This work is divided into two parts that are focused on the synthesis and assessment of photophysical properties of two structurally related compounds: (i) 9,9'-spirobifluorenes (SBFs) and (ii) dispiroindeno[2,1-c]fluorenes (DS-IFs). (i) In the first part, a five-step synthetic approach to SBFs was developed and as the crucial step was used an intermolecular [2+2+2] cyclotrimerization of symmetrically or unsymmetrically substituted diynols with alkynes catalyzed by Rh-complexes. Catalyst screening showed that Wilkinson's catalyst (RhCl(PPh3)3) had the highest efficiency in yielding 1,2,3,4-substituted fluorenols - the key intermediates. The fluorenols were then converted into SBFs bearing various electron-donating and -withdrawing groups, aromatic substituents, and -extended aromatic hydrocarbon moieties (PAHs). Altogether 19 different SBFs were prepared and their photophysical properties screened. The fluorescent emission maxima em were in the range of 315-389 nm with excellent quantum yields s (up to 1.00). As far as the substituent effect is concerned the presence of electron-withdrawing substituents on the SBF scaffold results in the red-shift of the emission maxima. (ii) In the second part, a similar synthetic strategy was applied for synthesis DS-IFs. In this instance was utilized again the...

The purpose of this thesis is to examine some of the potential fates of processing reagents in a coal preparation plant.  The focus is specifically on petro-diesel (termed "diesel" in this paper), which is used as a collector in the flotation of fine coal.  Diesel range organics (DRO) and polyaromatic hydrocarbons (PAHs) are measured in aqueous samples using gas chromatography equipped with either a flame ionization detector (GC-FID) or a mass spectrometer (GC-MS).  Samples are subjected to a variety of test conditions in order to understand the behavior of diesel compounds in coal processing streams. Results show that frother and collector reagents are not likely to partition completely to a single fraction of the process slurry.  Further test work has shown that sub-ppm levels of DRO dominated by the water soluble fraction of diesel are expected to be present in process waters; however, PAHs and insoluble DRO may be removed via volatilization and/or degradation.  DRO and PAHs are also expected to be desorbed from coal particles when contacted with fresh water.  Flotation tests have revealed that low levels of DRO are found in both the concentrate and tailings processing streams with slightly higher concentrations being found in the concentrate stream.  From the tests performed in this thesis, it appears as though there is no apparent environmental concern when coal preparation plants are operating under normal conditions. / Master of Science

Philosophiae Doctor - PhD / The thesis presents a simple, sensitive, low cost and a novel graphenated polyaniline doped tungsten trioxide nanocomposite, as an electrochemical sensor for the detection and quantitative and determination of PAHs, which are ubiquitous, toxic, as well as dangerous organic pollutant compounds in the environment. The selected PAHs (anthracene, phenanthrene and pyrene) in wastewater were given priority as a result of their threat to human nature and that of the environment. In order for a healthy, non-polluted and well sustainable environment, there is need for an instrument that is capable of detecting and quantifying these organic pollutants onsite and also for constant monitoring. The nanocomposites were developed by chemical and electrochemical methods of preparations, exploiting the intrinsic properties of polyaniline, graphene and tungsten trioxide semiconducting materials. Chemically, graphene-polyaniline (GR-PANI) nanocomposite was synthesised by in situ polymerisation method, then casted on a surface of glassy carbon electrode to form GR-PANI modified electrode. The properties of the prepared electrode were investigated through morphological and spectroscopic techniques, which confirmed the formation of the composite. The electroactivity of the prepared modified electrode revealed great improvement in cyclic and square wave voltammetric response on anthracene. A dynamic range of 2.0 × 10-5 to 1.0 × 10-3 M and detection limit of 4.39 x 10-7 M was established.

Made available in DSpace on 2014-06-11T19:27:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-03-29Bitstream added on 2014-06-13T18:31:32Z : No. of bitstreams: 1 furlan_b_me_rcla.pdf: 3556255 bytes, checksum: b8dadd1a50eb8caa4d6eb51e31dc8f1e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O gênero Burkholderia compreende um grupo de bactérias muito diversificado, ocupando vários nichos ecológicos e possui espécies que causam doenças, mas outras espécies apresentam habilidades importantes para os ramos da agricultura, biotecnologia e do ambiente, como a biodegradação. Essas bactérias são morfologicamente semelhantes e o gênero está dividido em dezessete genomovars, onde espécies semelhantes geneticamente são agrupadas, formando o Complexo Burkholderia cepacia (CBC). Por meio de estudos moleculares do gene 16S rRNA e do gene recA foi possível fazer a classificação adequada em espécies dos 450 isolados obtidos da Terra Preta Antropogênica (TPA) e adjacentes, em quatro sítios (TPA Caldeirão Cultivado; TPA Caldeirão Capoeira; TPA Hatahara e TPA Mina-I), foram obtidos 177 isolados do gênero Burkholderia. Desses isolados, pela análise do gene 16S rRNA foi possível classificar 157 isolados ao nível de espécie e pela análise do gene recA somente 105 isolados foram classificados neste mesmo nível. Esses isolados foram utilizados no teste de biodegradação dos hidrocarbonetos. Os hidrocarbonetos poliaromáticos (HPAs) são compostos orgânicos resultantes da combustão incompleta da matéria orgânica e dos derivados de petróleo, são pouco solúveis em água e muito tóxicos para as células, por isso, não são metabolizados por muitos micro-organismos e acabam contaminando e inviabilizando os ambientes. Nos testes de biodegradação os substratos utilizados foram o naftaleno, o fenantreno e o diesel, juntamente com o indicador redox 2,6- diclorofenol-indofenol (DCPIP), que sofre descoloração (de azul para incolor) quando as células utilizam os substratos como fonte de carbono para o crescimento celular, gerando elétrons que vão reduzir o indicador. Pela análise do teste, 19 isolados degradaram o naftaleno, 16 degradaram... / The genus Burkholderia comprises a very diverse group of bacteria occupying various ecological niches and has species that cause disease, but other species have important skills to the branches of agriculture, biotechnology and the environment, as biodegradation. These bacteria are morphologically similar genus and is divided into seventeen genomovars, where genetically similar species are grouped together, forming the Burkholderia cepacia complex (BCC). Through molecular studies of 16S rRNA and recA gene was possible to make the appropriate classification of species in 450 isolates of Terra Preta Antropogênica (TPA) and adjacent at four sites (TPA Caldeirão Cultivado; TPA Caldeirão Capoeira; TPA Hatahara e TPA Mina-I) were obtained 177 isolates of the genus Burkholderia. These isolates by 16S rRNA gene analysis was possible to classify 157 isolates to species level and the recA gene analysis only 105 isolates were classified in the same level. These isolates were used to test the biodegradation of hydrocarbons. Polyaromatic hydrocarbons (PAHs) are organic compounds resulting from incomplete combustion of organic matter and petroleum derivatives, are not very soluble in water and very toxic to cells, therefore, are not metabolized by many microorganisms to contaminate and render environments. In biodegradation tests the substrates used were naphthalene, phenanthrene and the diesel, along with the redox indicator 2,6- dichlorophenol-indophenol (DCPIP), who suffers discoloration (blue to colorless) when cells use the substrates as a source of carbon for cell growth, generating electrons that will reduce the indicator. By analysis of the test, 19 isolates degraded naphthalene, phenanthrene degraded the 16 and 126 degraded diesel, generating a total of 132 isolates of the genus Burkholderia that have the ability to degrade at least... (Complete abstract click eletronic access below)

Made available in DSpace on 2014-12-17T15:01:24Z (GMT). No. of bitstreams: 1 CelynaKOS_DISSERT.pdf: 1291622 bytes, checksum: 6aba20d221ab35537c160d478e6ac5f7 (MD5) Previous issue date: 2010-12-16 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The soil contamination with petroleum is one of the major concern of industries operating in the field and also of environmental agencies. The petroleum consists mainly of alkanes and aromatic hydrocarbons. The most common examples of hydrocarbons polyaromatic are: naphthalene, anthracene, phenanthrene, benzopyrene and their various isomers. These substances cause adverse effects on human and the environment. Thus, the main objective of this work is to study the advanced oxidation process using the oxidant potassium permanganate (KMnO4) for remediation of soils contaminated with two polyaromatic hydrocarbons (PAHs): anthracene and phenanthrene. This study was conducted at bench scale, where the first stage was at batch experiment, using the variables: the time and oxidant dosage in the soil. The second stage was the remediation conducted in continous by a fix column, to this stage, the only variable was remediation time. The concentration of oxidant in this stage was based on the best result obtained in the tests at batch, 2,464 mg / L. The results of degradation these contaminants were satisfactory, at the following dosages and time: (a) 5g of oxidant per kg soil for 48 hours, it was obtained residual contaminants 28 mg phenanthrene and 1.25 mg anthracene per kg of soil and (b) for 7g of oxidant per kg soil in 48 hours remaining 24 mg phenanthrene and anthracene 0.77 mg per kg soil, and therefore below the intervention limit residential and industrial proposed by the State Company of Environmental Sao Paulo (CETESB) / A contamina??o de solo com petr?leo ? uma das grandes preocupa??es das ind?strias que atuam no ramo e tamb?m dos ?rg?os ambientais. O petr?leo ? constitu?do basicamente por hidrocarbonetos alcanos e arom?ticos. Os exemplos mais comuns dos hidrocarbonetos poliarom?ticos s?o: naftaleno, antraceno, fenantreno, benzopireno e seus v?rios is?meros. Estas subst?ncias apresentam efeitos nocivos ao ser humano e ao meio ambiente. Logo, este trabalho tem como principal objetivo, estudar o processo de oxida??o avan?ada, utilizando o oxidante permanganato de pot?ssio (KMnO4), na remedia??o de solos contaminados com dois hidrocarbonetos poliarom?ticos (HPAs): antraceno e fenantreno. Este estudo foi realizado em escala de bancada, sendo a primeira etapa realizada experimentos em batelada, utilizando as vari?veis: tempo de remedia??o e dosagem do oxidante. Na segunda etapa, a remedia??o foi realizada em regime cont?nuo utilizando coluna de leito fixo, para esta etapa a ?nica vari?vel foi tempo de remedia??o. A concentra??o do oxidante nesta etapa, foi baseada no melhor resultado obtido nos ensaios em batelada, 2464 mg/L. Os resultados da degrada??o destes contaminantes foram satisfat?rios, nas seguintes dosagens de oxidante e tempo de remedia??o: (a) 5g de oxidante por kg de solo em 48 horas, foram obtidos contaminantes residuais de 28 mg de fenantreno e 1,25 mg de antraceno por kg de solo e (b) para 7g de oxidante por kg de solo em 48 horas restaram 24 mg de fenantreno e 0,77 mg de antraceno por kg de solo, ficando abaixo dos valores de interven??o residencial e industrial propostos pela Companhia Ambiental do Estado de S?o Paulo (CETESB)

Native and naturalized California plant species were screened for their phytoremediation potential for the cleanup of soil contaminated with petroleum hydrocarbons (PHCs), poly-aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated dioxins/furans, and heavy metals. This screening was followed by controlled greenhouse experiments to further evaluate the phytoremediation potential of the best candidates. Field specimens and soils used for this study were collected from the former Energy Technology Engineering Center (ETEC) at the Santa Susana Field Laboratory in Southern California that was operated by the Department of Energy (DOE). Soils at this site contain all of the contaminants of interest (COIs). Nine plant species were screened in the field: Purple Needlegrass (Nassella pulchra), Blue Elderberry (Sambucus nigra), Laurel Sumac (Malosma laurina), Mule Fat (Baccharis salicifolia), Palmer’s Goldenbush (Ericameria palmeri), Summer Mustard (Hirschfeldia incana), Narrowleaf Milkweed (Asclepias fascicularis), Coyote Brush (Baccharis pilularis), and Thickleaf Yerba Santa (Eriodictyon crassifolium). In the field three samples of each species growing in contaminated soil and one of each species growing in uncontaminated soil were selected for harvesting and analysis. The roots, above ground plant tissue, and soil around the roots were sampled separately and analyzed for the COIs: PHCs, PAHs, PCBs, chlorinated dioxins/furans, and metals (which include mercury, silver, cadmium, and lead). All of the plants in the field appeared to generate compounds which result in higher measured PHC concentrations than those measured in the associated soil. The highest concentrations of PAHs in the roots were observed for Blue Elderberry (1740 ug/kg), Purple Needlegrass (703 ug/kg), and Yerba Santa (200 ug/kg). No uptake of PCBs was observed in the roots or foliage of any species. The highest concentrations of total chlorinated dioxins/furans in the roots were observed for Purple Needlegrass (2237 ng/kg), Blue Elderberry (1026 ng/kg), Palmer’s Goldenbush (432 ng/kg), and Yerba Santa (421 ng/kg). The highest concentrations of total chlorinated dioxins/furans in the foliage were observed for Yerba Santa (901 ng/kg), Palmer’s Goldenbush (757 ng/kg), and Purple Needlegrass (694 ng/kg). No uptake of mercury was observed in the roots or foliage of any species. The highest concentration of silver in the roots was observed for Laurel Sumac (7.34 mg/kg). Summer Mustard (SM) was the only species that showed uptake of silver into the foliage (0.405 mg/kg). The highest concentrations of cadmium in the roots and foliage were observed for Mule Fat (1.84 mg/kg and 3.64 mg/kg) and Coyote Brush (1.52 mg/kg and 2.12 mg/kg) and the greatest concentration of lead in the roots and foliage was observed for Purple Needlegrass (8.92 mg/kg and 1.17 mg/kg). Plants with a wide variety of observed contaminant uptake in the field were selected for a second phase of research in which three of the most promising species were grown in greenhouse microcosms to quantify the removal of contaminants from the soil. The three species selected based on preliminary results from the field study were Coyote Brush, Mule Fat, and Purple Needlegrass. Microcosms consisted of 2.17 kg of soil in 4-L glass jars with glass marbles for an underdrain. Plants were watered with deionized water and no leachate was collected. Five replicates of each microcosm type were created and incubated for 211 days with soil sampling at 85 and 211 days. Soil, plant roots/above ground tissue, and volatilization from the plants were analyzed for COIs to determine the mechanisms of phytoremediation. One set of microcosms was used to test the effect of addition of achelating agent (ethylenediaminetetraacetic acid) and another set was used to test the effect of fertilizer addition on phytoremediation potential. Three control treatments were tested: sterilized (gamma irradiation) soil planted with Purple Needlegrass, unplanted soil, and sterilized unplanted soil. None of the plant species demonstrated volatilization of COIs under these conditions. Volatilization of mercury was not tested for. The average PCB concentration (measured as Aroclor 1260) reductions in soils with Purple Needlegrass and chelated Coyote Brush were 49.4% and 51.4% respectively (p < 0.05). However, the sterilized unplanted control also had a decrease of Aroclor 1260 concentrations in the soil of 36.6% (p < 0.05). None of the species phytoextracted PCBs, so the mechanism of PCB remediation appears to be phytostimulation of the rhizosphere. Purple Needlegrass showed the greatest uptake of dioxins/furans into the foliage but did not appear to reduce the dioxin/furan concentrations in the soil. Coyote Brush, fertilized Coyote Brush, and Mule Fat also showed uptake of dioxins/furans into the roots and foliage. Only the Coyote Brush and fertilized Coyote Brush significantly (p = 0.036, p = 0.022) reduced the total dioxin/furan concentration in the soil (17.8% and 19.8% respectively). Coyote Brush may have stimulated microbes in the rhizosphere to better degrade the dioxins/furans. None of the plants were identified as hyper-accumulators of metals, and none of the soil metal concentrations significantly decreased in any of the microcosms. All of the metals (except mercury) were taken into the roots of plants to some degree, with Purple Needlegrass showing the most promise for metal extraction as it showed some of the highest concentrations of metals in roots and was the only species that contained mercury and silver in the foliage. This study suggests that there is some potential for phytoremediation of PCBs and chlorinated dioxins/furans. The results for petroleum hydrocarbons were inconclusive. Metal uptake was not substantial enough to lower metal concentrations in the soils. Thus phytoremediation of COIs at the site is limited and more aggressive forms of remediation may be required to reduce the concentrations of COIs quickly.

Motorboat activity can adversely effect the water quality of a reservoir. The potential impacts of motorboat activity on the Occoquan Reservoir's water and sediments were evaluated. Thirty-one sites, both marina and nonmarina, along the reservoir were selected. Sediment and water samples were collected in 1990, during peak boating activity, and in October, during low boating activity. The objectives of this research were to determine the concentrations of polyaromatic hydrocarbons (PAHs) in water and sediment samples and to determine if their presence was related to boating activity. The presence of other non-PAH organics was also determined. Contours of total PAH concentrations, boxplots and ANOVA analyses between marina and nonmarina sites were generated from gathered data in order to meet these objectives. PAHs were present in the water during peak boating activity and not detected during low boating activity, while PAHS were detected in the sediments during both sampling periods. The aqueous and sediment PAH concentrations were at or below the method detection limits. The PAH ratios of unalkylated PAHs confirmed PAH contamination to be of a combustion source. Boating was shown to be a PAH source to the water column, during peak boating activity, throughout the entire Occoquan Reservoir. An ANOVA between marina and nonmarina sites for the aqueous total PAH concentrations did not show a significant difference in June. This implied that boating did not cause any localized impacts to the water column and that there was another PAH source. There was a significant difference for total PAH concentrations between the marina and nonmarina sites for the sediment samples in June, showing localized impacts at marina areas due to boating activity. PAH profiles showed urban runoff as another major contributor to the PAH concentration in the water and sediments. The urbanization of Hooes Run and the hydrology of the reservoir caused urban runoff to impact localized areas. Finally, atmospheric deposition was also a source of PAHs to the sediments throughout the entire reservoir. Non-PAH organics found in a few of the water and sediment samples were the pesticides atrazine and p,p'-DDD, alkyl phosphates, alcohols and C₈ to C₁₂ hydrocarbons. / Master of Science

In this work the organic markers that serve for identification of sources of aerosols are monitored. Theoretic part deals with detailed survey of organic markers emitted from the most significant sources of atmospheric aerosols (biomass combustion, combustion of fossil fuels and traffic) as well as with sampling of aerosols and analysis of organic markers by analytical techniques. Monosaccharide anhydrides (emissions from biomass combustion) and polyaromatic hydrocarbons (emissions from traffic and incomplete combustion) were observed especially. Hopanes and steranes (traffic, coal combustion) and fatty acids (cooking) were next groups of monitored organic markers. Markers were studied mainly in size fraction PM1 because this fraction of aerosols is the most harmful to human health. Aerosols were sampled in two seasons (winter and summer) in two towns in 2009. Higher concentrations of aerosols and organic compounds were found in winter season, which resulted from increased combustion of biomass, coal and other organic material while traffic was the most significant source of aerosols in summer.

La réduction des inégalités d’exposition environnementale constitue un axe majeur en santé publique en France comme en témoignent les priorités des différents Plan Nationaux Santé Environnement (PNSE). L’objectif de cette thèse est de développer une approche intégrée pour la caractérisation des inégalités environnementales et l’évaluation de l’exposition spatialisée de la population aux HAP en France.Les données produites dans le cadre des réseaux de surveillance de la qualités des milieux environnementaux sont le reflet de la contamination réelle des milieux et de l’exposition globale des populations. Toutefois, elles ne présentent généralement pas une représentativité spatiale suffisante pour caractériser finement les expositions environnementales, ces réseaux n’ayant pas été initialement conçus dans cet objectif. Des méthodes statistiques sont développées pour traiter les bases de données d’entrée (concentrations environnementales dans l’eau, l’air et le sol) et les rendre pertinentes vis à vis des objectifs définis de caractérisation de l’exposition. Un modèle multimédia d’exposition, interfacé avec un Système d’Information Géographique pour intégrer les variables environnementales, est développé pour estimer les doses d’exposition liées à l’ingestion d’aliments, d’eau de consommation, de sol et à l’inhalation de contaminants atmosphériques. La méthodologie a été appliquée pour trois Hydrocarbures Aromatiques Polycycliques (benzo[a]pyrène, benzo[ghi]pérylène et indéno[1,2,3-cd]pyrène) sur l’ensemble du territoire français. Les résultats permettent de cartographier des indicateurs d’exposition, d’identifier les zones de surexposition et de caractériser les déterminants environnementaux. Dans une logique de caractérisation de l’exposition, la spatialisation des données issues des mesures environnementales pose un certain nombre de questions méthodologiques qui confèrent aux cartes réalisées de nombreuses incertitudes et limites relatives à l’échantillonnage et aux représentativités spatiales et temporelles des données. Celles-ci peuvent être réduites par l’acquisition de données supplémentaires et par la construction de variables prédictives des phénomènes spatiaux et temporels considérés.Les outils de traitement statistique de données développés dans le cadre de ces travaux seront intégrés dans la plateforme PLAINE pour être déclinés sur d’autres polluants en vue de prioriser les mesures de gestion à mettre en œuvre. / Reducing environmental exposure inequalities has become a major focus of public health efforts in France, as evidenced by the French action plans for health and the environment. The aim of this thesis is to develop an integrated approach to characterize environmental inequalities and evaluate the spatialized exposure to PAH in France.The data produced as part of the monitoring quality networks of environmental media reflect the actual contamination of the environment and the overall exposure of the populations. However they do not always provide an adequate spatial resolution to characterize environmental exposures as they are usually not assembled for this specific purpose. Statistical methods are employed to process input databases (environmental concentrations in water, air and soil) in the objective of characterizing the exposure. A multimedia model interfaced with a GIS, allows the integration of environmental variables in order to yield exposure doses related to ingestion of food, water and soil as well as atmospheric contaminants' inhalation.The methodology was applied to three Polycyclic Aromatic Hydrocarbon substances, (benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene), in France. The results obtained, allowed to map exposure indicators and to identify areas of overexposure and characterize environmental determinants. In the context of exposure characterization, the direct spatialization of available data from environmental measurement datasets poses a certain number of methodological questions which lead to uncertainties related to the sampling and the spatial and temporal representativeness of data. These could be reduced by acquiring additional data or by constructing predictive variables for the spatial and temporal phenomena considered.Data processing algorithms and calculation of exposure carried out in this work, will be integrated in the French coordinated integrated environment and health platform-PLAINE in order to be applied on other pollutants and prioritize preventative actions.

Les travaux présentés dans ce manuscrit de thèse s’articulent autour de la synthèse de nouvelles architectures moléculaires tridimensionnelles et de l’évaluation de ces architectures en tant que canaux ioniques synthétiques capables de promouvoir le transport transmembranaire d’ions. La première partie concerne la mise au point d’une voie d’accès à ces édifices ayant comme plateforme centrale une brique naphtothiophène, aromatique ou partiellement hydrogénée, ainsi que l’étude prospective de la conversion de ces architectures en plateforme hélicoïdale. Les propriétés de ces édifices sont étudiées à l’état solide et par voie de calculs théoriques, permettant de mettre en avant des informations quant à la topologie globale adoptée ainsi que la compréhension de certaines réactivités observées. Une seconde partie est dédiée à la fonctionnalisation de ces édifices en molécules présentant des propriétés amphiphiles puis à l’étude de la capacité de ces dernières à s’insérer dans une bicouche lipidiques modèle afin de promouvoir le transport d’ions à travers la membrane via la formation de canaux ioniques dits synthétiques. En outre, des études alliant des analyses de spectrométrie de masse et des calculs théoriques sont présentés afin de comprendre les interactions intervenant dans le processus de transport d’ions à travers la membrane lipidique. / The work presented in this manuscript is dealing with the synthesis of new three-dimensional molecular architectures and their evaluation as synthetic ion channels capable of promoting ion transmembrane transport. The first part aims at developing a straightforward approach to the synthesis of novel architectures based on a naphthothiophene platform, aromatic or partially hydrogenated, as well as the development of a strategy the convert 9-arylnaphthothiophene architectures into helical platforms. The properties of these molecules were studied in the solid state and were completed by theoretical calculations to highlight global topologies adopted. Theoretical calculations allowed us to understanding some reactivities observed. A second part is dedicated firstly to the functionalisation of these molecular architectures into amphiphilic molecules and secondly to study their abilities to insert themselves into a model bilayer lipid membrane by forming channels. Besides, in order to gain a better understanding of the interactions in play in the process, mass spectrometry analysis combined to theoretical calculations were set up.