Les microscopes en champ proche permettent d'obtenir la topographie d'un échantillon avec une résolution pouvant atteindre la résolution atomique. Ces techniques permettent également d'accéder à certaines propriétés locales de la surface telles que le potentiel, l'élasticité, la densité d'états... Ces spectroscopies locales sont de type 'contraste' et ne permettent pas de dresser la cartographie chimique de la surface sans connaissance a priori des éléments qui la composent. Les spectroscopies de rayons-X sont des méthodes de caractérisation puissantes qui permettent de déterminer la composition et la structure élémentaire de l'échantillon avec une précision inférieure à l'Ångström. La résolution latérale est essentiellement limitée par la taille du faisceau primaire, couramment de plusieurs μm². Deux voies sont possibles pour l'améliorer: - réduire l'étendue du faisceau primaire excitateur; - limiter la collecte du rayonnement émis à une portion du volume excité, tout en approchant le détecteur au maximum pour garder un rapport signal/bruit suffisant. C'est cette deuxième option que nous avons choisi de développer. Pour cela nous avons collecté localement la luminescence visible issue de l'échantillon par la pointe-sonde d'un microscope à force de cisaillement, constituée d'une fibre optique effilée de faible ouverture. Cette technique a été utilisée pour caractériser des échantillons semiconducteurs micro- et nano-structurés afin d'en obtenir simultanément la topographie et la cartographie de luminescence locale. Ces résultats ont été obtenus non seulement sur une ligne synchrotron mais également à l'aide d'une microsource de laboratoire équipée d'une lentille polycapillaire. Afin de pouvoir étendre ce concept à d'autres types de matériaux, la faisabilité de la collecte de la fluorescence X locale a été évaluée avec la microsource. Pour cela la fluorescence X émise par un échantillon de cobalt a été collectée par un capillaire cylindrique équipant un détecteur EDX. L'influence du diamètre du capillaire sur le niveau de signal a été mesurée. Une simulation numérique a été développée afin d'estimer le niveau de signal obtenu en utilisant un capillaire de 1 μm de diamètre et d'optimiser la géométrie du système. En couplant la microscopie en champ proche et l'analyse XRF, à la lumière de ces résultats, il sera possible d'atteindre 100 nm de résolution latérale en environnement synchrotron et moins de 1 μm à l'aide d'une source de laboratoire. Il serait alors possible de sélectionner un objet particulier sur une surface et d'en faire l'analyse élémentaire.

L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l'arsenic geogénique et anthropogénique dans l'environnement.La contamination à l'arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d'écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l'appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement.

In the spring of 2018, a prospection and subsequent research excavation of a previously unstudied area related to the rampart of the Viking age town of Birka, Sweden, was undertaken by students and professors from the archaeological science department affiliated with Stockholm University.The purpose of this paper is to examine and categorise the various excavated finds, the ensuing conservation and preservation of the metal objects as well as to investigate the context and possible function of the site regarding the spatial distribution of said finds.The main method used is that of metal conservation with the wet-chemical technique EDTA; a method that was deemed adequate for the treatment of the dry metal finds from the rampart excavation.The conservation and categorisation suggest that the metal posts consist of assorted metal objects, predominately rivets and nails as well as unidentified fragmented objects; the occasional slag fragment was evident. The material category of clay and ceramics contains assorted burnt clay and ceramic sherd fragments, some with decoration. Whetstone (or hone stone) and flint fragments make up most of the stone finds while the category of glass consists of a few bead fragments. The bulk of the osteological material consists of burnt and unburnt animal bones, some with slaughter marks in the form of cuts and hacks. Two human bone fragments were found; a humerus- and cranial fragment.Post holes and charcoal in the context of the rampart suggests the possibility of wooden supports and/or a superimposed wooden structure on the rampart itself that likely burnt at some point in time. The interpretation of the excavated area, based on the distribution of the finds and material categories, is that of a dumping site for discarded town refuse, most likely set against or near a walled construction; the rampart. The dating of the site is based on object similarities as well as stratigraphy and set to; Early to Late Viking Period, c. A.D. 820-1000(1150).The analyses, materials and the stratigraphy of the site together with a contextual analysis of the objects in question furthers the knowledge of Birka’s rampart and will enable future scientific inquiries into this specific rampart as well as similar fortification structures.

In the Circum-Caribbean, long timescale paleoenvironmental records, which are used to establish important baseline data for climatological phenomena such as droughts, floods, and hurricanes, are rare. This project uses geological and geochemical proxies (X-Ray fluorescence core scanning data, grain-size analysis, loss on ignition) from a nine-meter-long sediment core from a coastal karst basin near Haiti’s southwestern peninsula to reconstruct Holocene environmental and climatic changes in a region that is both understudied and highly sensitive to the effects of storms, sea level change, tectonics, and anthropogenic impacts. The chronology of the core is established with 4 AMS dates from terrestrial organic matter and shows continuous sedimentation from ~8500 cal BP to the present, with an abrupt increase in sedimentation rate at ~2900 cal BP. High values of Ti and Ti/Ca are associated with finer sediments in the core and indicate relatively humid conditions at ~6500 cal BP, followed by a gradual drying trend. This is consistent with data from elsewhere in the Caribbean that reflects a southward migration of the ITCZ during the early Holocene. After 2500 cal BP, a series of large and abrupt increases in Ti and Ti/Ca are associated with an influx of finer, terrestrially-derived sediment into the bay due to enhanced discharge from the nearby Baradères River, possibly as a result of short-duration shifts to wetter climate conditions, hurricane-induced precipitation, and/or prehistoric-era human settlement. Variations in silicate input (e.g., K/Ti), marine productivity (e.g., Ca/Ti), and redox conditions (e.g., Mn/Fe) are linked to local climate changes and resulting changes in the depositional environment, while peaks in Rb/Sr and Ti/Ca could be signals for erosion related to events such as hurricanes and/or land use changes. Finally, high values of silt and clay, in conjunction with enhanced organics, Ti, Fe, K and P over the last couple centuries reflect historic-era deforestation and erosion. This study presents an excellent opportunity to further our understanding of the diverse relationships between ecosystem dymanics, climate, and anthropogenic forcings and adds to the growing inventory of paleoclimatological records in the Caribbean, improving the spatial distribution of such studies, and ultimately improving our understanding of the driving forces of both short- and long-term climate variability.

This thesis demonstrates the advantages of using the Energy-dispersive X-ray fluorescence (ED-XRF) system to quantify the mercury content in fiber banks at first. The Monte Carlo N-Particle (MCNP) code was then used to simulate the XRF system model with suitable parameters such as the input X-ray energy level, the detector material, and the environmental factor (water depth). The SNR results of the mercury spectrum when applying different parameters were obtained. Then, the limit of detection (LOD) and limit of quantification (LOQ) based on the SNR approach are considered. Finally, system parameters were determined in order to obtain more accurate qualitative and quantitative analysis results for future environmental measurements.

X-ray fluorescence is a fast, non-destructive method to measure substances. This method can be used to detect elements in an environmental sample for elemental analysis. Commercially available XRF units exists, but their scope of application is limited. In the university lab, a more generalized XRF setup is available. At present, the environmental samples can only be sampled and brought into the laboratory for testing. During the sample transport, some changes may occur in the sample. At the same time, in the laboratory test, the sample parameters in the current environment cannot be obtained in real time. So we consider the design of a battery power supply. At the same time, there are different ways to reduce power consumption. This paper considers usability and reduction of power consumption in various aspects to bring the X-ray source and spectrometer to the environment for element detection. We have to choose the battery to achieve the best length of operating time. The system design includes the selection of a DC/DC converter boost regulator to adjust the battery output to meet the input voltage requirements of the X-ray source and of the X-ray spectrometer.

The thesis Geobiocenologické geological characteristics of selected quarries the Kutná Hora, is related to the antropogenic montainery landscape unites and theeir wider sur-roundings with a special focus on soil environment, tree evolution and succession and their ecophysiology affected by their habitat, environment, soil and bedrock geochem-istry. The thesis describes the geological phenomens and history if mining and uses of select-ed quarries Vlastějovice, Bernartice, Malešova and their surroundings in relation to the studied localities. Furthermore, quarries of Vlastějovice and Bernartice are currently still in operation. The author gives an overview of a number of characteristics of the territory. In the practical part are compared pedological conditions in quarries, with regard to the diversity of soils and their chemical composition in relation to bedrock. Greater emphasis is placed on influencing tree evolution and their ecophysiology in relation to soil, parental bedrock and distribution of elements contained in different soil horizons and trees. Comparison is based on the author's own field investigations and laboratory analyzes of soil chemistry conquered by XRF spectrometry analysis, as well as soil physics and influence to trees by all these mentioned factors. The paper also describes botanical and climatic characteristics of all quarries, forest typology and phytocenology in quarries and surrounding regions. The results are briefly discussed in chapter discussion and results of thesis are ilustrated by graphs, photographs and tables placed in the Annexes to this thesis.

Every investigation technique has its specific advantages: this is the reason why, in modern research, it is common to combine many investigation techniques – especially the non-destructive ones - to achieve deeper structural information about a sample. X-ray diffraction (XRD) and fluorescence (XRF) techniques are useful non-destructive analytical techniques, with applications not only in industrial field and mining but also in environmental control and cultural heritage monitoring and conservation. In the present research, the advantages of a combined approach with XRF and XRD techniques are considered, due to their complementarity, and a new method of combining data is presented, executing the simultaneous computation of the refinement both for XRF and XRD. In this case, instead of the common approach with an iterative refinement, passing from XRF to XRD and vice versa, both XRF and XRD data are processed simultaneously with a combined Rietveld refinement. This innovative approach has been implemented in the program MAUD, combining original XRD algorithm with the XRF module implementation from the GimPy and JGIXA programs, creating comprehensive radiation–matter interaction model, which takes care of both elastic scattering and photoelectric absorption/fluorescence. Moreover, through a plugin-based application container, Eagle-X, specifically developed for this research project, some easy external wizards have been developed using JAVA language for preliminary XRF analysis and model set-up, which will be in the next future integrated into the MAUD current interface. This new approach has been applied to two case studies. The first study was in the cultural heritage field with the analysis of ancient Venetian coins, called sesini, which were never investigated before. These coins were widely used in the Venetian Republic over a time span ranging from the second half of the 16th until the early years of the 17th century. The rationale of the study was to establish a multilayer model that once validated could be used for fully non-destructive characterization of similar items. The approach, applied to 20 samples from different time periods, has given interesting results. First, the actual composition of the copper-based alloy used for these specific types of Venetian coin has been measured for the first time, using a three-layer model, with also direct measurements on the coin cross-section for validating the data obtained. Second, the detailed characterization of the coins provided essential background knowledge for fully non-destructive characterization of the same kind of coins. Third, the data obtained were very interesting from a historical point of view, because the silver depletion, which this research has investigated over the coin series, reflects a political and economic situation in strong evolution for the Venetian Republic in the second half of 16th century. Political and economic competitors and a continuous effort in military confrontations obliged Venice to revise its coin system and values not only for sesini but also for the other silver-based coins, with larger value, in a process called debasement. The second application of the combined approach regarded an industrial application concerning a sintered titanium alloy, Ti6AlV4, that has the widest use (about 45% of the total production), because of good machinability and excellent mechanical properties. This is an alloy which contains the two allotropic forms of Ti, the Ti-alpha, which has compact hexagonal cell, stable at room temperature, and Ti-beta phase, which has a body-centred cubic lattice, stable over 882°C. The presence of the two phases is related to the presence of atomic elements which are alpha- and beta-stabilizers. In this case study six samples, produced with Selective Laser Melting (SLM) technology, with different production parameters, has been considered, and a model based on a surface layer of compact oxide and a bulk with the alloy only has been adopted. The model has evidenced the presence of the TiO2 oxide on the surface, as attended from existing literature, and confirmed the quality of the alloy because for all the samples, the investigated areas report Al e V content inside the ranges required by ASTM and ISO specifications. The analysis has allowed also to investigate the presence of contaminants like copper due to the cutting process by Electrical Discharge Machining (EDM), and to find a correlation between the content of Ti-beta phase inside the samples and the combined presence of iron and silicon, which increases as soon as increase also the two elements. Moreover, the increase of Ti-beta phase is boosted by the contemporary increase in energy density during SLM production process. This is consistent with the fact that higher energy allows a higher localized temperature in SLM process and the equilibrium fraction of beta phase rises at high temperatures. This then leads to a higher fraction of alpha+beta phases at room temperature and, because the cooling rate was the same for all samples, this means a higher fraction of  phase at room temperature. The application of the technique to the two case studies is very productive from the informational point of view, but a critical aspect for a successful application of the technique is the sample. No preparation is virtually needed for analysis but, of course, this is immediately true for industrial components as soon as they are produced, but it is not so true for archaeological artefacts, where the condition of production, history and store conditions are unknown. Corrosion patinas can alter the read of the data, and some care must be taken for analysis, not only because the patinas may not be homogenous, but also because the depth of penetration for XRF and XRD are not the same, respect to the same substrate. The cleaning of the artefacts is not always possible or desired by the owners, so this can at first stage complicate the approach to combined analysis, regarding the model to be adopted in material simulation for data interpretation. In any case, the combined analysis remains a valid approach provided that the user is conscious of the limits in terms of depth of analysis, linked to the analysis tool (X-ray beam, detector, etc...) and to the surface conditions of the sample.

No description available.

<p>As secondary colorectal liver cancer is the most widespread malignancy in patients with colorectal cancer, the main aim of this study is to identify and differentiate between benign and malignant secondary colorectal liver cancer tissue. Low energy X-ray interaction techniques were used. XRF and coherent scattering data were collected for all 24 normal and 24 tumour matched pair tissues. Measurements of these parameters were made using a laboratory experimental set-up comprising a Mo X-ray tube, Si Drift detector and Scintillation (NaI) detector.</p> <p>Twelve elements of interest were statistically explored for normal and tumour samples. Comparing normal and tumour tissues, statistically significant differences have been determined for K, Ca, Cr, Fe, Cu, Zn, Br and Rb. However, for P, S, As and Se, no statistically significant differences have been found.</p> <p>Coherent scatter profiles were collected and fitted for all the samples and three peaks were observed at momentum transfer values: adipose peak: 1.1 nm^-1, fibrous peak: 1.6 nm^-1 and water content peak: 2.2 nm^-1. The Amplitude, FWHM and area under these peaks were statistically analysed. These parameters were found to be significantly higher in secondary colorectal liver tumour compared to surrounding normal liver tissue for both fibrous and water content peaks. However, no significant differences were found for adipose peak parameters.</p> <p>Multivariate analysis was performed using the XRF, coherent scatter and elemental ratios data separately and the accuracy of classification results of 20 unknown samples was found. However when all the variables were combined together, the classification models were improved. This study has shown that the XRF and coherent scatter data of normal and secondary colorectal liver cancer are statistically different and the combination of these variables in multivariate analysis has the potential to be used as a method of distinguishing normal liver tissue from the malignant tumour tissue.</p> / Master of Science (MSc)