[Truncated abstract] The sale of fraudulent South-East Asian ceramics constitutes a large proportion of the illegal artefact and antique trade and threatens to undermine the legitimate international market. The sophistication and skill of forgers has reached a level where, using traditional appraisal by eye and hand, even the most experienced specialist is often unable to distinguish between a genuine and fraudulent piece. In addition, the current scientific method of authentication used by the international antiques and art industry, thermoluminescence (TL) dating, carries severe limitations. The technique has an error margin of +/-20 % and requires the removal of a significant piece of the sample being tested, which decreases both the monetary and cultural value of the artefact. Of more concern, forgers have developed methods which produce false test results and which appear to corroborate false claims for the age of artefacts. Consequently, the use of TL dating for authentication of ancient ceramics, especially those of South-East Asian origin, has now come into serious question. The most suitable method for authenticating ceramics is through provenance establishment. Studies published in the literature have investigated the application of various analytical techniques to provide this information for ceramic wares and have highlighted their potential to be used for provenance establishment. However, the value of each of these techniques is limited rendering them generally unsuitable for practical use in the international antiques and art world to authenticate high-value South-East Asian artefacts. Consequently, there is a desperate need for the development of a robust, accurate and non-destructive method which can be practically applied in the industry to authenticate South-East Asian ceramics. ... Minor variations between spectral profiles of artefacts produced in the same country have also been used to further provenance artefacts to a specific production region or kiln site. The results of analyses have been compiled to form a unique reference database which can be added to in the future and used by experts internationally. Adaptation of the developed sampling and analytical methodologies to allow in-situ sampling of large artefacts using the

Magister Scientiae - MSc (Biotechnology) / Soybean have been listed as a priority commodity crop in South Africa (SA) and provide a good source of protein to the population. Therefore, soybean has been earmarked as an important food security crop and strategies are currently being discussed at governmental level to increase and sustain soybean production. However, the SA landscape poses many challenges to the agricultural sector such as prolong drought periods, flooding, nutrient poor soils, saline soils and heavy metal contaminated soils. Heavy metal (HM) contamination is becoming a serious concern and is aggravated by historical mining in SA. Indeed, SA has established itself as the number one ranked mining country in the world and is frequently mining metals such as chromium, vanadium, gold, zirconium, platinum, and antimony. Prolong rainfall near mining areas leads to acid mine drainage which lowers the soil pH to approximately two. These highly acidic soils will solubilize the metals and cause the metals to leach into river systems as well as the water table leading to increase heavy metal contamination in nearby soil sites. This increase metal content negatively affects seed germination and overall plant development. Nonetheless, plants have evolved numerous internal mechanisms that help them to survive HM toxicity; by either avoiding or tolerating the stress. Two stress-activated pathways that help the plant tolerate stress have attracted much interest i.e. the glyoxalase system and reactive oxygen species (ROS) - antioxidant system as they detoxify methylglyoxal (MG) and ROS. / 2021-08-31

This work deals with the content of iodine in soils, furthermore with obtaining and processing samples from four selected sampling areas, all of which are in the proximity of the Arnoštov settlement in district Prachatice in the foothills of Šumava. The soil samples were obtained from forest, meadow, pasture and fallow soil in 2009 to 2011. The iodine content in the soils was determined by using the spectrophotometric method, which had been optimized for the soil samples. Iodine concentration in lysimeter water was determined by using method inductively coupled plasma - mass spectrometry. The results obtained from each sampling areas were compared with each other and with the results from other areas. Consequently, the iodine concentration results in the soils were compared with the iodine concentration in lysimeter waters. It was found, that the highest iodine content in soils was measured in a sample obtained from Area 1 (meadow), part B in a depth of 16 - 30 cm in June of 2009, namely a content of 8,67 mg of I per kg of dry soil. The lowest content of 1,42 mg of I per kg of soil was found in the area 4 (forest), sample obtained in June of 2010, in the L horizon. By comparing iodine content with iodine concentrations in lysimeter waters, it was concluded that the concentration of iodine in lysimeter waters does not depend on iodine concentrations in soils and that it does not even represent the absolute iodine content in soil, as was determined by comparing the results from Arnoštov with data acquired from Agrovýzkum Rapotín in Jeseníky.

Les nanostructures de semi-conducteurs de faibles dimensions (comme les nanofils(NFs)) sont devenues l'objet de recherches intensives pour explorer de nouveaux phénomènes émergents à l'échelle nanométrique et sonder leur possibilités d’ utilisation dans l'électronique du futur. Parmi les différents nanofils semi-conducteurs, SiC a des propriétés très particulières, comme une large bande interdite, une excellente conductivité thermique, un haut champ électrique de claquage, une stabilité chimique et physique, une haute mobilité des électrons et une haute biocompatibilité.Nous proposons dans cette étude ; d'examiner une nouvelle approche pour fabriquer des nanostructures de SiC par l'approche « top-down ». Cela permet l'élaboration de nanostructures cristallines de SiC de haute qualité monocristalline avec un niveau de dopage contrôlé. Le comportement de nanostructures de SiC gravées a également été étudié en fonction de polytypes et des orientations cristallographiques.Nous avons également étudié les trois principaux sujets de SiC nano-devices pour atteindre une excellente performance. Pour répondre à ces questions, deux types de SiC nanoFET (SiC NFFET et SiC NPFET) ont été fabriqués et caractérisés par l'utilisation de nanofils de SiC et de nanopiliers de SiC préparés respectivement par les méthodes « bottom-up » et « top-down ». / Low dimensional semiconductor nanostructures, such as nanowires (NWs), have become the focus of intensive research for exploring new emergent phenomena at the nanoscale and probing their possible use in future electronics. Among these semiconductor NWs, Silicon Carbide (SiC) has very unique properties, such as wide bandgap, excellent thermal conductivity, chemical and physical stability, high electron mobility and biocompatibility. These factors makes SiC a long standing candidate material to replace silicon in specific electronic device applications operating in extreme conditions or/and harsh environments. SiC nanostructures have been studied extensively and intensively over the last decade not only for their fabrication and characterization, but also for their diverse applications. I have outlined the growth of SiC nanostructures based on different growth methods, a noteworthy feature of their characteristic properties and potential applications in the chapter one. As-grown SiC NWs fabricated by bottom-up method present a high density of structural defects, such as stacking faults. This kind of defect is one of the factors which lead to poor electrical performance (such as weak gate effect and low mobility) of the related devices. Therefore, it is required to develop a high quality of SiC nanostructures with low density of the structural defects using an alternative method, such as top-down process. Main objectives of this thesis are divided into three main parts. The first part of the thesis (Chapter two), we present the simulation results of the electrical transport and thermoelectric properties of SiC NWs. I have investigated the thermoelectric enhancement by studying the complex interplay of the size of NWs, temperature and surface roughness. Our simulation results show that the ZT of C terminated SiC NW (2.05×2.05 nm2) reaches a maximum value of 1.04 at 600K. The second part of the thesis (Chapter there) is devoted to the fabrication of high quality SiC nanostructures with controlled doping level. I have developed a top-down fabrication technique for high quality nanometer scale SiC nanopillars (NPs) using inductively coupled plasma etching. The etching behavior of SiC NPs has also been studied depending on polytypes and crystallographic orientations. Under the optimal etching conditions using a large circular mask pattern with 370 nm diameter, the obtained 4H-SiC nanopillars exhibit high anisotropy features (6.4) with a large etch depth (>7μm). A hexagonal, rhombus and triangle based pillar structures have been obtained using α-SiC (0001), 3C-SiC (001) and 3C-SiC (111) substrates, respectively. The last part of the thesis (Chapter four) is dedicated to the design and the electrical characterization of SiC nanodevices. To investigate the electrical properties of SiC nanostructures, two different kinds of SiC nanoFETs (SiC NWFET and SiC NPFET) have been fabricated by using SiC NWs and SiC NPs prepared via bottom-up method and top-down methods, respectively. In case of SiC NWFET, low resistivity ohmic contacts (378 kΩ) have been obtained after the annealing at 650 °C. Ni silicide intrusion into the SiC NW channel has been observed the annealing at 700 °C. This temperature is compared to one of other group IV materials. In case of SiC NPFET, two different types of NPFET (3C-SiC (001) and 4H-SiC (0001)) have been fabricated using our SiC nanopillars, obtained by top-down approach. The estimated values of the field-effect carrier mobility are 232.7 cm2⋅V-1s-1 for 3C-SiC (001) NPFET (#2) and 53.6 cm2⋅V-1s-1 for 4H-SiC (0001) NPFET, which is higher than the best values reported in the literature (15.9 cm2⋅V-1s-1).

A espectrometria de massas com plasma acoplado indutivamente com simples quadrupolo (q-ICP-MS) e cela de reação dinâmica (DRC-ICP-MS) foi avaliada para determinação seqüencial de Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V e Zn em sangue. Para as análises, amostras de sangue (200 µL) foram diluídas 1:50 em uma solução contendo 0,01% v/v Triton® X-100 e 0,5% v/v de ácido nítrico. As calibrações foram realizadas com ajuste de matriz, utilizando sangue ovino. Como gás de reação utilizou-se a NH3. O uso do DRC foi fundamental para a determinação de Cr e V. A escolha da melhor vazão do gás e a otimização do parâmetro de rejeição (RPq) foram estudadas utilizando sangue base ovino ou uma solução de matriz sintética (SMS), de acordo com a concentração do analito no sangue base. Os limites de detecção (3s/coeficiente angular) para determinação de 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl e 66Zn em sangue por q-ICP-MS foram 0,223; 0,014; 0,003; 0,011; 0,304; 0,009; 0,009; 0,003; 0,001; 0,005; 0,264; 0,006; 0,010; 0,001; 0,834 µg L-1, respectivamente, e para determinação de 52Cr e 51V em sangue por DRC-ICP-MS utilizando o gás de reação amônia os limites de detecção foram de 0,007 e 0,006 µg L-1. Para a determinação de 27Al, 63Cu, 65Cu, 64Zn e 66Zn em sangue por q-ICP-MS através da calibração com ajuste de matriz com SMS os limites de detecção foram 0,083; 0,090; 0,055; 0,281; 0,306 µg L-1, respectivamente. A validação do método foi realizada por meio da análise de materiais de referência do INSP-Canadá, NYSDOH-EUA e Seronorm-Noruega. / The use of inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) was evaluated for sequential determination of Al, As, Cd, Co, Cu, Cr, Mn, Mo, Pb, Pt, Sb, Se, Sn, Te, Tl, V and Zn in whole blood by q-ICP-MS or DRC-ICP-MS methods. Prior to analysis, sample (200 µL) were diluted 1:50 v/v in a solution containing 0.01% v/v Triton® X-100 and 0.5% v/v nitric acid. For all elements, except Cr and V, the instrument was operated in q-ICP-MS mode. The use of DRC was only mandatory for Cr and V. NH3 was evaluated as the reaction gas. Selection of best flow rate of reaction gas and optimization of the quadrupole dynamic bandpass rejection parameter (RPq) were carried out, using base whole blood or synthetic matrix solution (SMS), in according with element base blood concentration. Method detection limits (3s/slope) for 27Al, 75As, 111Cd, 59Co, 63Cu, 55Mn, 98Mo, 208Pb, 195Pt, 123Sb, 82Se, 120Sn, 130Te, 205Tl and 66Zn determination in whole blood by q-ICP-MS against matrix matching calibration (base blood) were 0.223; 0.014; 0.003; 0.011; 0.304; 0.009; 0.009; 0.003; 0.001; 0.005; 0.264; 0.006; 0.010; 0.001; 0.834 µg L-1, respectively, and for 52Cr and 51V determination in whole blood by DRC-ICP-MS the detection limits were 0.007 e 0.006 µg L-1. For 27Al, 63Cu, 65Cu, 64Zn and 66Zn determination by q-ICP-MS through matrix matching calibration with SMS the detection limits were 0.083; 0.090; 0.055; 0.281; 0.306 µg L-1, respectively. Method validation was accomplished by the analysis of reference materials from INSP-Canada, NYSDOH-USA, Seronorm-Norway.

Ce travail s'inscrit dans une démarche visant à quantifier l'impact de la diagenèse sur les ratios élémentaires Sr/Ca, Mg/Ca et U/Ca caractéristiques de l'exosquelette (aragonite biogénique) de coraux Porites sp. Ces ratios élémentaires sont très utilisés comme paléo thermomètres en paléo climatologie tropicale pour reconstruire les paléo variables environnementales comme la température de surface de l'océan. On considère dans un premier temps un corail moderne prélevé in vivo et un corail fossile daté au 14C de l'Holocène Moyen (5445 ans BP). Les deux coraux ne présentent aucune trace d'altération diagénétique. On mesure Sr/Ca, Mg/Ca, U/Ca dans l'exosquelette par spectrométrie de masse couplée à un plasma inductif et à la microsonde de Castaing pour Sr/Ca. Les températures de l'océan du temps du vivant des coraux sont alors reconstruites à partir de la géochimie des échantillons et validées. L'approche est ensuite étendue à des coraux pléistocènes (~125000 ans BP) altérés par la diagénèse e.g., apparition de calcite au détriment de l'aragonite initiale sous l'action de l'eau douce percolant dans les récifs. Cette calcitisation affecte les ratios Sr/Ca et Mg/Ca originels et est susceptible d'entacher les reconstructions d'un biais qu'il est important de bien connaître. En s'appuyant sur la spectrométrie Raman et la microanalyse X, on confirme les tendances qualitatives rapportées dans la littérature sur l'impact de la calcite sur les proxies du climat : la présence de calcite diminue (resp. rehausse) le ratio Sr/Ca (resp. Mg/Ca) créant donc des artéfacts chauds dans les températures reconstruites. / This work is part of an approach aimed at quantifying the impact of diagenesis upon the Sr/Ca, Mg/Ca and U/Ca elemental ratios that typify the exoskeleton (biogenic aragonite) of Porites sp corals. These elemental ratios are indeed routinely used as paleothermometers in tropical paleoclimatology in order to reconstruct environmental paleovariables such as the Sea Surface Temperature (SST). In a first step, we analyze a modern coral collected in vivo and a fossil coral dated by 14C to mid-Holocene (5545 year BP). Both corals are in pristine state. The Sr/Ca, Mg/Ca and U/Ca ratios are measured by inductively coupled plasma mass spectrometry (ICP-MS) and with a Castaing microprobe for Sr/Ca. The SSTs at the time when the corals were alive are reconstructed from the geochemistry of the samples and validated against in situ measurements / previous work in the same area. Next, the approach is extended to Pleistocene fossil corals (~125000 year BP) that have been altered by diagenesis e.g., calcitization of the samples to the detriment of the original aragonite due to the fresh water that percolates through the coral reefs. Calcitization alters the original Sr/Ca and Mg/Ca. The reconstructed SSTs can therefore include nontrivial biases whose magnitude must be evaluated. Relying on Raman spectrometry, we confirm published qualitative trends on the impact of calcite upon the climate proxies : calcite lowers (resp. increases) the Sr/Ca (resp. Mg/Ca) ratio leading therefore to warm artifacts in the reconstructed SSTs.

This thesis investigates the chemistry of 25 ascidian species collected from Algoa Bay, South Africa with a concerted focus on metal accumulation by these ascidians and the possible interaction of these metals with ascidian metabolites. Chapter 2 details the screening techniques employed to establish the presence of nitrogenous metabolites (1H- 15N HMBC), hyper-accumulated metal ions (ICP-MS) and potential metal ion/ ascidian metabolite complexes (LC-ICP-MS/ESI-MS). Unfortunately, exhaustive attempts to detect intact metal ion/ascidian metabolite complexes through the use of liquid chromatography with parallel inductively coupled plasma mass spectrometry/electrospray mass spectrometry (LC-ICPMS/ ESI-MS) were unsuccessful. However, the LC-ICP-MS/ESI-MS data obtained for the crude organic extracts of six of the Algoa Bay ascidian species, Distaplia skoogi, Aplidium monile, Aplidium sp., Didemnum sp., Leptoclindines sp. and Polycitor sp. enabled identification of a number of ten halogenated metabolites, namely the indoles 2.28-2.30, and the tyramine and tyrosine derivatives (2.31-2.33, 2.41, 2.43, 2.44 and 2.46), within the ascidian extracts. This study confirmed that LC-ICP-MS/ESI-MS is a powerful tool for the dereplication of halogenated metabolites in complex mixtures especially where these compounds are present in very small amounts. This study is also the first report of these compounds (eight of which are known) in African ascidians. Compounds 2.32 and 2.46 have not been reported before from a marine source. Compounds 2.28-2.30 and 2.33 were present in sufficient amounts in the respective ascidian extracts to allow their isolation and structure elucidation using standard spectroscopic techniques Chapter 3 explores the ability of ascidians to accumulate a wide range of metal ions at concentrations which are often orders of magnitude higher than those of the surrounding sea water. Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the total ion concentrations of 24 metals in 25 Algoa Bay ascidian species. To the best of our knowledge this is the largest and most extensive investigation of metal concentrations in a group of different ascidians occurring in the same area. Hypotheisizing that the metal ion concentrations for each ascidian specimen screened may represent a unique fingerprint for each specimen principal component analysis (PCA) was used in an attempt to establish whether there were spatial, temporal or phylogenetic relationships associated with the metal concentration fingerprints of the ascidians that formed part of this study. The PCA results showed that there were no statistically significant relationships between ascidian metal ion concentrations and either the collection year or the collection site of the ascidians. However, species from the family Didemnidae provided the clearest statistical evidence supporting a phylogenetic relationship between these ascidians and their hyperaccumulated metal ion profiles. Furthermore, these results suggested that ascidian species are indeed actively concentrating metal ions from the surrounding sea water and are not simply sinks for passively accumulated metal ions. Interestingly, the concentration of vanadium in the set of ascidians studied did not appear to correlate with any of the other metals accumulated by these ascidians suggesting that there is possibly a unique method employed for the accumulation of vanadium by ascidians. Chapter 4 investigated this possibility further after the nucleosides 4.10, 4.11, 4.13, 4.15, 4.17 and 4.40 were isolated from the vanadium accumulating ascidian Aplidium monile. Studies into the interactions between nucleosides and vanadyl are unfortunately rare and usually qualitative in nature with limited information provided about the stability or structures of the complexes formed. The vanadyl accumulating aplousobranch ascidians e.g. Aplidium monile dominated our study of Algoa Bay ascidians therefore providing us with the rationale to investigate the relatively little studied binding ability and stability of vandyl-nucleoside complexes. Potentiometric studies were conducted to determine the stability constants of complexes formed between the oxovanadium ion vanadyl (VO2+) and the commercially available nucleosides 4.10-4.14. The data afforded by this analysis clearly confirmed the complexity of the vanadyl/nucleoside complexation and suggested that guanosine (4.12) formed the most stable complex with oxovanadium ions. We were also able to establish a third protonation constant for the hydroxyl moiety in 4.12 with a logK 8.87 which has not been previously reported. Finally, Chapter 5 revisited the cytoxicity two Algoa Bay ascidians, Clavelina sp. and Atriolum marinense the extracts from which produced promising bioactivity results in previous studies against oesophageal cancer cells. The HP-20 fractionated extracts of Clavelina sp. and Atriolum marinense proved to be similalrly cytotoxic to breast cancer cells. With the exception for the 100% acetone(aq)fractions the NMR data for both species suggested that most active non polar fractions were dominated by what appeared to be structurally unremarkable fatty acid glycerides and as such were not pursued further. Purification of the 100% acetone(aq)fraction of A. marinense resulted in the isolation of a styrene trimer, 5.1, common to both ascidian extracts. The NMR simulation software WIN-DAISY was employed to confirm the structure of 5.1. Attempts to establish if 5.1 was an isolation artefact or a product of marine pollution were inconclusive

Tato diplomová práce se zabývá problematikou plazmového nanášení bioaktivních keramických povlaků hydroxylapatitu s využitím technologie radio-frekvenčně buzeného indukčně vázaného plazmatu. Cílem bylo optimalizovat proces a nanést kompaktní hydroxylapatitové povlaky na substráty z titanové slitiny Ti6Al4V. Nanesené vzorky byly následně podrobeny analýzám povrchové drsnosti, mikrostruktury a fázového složení. Ze získaných výsledků byly vyvozeny závěry, které byly srovnány s dalšími odbornými pracemi zabývajícími se příbuznou problematikou.

The aim of diploma thesis is occurrence of toxic and essential elements in vegetables and fruit, especially in fruity baby food. The diploma thesis also dedicates processing of vegetables and fruit for production of baby food. Attention is direct to monitoring of baby food quality in the analytical aspects and also to legislative that is in this area. Samples for analysis are prepared using microwave mineralization and ICP-MS for detection. This is described in the experimental part of the diploma thesis.

The aim of this study is to determine the content of selected metals (As, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Se, Sn, Sr, Pb, V, Zn) in samples of leaves and grapes produced by ecologic agriculture and compare to results with leaves and grapes produced by integrated agriculture. The measured results used to assess the impact of agricultural technology on the quality of vines and grapes. The amount of elements was analysed using inductively coupled plasma mass spectrometry after previous digestion of sapmles using microwaves. Concentrations of elements in leaves and grapes from organic and integrated farming did not differ significantly only in the case of copper concentrations were measured higher concentrations in samples from organic farming. This difference is probably caused by different doses of authorized protective equipment based on copper in the organic and integrated farming.