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Structural and spectroscopical study of crystals of 1,3,4-oxadiazole derivatives at high pressure
(2002)
In recent years the search for new materials of technological interest has given new impulses to the study of organic compounds. Organic substances possess a great number of advantages such as the possibility to adjust their properties for a given purpose by different chemical and physical techniques in the preparation process. Oxadiazole derivatives are interesting due to their use as material for light emitting diodes (LED) as well as scintillators. The physical properties of a solid depend on its structure. Different structures induce different intra- and intermolecular interactions. An advantageous method to modify the intra- as well as the intermolecular interactions of a given substance is the application of high pressure. Furthermore, using this method the chemical features of the compound are not influenced. We have investigated the influence of high pressure and high temperature on the super-molecular structure of several oxadiazole derivatives in crystalline state. From the results of this investigation an equation of state for these crystals was determined. Furthermore, the spectroscopical features of these materials under high pressure were characterized.
Deep convection is an essential part of the circulation in the North Atlantic Ocean. It influences the northward heat transport achieved by the thermohaline circulation. Understanding its stability and variability is therefore necessary for assessing climatic changes in the area of the North Atlantic. This thesis aims at improving the conceptual understanding of the stability and variability of deep convection. Observational data from the Labrador Sea show phases with and without deep convection. A simple two-box model is fitted to these data. The results suggest that the Labrador Sea has two coexisting stable states, one with regular deep convection and one without deep convection. This bistability arises from a positive salinity feedback that is due to the net freshwater input into the surface layer. The convecting state can easily become unstable if the mean forcing shifts to warmer or less saline conditions. The weather-induced variability of the external forcing is included into the box model by adding a stochastic forcing term. It turns out that deep convection is then switched "on" and "off" frequently. The mean residence time in either state is a measure of its stochastic stability. The stochastic stability depends smoothly on the forcing parameters, in contrast to the deterministic (non-stochastic) stability which may change abruptly. The mean and the variance of the stochastic forcing both have an impact on the frequency of deep convection. For instance, a decline in convection frequency due to a surface freshening may be compensated for by an increased heat flux variability. With a further simplified box model some stochastic stability features are studied analytically. A new effect is described, called wandering monostability: even if deep convection is not a stable state due to changed forcing parameters, the stochastic forcing can still trigger convection events frequently. The analytical expressions explicitly show how wandering monostability and other effects depend on the model parameters. This dependence is always exponential for the mean residence times, but for the probability of long nonconvecting phases it is exponential only if this probability is small. It is to be expected that wandering monostability is relevant in other parts of the climate system as well. All in all, the results demonstrate that the stability of deep convection in the Labrador Sea reacts very sensitively to the forcing. The presence of variability is crucial for understanding this sensitivity. Small changes in the forcing can already significantly lower the frequency of deep convection events, which presumably strongly affects the regional climate. ----Anmerkung: Der Autor ist Träger des durch die Physikalische Gesellschaft zu Berlin vergebenen Carl-Ramsauer-Preises 2003 für die jeweils beste Dissertation der vier Universitäten Freie Universität Berlin, Humboldt-Universität zu Berlin, Technische Universität Berlin und Universität Potsdam.
Semi-arid areas are, due to their climatic setting, characterized by small water resources. An increasing water demand as a consequence of population growth and economic development as well as a decreasing water availability in the course of possible climate change may aggravate water scarcity in future, which often exists already for present-day conditions in these areas. Understanding the mechanisms and feedbacks of complex natural and human systems, together with the quantitative assessment of future changes in volume, timing and quality of water resources are a prerequisite for the development of sustainable measures of water management to enhance the adaptive capacity of these regions. For this task, dynamic integrated models, containing a hydrological model as one component, are indispensable tools. The main objective of this study is to develop a hydrological model for the quantification of water availability in view of environmental change over a large geographic domain of semi-arid environments. The study area is the Federal State of Ceará (150 000 km2) in the semi-arid north-east of Brazil. Mean annual precipitation in this area is 850 mm, falling in a rainy season with duration of about five months. Being mainly characterized by crystalline bedrock and shallow soils, surface water provides the largest part of the water supply. The area has recurrently been affected by droughts which caused serious economic losses and social impacts like migration from the rural regions. The hydrological model Wasa (Model of Water Availability in Semi-Arid Environments) developed in this study is a deterministic, spatially distributed model being composed of conceptual, process-based approaches. Water availability (river discharge, storage volumes in reservoirs, soil moisture) is determined with daily resolution. Sub-basins, grid cells or administrative units (municipalities) can be chosen as spatial target units. The administrative units enable the coupling of Wasa in the framework of an integrated model which contains modules that do not work on the basis of natural spatial units. The target units mentioned above are disaggregated in Wasa into smaller modelling units within a new multi-scale, hierarchical approach. The landscape units defined in this scheme capture in particular the effect of structured variability of terrain, soil and vegetation characteristics along toposequences on soil moisture and runoff generation. Lateral hydrological processes at the hillslope scale, as reinfiltration of surface runoff, being of particular importance in semi-arid environments, can thus be represented also within the large-scale model in a simplified form. Depending on the resolution of available data, small-scale variability is not represented explicitly with geographic reference in Wasa, but by the distribution of sub-scale units and by statistical transition frequencies for lateral fluxes between these units. Further model components of Wasa which respect specific features of semi-arid hydrology are: (1) A two-layer model for evapotranspiration comprises energy transfer at the soil surface (including soil evaporation), which is of importance in view of the mainly sparse vegetation cover. Additionally, vegetation parameters are differentiated in space and time in dependence on the occurrence of the rainy season. (2) The infiltration module represents in particular infiltration-excess surface runoff as the dominant runoff component. (3) For the aggregate description of the water balance of reservoirs that cannot be represented explicitly in the model, a storage approach respecting different reservoirs size classes and their interaction via the river network is applied. (4) A model for the quantification of water withdrawal by water use in different sectors is coupled to Wasa. (5) A cascade model for the temporal disaggregation of precipitation time series, adapted to the specific characteristics of tropical convective rainfall, is applied for the generating rainfall time series of higher temporal resolution. All model parameters of Wasa can be derived from physiographic information of the study area. Thus, model calibration is primarily not required. Model applications of Wasa for historical time series generally results in a good model performance when comparing the simulation results of river discharge and reservoir storage volumes with observed data for river basins of various sizes. The mean water balance as well as the high interannual and intra-annual variability is reasonably represented by the model. Limitations of the modelling concept are most markedly seen for sub-basins with a runoff component from deep groundwater bodies of which the dynamics cannot be satisfactorily represented without calibration. Further results of model applications are: (1) Lateral processes of redistribution of runoff and soil moisture at the hillslope scale, in particular reinfiltration of surface runoff, lead to markedly smaller discharge volumes at the basin scale than the simple sum of runoff of the individual sub-areas. Thus, these processes are to be captured also in large-scale models. The different relevance of these processes for different conditions is demonstrated by a larger percentage decrease of discharge volumes in dry as compared to wet years. (2) Precipitation characteristics have a major impact on the hydrological response of semi-arid environments. In particular, underestimated rainfall intensities in the rainfall input due to the rough temporal resolution of the model and due to interpolation effects and, consequently, underestimated runoff volumes have to be compensated in the model. A scaling factor in the infiltration module or the use of disaggregated hourly rainfall data show good results in this respect. The simulation results of Wasa are characterized by large uncertainties. These are, on the one hand, due to uncertainties of the model structure to adequately represent the relevant hydrological processes. On the other hand, they are due to uncertainties of input data and parameters particularly in view of the low data availability. Of major importance is: (1) The uncertainty of rainfall data with regard to their spatial and temporal pattern has, due to the strong non-linear hydrological response, a large impact on the simulation results. (2) The uncertainty of soil parameters is in general of larger importance on model uncertainty than uncertainty of vegetation or topographic parameters. (3) The effect of uncertainty of individual model components or parameters is usually different for years with rainfall volumes being above or below the average, because individual hydrological processes are of different relevance in both cases. Thus, the uncertainty of individual model components or parameters is of different importance for the uncertainty of scenario simulations with increasing or decreasing precipitation trends. (4) The most important factor of uncertainty for scenarios of water availability in the study area is the uncertainty in the results of global climate models on which the regional climate scenarios are based. Both a marked increase or a decrease in precipitation can be assumed for the given data. Results of model simulations for climate scenarios until the year 2050 show that a possible future change in precipitation volumes causes a larger percentage change in runoff volumes by a factor of two to three. In the case of a decreasing precipitation trend, the efficiency of new reservoirs for securing water availability tends to decrease in the study area because of the interaction of the large number of reservoirs in retaining the overall decreasing runoff volumes.
Value education of youth
(2002)
The value priorities of students and teachers were measured at eight different schools at the beginning and the end of the school year 2000/2001. This study once again confirmed the theoretical model of a universal structure of human values (Schwartz, 1992). At both measurement times, similar gender differences, as well as positive correlations between religiosity and school commitment were found. The students from the non-religious schools determined Hedonism as their highest, and Tradition as their lowest value priority. In the religious schools, Benevolence and Self-Direction were the highest values, whereas Power was found to be the lowest value priority. The change of the values Conformity, Hedonism, and Universalism was predicted both through the students′ religiosity and their type of school. The change of the values Power, Tradition, Benevolence, and Achievement, however, was mainly predicted through their religiosity. In three out of four schools the student-teacher similarity correlated positively with the school commitment of the students. Across all schools student-teacher similarity correlated positively with academic achievement.