In der vorliegenden Arbeit wird das Konzept einer druckbasierten Analyse von Fest-Gas-Gleichgewichten hinsichtlich theoretischer wie experimenteller Zusammenhänge untersucht. Hierfür erfolgt eine gezielte Nutzung der Beziehungen von theoretischen und experimentell zugänglichen physikalischen Parametern, um so die Grundlage für eine spätere Anwendung im Kontext der Syntheseplanung zu ermöglichen. Im Speziellen handelt es sich im vorgestellten Konzept um die aus festkörperanalytischer Sicht häufig vernachlässigte Beziehung zwischen dem Dampfdruck von Festkörpern und dem chemischen Potenzial. Neben der theoretischen Erarbeitung des Analysekonzeptes befasst sich die vorgestellte Arbeit zusätzlich mit dessen experimenteller Umsetzung anhand der Entwicklung bzw. Optimierung der Analyseverfahren der Hochtemperatur-Gasphasenwaage sowie des automatisierten Membrannullmanometers. Abgeschlossen wird die Arbeit zudem durch die anschauliche Vorstellung der praktischen Anwendung des Konzeptes hinsichtlich unterschiedlicher Fragestellungen (Theorie vs. Experiment: Quecksilber/Phosphor/Iod, Analyse der Phasenbildung: Arsen/Phosphor, rationale Syntheseplanung: IrPTe, Syntheseoptimierung: Bi13P3I7, Kinetik: FeAs).

Rain forest canopies are renowned for their very high biodiversity and the critical role they play in key ecological processes and their influence on global climate. Despite that New Zealand supports one of the most diverse and extensive epiphyte flora of any temperate forest system, few studies have investigated epiphyte communities and their invertebrate fauna along with factors that influence their distribution and composition. This thesis represents the first comprehensive study of entire epiphyte communities and their resident invertebrate fauna in the canopy of New Zealand’s indigenous forests. The aim of this study was to determine spatial patterns of epiphyte and invertebrate species richness, abundance and community composition in relation to abiotic variables, and in particular, the responses of these communities to elevated temperature and rainfall. This study was carried out in coastal lowland podocarp-broadleaved forests at two sites on the West Coast of the South Island of New Zealand. Samples from 120 mat-forming epiphyte assemblages located on inner canopy branches of 40 northern rata (Metrosideros robusta) trees were studied to characterise the component flora and fauna. Additionally, biomass, branch and tree characteristics and community responses to treatments designed to elevate temperature and rainfall to simulate predicted climate change were measured. This investigation revealed astonishing diversity and functional complexity of epiphyte and invertebrate life in this ecosystem. The 30.6 kg (dry weight) of epiphyte material collected contained a total of 567 species, 170 epiphyte and 397 invertebrate (excluding immature specimens and mites) species, including at least 10 species new to science and many undescribed species Epiphyte communities were found to be dominated by non-vascular plants (80 % of the total species richness), particularly liverworts and invertebrate communities were dominated with respect to abundance (~ 80 % of the total individuals) by Acari, Collembola and Hymenoptera (primarily ants) and functionally by scavengers and ants. Epiphyte and invertebrate communities were highly variable with respect to spatial patterning of species richness, abundance and composition across sites, among trees within sites and among branches within trees. Overall, a highly significant proportion, > 75 %, of the variance could be attributed to differences at the branch level, but these differences could not be explained by the environmental factors measured. There were no consistent relationships between the spatial pattern of epiphytes and invertebrates, or between vascular and non-vascular plants. However, there were significant positive correlations between epiphyte biomass and invertebrate species richness (r = 0.472; p < 0.0001) and abundance (r = -0.395; p < 0.0001), as well as non-living epiphyte biomass and scavenger species richness (r = 0.4; p < 0.0001). Microclimatic measurements taken on epiphyte mats were also highly variable with respect to temperature and relative humidity at similar physical locations within the same tree as well as across trees within sites. There was also considerable variation in the intensity and frequency of climatic extremes, although potentially harmful climatic conditions were experienced by all the epiphyte mats for which weather variables were measured. Negative correlations existed between both epiphyte and invertebrate community composition and increased temperatures expressed as cumulative degree days above 5˚C. However, variability was such that there was no direct evidence that increased temperature and rainfall treatments had an effect on invertebrate species richness, abundance or diversity. Northern rata host trees harbour an astonishingly diverse and complex canopy flora and fauna that is characterised by high spatial variability. Such variability highlights that to determine species distribution and community dynamics in canopy habitats in response to disturbance caused either by climate change or invasive species the structure of entire communities at different taxonomic and spatial scales, along with their responses to microclimatic factors, need to be studied. If such complexities are not taken into account, inappropriate interpretation may result in poor decisions concerning the conservation status, vulnerability and subsequent management of such unique ecosystems.

La détermination des propriétés physiques de l’eau pure, notamment la pression de vapeur saturante en fonction de la température, est un enjeu majeur en humidité et identifié comme tel par le Comité Consultatif de Thermométrie (CCT-WG6) sous-groupe Humidité du Comité Technique de Température (TC-T) afin d’améliorer les incertitudes des références nationales en humidité. A cette fin, le LNE-CETIAT et le LNE-Cnam ont développé conjointement un dispositif expérimental permettant d’accéder au couple température / pression de vapeur saturante de l’eau pure. Le principe est basé sur une mesure statique de la pression et de la température dans une cellule d’équilibre associée à un calorimètre quasi-adiabatique. La gamme de température d’équilibre couverte s’étend de 193,15 K à 373,15 K, correspondant à une pression de vapeur saturante allant de 0,06 Pa à 105 Pa.Ce travail présente la description, la réalisation et la caractérisation métrologique de ce nouveau dispositif expérimentale. Les résultats des mesures expérimentales sont comparés avec les travaux théoriques et expérimentaux les plus récents. Le budget d'incertitude finale prend en compte la contribution de la mesure de pression, de la mesure de température et des effets parasites telles que la transpiration thermique et la pression aérostatique. Grace aux différentes solutions mises en œuvre, la contribution des mesures de température dans le bilan d’incertitude globale est réduite. La part prépondérante reste essentiellement associée à la mesure de pression. / The determination of the physical properties of pure water, especially the vapor-pressure curve, is one of the major issues identified by the Consultative Committee for Thermometry (CCT) of the technical committee in thermometry sub-field hygrometry to improve the accuracy of the national references in humidity.In order to achieve this objective, the LNE-CETIAT and the LNE-Cnam have jointly built a facility dedicated to the measurement of the saturation vapor pressure and temperature of pure water. The principle is based on a static measurement of the pressure and the temperature of pure water in a closed, temperature-controlled thermostat, conceived like a quasi-adiabatic calorimeter. The explored temperature range lies between 193,15 K and 373,15 K, and the pressure range between 0,06 Pa and 105 Pa.This work presents a full description of this facility and the preliminary results obtained for its characterization. The obtained results have been compared with available literature data. The final uncertainty budget took into account several components: pressure measurements, temperature measurements and environmental error sources such as thermal transpiration and hydrostatic pressure correction. Thanks to the employment of several technical solutions, the thermal contribution to the overall uncertainty budget is reduced, and the remaining major part is mainly due to pressure measurements.

In der vorliegenden Arbeit wird das Konzept einer druckbasierten Analyse von Fest-Gas-Gleichgewichten hinsichtlich theoretischer wie experimenteller Zusammenhänge untersucht. Hierfür erfolgt eine gezielte Nutzung der Beziehungen von theoretischen und experimentell zugänglichen physikalischen Parametern, um so die Grundlage für eine spätere Anwendung im Kontext der Syntheseplanung zu ermöglichen. Im Speziellen handelt es sich im vorgestellten Konzept um die aus festkörperanalytischer Sicht häufig vernachlässigte Beziehung zwischen dem Dampfdruck von Festkörpern und dem chemischen Potenzial. Neben der theoretischen Erarbeitung des Analysekonzeptes befasst sich die vorgestellte Arbeit zusätzlich mit dessen experimenteller Umsetzung anhand der Entwicklung bzw. Optimierung der Analyseverfahren der Hochtemperatur-Gasphasenwaage sowie des automatisierten Membrannullmanometers. Abgeschlossen wird die Arbeit zudem durch die anschauliche Vorstellung der praktischen Anwendung des Konzeptes hinsichtlich unterschiedlicher Fragestellungen (Theorie vs. Experiment: Quecksilber/Phosphor/Iod, Analyse der Phasenbildung: Arsen/Phosphor, rationale Syntheseplanung: IrPTe, Syntheseoptimierung: Bi13P3I7, Kinetik: FeAs).

No description available.