  相似文献