Modeling the gas and aqueous phase chemistry of the marine boundary layer

Ein eindimensionales numerisches Modell der maritimenGrenzschicht (MBL) wurde erweitert, um chemische Reaktionenin der Gasphase, von Aerosolpartikeln und Wolkentropfen zu beschreiben. Ein Schwerpunkt war dabei die Betrachtung derReaktionszyklen von Halogenen. Soweit Ergebnisse vonMesskampagnen zur Verfuegung standen, wurden diese zurValidierung des Modells benutzt. Die Ergebnisse von frueheren Boxmodellstudien konntenbestaetigt werden. Diese zeigten die saeurekatalysierteAktivierung von Brom aus Seesalzaerosolen, die Bedeutung vonHalogenradikalen fuer die Zerstoerung von O3, diepotentielle Rolle von BrO bei der Oxidation von DMS und dievon HOBr und HOCl in der Oxidation von S(IV). Es wurde gezeigt, dass die Beruecksichtigung derVertikalprofile von meteorologischen und chemischen Groessenvon grosser Bedeutung ist. Dies spiegelt sich darin wider,dass Maxima des Saeuregehaltes von Seesalzaerosolen und vonreaktiven Halogenen am Oberrand der MBL gefunden wurden.Darueber hinaus wurde die Bedeutung von Sulfataerosolen beidem aktiven Recyceln von weniger aktiven zu photolysierbarenBromspezies gezeigt. Wolken haben grosse Auswirkungen auf die Evolution und denTagesgang der Halogene. Dies ist nicht auf Wolkenschichtenbeschraenkt. Der Tagesgang der meisten Halogene ist aufgrundeiner erhoehten Aufnahme der chemischen Substanzen in die Fluessigphase veraendert. Diese Ergebnisse betonen dieWichtigkeit der genauen Dokumentation der meteorologischenBedingungen bei Messkampagnen (besonders Wolkenbedeckungsgrad und Fluessigwassergehalt), um dieErgebnisse richtig interpretieren und mit Modellresultatenvergleichen zu koennen. Dieses eindimensionale Modell wurde zusammen mit einemBoxmodell der MBL verwendet, um die Auswirkungen vonSchiffemissionen auf die MBL abzuschaetzen, wobei dieVerduennung der Abgasfahne parameterisiert wurde. DieAuswirkungen der Emissionen sind am staerksten, wenn sie insauberen Gebieten stattfinden, die Hoehe der MBL gering istund das Einmischen von Hintergrundluft schwach ist.Chemische Reaktionen auf Hintergrundaerosolen spielen nureine geringe Rolle. In Ozeangebieten mit schwachemSchiffsverkehr sind die Auswirkungen auf die Chemie der MBL beschraenkt. In staerker befahrenen Gebieten ueberlappensich die Abgasfahnen mehrerer Schiffe und sorgen fuerdeutliche Auswirkungen. Diese Abschaetzung wurde mitSimulationen verglichen, bei denen die Emissionen alskontinuierliche Quellen behandelt wurden, wie das inglobalen Chemiemodellen der Fall ist. Wenn die Entwicklungder Abgasfahne beruecksichtigt wird, sind die Auswirkungendeutlich geringer da die Lebenszeit der Abgase in der erstenPhase nach Emission deutlich reduziert ist.

Sustainability indicators for environmental management and decision making

The general objective of this research is to explore theories and methodologies of sustainability indicators, environmental management and decision making disciplines with the operational purpose of producing scientific, robust and relevant information for supporting system understanding and decision making in real case studies. Several tools have been applied in order to increase the understanding of socio-ecological systems as well as providing relevant information on the choice between alternatives. These tools have always been applied having in mind the complexity of the issues and the uncertainty tied to the partial knowledge of the systems under study. Two case studies with specific application to performances measurement (environmental performances in the case of the K8 approach and sustainable development performances in the case of the EU Sustainable Development Strategy) and a case study about the selection of sustainable development indicators amongst Municipalities in Scotland, are discussed in the first part of the work. In the second part of the work, the common denominator among subjects consists in the application of spatial indices and indicators to address operational problems in land use management within the territory of the Ravenna province (Italy). The main conclusion of the thesis is that a ‘perfect’ methodological approach which always produces the best results in assessing sustainability performances does not exist. Rather, there is a pool of correct approaches answering different evaluation questions, to be used when methodologies fit the purpose of the analysis. For this reason, methodological limits and conceptual assumptions as well as consistency and transparency of the assessment, become the key factors for assessing the quality of the analysis.

Abiotic and prebiotic phosphorus chemistry

The chief obstacle to understand the metabolic origin of life or RNA-based life is to identify a plausible mechanism for overcoming the clutter wrought by abiotic chemistry. Probably trough simple abiotic and then prebiotic reactions we could arrive to simple pre-RNA molecules. Here we report a possible preibiotic synthesis for heterocyclic compounds, and a self-assembling process of adenosine phosphates a constituent of RNA. In these processes we use a simple and prebiotic phosphorus cyclic compounds, as P4O10 and its derivatives. The processes are driven by the formation of hypercoordinated species that activate the processes by a factor of 106-8.

Integration of cognitive and affective processes in perception and decision-making

The relationship between emotion and cognition is a topic that raises great interest in research. Recently, a view of these two processes as interactive and mutually influencing each other has become predominant. This dissertation investigates the reciprocal influences of emotion and cognition, both at behavioral and neural level, in two specific fields, such as attention and decision-making. Experimental evidence on how emotional responses may affect perceptual and attentional processes has been reported. In addition, the impact of three factors, such as personality traits, motivational needs and social context, in modulating the influence that emotion exerts on perception and attention has been investigated. Moreover, the influence of cognition on emotional responses in decision-making has been demonstrated. The current experimental evidence showed that cognitive brain regions such as the dorsolateral prefrontal cortex are causally implicated in regulation of emotional responses and that this has an effect at both pre and post decisional stages. There are two main conclusions of this dissertation: firstly, emotion exerts a strong influence on perceptual and attentional processes but, at the same time, this influence may also be modulated by other factors internal and external to the individuals. Secondly, cognitive processes may modulate emotional prepotent responses, by serving a regulative function critical to driving and shaping human behavior in line with current goals.

CCSD(T), W1, and other model chemistry predictions for gas-phase deprotonation reactions

A series of CCSD(T) single-point calculations on MP4(SDQ) geometries and the W1 model chemistry method have been used to calculate ΔH° and ΔG° values for the deprotonation of 17 gas-phase reactions where the experimental values have reported accuracies within 1 kcal/mol. These values have been compared with previous calculations using the G3 and CBS model chemistries and two DFT methods. The most accurate CCSD(T) method uses the aug-cc-pVQZ basis set. Extrapolation of the aug-cc-pVTZ and aug-cc-pVQZ results yields the most accurate agreement with experiment, with a standard deviation of 0.58 kcal/mol for ΔG° and 0.70 kcal/mol for ΔH°. Standard deviations from experiment for ΔG° and ΔH° for the W1 method are 0.95 and 0.83 kcal/mol, respectively. The G3 and CBS-APNO results are competitive with W1 and are much less expensive. Any of the model chemistry methods or the CCSD(T)/aug-cc-pVQZ method can serve as a valuable check on the accuracy of experimental data reported in the National Institutes of Standards and Technology (NIST) database.

Culture's Calling: Mobile Phones, Gender, and the Making of an African Migrant Village in Lisbon

In this article, I explore how immigrants from the West African nation of Guinea-Bissau living in Portugal use mobile phones in their daily lives in Lisbon. Whereas one might assume that mobile phones and other new information technologies facilitate transnational communication between Africa and Portugal, the ethnographic fieldwork that I conducted in Lisbon from 1999 to 2003 revealed a different scenario. Instead, mobile phones as imagined and used by the Guinean immigrants I met in Lisbon revealed less about transnationalism and globalization than they did about constructing community and identity in a new locale. As Guinean immigrants in Portugal reconfigured their relationship to their former colonizers and struggled to make their way in a new, multicultural Europe, they used their mobile phones to engage local networks, shape local identities, and transform Lisbon's sprawl into an African migrant village. Here, I highlight the gendered dimensions of this process and contend that Guinean men's and women's varied uses of mobile phones in Lisbon underscore contrasting experiences of migration, mobility, and belonging.

Culture's Calling: Mobile Phones, Gender, and the Making of an African Migrant Village in Lisbon

In this article, I explore how immigrants from the West African nation of Guinea-Bissau living in Portugal use mobile phones in their daily lives in Lisbon. Whereas one might assume that mobile phones and other new information technologies facilitate transnational communication between Africa and Portugal, the ethnographic fieldwork that I conducted in Lisbon from 1999 to 2003 revealed a different scenario. Instead, mobile phones as imagined and used by the Guinean immigrants I met in Lisbon revealed less about transnationalism and globalization than they did about constructing community and identity in a new locale. As Guinean immigrants in Portugal reconfigured their relationship to their former colonizers and struggled to make their way in a new, multicultural Europe, they used their mobile phones to engage local networks, shape local identities, and transform Lisbon's sprawl into an African migrant village. Here, I highlight the gendered dimensions of this process and contend that Guinean men's and women's varied uses of mobile phones in Lisbon underscore contrasting experiences of migration, mobility, and belonging.