No description available.

No description available.

Several hydrides of Group 2 and 12 elements were generated in the gas phase using an emission source that combines an electrical discharge with a high temperature furnace, and their high-resolution infrared emission spectra were recorded with a Fourier transform spectrometer. Two classes of molecules were studied: <em>a)</em> diatomic metal hydrides BeH, MgH, CaH, SrH, ZnH and CdH; <em>b)</em> linear triatomic metal hydrides BeH₂, MgH₂, ZnH₂ and HgH₂. <br /><br /> Infrared emission spectra of BeH, MgH, CaH, SrH, ZnH and CdH free radicals contained several vibration-rotation bands in their ²SIGMA⁺ ground electronic state. The new data were combined with all the previous ground state data from diode laser infrared spectra and pure rotation spectra available in the literature. Spectroscopic constants, i. e. , vibrational band origins, rotational, centrifugal distortion, and spin-rotation interaction constants, were determined for each observed vibrational level by least-squares fitting of all the data. In addition, the data from all isotopologues were fitted simultaneously using the empirical Dunham-type energy level expression for ²SIGMA⁺ states, and correction parameters due to the breakdown of the Born-Oppenheimer approximation were determined. The equilibrium internuclear distances (<em>r</em>_e) of ⁹BeH, ²⁴MgH, ⁴⁰CaH, ⁸⁸SrH, ⁶⁴ZnH and ¹¹⁴CdH were determined to be 1. 342424(2), 1. 729721(1), 2. 002360(1), 2. 146057(1), 1. 593478(2) and 1. 760098(3) angstroms, respectively, and the corresponding <em>r</em>^e distances for ⁹BeD, ²⁴MgD, ⁴⁰CaD, ⁸⁸SrD, ⁶⁴ZnD and ¹¹⁴CdD are 1. 341731(2), 1. 729157(1), 2. 001462(1), 2. 145073(1), 1. 593001(2) and 1. 759695(2) angstroms, respectively. <br /><br /> Gaseous BeH², MgH², ZnH² and HgH² molecules were discovered and unambiguously identified by their high-resolution infrared emission spectra. The &nu;₃ antisymmetric stretching fundamental band and several hot bands in the &nu;₃ region were rotationally analyzed, and spectroscopic constants were obtained for almost all naturally-occurring isotopologues. The rotational constants of the 000 ground states were used to determine the <em>r</em>₀ internuclear distances. For BeH₂, ZnH₂, ZnD₂, HgH₂ and HgD₂ molecules, the rotational constants of the 000, 100, 01¹0 and 001 levels were used to determine the equilibrium rotational constants (<em>B</em>_e) and the associated equilibrium internuclear distances <em>r</em>_e. The <em>r</em>_e distances of ZnH₂ and ZnD₂ differed by about 0. 01%, and those of HgH₂ and HgD₂ differed by about 0. 005%. These discrepancies were larger than the statistical uncertainties by one order of magnitude, and were attributed to the breakdown of the Born-Oppenheimer approximation.

Cette thèse a permis de comparer les caractéristiques spectrales des supernovæ de type Ia en fonction du<br />décalage vers le rouge ("évolution"). Dans le cadre des collaborations Supernova Cosmology Project (SCP) et SuperNova Legacy Survey (SNLS), dont l'objectif scientique commun est l'étude de l'énergie noire à l'aide de supernovæ de type Ia à grand décalage vers le rouge, une part importante du travail de thèse est consacrée à la réduction des données spectrales,<br />étape nécessaire pour obtenir le spectre physiquement exploitable à partir de données observées. La réduction de l'ensemble des spectres SCP issus du spectrographe à échellettes Keck-ESI a permis d'obtenir des supernovæ de type Ia parmi les plus lointaines jamais observées. Dans l'expérience SNLS, l'identication spectroscopique est essentiellement réalisée avec le spectrographe longue fente FORS1 monté au foyer du VLT UT1. Pour le SNLS, il s'agit de réduire et d'identier une dizaine de spectres par lunaison pendant 5 ans. Dans le cadre de cette thèse, un logiciel d'identication en temps réel de SNIa a été developpé, il permet d'établir le type, le décalage vers le rouge et l'âge du candidat quasi automatiquement. Il évalue aussi la contamination<br />de la galaxie hôte (dont on peut aussi estimer la morphologie) dans le spectre. Le logiciel a été testé sur un échantillon de spectres analysés en détail.<br />Par ailleurs, pour certains d'entre eux, on a mesuré la vitesse du CaH&K (3945.12Å) dans la photosphère puis<br />on a comparé les résultats avec les mêmes mesures réalisées sur un lot de spectres proches. Ce résultat a permis de conrmer l'hypothèse de standardité des SNIa à grand décalage vers le rouge. C'est une hypothèse fondamentale pour mesurer les paramètres cosmologiques avec les supernovæ de type Ia.

Several hydrides of Group 2 and 12 elements were generated in the gas phase using an emission source that combines an electrical discharge with a high temperature furnace, and their high-resolution infrared emission spectra were recorded with a Fourier transform spectrometer. Two classes of molecules were studied: <em>a)</em> diatomic metal hydrides BeH, MgH, CaH, SrH, ZnH and CdH; <em>b)</em> linear triatomic metal hydrides BeH₂, MgH₂, ZnH₂ and HgH₂. <br /><br /> Infrared emission spectra of BeH, MgH, CaH, SrH, ZnH and CdH free radicals contained several vibration-rotation bands in their ²SIGMA⁺ ground electronic state. The new data were combined with all the previous ground state data from diode laser infrared spectra and pure rotation spectra available in the literature. Spectroscopic constants, i. e. , vibrational band origins, rotational, centrifugal distortion, and spin-rotation interaction constants, were determined for each observed vibrational level by least-squares fitting of all the data. In addition, the data from all isotopologues were fitted simultaneously using the empirical Dunham-type energy level expression for ²SIGMA⁺ states, and correction parameters due to the breakdown of the Born-Oppenheimer approximation were determined. The equilibrium internuclear distances (<em>r</em>_e) of ⁹BeH, ²⁴MgH, ⁴⁰CaH, ⁸⁸SrH, ⁶⁴ZnH and ¹¹⁴CdH were determined to be 1. 342424(2), 1. 729721(1), 2. 002360(1), 2. 146057(1), 1. 593478(2) and 1. 760098(3) angstroms, respectively, and the corresponding <em>r</em>^e distances for ⁹BeD, ²⁴MgD, ⁴⁰CaD, ⁸⁸SrD, ⁶⁴ZnD and ¹¹⁴CdD are 1. 341731(2), 1. 729157(1), 2. 001462(1), 2. 145073(1), 1. 593001(2) and 1. 759695(2) angstroms, respectively. <br /><br /> Gaseous BeH², MgH², ZnH² and HgH² molecules were discovered and unambiguously identified by their high-resolution infrared emission spectra. The &nu;₃ antisymmetric stretching fundamental band and several hot bands in the &nu;₃ region were rotationally analyzed, and spectroscopic constants were obtained for almost all naturally-occurring isotopologues. The rotational constants of the 000 ground states were used to determine the <em>r</em>₀ internuclear distances. For BeH₂, ZnH₂, ZnD₂, HgH₂ and HgD₂ molecules, the rotational constants of the 000, 100, 01¹0 and 001 levels were used to determine the equilibrium rotational constants (<em>B</em>_e) and the associated equilibrium internuclear distances <em>r</em>_e. The <em>r</em>_e distances of ZnH₂ and ZnD₂ differed by about 0. 01%, and those of HgH₂ and HgD₂ differed by about 0. 005%. These discrepancies were larger than the statistical uncertainties by one order of magnitude, and were attributed to the breakdown of the Born-Oppenheimer approximation.

Chlorinated aliphatic hydrocarbons (CAH´s) were used widely within dry cleaning facilities and for metal degreasing until their toxicity was discovered. PCE is still used as dry cleaning liquid. Today CAH´s are found in soil environment at places where they have been used in the past. The CAH-concentration in trees growing on contaminated land has quite recently received attention as a cheap and effective way of assessing the extent of a CAH-contamination. The method has however, not been put into use in Sweden. The aim of the study has been to investigate whether the CAH-concentration in tree cores could be used to delineate the spread of CAH in a soil environment under Swedish conditions in different seasons. The aim has also been to gain an understanding of the uptake process, as well as to identify the limitations of the method and important issues to consider when sampling. Trees were sampled in March and June on Helgö 1:25, 1:26 in Växjö, Småland. Metal degreasing earlier conducted at this site has lead to the CAH contamination of soil and groundwater (PCE, TEC c-DACE). Mostly PCE, TCE, and chloroform were detected in tree cores. The CAH concentration was higher in June. Using the sum of PCE+TCE+c-DCE in trees to delineate the spread gave a result that was quite consistent with a delination done based on groundwater sampling. The uptake of CAH by trees is governed by the uptake of water at the root. The water usage, together with the origin of the water used is important for the ability of the tree to take up CAH. The CAH concentration within trees is also dependent on the chemical properties of the compound (Log kow, solubility etc), the concentration of the compound in the soil as well as degradation processeses. The position and height of sampling in the trees, tree species as well as tree size are important factors to consider when sampling. Sampling during summer is preferred when the concentration of CAH in trees is likely to be higher. The analysis of CAH in tree cores has potential to be used as a screening tool in soil investigations under Swedish conditions. It is a cheap and easy to use method, which would be a good complement to other investigative measures. However, an increased understanding of the processes involved, together with more analysis are needed., as this is a new method. / Klorerade lösningsmedel (CAH) användes i stor omfattning som bl a kemtvättmedel och avfettningsmedel tills dess att deras toxiska egenskaper blev kända. Perkloretylen (PCE) används än idag som kemtvättmedel. CAH återfinns ofta i markmiljö på de platser där de tidigare använts. Analys av CAH-koncentration i trädkärnor har uppmärksammats som en billig och effektiv metod för att översiktligt bedöma utbredningen av dessa föroreningar. Metoden har inte tidigare använts i Sverige. Syftet med detta examensarbete är att undersöka om trädprovtagning kan användas för att bedöma utbredningen av föroreningar i markmiljö under svenska förhållanden vid olika årstider. Analyserade CAH-halter i träd har jämförts med tidigare registrerade halter av CAH i grundvatten. Syftet har också varit att beskriva CAH-upptaget i träd, undersöka metodens begränsningar samt att sammanfatta viktiga aspekter vid provtagning. Provtagningar av träd har genomförts under mars och juni på fastigheterna Helgö 1:25 och 1:26 i Växjö, där tidigare metallavfettning har medfört att mark och grundvattnet förorenats av CAH; perkloretylen (PCE), trikloretylen (TCE) och nedbrytningsprodukten dikloretylen (c1,2-DCE). Vid analys av trädkärnor detekterades främst PCE, TCE samt TCM (kloroform). Koncentrationen av CAH var högre i juni. Halten PCE+TCE+c-DCE i trädproverna gav en översiktlig bild av föroreningssituationen som överensstämde väl med de grundvattenprover som tidigare tagits på fastigheten. CAH tas upp i vattenlöst fas vid trädens rötter. Trädets vattenbehov och vilket vatten det utnyttjar är därför viktigt för dess möjlighet att ta upp CAH. Ämnets kemiska egenskaper (log kow, flyktighet, mm.), samt förekomst och nedbrytning påverkar den halt som registreras i trädet. Vid provtagning bör provtagningspunkternas höjd över marken och position, trädart samt trädstorlek beaktas. Provtagning under sommaren är att föredra eftersom halterna då är högre. Jämförelsen med grundvattenprovtagning visar att metoden har potential att användas i Sverige för att bedöma utbredningen av en CAH-förorening i markmiljö. Den är enkel att använda och kan vara ett alternativ på platser där konventionella metoder är svåra att genomföra. En ökad förståelse för involverade processer, samt utökade undersökningar av metoden är nödvändiga då metoden är ny.

Le contexte de l’étude est celui des mouvements de terrain susceptibles de se produire à la suite d’un affaissement minier caractéristique de Lorraine et de leurs conséquences sur les habitations en maçonnerie traditionnelle. Quand de tels affaissements se produisent, ces habitations subissent en effet des désordres qui résultent des efforts engendrés dans la structure par les mouvements du terrain. La réponse qui caractérise alors l’état global de la structure dépend des caractéristiques géométriques, physiques et mécaniques. Or, la nature discontinue des maçonneries et la complexité des interactions entre blocs dans ces maçonneries rend complexe et difficile la détermination de cette réponse. Il en est de même de l’interaction sol-structure. L’objectif de la recherche consiste donc à étudier, par modélisation numérique avec la méthode des éléments distincts et par la technique des plans d’expérience et des surfaces de réponse, le comportement d’ouvrages en maçonnerie soumis à un affaissement minier caractéristique et à dégager de cette étude des critères permettant d’estimer, à l’échelle d’une ville entière, la vulnérabilité de tous ses bâtiments en maçonnerie. Une première analyse simplifiée expose le principe de la démarche mise en œuvre à l’échelle de la ville de Joeuf, utilisée comme site pilote. Elle repose sur l’analyse de la longueur cumulée des joints ouverts, assimilés à la formation de fissures dans la structure. Ensuite, une analyse typologique permet de distinguer 4 groupes de maisons aux caractéristiques proches. Sur chacun de ces groupes, la démarche est ensuite appliquée de manière systématique. Elle prend en considération des caractéristiques géométriques des façades et aboutit à la formulation de fonctions de vulnérabilité qui font appel à la technique de régression orthogonale / The context of our study concerns ground movements that may occur in Lorraine as a result of mining subsidence events and their impact on traditional masonry houses. When such an event occurs, houses suffer disorders resulting from efforts in the structure caused by the movement of the ground. The response that characterizes the state of the structure depends on the geometrical, physical and mechanical characteristics. However, the discontinuous nature of the masonry and the interactions complexity between masonry blocks makes it difficult to determine that response. The same is true about the soil-structure interaction. The purpose of this research is to study, by numerical modelling with the distinct element method, experimental design planning and response surfaces, the behaviour of masonry structures subjected to a typical mining subsidence event and to define from this study some criteria making possible the estimation of the vulnerability of all the buildings of a city. A first simplified analysis describes the principle of the used methodology which is then applied to the study of all houses of the city of Joeuf, used as a pilot site. This methodology is based on an analysis of the total length of the opened joints, which are considered as similar to cracks in the structure. Then, a typology analysis helps first to distinguish 4 groups (types) of houses which have similar characteristics. On each of these groups, the methodology is applied consistently, based on the geometrical characteristics of the houses facades and then leads to the formulation of vulnerability functions that use the technique of orthogonal regression

No description available.

No description available.

In the perilous waters of the Mediterranean Sea, migrants find themselves facing limited choices when in distress. Their options are stark: either to rely on the lifesaving efforts of Non- Governmental Organisations (NGO) aid workers conducting Search and Rescue (SAR) Operations, to be intercepted by the Libyan Coast Guard (LCG) and subsequently detained in Libya where their human rights are gravely violated, or to face the tragic fate of perishing at sea. Unfortunately, the criminalisation of SAR Operations, spearheaded by NGO aid workers, hinders the rescue of migrants, thereby exacerbating the risks they face and leaving them vulnerable to interception by the LCG. This interception, as argued in this thesis, inevitably leads to the perpetration of Crimes Against Humanity (CAH) against these vulnerable migrants. This thesis sheds light on the issue of Italy’s increasing criminalisation and vilification of humanitarian aid workers engaged in SAR missions in the Mediterranean Sea. It critically examines the consequences of such criminalisation on the lives and rights of migrants, exploring the complex dynamics between SAR Operations, interception by the LCG, and the commission of CAH. Drawing upon a comprehensive lens of interpretation that integrates legal analysis, human rights principles, and the international legal framework, this study concludes that criminalisation of SAR operations is indeed a contributing factor towards the CAH faced by migrants in Libya. Moreover, it identifies the potential liability of Italian State Officials (ISO) at the International Criminal Court (ICC) for their role in enacting legislations that effectively criminalises SAR operations.