In practice there is a long tradition of actuaries calculating reserve estimates according to deterministic methods without explicit reference to a stochastic model. For instance, the chain-ladder was originally a deterministic reserving method. Moreover, the actuaries often make ad hoc adjustments of the methods, for example, smoothing of the chain-ladder development factors, in order to fit the data set under analysis. However, stochastic models are needed in order to assess the variability of the claims reserve. The standard statistical approach would be to first specify a model, then find an estimate of the outstanding claims under that model, typically by maximum likelihood, and finally the model could be used to find the precision of the estimate. As a compromise between this approach and the actuary's way of working without reference to a model the object of the research area has often been to first construct a model and a method that produces the actuary's estimate and then use this model in order to assess the uncertainty of the estimate. A drawback of this approach is that the suggested models have been constructed to give a measure of the precision of the reserve estimate without the possibility of changing the estimate itself. The starting point of this thesis is the inconsistency between the deterministic approaches used in practice and the stochastic ones suggested in the literature. On one hand, the purpose of Paper I is to develop a bootstrap technique which easily enables the actuary to use other development factor methods than the pure chain-ladder relying on as few model assumptions as possible. This bootstrap technique is then extended and applied to the separation method in Paper II. On the other hand, the purpose of Paper III is to create a stochastic framework which imitates the ad hoc deterministic smoothing of chain-ladder development factors which is frequently used in practice.

Relevance is an essential concept in information retrieval (IR) and relevance estimation is a fundamental IR task. It involves not only document relevance estimation, but also estimation of user's information need. Relevance-based language model aims to estimate a relevance model (i.e., a relevant query term distribution) from relevance feedback documents. The true relevance model should be generated from truly relevant documents. The ideal estimation of the true relevance model is expected to be not only effective in terms of mean retrieval performance (e.g., Mean Average Precision) over all the queries, but also stable in the sense that the performance is stable across different individual queries. In practice, however, in approximating/estimating the true relevance model, the improvement of retrieval effectiveness often sacrifices the retrieval stability, and vice versa. In this thesis, we propose to explore and analyze such effectiveness-stability tradeoff from a new perspective, i.e., the bias-variance tradeoff that is a fundamental theory in statistical estimation. We first formulate the bias, variance and the trade-off between them for retrieval performance as well as for query model estimation. We then analytically and empirically study a number of factors (e.g., query model complexity, query model combination, document weight smoothness and irrelevant documents removal) that can affect the bias and variance. Our study shows that the proposed bias-variance trade-off analysis can serve as an analytical framework for query model estimation. We then investigate in depth on two particular key factors: document weight smoothness and removal of irrelevant documents, in query model estimation, by proposing novel methods for document weight smoothing and irrelevance distribution separation, respectively. Systematic experimental evaluation on TREC collections shows that the proposed methods can improve both retrieval effectiveness and retrieval stability of query model estimation. In addition to the above main contributions, we also carry out initial exploration on two further directions: the formulation of bias-variance in personalization and looking at the query model estimation via a novel theoretical angle (i.e., Quantum theory) that has partially inspired our research.

<p>The inverse problem of modeling biochemical processes mathematically from measured time course data falls into the category of system identification and parameter estimation. Analyzing the time course data would provide valuable insights into the model structure and dynamics of the biochemical system. Based on the types of biochemical reactions, such as metabolic networks and genetic networks, several modeling frameworks have been proposed, developed and proved effective, including the Michaelis-Menten equation, the Biochemical System Theory (BST), etc. One bottleneck in analyzing the obtained data is the estimation of parameter values within the system model.</p> <p>As most models for molecular biological systems are nonlinear with respect to both parameters and system state variables, estimation of parameters in these models from experimental measurement data is thus a nonlinear estimation problem. In principle, all algorithms for nonlinear optimization can be used to deal with this problem, for example, the Gauss-Newton iteration method and its variants. However, these methods do not take the special structures of biological system models into account. When the number of parameters to be determined increases, it will be challenging and computationally expensive to apply these conventional methods.</p> <p>In this research, several methods are proposed for estimating parameters in two classes of widely used biological system models: the S-system model and the linear fractional model (LFM), by utilizing their structure specialties. For the S-system, two estimation methods are designed. 1) Based on the two-term structure (production and degradation) of the model, an alternating iterative least squares method is proposed. 2) A separation nonlinear least squares method is proposed to deal with the partially linear structure of the model. For the LFM, two estimation methods are provided. 1) The separation nonlinear least squares method can also be adopted to treat the partially linear structure of the LFM, and moreover a modified iterative version is included. 2) A special strategy using the separation principle and the weighted least squares method is implemented to turn the cost function into a quadratic form and thus the estimates for parameters can be analytically solved. Simulation results have demonstrated the effectiveness of the proposed methods, which have shown better performance in terms of estimation accuracy and computation time, compared with those conventional nonlinear estimation methods.</p>

<p>The inverse problem of modeling biochemical processes mathematically from measured time course data falls into the category of system identification and parameter estimation. Analyzing the time course data would provide valuable insights into the model structure and dynamics of the biochemical system. Based on the types of biochemical reactions, such as metabolic networks and genetic networks, several modeling frameworks have been proposed, developed and proved effective, including the Michaelis-Menten equation, the Biochemical System Theory (BST), etc. One bottleneck in analyzing the obtained data is the estimation of parameter values within the system model.</p> <p>As most models for molecular biological systems are nonlinear with respect to both parameters and system state variables, estimation of parameters in these models from experimental measurement data is thus a nonlinear estimation problem. In principle, all algorithms for nonlinear optimization can be used to deal with this problem, for example, the Gauss-Newton iteration method and its variants. However, these methods do not take the special structures of biological system models into account. When the number of parameters to be determined increases, it will be challenging and computationally expensive to apply these conventional methods.</p> <p>In this research, several methods are proposed for estimating parameters in two classes of widely used biological system models: the S-system model and the linear fractional model (LFM), by utilizing their structure specialties. For the S-system, two estimation methods are designed. 1) Based on the two-term structure (production and degradation) of the model, an alternating iterative least squares method is proposed. 2) A separation nonlinear least squares method is proposed to deal with the partially linear structure of the model. For the LFM, two estimation methods are provided. 1) The separation nonlinear least squares method can also be adopted to treat the partially linear structure of the LFM, and moreover a modified iterative version is included. 2) A special strategy using the separation principle and the weighted least squares method is implemented to turn the cost function into a quadratic form and thus the estimates for parameters can be analytically solved. Simulation results have demonstrated the effectiveness of the proposed methods, which have shown better performance in terms of estimation accuracy and computation time, compared with those conventional nonlinear estimation methods.</p>

In this thesis, we present two fairly general classes of so called overflow queueing networks. These networks consist of two queues, where the capacity of the first queue is always finite. Customers arriving at the first queue have an overflow capability from the first to the second queue if the first queue operates at a certain fixed capacity, i.e., under certain conditions, demands arriving at the first queue are allowed to join the second queue. The overflow stream will additionally be weighted with a parameter p. This parameter can be used as a control parameter or to model the customers´ impatience. We reduce the number of unknown steady-state probabilities of these system in a considerable amount by a generating functions approach and a separation technique.

La télédétection en imagerie hyperspectrale infrarouge thermique est l'étude d'images en luminance, acquises depuis un avion ou un satellite dans le domaine spectral de l'infrarouge thermique. Ces images sont liées à l'émissivité et à la température, estimées par les méthodes de découplage température/émissivité (T/E), ainsi qu'à l'abondance, estimée par les méthodes de démélange, des matériaux présents dans la scène. Si les méthodes de découplage T/E ont été largement étudiées, les méthodes de démélange dans ce domaine spectral restent peu explorées : c'est l'objectif de cette thèse. Pour cela, nous avons mis en place trois stratégies de démélange. Dans un premier temps, le démélange est effectué sur les luminances. Cette stratégie donne globalement de bons résultats mais est relativement sensible aux variations spatiales de la température. La deuxième stratégie, démélangeant à partir des estimations d'émissivité des méthodes de découplage T/E, s'affranchit de cette variation spatiale mais donne des résultats plus bruités. Enfin, une méthode de démélange basée sur l'estimation conjointe de la température et des abondances a été élaborée. Cette méthode s'appelle Thermal Remote sensing Unmixing for Subpixel Temperature (TRUST) et donne de meilleurs résultats que la première stratégie tout en étant robuste aux variations spatiales de la température. / Thermal hyperspectral remote sensing provides information about materials from the measured radiance image. It is achieved using temperature and emissivity separation (TES) methods, estimating the emissivity and the temperature of the materials, and using unmixing methods, estimating their abundances. TES methods have been well investigated while too few studies have been working on unmixing in thermal infrared domain : this is the objective of this PhD. Therefore, three strategies have been studied. First, the unmixing is applied on radiance. It achieves good results but depends on the spatial variation of temperature. Applying the unmixing on the emissivities, estimated using the TES methods, gets rid of the spatial variation of temperature but provides a noisy abundance estimation. Eventually, a new method called Thermal Remote sensing Unmixing for Subpixel Temperature (TRUST) is designed to jointly estimate the abundance and the temperature of materials within the pixels. It gives better results than the first strategy and is more robust to spatial variation of temperature.

A formação dos monoalquil carbonatos (MACs) em meio aquoso - produzidos pela reação de um álcool e bicarbonato foi investigada por eletroforese capilar (CE) com detecção condutométrica sem contato (C4D). Foram estudadas ao todo 29 substâncias, das quais 25 apresentaram formação de adutos aniônicos monocarregados e 2 delas, adutos aniônicos com dupla carga. A eletroforese capilar proporcionou a obtenção de medidas de propriedades físico-químicas. Através do tempo de migração, foram obtidos mobilidade, coeficiente de difusão e raio iônico hidratado. Para os n-álcoois de 1 a 5 átomos de carbono, os adutos apresentaram raio iônico hidratado entre 216 pm e 310 pm. Os MACs têm raio iônico proporcional ao do álcool gerador, sendo sistematicamente maiores devidos à anexação do grupo carbonato. Quando comparado a ácidos carboxílicos de cadeia carbônica similar, os MACs possuem menor raio iônico hidratado. A obtenção dos valores da cinética de formação e hidrólise foi possível pela utilização de dupla detecção condutométrica, a qual permitia determinar a concentração do MAC em dois momentos diferentes ao longo da coluna. Devido à impossibilidade de uma calibração direta - já que os sais de MACs se decompõem em água - foi introduzida uma nova técnica de calibração que dispensa o uso de uma solução padrão do analito em favor de uma com espécie de mobilidade similar. As constantes cinética e termodinâmica foram comparadas com aquelas disponíveis na literatura, mostrando boa concordância, como no caso dos adutos para o metanol e etanol (a 25 ºC em meio aquoso), cujos valores da constante termodinâmica sugeridos pela literatura são de 3,57 e 1,80, respectivamente, enquanto que os valores calculados em nosso trabalho são de 4,2 e 2,3, a 25ºC. De forma similar ao ácido carbônico, os ácidos alquilcarbônicos (ACAs) se decompõem em meio ácido, o que dificulta a determinação da verdadeira constante de dissociação. Ainda assim, estudos em pH de 3 a 9, permitiram estimar os valores de pKa dos ácidos derivados de metanol, etanol e propanol como estando algo abaixo de 4, o que estaria em acordo com o valor de 3,6 do ácido carbônico. A formação de MACs também foi observada para dióis, como o etileno glicol e polióis, como o glicerol e manitol. Foi também possível observar, por eletroforese capilar, a formação de adutos aniônicos monovalentes para açúcares, tais como a sacarose, glicose e frutose. Por fim, a pesquisa revelou a possibilidade da formação de adutos com dupla carga - os bis(carbonatos) - para alguns dióis: o 1,4-butanodiol e o 1,6-hexanodiol. Esta é a primeira vez que estas espécies foram observadas. Estes resultados sugerem a formação de adutos aniônicos para várias outras classes de compostos, as quais possuam a hidroxila na cadeia carbônica. Embora, em meio predominantemente aquoso, estas espécies não estejam em alta concentração, trata-se de um novo conjunto de espécies a serem consideradas quando se trabalha em condições propícias. / The formation of monoalkyl carbonates (MACs) in aqueous medium - resulting from an alcohol and bicarbonate - was investigated by using capillary electrophoresis with capacitively coupled contactless conductivity detection (C4D). Twenty nine substances were studied. The mono-charged anionic adducts were observed for 25 of them and double-charged species were observed for 2. Capillary electrophoresis allowed us to obtain some physical-chemical properties. The migration time was used to calculate the ionic mobility, coefficient of diffusion, and hydrodynamic radius. The radii ranged from 216 to 310 pm for the adducts formed from the n-alcohols of 1 to 5 carbon atoms, respectively. The MACs have radii proportional to the size of the alcohol, being systematically greater because of the attached carbonate group. When compared to carboxylic acids of similar carbonic chain, the MACs have smaller radii. The calculation of the kinetic constants was possible due to the double C4D detection, which allows quantitation of the MAC at two different moments along the capillary. Due to the decomposition of the MAC salt in water, a direct quantitation was not possible. Thus an indirect calibration approach was introduced, where the analyte is substituted by a stable species of similar mobility. Good agreement was obtained between the kinetic and thermodynamic constants obtained by this method and those ones available in literature. For instance, the methanol and ethanol adducts were 4.2 and 2.3 (at 25 ºC), respectively, while the literature\'s values are 3.57 and 1.80. Similarly to carbonic acid, the alkyl carbonic acids (ACAs) decompose in acid medium, which impairs the determination of the dissociation constant. Even so, studies from pH between 3 and 9 allowed us to estimate that the pKa values of the adducts for methanol, ethanol, and propanol are somewhat below 4, which is in agreement with the value 3.6 for the carbonic acid. MACs were also observed for diols and polyols as well as for sugars. Finally, double-charged species bis(carbonates) were formed with 1,4-butanediol and 1,6-hexanediol. This is the first time that these species are reported. Although the concentrations of these species are not high in an aqueous medium, they form a new set of substance to be considered in aqueous solution when the conditions are favorable.

The context of this thesis is the numerical simulation of turbulent flows at moderate Reynolds numbers and the improvement of the capabilities of an in-house 3D unsteady and incompressible flow solver called SFELES to simulate such flows. In addition to this abstract, this thesis includes five other chapters. The second chapter of this thesis presents the numerical methods implemented in the two CFD solvers used as part of this work, namely SFELES and PHASTA. The third chapter concentrates on the implementation of a new library called FlexMG. This library allows the use of various types of iterative solvers preconditioned by algebraic multigrid methods, which require much less memory to solve linear systems than a direct sparse LU solver available in SFELES. Multigrid is an iterative procedure that relies on a series of increasingly coarser approximations of the original 'fine' problem. The underlying concept is the following: low wavenumber errors on fine grids become high wavenumber errors on coarser levels, which can be effectively removed by applying fixed-point methods on coarser levels. Two families of algebraic multigrid preconditioners have been implemented in FlexMG, namely smooth aggregation-type and non-nested finite element-type. Unlike pure gridless multigrid, both of these families use the information contained in the initial fine mesh. A hierarchy of coarse meshes is also needed for the non-nested finite element-type multigrid so that our approaches can be considered as hybrid. Our aggregation-type multigrid is smoothed with either a constant or a linear least square fitting function, whereas the non-nested finite element-type multigrid is already smooth by construction. All these multigrid preconditioners are tested as stand-alone solvers or coupled with a GMRES (Generalized Minimal RESidual) method. After analyzing the accuracy of the solutions obtained with our solvers on a typical test case in fluid mechanics (unsteady flow past a circular cylinder at low Reynolds number), their performance in terms of convergence rate, computational speed and memory consumption is compared with the performance of a direct sparse LU solver as a reference. Finally, the importance of using smooth interpolation operators is also underlined in this work. The fourth chapter is devoted to the study of subgrid scale models for the large eddy simulation (LES) of turbulent flows. It is well known that turbulence features a cascade process by which kinetic energy is transferred from the large turbulent scales to the smaller ones. Below a certain size, the smallest structures are dissipated into heat because of the effect of the viscous term in the Navier-Stokes equations. In the classical formulation of LES models, all the resolved scales are used to model the contribution of the unresolved scales. However, most of the energy exchanges between scales are local, which means that the energy of the unresolved scales derives mainly from the energy of the small resolved scales. In this fourth chapter, constant-coefficient-based Smagorinsky and WALE models are considered under different formulations. This includes a classical version of both the Smagorinsky and WALE models and several scale-separation formulations, where the resolved velocity field is filtered in order to separate the small turbulent scales from the large ones. From this separation of turbulent scales, the strain rate tensor and/or the eddy viscosity of the subgrid scale model is computed from the small resolved scales only. One important advantage of these scale-separation models is that the dissipation they introduce through their subgrid scale stress tensor is better controlled compared to their classical version, where all the scales are taken into account without any filtering. More precisely, the filtering operator (based on a top hat filter in this work) allows the decomposition u' = u - ubar, where u is the resolved velocity field (large and small resolved scales), ubar is the filtered velocity field (large resolved scales) and u' is the small resolved scales field. At last, two variational multiscale (VMS) methods are also considered. The philosophy of the variational multiscale methods differs significantly from the philosophy of the scale-separation models. Concretely, the discrete Navier-Stokes equations have to be projected into two disjoint spaces so that a set of equations characterizes the evolution of the large resolved scales of the flow, whereas another set governs the small resolved scales. Once the Navier-Stokes equations have been projected into these two spaces associated with the large and small scales respectively, the variational multiscale method consists in adding an eddy viscosity model to the small scales equations only, leaving the large scales equations unchanged. This projection is obvious in the case of a full spectral discretization of the Navier-Stokes equations, where the evolution of the large and small scales is governed by the equations associated with the low and high wavenumber modes respectively. This projection is more complex to achieve in the context of a finite element discretization. For that purpose, two variational multiscale concepts are examined in this work. The first projector is based on the construction of aggregates, whereas the second projector relies on the implementation of hierarchical linear basis functions. In order to gain some experience in the field of LES modeling, some of the above-mentioned models were implemented first in another code called PHASTA and presented along with SFELES in the second chapter. Finally, the relevance of our models is assessed with the large eddy simulation of a fully developed turbulent channel flow at a low Reynolds number under statistical equilibrium. In addition to the analysis of the mean eddy viscosity computed for all our LES models, comparisons in terms of shear stress, root mean square velocity fluctuation and mean velocity are performed with a fully resolved direct numerical simulation as a reference. The fifth chapter of the thesis focuses on the numerical simulation of the 3D turbulent flow over a re-entry Apollo-type capsule at low speed with SFELES. The Reynolds number based on the heat shield is set to Re=10^4 and the angle of attack is set to 180º, that is the heat shield facing the free stream. Only the final stage of the flight is considered in this work, before the splashdown or the landing, so that the incompressibility hypothesis in SFELES is still valid. Two LES models are considered in this chapter, namely a classical and a scale-separation version of the WALE model. Although the capsule geometry is axisymmetric, the flow field in its wake is not and induces unsteady forces and moments acting on the capsule. The characterization of the phenomena occurring in the wake of the capsule and the determination of their main frequencies are essential to ensure the static and dynamic stability during the final stage of the flight. Visualizations by means of 3D isosurfaces and 2D slices of the Q-criterion and the vorticity field confirm the presence of a large meandering recirculation zone characterized by a low Strouhal number, that is St≈0.15. Due to the detachment of the flow at the shoulder of the capsule, a resulting annular shear layer appears. This shear layer is then affected by some Kelvin-Helmholtz instabilities and ends up rolling up, leading to the formation of vortex rings characterized by a high frequency. This vortex shedding depends on the Reynolds number so that a Strouhal number St≈3 is detected at Re=10^4. Finally, the analysis of the force and moment coefficients reveals the existence of a lateral force perpendicular to the streamwise direction in the case of the scale-separation WALE model, which suggests that the wake of the capsule may have some preferential orientations during the vortex shedding. In the case of the classical version of the WALE model, no lateral force has been observed so far so that the mean flow is thought to be still axisymmetric after 100 units of non-dimensional physical time. Finally, the last chapter of this work recalls the main conclusions drawn from the previous chapters.

This thesis is focused on the methods of separation of baseflow and comparing of these metods. It is analyzing concentrations of total phosphorus in the total runoff and influence of baseflow to concentrations of phosphorus in total runoff. The studied area is subcatchment P52 in the catchment Kopaninský flow. Subcatchments P52 is small (64,93 hectares), drained agro-forestry catchment in Českomoravská vrchovina (Czech-Moravian highlands), with a large proportion of forest area (64% forest and 31% of arable land). Studied the period is hydrological period 2009 - 2011. To obtain the necessary results are used daily flow, daily concentrations, daily precipitation of rain gauge station Velký Rybník and monthly precipitation from rain gauge stations of the ČHMŮ (Czech Hydrometeorological Institute) in Humpolec. For the separation of the baseflow and comparison of methods were selected five methods: - method of digital filter according to Chapman (1999), - method UKIH designed by Institute of hydrology (1980), - method RDF proposed by LINE AND Hollick (1979), - method FUKIH proposed by AKOSY AT. AL. (2009) and - method of Kille (1970). All methods are simple to perform and not challenging to input data. When comparing methods, the main problem is that, the results obtained by different methods are very different. Another point of this work is to evaluate the concentrations of total phosphorus in the tatal runoff. Here is analyzed series of daily concentrations of total phosphorus and monthly and annual average concentrations. Low and high concentrations are compared with the values ??of precipitation and clinks are searched between these values. The main problem is that, the concentration of phosphorus are not dependent only on precipitation. The last point is solution of influnence of baseflow to the amount of total phosphorus in the runoff. Here is used the procedure which described BYSTŘICKÝ in its work (2012). There are determined values concentrations typical of baseflow, for direct runoff and total runoff. Groups of values ??are mutually tested and compared. The results show that, the baseflow is negligible contributor of phosphorus to the total runoff, but to achieve more accurate results would be needed to analyse a longer time period (eg 10 years) and compare the results with several different river basins.

A formação dos monoalquil carbonatos (MACs) em meio aquoso - produzidos pela reação de um álcool e bicarbonato foi investigada por eletroforese capilar (CE) com detecção condutométrica sem contato (C4D). Foram estudadas ao todo 29 substâncias, das quais 25 apresentaram formação de adutos aniônicos monocarregados e 2 delas, adutos aniônicos com dupla carga. A eletroforese capilar proporcionou a obtenção de medidas de propriedades físico-químicas. Através do tempo de migração, foram obtidos mobilidade, coeficiente de difusão e raio iônico hidratado. Para os n-álcoois de 1 a 5 átomos de carbono, os adutos apresentaram raio iônico hidratado entre 216 pm e 310 pm. Os MACs têm raio iônico proporcional ao do álcool gerador, sendo sistematicamente maiores devidos à anexação do grupo carbonato. Quando comparado a ácidos carboxílicos de cadeia carbônica similar, os MACs possuem menor raio iônico hidratado. A obtenção dos valores da cinética de formação e hidrólise foi possível pela utilização de dupla detecção condutométrica, a qual permitia determinar a concentração do MAC em dois momentos diferentes ao longo da coluna. Devido à impossibilidade de uma calibração direta - já que os sais de MACs se decompõem em água - foi introduzida uma nova técnica de calibração que dispensa o uso de uma solução padrão do analito em favor de uma com espécie de mobilidade similar. As constantes cinética e termodinâmica foram comparadas com aquelas disponíveis na literatura, mostrando boa concordância, como no caso dos adutos para o metanol e etanol (a 25 ºC em meio aquoso), cujos valores da constante termodinâmica sugeridos pela literatura são de 3,57 e 1,80, respectivamente, enquanto que os valores calculados em nosso trabalho são de 4,2 e 2,3, a 25ºC. De forma similar ao ácido carbônico, os ácidos alquilcarbônicos (ACAs) se decompõem em meio ácido, o que dificulta a determinação da verdadeira constante de dissociação. Ainda assim, estudos em pH de 3 a 9, permitiram estimar os valores de pKa dos ácidos derivados de metanol, etanol e propanol como estando algo abaixo de 4, o que estaria em acordo com o valor de 3,6 do ácido carbônico. A formação de MACs também foi observada para dióis, como o etileno glicol e polióis, como o glicerol e manitol. Foi também possível observar, por eletroforese capilar, a formação de adutos aniônicos monovalentes para açúcares, tais como a sacarose, glicose e frutose. Por fim, a pesquisa revelou a possibilidade da formação de adutos com dupla carga - os bis(carbonatos) - para alguns dióis: o 1,4-butanodiol e o 1,6-hexanodiol. Esta é a primeira vez que estas espécies foram observadas. Estes resultados sugerem a formação de adutos aniônicos para várias outras classes de compostos, as quais possuam a hidroxila na cadeia carbônica. Embora, em meio predominantemente aquoso, estas espécies não estejam em alta concentração, trata-se de um novo conjunto de espécies a serem consideradas quando se trabalha em condições propícias. / The formation of monoalkyl carbonates (MACs) in aqueous medium - resulting from an alcohol and bicarbonate - was investigated by using capillary electrophoresis with capacitively coupled contactless conductivity detection (C4D). Twenty nine substances were studied. The mono-charged anionic adducts were observed for 25 of them and double-charged species were observed for 2. Capillary electrophoresis allowed us to obtain some physical-chemical properties. The migration time was used to calculate the ionic mobility, coefficient of diffusion, and hydrodynamic radius. The radii ranged from 216 to 310 pm for the adducts formed from the n-alcohols of 1 to 5 carbon atoms, respectively. The MACs have radii proportional to the size of the alcohol, being systematically greater because of the attached carbonate group. When compared to carboxylic acids of similar carbonic chain, the MACs have smaller radii. The calculation of the kinetic constants was possible due to the double C4D detection, which allows quantitation of the MAC at two different moments along the capillary. Due to the decomposition of the MAC salt in water, a direct quantitation was not possible. Thus an indirect calibration approach was introduced, where the analyte is substituted by a stable species of similar mobility. Good agreement was obtained between the kinetic and thermodynamic constants obtained by this method and those ones available in literature. For instance, the methanol and ethanol adducts were 4.2 and 2.3 (at 25 ºC), respectively, while the literature\'s values are 3.57 and 1.80. Similarly to carbonic acid, the alkyl carbonic acids (ACAs) decompose in acid medium, which impairs the determination of the dissociation constant. Even so, studies from pH between 3 and 9 allowed us to estimate that the pKa values of the adducts for methanol, ethanol, and propanol are somewhat below 4, which is in agreement with the value 3.6 for the carbonic acid. MACs were also observed for diols and polyols as well as for sugars. Finally, double-charged species bis(carbonates) were formed with 1,4-butanediol and 1,6-hexanediol. This is the first time that these species are reported. Although the concentrations of these species are not high in an aqueous medium, they form a new set of substance to be considered in aqueous solution when the conditions are favorable.