Micronization of Pharmaceuticals and Food Ingredients using Supercritical Fluid Techniques

Micronization techniques based on supercritical fluids (SCFs) are promising for the production of particles with controlled size and distribution. The interest of the pharmaceutical field in the development of SCF techniques is increasing due to the need for clean processes, reduced consumption of energy, and to their several possible applications. The food field is still far from the application of SCF micronization techniques, but there is increasing interest mainly for the processing of products with high added value. The aim of this study is to use SCF micronization techniques for the production of particles of pharmaceuticals and food ingredients with controlled particle size and morphology, and to look at their production on semi-industrial scale. The results obtained are also used to understand the processes from the perspective of broader application within the pharmaceutical and food industries. Certain pharmaceuticals, a biopolymer and a food ingredient have been tested using supercritical antisolvent micronization (SAS) or supercritical assisted atomization (SAA) techniques. The reproducibility of the SAS technique has been studied using physically different apparatuses and on both laboratory and semi-industrial scale. Moreover, a comparison between semi-continuous and batch mode has been performed. The behaviour of the system during the SAS process has been observed using a windowed precipitation vessel. The micronized powders have been characterized by particle size and distribution, morphology and crystallinity. Several analyses have been performed to verify if the SCF process modified the structure of the compound or caused degradation or contamination of the product. The different powder morphologies obtained have been linked to the position of the process operating point with respect to the vapour-liquid equilibrium (VLE) of the systems studied, that is, mainly to the position of the mixture critical point (MCP) of the mixture. Spherical micro, submicro- and nanoparticles, expanded microparticles (balloons) and crystals were obtained by SAS. The obtained particles were amorphous or with different degrees of crystallinity and, in some cases, had different pseudo-polymorphic or polymorphic forms. A compound that could not be processed using SAS was micronized by SAA, and amorphous particles were obtained, stable in vials at room temperature. The SCF micronization techniques studied proved to be effective and versatile for the production of particles for several uses. Furthermore, the findings of this study and the acquired knowledge of the proposed processes can allow a more conscious application of SCF techniques to obtain products with the desired characteristics and enable the use of their principles for broader applications.

Fire management, climate change and their interacting effects on birds in complex Mediterranean landscapes: dynamic distribution modelling of an early-successional species - the near-threatened Dartford Warbler (Sylvia undata)

The current challenge in a context of major environmental changes is to anticipate the responses of species to future landscape and climate scenarios. In the Mediterranean basin, climate change is one the most powerful driving forces of fire dynamics, with fire frequency and impact having markedly increased in recent years. Species distribution modelling plays a fundamental role in this challenge, but better integration of available ecological knowledge is needed to adequately guide conservation efforts. Here, we quantified changes in habitat suitability of an early-succession bird in Catalonia, the Dartford Warbler (Sylvia undata) ― globally evaluated as Near Threatened in the IUCN Red List. We assessed potential changes in species distributions between 2000 and 2050 under different fire management and climate change scenarios and described landscape dynamics using a spatially-explicit fire-succession model that simulates fire impacts in the landscape and post-fire regeneration (MEDFIRE model). Dartford Warbler occurrence data were acquired at two different spatial scales from: 1) the Atlas of European Breeding Birds (EBCC) and 2) Catalan Breeding Bird Atlas (CBBA). Habitat suitability was modelled using five widely-used modelling techniques in an ensemble forecasting framework. Our results indicated considerable habitat suitability losses (ranging between 47% and 57% in baseline scenarios), which were modulated to a large extent by fire regime changes derived from fire management policies and climate changes. Such result highlighted the need for taking the spatial interaction between climate changes, fire-mediated landscape dynamics and fire management policies into account for coherently anticipating habitat suitability changes of early succession bird species. We conclude that fire management programs need to be integrated into conservation plans to effectively preserve sparsely forested and early succession habitats and their associated species in the face of global environmental change.

Mittausmenetelmien kehittaminen kuplakolonnille

Kuplakolonnireaktoreiden CFD-mallinnus on talla hetkella voimakkaasti kehittyva tutkimusalue. Kaksifaasivirtauksen luotettava simulointi ja mallintaminen on haastavaa kuplakolonnireaktorissa tapahtuvien ilmioiden monimutkaisuuden vuoksi. Reaktorin kayttaytymiseen vaikuttavat tekijat, kuten kolonnin hydrodynamiikka ja aineensiirto, tulee tuntea hyvin ennen mallien tekoa. Tassa tyossa on kokeellisesti tutkittu erilaisten mittausmenetelmien soveltuvuutta kuplakolonnin hydrodynamiikan tutkimiseen. Mittausmenetelmissa on keskitytty erityisesti CFD-mallien vaatimiin paikallisiin mittauksiin. Lisaksi tyossa on arvioitu mittausmenetelmien soveltuvuutta j a luotettavuutta CFD-mallien validointiin. Tyon kirjallisuusosassa on perehdytty kuplakolonnireaktorin hydrodynaamiseen kayttaytymiseen ja siihen vaikuttaviin tekijoihin. Naita ovat mm. reaktorityypit, kaasun dispergointi, virtaustyypit ja -alueet, kaasun tilavuusosuus, kaasukuplan koko ja kuplan nousunopeus. Mittauksia tehtiin kahdessa erikokoisessa kuplakolonnissa, joista pienemman halkaisija oli 0,078 m ja suuremman 0,182 m. Molempien kolonnien nestepinnan korkeus oli 4,62 m. Mittaukset tehtiin vesijohtovedella ja epaorgaanisella prosessiliuoksella. Hydrodynaamisista ominaisuuksista mitattiin kaasun tilavuusosuus, kaasukuplan koko seka kaasukuplan nousunopeus. Kaasun tilavuusosuusmittaukset tehtiin paaasiassa paine-eromittauksella ja joissakin tapauksissa pinnanmittausmenetelmalla. Kuplakoko- ja kuplan nousunopeusmittaukset tehtiin suumopeusvideokameralla ja laser Doppler-anemometrilla. Mittauksissa kaytettiin kahdeksaa erilaista kaasunjakolaitetta, joilla selvitettiin kaasunjakolaitteen ominaisuuksien vaikutusta kolonnin hydrodynamiikkaan. Tuloksista havaittiin, etta nestefaasin ominaisuuksilla oli suuri vaikutus kolonnin hydrodynaamiseen kayttaytymiseen. En kaasunjakolaitteilla vesijohtovedella mitatut hydrodynaamiset ominaisuudet eivat poikenneet paljoa toisistaan, kun taas prosessiliuoksella kaasunjakolaitteiden valille saatiin huomattavat erot. Mittausmenetelmista laser Doppler-anemometri ei kaytettavissa olleella optiikalla soveltunut kaasukuplien mittaamiseen. Kuplat olivat menetelmalle liian suuria. Suumopeusvideokamerallaja paine-eromittauksella paastiin hyviin tuloksiin.

Cardiovascular magnetic resonance imaging techniques for motion-suppressed multi-dimensional coronary artery imaging with high spatial and temporal resolution

L'imagerie par résonance magnétique (IRM) peut fournir aux cardiologues des informations diagnostiques importantes sur l'état de la maladie de l'artère coronarienne dans les patients. Le défi majeur pour l'IRM cardiaque est de gérer toutes les sources de mouvement qui peuvent affecter la qualité des images en réduisant l'information diagnostique. Cette thèse a donc comme but de développer des nouvelles techniques d'acquisitions des images IRM, en changeant les techniques de compensation du mouvement, pour en augmenter l'efficacité, la flexibilité, la robustesse et pour obtenir plus d'information sur le tissu et plus d'information temporelle. Les techniques proposées favorisent donc l'avancement de l'imagerie des coronaires dans une direction plus maniable et multi-usage qui peut facilement être transférée dans l'environnement clinique. La première partie de la thèse s'est concentrée sur l'étude du mouvement des artères coronariennes sur des patients en utilisant la techniques d'imagerie standard (rayons x), pour mesurer la précision avec laquelle les artères coronariennes retournent dans la même position battement après battement (repositionnement des coronaires). Nous avons découvert qu'il y a des intervalles dans le cycle cardiaque, tôt dans la systole et à moitié de la diastole, où le repositionnement des coronaires est au minimum. En réponse nous avons développé une nouvelle séquence d'acquisition (T2-post) capable d'acquérir les données aussi tôt dans la systole. Cette séquence a été testée sur des volontaires sains et on a pu constater que la qualité de visualisation des artère coronariennes est égale à celle obtenue avec les techniques standard. De plus, le rapport signal sur bruit fourni par la séquence d'acquisition proposée est supérieur à celui obtenu avec les techniques d'imagerie standard. La deuxième partie de la thèse a exploré un paradigme d'acquisition des images cardiaques complètement nouveau pour l'imagerie du coeur entier. La technique proposée dans ce travail acquiert les données sans arrêt (free-running) au lieu d'être synchronisée avec le mouvement cardiaque. De cette façon, l'efficacité de la séquence d'acquisition est augmentée de manière significative et les images produites représentent le coeur entier dans toutes les phases cardiaques (quatre dimensions, 4D). Par ailleurs, l'auto-navigation de la respiration permet d'effectuer cette acquisition en respiration libre. Cette technologie rend possible de visualiser et évaluer l'anatomie du coeur et de ses vaisseaux ainsi que la fonction cardiaque en quatre dimensions et avec une très haute résolution spatiale et temporelle, sans la nécessité d'injecter un moyen de contraste. Le pas essentiel qui a permis le développement de cette technique est l'utilisation d'une trajectoire d'acquisition radiale 3D basée sur l'angle d'or. Avec cette trajectoire, il est possible d'acquérir continûment les données d'espace k, puis de réordonner les données et choisir les paramètres temporel des images 4D a posteriori. L'acquisition 4D a été aussi couplée avec un algorithme de reconstructions itératif (compressed sensing) qui permet d'augmenter la résolution temporelle tout en augmentant la qualité des images. Grâce aux images 4D, il est possible maintenant de visualiser les artères coronariennes entières dans chaque phase du cycle cardiaque et, avec les mêmes données, de visualiser et mesurer la fonction cardiaque. La qualité des artères coronariennes dans les images 4D est la même que dans les images obtenues avec une acquisition 3D standard, acquise en diastole Par ailleurs, les valeurs de fonction cardiaque mesurées au moyen des images 4D concorde avec les valeurs obtenues avec les images 2D standard. Finalement, dans la dernière partie de la thèse une technique d'acquisition a temps d'écho ultra-court (UTE) a été développée pour la visualisation in vivo des calcifications des artères coronariennes. Des études récentes ont démontré que les acquisitions UTE permettent de visualiser les calcifications dans des plaques athérosclérotiques ex vivo. Cepandent le mouvement du coeur a entravé jusqu'à maintenant l'utilisation des techniques UTE in vivo. Pour résoudre ce problème nous avons développé une séquence d'acquisition UTE avec trajectoire radiale 3D et l'avons testée sur des volontaires. La technique proposée utilise une auto-navigation 3D pour corriger le mouvement respiratoire et est synchronisée avec l'ECG. Trois échos sont acquis pour extraire le signal de la calcification avec des composants au T2 très court tout en permettant de séparer le signal de la graisse depuis le signal de l'eau. Les résultats sont encore préliminaires mais on peut affirmer que la technique développé peut potentiellement montrer les calcifications des artères coronariennes in vivo. En conclusion, ce travail de thèse présente trois nouvelles techniques pour l'IRM du coeur entier capables d'améliorer la visualisation et la caractérisation de la maladie athérosclérotique des coronaires. Ces techniques fournissent des informations anatomiques et fonctionnelles en quatre dimensions et des informations sur la composition du tissu auparavant indisponibles. CORONARY artery magnetic resonance imaging (MRI) has the potential to provide the cardiologist with relevant diagnostic information relative to coronary artery disease of patients. The major challenge of cardiac MRI, though, is dealing with all sources of motions that can corrupt the images affecting the diagnostic information provided. The current thesis, thus, focused on the development of new MRI techniques that change the standard approach to cardiac motion compensation in order to increase the efficiency of cardioavscular MRI, to provide more flexibility and robustness, new temporal information and new tissue information. The proposed approaches help in advancing coronary magnetic resonance angiography (MRA) in the direction of an easy-to-use and multipurpose tool that can be translated to the clinical environment. The first part of the thesis focused on the study of coronary artery motion through gold standard imaging techniques (x-ray angiography) in patients, in order to measure the precision with which the coronary arteries assume the same position beat after beat (coronary artery repositioning). We learned that intervals with minimal coronary artery repositioning occur in peak systole and in mid diastole and we responded with a new pulse sequence (T2~post) that is able to provide peak-systolic imaging. Such a sequence was tested in healthy volunteers and, from the image quality comparison, we learned that the proposed approach provides coronary artery visualization and contrast-to-noise ratio (CNR) comparable with the standard acquisition approach, but with increased signal-to-noise ratio (SNR). The second part of the thesis explored a completely new paradigm for whole- heart cardiovascular MRI. The proposed techniques acquires the data continuously (free-running), instead of being triggered, thus increasing the efficiency of the acquisition and providing four dimensional images of the whole heart, while respiratory self navigation allows for the scan to be performed in free breathing. This enabling technology allows for anatomical and functional evaluation in four dimensions, with high spatial and temporal resolution and without the need for contrast agent injection. The enabling step is the use of a golden-angle based 3D radial trajectory, which allows for a continuous sampling of the k-space and a retrospective selection of the timing parameters of the reconstructed dataset. The free-running 4D acquisition was then combined with a compressed sensing reconstruction algorithm that further increases the temporal resolution of the 4D dataset, while at the same time increasing the overall image quality by removing undersampling artifacts. The obtained 4D images provide visualization of the whole coronary artery tree in each phases of the cardiac cycle and, at the same time, allow for the assessment of the cardiac function with a single free- breathing scan. The quality of the coronary arteries provided by the frames of the free-running 4D acquisition is in line with the one obtained with the standard ECG-triggered one, and the cardiac function evaluation matched the one measured with gold-standard stack of 2D cine approaches. Finally, the last part of the thesis focused on the development of ultrashort echo time (UTE) acquisition scheme for in vivo detection of calcification in the coronary arteries. Recent studies showed that UTE imaging allows for the coronary artery plaque calcification ex vivo, since it is able to detect the short T2 components of the calcification. The heart motion, though, prevented this technique from being applied in vivo. An ECG-triggered self-navigated 3D radial triple- echo UTE acquisition has then been developed and tested in healthy volunteers. The proposed sequence combines a 3D self-navigation approach with a 3D radial UTE acquisition enabling data collection during free breathing. Three echoes are simultaneously acquired to extract the short T2 components of the calcification while a water and fat separation technique allows for proper visualization of the coronary arteries. Even though the results are still preliminary, the proposed sequence showed great potential for the in vivo visualization of coronary artery calcification. In conclusion, the thesis presents three novel MRI approaches aimed at improved characterization and assessment of atherosclerotic coronary artery disease. These approaches provide new anatomical and functional information in four dimensions, and support tissue characterization for coronary artery plaques.

Regression-based techniques for statistical decision making in single-case designs

The present study evaluates the performance of four methods for estimating regression coefficients used to make statistical decisions regarding intervention effectiveness in single-case designs. Ordinary least squares estimation is compared to two correction techniques dealing with general trend and one eliminating autocorrelation whenever it is present. Type I error rates and statistical power are studied for experimental conditions defined by the presence or absence of treatment effect (change in level or in slope), general trend, and serial dependence. The results show that empirical Type I error rates do not approximate the nominal ones in presence of autocorrelation or general trend when ordinary and generalized least squares are applied. The techniques controlling trend show lower false alarm rates, but prove to be insufficiently sensitive to existing treatment effects. Consequently, the use of the statistical significance of the regression coefficients for detecting treatment effects is not recommended for short data series.

La motivació al canvi dels agressors de parella que realitzen un programa formatiu: Disseny d’un pla d’intervenció motivacional

En aquesta recerca es presenta el Pla d’Intervenció Motivacional (PIM) per subjectes que han de realitzar un programa formatiu (PF) en matèria de violència domèstica com a mesura penal alternativa. La finalitat principal d’aquest programa motivacional és que els usuaris iniciïn el PF en condicions òptimes per així augmentar l’eficàcia de la mesura i la seva reinserció en la societat. El PIM s’ha fonamentat en els models teòrics sobre motivació al canvi i en les tècniques terapèutiques que resulten més rellevants i eficaces, segons la revisió bibliogràfica exhaustiva feta en la recerca El PIM és un programa d’intervenció individualitzat amb una duració d‘entre 4 i 6 sessions, segons la intensitat de la seva aplicació. El programa vol ajudar als participants a identificar els aspectes positius derivats d’aquest canvi i les seves capacitats personals per aconseguir-lo. Per portar-ho terme, s’utilitza un estil terapèutic basat en el diàleg socràtic mitjançant el qual es treballen els aspectes següents: resolució de l’ambivalència, sentiment d’autoeficàcia, identificació d’objectius específics i desenvolupament d’un pla d’acció alternatiu. Mitjançant l’elaboració dels exercicis i tasques descrits en aquesta memòria, el professional guia a l’usuari per aconseguir augmentar la seva motivació per canviar la conducta problemàtica que ha estat objecte de la imposició de la mesura penal.

La motivación al cambio de los agresores de pareja que realizan un programa formativo: Diseño de un plan de intervención motivacional

En este estudio se presenta el Plan de Intervención Motivacional (PIM) para sujetos que deben realizar un programa formativo (PF) en materia de violencia doméstica como medida penal alternativa. La finalidad principal de este programa motivacional es que los usuarios de medidas penales alternativas inicien el PF en condiciones óptimas para así aumentar la eficacia de la medida y su reinserción en la sociedad. El programa PIM se fundamenta en los modelos teóricos sobre motivación al cambio y en las técnicas terapéuticas que resultan más relevantes y eficaces, según la revisión bibliográfica exhaustiva llevada a cabo en la investigación. El PIM es un programa de intervención individualizada de una duración de entre 4 y 6 sesiones, según la intensidad de su aplicación. El programa tiene como objetivo ayudar a los participantes a identificar los aspectos positivos derivados del cambio y sus capacidades personales para llevarlo a cabo. Para ello, emplea un estilo terapéutico basado en el diálogo socrático mediante el cual se trabajan los aspectos siguientes: resolución de la ambivalencia, sentimiento de auto eficacia, identificación de objetivos específicos y desarrollo de un plan de acción alternativo. Mediante la elaboración de los ejercicios y tareas descritos en esta memoria el profesional guía al usuario para aumentar su motivación para cambiar la conducta problemática objeto de la imposición de la medida penal.

Magnetic, thermal and spectral behaviour of 3-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Physico-chemical properties of 3-chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II) were synthesized and studied. The complexes were obtained as mono- and dihydrates with a metal ion to ligand ratio of 1 : 2. All analysed 3-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II) and blue for Cu(II) complexes. Their thermal decomposition was studied in the range of 293 ­ 523 K, because it was found that on heating in air above 523 K 3-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10-4 ­ 10-2 mol / dm³. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 3-chloro-2-nitrobenzoates experimentally determined at 76 ­ 303 K change from 3.67µB to 4.61µB for Co(II) complex, from 2.15µB to 2.87µB for Ni(II) 3-chloro-2-nitrobenzoate and from 0.26µB to 1.39µB for Cu(II) complex. 3-Chloro-2-nitrobenzoates of Co(II) and Ni(II) follow the Curie-Weiss law. Complex of Cu(II) forms dimer.

Salesperson's customer orientation in the personal selling process and in the use of personal selling techniques in the business-to-business setting

Selling is much maligned, often under-valued subject whose inadequate showing in business schools is in inverse proportion to the many job opportunities it offers and the importance of salespeople bringing incomes to companies. The purpose of this research is to increase the understanding of customer-oriented selling and examine the influence of customer-oriented philosophy on selling process, the applicability of selling techniques to this philosophy and the importance of them to salespeople. The empirical section of the study is two-fold. Firstly, the data of qualitative part was collected by conducting five thematic interviews among sales consultants and case company representatives. The findings of the study indicate that customer-oriented selling requires the activity of salespeople. In the customer-oriented personal selling process, salespeople invest time in the preplanning, the need analysis and the benefit demonstration stages. However, the findings propose that salespeople today must also have the basic capabilities for executing the traditional sales process, and the balance between traditional and consultative selling process will change as the duration of the relationship between the salesperson and customer increases. The study also proposes that selling techniques still belong to the customer-oriented selling process, although their roles might be modest. This thesis mapped 75 selling techniques and the quantitative part of the study explored what selling techniques are considered to be important by salespeople in direct selling industry when they make sales with new and existing customers. Response rate of the survey was 69.5%.

Searchig the links between "knowledge governance mechanisms", "the individual conditions of knowledge sharing", and "individual's knowledge sharing behaviour".

The objective of this study was to understand how organizational knowledge governance mechanisms affect individual motivation, opportunity, and the ability to share knowledge (MOA framework), and further, how individual knowledge-sharing conditions affect actual knowledge sharing behaviour. The study followed the knowledge governance approach and a micro-foundations perspective to develop a theoretical model and hypotheses, which could explain the casual relationships between knowledge governance mechanisms, individual knowledge sharing conditions, and individual knowledge sharing behaviour. The quantitative research strategy and multivariate data analysis techniques (SEM) were used in the hypotheses testing with a survey dataset of 256 employees from eleven military schools of Finnish Defence Forces (FDF). The results showed that “performance-based feedback and rewards” affects employee’s “intrinsic motivation towards knowledge sharing”, that “lateral coordination” affects employee’s “knowledge self-efficacy”, and that ”training and development” is positively related to “time availability” for knowledge sharing but affects negatively employee’s knowledge self-efficacy. Individual motivation and knowledge self-efficacy towards knowledge sharing affected knowledge sharing behaviour when work-related knowledge was shared 1) between employees in a department and 2) between employees in different departments, however these factors did not play a crucial role in subordinate–superior knowledge sharing. The findings suggest that individual motivation, opportunity, and the ability towards knowledge sharing affects individual knowledge sharing behaviour differently in different knowledge sharing situations. Furthermore, knowledge governance mechanisms can be used to manage individual-level knowledge sharing conditions and individual knowledge sharing behaviour but their affect also vary in different knowledge sharing situations.

Surface studies of limestones and dolostones : characterisation using various techniques and batch dissolution experiments with hydrochloric acid solutions

In this thesis, stepwise titration with hydrochloric acid was used to obtain chemical reactivities and dissolution rates of ground limestones and dolostones of varying geological backgrounds (sedimentary, metamorphic or magmatic). Two different ways of conducting the calculations were used: 1) a first order mathematical model was used to calculate extrapolated initial reactivities (and dissolution rates) at pH 4, and 2) a second order mathematical model was used to acquire integrated mean specific chemical reaction constants (and dissolution rates) at pH 5. The calculations of the reactivities and dissolution rates were based on rate of change of pH and particle size distributions of the sample powders obtained by laser diffraction. The initial dissolution rates at pH 4 were repeatedly higher than previously reported literature values, whereas the dissolution rates at pH 5 were consistent with former observations. Reactivities and dissolution rates varied substantially for dolostones, whereas for limestones and calcareous rocks, the variation can be primarily explained by relatively large sample standard deviations. A list of the dolostone samples in a decreasing order of initial reactivity at pH 4 is: 1) metamorphic dolostones with calcite/dolomite ratio higher than about 6% 2) sedimentary dolostones without calcite 3) metamorphic dolostones with calcite/dolomite ratio lower than about 6% The reactivities and dissolution rates were accompanied by a wide range of experimental techniques to characterise the samples, to reveal how different rocks changed during the dissolution process, and to find out which factors had an influence on their chemical reactivities. An emphasis was put on chemical and morphological changes taking place at the surfaces of the particles via X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Supporting chemical information was obtained with X-Ray Fluorescence (XRF) measurements of the samples, and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) measurements of the solutions used in the reactivity experiments. Information on mineral (modal) compositions and their occurrence was provided by X-Ray Diffraction (XRD), Energy Dispersive X-ray analysis (EDX) and studying thin sections with a petrographic microscope. BET (Brunauer, Emmet, Teller) surface areas were determined from nitrogen physisorption data. Factors increasing chemical reactivity of dolostones and calcareous rocks were found to be sedimentary origin, higher calcite concentration and smaller quartz concentration. Also, it is assumed that finer grain size and larger BET surface areas increase the reactivity although no certain correlation was found in this thesis. Atomic concentrations did not correlate with the reactivities. Sedimentary dolostones, unlike metamorphic ones, were found to have porous surface structures after dissolution. In addition, conventional (XPS) and synchrotron based (HRXPS) X-ray Photoelectron Spectroscopy were used to study bonding environments on calcite and dolomite surfaces. Both samples are insulators, which is why neutralisation measures such as electron flood gun and a conductive mask were used. Surface core level shifts of 0.7 ± 0.1 eV for Ca 2p spectrum of calcite and 0.75 ± 0.05 eV for Mg 2p and Ca 3s spectra of dolomite were obtained. Some satellite features of Ca 2p, C 1s and O 1s spectra have been suggested to be bulk plasmons. The origin of carbide bonds was suggested to be beam assisted interaction with hydrocarbons found on the surface. The results presented in this thesis are of particular importance for choosing raw materials for wet Flue Gas Desulphurisation (FGD) and construction industry. Wet FGD benefits from high reactivity, whereas construction industry can take advantage of slow reactivity of carbonate rocks often used in the facades of fine buildings. Information on chemical bonding environments may help to create more accurate models for water-rock interactions of carbonates.

The effectiveness of interpretive methods in informal educational facilities : an experimental study with reference to marine parks

Interpretation has been used in many tourism sectors as a technique in achieving building hannony between resources and human needs. The objectives of this study are to identify the types of the interpretive methods used, and to evaluate their effectiveness, in marine parks. This study reviews the design principles of an effective interpretation for marine wildlife tourism, and adopts Drams' five design principles (1997) into a conceptual framework. Enjoyment increase, knowledge gain, attitude and intention change, and behaviour modification were used as key indicators in the assessment of the interpretive effectiveness of the Vancouver Aquarium (VA) and Marineland Canada (MC). Since on-site research is unavailable, a virtual tour is created to represent the interpretive experiences in the two study sites. Self-administered questionnaires are used to measure responses. Through comparing responses to the questionnaires (pre-, post-virtual tours and follow-up), this study found that interpretation increased enjoyment and added to respondents' knowledge. Although the changes in attitudes and intentions are not significant, the findings indicate that attitude and intention changes did occur as a result of interpretation, but only to a limited extent. Overall results suggest that more techniques should be added to enhance the effectiveness of the interpretation in marine parks or self-guiding tours, and with careful design, virtual tours are the innovative interpretation techniques for marine parks or informal educational facilities.

Bullying as a social process : factors influencing bystander behaviour

Bullying was approached as a social phenomenon in the present study. The central aim of this thesis was to uncover some of the factors that contribute to the attitudes and behavioural choices of bystanders during bullying situations. With this type of information, interventions can be tailored to change the behaviour of bystanders during bullying situations, and thus the ethos of the larger group. Thus, acting to alter the available sources of reinforcement for bullying behaviour and peer intervention attempts. Six hundred and twenty-six students participated. Students were sampled from grades 4 (n=140), 5 (n=l 13), 7 (n=205), and 8 (n=168). Students were measured for their involvement in bullying and victimization, as well as for involvement in the following bystander behaviours: encouraging, onlooking, defending, and seeking adult support. In addition, students were measured for tolerance of deviance, pro-victim attitudes, social anxiety and fear, and self-efficacy for peer intervention. Last, students were asked to complete a series of qualitative measures, including a series of hypothetical vignettes and open-ended questions. Analyses centered on the following areas: 1) rates of bullying, victimization, and bystander behaviour; 2) the influence of age and gender on bystander behaviour; 3) the characteristics associated with students who predominantly report involvement with defending, seeking adult assistance, encouraging, and onlooking behaviour; and 4) the influence of past involvement with bullying and victimization on bystander behaviour. b .--' -i . k Rates of bullying, victimization, and bystander behaviour were comparable to findings in the existing literature, where male students were more likely than female students to report involvement in both bullying and victimization. Boys were more likely than girls to report participation in encouraging and onlooking behaviours, while being less likely to report involvement in defending and seeking adult assistance. Partly consistent with existing findings, older students were more likely to report involvement in bullying, encouraging, and onlooking behaviour than younger students, who were more likely to report victimization, defending, and seeking adult assistance. Self-identified encouragers and onlookers reported a similar array of characteristics, in that they tended express high levels of tolerance of deviance, while expressing low levels of pro-victim attitudes and self-efficacy for peer intervention. Likewise, self-identified defenders and seekers of adult assistance tended to report a similar array of characteristics to each other, in that they tended to report low levels of tolerance of deviance, while expressing high levels of pro-victim attitudes and self efficacy for peer intervention. Additionally, self-identified bullies and self-identified bully-victims tended to report increased involvement in encouraging and onlooking, whereas self-identified victims tended to report increased involvement in defending behaviour and seeking adult assistance. Results are discussed in terms of implications for bullying prevention and intervention. Specifically, evidence from the present study suggests that as bystanders, students predominantly act to either support bullying acts or to support the victims of these acts, or alternatively, to actively remain outside bullying situations. Thus, encouraging students to make small changes in the way they express these sentiments during bullying situations would act to alter the culture of the larger peer group and the sources of reinforcement available for bullying acts as well as peer intervention attempts.

Aerobic exercise in adolescence : self-efficacy and stage of change

The purpose of this cross-sectional exploratory study was to examine the relationships among self-efficacy, stage of change, and exercise behaviour in a sample of younger (Grade 9) and older (Grade 12) adolescents. A secondary objective of this study was to apply the transtheoretical model of Stage of Change, as a measure of intention to change, in order to discover the applicability of the model to an adolescent cohort in relation to exercise behaviour. This five-stage model is a self-report measure of an individual's readiness to adopt a new behaviour (e.g., regular exercise). The transtheoretical model incorporates Bandura's self-efficacy factor, which is purported to be a predictive measure of exercise behaviour and a covariant of stage. Exercise behaviour was measured with the Physical Activity Scale, and the University of Rhode Island Change Assessment Scale (URleA) was used to measure the stage of change and self-efficacy variables. The results of this study indicated significant differences between younger and older adolescents, and between males and females in their exercise behaviour. No significant differences were found for grade and gender on stage of change as measured by either a single-item question or a continuous measure of stage. Although grade and gender subgroups were not significantly different in their self-efficacy, significant interaction was found in the grade*gender variable.

Behavioural characteristics in phylogenetics : a case study using black fly (Diptera: Simuliidae) cocoon spinning behaviour

1-1 is torically, the predominan t method of reconstructing phylogenies has been through the use of morphological characters. There are new techniques now gaining acceptance, including molecular techniques al1d chromosomal information. Altl10ugh the study of behaviour has been used in a comparative framework, these analyses have, historically, been based on intuition. Hennig (1966) devised a neV\' method of reconstructing phylogenies which provided a 110ncircular method for formulating, testing and refining phylogenies. Subsequent s)Tstematists had virtually abandoned ecological and beha\lioural data as primary indicators of phylogenetic relationships (Brooks and McLennan 1991). Therefore, in a modern cladistic framework (sensu Hennig) the analysis of behavioural traits remains underrepresented as a method of reconstructing phylogenies. This thesis will reconstruct the phylogeny for species of black flies (Diptera: Simuliidae), using two steps. The first step is to thoroughl)' understand and explain the cocoon spinning in black fly larvae. There have bee115 previous descriptions of cocoon spinning, but all were incomplete or erroneous. The advances in technology, including video recorders and VCRs, have allowed this behaviour to be analyzed in great detail in 20 different species. A complete description of the cocoon spinning of Simulium \littatum is given. This description will be used as a template for the other species observed. The description and understanding of cococ)n spinning was the first step in undertaking a phylogenetic analysis using this behaviour. The behaviour was then broken down and analyzed, revealing 23 characters, 3 either qualitative and quantitative in nature. These characters were assessed in a cladistic framework (sensu Hennig) and a phylogenetic tree was reconstructed with a e.I of 0.91 and an R.I. of 0.96. This phylogenetic tree closely resembles a previously established pllylogenetic tree produced from morphological and cytological information. The importance of this result is the indication that, contrary to some authors, behavioural characters, if used properly, can add very informative characters to a data set.