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A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively.  相似文献   
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Carbonaceous dolomites and shales of the 1.64 billion years (Ga) old Barney Creek Formation (BCF), McArthur Basin, northern Australia contain the oldest, clearly indigenous biomarkers. We describe three new series of regularly branched aryl isoprenoids with base ions at m/z 119, 161 and 175. The m/z 119 compounds were identified as a complete series of C15–C40 oligoprenyl-perhydro-ar-curcumenes (oligoprenyl-curcumanes). Their likely biogenic precursors are oligoprenyl-β-curcumenes that occur in a wide range of bacterial phyla.  相似文献   
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Various land–atmosphere coupling mechanisms exist that may lead to large-scale impacts on climate and hydrology. Some of them are still less understood and not adequately represented in state-of-the-art climate modelling. But, as the current generation of climate models enables consideration and implementation of important coupling processes, the present study provides perspectives for the modelling of relevant climate–hydrology interactions. On a more short-term perspective, these comprise anthropogenic land use and especially irrigation, which has been shown that it may even affect remote regions. On a long-term perspective, the coupling of hydrology to carbon cycle and vegetation becomes important, specifically the dynamics of permafrost and wetlands. Here, we present a review of current knowledge combined with some exemplary studies from a large-scale point of view. Therefore, we focus on climate–hydrology interactions that are relevant on scales utilized in the current or forthcoming global and regional climate modelling exercises.  相似文献   
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Extensive published data sets and some new data on the clay mineral composition of surface sediments in the Aegean Sea, northeastern Mediterranean Sea, have been compiled in order to map the distribution patterns of clay mineral assemblages and to decipher source areas and transport paths. We distinguished six provinces, a Northwest Aegean Province, a Marmara-Dardanelles Province, a West Turkey Province, a Southeast Aegean Province, a Kithira Province and a Central Aegean Province. The clay mineral assemblages in the coastal and shelf areas carry the signature of the riverine sediment discharge from southeast Europe and Turkey, respectively. The southern Aegean Sea is probably influenced by the River Nile discharge and transport of clay minerals by surface currents. The clay minerals in the central Aegean Sea form a mixed assemblage comprising components of the other assemblages. A dispersion and dilution of clay minerals by surface currents is obvious.  相似文献   
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This paper analyzes the potential of earthquake early-warning systems for transport lines. The interdisciplinary work focuses on rapidly producing an alert map during an ongoing earthquake as well as providing a damage map immediately after the strong-motion phase that visualizes potential damages to the railway infrastructure. In order to meet these application requirements, a service-oriented architecture based on geospatial standards is specified. This ensures the portability of the system architecture to different geographic regions as well as a potential transfer to other natural disasters and infrastructure systems. The first part of the paper describes the standard-based services of the system architecture together with design principles that are useful for the realization of early-warning systems. In the second part of the paper, an online demonstrator for the exemplary test area in the federal state of Baden-Württemberg, Germany, is presented. The system architecture of the demonstrator includes an earthquake early-warning methodology based on artificial neural networks and an infrastructure-specific damage assessment. The third part of the paper analyzes the potential of implementing low-cost sensors in the track, which would provide a dense network directly at the railway infrastructure.  相似文献   
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