High pressure surface plasmon spectroscopy

Der Einfluß von Druck auf die Eigenschaften dünner dielektrischer Filme wurde mit Hilfe von Oberflächenplasmonen-Spektroskopie untersucht. Die Arbeit kann aus der Perspektive der Materialcharakterisierung und aus apparativer Sicht betrachtet werden, da z.B. eine neue Hochdruckzelle konstruiert wurde, die kombinierte Oberflächenplasmonen-Elektrochemie Messungen erlaubt. SiO2-Solgel Filme wurden optimiert und auf ihre Widerstandsfähigkeit in Bufferlösungen und ihre Oberflächeneigenschaften hin untersucht. Eine Anwendung lag in der Charakterisierung von thermoresponsiven Acrylsäureisopropylamid Hydrogelen, die einen Volumenphasenübergang aufwiesen, dessen Eigenschaften durch Druck und die Beschränktheit des Films auf die Oberfläche beeinflußt wurden.Die Charakterisierung von DNA Hybridisierungsreaktionen an Oberflächen wurde mit einer Fluoreszenz-erweiterten Hochdruckapparatur durchgeführt. Zunächst wurde die Stabilität der zugrundeliegenden Bindematrix sichergestellt. Bei DNA Einzelsträngen führten Temperatur und Druck zu jeweils verringertem bzw. erhöhtem Signal. Entropie und Änderungen der Lösungsmitteleigenschaften wurden für die Signaländerungen verantwortlich gemacht. Die Eigenschaften der Doppelhelix wurden im Langmuir-Bild beschrieben. Der Brechungsindex von Kohlendioxid wurde bis zu 200 MPa gemessen und mit vorhandenen Gleichungen verglichen. Weiterhin wurde das Schwellverhalten von PMMA in scCO2/MMA-Mischungen untersucht. Mit Druck und MMA-Konzentration nimmt das Polymer vermehrt Kohlendioxid auf. Dadurch schwillt es an und sein Brechungsindex nimmt ab. Berechnungen unter Annahme einer idealen Mixtur ergaben gute qualitative Übereinstimmung mit den Meßwerten.Abschließend wurde eine neue Elektrochemie-Hochdruckzelle vorgestellt, die an Kaliumhexacyanoferrat(III)-(II) getestet wurde. Die Elektropolymerisation von Thiophen optisch untersucht.

Potential vorticity and moisture in extratropical cyclones : climatology and sensitivity experiments

The development of extratropical cyclones can be seen as an interplay of three positive potential vorticity (PV) anomalies: an upper-level stratospheric intrusion, low-tropospheric diabatically produced PV, and a warm anomaly at the surface acting as a surrogate PV anomaly. In the mature stage they become vertically aligned and form a “PV tower” associated with strong cyclonic circulation. This paradigm of extratropical cyclone development provides the basis of this thesis, which will use a climatological dataset and numerical model experiments to investigate the amplitude of the three anomalies and the processes leading in particular to the formation of the diabatically produced low-tropospheric PV anomaly.rnrnThe first part of this study, based on the interim ECMWF Re-Analysis (ERA-Interim) dataset, quantifies the amplitude of the three PV anomalies in mature extratropical cyclones in different regions in the Northern Hemisphere on a climatological basis. A tracking algorithm is applied to sea level pressure (SLP) fields to identify cyclone tracks. Surface potential temperature anomalies ∆θ and vertical profiles of PV anomalies ∆PV are calculated at the time of the cyclones’ minimum SLP and during the intensification phase 24 hours before in a vertical cylinder with a radius of 200 km around the surface cyclone center. To compare the characteristics of the cyclones, they are grouped according to their location (8 regions) and intensity, where the central SLP is used as a measure of intensity. Composites of ∆PV profiles and ∆θ are calculated for each region and intensity class at the time of minimum SLP and during the cyclone intensification phase.rnrnDuring the cyclones’ development stage the amplitudes of all three anomalies increase on average. In the mature stage all three anomalies are typically larger for intense than for weak winter cyclones [e.g., 0.6 versus 0.2 potential vorticity units (PVU) at lower levels, and 1.5 versus 0.5 PVU at upper levels].rnThe regional variability of the cyclones’ vertical structure and the profile evolution is prominent (cyclones in some regions are more sensitive to the amplitude of a particular anomaly than in other regions). Values of ∆θ and low-level ∆PV are on average larger in the western parts of the oceans than in the eastern parts. In addition, a large seasonal variability can be identified, with fewer and weaker cyclones especially in the summer, associated with higher low-tropospheric PV values, but also with a higher tropopause and much weaker surface potential temperature anomalies (compared to winter cyclones).rnrnIn the second part, we were interested in the diabatic low-level part of PV towers. Evaporative sources were identified of moisture that was involved in PV production through condensation. Lagrangian backward trajectories were calculated from the region with high PV values at low-levels in the cyclones. PV production regions were identified along these trajectories and from these regions a new set of backward trajectories was calculated and moisture uptakes were traced along them. The main contribution from surface evaporation to the specific humidity of the trajectories is collected 12-72 hours prior to therntime of PV production. The uptake region for weaker cyclones with less PV in the centre is typically more localized with reduced uptake values compared to intense cyclones. However, in a qualitative sense uptakes and other variables along single trajectories do not vary much between cyclones of different intensity in different regions.rnrnA sensitivity study with the COSMO model comprises the last part of this work. The study aims at investigating the influence of synthetic moisture modification in the cyclone environment in different stages of its development. Moisture was eliminated in three regions, which were identified as important moisture source regions for PV production. Moisture suppression affected the cyclone the most in its early phase. It led to cyclolysis shortly after its genesis. Nevertheles, a new cyclone formed on the other side of a dry box and developed relatively quickly. Also in other experiments, moisture elimination led to strong intensity reduction of the surface cyclone, limited upper-level development, and delayed or missing interaction between the two.rnrnIn summary, this thesis provides novel insight into the structure of different intensity categories of extratropical cyclones from a PV perspective, which corroborates the findings from a series of previous case studies. It reveals that all three PV anomalies are typically enhanced for more intense cyclones, with important regional differences concerning the relative amplitude of the three anomalies. The moisture source analysis is the first of this kind to study the evaporation-condensation cycle related to the intensification of extratropical cyclones. Interestingly, most of the evaporation occurs during the 3 days prior to the time of maximum cyclone intensity and typically extends over fairly large areas along the track of the cyclone. The numerical model case study complements this analysis by analyzing the impact of regionally confined moisture sources for the evolution of the cyclone.