The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for µXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for µXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for µXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Le soufre est présent dans les systèmes pétroliers à la fois sous forme organique et minérale. Il est impliqué dans de nombreuses réactions d'oxydoréduction qui affectent la qualité des huiles (par des réactions de sulfuration ou de désulfuration) et du gaz naturel (par la génération de H2S en contexte de réduction thermochimique des sulfates), ainsi que la porosité des roches réservoirs (par la dissolution de l'anhydrite ou la précipitation de soufre élémentaire ou de pyrobitume). Ces réactions sont gouvernées par la température (et dans une moindre mesure la pression), les conditions d'oxydoréduction et la composition chimique globale du système. La thèse comporte trois parties : (1) une étude thermodynamique des réactions chimiques impliquant le soufre dans les bassins sédimentaires ; (2) une étude expérimentale des réactions de sulfuration et de désulfuration des composés organiques ainsi que de la réduction thermochimique des sulfates; (3) une étude pétrographique et d'inclusions fluides sur des échantillons d'un réservoir carbonaté du bassin Pré-Caspien / Sulfur occurs in petroleum systems as both organic compounds and minerals as well as under different oxidation states. It is involved in a number of redox reactions which may impact the quality of crude oils (through sulfurization or desulfurization reactions) and natural gas (through the generation of H2S during thermochemical sulfate reduction), as well as the petrophysical properties of reservoir rocks (through the dissolution of anhydrite and the precipitation of elemental sulfur and pyrobitumen). These reactions are controlled by temperature (and to a lesser extent pressure), the redox conditions, and the overall chemical composition of the system representing the petroleum reservoir. The thesis consists of three parts: (1) a thermodynamic study of chemical reactions involving sulfur which occur in sedimentary basins; (2) an experimental simulation of sulfurization and desulfurization reactions of organic compounds, as well as of thermochemical sulfate reduction; and (3) a petrographic and fluid inclusion study of carbonate rock samples from a sulfur-rich hydrocarbon reservoir of the northern Caspian Sea

Le rôle des particules de poussières comporte une grande incertitude des modèles climatiques, alors qu’ils constituent une grande influence sur le bilan radiatif global et l’apport en nutriments pour divers écosystèmes. Ce projet de recherche permet d’évaluer la composition de particules de poussières en Namibie, en fonction de trois vallées constituées de rivières éphémères en région côtière. La sélection des vallées s’est basée sur leur fréquence importante d’émissivité, observée par image satellitaire. En 2017, des mesures en temps réel ont été prises ainsi que des échantillons de surface, dont l’analyse des sols et filtres s’est effectuée en laboratoire. Les propriétés des sols, c’est-à-dire la distribution de la taille, de la minéralogie et composition élémentaire, seront traitées dans ce mémoire. Le but étant d’évaluer les sources d’émission et le potentiel de transport des poussières, par une meilleure connaissance de l’interaction des sols en relation avec les particules transportées par le vent. Il a été observé que le transect de la vallée du Huab possède une taille de particule plus fine en raison de divers facteurs, dont une rivière éphémère plus active. Le transect de la vallée de Omaruru quant à lui possède une composition en minéraux plus variée, dont une petite concentration en éléments lourds. Pour le transect de la vallée du Kuiseb, en raison du site d’échantillonnage et une forte influence de la mer de sable, des particules plus près de la fraction du sable ont été identifiés en plus grande quantité par rapport aux autres sites. Il est donc suggéré que, malgré une grande concentration de particules fines pour le Huab, son processus d’émission demande une fréquence de vent et un environnement propice à l’émission des particules par suspension. Contrairement à certaines vallées telles que le Hoanib ou le Hunkab, le Kuiseb et le Omaruru semblent influencés par la désintégration des argiles lors de la saltation et le bombardement de particules plus grossières. / Dust particles are primarily known to modify radiative forcing as well as nutrient contribution of coastal regions, but account for an important part of climatic model uncertainties. This project evaluates the characteristics of dust particles in river valleys of Namibia within three valleys of the coastal region. The selection of sites was determined by their frequency of emissions observed by satellite imagery. In 2017, fieldwork measures were taken as well as surfaces samples, which were analysed for their particle size distribution, their mineralogy as well as their elemental composition. The results presented in this thesis look at potential transport emission, to better understand interactions between soil and airborne particles. It was observed that the transect of the Huab valley presents the finest distribution of particles, primarily because of its active river providing finer particles to dust sources. The transect of the Omaruru has a more varied particle size distribution relative to the Huab valley and the Kuiseb, but has some coarser particles present in small quantities. Because of its location, the transect of the Kuiseb is strongly influenced by the Namib sand sea, which is reflected in its particle size distribution. Because of existing literature about dust particles, it is possible to suggest that the Huab valley needs stronger winds to be able to be emissive as it erodes predominantly through a modified direct suspension mechanism. Saltation and bombardment seem to play a more important role in the Kuiseb valley than the other valleys along the coast, such as the Hoanib or the Hunkab, because of its important composition of sand and geomorphology proprieties.

This diploma thesis deals with the influence of dry hopping on selected analytical and sensory properties of beer. The effect of dry hopping was observed using Czech hop varieties Kazbek and Uran, which were added to the wort during the main fermentation phase in doses of 3 and 6 gdm-3. The contact time of hops with wort was 3, 6 and 9 days. The experimental part describes the technology of preparation of the reference beer, in which dry hopping were subsequently performed. A parallel measurement was performed on each sample. In terms of the basic parameters of beer, the effect of dry hopping, especially its length, on the ethanol content was observed. With a longer period of dry hopping, the concentration of ethanol in beer increased. The higher alcohol concentration was also associated with a decrease in the apparent extract. In terms of color and pH of beer, the effect of dry hopping has not been proven. Elemental analysis performed by optical emission spectrometry with inductively coupled plasma revealed an increase in the concentration of calcium, magnesium, and iron due to dry hopping. No statistically significant difference was observed for manganese and barium compared to the reference. In terms of bitterness, a significant increase was identified in dry hopped beers compared to the reference, the value being dependent on the dose of hops used. The effect of the hop variety has not been proved. Concentrations of organic acids determined by ion-exchange chromatography with a conductivity detector were affected by dry hopping only in the case of lactic acid and acetic acid. An increase in lactic acid was observed compared to the reference, also related to the degree of fermentation. While in the acetic acid content the hop samples showed a lower concentration than the reference sample. The concentrations of myrcene, humulene and geraniol were determined by gas chromatography with a mass detector. These are volatile components of hop essential oils. Dry hopped samples recorded significantly higher concentrations of all aromatic substances compared to the reference. In terms of hop time, the highest concentrations were shown by samples hopped for three days. The results of the sensory analysis show that the overall best rated sample is a sample hopped with the Kazbek variety with a dose of 3 gdm-3 for three days. Beer which was dry hopped for the shortest time also showed the lowest intensity of bitterness, which was perceived positively.

Elemental carbon (EC), a product of incomplete combustion of fossil fuels and biomass, contributes to climate warming and poor air quality. In urban areas, diesel fuel trucks are the main source of EC emissions from mobile sources. After emission, EC is deposited to receptor surfaces via two main pathways: precipitation (wet deposition) and directly as particles (dry deposition). Urban trees may play an important role in removing EC from the atmosphere by intercepting and delivering it directly to the soil. The goal of this research was to quantify the magnitude of EC retention in leaf waxes (in-wax EC) and EC fluxes to the soil via leaf litterfall in the City of Denton, Texas. Denton is a rapidly growing urban location in the Dallas-Fort Worth metropolitan area. A foliar extraction technique was used to determine EC retention in leaf waxes. Foliar samples were collected monthly, from April through July, from pairs of Quercus stellata (post oak, n=10) and Quercus virginiana (live oak, n = 10) trees. Samples were rinsed with water and chloroform in a two-step process to determine EC retained in leaf waxes. A Sunset OC/EC aerosol analyzer was utilized to analyze the EC content of extracts filtered onto quartz-fiber filters. From April through July, leaf litter was collected bi-weekly under 35 trees (20 post oak, 15 live oak), and oven dried to determine dry weight. EC retained by tree canopies was estimated by multiplying in-wax EC by canopy leaf area index, while EC flux to soil was estimated by multiplying in-wax EC by leaf litterfall mass. This study shows that through retention of EC in leaf waxes, urban tree canopies represent important short-term sinks for soot in urban areas.

This paper builds on previous research of aminoclay complexes in undergraduate studies. Theoretical part deals with study of current problems of aminoclay complexes with bioactive substances and the choice of substances for complexing with aminoclay. The experimental part consists of preparation of aminoclay complexes with selected bioactive agents at various concentrations. Verification of binding of bioactive agents to the aminoclay matrix was performed by Elemental Analysis (EA) and Fourier-transform infrared spectroscopy (FT-IR). For finding of the bound amount of bioactive substance were used the Ultra Performance Liquid Chromatography (UPLC®) and analysis of the cytotoxic properties of the formed complexes by used by the MTT assay. The main motivation of this study is to create new complexes with improved characteristics that would replace existing forms of substances used in pharmaceutical and biomedical applications.

This diploma thesis researches coffee authenticity problematice, mainly focusing on the authenticity of geographic origin. In the theoretical part of this work, botanical classification is described as well as production technology and processes. The work also includes chemical composition of coffee, describing the major components and changes during production phases. It describes major production areas of the world, in terms of general description and brief history. Problematics with coffee fraud and its identification are also described. Theoretical part also includes general geological description of 17 studied coffee growing regions. Experimental part is devoted to trace amount analysis of selected elements and volatile compounds. The element analysis was conducted using mass spectrometry or optical emission spectrometry, volatile compounds were determined using gas chromatography combined with mass spectrometry detection. Results were statistically described and analyzed, resulting in several discrimination models based on geographic origin.

The aim of this diploma thesis is determination of selected metals in unconventional fruit species, specifically in cornelian cherry (Cornus mas), sea buckthorn (Hippophae rhamnoides) and medlar (Mespilus germanica).There is informationabout 16 analysed metals – As, B, Be, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Se, Sn, Pb, V, Zn. There are described analytical techniques for elemental analysis and methods for destruction biological material. Samples for analysis are prepared by using microwave mineralization and ICP-MS for detection. This is described in the experimental part of the diploma thesis. Analysis confirmed that unconventional fruits are rich sources of trace elements.

The aim of this thesis is to calculate the stoichiometric balance of boilers and boiler fuel for normal monture to 60%. Determine the monture, content depending on the conditions of the fuel in the combustion chamber and conditions of combustion. Experimental analysis of the current state of the boiler ZKG measurements using this device and propose modifications and solutions.

MSc (Chemistry) / Department of Chemistry / Increasing health and environmental concern about the effects of most toxic heavy metals emitted from cement plants in developing countries, which are going through rapid development, has led to this study. Cement industry in South Africa has been the primary industry over the years contributing immensely to infrastructure development and economic growth. Cement has been used to build many large cities, industries, homes, bridges and shopping malls around the country and still continue to be used by constructors. At this point, there has been no other substitute for cement and it will continue to be produced for decades to come. Unfortunately, this industry is now known to be amongst the major environmental polluters. Less has been done to address the adverse effects that comes with the production of cement, especially in the developing countries where there is huge demand for cement. This study focusses on dust emanating from production processes especially cement manufacturing from rotary kiln stage during production of cement and cement bricks. The production of cement and cement bricks generate dust, which is distributed over large areas of the environment. In South Africa, there are a number of factories in operation without proper planning of pollution prevention and compliance to environmental legislature. Since the production of cement is associated with the release of dust containing heavy metals, the dust is atmospherically deposited on the land, water surfaces and residential areas. The soil, street pavements, wetlands and water surfaces have become the sinks of heavy metals. Heavy metals that are being deposited include arsenic, cadmium, chromium, manganese, cobalt, copper, barium, antimony, selenium, vanadium, nickel and lead. Such metals pose health threat to the animals, plants and human beings living around the cement factories. These metals can easily be leached out from the soil and washed to the water bodies causing water pollution. Old processing techniques have been found to be inefficient to prevent emission of dust to the atmosphere. Hence, the emission of the toxic heavy metals to the environment was uncontrollable. Since cement is used to produce cement bricks, the whole process is subjected to heavy metals being discharged with dust from the factory to the surrounding environment. Four papers (I, II, III and V) were written to assess the level of heavy metals. In paper I, water and plants samples (Bidens Pilosa, Phragimites Australis and Xanthium Strumarium) were collected in the Mvudi River nearby a cement factory. Sampling was done before, within and after the wetland. Samples were digested with nitric acid for analysis. The concentration of zinc, chromium and lead were determined in the samples using a graphite furnace atomic absorption spectromentry. Results showed that the concentrations of zinc, chromium and lead were above the permissible limits in different parts of the plants analysed and water. The pH of water samples were below the threshold recommended by Department of water affairs and forestry (DWAF) and World health organisation (WHO). In paper II, seven soils at different distance, seven soils below soil surface at seven different layers and a bulk were sampled nearest to the cement brick making factory. Bulk sample was separated into five particle sizes (2 - 3 mm, 1 - 2 mm, 0.5 - 1 mm, 0.5 mm). Five sediments samples were also collected before, within and after the wetland along Mvudi river. Modified three step BCR sequential extraction was applied to the 23 samples in order to obtain the metal distribution in the samples. Heavy metal concentrations of nickel and chromium were determined using graphite atomic absorption spectrometry. Results showed that the levels of nickel and chromium exceeded the permissible limits recommended by WHO. Elevated concentrations Ni and Cr in soil and sediments also showed that the cement brick making factory is the main source of pollution in the area. To assess the contribution of cement dust to heavy metal pollution from the cement plants to the surrounding environment, two studies were carried out in the vicinity of two cement plants one in Thabazimbi and the other in Pretoria. Two papers (III and IV) were written from the studies and were summarised as follows: In paper III, dust samples were collected along the road leading to and passing by the cement plant in Thabazimbi, South Africa. The samples were collected using a brush and pan into sampling bags. After sampling dust samples were sieved into three particle size fractions (PM125, PM75, and PM32). A bulk and five samples were collected beneath the soil at different depth for depth analysis nearest to the cement plant. Water samples were collected along the Crocodile River before and after the cement plant site. The samples were digested using aqua ragia and extracted using Modified BCR sequential extraction. The samples were analysed using inductive coupled plasma optical emission spectrometry (ICP-OES) for concentration of platinum group metals and x-ray fluorescence for elementary analysis (XRF). Analysis of samples included characterisation of the dust samples using x-ray diffraction (XRD). The vi concentrations were also compared to that of the control study (blank) area to find out if the metals were discharged from the cement factories of interest. In paper IV, street dust samples were collected randomly on the paved surfaces, on the streets and accessible residential and roadsides on locations close to the cement plant in Pretoria. Some samples were collected along the road leading to the gate of the factory and also on the road near the cement plant. The samples were collected into sampling bags using a brush and pan. After sampling dust samples were sieved into three particle size fractions (PM125, PM75 and PM32). A bulk and five samples were collected beneath the soil at different depth for depth analysis nearest to the cement plant. Water samples were collected along the Apies River before and after the cement plant. All samples were kept in a cooler box with ice bags to keep them in good condition. The samples were digested using aqua ragia and extracted using Modified BCR sequential extraction. Results were used to establish spatial distribution of the heavy metals around the urban streets. The samples were analysed using ICP-OES for concentration of heavy metals and XRF. Analysis of samples included characterisation of the dust samples using XRD. The concentrations were also compared to that of the control study (blank) area to find out if the metals were discharged from the cement factories of interest. In paper V, seven different vegetables (spinach/Spinacia oleracea, Chinese cabbage/Brassica rapa, onion/Allium cepa, beetroot/Beta vulgaris, sweet potatoes/Ipomoea batatas, tomatoes/ Lycopersicon esculentum and cabbage/Brassica pekinensis), fruits (bananas/Musa acuminate) and their soils taken after uprooting them were sampled in farming area close to Thohoyandou town and the cement factory. The concentrations of cadmium, nickel and manganese were measured using the graphite atomic absorption spectrometry (GFAAS). Cadmium, nickel and manganese levels were found above permissible limits proposed by Food agricultural organisation (FAO) and WHO in edible parts of vegetables, fruits and soils and hence, may pose a health risk to consumers. Similarly the results from XRF also showed high concentration of the heavy metals in soil analysed. The aim of this project is to determine the levels of toxic heavy metals carried with dust emanating from cement factories. This assessment is meant to identify and highlight the levels of heavy metals in areas that are close to cement factories. The study will develop a database of heavy metals in affected areas and the pollution impact to the affected environments. / NRF