Det största hotet mot våra vattenmiljöer idag är eutrofieringen - överskottet av näringsämnen orsakat av avlopp och jordbruk. För att motverka detta krävs mer kunskap kring uppträdandet av fosfor i jord och, mer specifikt, fosforsorptionskapaciteten i sand- och grusjordar. Särskilt intressant är detta då enskilda avlopp (som är en stor källa till fosforutsläpp i Sverige) är uppbyggda av infiltrationsbäddar bestående av sand- och grusjordar. Syftet med denna rapport har varit att bestämma fosforsorptionskapaciteten i olika sand- eller grusbaserade jordar. Undersökningen har genomförts med hjälp av skakförsök och verktyg såsom MS Excel och Visual MINTEQ, och resultaten modellerades utifrån Freundlichekvationen. Även kemisk analysutrustning såsom ICP och AutoAnalyzer har använts för att analysera elementkoncentrationer i jordproverna. Resultaten visar att det finns ett positivt linjär-logaritmiskt samband mellan mängden adsorberat P och mängden tillsatt P i proverna. Det visade sig att de undersökta jordarna i snitt kunde binda 0.56 mmol fosfor/kg jord, eller 26.01 g fosfor per m3 jord. Vidare konstaterades även att mängden adsorberat P korrelerar linjärt med mängden oxalatlösligt Al och Fe i jordprovet. För majoriteten av jordproverna som uppvisade ett pH-värde högre än 8, verkade utfällningar av kalciumfosfater öka mängden bunden P. Då svenska mineraljordar med låg halt humusämnen oftast har ett pH-värde på 5.2-5.4, kan det argumenteras för att Al- och Fe-(hydr)oxider är av större betydelse för lösligheten av P än förekomsten av kalcium. Vidare undersökningar skulle kunna genomföras för att öka förståelsen för hur närvaron av humusämnen och jorddjupet påverkar fosforsorptionen, samt dess pH-beroende. / The eutrophication of our seas, lakes, and rivers is one of today's biggest threats to the aquatic environment. To counteract this, more knowledge concerning the behavior of phosphorus in soils and, more specifically, the efficiency of phosphate removal in sand and gravel soils is, greatly needed. This is particularly the case as most private wastewater systems (a considerable source of phosphorus leakage in Sweden) are based on infiltration beds consisting of sand and/or gravel soils. The objective of this research has been to determine the phosphorus sorption capacity of different sand or gravel-based soils. The study has been carried out using batch experiments and tools such as MS Excel and Visual MINTEQ, and the results were modeled according to the Freundlich equation. Chemical analysis equipment such as an ICP and AutoAnalyzer were also used to determine element concentrations in the soil samples. The results show that there is a positive linear logarithmic relationship between the amount of sorbed P and the amount of added P to the sample. It was concluded that the analyzed soils on average bound 0.56 mmol P per kg soil, or alternatively, 26.01 g P per m3 soil. Furthermore, it was found that the amount of sorbed P correlated linearly with the amount of oxalate-extractable Al and Fe in the soil sample. For most of the samples with a pH exceeding 8, precipitation of calcium-phosphates appeared to increase the amount of sorbed P. Since most Swedish mineral soils with a low organic content have a pH of 5.2-5.4, it can be argued that Al- and Fe-(hydr)oxides play a larger role in the adsorption of phosphorus than precipitation of calcium-phosphates. Further testing should be carried out to determine the pH-dependency, influence of soil depth, and influence of organic compounds on the phosphorus sorption capacity in sand- and gravel soils.

Title: Biomechanical aspects of the dynamics of intracranial pressure in traumatic brain injury Author: Ing. Martin Mayer e-mail: mayercz@seznam.cz Department: Department of Anatomy and Biomechanics Supervisor: doc. PaedDr. Karel Jelen, CSc. This PhD thesis "Biomechanical aspects of the dynamics of intracranial pressure in traumatic brain injury" is about the dynamics of intracranial pressure, particularly in relation to the external mechanical action of the patient. Severe head injury is the leading cause of death in patients under 35 years of age. Despite constantly-improving medical and nursing care only one third of patients, after recovery, regained the ability to live independently in the long term. Two-thirds of patients were severely disabled or died. The lifetime cost of such a patient who was not completely cured has been calculated to be $4,000,000. A significant consequence of craniocerebral injuries are secondary brain lesions, which among other means the rise in intracranial pressure (ICP), which can further exacerbate due to intracerebral or extracerebral causes. Therefore, the objective of the treatment is minimizing secondary injury, optimally at the phase of the primary lesion. However, realization of this requirement, about which we can say that is a conditio sine qua non, sometimes leads...

Les nanoparticules d’argent (Ag NPs) sont considérablement utilisées dans l’industrie alimentaire. Elles sont fortement appliquées comme enrobages d’emballages alimentaires afin d’assurer une meilleure qualité des aliments et une plus longue durée de conservation sur les étagères des supermarchés. En revanche, les risques associés aux Ag NPs sont inquiétants. Leurs effets potentiels sur les humains et sur l’environnement suscitent un grand intérêt scientifique. C’est pourquoi il est important de valider des méthodes analytiques pour détecter, caractériser et quantifier les Ag NPs dans la nourriture mise en contact avec ce type de contenant. Les méthodes permettront de mieux comprendre la migration de l'argent vers les aliments directement ingérés par l’humain. La spectrométrie de masse à plasma à couplage inductif en mode particule unique (SP-ICP-MS) est une technique prometteuse pour caractériser et quantifier de petites particules (de quelques nanomètres) à de faibles concentrations (dans l'ordre du ng L-1). Contrairement aux techniques analytiques conventionnelles, telles que les techniques de microscopie et de diffusion de la lumière, le SP-ICP-MS distingue la forme ionique de la forme particulaire de l'analyte. Cette présente étude valide une méthode pour la caractérisation et la quantification des Ag NPs et de l’argent ionique dans deux boissons et trois simulants: jus d'orange, préparation en poudre pour nourrissons, eau Milli-Q, acide acétique à 3% et éthanol à 10%. De plus, une meilleure compréhension du devenir et de la migration de l’argent provenant d'emballages alimentaires nano-activés a pu être obtenue. En effet, les milieux acides et les traitements thermiques ont engendré de plus grands relargages d’argent, sous forme ionique, contrairement aux milieux dits « lipophiles » tels que la préparation pour nourrissons et l’éthanol. En conclusion, ce mémoire nous démontre que les voies de libération des NPs des contenants nano-activés ne sont pas encore très bien comprises. De plus amples études doivent être entreprises afin de pouvoir établir des modèles de migration clairs et afin de mieux comprendre les risques associés à leurs utilisations. / Silver nanoparticles (Ag NPs) are increasingly used in the food industry. They are integrated into coatings of various food packaging to help ensure longer product shelf life. However, the risks associated with Ag NPs are currently not well known and their potential effects on humans are causing growing concern. Furthermore, it is not clear whether NPs have greater or lesser risk than dissolved silver ions or bulk phase Ag. Consequently, it is necessary to detect and to characterize the release of silver from silver-enhanced containers into real food matrices using sensitive analytical techniques that allow one to distinguish between silver ions and nanoparticles. Single particle ICP-MS is a promising technique to count and size small particles at low concentrations. Compared to other conventional instrumentation, it can distinguish between ionic and particulate forms of the analyte. This thesis focused firstly on the validation of an analytical method for the analysis of Ag NPs and ionic silver in three different food simulants (Milli-Q water, 10% ethanol and 3% acetic acid) and in two drinks (orange juice and infant milk formula). A better understanding of the aging and of the migration of silver has been reached in these matrices. Essentially, acidic media caused significant NP oxidation whereas organic macromolecules like lipids, proteins and polysaccharides appeared to increase the stability of the NPs. Subsequently, a migration study from silver-enhanced containers showed significant release of dissolved Ag in 3% acetic acid and a lower release in milk formula. Also, heating led to a considerable release of silver from the container. To conclude, further studies are needed to obtain clear release models to better understand the risk on humans and on the environment.

[pt] Os metais estão presentes em diversos materiais e muitos deles, como o níquel e o cromo, possuem papeis significativos em diversos setores industriais. A quantificação desses metais é importante tanto para obtenção de informações relevantes a respeito desses materiais, como para avaliação de possíveis contaminações ambientais. No presente trabalho, foram desenvolvidos métodos analíticos para a determinação de níquel e cromo em amostras de asfalto, brita e CAP por espectrometria de massa com plasma indutivamente acoplado usando calibração externa e diluição isotópica. Para a avaliação da exatidão dos métodos foram utilizados os materiais de referência certificados NIST 1084a e NBS 688. Como métodos de preparo de amostra, foram estudadas a decomposição ácida em bloco digestor, e a diluição em uma mistura de xileno/butanol na proporção 60:40 v:v (para amostras de óleo). Para a correção da interferência da espécie 40Ar12C positivo sobre o isótopo de 52Cr foi utilizada a célula de reação dinâmica com introdução de CH4 como gás de reação, o que reduziu de forma significativa o sinal de fundo característico para o isótopo de cromo. Os métodos desenvolvidos se mostraram eficientes na determinação dos metais. As recuperações obtidas para os SRMs se encontram entre 80-120 porcento. As concentrações médias, em mg kg-1 , encontradas para Ni pelos diferentes métodos nas amostras de CAP, brita e asfalto foram, respectivamente 39,9 mais ou menos 0,6, 6,7 mais ou menos 0,5 e 11,2 mais ou menos 0,8, enquanto para Cr as concentrações foram 1,8 mais ou menos 0,1, 15,3 mais ou menos 0,3, 16,6 mais ou menos 0,4. O sucesso da aplicação da diluição isotópica em amostras dissolvidas em solvente orgânico mostrou-se muito promissor, pois elimina a necessidade da decomposição ácida das matrizes tornando o preparo das amostras mais rápido e menos trabalhoso. / [en] Metals are present in several samples and many of them, such as nickel and chromium, have significant roles in several industry sectors. The quantification of these metals is important both for obtaining relevant information regarding these materials, and for evaluating possible environmental contaminations. In the present work, analytical methods were developed for the determination of nickel and chromium in asphalt, crushed stone and CAP samples by inductively coupled plasma mass spectrometry using both external calibration technique and isotopic dilution. To evaluate accuracy of the method, the certified reference materials NIST 1084a and NBS 688 were used. Two different methods of sample preparation were employed, block digestion and direct dilution in a xylene / butanol mixture using a 60:40 v:v ratio (for the oil samples). For the interference correction imposed by 40Ar12C over 52Cr, the dynamic reaction cell was used with CH4 as the reaction gas, which significantly reduced the characteristic background signal of the chromium isotope. The methods developed proved to be efficient in the determination of the metals in question. The recovery values obtained for the SRMs were between 80-120 percent. The average concentrations, in mg kg-1 , found for Ni by the different methods in CAP, crushed stone and asphalt samples were, respectively, 39,9 more or less 0,6, 6,7 more or less 0,5 and 11,2 more or less 0,8, while for Cr the concentrations were 1,8 more or less 0,1, 15,3 more or less 0,3, 16,6 more or less 0,4. The successful application of isotope dilution in samples dissolved in organic solvent is very promising because it eliminates the need for acid digestion, making the sample preparation faster and less labor intensive.

[pt] Tinturas de cabelo, amplamente utilizadas em cosméticos, demandam atenção especial para garantir a ausência de substâncias prejudiciais à saúde. A Agência Nacional de Vigilância Sanitária (ANVISA) estabelece limites de impurezas, como 20 mg kg(-1) para Pb e 100 mg kg(-1) para a soma dos demais elementos potencialmente tóxicos. A fim de avaliar a ocorrência de elementos potencialmente tóxicos em tinturas comercializadas no Brasil, a espectrometria de massa com plasma indutivamente acoplado (ICP-MS) foi empregada neste estudo para determinar as concentrações de Al, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Ti e Zn em 26 amostras de tinturas de cabelo. A maioria das amostras apresentou baixas concentrações dos elementos estudados (< 1 mg kg(-1) ), exceto Pb em duas amostras (T01 e T09), tinturas à base de acetato de chumbo, que apresentaram concentrações de até 3.500 mg kg(-1) , e Al com concentrações de até 480 mg kg(-1) para a amostra H01. Utilizando metodologia do Scientific Committee on Consumer Safety da União Europeia, foram avaliados os riscos à saúde associados à exposição prolongada a esses elementos. Alguns elementos demonstram margens de segurança (MS) maiores do que 100, indicando exposição segura de acordo com a Environment Protection Agency (EPA). No entanto, Al, Pb, Cr, Mn e Ni apresentaram valores de MS abaixo de 100, suscitando preocupações em relação ao uso prolongado de algumas tinturas comerciais por apresentarem um valor de MS considerado inseguro (MS < 100) pela EPA. / [en] Hair dyes, widely used in cosmetics, require special attention to ensure the absence of harmful substances to health. The Agência Nacional de Vigilância Sanitária (ANVISA) establishes limits for impurities, such as 20 mg kg(-1) for Pb and 100 mg kg(-1) for the sum of other potentially toxic elements. In order to assess the occurrence of potentially toxic elements in hair dyes marketed in Brazil, inductively coupled plasma mass spectrometry (ICP-MS) was employed in this study to determine the concentrations of Al, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Ti, and Zn in 26 hair dye samples. Most samples showed low concentrations of the studied elements (< 1 mg kg(-1) ), except for Pb in two samples (T01 and T09), lead acetate-based dyes, which showed concentrations of up to 3,500 mg kg(-1) , and Al with concentrations of up to 480 mg kg(-1) for sample H01. Using the methodology of the Scientific Committee on Consumer Safety of the European Union, health risks associated with prolonged exposure to these elements were assessed. Some elements demonstrate margin of safety (MS) greater than 100, indicating safe exposure according to the Environmental Protection Agency (EPA). However, Al, Pb, Cr, Mn, and Ni showed MS values below 100, raising concerns regarding the prolonged use of some commercial dyes as they present a MS value considered unsafe (MS < 100) by the EPA.

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.

The Eagle Ford Shale and equivalent Boquillas Formation (Late Cretaceous) contain abundant volcanic ash beds of varying thickness. These ash beds represent a unique facies that displays a range of sedimentary structures, bed continuity, and diagenetic alteration. They are prominent not only in West Texas outcrops, but also in the subsurface of South Texas where hydrocarbon production is actively occurring. The ash beds have the potential to be used for stratigraphic correlation for understanding early diagenesis and — most importantly — for obtaining high-resolution geochronology, which can then be used for defining depositional rates and chronostratigraphy. Study of the ash beds was conducted at outcrops along U.S. 90, west of Comstock, Texas, the subsurface in Atascosa and Karnes County, and at a construction site in South Austin. Bed thicknesses range from 0.1–33 cm and were collected throughout the entirety of the Eagle Ford succession. Mineral separation yielded abundant non-detrital zircons for U-Pb dating. Dating was conducted using LA-ICP-MS at The University of Texas at Austin, to attain a base level understanding of the age range for the Eagle Ford. High-resolution ages for the base and top of the Eagle Ford were obtained, in addition to radioisotopically defining the Cenomanian-Turonian boundary within the section. U-Pb ages for the Eagle Ford Shale range from Early Cenomanian to Late-Coniacian near Comstock, Mid-Cenomanian to the Turonian-Coniacian boundary in the subsurface, and Early Cenomanian to Late Turonian in Austin area. These findings contrast with many of the regional biostratigraphic studies across the Eagle Ford and indicate a more prolonged period of Eagle Ford deposition than previously observed. / text

Les carbonatites sont des roches magmatiques essentiellement composées de carbonates (calcite et/ou dolomite) d'origine magmatique. Leur statut pétrographique en tant que liquide magmatique ou cumulat reste à l'heure actuelle fort contreversé. Cette thèse de doctorat à pour objectif une étude pétrographique fine de ces roches couplée à des microanalyses in-situ des éléments en trace des principaux minéraux (carbonate, apatite).

This thesis concerns detection and recognition of ground object using data from laser radar systems. Typical ground objects are vehicles and land mines. For these objects, the orientation and articulation are unknown. The objects are placed in natural or urban areas where the background is unstructured and complex. The performance of laser radar systems is analyzed, to achieve models of the uncertainties in laser radar data. A ground object recognition method is presented. It handles general, noisy 3D point cloud data. The approach is based on the fact that man-made objects on a large scale can be considered be of rectangular shape or can be decomposed to a set of rectangles. Several approaches to rectangle fitting are presented and evaluated in Monte Carlo simulations. There are error-in-variables present and thus, geometric fitting is used. The objects can have parts that are subject to articulation. A modular least squares method with outlier rejection, that can handle articulated objects, is proposed. This method falls within the iterative closest point framework. Recognition when several similar models are available is discussed. The recognition method is applied in a query-based multi-sensor system. The system covers the process from sensor data to the user interface, i.e., from low level image processing to high level situation analysis. In object detection and recognition based on laser radar data, the range value’s accuracy is important. A general direct-detection laser radar system applicable for hard-target measurements is modeled. Three time-of-flight estimation algorithms are analyzed; peak detection, constant fraction detection, and matched filter. The statistical distribution of uncertainties in time-of-flight range estimations is determined. The detection performance for various shape conditions and signal-tonoise ratios are analyzed. Those results are used to model the properties of the range estimation error. The detector’s performances are compared with the Cramér-Rao lower bound. The performance of a tool for synthetic generation of scanning laser radar data is evaluated. In the measurement system model, it is possible to add several design parameters, which makes it possible to test an estimation scheme under different types of system design. A parametric method, based on measurement error regression, that estimates an object’s size and orientation is described. Validations of both the measurement system model and the measurement error model, with respect to the Cramér-Rao lower bound, are presented.

There is an understanding of surface photovoltage (SPV) behavior for GaN, yet little is known about the SPV behavior for AlGaN. In this work, a Kelvin probe was used to measure the SPV for p-type AlGaN. Very slow SPV transients were found in AlGaN, which could not be explained with a simple thermionic model. A possible explanation of this behavior is the segregation of impurities to the surface, which causes significant reduction of the depletion region width (down to 2 nm), with carrier tunneling and hopping becoming the dominant mechanisms responsible for the SPV transients. To verify this assumption, the near-surface defective region (about 40 nm) has been removed through the ICP-RIE process. After the etching, the SPV transients became fast and increased in magnitude by about 0.6 eV. By using the thermionic model, band bending was estimated to be -1 eV.