The normal operation of the endocrine (hormonal) system can be disrupted by a number of man-made and naturally-occurring chemicals, thereby affecting those physiological processes that are under hormonal control. Such substances are called endocrine disrupting compounds (EDCs). The endocrine disruption issue has alarmed the environmental authorities since the substances involved can hinder hormonal processes causing far-reaching effects on reproduction and development in current and future human and wildlife generations. Effects on some species of fish triggered worldwide concern and initiated a research scheme which is being undertaken by various organisations e.g. United States Environmental Protection Agency (USEPA), United Kingdom Environment Agency (UKEA), Oslo and Paris Commission (OSPAR), Japan Environment Agency (JEA) and World Wildlife Fund (WWF) in order to assess the effects (present and potential), point of generation, levels of contamination and exposure limits. The findings showed that most of the oestrogens are produced by humans and animals and get discharged into river streams mainly through sewage effluents. Fish in particular have been found to be affected the most even when the oestrogenic levels in water are very low. The probability of future European legislation to eliminate hormonally active compounds from wastewaters suggests that new and alternative methods should be developed for their removal. In this work, the adsorption of 17ß-oestradiol (E2) and 17a-ethinyl oestradiol (EE2) onto several granular activated carbons and Hypersol-Macronet hypercrosslinked polymers was investigated by batch experiments after a low level detection system had been developed using Gas Chromatography Mass Spectrometry (GC/MS). Equilibrium experiments were carried out for all adsorbents to quantify the sorption capacity for E2 and EE2. For better assessment of the sorbents performance, their physical properties such as surface area, average pore diameter and micropore volume and chemical structure were characterised by N2 adsorption experiments, scanning electron microscopy (SEM), FTIR spectroscopy, elemental analysis, sodium capacity determination, pH titration, proton binding curves and zeta potential measurements. Adsorption isotherm data were fitted to the Langmuir and Freundlich equations. Activated carbons were found to be preferable to Hypersol-Macronet hypercrosslinked polymers for adsorption purposes. The adsorption of oestrogens appears to be controlled by hydrophobic interactions. Kinetic experiments were performed with different size ranges of adsorbents at different concentrations and the results were analysed by a particle diffusion model. It was found that concentration did not seem to influence the kinetics of the oestrogen sorption whereas the particle size of the adsorbents influenced the adsorption rate of both molecules. The particle diffusion model seemed to fit the data collected for the adsorption rate of 17B-oestradiool onto the adsorbents but gave a poor fit for most of the data collected for 17a-ethinyl oestradiol.

Afin d’identifier les composés responsables de l’arôme du gin, une procédure GC-O-MS se basant sur la fréquence de détection a été développée. Elle a permis de déterminer l’intensité odorante des composés volatils. Leur qualité d’odeur a pu être définie par le développement d’une roue des odeurs utilisée pour catégoriser les descripteurs obtenus. Cette approche nous a dans un premier temps permis d’identifier les composés potentiellement importants pour l’arôme du gin. L’origine de ces composés a ensuite été déterminée par l’étude de la fraction volatile de différents « botanicals » appartenant à la recette du gin. Cette stratégie nous a permis de constater que les baies de genièvre et les graines de coriandre étaient les principaux contributeurs en composés volatils d’impact. A l’opposé, les racines d’iris, la réglisse et les amandes ont semblé n’en apporter aucun. Nous avons donc distingué les « botanicals majeurs » et les « botanicals mineurs » selon leurs apports en composés volatils d’impact. Cette hypothèse a été globalement validée par différents tests sensoriels sur des mélanges de distillats. Enfin, une stratégie de recombinaison a été proposée dans le but de valider une sélection des composés d’impact. Une approche multicritères (intensité odorante, qualité d’odeur, propriétés physico-chimiques…) a abouti à la création de plusieurs recombinaisons. Celles-ci ont ensuite été analysées sensoriellement grâce à un test de tri-libre qui a permis de déterminer leur proximité avec le gin cible ainsi que les distances entre elles. Ainsi, une quinzaine de composés ont pu être identifiés comme influençant de manière importante la qualité aromatique du gin / In order to identify the compounds responsible for gin aroma, a GCO-MS procedure based on detection frequency analysis has been developed. It allowed the determination of volatile compound odorant intensity. Their odor quality has been defined thanks to a developed aroma wheel, used to categorize the obtained descriptors. This approach permitted the identification of gin aroma potential impact compounds. The origin of these compounds has then been determined by studying the different botanicals involved in the gin recipe. The obtained results showed that juniper berries and coriander seeds were the main contributors in terms of volatile impact compounds. At the opposite, orris roots, liquorice and almond did not seem to provide any of them. We thus differentiated the “major botanicals” from the “minor botanicals” according to their supply in volatile impact compounds. This hypothesis has been globally validated by different sensory tests on botanical distillate mixtures. Finally, a recombination procedure has been proposed in order to validate a selection of impact compounds. A multicriteria approach (odor intensity, odor quality, physic-chemical properties…) led to the creation of several recombinates. They have been sensorially analyzed by a free sorting task, which allowed determining their proximity with the target gin and the distance between them. Thus, around fifteen compounds have been identified as key compounds for gin aroma

Today, over 15,000 Ion Mobility Spectrometry (IMS) analyzers are employed at worldwide security checkpoints to detect explosives and illicit drugs. Current portal IMS instruments and other electronic nose technologies detect explosives and drugs by analyzing samples containing the headspace air and loose particles residing on a surface. Canines can outperform these systems at sampling and detecting the low vapor pressure explosives and drugs, such as RDX, PETN, cocaine, and MDMA, because these biological detectors target the volatile signature compounds available in the headspace rather than the non-volatile parent compounds of explosives and drugs. In this dissertation research volatile signature compounds available in the headspace over explosive and drug samples were detected using SPME as a headspace sampling tool coupled to an IMS analyzer. A Genetic Algorithm (GA) technique was developed to optimize the operating conditions of a commercial IMS (GE Itemizer 2), leading to the successful detection of plastic explosives (Detasheet, Semtex H, and C-4) and illicit drugs (cocaine, MDMA, and marijuana). Short sampling times (between 10 sec to 5 min) were adequate to extract and preconcentrate sufficient analytes (> 20 ng) representing the volatile signatures in the headspace of a 15 mL glass vial or a quart-sized can containing ≤ 1 g of the bulk explosive or drug. Furthermore, a research grade IMS with flexibility for changing operating conditions and physical configurations was designed and fabricated to accommodate future research into different analytes or physical configurations. The design and construction of the FIU-IMS were facilitated by computer modeling and simulation of ion’s behavior within an IMS. The simulation method developed uses SIMION/SDS and was evaluated with experimental data collected using a commercial IMS (PCP Phemto Chem 110). The FIU-IMS instrument has comparable performance to the GE Itemizer 2 (average resolving power of 14, resolution of 3 between two drugs and two explosives, and LODs range from 0.7 to 9 ng). The results from this dissertation further advance the concept of targeting volatile components to presumptively detect the presence of concealed bulk explosives and drugs by SPME-IMS, and the new FIU-IMS provides a flexible platform for future IMS research projects.

Cette thèse porte sur la dégradation photochimique des résines naturelles utilisées dans la fabrication de vernis à tableaux. Différentes résines ont été choisies pour notre étude : la sandaraque, le copal de Manille, la colophane, le mastic et la dammar. Des vernis à tableaux ont été fabriqués à partir de ces résines dissoutes dans de l’alcool, de l’huile ou de l’essence de térébenthine selon d’anciennes recettes. Ils ont par la suite été vieillis artificiellement en enceinte d’irradiation. L’étude en spectrométrie infrarouge a permis de montrer qu’une identification du type de résine était possible par cette technique. De nombreuses bandes d’absorption spécifiques ont été mises en évidence mais tendent à disparaître tout au long du photovieillissement. Néanmoins, la bande des CH (2850-3050 cm-1) permet de séparer les résines diterpéniques et triterpéniques, et l’analyse en composante principale des données permet d’affiner les identifications. Les analyses en CPG-SM nous ont permis d’identifier la plupart des molécules présentes au sein de nos vernis grâce à l’étude des fragmentations en spectrométrie de masse. Dans ce cadre, une étude poussée du comportement des molécules a été effectuée, notamment par des expériences en SM/SM. Quatre phénomènes de photodégradation ont été observés : l’isomérisation, la scission, l’hydroxylation et l’oxydation de type Norrish I des terpènes présents. Le choix du solvant utilisé dans la fabrication du vernis influence fortement la composition du vernis et sa cinétique de dégradation, en particulier dans le cas d’un vernis à l’huile. La présence d’une vitre devant le vernis a également une influence, plus ou moins importante, sur les mécanismes photochimiques. Des vernis anciens récupérés auprès de conservateurs-restaurateurs ont été identifiés grâce à la base de données effectuée à partir de nos expérimentations, validant notre méthodologie. Les premiers essais de polymères à empreinte moléculaire ont également été effectués donnant des résultats encourageants pour l’étude de mélanges de terpènes / This thesis presents a study on the photochemical degradation of natural resins used in the manufacture of painting varnishes. Following the literature, five resins were chosen for our experiments: sandarac, Manila copal, colophony, mastic and dammar. Varnishes were made from those resins dissolved in alcohol, oil or turpentine spirit, as found in old recipes. They were then photo-aged by irradiation under artificial light. The study by infrared spectrometry enabled the identification of the type of resin. Although various specific absorption bands were highlighted, they tend to disappear all along the photoageing process. Nevertheless, the C-H band situated between 2850 and 3050 cm-1 allows to separate diterpenic and triterpenic resins and the analysis by principal components can help the identification. Thanks to the study by GC-MS we could identify most of the molecules present in our varnishes by developing the fragmentation study in mass spectrometry. An advanced study of the molecules behaviour was done, especially by MS/MS experiments. Four photo-degradation reactions were observed: isomerisation, cleavage, hydroxylation and Norrish I oxidation of the terpenoids. The choice of the solvent used in the varnish can affect its composition and degradation kinetic, mostly for oil varnishes. Besides, a window pane placed before the varnish will influence the photochemical mechanisms. Ancient varnishes collected by conservator-restorers were analysed and identified thanks to the database elaborated from our results, validating our methodology. The first experiments of molecularly imprinted polymers were carried out with some encouraging results for the analysis of mixed terpenoids

Submitted by Renata Lopes (renatasil82@gmail.com) on 2015-12-18T17:00:14Z No. of bitstreams: 1 faustomoreiraaraujo.pdf: 3458303 bytes, checksum: 1018968a4d60b355a7d1902eb73fe9b7 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-01-25T15:35:15Z (GMT) No. of bitstreams: 1 faustomoreiraaraujo.pdf: 3458303 bytes, checksum: 1018968a4d60b355a7d1902eb73fe9b7 (MD5) / Made available in DSpace on 2016-01-25T15:35:15Z (GMT). No. of bitstreams: 1 faustomoreiraaraujo.pdf: 3458303 bytes, checksum: 1018968a4d60b355a7d1902eb73fe9b7 (MD5) Previous issue date: 2015-03-20 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho foi realizada a determinação de hidrocarbonetos alifáticos (n-alcanos e isoprenóides) marcadores biogeoquímicos do petróleo e de seus derivados, em amostras de sedimento do rio Paraibuna. A amostragem foi feita para 16 pontos ao longo do rio no município de Juiz de Fora-MG, coletados com draga Petersen. Para a extração dos analitos da matriz, realizou-se otimização da condição de extração por planejamento Box-Bahnken 33 por ultrassom. A condição escolhida para extrair os analitos foi de um tempo de sonicação de 10 minutos, com 10 mL de solvente e composição da mistura de solventes composta por n-hexano e acetona (25:75). Os extratos foram eluidos em coluna de adsorção constituída por sílica, alumina e sulfato de sódio utilizando 16 mL de n-hexano para total eluição dos extratos. A análise do eluato foi realizada pela técnica de cromatografia a gás acoplada à espectrometria de massas. Para complemento dos resultados, foi determinado a granulometria do sedimento e teores de carbono orgânico total (COT) em cada ponto. Obteve-se forte correlação do COT, com os teores de silte + argila. De maneira geral, o sedimento do rio Paraibuna é basicamente constituído por areia. Para pontos que o teor de silte e argila foram baixos, não foi possível a quantificação de vários analitos. A concentração de alifáticos totais encontrada variou de 0,78 a 1318,18 μg g-1 peso seco, e de n-alcanos totais de 0,07 a 5,49 μg g-1 peso seco, sendo observado um aumento da concentração dos compostos ao longo do rio na direção e sentido de seu fluxo. O índice preferencial de carbono obtido abrangeu de 0,94 a 4,75, indicando introdução de n-alcanos no sedimento do rio por fontes antrópicas para algumas amostras. Dos 16 pontos coletados, 12 apresentaram mistura complexa não resolvida, sendo 50% de perfil unimodal, e 50% bimodal, em decorrência de poluição por combustíveis e derivados do petróleo. A razão terrestre/aquática associada com a razão C31/C19 apontaram domínio das contribuições terrígenas por plantas vascularizadas para todos os pontos coletados. / In this work, it was performed the determination of n-alkanes (C10-C40) biomarkers crude oil and its derivatives, in river sediment samples. The sampling was performed with 16 points along Paraibuna river in Juiz de Fora-MG, collected with Petersen dredge. A 33 Box-Behnken experimental design was used to optimize the ultrasound-assisted extraction conditions. The optimized conditions was 10 minutes of sonication with 10 mL solvent mixture and the mixture composition was n-hexane and acetone (25:75). The extracts were eluted in an adsorption column containing silica, alumina and sodium sulfate, using 16 mL of n-hexane for total elution of the extract. The eluated analysis was performed by gas chromatography coupled with mass spectrometry. In addition, it was verified the sediment granulometry and the total organic carbon (TOC) determination for each sampling. We obtained a strong correlation between TOC and the silt + clay. In general, Paraibuna river’s sediment are basically constituted by sand. For points that the concentration of silt + clay were low, it was not possible to detect several analytes. The concentration of total aliphatic ranged from 0.78 to 1318.18 μg g-1 dry weight and the total n-alkanes ranged from 0.07 to 5.49 μg g-1 dry weight, being observed an increase in the concentration of compounds in the direction of river flows. The obtained carbon preference index ranged from 0.94 to 4.75, indicating introduction of n-alkanes by anthropogenic sources for some samples. From the 16 collected points, 12 presented an unresolved complex mixture, being 50% of unimodal profile and 50% bimodal, as result of pollution from fuel oil and other petroleum derivatives. In all points, it was observed the domain of terrigenous sources contributions over the aquatic sources.

The stem bark of the protected tree species, Curtisia dentata (Burm. f.)C.A.Sm., is one of the most popular plant species harvested and traded at traditional medicine markets in South Africa. The overexploitation of C. dentata trees lead to a “Near Threatened” conservation status and the population trend is portrayed as “declining”. In the KwaZulu-Natal Province of South Africa, C. dentata is completely conservation dependent. This study is not based on drug discovery or toxicological studies, but on the concern that the stem bark of C. dentata trees are harvested, prepared into remedies and consumed as traditional medicine without knowledge regarding the chemical compounds in the stem bark, particularly since the chemical composition of C. dentata stem bark was unknown to date. Phytochemical analyses were firstly conducted to determine the chemical composition of C. dentata stem bark using various solvents and various analytical methods, and secondly, to determine how seasons and regional separation of C. dentata trees affect the chemical profiles of C. dentata stem bark from an environmental and nature conservation perspective. Plants are known to contain numerous chemical compounds. Compounds isolated from a particular plant species are therefore not the only compounds present in that species, and although a plant has proven pharmacological properties, they can still cause harm. Previous studies on C. dentata aimed at validating the plant species as a medicinal plant by examining extracts of the leaves, twigs and stem bark’s potentials against known pathogens and selected cancer cells in vitro and in vivo, and its anti-inflammatory, antioxidant and antiverotoxic properties. Four pentacyclic triterpenoids and one steroidal compound were also previously isolated from C. dentata leaves, however, the leaves are not used in traditional medicines, but were suggested as alternative for stem bark as the harvesting of leaves is less destructive. The efficacy of these compounds as therapeutic agents is, however, compromised by their low solubility in water and thus their potential to penetrate permeating biological membranes. Moreover, in vitro toxicity studies distort the picture of its actual potentials on human health as the whole human metabolome and all its processes, including uptake and phase I and phase II biotransformation are not included. In vivo toxicity studies on mammalian animal species may also not present a true picture of a chemical or extract’s toxic effects on humans as animal metabolisms differ from those of humans. The chemical composition of leaves and stem bark may furthermore also be in contrast to some extent, and therefore chemical compounds were also isolated from C. dentata stem bark in this study. Scientific studies on plant-based medicines generally involve the discovery or identification of compounds that may be beneficial, and which can be exploited in future. Chemical compounds in traditional medicines or other plant-based health products which may cause adverse effects are generally ignored. Moreover, scientific studies that consider that some compounds present in plant extracts may derive from contaminants are equally limited. Traditional plant-based medicines are neither standardized nor regulated in South Africa. Users of traditional plant-based traditional medicines therefore consume uncertain dosages of both beneficial and hazardous substances, as well as contaminants simultaneously. Certain chemical compounds are carcinogens or mutagens or have the ability to accumulate in human tissues. Adverse effects may therefore only manifest after several years of use and will subsequently not be connected to the use of a particular traditional plant-based medicine. The goal of the thesis is therefore to provide a holistic portrayal of the full spectrum of chemical compounds in extracts of C. dentata stem bark and to discuss, where literature is available, the effect(s) each chemical compound may have on human health. Moreover, this thesis investigates variations in chemical composition and concentration in individual trees, seasonal variations and variations in composition and concentrations in the stem bark of C. dentata trees from geographically distinct regions. Most unexpected was that not all C. dentata stem bark samples contained chemical compounds with known beneficial potentials at each sampling date, and that chemical compounds may be region-specific and also tree-specific, which confirms that plants produce secondary metabolites according to the needs of each individual plant. Additional insight into the chemical composition and concentration of C. dentata trees is provided by the distribution profiles of amino acids in C. dentata stem bark. Extreme variations within populations and between geographical areas support the need for the cultivation of C. dentata trees to ensure sustainable production of homogenous material for chemical homogeneity. / Environment Science / PhD. (Environment Science)

The thesis is focused on a determination of polycyclic aromatic hydrocarbons (PAHs) contained in dried pelletized sewage sludge and pelletized biochar. Biochars were made in mild conditions by microwave torrefaction of prepared sewage sludge. There were analyzed and quantified the 34 of standardized PAHs compounds in two series. The first serie, also called “Sada 1”, has been aimed at comparison of extraction methods for the chosen sample of sewage sludge and the sample of biochar. In serie “Sada 1”, there were compared efficiencies of chosen type of solvent or solvent mixture by comparison of yields for 34 standardized analytes in a sample of biochar and a sample of sewage sludge. There were compared also to total yields of PAHs and to number of quantified compounds in analyzed samples. The most reliable extraction method has been used for the next analyses of samples in the second serie called “Sada 2”. In Sada 2, there were compared different samples of the same type (e.g. biochar, sludge). The origin of sewage sludge (small or big sewage treatment plant expressed as PE) and used additives (cellulose, chaff, hay) as modificators for torrefaction process were variables for different type of sample. The results of analysis were identification of the most suitable sewage sludge and additive to be used as modificator for microwave torrefaction process. The main goal of correctly chosen sludge and additive was to minimize production of PAH’s during torrefaction and in samples of biochar.

Aronia (Aronia melanocarpa) is a berry fruit with distinctive sensory characteristics and health-promoting properties. Polyphenols are the main bioactive compounds found in aronia including natural pigments – anthocyanins. Bioactive compounds are usually obtained from natural materials by extraction, in this work, two methods of extraction were compared – maceration and PHWE. Based on the total phenolic content, maceration was chosen as a more suitable method and then was optimized with statistical model – Design of Experiment. Optimal conditions were set to temperature of 30 °C, extraction agent 50 % ethanol, solid-solvent ratio 10 g per 50 ml and time of extraction for 30 minutes. Extract obtained under these conditions was characterised by total phenolic content – 1441 ± 90 mg/100 g DW, total anthocyanin content 943 ± 8 mg/100 g DW and antioxidation activity by ABTS 24,78 ± 0,09 molTE/g. In total of 25 volatile compounds were indentified in the optimal extract with content > 0,5 %. Major part created aldehydes and esters, with the main compounds being benzaldehyde (32,25 %) and methyl hexanoate (21,37 %).

Musk compounds (MUSK) or synthetic fragrances are organic substances commonly used as fragrant constituents of detergents, soaps, cosmetics, personal care products, industrial and in-house cleaning agents, industrial plasticizers, chewing tobacco and fresheners. The big attention is pushed ahead studying these compounds, their fate in different parts of ecosystems and studying their characteristics at present, because musks infiltrate many environmental components, particularly aquatic and marine ecosystems, through their large application and their ability to be perzistant. This diploma thesis was focused on four synthetic “classical” fragrances used over the world. The aim of this study was to perform a method optimisation for the determination of selected fragrances in biotic matrix. There was made an evalution of ability of selected water treatment plant to clear away musks from water, these results were used for evaluating contamination measurement of aquatic ecosystem. The identification and quantification of analytes was carried out by high resolution gas chromatography - mass spectrometry (HRGC/MS).

In der Arbeit werden Moeglichkeiten der Charakterisierung des Beschichtungsprozesses von C-Fasern mit pyro-Kohlenstoff vorgestellt. Dabei liegt der Schwerpunkt der Untersuchungen auf der ramanspektroskopischen Charakterisierung der Ober- flaechenstruktur von modifizierten Fasern. Die Unter- suchungen zeigen den Einfluss verschiedener Prozessparameter (Reaktortemperatur, Gasphasenkonzentration, Auswahl des jeweiligen Precursors etc.) auf die Oberflaechenstruktur der abgeschiedenen Schichten. Der Nachweis einer Vorzugsorientierung der Graphitmikro- kristallite auf der Faseroberflaeche wird mit verschiedenen Analysenmethoden durchgefuehrt. Dabei werden die ramanspektroskopischen Messergebnisse mit Ergebnissen anderer Methoden (wie Elektronenbeugung und Elektronenmikroskopie) verglichen. Waehrend des Beschichtungsprozesses wird die Gasphasen- zusammensetzung im Reaktor analysiert. Das Zersetzungs- verhalten von unterschiedlichen Precursoren bei verschiedenen Temperaturen wird untersucht. Korrelationen zwischen den einzelnen Precursoren aufgezeigt.