ELECTROCHEMISTRY AND IN-SITU IR MICROSPECTROELECTROCHEMISTRY IN A VERSATILE THIN-LAYER REFLECTION FOURIER-TRANSFORM IR MICROSPECTROELECTROCHEMICAL CELL

A simple, convenient and versatile thin layer reflection Fourier transform IR microspectroelectrochemical (FTIRMSEC) cell has been described and characterized. Electrochemistry and in situ FTIR microspectroscopy were studied by using the hexacyanoferrate redox couple in aqueous sulphate solution, indicating that this type of cell is characteristic of both micro- or ultramicroelectrode and thin layer spectroelectrochemistry. Furthermore, the application of this FTIRMSEC cell to IR for characterization of the products of electrochemical reactions was carried out for the oxidation of (mesotetraphenylporphinato)manganese(III) perchlorate in dichloromethane + tetrabutylammonium perchlorate solution. Finally, the advantages and problems of this type of cell compared with a conventional optically transparent thin layer FTIR spectroelectrochemical cell were discussed.

DILUTE SOLUTION PROPERTIES OF RING-SHAPED POLYSTYRENE II. THE SECOND VIRIAL COEFFICIENTS

Using a low angle laser light scattering photometer (LALLS) the second virial coefficients(A_2) of ring-shaped and linear polystyrene (RPS and LPS) samples were determined in both toluene and butanone solutions. The A_2 of RPS in the good solvent (toluene) is smaller than that of LPS with the same molecular weight, but in the poor solvent (butanone) these two are very close. For RPS in the molecular weight range of 4×10~4——2.2×10~5, we haveA_(2r)=1.28×10~(-2)M_w~(-0.283) (Toluene 25℃) and A_(2r)=5.06×10~(-2...

Roles of equatorial waves and western boundary reflection in the seasonal circulation of the equatorial Indian Ocean

An ocean general circulation model (OGCM) is used to study the roles of equatorial waves and western boundary reflection in the seasonal circulation of the equatorial Indian Ocean. The western boundary reflection is defined as the total Kelvin waves leaving the western boundary, which include the reflection of the equatorial Rossby waves as well as the effects of alongshore winds, off-equatorial Rossby waves, and nonlinear processes near the western boundary. The evaluation of the reflection is based on a wave decomposition of the OGCM results and experiments with linear models. It is found that the alongshore winds along the east coast of Africa and the Rossby waves in the off-equatorial areas contribute significantly to the annual harmonics of the equatorial Kelvin waves at the western boundary. The semiannual harmonics of the Kelvin waves, on the other hand, originate primarily from a linear reflection of the equatorial Rossby waves. The dynamics of a dominant annual oscillation of sea level coexisting with the dominant semiannual oscillations of surface zonal currents in the central equatorial Indian Ocean are investigated. These sea level and zonal current patterns are found to be closely related to the linear reflections of the semiannual harmonics at the meridional boundaries. Because of the reflections, the second baroclinic mode resonates with the semiannual wind forcing; that is, the semiannual zonal currents carried by the reflected waves enhance the wind-forced currents at the central basin. Because of the different behavior of the zonal current and sea level during the reflections, the semiannual sea levels of the directly forced and reflected waves cancel each other significantly at the central basin. In the meantime, the annual harmonic of the sea level remains large, producing a dominant annual oscillation of sea level in the central equatorial Indian Ocean. The linear reflection causes the semiannual harmonics of the incoming and reflected sea levels to enhance each other at the meridional boundaries. In addition, the weak annual harmonics of sea level in the western basin, resulting from a combined effect of the western boundary reflection and the equatorial zonal wind forcing, facilitate the dominance by the semiannual harmonics near the western boundary despite the strong local wind forcing at the annual period. The Rossby waves are found to have a much larger contribution to the observed equatorial semiannual oscillations of surface zonal currents than the Kelvin waves. The westward progressive reversal of seasonal surface zonal currents along the equator in the observations is primarily due to the Rossby wave propagation.

复杂条件地层滤波预测的理论与关键技术研究

The theory researches of prediction about stratigraphic filtering in complex condition are carried out, and three key techniques are put forward in this dissertation. Theoretical aspects: The prediction equations for both slant incidence in horizontally layered medium and that in laterally variant velocity medium are expressed appropriately. Solving the equations, the linear prediction operator of overlaid layers, then corresponding reflection/transmission operators, can be obtained. The properties of linear prediction operator are elucidated followed by putting forward the event model for generalized Goupillaud layers. Key technique 1: Spectral factorization is introduced to solve the prediction equations in complex condition and numerical results are illustrated. Key technique 2: So-called large-step wavefield extrapolation of one-way wave under laterally variant velocity circumstance is studied. Based on Lie algebraic integral and structure preserving algorithm, large-step wavefield depth extrapolation scheme is set forth. In this method, the complex phase of wavefield extrapolation operator’s symbol is expressed as a linear combination of wavenumbers with the coefficients of this linear combination in the form of the integral of interval velocity and its derivatives over depth. The exponential transform of the complex phase is implemented through phase shifting, BCH splitting and orthogonal polynomial expansion. The results of numerical test show that large-step scheme takes on a great number of advantages as low accumulating error, cheapness, well adaptability to laterally variant velocity, small dispersive, etc. Key technique 3: Utilizing large-step wavefield extrapolation scheme and based on the idea of local harmonic decomposition, the technique generating angle gathers for 2D case is generalized to 3D case so as to solve the problems generating and storing 3D prestack angle gathers. Shot domain parallel scheme is adopted by which main duty for servant-nodes is to compute trigonometric expansion coefficients, while that for host-node is to reclaim them with which object-oriented angle gathers yield. In theoretical research, many efforts have been made in probing into the traits of uncertainties within macro-dynamic procedures.

基于广义Lippmann-Schwinger方程的地震波场模拟算法与应用

In the last several decades, due to the fast development of computer, numerical simulation has been an indispensable tool in scientific research. Numerical simulation methods which based on partial difference operators such as Finite Difference Method (FDM) and Finite Element Method (FEM) have been widely used. However, in the realm of seismology and seismic prospecting, one usually meets with geological models which have piece-wise heterogeneous structures as well as volume heterogeneities between layers, the continuity of displacement and stress across the irregular layers and seismic wave scattering induced by the perturbation of the volume usually bring in error when using conventional methods based on difference operators. The method discussed in this paper is based on elastic theory and integral theory. Seismic wave equation in the frequency domain is transformed into a generalized Lippmann-Schwinger equation, in which the seismic wavefield contributed by the background is expressed by the boundary integral equation and the scattering by the volume heterogeneities is considered. Boundary element-volume integral method based on this equation has advantages of Boundary Element Method (BEM), such as reducing one dimension of the model, explicit use the displacement and stress continuity across irregular interfaces, high precision, satisfying the boundary at infinite, etc. Also, this method could accurately simulate the seismic scattering by the volume heterogeneities. In this paper, the concrete Lippmann-Schwinger equation is specifically given according to the real geological models. Also, the complete coefficients of the non-smooth point for the integral equation are introduced. Because Boundary Element-Volume integral equation method uses fundamental solutions which are singular when the source point and the field are very close，both in the two dimensional and the three dimensional case, the treatment of the singular kernel affects the precision of this method. The method based on integral transform and integration by parts could treat the points on the boundary and inside the domain. It could transform the singular integral into an analytical one both in two dimensional and in three dimensional cases and thus it could eliminate the singularity. In order to analyze the elastic seismic wave scattering due to regional irregular topographies, the analytical solution for problems of this type is discussed and the analytical solution of P waves by multiple canyons is given. For the boundary reflection, the method used here is infinite boundary element absorbing boundary developed by a pervious researcher. The comparison between the analytical solutions and concrete numerical examples validate the efficiency of this method. We thoroughly discussed the sampling frequency in elastic wave simulation and find that, for a general case, three elements per wavelength is sufficient, however, when the problem is too complex, more elements per wavelength are necessary. Also, the seismic response in the frequency domain of the canyons with different types of random heterogeneities is illustrated. We analyzed the model of the random media, the horizontal and vertical correlation length, the standard deviation, and the dimensionless frequency how to affect the seismic wave amplification on the ground, and thus provide a basis for the choice of the parameter of random media during numerical simulation.

人工源宽角地震资料中的广角效应及其对地壳速度成像的影响

The seismic wide-angle reflection/refraction method is the one of the most effective method for probing the crustal and upper mantle structure. It mainly uses the wide-angle reflection information from the boundary in the crust and the top boundary of the upper mantle to rebuild the crust and upper mantle structure. Through analyzing the reflection and transmission coefficients of various incident waves on the interface, we think relative to the pre-critical angle reflection information the post critical angle reflection information that received by wide-angle seismic data exists a time-shift effect with the offset variation, and then it must cause the error for velocity analysis and structure image. The feature of the wide-angle seismic wave field of the fourteen representative crust columns tell us that the wide-angle effects in the different representative tectonic units for the interface depth and the interval velocity in crust. We studied the features of the wide-angle seismic wave field through building the crust model and inverse its travel time by GA method to know the wide-angle influence on crustal velocity image. At last we finished the data processing of the Tunxi-Wenzhou wide-angle seismic profile. The results are as following: (1) Through building crust model, we labeled the travel time for all the phases by ray tracing method and remove wide-angle effects method, it revealed the wide-angle effect exists in the seismic data. (2) The travel time inversion by GA method can tell us that the depth by traditional ray tracing method is shallower than the result by remove wide-angle effects method, the latter can recover the crust structure model in effect. (3) We applied the two method mentioned before to the fourteen representative crust columns in China. It indicates that the removed wide-angle effect method in travel time inversion is reasonable and effective. (4) The real data processing from Tunxi-Wenzhou wide-angle seismic profile give us the basic structure through the two ways. The main influence exhibits in the difference of the interval velocity of the curst, and the wide-angle effects in shallow interface are stronger than the deep interface.

Estimation of soil organic partition coefficients: from retention factors measured by soil column chromatography with water as eluent

The retention factors (k) of 104 hydrophobic organic chemicals (HOCs) were measured in soil column chromatography (SCC) over columns filled with three naturally occurring reference soils and eluted with Milli-Q water. A novel method for the estimation of soil organic partition coefficient (K-oc) was developed based on correlations with k in soil/water systems. Strong log K-oc versus log k correlations (r>0.96) were found. The estimated K-oc values were in accordance with the literature values with a maximum deviation of less than 0.4 log units. All estimated K-oc values from three soils were consistent with each other. The SCC approach is promising for fast screening of a large number of chemicals in their environmental applications. (C) 2002 Elsevier Science B.V. All rights reserved.

Prediction of soil adsorption coefficients from retention parameters on three reversed-phase liquid chromatographic columns

Reversed-phase high-performance liquid chromatographic (RP-HPLC) retention parameters, which are determined by the intermolecular interactions in retention process, can be considered as the chemical molecular descriptors in linear free energy relationships (LFERs). On the basis of the characterization and comparison of octadecyl-bonded silica gel (ODS), cyano-bonded silica gel (CN), and phenyl-bonded silica gel (Ph) columns with linear solvation energy relationships (LSERs), a new multiple linear regression model using RP-HPLC retention parameters on ODS and CN columns as variables for estimation of soil adsorption coefficients was developed. It was tested on a set of reference substances from various chemical classes. The results showed that the multicolumn method was more promising than a single-column method was for the estimation of soil adsorption coefficients. The accuracy of the suggested model is identical with that of LSERs.

A column method for determination of soil organic partition coefficients of eight pesticides

A column method was developed to conveniently and reliably determine the soil organic partition coefficients (K-oc) of three insecticides (methiocarb, azinphos-methyl, fenthion), four fungicides (triadimenol, fuberidazole, tebuconazole, pencycuron), and one herbicide (atrazine), in which real soil acted as a stationary phase and the water solution of pesticide as an eluent. The processes of sorption equilibrium were directly shown through a breakthrough curve(BTC). The log K-oc values are 1.69, 1.95, 2.25, 2.55, 2.69, 2.67, 3.10, and 3.33 for atrazine, triadimenol, methiocarb, fuberidazole, azinphos-methyl, tebuconazole, fenthion and pencycuron, respectively.

Soil column chromatography for correlation between capacity factors and soil organic partition coefficients for eight pesticides

A soil column chromatographic method was developed to measure the capacity factors (k') of pesticides, in which soil acted as a stationary phase and methanol-water mixture as an eluent. The k' values of eight pesticides, including three insecticides (methiocarb, azinphos-methyl, fenthion), four fungicides (triadimenol, fuberidazole, tebuconazole, pencycuron), and one herbicide (atrazine), were found to be well fitted to a retention equation, ln k'=ln k(w)'-S-phi. Due to similar interactions of solutes with soil and solvent in both sorption determination and retention experiment, log k' has a good linear correlation with log K-oc for the eight pesticides from different classes, in contrast with poor correlation between log k' from C-18 column and log K-oc. So the method provides a tool for rapid estimation of K-oc from experimental k'. (C) 1999 Elsevier Science Ltd. All rights reserved.

A new method for determination of adsorption and desorption coefficients of pesticides with soil column liquid chromatography

The adsorption and desorption coefficients of atrazine, methiocarb and simazine on a sandy loam soil were measured in this study with soil column liquid chromatographic (SCLC) technique. The adsorption and desorption data of all the three pesticides followed Freundlich isotherms revealing the existence of hysteresis. In comparing with other methods, SCLC method showed some characteristics such as rapidity, online and accuracy.