Muddringsprojekt är en global företeelse och görs av flera olika anledningar, till exempel för miljömässiga aspekter och för breddning av farleder. För att få en hållbar utveckling är det viktigt att finna bra lösningar på frågan hur förorenade sediment skall hanteras . I Mälaren kommer olika muddringsprojekt att genomföras för att bredda farleden från slussen i Södertälje till hamnarna i Köping och Västerås. Muddringsprojekten skall genomföras av Sjöfartsverket, Köpings kommun och Västerås stad. En metod för att omhänderta muddermassorna är att stabilisera/solidifiera dem genom att blanda i ett bindemedel bestående av en blandning av cement, masugnsslagg och aktivt kol och låta dem härda. Detta görs för att förbättra materialets geotekniska egenskaper samt för att immobilisera föroreningar. Syftet med detta examensarbete var att undersöka om det går att använda krossade stabiliserade/solidifierade muddermassor ovan vattenytan till exempel i vägkonstruktioner alternativt som fyllnadsmaterial. Möjligheten för användandet av de stabiliserade/solidifierade materialet utvärderades genom att materialets geotekniska och miljömässiga egenskaper undersöktes. Den miljöpåverkan som de stabiliserade/solidifierade materialet skulle kunna ha på den omgivning där de används har undersökts genom analyser av totala föroreningshalter samtkoncentrationer vid lakning. Detta gjordes dels genom egna skakförsök och dels genom utvärdering av resultat från undersökningar som Statens geotekniska instituts (SGI)miljölaboratorium gjort. När det gäller materialets geotekniska egenskaper utvärderades resultat från undersökningar genomförda av SGIs geotekniska laboratorium. Stabiliseringen/solidifiering gjorde att de undersökta metallerna som förekommer som katjoner immobiliserades, vilket ledde till att lakningen minskade. Däremot fungerade imobiliseringen inte för anjoner; om det skulle ha förekommit höga halter av toxiska anjoner som till exemple arsenik, vanadin och molybden skulle dessa ha lakats ut. Ur ett miljömässigt perspektiv skulle det gå bra att använda det undersökta materialet då koncentrationen i lakvätskan låg under de båda gränsvärden som används; gränsvärden för inert avfall och gränsvärden för mindre än ringa risk vid användning av avfall för anläggningsändamål. När det gäller hållfasthet uppfyllde materialet efter 28 dagars härdning inte kraven som ställs för användning i vägkonstruktion. Däremot hade materialets geotekniska egenskaper förbättrats jämfört med de obehandlade sedimenten. / Dredging is a global phenomenon carried out for several different reasons, e.g. environmental remediation and expansion of shipping lanes. A sustainable solution to the problem of how contaminated sediment should be handled is thus important to achieve a more sustainable development. Several dredging projects will be implemented in the lake Mälaren to widen the shipping lane from the lock in Södertälje to the ports of Köping and Västerås. The dredging will be carried out as a joint effort by the Swedish Maritime Administration, the City of Västerås and Köping municipality. One method used for treating dredged sediments is stabilization/solidification. This is carried out to improve the geotechnical properties of the material and to immobilize contaminants. The method works as follows: Sediments are dragged form the lake, mixed with a binding agent consisting of cement, granulated blastfurnace slag and active carbon and then left to harden. The objective of this master thesis was to investigate the feasibility of using the stabilized/solidified material on land above the water surface. Examples of applications for the crushed material are in road construction or as fillers for vegetation surfaces. The stabilized/solidified material was evaluated with respect to environmental factors and geotechnical properties to determine if it was appropriate to use for these applications. To investigate the potential impact of the stabilized/solidified material on the surrounding environment, analysis of total contamination content and leaching tests were evaluated. In this thesis, batch-leaching tests for metals were performed as well as evaluation of lab results from surveys conducted in the environmental laboratory at the Swedish Geotechnical Institute. The geotechnical properties of the material were evaluated based on results from experimentsconducted by the geotechnical laboratory at the Swedish Geotechnical Institute. The results from the treatment with stabilization/solidification showed that most of the studied metals were immobilized, and the leaching of these metals decreased. From an environmental perspective it would be feasible to use the material, as the results of the leaching test were below the limit values used in the assessment; limits for inert waste and limits for less than small risk (‘mindre än ringa risk’) in use of waste for construction purposes. In terms of the geotechnical features, after 28 days of hardening the material did not meet the requirements for use in road construction. However, the material's geotechnical properties such as strength had improved compared to the untreated sediments.

Polycyclic Aromatic Hydrocarbons (PAH) are an organic compound group consisting of cyclic molecules of two or more condensed benzene rings. All PAH are toxic to living organisms and their toxicity increases with increasing molecular weight. PAH are classified as environmental toxins but are currently not prohibited from emitting. The absence of a ban is based on the fact that the emission sources are difficult to eliminate. The present emissions mainly stem from wood burning, where heating is the primary purpose. Historically, PAH have also been released from various industrial activities. PAH are formed by incomplete combustion of organic matter at temperatures around 600°C. Thousands of tonnes are released annually and deposite over time in soils. The larger compounds become relatively immobile due to their unpolar properties. The longer the deposition takes place, the harder the PAH bind to the organic matter in the soil and cause that the decontamination work becomes more difficult over time. The remediation work is costly and because emissions are ongoing, this means that land that has been cleaned up in the long term will be re-contaminated.   The original purpose of this study has been to investigate the PAH contamination rate in a specific soil area. Originally, the purpose was also to investigate which factors affect the development of the contamination rate and potentially make the calculation work more difficult. Hypothetically, an average contamination rate could be obtained by combining measured concentrations of the PAH-16 standard from previous measurements at the same location with a current concentration from the same area plotted against time. However, measured values ​​from repeated measurements are missing. Thus, the recontamination rate at present cannot be calculated, at least not by this method. As part of future studies, it would be advisable to start taking soil samples, analyzing the PAH-16 and storing the values ​​in an existing environmental database in order to be able to monitor concentrations in soils over time. Part of the problem with this is that it is difficult to take a test at exactly the same location twice and concentrations can differ markedly even in small areas. A method for the precise selection of sampling site would therefore be appropriate to develop. The study describes the problems that are found in connection with extraction and analysis of PAH. In the extraction and analysis work itself, the most critical elements have been shown to be to extract all PAH substance from the soil sample and subsequently to avoid laboratory-related losses and to detect all compounds in the analysis. The study also reports on a number of factors that make it difficult to calculate the recontamination rate in the absence of measurement series missing.

Os hidrocarbonetos policíclicos aromáticos (HPAs) e seus derivados nitrados (nitro-HPAs) e oxigenados (oxi-HPAs) são compostos de grande interesse devido seus efeitos deletérios à saúde. Estes compostos são encontrados associados ao material particulado atmosférico e são formados durante a combustão de compostos orgânicos, no caso dos HPAs, e também por reações in situ através dos HPAs precursores, no caso dos nitro- e oxi-HPAs. Para avaliar a influência da queima de cana-de-açucar, amostras de material particulado foram coletadas nas cidades de Ourinhos e Araraquara (Estado de São Paulo), regiões afetadas pela queima de cana-de-açucar. Os filtros carregados foram submetidos à extração por Soxhlet, o extrato orgânico foi fracionado por HPLC e as frações de interesse foram analisadas por cromatografia a gás. Foram investigados 12 HPAs, 7 nitro-HPAs e 3 oxi-HPAs. Na cidade de Ourinhos coletou-se material particulado total (MPT) e material particulado em diferentes tamanhos. Os HPAs e a benzantrona (oxi-HPA) apresentaram concentrações maiores nas partículas menores, ao passo que nitro-HPA e os outros dois oxi-HPAs estudados (9-fluorenona e 9,10-antrona) predominaram nas partículas maiores. Em Araraquara foram coletadas amostras de MPT nos períodos diurno e noturno, e amostras de 24h nos períodos de safra e entressafra. Os HPAs e a benzantrona apresentaram predominância no período noturno, sugerindo que esses compostos devem ter sido provenientes de emissões da queima da cana-de-açucar, ao passo que os outros dois oxi-HPAs estudados (9-fluorenona e 9,10-antraquinona) não apresentaram esse comportamento. Os nitro-HPAs foram detectados em poucas amostras noturnas, provavelmente devido ao processo de remoção destes compostos por fotólise durante o dia. As correlações altas entre HPAs e alguns nitro-HPAs sugerem que tais compostos são provenientes provavelmente das mesmas fontes que os HPAs, embora alguns nitro-HPAs possam também ser formados in situ. Os compostos oxi-HPAs apresentaram correlações com alguns HPAs, mas devem ser também oriundos de outras fontes de emissão além da queima da cana-de-açúcar. De um modo geral, a queima desse tipo de biomassa parece influenciar nos níveis atmosféricos dos compostos estudados. / The polycyclic aromatic hydrocarbons (PAH) and their nitrated (nitro-PAH) and oxygenated (oxy-PAH) derivatives are compound of great interest due to their noxious effects on health. These compounds are found associated to the atmospheric particulate matter and are formed during the organic compound combustion, in case of PAH, and also by in situ reactions through the PAH precursors, in case of nitro- and oxy-PAH. In order to evaluate the sugar cane burning influence, particulate matter samples were collected at Ourinhos and Araraquara cities and submitted to Soxhlet extraction, frationating by HPLC and analized by gas-chromatography. 12 PAH, 11 nitro-PAH and 3 oxy-PAH were investigated. Total particulate matter and particulate matter in different particle sizes were collected at Ourinhos. Particulate matter in different particle sizes presented maximum concentration of PAH and benzanthrone (oxi-PAH) in the smaller particles, while nitro-PAH and the two other oxy-PAH (9-fluorenone and 9,10-anthraquinone) predominated in the larger particles. The sampling of total particulate matter in Araraquara was carried out in daytime and nighttime periods and also 24h sampling in harvest and post-harvest seasons. The PAH and the benzanthrone presented predominance in the nighttime period, suggesting sugar cane burning emissions. Moreover, the other two oxy-PAH (9-fluorenone and 9,10-anthraquinone) did not show that behavior. The nitro-PAH were detected in a few samples, and only at nighttime period in some cases. This is probably due to removal by photolysis during the daytime. The correlations between the compounds suggest a commom source between PAH and some nitro-PAH, although nitro-PAH can also be formed in situ. The oxy-PAH presented some correlations with PAH, but it seems that oxygenated PAH have another emission sources appart from burning. Biomass burning seems to influenciate the PAH and derivative levels in atmosphere.

Os hidrocarbonetos policíclicos aromáticos (HPAs) e seus derivados nitrados (nitro-HPAs) e oxigenados (oxi-HPAs) são compostos de grande interesse devido seus efeitos deletérios à saúde. Estes compostos são encontrados associados ao material particulado atmosférico e são formados durante a combustão de compostos orgânicos, no caso dos HPAs, e também por reações in situ através dos HPAs precursores, no caso dos nitro- e oxi-HPAs. Para avaliar a influência da queima de cana-de-açucar, amostras de material particulado foram coletadas nas cidades de Ourinhos e Araraquara (Estado de São Paulo), regiões afetadas pela queima de cana-de-açucar. Os filtros carregados foram submetidos à extração por Soxhlet, o extrato orgânico foi fracionado por HPLC e as frações de interesse foram analisadas por cromatografia a gás. Foram investigados 12 HPAs, 7 nitro-HPAs e 3 oxi-HPAs. Na cidade de Ourinhos coletou-se material particulado total (MPT) e material particulado em diferentes tamanhos. Os HPAs e a benzantrona (oxi-HPA) apresentaram concentrações maiores nas partículas menores, ao passo que nitro-HPA e os outros dois oxi-HPAs estudados (9-fluorenona e 9,10-antrona) predominaram nas partículas maiores. Em Araraquara foram coletadas amostras de MPT nos períodos diurno e noturno, e amostras de 24h nos períodos de safra e entressafra. Os HPAs e a benzantrona apresentaram predominância no período noturno, sugerindo que esses compostos devem ter sido provenientes de emissões da queima da cana-de-açucar, ao passo que os outros dois oxi-HPAs estudados (9-fluorenona e 9,10-antraquinona) não apresentaram esse comportamento. Os nitro-HPAs foram detectados em poucas amostras noturnas, provavelmente devido ao processo de remoção destes compostos por fotólise durante o dia. As correlações altas entre HPAs e alguns nitro-HPAs sugerem que tais compostos são provenientes provavelmente das mesmas fontes que os HPAs, embora alguns nitro-HPAs possam também ser formados in situ. Os compostos oxi-HPAs apresentaram correlações com alguns HPAs, mas devem ser também oriundos de outras fontes de emissão além da queima da cana-de-açúcar. De um modo geral, a queima desse tipo de biomassa parece influenciar nos níveis atmosféricos dos compostos estudados. / The polycyclic aromatic hydrocarbons (PAH) and their nitrated (nitro-PAH) and oxygenated (oxy-PAH) derivatives are compound of great interest due to their noxious effects on health. These compounds are found associated to the atmospheric particulate matter and are formed during the organic compound combustion, in case of PAH, and also by in situ reactions through the PAH precursors, in case of nitro- and oxy-PAH. In order to evaluate the sugar cane burning influence, particulate matter samples were collected at Ourinhos and Araraquara cities and submitted to Soxhlet extraction, frationating by HPLC and analized by gas-chromatography. 12 PAH, 11 nitro-PAH and 3 oxy-PAH were investigated. Total particulate matter and particulate matter in different particle sizes were collected at Ourinhos. Particulate matter in different particle sizes presented maximum concentration of PAH and benzanthrone (oxi-PAH) in the smaller particles, while nitro-PAH and the two other oxy-PAH (9-fluorenone and 9,10-anthraquinone) predominated in the larger particles. The sampling of total particulate matter in Araraquara was carried out in daytime and nighttime periods and also 24h sampling in harvest and post-harvest seasons. The PAH and the benzanthrone presented predominance in the nighttime period, suggesting sugar cane burning emissions. Moreover, the other two oxy-PAH (9-fluorenone and 9,10-anthraquinone) did not show that behavior. The nitro-PAH were detected in a few samples, and only at nighttime period in some cases. This is probably due to removal by photolysis during the daytime. The correlations between the compounds suggest a commom source between PAH and some nitro-PAH, although nitro-PAH can also be formed in situ. The oxy-PAH presented some correlations with PAH, but it seems that oxygenated PAH have another emission sources appart from burning. Biomass burning seems to influenciate the PAH and derivative levels in atmosphere.

Spilled heavy fuel oil (HFO) sinks within the water column and accumulates in sediments, affecting aquatic organisms that are not typically exposed to oils that float. Previously, the 3-4 ring alkyl substituted polycyclic aromatic hydrocarbons (PAHs) have been identified as the major toxic components in crude oil. Since HFO is comprised of higher concentrations of 3-4 ringed alkyl PAH and an abundance of 5-6 ringed PAH relative to crude oil, it is predicted to be more toxic to the early life stages of fish. An effects-driven chemical fractionation (EDCF) of HFO 7102 was undertaken to establish the toxicity relative to crude oil, and to identify the compounds that are bioavailable and chronically toxic to the early life stages of fish. In this EDCF, the complex HFO 7102 mixture was separated by low temperature vacuum distillation into three distinct fractions, 2, 3 and 4. Each fraction was assessed using a chronic bioassay to determine whether it contained components that caused toxicity to rainbow trout embryos similar to that of the whole oil. Acute bioassays with juvenile trout demonstrated the presence of compounds that induce cytochrome P450 enzymes, an indicator of exposure to PAH. Fraction 3, the fraction more toxic than the parent mixture, was further separated by cold acetone extraction into fraction 3-1 (PAH-rich extract) and fraction 3-2 (wax residue), and assessed with the same bioassays. Simultaneous chemical analysis with bioassays guided the fractionation, and identified compounds abundant and consistently present in toxic fractions. Due to resistance to dispersion of HFO, a chemical dispersant was used with vigorous mixing to drive the maximum amount of oil into solution to minimize the potential for false negatives and the volume of test material used. The potency of HFO 7102 and its fractions were also measured using water accommodated fractions (WAFs) produced by a continuous flow system of water flowing through oil coated gravel. Both exposure methods traced the toxicity from whole oil into fractions containing higher concentrations of 3-4 ring alkyl PAH, similar to crude oil. This research is the first toxicological assessment of HFO 7102, which is essential for determining the risk of spills of HFO to fish, and whether the risk of oils can be predicted from their alkyl PAH composition. / Thesis (Master, Biology) -- Queen's University, 2013-01-24 14:14:16.278

Les travaux de la thèse portent sur l'implication de la voie de signalisation Akt (sérine/thréonine kinase Akt) et mTOR (mammalian target of rapamycin) dans la physiopathologie de l'hypertension artérielle pulmonaire (HTAP) expérimentale. L'HTAP résulte d'une prolifération exagérée des cellules constitutives des vaisseaux pulmonaires, principalement les cellules musculaires lisses artérielles pulmonaires (CML-AP). De nombreux effecteurs biologiques et physiques préalablement identifiés agissent sur les CML-AP et participent à l'hyperplasie de celles-ci. Nous montrons que ces nombreux effecteurs convergent vers une voie de signalisation intracellulaire commune, la voie Akt/mTOR, qui de fait représente une cible thérapeutique pour le traitement de l'HTAP, et pourrait conditionner l'hyperplasie des CML-AP. mTOR est présent dans la cellule sous forme de deux complexes, mTORC1 et mTORC2, qui phosphorylent des substrats variés contrôlant la prolifération cellulaire. Les effecteurs de mTORC1 incluent les S6 kinases (S6K1 and S6K2) et les "eIF4E-binding proteins" (4EBP) alors que mTORC2 active la sérine/thréonine kinase Akt et parmi les kinases sous-jacentes, la kinase GSK3. La première étude est consacrée à l'évaluation des effets des inhibiteurs de protéases du VIH (ritonavir, amprenavir, nelfinavir) sur la progression de HTAP expérimentale, induite par la monocrotaline ou l'hypoxie. Nous montrons que ces deux formes d'HTAP sont associées à une activation de la voie Akt/mTOR dans les artères pulmonaires. Les traitements respectifs par les trois inhibiteurs des protéases du VIH durant 3 semaines induisent une réversibilité de l'HTAP, de l'hypertrophie ventriculaire droite et du remodelage des vaisseaux pulmonaires, de même qu'une inhibition de la phosphorylation d'Akt, de S6K et de GSK3. La prolifération des CML-AP induite par le PDGF ou le SVF 5%, associée à une augmentation de p-Akt et p-GSK3, est également bloquée par les inhibiteurs des protéases, de façon similaire et non additive à celle d'inhibiteurs spécifiques de la PI3 kinase et de GSK3. La conclusion est que ces traitements antirétroviraux inihibent la progression de l'HTAP en inhibant la voir Akt/mTOR dans les CML-AP. Cette proposition permettrait d'expliquer l'effet suspecté en clinique des traitements antirétroviraux sur l'HTAP compliquant l'infection par le VIH.Dans la seconde étude, nous montrons que les CML-AP en culture prélevées à partir de rats ayant développé une HTAP induite par la monocrotaline proliférent de façon exagérée en comparaison avec les cellules de rats témoins. Ce phénotype prolifératif est observé en présence de nombreux facteurs mitogènes parmi lesquels le SVF 5%, le PDGF, la sérotonine ou 5-HT, l'IGF1 ou l'IL1-beta, et est associé à une activation des substrats de mTORC1 et mTORC2. Le traitement in vitro par la rapamycine des CML-AP de rats avec HTAP établie permet d'inhiber la prolifération de ces cellules et de bloquer à la fois mTORC1 et mTORC2. De même, le traitement par la rapamycine de rats porteurs de l'HTAP préétablie pendant une semaine permet de normaliser la prolifération des CML-AP in vitro et in vivo et d'inhiber mTORC1 et mTORC2, effets non observés par l'Imatinib ou la Fluoxetine. De plus, le traitement des rats par la rapamycine prévient ou corrige l'HTAP induite par la monocrotaline de façon plus importante que l'Imatinib ou la Fluoxétine.Ces résultats indiquent donc que l'activation de la voie Akt/mTOR, très étroitement associée au développement de l'HTAP expérimentale, pourrait expliquer le phénotype prolifératif anormal des CML-AP inhérent à la pathologie, et ainsi représenter une cible thérapeutique de choix pour le traitement de l'HTAP humaine. / The major objectives of research described in this thesis is focused on the cell signaling pathway of Akt (serine/threonine kinase Akt) and mTOR (mammalian target of rapamycin) in the patho-physiology of experimental pulmonary arterial hypertension (PAH). PAH occurs as a result ofhyperplasia of the components of pulmonary vessels, principally the pulmonary arterial smooth muscle cells (PA-SMCs). Numerous previously identified biological and physical effectors act on the PA-SMCs and participate in PA-SMC hyperplasia. Here we show studied that these different effectors converge into a common intracellular signaling pathway, Akt/mTOR signaling pathway, which represents actually a therapeutic target for PAH treatment, and could be involved in the hyperplasia of PA-SMCs. In cells mTOR, is presented in the form of two complexes, mTORC1 and mTORC2, which phosphorylate various substrates controlling the cellular proliferation. The effectors of mTORC1 include the S6 kinases (S6K1 and S6K2) and eIF4E-binding proteins (4EBP), meanwhile mTORC2 activates the serine/threonine kinase Akt and the underlying kinases, e.g. GSK3 kinase.The first study is devoted to evaluate the effects of the protease inhibitors of HIV (ritonavir, amprenavir, nelfinavir) on experimental PAH development induced by monocrotaline or hypoxia. We studied that the two forms of PAH are associated with an activation of Akt/mTOR signaling pathway in pulmonary arteries. The treatment by the three protease inhibitors of HIV during 3 weeks causes reversibility in experimental PAH with decreased right ventricular hypertrophy and pulmonary vascular remodeling as well as inhibition of phosphorylation of Akt, S6K and GSK3. The proliferation of PA-SMCs stimulated by PDGF or FCS 5%, which is associated with an increased p-Akt and p-GSK3, is also blocked by the proteases inhibitors, in a similar and non additive way like the specific inhibitors of PI3 kinase and GSK3. We conclude that the antiretroviral treatments significantly inhibits PAH development by inhibiting Akt/mTOR signaling pathway in PA-SMCs. This proposition allows explaining the effect of antiretroviral treatments of PAH accompanied with HIV in patients.In the second study, we studied that the cultured PA-SMCs extracted from the rats with monocrotaline induced-PAH(MCT-PAH) proliferates faster as compared to control. This proliferative phenotype is observed in the presence of different mitogenic factors including FCS 5%, PDGF, 5-HT, IGF1 or IL-1β, and is associated with an activation of the substrates of mTORC1 and mTORC2. Treatment with rapamycin in the PA-SMCs extracted from the rats with PAH in vitro inhibits the proliferation and also blocks the activation of mTORC1 and mTORC2. The treatment by rapamycin in the rats with PAH during one week allows normalizing the proliferation of PA-SMCs in vitro and inhibiting the activation of mTORC1 and mTORC2 in vivo. These effects were not observed when treated with imatinib or fluoxetine. Moreover, treatment with rapamycin prevents or reverse MCT induced PAH more significantly than that by imatinib or fluoxetine.These results indicate that the activation of Akt/mTOR signaling pathway isclosely related to experimental PAH development, which can explain the abnormal proliferative phenotype of PA-SMCs involved in the patho-physiology of PAH, and represent a therapeutic target for the treatment of PAH in human.

As atividades a serem realizadas na área do empreendimento RMB (Reator Multipropósito Brasileiro), cujas instalações e infraestrutura agregadas serão localizadas no estado de São Paulo, no município de Iperó, podem envolver a liberação de efluentes para o meio ambiente, seja de forma controlada ou não, do mesmo modo que qualquer outra instalação. Os hidrocarbonetos policíclicos aromáticos (HPAs) estudados neste trabalho apresentam comportamento ubíquo, são considerados compostos químicos com alta toxicidade, persistência no meio ambiente, potencial bioacumulativo e forte tendência de se biomagnificar. O objetivo desse trabalho foi determinar 14 dos 16 HPAs majoritários, classificados pela USEPA, nas amostras de águas superficiais e subterrâneas da área de instalação do RMB e seu entorno. Foram avaliados quatro períodos distintos utilizando uma metodologia já desenvolvida e validada por Brito (2009). Foi verificado o cenário atual em relação às concentrações dos HPAs nas águas da região que será construído o empreendimento, RMB, fornecendo uma visão geral do grau de contaminação ou não dos corpos hídricos, o que contribuirá com um banco de dados para pesquisas futuras. Paralelamente, foi validado e aplicado um método analítico já existente para avaliação de HPAs nos sólidos suspensos da coluna d\'água das amostras coletadas. A avaliação preliminar da área estudada demonstrou que o local do projeto RMB é preservado, mas alguns corpos d\'água ao redor da área, como o rio Sorocaba, apresentam concentrações significativas de HPAs, provavelmente em razão das atividades antropogênicas no entorno, indicando que a área precisa de uma maior atenção. Utilizando a técnica analítica de HPLC com detecção UV/vis, foram quantificados compostos como Acenaftileno Fluoreno e Fenantreno acima do valor legislado nas amostras de água. Foram observadas baixas concentrações de praticamente todos os compostos estudados no material em suspensão e alguns compostos como Fluoreno, Acenafteno, Acenaftileno e Benzo[b]fluoranteno, em concentrações mais altas, é necessário um programa de monitoramento constante, para que a partir dos dados obtidos, possa-se tomar decisões concisas de controle. / The activities to be carried out in the area of the RMB (Brazilian Multipurpose Reactor) project, whose aggregate facilities and infrastructure will be located in the state of São Paulo, in the municipality of Iperó, may release effluents into the environment, either in a controlled or not in the same way as any other installation. The polycyclic aromatic hydrocarbons (PAHs) studied in this work are ubiquitous and considered chemical compounds with high toxicity, persistence in the environment, bio accumulative potential and strong tendency to bio magnify. The objective of this study was to determine 14 of the 16 major PAHs, classified by the USEPA, in the surface and groundwater samples of the RMB installation area and its surroundings. Four distinct periods were evaluated using a methodology already developed and validated. The current scenario was verified regarding the PAHs concentrations in the waters of the region that will be built the RMB, providing an overview of the degree of contamination of the water bodies, which will contribute to a database for future research. At the same time, an analytical method was validated and applied to evaluate PAHs in the suspended solids of the water column of the collected samples. The preliminary evaluation of the studied area demonstrated that the site of the RMB project is preserved, but some water bodies around the area, such as the Sorocaba River, present significant concentrations of PAHs, probably due to the anthropogenic activities in the surroundings, indicating that the area needs more attention. Using the analytical HPLC technique with UV/vis detection, compounds such as acenaphthylene, fluorene and phenanthrene were quantified above the legislated value in the water samples. Although low concentrations of practically all compounds studied in the suspended material have been observed and some compounds such as fluorene, acenaphthene, acenaphthylene, and benzo[b]fluoranthene at high concentrations, a constant monitoring program is required to that from the data obtained, one can make concise decisions of command and control.

The drift time spectra of polycyclic aromatic hydrocarbons (PAH), alkylbenzenes and alkylphenylethers were recorded with a laser-based ion mobility (IM) spectrometer. The ion mobilities of all compounds were determined in helium as drift gas. This allows the calculation of the diffusion cross sections (Omegacalc) on the basis of the exact hard sphere scattering model (EHSSM) and their comparison with the experimentally determined diffusion cross sections (Omegaexp). These Omegaexp/Omegacalc-correlations are presented for molecules with a rigid structure like PAH and prove the reliability of the theoretical model and experimental method. The increase of the selectivity of IM spectrometry is demonstrated using resonance enhanced multiphoton ionisation (REMPI) at atmospheric pressure, realized by tuneable lasers. The REMPI spectra of nine alkylbenzenes and alkylphenylethers are investigated. On the basis of these spectra, the complete qualitative distinction of eight compounds in a mixture is shown. These experiments are extended to alkylbenzene isomer mixtures.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants known for their photoinduced toxicity. There are two mechanisms through which this may occur: photosensitization and photomodification. Photosensitization generally leads to the production of singlet oxygen, a reactive oxygen species (ROS), which is highly damaging to biological molecules. Photomodification of PAHs, usually via oxygenation, results in the formation of new compounds (oxyPAHs), and can occur under environmentally relevant levels of actinic radiation. <br /><br /> PAHs and oxyPAHs readily adsorb to the organic phase of particulate matter in the environment such as sediments. It is logical to conclude that sediment transport will also facilitate the transport of these contaminants, and it has been shown that in the course of transport, degradative processes evoke a change in the profile of the PAHs present. Sediment samples taken along a transect from Hamilton Harbour were fractionated, and analyzed using a 2D HPLC method. All sediments contained intact and modified PAHs, although a marked change was noted in the profile of compounds present in the samples, which differ in distance from shore. Fractions of sediment extract were tested for toxicity using a bacterial respiration assay. Toxicity was observed in fractions containing modified PAHs, and was similar to that of intact PAH-containing fractions. <br /><br /> Subsequently, the toxicities of 16 intact PAHs were assessed to <i>Daphnia magna</i> under two ultraviolet radiation (UV) conditions. The toxicity of intact PAHs generally increased in the presence of full spectrum simulated solar radiation (SSR), relative to visible light plus UVA only. To expand the existing data on the effects of PAH photoproducts to animals, fourteen oxyPAHs were also assayed with <i>D. magna</i>, most of which were highly toxic without further photomodification. The data presented highlight the effects of UV radiation on mediating PAH toxicity. The importance of the role of photomodification is also stressed, as several oxyPAHs were highly toxic to <i>D. magna</i>, a key bioindicator species in aquatic ecosystems. <br /><br /> A QSAR model previously developed for <i>Lemna gibba</i> showed that a photosensitization factor (PSF) and a photomodification factor (PMF) could be combined to describe toxicity. To determine whether it was predictive for <i>D. magna</i>, toxicity was assessed as both EC50 and ET50. As with <i>L. gibba</i> and <i>Vibrio fischeri</i>, neither the PSF nor the PMF alone correlated to D. magna toxicity. However, a PSF modified for <i>D. magna</i> did in fact exhibit correlation with toxicity, which was further improved when summed with a modified PMF. The greatest correlation was observed with EC50 toxicity data. This research provides further evidence that models that include factors for photosensitization and photomodification will likely be applicable across a broad range of species. To gain further knowledge of the roles that the variables contributing to the photosensitization and photomodification, a structural equation model was constructed based on the <i>D. magna</i> QSAR. This model accounted for a high amount of variance in six sets of toxicity data, as well as insight into the mechanisms of phototoxicity affecting different aquatic organisms.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants known for their photoinduced toxicity. There are two mechanisms through which this may occur: photosensitization and photomodification. Photosensitization generally leads to the production of singlet oxygen, a reactive oxygen species (ROS), which is highly damaging to biological molecules. Photomodification of PAHs, usually via oxygenation, results in the formation of new compounds (oxyPAHs), and can occur under environmentally relevant levels of actinic radiation. <br /><br /> PAHs and oxyPAHs readily adsorb to the organic phase of particulate matter in the environment such as sediments. It is logical to conclude that sediment transport will also facilitate the transport of these contaminants, and it has been shown that in the course of transport, degradative processes evoke a change in the profile of the PAHs present. Sediment samples taken along a transect from Hamilton Harbour were fractionated, and analyzed using a 2D HPLC method. All sediments contained intact and modified PAHs, although a marked change was noted in the profile of compounds present in the samples, which differ in distance from shore. Fractions of sediment extract were tested for toxicity using a bacterial respiration assay. Toxicity was observed in fractions containing modified PAHs, and was similar to that of intact PAH-containing fractions. <br /><br /> Subsequently, the toxicities of 16 intact PAHs were assessed to <i>Daphnia magna</i> under two ultraviolet radiation (UV) conditions. The toxicity of intact PAHs generally increased in the presence of full spectrum simulated solar radiation (SSR), relative to visible light plus UVA only. To expand the existing data on the effects of PAH photoproducts to animals, fourteen oxyPAHs were also assayed with <i>D. magna</i>, most of which were highly toxic without further photomodification. The data presented highlight the effects of UV radiation on mediating PAH toxicity. The importance of the role of photomodification is also stressed, as several oxyPAHs were highly toxic to <i>D. magna</i>, a key bioindicator species in aquatic ecosystems. <br /><br /> A QSAR model previously developed for <i>Lemna gibba</i> showed that a photosensitization factor (PSF) and a photomodification factor (PMF) could be combined to describe toxicity. To determine whether it was predictive for <i>D. magna</i>, toxicity was assessed as both EC50 and ET50. As with <i>L. gibba</i> and <i>Vibrio fischeri</i>, neither the PSF nor the PMF alone correlated to D. magna toxicity. However, a PSF modified for <i>D. magna</i> did in fact exhibit correlation with toxicity, which was further improved when summed with a modified PMF. The greatest correlation was observed with EC50 toxicity data. This research provides further evidence that models that include factors for photosensitization and photomodification will likely be applicable across a broad range of species. To gain further knowledge of the roles that the variables contributing to the photosensitization and photomodification, a structural equation model was constructed based on the <i>D. magna</i> QSAR. This model accounted for a high amount of variance in six sets of toxicity data, as well as insight into the mechanisms of phototoxicity affecting different aquatic organisms.