Appendices data can be found at: A: http://dx.doi.org/10.15142/T35P49 B: http://dx.doi.org/10.15142/T3201B C: http://dx.doi.org/10.15142/T3X59V D: http://dx.doi.org/10.15142/T3SG6K F: http://dx.doi.org/10.15142/T3NP4N

Le Bassin d’Arcachon est une lagune très riche écologiquement et suscite un attrait touristique et ostréicole important. Cette pression anthropique a soulevé ces dernières années des questions sociétales quant à sa qualité environnementale. Ainsi, ancrés dans des projets soutenus par les acteurs locaux (Région Aquitaine, Syndicat Intercommunal du Bassin d’Arcachon, Conseil général de la Gironde), ces travaux de thèse ont permis de dresser un bilan de la qualité de ce système et de ses bassins versants relativement à l’introduction des hydrocarbures aromatiques polycycliques (substances prioritaires selon la directive cadre sur l’eau, UE, 2000). Ces polluants organiques sont présents dans les différents compartiments environnementaux suivis (sédiments, colonne d’eau) de la lagune, en concentrations élevées pour quelques sites et pouvant induire des effets toxiques chez le biota aquatique. Ils sont généralement présents dans les eaux et sédiments des tributaires à un niveau bruit de fond, mais des concentrations importantes ont été observées pour un ruisseau, ainsi que lors d’un évènement de tempête. Ils sont principalement issus des processus de combustion incomplète de matières organiques (gaz d’échappement, chauffage, feux de forêt) ; des apports terrigènes et diagénétiques de pérylène ont également pu être mis en évidence. Les transferts des HAP vers le biota benthique (huître), et leur bioaccumulation sont effectifs malgré des capacités de dépuration importante relativement à d’autres classes de composés organiques hydrophobes. Comme alerté par le réseau national d’observation coordonné par IFREMER, les teneurs dans les organismes augmentent depuis une dizaine d’année, et s’approchent aujourd’hui de la valeur guide AFSSA pour la consommation humaine. Outre l’aspect de qualité environnementale, ces résultats peuvent apporter des informations quant aux problématiques nationales actuelles de surveillance chimique des productions conchylicoles (DGAL, 2008 ; AFSSA, 2008). / Abstract

Orientador: Altair Benedito Moreira / Banca: Eduardo Alves de Almeida / Banca: Ronaldo José Torres / Resumo: Hidrocarbonetos Policíclicos Aromáticos (HPA) fazem parte de uma classe de compostos denominados Substâncias Tóxicas Persistentes, tendo como principais características elevada toxicidade e persistência no ambiente, sendo as fontes petrogênicas, pirogênicos e biogênicas as que mais contribuem para o aporte destes compostos. A Bacia Hidrográfica do Turvo/Grande (BHTG) é caracterizada por pequenos parques industriais e intensa atividade agrícola com destaque a cana-de-açúcar, que vem acompanhada por processos de queimadas. Neste contexto, este trabalho teve como principal objetivo utilizar a determinação de 1-hidróxipireno em bílis de peixes como biomarcador de exposição para HPA e também determinar o histórico destes em sedimentos de rios da BHTG. As coletas de amostras de peixe (160 amostras) e sedimento (superficial e profundidade) nos rios Preto (CAPRP), Turvo (PORTUR e RTURG) e Grande (RGRANDE) foram feitas em dois períodos distintos: fevereiro e julho de 2010. A determinação do 1-hidroxipireno nas amostras de bílis de peixes foi realizada de acordo com o método proposto por Ariase et alii (1993). Os HPA dos sedimentos foram extraídos de acordo com o método 3540C (EPA) e a quantificação foi realizada empregando Cromatografia Líquida de Alta Eficiência com detector de Fluorescência (HPLC-DF). As concentrações do 1-hidróxipireno no ponto RTURG da coleta de fevereiro de 2010 variaram na faixa de 210 a 1025 µg L-1, com valor médio de 780 ± 281 µg L-1. Para as amostras de peixes coletadas em julho de 2010 no ponto CAPRP, os valores estiveram na faixa de 397 - 6463 µg L-1, com valor médio de 1300 ± 1130 µg L-1. Para os pontos PORTUR e RTURG, os valores médios de concentração de 1-hidróxipireno na bílis dos peixes foram... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Polycyclic Aromatic Hydrocarbons (PAHs) constitute a class of compounds denominated as Persistent Toxic Substances, having as main characteristics high toxicity and persistence in the environment, being that the sources petrogenic, pyrogenic and biogenic contribute most to the intake of these compounds. Turvo/Grande watershed (BHTG) is characterized by a small industrial facilities and intensive agriculture especially sugarcane activity, which is accompanied by the burning process. In this context, this work aimed to use the determination of 1-hydroxypyrene in fish bile as a biomarker of exposure to PAHs and also determine the history of these in the sediments from BHTG rivers. The sampling of fish (160 samples) and sediment (surface and deep) in the Preto (CAPRP), Turvo (PORTUR e RTURG) e Grande (RGRANDE) rivers, were made in two distinct periods: February and July of 2010. The determination of 1-hydroxypyrene in fish bile samples was performed according to the method proposed by Ariase et alii (1993). PAHs were extracted of the sediments according to the method 3540C (EPA) and the quantification was performed using high performance liquid chromatography with fluorescence detector (HPLC-FD). Concentrations of 1-hydroxypyrene is fish bile samples collected in RTURG (February 2010) ranged from 210 to 1025 µg L-1, the average values 780 ± 281 µg L-1. For fish samples collected in CAPRP in July 2010 , values ranged 397-6463 µg L-1, with an average of 1300 ± 1130 µg L-1. For PORTUR and RTURG, the mean concentration of 1-hydroxypyrene in fish bile were 1643 ± 744 µg L-1 and 588 ± 183 µ g L-1, respectively. PAHs concentration along the sediment profile showed similar behavior. In general, for all PAHs there was a trend of reduction with increasing depth in sediment cores. The total concentration... (Complete abstract click eletronic access below) / Mestre

Thesis advisor: Lawrence T. Scott / Thesis advisor: James P. Morken / Expeditious establishment of molecular complexity in a stereoselective manner is a prominent goal in organic synthesis. In this regard, multicomponent coupling reactions have received substantial attention due to their ability to access complex molecules from simple starting materials in a single step. Chapter 1 is a comprehensive review on catalytic bismetallative multicomponent reactions. The scope of this process in terms of both bismetallic reagents and the pi components are broad enough to be generally applied to more elaborate synthetic sequences. Particularly, contemporary applications of the bismetallative multicomponent coupling reactions, in which high enantio- and/or diastereoselectivities are displayed, have enabled the study of this area to make a significant step forward. Chapter 2 presents nickel-catalyzed coupling reactions of aldehyde, diene, and a diboron reagent in the presence of a trialkyl phosphine ligand. Compared to borylation reactions with one pi-component, these borylative multicomponent reactions (involving two pi components) lead to formation of a new C-C bond between the pi components as well as generation of highly functionalized, stereodefined products. Chapter 3 describes a remarkable turnover in regioselectivity of the borylative multicomponent coupling when PCy3 is replaced with P(SiMe3)3. In particular, the products from the reactions with P(SiMe3)3 feature three contiguous stereocenters and an alpha-chiral allylboronate. The effect of P(SiMe3)3 ligand on the product selectivity is intriguing. According to the experimental and computational results, it has an ability to act as an electron acceptor, which will facilitate reductive elimination from the intermediate nickel complex during the course of the reaction. In Chapter 4, we show that borylative ketone-diene coupling reactions can be accomplished in high yields and with excellent levels of diastereocontrol. This reaction occurs in a predictable fashion, yet with regioselection that is distinct from related aldehyde-diene coupling reactions. The reaction products from these coupling processes, which possess tertiary alcohol functionality and an allylic alcohol moiety, are particularly well suited for the preparation of polyketide natural products. Chapter 5 presents investigations on bowl-shaped geodesic polyarenes, which are the missing links between the "classic" planar polycyclic aromatic hydrocarbons (PAHs) and the spheroidal fullerenes. The present study has shown that open geodesic polyarenes can feature chemistry inherent to both classes of aromatics. The curved pi system induces unequal environments on the two faces of circumtrindene, significant strain energy to the molecule, and non-identical bond lengths. Along with the electronic effects, the stereoelectronic effect enabled the site-selective functionalization with fullerene-type chemistry. On the other hand, the edge carbons, which are not present in fullerenes, still possess reactivity of common planar PAHs. Chapter 6 describes the intermolecular oxidative cyclotrimerization reactions of alkenes and aromatic compounds with DDQ and trifluoromethanesulfonic acid. The Scholl-type oxidation reactions involving alkenes have never been demonstrated. Moreover, the DDQ/acid system has never been used for the intermolecular oxidative cyclization reactions. This convenient non-metallic reagent system (DDQ/TfOH) is advantageous over the metal-based Scholl-type oxidants because it eliminates the possibility of halogenation of aromatic compounds and the reduced oxidant can be reoxidized. In Chapter 7, the regioselective formation of cyclic trimers from substituted benzenes and heteroaromatic compounds is demonstrated. This DDQ/TfOH method provides a simple and convenient synthetic route toward star-shaped oligomers containing triphenylene or isotruxene cores. Furthermore, the experimental outcome suggests that this oxidative process proceeds by an electron transfer mechanism. This is the first experimental evidence for mechanistic details on the Scholl-type oxidation. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

No description available.

Aldol cyclotrimerizations have been used to achieve the rational chemical synthesis of both fullerenes and fullerene fragments in the past. Under certain conditions this reaction produces the corresponding cyclotetramer which has sometimes been regarded as an undesired byproduct. This work details efforts to synthesize and use these cyclotetramers toward a synthesis of a C240 fullerene fragment. One principal focus in this work is tridecacyclene, a cyclic tetramer of acenaphthylene given its name by our group for its thirteen rings. Relatively low yields for the synthesis of tridecacyclene and its derivatives drove us to investigate the mechanism of its formation and attempt to optimize its production. During this process, novel dione products were isolated from the attempted cyclotetramerization of two dimeric species. Characterization of these products by X-ray crystallography gave valuable insight into the reaction pathway, leading us to a new proposed mechanism of formation for the cyclotetramerization products observed in these aldol reactions. β-hydroxy-α-diazoketones are suitable progenitors to vinyl cation intermediates whose use in chemical synthesis is relatively unexplored. As part of an extensive project to develop the chemistry of vinyl cations for use in carbon-carbon bond forming reactions to build important molecular scaffolds, a range of β-hydroxy-α-diazoketones containing a pendent nucleophilic alkene were synthesized. Treatment of these compounds with Lewis acids gave either lactone or cyclopentenone products depending on the substrate used. Proposed herein is a mechanism involving a key acylium intermediate which, depending on the position of the pendent alkene, results in different product outcomes. In a collaborative effort to further investigate the known anti-cancer properties of fusarochromanone, a fungal metabolite that is isolated from Fusarium-infected feed from cold climates, a large-scale synthesis of this natural product was explored. An efficient, scalable synthesis of the previously prohibitively expensive amidochromanone starting material has been achieved and its elaboration to fusarochromanone has been demonstrated.

Urban centers are major sources of contaminants to the surrounding air, water and soils. Above all, combustion-derived carbonaceous aerosols, especially black carbon (BC) and associated polycyclic aromatic hydrocarbons (PAHs), make significant contributions to the pollution in these systems. Here sedimentary records are used to produce a series of historical reconstructions of such contaminants to the Houston Ship Channel (HSC) system and compare these to point source inputs of hydrophobic organic contaminants (HOC). Analytical data on total organic carbon (TOC), BC, PAHs, dioxins and lignin (likely discarded from a pulp and paper mill along the Channel) were determined. This multi-proxy approach revealed that over the last several decades, HOC inputs to the system have been derived from a complex mixture of combustion processes, industrial point-sources, and oil spills. In particular, widespread dioxin contamination was observed throughout the study region with a particular site of the HSC showing total concentrations over 20,000 pg/g and 5000 pg toxic equivalent (TEQ)/g dry weight of sediment. Using two models based on sorption constants of total OC and BC, porewater concentrations were estimated to be lower than expected, at 20 pg/L and 5 pg TEQ/L. These values, however, are recognized as being extremely high for freely dissolved concentrations in porous media. The pulp and paper waste pit has recently been declared a Superfund site based on dioxin concentrations alone. The relationship between lignin biomarkers and dioxins observed in these sediments confirms that discharges of pulp and paper effluents were responsible for such high dioxin levels. Concentrations of BC, amorphous OC, and TOC were then used to calculate sediment binding of dioxins in sediments of the HSC. Our study found BC to be extremely low in HSC sediments (0.04 to 0.20%) indicating minimal dioxin sorption capacity. This suggests strong potential for fluxes of dioxins from sediments to the water column both through passive diffusion and physical mixing during natural and anthropogenic sediment remobilization events in this shallow system (hurricanes, storms, and dredging). The purposeful addition of BC to these sediments might be promising as a remediation strategy.

Polycyclic aromatic hydrocarbons (PAHs) are one of major classes of organic pollutants. As semi-volatile organic compounds, PAHs can be transported in the atmosphere and scavenged according to various processes (dry and wet deposition). Atmospheric deposition is an important pathway for the transfer of pollutants from atmosphere to the terrestrial and water surfaces. The objective of this research is to quantify the dry and wet deposition of the atmospheric PAHs in the Kaohsiung coastal area. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were also performed with diagnostic ratios to determine the potential sources of PAHs. The mean dry and wet deposition fluxes of atmospheric total suspended particles (TSP) during the study period (January-December 2010) were estimated to be 44.3 (6.60-384) and 211 (56.1-738) mg/m2d, respectively. The annual mean total PAH fluxes in dry and wet deposition were 1500 (749-3760) and 8470 (2280-46000) ng/m2d, respectively. Both concentrations and dry deposition fluxes of TSP were much higher during dust storm. During Ghost Month, however, they were comparable with other sampling events. By comparing with literatures, the total PAH concentrations of TSP were relatively low during Ghost Month, suggesting that wind direction and precipitation might be plausible. The ratio of PM2.5/PM10 had a relatively low value during dust storm, indicating that coarse particle might be predominant. In addition, during dust storm, both TSP dry deposition velocity and total PAH dry deposition velocity were higher than other sampling events. Our findings in this study showed that previous attempts in literature to estimate total PAH dry deposition fluxes by using TSP dry deposition velocity and PAH concentrations could lead to overestimate fluxes in the field. TSP dry deposition fluxes were positively correlated with atmospheric total TSP concentrations and TSP dry deposition velocity, but were correlated negatively with intensity of precipitation. In addition, TSP dry deposition velocity showed a positive correlation with TSP concentrations. Total PAH dry deposition fluxes were correlated positively with atmospheric total particulate concentrations and total PAH dry deposition velocity, but negatively with intensity of precipitation and temperature. However, TSP and total PAH fluxes in wet deposition were both correlated positively with intensity of precipitation. Diagnostic ratios showed that diesel exhaust was the main source of combustion-derived PAHs in the study. HCA and PCA analysis indicated that emissions from the ships and vehicles, and fuel used were the main sources of combustion-derived PAHs, while during special events, such as dust storm and Ghost Month, suggesting a different source of PAHs.

Cores and sediment traps collected from Kao-ping Canyon were used to reconstruct historical record of PAHs contamination and find out the possible sources, distributions, trends and flux of PAHs. The sedimentary record of PAHs shows that the average concentration of total PAHs was 310 ng/g dry wt. (264¡ã364 ng/g) which was lower than coasts of the other countries. According to diagnostic ratios and statistical analysis, we identify sources of PAHs and suggest that all up-cores were dominated by petrogenic sources, but all down-cores except for C980 and S1 were tended to pyrogenic or mixed sources. In contrast, both C980 and S1 were showed higher perylene/£UPAHs (%), which suggests that biogenic sources dominate in C980 and S1. In comparison with sediment quality guidelines (SQGs), the PAHs concentrations of all sediment cores weren¡¦t exceeded the criteria, which suggests that no evident adverse biological effects exist caused by PAHs in Kao-ping Canyon. It shows that the transition from coal to petroleum fuel use corresponding to the total concentrations of PAHs decrease recorded during 1893-1935 period in the sediment core. A PAHs concentration peak also recorded during the World War ¢º, 1893-1935. Because of increase of importing fossil fuel and the growth of heavy industrials in Kao-Ping area, the total concentrations of PAHs were shown evidence of increase again since 1950s in the core from Kao-ping Canyon. The average PAHs flux in the upper and lower mooring deployed in Kao-ping Canyon were 66 and 108 £gg/m2/d, respectively, which were higher than coasts of the other countries. The PAHs sources of sinking particles were dominated by petrogenic sources which were as similar sources as all up-cores.

Turning back to look Kaohsiung city¡¦s development and history of exploitation, both of them had a close relationship with the Love River and Chianjen River. Along the rivers, there are numerous industrial estates and large population. The basin of the rivers is important in politics and economy to Kaohsiung. However, the development of Kaohsiung also causes organic pollution, such as polycyclic aromatic hydrocarbon (PAHs), released to water system. Furthermore, some of these pollutants are carcinogenic, so that this topic is quite important. This study investigates PAHs concentrations and seasonal variations in sediments and suspended solids of these two rivers. Total PAHs concentrations varied from 110 to 4300(ng g-1 dry wt) in sediments and 1500 to 7000(ng g-1 dry wt) in suspended solids of the Love River. Total PAHs concentrations of sediments and suspended solids of the Chianjen River exhibited in the range of 230-3900 (ng g-1 dry wt) and 490-9200 (ng g-1 dry wt), respectively. The average PAHs concentration during rain/ dry season of the Chianjen River is significantly higher than those of the Love River. Compared with global data in literature, level of total PAHs concentrations in sediments and suspended solids of the Love River and Chianjen River belongs to moderate pollution. Total PAHs and total organic carbon (TOC) is significantly related except suspended solids of the Chianjen River. However, the relationship between total PAHs concentrations and mean particle size is not significant because of inequilibrium resulted from different sources. Referring to Sediment quality guidelines (SQGs), most of stations are in safe range, only total PAHs concentrations at station L8 in rainy season is significantly higher than the standard ERL value. For each individual compound, the concentrations of many low-molecular-weight PAHs are higher than their standard ERL¡BLET and LAET values. The result of HCA shows that in both dry and rain season, these two rivers¡¦ sediments and suspended solids are separated into upstream and downstream groups. It is believed that the existence of an intercept device set up in midstream of both rivers is the reason. The PAHs in sediments of the Love River is mainly contributed from automobile exhaustion, while suspended solids in the Love River is mainly contributed from petrogenic source. However, both sediments and suspended solids in the Chianjen River are mainly contributed from combustion pollution.