Diesel particulate matter (DPM) is the solid portion of diesel exhaust. DPM occurs primarily in the submicron range, and poses a number of respiratory and other health hazards including cardiovascular and pulmonary disease. Underground miners typically have the highest DPM exposures compared to other occupations. This is because many mines are characterized by confined work spaces and large diesel equipment fleets. Exposures can be a particularly high hazard in large opening mines where ventilation can be challenging. As such, DPM monitoring is critical to protecting miner health and informing a range of engineering decisions. DPM is primarily composed of two components, elemental carbon (EC) and organic carbon (OC), which are often summed to report total carbon (TC). The ratio of EC to OC, and presence of a number of other minor constituents such as sorbed metals, can vary with many factors such as engine operating conditions, maintenance, fuel types and additives, and the level and type of exhaust after-treatments used. Given its complexity, DPM cannot be measured directly, and either TC or EC are generally used as a surrogate. Currently, the Mining Safety and Health Administration (MSHA) limits personal exposures of underground metal/non-metal miners to 160 µg TC/m3 on an 8-hr time weighted average basis. Compliance is demonstrated by collecting full-shift personal filter samples, which are later analyzed using the NIOSH 5040 Standard Method. For engineering purposes, area samples can also be collected and analyzed. The typical lag time between sample collection and reporting of results is on the order of weeks, and this presents a real problem for identifying and remediating conditions that led to overexposures or high DPM in area samples. The handheld FLIR Airtec monitor was developed to provide real-time DPM data and allow immediate decision making. The monitor works on a laser extinction principle to measure EC, the black component of DPM, as mass accumulates on a filter. The Airtec has proven useful for personal monitoring and short-term DPM surveying. However, capabilities are needed for continuous, long-term monitoring. Continuous DPM monitoring would be highly valuable for applications such as design and operation of ventilation on demand systems, or engineering studies of new ventilation, exhaust treatment or other DPM controls. The work presented in this thesis considers three continuous monitors, two of which are already commercially available: Magee Scientific's AE33 black carbon (BC) Aethalometer and Sunset Laboratory's Semi-Continuous OCEC Field Analyzer. The third monitor, called the Airwatch, is still in development. The AE33 and Airwatch effectively operate on the same principle as the Airtec, but include a self-advancing filter tape to allow autonomous operation over relatively long periods of time. The OCEC field monitor is essentially a field version of the laboratory analyzer used for traditional 5040 Method analysis. The AE33 has been briefly demonstrated in mine environments in a couple of other studies, but further testing is needed. The current prototype of the Airwatch and the OCEC field monitor have never been mine-tested. Two separate studies are reported here. The first is a field study in an underground stone mine that tested the Airwatch prototype and AE33 head-to-head under relatively high DPM conditions. Results demonstrated that both instruments could track general trends, but that further work was needed to identify and resolve issues associated with use of both instruments in high-DPM environments – and with basic design elements of the Airwatch. Additionally, the need to calibrate the monitors' output data to the standard measure of EC (i.e., 5040 Method EC) was made clear. In the second study, laboratory testing was conducted under very controlled conditions to meet this need, and another round of field testing was also done. The second study also included the OCEC field monitor. The laboratory tests yielded data to allow interpretation of the AE33 and Airwatch results with respect to 5040 EC. These tests also shed light on the current range EC concentrations over which these monitors can provide reliable data – which is indeed a primary range of interest for mines. As expected, the OCEC field monitor was shown to produce lab-grade results across a wide range of concentrations. The field testing in the second study demonstrated that all three monitors could operate autonomously in a mine environment over extended periods of time (i.e., weeks to months). Overall, it can be concluded that the AE33 and OCEC field monitor represent off-the-shelf options for DPM monitoring in mines, and the Airwatch might be another option if fully developed in the future. Selection of a particular monitoring tool should include careful consideration of specific factors including data quality needs, conditions in the intended monitoring location(s), and general user friendliness of the monitor. / Master of Science

La présente recherche met en évidence un phénomène qui est le fond commun des manières d’apparaître analysées par la phénoménologie française contemporaine. Ce phénomène est mis en évidence par l’analyse des œuvres de Jean-Luc Marion, Mihel Henry et Emmanuel Lévinas. L’analyse de l’œuvre de Marion permet de définir la métaphysique : celle-ci considère que l’apparaître est nécessairement la prérogative d’un Je. Contre cette idée, la phénoménologie met en évidence un phénomène qui apparaît avant qu’un Je ne s’en reçoive. Ce qui se montre ainsi de soi-même est le phénoménal. C’est sur fond de ce phénoménal que la donation se déploie, et si la donation ne donne plus son contenu à l’apparaître, elle est déploiement des phases qui structurent la phénoménalité. L’analyse de l’œuvre de Henry permet de distinguer la manière d’apparaître du phénoménal de celle du Je. Le contenu de l’apparaître du phénoménal est identiquement sa manière d’apparaître, et en cela le phénoménal est affectivité. Mais cette affectivité est impersonnelle et se dit d’une foison de tonalités affectives. Elle doit donc être distinguée du fait de se sentir soi-même considéré en lui-même qu’est cette essence de l’affectivité où le Soi se saisit de son ipséité. L’analyse de l’œuvre de Lévinas permet de décrire le déploiement des phases de la phénoménalité en deux mouvements. Par un mouvement d’en-stase, l’essence de l’affectivité se distille du phénoménal. Par un mouvement d’extase, le gouffre de l’« il y a », l’idée d’infini et la distance phénoménologique s’évaporent du phénoménal. L’unité de ces deux mouvements contraires est nommée diastase, et cette diastase est comprise comme quête d’emphase. / This researh highlights a phenomenon that is the common bakground of the various modes of manifestation analysed by the french contemporary phenomenology. That phenomenon is highlighted by the analysis of the works of Jean-LucMarion, Mihel Henry and Emmanuel Levinas. The analysis of the works of Marion brings us to a definition of the metaphysics : it considers that the manifestation is always the prerogative of a subject. Against this idea, the phenomenology highlights a phenomenon that appears before any subject. The phenomenon that shows itself that way is the phenomenal. It’s on that that the donation spreads, and if that donation does not give its content to the manifestation, it is the deployment of the phases that structure the phenomenality. The analysis of the works of Henry brings us to a distinction between the way that the phenomenal appears and the way that the ego appears. The contents of the manifestation of the phenomenal is also its way of appearance, and in that sense, the phenomenal is affectivity. But that kind of affectivity is impersonal, and concerns an abundance of affective qualities. It must be distinguish from the fact to feel itself considered in itself whih is that essence of affectivity on whih the self seize its selfhood. The analysis of the works of Levinas allows a description of the deployment of the phases of the phenomenality in two movements. By a movement of enstasis, the essence of affectivity gets distilled from the phenomenal. By a movement of extasis, the gulf of the « there is », the idea of infinity, and the phenomenological distance, evaporates from the phenomenal. The unity of these two movements is called diastasis.

The first study focuses on the development of a laser based method for the elemental analysis of solid milk powder. Milk powder samples originating from five different countries were analyzed to determine any geographic differences. A LA-ICP-MS method was developed and compared to k0-INAA for several milk samples as well as a reference sample. Precision of 10% RSD or better and a bias of 10% was achieved for both techniques for most elements with LA-ICP-MS producing lower limits of detection (~ 1 ppm) for Sr. The comparison of LA-ICP-MS to k0-INAA showed overlap of the 95% confidence intervals for all comparison samples. The data for 68 authentic milk powder samples representing 5 different countries (Argentina, Russia, Singapore, Slovenia, and the United States) was collected and used as a preliminary database. Principle component analysis (PCA) shows different groupings for the United States, Argentina, Singapore, and Slovenia. However the large number and geographic distribution of samples from Russia were not able to be distinguished from the samples from the United States and Slovenia. The second study focuses on the use of trace element databases for the objective interpretation of forensic glass evidence. Ten laboratories conducting analysis of glass participated in three inter-laboratory exercises. The aims of these exercises were to evaluate the use of a standard method for the analysis and comparison of glass evidence and to investigate different statistical approaches for interpreting results. Elemental analysis was performed on 420 vehicle windshield samples collected from 210 different vehicles representing manufacturing dates between 2004-2017 and 26 vehicle manufacturers. Using a variation of a previously reported comparison criterion for comparing samples to a database, the false exclusion rate and false inclusion rate for the new vehicle database were calculated to be 1.9% and 0.1 % respectively. This criterion was used to calculate the frequency of an elemental profile for the case scenarios distributed as part of the inter-laboratory exercises. Similarities were observed between labs that calibrated their data the same way, thus showing it is possible for labs to use a central database.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-04-12T17:35:33Z No. of bitstreams: 1 viniciusdelimaalvim.pdf: 927927 bytes, checksum: 31972cd6d80a0897e5592467b0e4d65a (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-04-18T13:12:56Z (GMT) No. of bitstreams: 1 viniciusdelimaalvim.pdf: 927927 bytes, checksum: 31972cd6d80a0897e5592467b0e4d65a (MD5) / Made available in DSpace on 2017-04-18T13:12:56Z (GMT). No. of bitstreams: 1 viniciusdelimaalvim.pdf: 927927 bytes, checksum: 31972cd6d80a0897e5592467b0e4d65a (MD5) Previous issue date: 2014-05-20 / A dissertação explora o design do segundo jogo da série Witcher de jogos eletrônicos, visando focar e evidenciar aspectos do design que levam a determinadas correntes de pensamento e reflexão entre seus jogadores. Para tanto, buscamos compreender perspectivas fundamentais do design de jogos - explorar como seus designers criam e pensam os jogos eletrônicos, assim como evidenciar os termos e nomenclaturas utilizados dentro da área para determinadas práticas e correntes de pensamento. Utilizamo-nos então das publicações teóricas de game designers e outros pensadores que voltaram suas reflexões sobre esta mídia - entre eles Katie Salen, Eric Zimmerman e Jesse Schell. Após apresentar estes conceitos ao leitor, analisamos Witcher 2: Assassin of Kings sob a ótica destas perspectivas, evidenciando elementos fundamentais de seu design e observando especialmente aquelas características que acreditamos serem importante para a indução de determinados tipos de reflexão. Por fim, exploramos os fóruns oficiais da CD Projekt em busca de indícios que poderiam nos mostrar como certas escolhas feitas pelos designers na criação desta série de jogos impactaram a experiência de seus jogadores. / This dissertation explores the design of the second title in the Witcher series of videogames, aiming to focus and reveal aspects of the game's design that lead to certain trends of thoughts and reflections among its players. With that goal in mind, we strive to understand fundamental perspectives of game design - explore how the designers of videogames create and think about them. Also, we introduce our reader to the terms and jargons used in this field of knowledge to describe certain practices and trends of thought. To do this, we use the theoretical works of game designers and other researchers who dedicated their minds to this media - among them Katie Salen, Eric Zimmerman e Jesse Schell. After describing these concepts to our reader, we analyze The Witcher 2: Assassin of Kings under the gaze of such perspectives, pointing out fundamental elements on its design and emphasizing those traits that we believe are important for the induction of specific thought patterns. In the end, we explore the official foruns of CD Projekt, looking for evidence that could show us how certain choices made by the designers of this videogame series influenced the experience of its players.

The present PhD is focused on the development of new analytical methods based on ICP techniques to carry out the elemental and isotopic analysis of bioethanol samples and other specimens taken along the bioethanol production process. The total sample consumption system, so-called hTISIS, has been used as sample introduction system in ICP-OES for the quantification of major and minor metals, and ICP-MS for the determination of trace metals. The hTISIS has also been successfully set up to carry out the lead isotopic analysis of bioethanol samples. Additionally, metals found in bioethanol have been monitored along the production process of this biofuel to identify the origin of these metals. Finally, volatile organic compounds have been determined in different bioethanol samples to perform the characterization of the matrices and their effect on the accuracy of the methods based on ICP techniques, developed in the present PhD for the elemental and isotopic analysis of these kind of samples. / La presente Tesis Doctoral se centra en el desarrollo de nuevos métodos de análisis basados en técnicas de ICP para llevar a cabo el análisis elemental e isotópico de muestras de bioetanol y muestras tomadas a lo largo del proceso de obtención de dicho biocombustible. Se ha empleado un sistema de consumo total de muestra, conocido como hTISIS, como sistema de introducción de muestras en ICP-OES para la cuantificación de metales mayoritarios y minoritarios, y en ICP-MS para la determinación de metales traza en bioetanol. El sistema hTISIS también se ha empleado con éxito para llevar a cabo el análisis isotópico de plomo en dichas muestras. Además, los metales encontrados en las muestras de bioetanol han sido monitorizados a lo largo del proceso de obtención del mismo para identificar el origen de dichos metales. Finalmente, se han determinado los compuestos volátiles presentes en diferentes muestras de bioetanol, con el objetivo de caracterizar las matrices y como estas pueden afectar a la exactitud de los métodos desarrollados, que emplean técnicas ICP para el análisis elemental e isotópico de este tipo de muestras.

Vam monitoritzar paràmetres físics i químics, macroinvertebrats bentònics, clorofil·la a, productors primaris i matèria orgànica durant un any (2001-2002) per examinar els efectes d'una font puntual sobre la composició taxonòmica, la estructura de la comunitat, l'organització funcional, la utilització de l'habitat i la estoquiometria al riu la Tordera (Catalunya).Aigües avall de la font puntual, concentració de nutrients, cabal i conductivitat eren majors que al tram d'aigües amunt, mentre que oxigen dissolt era menor. La densitat de macroinvertebrats era més elevada al tram d'aigües avall però la biomassa era similar als dos trams. La riquesa taxonòmica al tram de dalt era un 20% més alt que al tram de baix. Els anàlisis d'ordenació separen clarament els dos trams en el primer eix, mentre que els dos trams presentaven una pauta temporal similar en el segon eix. La similaritat entre els dos trams en composició taxonòmica, densitats i biomasses després de les crescudes d'abril i maig de 2002, indiquen que les pertorbacions del cabal poden actuar com a un mecanisme de reinici de la comunitat bentònica i jugar un paper important per a la restauració d'ecosistemes fluvials.Els dos trams presentaven una biomassa de perifiton, plantes vasculars, CPOM i FPOM similars, mentre que clorofil·la a, algues filamentoses, molses i SPOM eren majors al tram d'aigües avall. La densitat relativa de trituradors era menor sota la font puntual mentre que col·lectors i filtradors van ser afavorits. La biomassa relativa de trituradors també era menor sota la font puntual, però la biomassa de col·lectors i depredadors va augmentar. Les relacions entre densitat de grups tròfics i els seus recursos eren rarament significatives. La relació s'explicava millor amb la biomassa de macroinvertebrats. Els dos trams compartien la mateixa relació per raspadors, col·lectors i filtradors però no per trituradors i depredadors.La densitat i la biomassa de macroinvertebrats es trobaven positivament correlacionades amb la quantitat de recursos tròfics i la complexitat d'habitat, mentre que la riquesa taxonòmica es trobava negativament relacionada amb paràmetres hidràulics. La influència dels substrats inorgànics prenia menor rellevància per a la distribució dels macroinvertebrats. Els anàlisis d'ordenació mostren com les variables del microhabitat de major rellevància eren CPOM, clorofil·la a, algues filamentoses i velocitat. La cobertura de sorra només era significativa per al tram d'aigües amunt i les molses, al d'aigües avall. El número de correlacions significatives entre macroinvertebrats i les variables del microhabitat era més elevat per al tram de dalt que per al de baix, bàsicament per diferències en composició taxonòmica. La biomassa de macroinvertebrats va aportar una informació semblant a la obtinguda per la densitat.Perifiton i molses tenien uns continguts de nutrients similars en els dos trams. Els %C i %N d'algues filamentoses també eren similars en els dos trams però el %P sota la font puntual era el doble que al tram de dalt. Les relacions estoquiomètriques en CPOM, FPOM i SPOM eren considerablement menors sota la font puntual. Els continguts elementals i relacions van ser molt variables entre taxons de macroinvertebrats però no van resultar significativament diferents entre els dos trams. Dípters, tricòpters i efemeròpters presentaven una estoquiometria similar, mentre que el C i el N eren inferiors en moluscs i el P en coleòpters. Els depredadors presentaven un contingut en C i N més elevat que la resta de grups tròfics, mentre que el P era major en els filtradors. Els desequilibris elementals entre consumidors i recursos eren menors en el tram d'aigües avall. A la tardor i l'hivern la major font de nutrients va ser la BOM mentre que a la primavera i a l'estiu va ser el perifiton. / We monitored physical and chemical parameters, benthic macroinvertebrates, chlorophyll a, primary producers, and organic matter for one year (2001-2002) to assess the effect of a point source input on the taxa composition, community structure, functional organization, microhabitat distribution, and elemental stoichiometry in La Tordera stream (Catalonia, NE Spain).Below the point source, nutrient concentrations, discharge, and specific conductance were higher than at the upstream reach, while dissolved oxygen decreased. Total macroinvertebrate density was higher at the downstream reach than at the upstream reach. The two reaches did not differ in macroinvertebrate total biomass. On average, taxa richness at the upstream reach was 20% higher than at the downstream reach. Ordination analysis clearly separated the samples of the two reaches in the first axis and corroborated the effect of the point source on the benthic community. The two reaches followed a similar temporal pattern with respect to the distribution of taxa along the second axis. Higher similarities between the two reaches in taxa composition, densities and biomass after the spates of April and May 2002, suggest that flooding events may act as a reset mechanism for benthic communities and play an important role in stream restoration.The two reaches did not differ in standing stocks of periphyton, vascular plants, CPOM and FPOM. Chlorophyll a, filamentous algae, mosses, and SPOM concentrations were increased by the point source. Relative density of shredders was reduced at the downstream reach, whereas gatherers and filterers were enhanced. Relative biomass of shredders decreased below the point source as well, but gatherers diminished and predators increased. The relationships between density of functional feeding groups and their presumed food resources were rarely significant. The relation between consumers and their food resources was best explained through macroinvertebrate biomass. The two reaches had the same relationship for scrapers, gatherers, and filterers, but differed for shredders and predators.Macroinvertebrate density and biomass were positively correlated with food resources and complexity of habitat architecture while taxa richness was negatively correlated with hydraulic parameters. Inorganic substrate exerted a lesser influence on macroinvertebrate distribution. Ordination analysis revealed that the microhabitat variables of major relevance at the two reaches were CPOM, chlorophyll a, filamentous algae, and maximum water velocity. Sand coverage was only retained at the upstream reach and moss, at the downstream reach. The number of significant correlations between macroinvertebrates and microhabitat variables was higher at the upstream reach than at the downstream reach mainly because of higher taxa richness. Macroinvertebrate biomass provided similar information to that obtained from density in our study case.Periphyton and mosses had similar nutrient contents in the two reaches. The %C and %N filamentous algae was also similar in the two reaches, but %P below the point source was two times higher than that at the upstream reach. Stoichiometric ratios for CPOM, FPOM, and SPOM decreased considerably below the point source. Elemental contents and ratios were highly variable among macroinvertebrate taxa but did not differ significantly between the two reaches, indicating homeostatic regulation. Dipterans, caddisflies, and mayflies had similar elemental contents and stoichiometry, whereas C and N were lower in mollusks and P in beetles. Predators had the higher C and N contents, while %P was higher in filterers and lower in scrapers. Elemental imbalances between consumers and resources were amended at the downstream reach relative to the upstream reach. Macroinvertebrates represented, on average, relatively low nutrient storage in the ecosystem. At the upstream reach, autochthonous production represented the major input of nutrients into the ecosystem food web, whereas the major source of P for heterotrophic production at the downstream reach was represented by allochthonous inputs.

La tesis doctoral realizada se enmarca dentro del ámbito de los estudios sobre la promoción de la lectura y el fomento de la interculturalidad en Educación Secundaria Obligatoria y Bachillerato. Los objetivos que perseguimos con su elaboración son fundamentalmente dos: el primero de ellos consiste en proponer un cambio en cuanto a las lecturas medievales de los siglos XIII y XIV que se recomiendan en los curricula de tercero de Educación Secundaria Obligatoria y de primero de Bachillerato con la finalidad de ofrecer a los estudiantes una visión más fidedigna de la literatura y de la sociedad de la época. El segundo procura que los alumnos conozcan y analicen los textos bajomedievales españoles de procedencia oriental desde una perspectiva literaria ecléctica, mediante la que se favorece el desarrollo de la educación en valores y de la competencia comunicativa intercultural. Persiguiendo la consecución de estos objetivos, hemos estructurado nuestra tesis doctoral en seis capítulos -los tres primeros de naturaleza teórica y los tres siguientes de índole más empírica- a través de los cuales planteamos un modelo didáctico de actividades. Dicho modelo se ha diseñado para desarrollar una formación integral de los estudiantes basada en tres tipos de conocimiento -de saberes del período medieval, de educación en valores y de desarrollo de la conciencia intercultural- que, aunque se pueden adquirir de forma separada, cobran un mayor sentido si se interrelacionan y se combinan las destrezas y habilidades necesarias para su obtención. Respecto a la metodología de análisis que hemos aplicado para la detección y clasificación de los valores educativos interculturales ha sido la técnica de análisis documental conocida como “análisis de contenido”. A través de su implementación determinamos el número y la naturaleza de los valores que contienen las obras seleccionadas y, así, escogemos los relatos más adecuados para su traslación a las aulas. Para ello, hemos acotado el contenido de los textos y entresacado de sus páginas un corpus compuesto por veinticinco fábulas y exempla siguiendo criterios como el de la variedad de argumentos narrativos, el de la adecuación de la temática abordada en ellos a la edad de los estudiantes a los que se dirigen y el de la originalidad de los mismos en relación con propuestas didácticas ya realizadas por otros estudiosos. Los resultados obtenidos del análisis cualitativo y cuantitativo en la antología de textos seleccionada nos han proporcionado los cinco exempla y las cinco fábulas más adecuados para realizar con ellos una propuesta de intervención didáctica en las aulas del tercer curso de Educación Secundaria Obligatoria y del primer curso de Bachillerato. A partir de los mismos hemos diseñado un conjunto de actividades para el trabajo de la literatura bajomedieval basadas en la interculturalidad y en la educación en valores. Hemos trabajado sobre cuatro relatos -dos fábulas y dos exempla- para el nivel obligatorio y seis relatos -tres fábulas y tres exempla- para el postobligatorio. Dichas actividades se vehiculan en torno al desarrollo de los tres núcleos temáticos que han vertebrado nuestra tesis doctoral como son la adquisición de saberes literarios de la época medieval, la consecución de unos valores morales óptimos y el desarrollo de la competencia comunicativa intercultural. / This completed dissertation belongs to the academic field of reading and interculturality in secondary and high school education. The fundamental goals we seek in carrying out this research are two: the first focuses on proposing a shift regarding the medieval readings texts of the 13th and 14th century suggested in the curricula of the third year of Secondary Education and first year of High School, with the purpose of offering the students a more reliable take on the literature and society of the period. The second endeavours to encourage the students to analyse and be acquainted with the Middle Age Spanish texts of eastern origins from a more eclectic viewpoint, by which the development in values education and the intercultural communicative competence is encouraged. In order to achieve these aims, this doctoral dissertation has been divided into six chapters -the first three establishing a theoretical framework and the following three of an empirical nature- throughout which a didactic model of activities is posed. This aforementioned model has been designed in order to provide a comprehensive education of the students based on three different types -of knowledge of the medieval period, of values education and of the betterment of intercultural awareness-. Although these can be attained separately, they make more sense when interconnecting and combining the skills and abilities required for their acquirement. In regard to the research methodology for the collection and classification of the intercultural educative values, the practice of documentary analysis known as “content analysis” has been applied. Owing to its implementation, the number and nature of the values contained in the texts have been determined, and thus the more suitable tales have been selected for use in the classrooms. In order to do so, we have refined the contents of the texts and derived from their pages a corpus made up of twenty-five fables and exempla. We have followed criteria such as the variety of narrative plots, the adequacy of the themes to the interests of the target age of the students, and their own innovative possibilities as didactic proposals compared to previous studies. The results obtained by the qualitative and quantitative analysis in the anthology of selected works has provided us with the five exempla and five tales most suited for the crafting of a didactic intervention proposal in the third year of Secondary Education and first year of High School’s classrooms. In conjunction with these works and so as to facilitate the study of medieval literature we have outlined a set of activities based on interculturality and values education. We have elaborated four texts -two fables and two exempla- for Secondary Education level and six -three fables and three exempla- for High School level. The already mentioned activities are encompassed within the development of the three thematic aspects that have structured our doctoral dissertation, which are the acquisition of knowledge of the medieval period, the attainment of a set of exemplary values and of the growth of intercultural communicative competence.

The work presented in this thesis has demonstrated that the use of elemental profiles for the quality control of herbal medicines can be applied to multiple stages of processing. A single method was developed for the elemental analysis of a variety of St John’s Wort (Hypericum perforatum) preparations using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES). The optimised method consisted of using 5 ml of nitric acid and microwave digestion reaching temperatures of 185⁰C. Using NIST Polish tea (NIST INCT-TL- 1) the method was found to be accurate and the matrix effect from selected St John’s Wort (SJW) preparations was found to be ≤22%. The optimised method was then used to determine the elemental profiles for a larger number of SJW preparations (raw herbs=22, tablets=20 and capsules=12). Specifically, the method was used to determine the typical concentrations of 25 elements (Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, In, Mg, Mn, Mo, Ni, Pb, Pt, Sb, Se, Sr, V, Y and Zn) for each form of SJW which ranged from not detected to 200 mg/g. To further interpret the element profiles, Principal Component Analysis (PCA) was carried out. This showed that different forms of SJW could be differentiated based on their elemental profile and the SJW ingredient used (i.e. extract or raw herb) identified. The differences in the profiles were likely due to two factors: (1) the addition of bulking agents and (2) solvent extraction. In order to further understand how the elemental profile changes when producing the extract from the raw plant, eight SJW herb samples were extracted with four solvents (100% water, 60% ethanol, 80% ethanol and 100% ethanol) and analysed for their element content. The results showed that the transfer of elements from the raw herb to an extract was solvent and metal dependent. Generally the highest concentrations of an element were extracted with 100% water, which decreased as the concentration of ethanol increased. However, the transfer efficiency for the element Cu was highest with 60% ethanol. The solvents utilised in industry (60% and 80% ethanol) were found to preconcentrate some elements; Cu (+119%), Mg (+93%), Ni (+183%) and Zn (+12%) were found to preconcentrate in 60 %v/v ethanol extracts and Cu (+5%) and Ni (+30%). PCA of the elemental profiles of the four types of extract showed that differentiation was observed between the different solvents and as the ethanol concentration increased, the extracts became more standardised. Analysis of the bioactive compounds rutin, hyperoside, quercetin, hyperforin and adhyperforin followed by subsequent Correlation Analysis (CA) displayed relationships between the elemental profiles and the molecular profiles. For example strong correlations were seen between hyperoside and Cr as well as Quercetin and Fe. This shows potential for tuning elemental extractions for metal-bioactive compounds for increased bioactivity and bioavailability; however further work in needed in this area.

Poor food quality can have large negative effects on zooplankton growth and this can also affect food web interactions. The main aims of this thesis were to study the importance of different food quality aspects in Daphnia, to identify potentially important differences among zooplankton taxa, and to put food quality research into a natural context by identifying the importance of food quality and quantity in lakes of different nutrient content. In the first experiment, the RNA:DNA ratio was positively related to the somatic growth rate of Daphnia, supporting a connection between P content, RNA content, and growth rate. The second experiment showed that EPA was important for Daphnia somatic growth, and 0.9 µg EPA mg C-1 was identified as the threshold below which negative effects on Daphnia growth occurred. A field survey identified patterns in the PUFA content of zooplankton that could be explained by taxonomy and trophic position. Cladocera enriched EPA and ARA relative to seston, and Copepoda primarily enriched DHA. In a whole-lake experiment, gentle fertilization of an oligotrophicated reservoir increased the seston P content and the biomass of high quality phytoplankton (Cryptophyceae, high EPA content). This was followed by increases in zooplankton and fish biomasses. An empirical model based on data from a literature survey predicted that food quantity is most important for zooplankton growth in oligotrophic lakes, and that food quality factors are more important in eutrophic lakes. Thus, zooplankton growth, and energy transfer efficiency in the food web, is predicted to be highest in mesotrophic lakes. The results predict that the strength and nature of food quantity and quality limitation of Daphnia growth varies with lake trophic state, and that some combination of food quantity and/or quality limitation should be expected in nearly all lakes.

Knorpel ist ein kompliziertes System aus einem kollagenen Netzwerk, gefüllt mit wasserbindenden Makromolekülen (Proteoglykanen) und darin eingebetteten Zellen. Störungen in den komplexen Wechselbeziehungen können zur Gefährdung der strukturellen Integrität des Knorpels führen. Die hochauflösende Magnetresonanztomographie (NMR-Mikroskopie) kann über die Analyse der Signalintensität interne Knorpelstrukturen darstellen (hypo- und hyperintense Zonen). Mit Hilfe ionenmikroskopischer Analysemethoden (PIXE, RBS, ERDA) wurden im Knorpel (femorale und tibiale Kondyle des Hausschweins) im Querschnitt die zweidimensionalen Verteilungen der Knorpelelemente (H, C, N, O, P, S, Cl, K und Ca) aufgenommen sowie die Konzentrationen in ausgewählten Zonen bestimmt. Ergänzend wurde mit STIM die Dichteverteilung im Knorpel untersucht. Es gelang auch mit STIM, erstmalig kollagene Fasern in ihrer, bis auf den Wasserentzug natürlichen, Umgebung im Knorpel und damit unverändert in ihrer Anordnung sichtbar zu machen (keine chemische Demaskierung nötig). Die Ergebnisse wurden mit NMR- und polarisationsmikroskopischen Untersuchungen verglichen und in ihrem Zusammenhang mit den histologischen Knorpelzonen diskutiert. In den NMR-hypointensen Zonen fanden sich eine erhöhte Chlorkonzentration und punktförmige Calciumanreicherungen. Diese Zonen waren (im gefriergetrockneten Zustand) durch eine, bis zu einem Faktor vier höhere Dichte gekennzeichnet, die im maximalen Gehalt der Matrixelemente, H, C, N, O, (höchste Kollagendichte) begründet liegt. Im tibialen Knorpel konnten in der NMR-hypointensen Zone radial verlaufende einzelne Kollagenfasern nachgewiesen werden. Im femoralen Knorpel wurden in dieser Zone keine Einzelfasern nachgewiesen. Es deutete sich eine tubuläre Anordnung der Kollagenfasern an. In der hypertrophen Zone zeigten sich hohe Konzentrationen an Phosphor (Zellorganellen), Schwefel (Proteoglykane), Kalium (alkalisches Milieu) und Calcium (Vorstufe der Kalzifizierung). Die Chlorkonzentration hatte dort ihr Minimum. In dieser Zone verlaufen die Kollagenfasern radial und münden senkrecht in den Kalkknorpel. In der Tangentialfaserschicht wurde eine erhöhte Konzentration an Calcium und Phosphor beobachtet (Einlagerung von Calciumphosphaten). In dieser Zone wurden tangential verlaufende Kollagenfasern und ihr Übergang zur stärkeren Vernetzung mit teilweise arkadenförmiger Überstruktur sichtbar gemacht. Zur genaueren Aufklärung der dreidimensionalen Anordnung der Kollagenen Strukturen wurden erste Experimente zur STIM-Tomographie durchgeführt.