La construction du réseau de failles d'un domaine géologique à l'aide d'un logiciel de géomodélisation peut être longue et fastidieuse pour des géométries et des contacts de failles complexes et peu marqués sur les données de subsurface. En utilisant une représentation implicite de ces surfaces de faille par des champs de potentiel calculés sur un maillage tétraédrique, le processus de création d'un modèle structural a été totalement automatisé. Les contacts de failles sont détectés et des surfaces avec une géométrie cohérente au niveau des contacts sont construites. Les champs de potentiel permettent la modification du réseau de failles tout en préservant la cohérence géologique du modèle. Une technique développée ici permet également de corriger la géométrie d'un maillage tétraédrique à proximité des failles. Ainsi, de nouvelles informations ou interprétations ou des perturbations représentant les incertitudes sur la position des failles sont intégrées au modèle géologique / One of the first steps when a geological study area is modelled in three-dimensional geomodelling software is to build the fault network. This can be tedious and time-consuming when fault geometry and branching are complex and difficult to locate from sub-surface data. The process of creating a three-dimensional structural model from various data types was entirely automated by using an implicit representation of fault surfaces by level sets computed on a tetrahedral mesh. Fault branching is detected automatically and surfaces with coherent contact geometry are built. Using level sets for fault surfaces also enables easy editing of the fault network while maintaining the geological consistency of the model. A further tetrahedral mesh editing technique was developed during this PhD in order to modify mesh geometry close to faults. New information or interpretations or perturbations which represent geometrical uncertainty on faults can thus be integrated to the geological model

In this study, we consider high frequency transaction data of NYSE, and apply statistical methods to characterize each trade into two classes, influential and ordinary liquidity trades. First, a median based approach is used to establish a high R-square price-volume model for high frequency data. Next, transactions are classified into four states based on the trade price, trade volume, quotes, and quoted depth. Volume weighted transition probability of the four states are investigated and shown to be distinct for informed trades and ordinary liquidity trades. Furthermore, four market reaction factors are introduced and studied. Logistic regression models of the influential trades are established based on the four factors and odds ratios are used to select the cutoff points.

No

No / Owing to unpredictable bed topography conditions in natural shallow flows, various numerical methods have been developed to improve the treatment of source terms in the shallow water equations. The surface gradient method is an attractive approach as it includes a numerically simple approach to model flows over topographically-varied channels. To further improve the performance of this method, this study deals with the numerical improvement of the shallow-flow source terms. The so-called surface gradient upwind method (SGUM) integrates the source term treatment in the inviscid discretization scheme. A finite volume model (FVM) with the monotonic upwind scheme for conservative laws is used. The Harten–Lax–van Leer-contact approximate Riemann solver is used to reconstruct the Riemann problem in the FVM. The proposed method is validated against published analytical, numerical, and experimental data, indicating that the SGUM is robust and treats the source terms in different flow conditions well.

Yes / Based on the common approach, the adaptation length in sediment transport is normally estimated in the temporal independence. However, this approach might not be theoretically justified as the process of reaching of the sediment transport equilibrium stage is affected by the flow conditions in time, especially for those fast sediment moving flows, such as scour-hole developing flow. In this study, the 2D shallow water formulation together with a sediment continuity-concentration (SCC) model were applied to flow with mobile sediment boundary. A time-varying approach was proposed to determine the sediment transport adaptation length to treat the flow sediment erosion-deposition rate. The proposed computational model was based on the Finite Volume (FV) method. The Monotone Upwind Scheme of Conservative Laws (MUSCL)-Hancock scheme was used with the Harten Lax van Leer-contact (HLLC) approximate Riemann solver to discretize the FV model. In the flow applications of this paper, a highly discontinuous dam-break fast sediment transport flow was used to calibrate the proposed time-varying sediment adaptation length model. Then the calibrated model was further applied to two separate experimental sediment transport flow applications documented in literature, i.e. a highly concentrated sediment transport flow in a wide alluvial channel and a sediment aggradation flow. Good agreements with the experimental data were presented by the proposed model simulations. The tests prove that the proposed model, which was calibrated by the discontinuous dam-break bed scouring flow, also performed well to represent the rapid bed change and the steady sediment mobility conditions. / The National Natural Science Foundation of China NSFC (Grant Number 20101311246), Major State Basic Research Development Program (973 program) of China (Grant Number 2013CB036402) and Open Fund of the State Key Laboratory of Hydraulics and Mountain River Engineering, Sichuan University of China (Grant Number SKLH-OF-1103).

The cyclic peroxides: diphenoyl peroxide (1), spiro-adamantyl-1,2-dioxetanone (2) and 4-(3-tert-butyldimethylsilyloxyphenyl)-4-methoxyspiro[1.2-dioxetane-3.2\'-adamantane] (3) synthesized, purified and characterized, also their kinetic and chemiluminescence (CL) properties were determined. The influence of solvent polarity on the chemiexcitation parameters of the catalyzed decomposition of 1 and 2, as well as the induced decomposition of 3 were examined in several binary solvent mixtures with different polarity and polarizability parameters, but similar viscosities. For solvents with low polarity, singlet quantum yields for the intermolecular catalyzed decomposition of diphenoyl peroxide (1,) and 1,2-dioxetanone (2) increase in function of medium polarity, showing maximum values in mediums of intermediate polarity, and decreasing in highly polar mixtures. For the induced decomposition of 3, the quantum yield showed to increase with increasing solvent polarity, including high polar solvent systems. In the binary solvent systems studied, the polarizability parameter showed to be contrary to the polarity values, therefore, it might appear that an increase of polarizability leads to a decrease in the singlet quantum yields for catalyzed decomposition of diphenoyl peroxide (1) and the induced decomposition of 3, however an increase in the singlet quantum yields for 1,2-dioxetanone 2. The three CL systems were also studied in binary solvent mixtures with different viscosities but similar polarity and polarizability parameters and singlet quantum yields showed an increase with increasing medium viscosity. Data were analyzed by using the collisional and the free volume models. The highly efficient intramolecular system induced 1,2-dioxetane 3 decomposition showed to be much more sensible to viscosity effects than the inefficient intermolecular systems. This surprising fact indicates that, even showing a significant solvent-cage effect, the induced 1,2-dioxetane should occur by an intramolecular electron back transfer. Moreover, chemiluminescence parameters of these systems were studied in several pure solvents. The obtained singlet quantum yields were correlated with viscosity, polarizability and polarity parameters by using multiple linear regression analysis. / Os peróxidos cíclicos: peróxido de difenoila (1), spiro-adamantil-1,2-dioxetanona (2) e 4-(3-terc-butildimetilsililoxifenil)-4-metoxispiro[1,2-dioxetano-3.2\'-adamantano] (3) foram sintetizados, purificados e caracterizados e as suas propriedades cinéticas e de quimiluminescência (CL) determinadas. A influência da polaridade do solvente sobre os parâmetros de quimi-excitação da decomposição catalisada de 1 e 2, e a decomposição induzida de 3 foi examinada em diversas misturas binárias de solventes com parâmetros de polaridade e polarizabilidade diferente, mas viscosidades semelhantes. Para solventes com baixa polaridade, os rendimentos quânticos singlete para a decomposição catalisada intermolecular do peróxido de difenoila (1) e 1,2-dioxetanona (2) aumentam em função da polaridade do meio, mostrando valores máximos em meios com polaridade intermediária, e diminuim para misturas altamente polares. Para a decomposição induzida de 3, o rendimento quântico mostrou aumentar com o aumento da polaridade do solvente, inclusive para sistemas com alta polaridade. Nos sistemas binários de solventes estudados, os parâmetros de polarizabilidade mostraram-se contrários aos valores de polaridade, portanto, parece que um aumento da polarizability leva a uma diminuição nos rendimentos quânticos singlete para a decomposição catalisada do peróxido de difenoila (1) e a decomposição induzida de 3, no entanto, um aumento nos rendimentos quânticos singlete para a 1,2-dioxetanona 2. Os três sistemas de CL também foram estudados em misturas binárias de solventes com diferentes viscosidades, mas com parâmetros de polaridade e polarizabilidade semelhantes e os rendimentos quânticos singlete mostraram aumentar com o aumento da viscosidade do meio. Os dados foram analisados usando tanto o modelos colisional quando o modelo de volume livre. Surpreendentemente, o sistema altamente eficiente decomposição induzida intramolecular do 1,2-dioxetano 3 mostrou-se muito mais sensível aos efeitos da viscosidade do que os sistemas intermoleculares ineficientes, o que indica claramente que a decomposição induzida do 1,2-dioxetano deve ocorrer por um processo de retro-transferência de elétron intramolecular. Além disso, os parâmetros de quimiluminescência destes sistemas foram estudados em vários solventes puros. Os rendimentos quânticos singlete obtidos foram correlacionados com parâmetros de viscosidade, polarizabilidade e polaridade usando análise de regressão linear múltipla.

The cyclic peroxides: diphenoyl peroxide (1), spiro-adamantyl-1,2-dioxetanone (2) and 4-(3-tert-butyldimethylsilyloxyphenyl)-4-methoxyspiro[1.2-dioxetane-3.2\'-adamantane] (3) synthesized, purified and characterized, also their kinetic and chemiluminescence (CL) properties were determined. The influence of solvent polarity on the chemiexcitation parameters of the catalyzed decomposition of 1 and 2, as well as the induced decomposition of 3 were examined in several binary solvent mixtures with different polarity and polarizability parameters, but similar viscosities. For solvents with low polarity, singlet quantum yields for the intermolecular catalyzed decomposition of diphenoyl peroxide (1,) and 1,2-dioxetanone (2) increase in function of medium polarity, showing maximum values in mediums of intermediate polarity, and decreasing in highly polar mixtures. For the induced decomposition of 3, the quantum yield showed to increase with increasing solvent polarity, including high polar solvent systems. In the binary solvent systems studied, the polarizability parameter showed to be contrary to the polarity values, therefore, it might appear that an increase of polarizability leads to a decrease in the singlet quantum yields for catalyzed decomposition of diphenoyl peroxide (1) and the induced decomposition of 3, however an increase in the singlet quantum yields for 1,2-dioxetanone 2. The three CL systems were also studied in binary solvent mixtures with different viscosities but similar polarity and polarizability parameters and singlet quantum yields showed an increase with increasing medium viscosity. Data were analyzed by using the collisional and the free volume models. The highly efficient intramolecular system induced 1,2-dioxetane 3 decomposition showed to be much more sensible to viscosity effects than the inefficient intermolecular systems. This surprising fact indicates that, even showing a significant solvent-cage effect, the induced 1,2-dioxetane should occur by an intramolecular electron back transfer. Moreover, chemiluminescence parameters of these systems were studied in several pure solvents. The obtained singlet quantum yields were correlated with viscosity, polarizability and polarity parameters by using multiple linear regression analysis. / Os peróxidos cíclicos: peróxido de difenoila (1), spiro-adamantil-1,2-dioxetanona (2) e 4-(3-terc-butildimetilsililoxifenil)-4-metoxispiro[1,2-dioxetano-3.2\'-adamantano] (3) foram sintetizados, purificados e caracterizados e as suas propriedades cinéticas e de quimiluminescência (CL) determinadas. A influência da polaridade do solvente sobre os parâmetros de quimi-excitação da decomposição catalisada de 1 e 2, e a decomposição induzida de 3 foi examinada em diversas misturas binárias de solventes com parâmetros de polaridade e polarizabilidade diferente, mas viscosidades semelhantes. Para solventes com baixa polaridade, os rendimentos quânticos singlete para a decomposição catalisada intermolecular do peróxido de difenoila (1) e 1,2-dioxetanona (2) aumentam em função da polaridade do meio, mostrando valores máximos em meios com polaridade intermediária, e diminuim para misturas altamente polares. Para a decomposição induzida de 3, o rendimento quântico mostrou aumentar com o aumento da polaridade do solvente, inclusive para sistemas com alta polaridade. Nos sistemas binários de solventes estudados, os parâmetros de polarizabilidade mostraram-se contrários aos valores de polaridade, portanto, parece que um aumento da polarizability leva a uma diminuição nos rendimentos quânticos singlete para a decomposição catalisada do peróxido de difenoila (1) e a decomposição induzida de 3, no entanto, um aumento nos rendimentos quânticos singlete para a 1,2-dioxetanona 2. Os três sistemas de CL também foram estudados em misturas binárias de solventes com diferentes viscosidades, mas com parâmetros de polaridade e polarizabilidade semelhantes e os rendimentos quânticos singlete mostraram aumentar com o aumento da viscosidade do meio. Os dados foram analisados usando tanto o modelos colisional quando o modelo de volume livre. Surpreendentemente, o sistema altamente eficiente decomposição induzida intramolecular do 1,2-dioxetano 3 mostrou-se muito mais sensível aos efeitos da viscosidade do que os sistemas intermoleculares ineficientes, o que indica claramente que a decomposição induzida do 1,2-dioxetano deve ocorrer por um processo de retro-transferência de elétron intramolecular. Além disso, os parâmetros de quimiluminescência destes sistemas foram estudados em vários solventes puros. Os rendimentos quânticos singlete obtidos foram correlacionados com parâmetros de viscosidade, polarizabilidade e polaridade usando análise de regressão linear múltipla.