Dans le cadre de la formation sélective d'oligomères cycliques à partir du cyclo-octène, des matériaux hybrides organiques-inorganiques mésostructurés bien-définis contenant les unités Ru-NHC dissymétriques le long des canaux poreux de leur matrice de silice ont été développés et caractérisés à un niveau moléculaire. Tous les systèmes obtenus ont montré des fortes activités et sélectivités en oligomères cycliques (dimères : 50% et trimères : 25%) en RO-RCM du cyclo-octène, contrairement aux complexes homogènes Ru-NHC analogues symétriques (G-II et GH-II), qui conduisent préférentiellement à la formation de polymères. La variation de la longueur et de la flexibilité des bras espaceurs, dans le cas des catalyseurs hétérogènes, a prouvé que les bras courts et flexibles stabilisent grandement les sites actifs Ru-NHC pendant la réaction de métathèse et ce, grâce à la présence d'interactions entre les sites Ru-NHC catalytiquement actifs et la surface silicique. La présence de telles interactions a été mise en évidence par RMN du phosphore 31 à l'état solide. Des études supplémentaires concernant les performances catalytiques de complexes organométalliques Ru-NHC dissymétriques (analogues aux sites Ru-NHC contenus dans les catalyseurs hétérogènes) et Ru-NHC symétriques (G-II et Nolan) ont clairement montré que le facteur clé influençant la sélectivité en oligomères cycliques est la dissymétrie des ligands NHC. Cette dissymétrie génère la présence de deux sites actifs de configurations différentes au sein même des espèces Ru-NHC. Un des sites favorise la réaction intramoléculaire de fermeture de cycle par métathèse alors que l'autre site permet la réaction intermoléculaire d'ouverture de cycle conduisant ainsi à la formation des oligomères cycliques de petite taille / In the context of the selective formation of cyclic oligomers from cyclooctene, well-defined hybrid organic-inorganic mesoporous materials containing unsymmetrical Ru-NHC units along the pore channel of their silica matrix have been developed and characterized at a molecular level. All systems displayed high activity and selectivity towards the formation of lower cyclic oligomers in the RO-RCM of cyclooctene yielding mainly the dimer and the trimer with 50% and 25% selectivity, respectively, in contrast to classical symmetrical homogeneous analogues (G-II and GH-II), which yield mainly to polymers. Variation of length and flexibility of the tethers showed that flexible short tethers were critical for high stability of the catalysts during metathesis, which is consistent with the stabilization of Ru-NHC active sites by surface functionalities; this surface interaction was further corroborated by the absence of a PCy3 ligand coordinated to Ru when short flexible linkers are used. Further investigations using homogeneous symmetrical (G-II and Nolan) and unsymmetrical (analogues to heterogeneous catalysts) Ru-NHC catalysts clearly showed that the key factor influencing the selectivity towards low cyclic oligomers is the unsymmetrical nature of NHC ligands, which creates dual site configuration in the catalyst architecture thus alternatively favouring one reaction over another, Ring Opening (ROM) vs. Ring Closing (RCM) Metathesis (propagation vs. backbiting), thus leading to the selective tandem RO RCM of cyclooctene. Finally, we have also investigated Grubbs Hoveyda-II (GH-II) type catalysts immobilized on silica support through adsorption, which showed the same product selectivity as that of the well-defined Ru-NHC materials. This result implies that the adsorbed symmetrical GH-II catalyst “becomes unsymmetrical upon adsorption”. Adsorbing unsymmetrical molecular GH II catalysts did not however improve the performances of these types of catalysts. Overall, the unique property of unsymmetrical NHC Ru catalyst, whether supported or not, opens new perspectives in the selective synthesis of macrocycles from other cyclic alkenes via metathesis

Exploring massive amount of user generated data with topics posits a new way to find useful information. The topics are assumed to be “hidden” and must be “uncovered” by statistical methods such as topic modeling. However, the user generated data is typically short and messy e.g. informal chat conversations, heavy use of slang words and “noise” which could be URL’s or other forms of pseudo-text. This type of data is difficult to process for most natural language processing methods, including topic modeling. This thesis attempts to find the approach that objectively give the better topics from short and messy text in a comparative study. The compared approaches are latent Dirichlet allocation (LDA), Re-organized LDA (RO-LDA), Gaussian Mixture Model (GMM) with distributed representation of words, and a new approach based on previous work named Neural Probabilistic Topic Modeling (NPTM). It could only be concluded that NPTM have a tendency to achieve better topics on short and messy text than LDA and RO-LDA. GMM on the other hand could not produce any meaningful results at all. The results are less conclusive since NPTM suffers from long running times which prevented enough samples to be obtained for a statistical test. / Att utforska enorma mängder användargenererad data med ämnen postulerar ett nytt sätt att hitta användbar information. Ämnena antas vara “gömda” och måste “avtäckas” med statistiska metoder såsom ämnesmodellering. Dock är användargenererad data generellt sätt kort och stökig t.ex. informella chattkonversationer, mycket slangord och “brus” som kan vara URL:er eller andra former av pseudo-text. Denna typ av data är svår att bearbeta för de flesta algoritmer i naturligt språk, inklusive ämnesmodellering. Det här arbetet har försökt hitta den metod som objektivt ger dem bättre ämnena ur kort och stökig text i en jämförande studie. De metoder som jämfördes var latent Dirichlet allocation (LDA), Re-organized LDA (RO-LDA), Gaussian Mixture Model (GMM) with distributed representation of words samt en egen metod med namnet Neural Probabilistic Topic Modeling (NPTM) baserat på tidigare arbeten. Den slutsats som kan dras är att NPTM har en tendens att ge bättre ämnen på kort och stökig text jämfört med LDA och RO-LDA. GMM lyckades inte ge några meningsfulla resultat alls. Resultaten är mindre bevisande eftersom NPTM har problem med långa körtider vilket innebär att tillräckligt många stickprov inte kunde erhållas för ett statistiskt test.

The vestibuloocular reflex can be manually elicited by tilting or rotating the head. Manual techniques serve their purpose well and is the golden standard in the clinical work, but they lack control of velocity and movement pattern. However, motion simulation platforms enable automatic control of both velocity and movement pattern. One motion simulation platform, named BIRGIT, has been built at the Department of Clinical Neurosciences at Karolinska Institutet but has not yet been in service and require a performance evaluation. The objectives with this thesis is to evaluate the accuracy and precision of BIRGIT and evaluate how bodyweight and movement direction impact the performance. The thesis also evaluate whether it is possible to stabilize the head of the patient during the acceleration phase. Repeated measurements of acceleration with different loads, desired ac- celeration, direction and motion type (rotational and translational), are per- formed. Dummies are used to simulate bodyweight in the performance study and real persons are used in the head stabilization study. Analysis of variance (ANOVA) is the main statistical tool. The results suggest that the platform does not perform equally at dif- ferent load or directions and that there is a bias between desired and true acceleration. The main problems are an inclination of the rails, upon which the chair is mounted, that causes differences between directions and an un- desirable performance characteristic for rotational motions. The stabilization study suggest that the head can be stabilized. / Den vestibulo-okul ̈ara reflexen kan framkallas genom att manuellt rotera eller rycka p ̊a huvudet. Att manuellt framkalla reflexen fungerar i de flesta sam- manhang va ̈l och a ̈r standard i m ̊anga underso ̈kningar. Dock g ̊ar det inte att till fullo kontrollera vare sig hastighet eller ro ̈relsebana perfekt. Emellertid g ̊ar detta att kontrollera genom att anva ̈nda sig av en s ̊a kallad ro ̈relsesimu- leringsplatform. En s ̊adan platform, d ̈opt till BIRGIT, har byggts vid Institutionen f ̈or kliniska neurovetenskaper vid Karolinska Institutet. Denna har ej bo ̈rjat anva ̈ndas ̈annu d ̊a dess prestanda fo ̈rst beho ̈ver utv ̈arderas. Syftet med denna uppsats ̈ar att utva ̈rdera precision och noggrannhet hos BIRGIT. Dessutom, att utv ̈ardera hur kroppsvikt och ro ̈relseriktning inverkar p ̊a prestandan. I arbetet ing ̊ar ̈aven att testa om det a ̈r m ̈ojligt att stabilisera huvudet under accelerationsfasen. Repeterade ma ̈tningar av sann acceleration med olika last, riktning, bo ̈rac- celeration och r ̈orelsetyp (rotation eller sidledes) genomfo ̈rdes. Testdockor anva ̈ndes fo ̈r att simulera lasten i prestandatesterna och riktiga testpersoner anva ̈ndes i huvudstabiliseringsdelen. Variansanalys (ANOVA) var det hu- vudsakliga statistiska verktyget. Resultatet antyder att last och ro ̈relseriktning inverkar p ̊a acceleratio- nen och prestandan och att den sanna accelerationen alltigenom a ̈r la ̈gre a ̈n bo ̈raccelerationen. Det finns tv ̊a sto ̈rre problem hos plattformen, det fo ̈rsta a ̈r att uppha ̈ngningen till stolen lutar och detta resulterar i en skillnad mellan riktningarna (det g ̊ar fortare nedf ̈ors). Det andra problemet a ̈r ett cykliskt uppfo ̈rande na ̈r flera rotationsr ̈orelser skall fo ̈lja p ̊a varandra. Stabiliseringsstudien visade att det g ̊ar att stabilisera huvudet.

>Magister Scientiae - MSc / Coal combustion accounts for over 40 % of the world's energy production and this figure is projected to increase with increasing human population and industrialization. The combustion of coal leads to the generation of waste products such as fly ash (FA), brine from water treatment, bottom ash, slag, flue gas desulphurization products (FGD) and gas emissions such as N20, and C02. The emissions contribute to air pollution and global warming, while FA, brines, and FGD are possible soil and water pollutants. In order to minimize the environmental impact of coal combustion, mitigation of the effects of coal burning processes such as the waste products (FA, brine, bottom ash, slag and FGD) and gas emissions is required. This study investigated utilization of the Secunda FA (class F) and reverse osmosis (RO) Tutuka brine to sequester C02 in an attempt to make coal power production more environmentally sustainable. It was hypothesized that South African FA and brine could sequester C02 through mineral carbonation. A statistical approach was undertaken to optimize the % CaC03 formed from FAlbrine/C02 interaction with input parameters of temperature, pressure, particle size and solid/liquid ratio (S/L) being varied. The ranges adopted for the input parameters were: temperature of 30°C or 90 °C; pressure of 1 Mpa or 4 Mpa; four particle sizes namely bulk ash, > 150 11m, < 20 11m and 20 urn- 150 11m particle size range; S/L ratios ofO.1, 0.5 or 1. The FA! brine dispersions were carbonated in a high pressure reactor varying the above mentioned input parameters. The fresh Secunda FA of various size fractions was characterized morphologically using scanning electron microscopy, chemically using X-ray fluorescence and mineralogically using qualitative X-ray diffraction. The carbonated solid residues on the other hand were characterized using quantitative X-ray diffraction, scanning electron microscopy, thermal gravimetic analysis and Chittick tests. The raw brine from Tutuka together with the carbonation leachates were characterized using inductively coupled mass spectrometry and ion chromatography. Total acid digestion was carried out to evaluate the differences in the total elemental content in both the fresh ash and the carbonated solid residues. The results suggested that South African FA from Secunda belongs to class F based on the CaO content as well as the total alumina, silica and ferric oxide content, while the RO brine from Tutuka were classified as NaS04 waters. Mineral carbonation occurred and ranged between 2.75 % and 6.5 % of CaC03 depending on the input parameters. Two polymorphs of CaC03 were identified in the carbonated residues i.e. calcite and aragonite. The carbonated ash/brine leachates were cleaner with respect to major and trace element concentration compared to raw brine thus the carbonation process could be used to improve the quality of brines generated in the power industry. Removal of the major elements from brine was as follows Ca-74.8 %, Na- 28.7 %, Mg- 98 %, K- 82.9 %, S04- 20.8 %. Hundred percent removal was observed for traces of Fe, Al, Mn, Cu, Zn, Pb, Ni, As, Ti, Sr, Se, Si and N03. However Mo, V, B, and Cl concentrations increased by 72.5 %, 94 %,48.2 % and 7.2 % respectively after carbonation at 90°C, 4 Mpa, S/L ratio of 1 using the bulk ash. The parameters found to be of most significance in the carbonation process were the main effects of temperature, particle size and S/L ratio while the interactions of temperature and particle size as well as the interaction of temperature with S/L ratio were also found to be significant. The statistical approach led to a clear understanding of the effect of each input parameter as well as the ansmg interactions. The conditions of 90°C, 4 Mpa, using bulk ash at a S/L ratio of 1 resulted in the highest yield of % CaC03 with a value of 6.5 %. Theoretically one ton of Secunda FA containing 9.2 % of CaO could sequester 0.083 tons of C02. With the optimized protocol developed in this study bearing in mind that the carbonation efficiency is 75.54%, 1 ton of Secunda FA could sequester 0.062 tons of CO2. This translates to 0.65 % of CO2 produced annually at Secunda plant being sequestered in the FAlbrine dispersions. In other words, 16 tons of FA are required to sequester a ton of C02 annually. It was also observed that carbonation using brine resulted in higher carbonation efficiency than carbonation using water as the Ca2+ component in the brine contributed towards the Ca 2+concentration.

>Magister Scientiae - MSc / Chemical speciation and the evaluation of species distribution is the key to understanding the potential of brines to form scale or corrode the water circuit as well as the potential of mobility and release trends of the pollutants into the environment. It is important to identify highly soluble free ions in water chemistry because toxicity of ions is related to mobility and consequently bioavailability. The chemical composition, character and chemical speciation modelling of saline effluents (brines) at Tutuka Power Station and Sasol Synthetic Fuels Complex in Secunda were studied. The form in which chemical species exist (chemical speciation) and the physical and chemical interactions of species in saline effluents at these two study sites is not fully understood. This study investigated how pH, temperature, alkalinity and chemical composition influenced chemical speciation, species distribution, scale forming and corrosion potentials of the different saline effluent streams at the two sites using computer programs PHREEQC and Aq.QA. Characterizations of the results were presented in Stiff and Piper diagrams generated by the Aq.QA computer software. Chemical speciation modelling of the brines showed that scale-forming minerals aragonite, calcite, hematite, anhydrite and gypsum have positive saturation indices between 0 and 20 in mine water, RO brine at Tutuka and Sasol Secunda, EDR brine at Sasol Secunda and VC brine at Tutuka Power Station. The water types at Tutuka Power Station were found to be mainly Na-S04 water types and those at Sasol Secunda were a mixture of Na-Cl and Na-S04 water types. Water treatment chemicals playa major role in increase were absent in the intake water. It was found that Sasol Secunda water streams are much more heavily contaminated than Tutuka water streams. The study also found that the mine water utilised at Sasol Secunda is two-fold more polluted than the mine water utilised at Tutuka although these sites are a mere 40 km apart. The sodium adsorption ratios showed that all the saline effluent streams at Tutuka and Sasol Secunda were unsuitable for irrigation, except for desalination product waters. Chemical speciation showed that the predominant species in the most concentrated saline effluent (VC brine) at Tutuka were the free cr ion at approximately 100 % with very minute quantities of FeCI+ and ZnCI+ and the predominant sodium species were the free Na+ ion which existed at 85 %. Magnesium species had the predominant form as the ionic compound MgS04 at 73 % and the carbonates were mainly in the form of NaC03- (53 %), HC03- (28 %) and CO{(7 %). The most concentrated brine analysed at Sasol Secunda was the TRO brine. PHREEQC did not predict the precipitation of CaC03 from the TRO brine at Sasol Secunda. The most abundant calcium species were Ca2+(59 %) ions and CaS04 (40 %). The brine was at a pH of 5.76 with dissolved CO2 at 73 % of the carbonate species. Trace elements were evaluated and the toxic trace elements varied from 0.07 mg/L (As) to 26.75 mg/L (Sr) at Sasol Secunda. At Tutuka Power Station the toxic trace elements in brines varied from 0.02 mg/L (As/Se) to 16.85 mg/L (Sr). Sr and B were found to be the most highly concentrated toxic elements. The major and trace ion chemistry, alkalinity, pH, sodium adsorption ratios, change in concentration of the water streams and the brine chemical composition after contact with ash was also evaluated. When saline effluents at Tutuka Power Station and Sasol Secunda are combined with ash, pH, Ca content and alkalinity of the resulting solution increased. The chemical composition of saline effluents can be influenced by the ingress of CO2 from the atmosphere. The study shows conclusively that brine composition and concentration is highly variable at these South African power utilities and processes such as RO, contact with ash and C02 ingress can have an impact upon the overall brine quality. Aq.QA was found to be a more accurate tool for classifying waters according to dominant ions than Stiff diagrams but Stiff diagrams still have the superior advantage of being a mapping tool to easily identify samples of similar composition as well as quickly identify what has been added or what has been removed from a water stream. Chemical speciation could identify effluent streams where C02 dissolution had taken place.

No description available.

The use of brackish water and seawater desalination for augmenting potable water supplies has focused primarily on pre-treatment, process optimization, energy efficiency, and concentrate management. Much less has been documented regarding the impact of post-treatment requirements with respect to distribution system. The goals of this study were to review current literature on post-treatment of permeate water, use survey questionnaires to gather information on post-treatment water quality characteristics, gather operation information, review general capital and maintenance cost, and identify appropriate "lessons learned" with regards to post-treatment from water purveyors participating in the Project. A workshop was organized where experts from across the United States, Europe and the Caribbean active in brackish and seawater desalination, gathered to share technical knowledge regarding post-treatment stabilization, identify solutions for utilities experiencing problems with post-treatment, note lessons learned, and develop desalination water post-treatment guidelines. In addition, based on initial workshop discussions, the iodide content of reverse osmosis and nanofiltration permeate from two seawater desalination facilities was determined. The literature review identified that stabilization and disinfection are required desalination post-treatment processes, and typically are considerations when considering 1) blending, 2) re-mineralization, 3) disinfection, and 4) materials used for storage and transport of product water. Addition of chemicals can effectively achieve post-treatment goals although considerations relating to the quality of the chemical, dosage rates, and possible chemical reactions, such as possible formation of disinfection by-products, should be monitored and studied. The survey gathered information on brackish water and seawater desalination facilities with specific regards to their post-treatment operations. The information obtained was divided into seven sections 1) general desalination facility information, 2) plant characteristics with schematics, 3) post-treatment water quality, 4) permeate, blend, and point of entry quality, 5) post-treatment operation, 6) operation and maintenance costs, 7) and lessons learned. A major consideration obtained from the survey was that facilities should conduct post-treatment pilot studies in order to identify operational problems that may impact distributions systems prior to designing the plant. Effective design and regulation considerations will limit issues with permitting for the facility. The expert workshop identified fourteen priority issues pertaining to post-treatment. Priority issues were relating to post-treatment stabilization of permeate water, corrosion control, disinfection and the challenges relating to disinfection by-product (DBP) formation, water quality goals, blending, and the importance of informing the general public. For each priority issues guidelines/recommendations were developed for how facilities can effectively manage such issues if they arise. One of the key priorities identified in the workshop was related to blending of permeate and formation of DBPs. However, it was identified in the workshop that the impact of iodide on iodinated-DBP formation was unknown. Consequently, screening evaluations using a laboratory catalytic reduction method to determine iodide concentrations in the permeate of two of the workshop participants: Tampa Bay and Long Beach seawater desalination facilities. It was found that the permeate did contain iodide, although at levels near the detection limit of the analytical method (8 [micro]g/L).

No description available.

no / The optimal operation policy of flexible RO systems is studied in this work. The design and operation of RO process is optimized and controlled considering variations in water demands and changing seawater temperature throughout the day. A storage tank is added to the system layout to provide additional operational flexibility and to ensure the availability of freshwater to customer at all times. A steady state model for the RO process is developed and linked with a dynamic model for the storage tank. The membrane modules are divided into a number of groups to add flexibility in operation to RO network. The total operating cost of the RO process is minimized in order to find the optimal layout and operating variables at discreet time intervals for three design scenarios. (C) 2013 Elsevier Ltd. All rights reserved.

Die gegenwärtige Politik betrachtet Windenergieanlagen als ein entscheidendes Mittel für die Gestaltung einer nachhaltigen Zukunft. Dennoch lehnen die BewohnerInnen der griechischen Insel Amorgos Anträge zum Bau von Windenergieanlagen ab. In der vorliegenden Untersuchung analysiere ich, wie die InselbewohnerInnen die Option der Windenergie beurteilen. Die Analyse basiert auf einem interdisziplinären theoretischen Ansatz und einem neu entwickelten analytischen Rahmenwerk, dem Institutions - Habits - Intuitions (IHI) framework. Qualitative Forschungsmethoden, insbesondere persönliche Befragungen und teilnehmende Beobachtungen, sind wesentliche Elemente der Datenerhebung und erlauben mir, mich umfassend in den amorgianischen Kontext zu vertiefen. Die Forschungsergebnisse zeigen, dass der Beurteilungsprozess auf dem Zusammenwirken von Kosten-Nutzen Kalkulationen, der Infragestellung der Thematik der Windenergie und intuitivem Handeln basiert. Die Option der Windenergie erschüttert die herkömmlichen Interaktionen der InselbewohnerInnen, die die lokale Tourismuswirtschaft und Gemeindeverwaltung bestimmen. Die Kombination pre-formeller Institutionen, eingefahrener Gepflogenheiten und intuitives Agierens aufgrund bisheriger Erfahrungen bringt die amorgianische Gesellschaft dazu, Windenergieprojekte abzulehnen. Die Analyse beruht auf der Anwendung von Ansätzen der Sozialpsychologie und der Institutionenökonomik. Damit wird u.a. die gängige Annahme, der Mensch sei a priori ein Investor hinterfragt und die Absicht verfolgt, die Kluft zwischen Wirtschaftswissenschaften und ‘realer Welt’ zu verringern. Die Insel von Amorgos ist ein beispielhafter Mikrokosmos in und für Griechenland als Ganzes. Energiepolitische Strategien und die lokalen und nationalen Beurteilungsprozesse dieser sind dabei nur zu verstehen, wenn die mit dem Neoliberalismus zusammenhängende, tiefgreifende sozio-ökonomische Krise Griechenlands in den Blick genommen wird. / Locals of the Greek island of Amorgos refuse wind energy proposals, while contemporary politics regards wind farms as a crucial means of pursuing a sustainable future. On the basis of an interdisciplinary theoretical approach, I develop a new analytical framework called Institutions - Habits - Intuitions (IHI) framework to explain the way Amorgians judge the option of wind energy development on their island. The data collection relies on qualitative research methods, that is, face-to-face interviews and participant observations, which enable me to delve into the particular Amorgian context. The research results show that the synergy of locals’ calculation (cost-benefit analysis), reflection and intuitive action influences their deliberation on the wind energy issue. The option of wind energy development shocks the ordinary run of things on the island, which is characterised by off-the-record interactions that shape both the tourism economy and the municipal administration. The combination of local pre-formal institutions, entrenched habits and intuitive responses causes Amorgian society to resist wind farms. Analysing the Amorgian case through applying approaches derived from social psychology and institutional economics, I aim at bringing the readers of this book to reflect on the discourse on sustainability and narrowing the gap between the discipline of economics and the real world. My analysis questions the utilitarian assumption that man is a priori an investor, and goes beyond the case of Amorgos, which constitutes a microcosm of Greece, which currently experiences a deep socio-economic crisis. I draw attention to the fact that locals of Amorgos act and interact within the context of this crisis, which is related to the political economic thinking attributed to neoliberalism. Finally, I claim that increasing bureaucratisation of social life clashes with local ethics, thereby affecting responses to politics of climate change mitigation.