Σκοπός της παρούσας μελέτης είναι η κατανόηση του μηχανισμού ρόφησης του φαινανθρενίου σε δείγματα γαιανθράκων και των αντίστοιχων χουμικών τους οξέων και η διερεύνηση της καταλληλότητας τους ως ροφητικών υλικών για την απορρύπανση ποτάμιων και λιμναίων συστημάτων, στα οποία υπάρχει πρόβλημα ρύπανσης από πολυκυκλικούς αρωματικούς υδρογονάνθρακες. Για την επίτευξη του σκοπού αυτού μελετήθηκαν τέσσερα δείγματα λιγνίτη και δύο δείγματα τύρφης και τα αντίστοιχα δείγματα των χουμικών οξέων. Η μεθοδολογία που ακολουθήθηκε για την απομόνωση των χουμικών οξέων βασίστηκε στην τροποποιημένη μεθοδολογία, που προτείνεται από την IHSS (International Humic Substances Society). Για τη μελέτη της ρόφησης φαινανθρενίου κατασκευάστηκαν οι ισόθερμες καμπύλες ρόφησης, ύστερα από την πραγματοποίηση πειραμάτων ρόφησης με συγκεντρώσεις φαινανθρενίου σε υδατικά διαλύματα 30, 50, 100, 300 και 500 μg/l. Τα αποτελέσματα δείχνουν ότι η ρόφηση στα περισσότερα δείγματα των χουμικών οξέων είναι μεγαλύτερη από ό,τι στα αντίστοιχα δείγματα των μητρικών τους γαιανθράκων. Επίσης στα δείγματα των γαιανθράκων παρατηρείται μεγαλύτερη ρόφηση στις χαμηλές συγκεντρώσεις φαινανθρενίου από ό,τι στις υψηλές, με αποτέλεσμα η ρόφηση να μην είναι γραμμική. Σχετικά με τη χρήση τους ως ροφητικά υλικά για απορρύπανση για δυο δείγματα λιγνίτη προτείνεται η χημική τους επεξεργασία, προκειμένου να χρησιμοποιηθούν ως ροφητικά υλικά, ενώ για τα υπόλοιπα δείγματα η διαφορά στη ροφητική ικανότητα μεταξύ των μητρικών γαιανθράκων και των παραγόμενων χουμικών οξέων δεν είναι τόσο σημαντική, με αποτέλεσμα να μπορεί να χρησιμοποιηθεί απευθείας το μητρικό υλικό / The scope of this study is the determination of the phenanthrene sorption mechanism for some Greek lignite and peat samples, as well as for their extracted humic acids. The scope is to assess their suitability for application in remediation of fresh water environments from polycyclic aromatic hydrocarbons (PAHs) For the extraction of the humic acids, the methodology provided by the IHHS (International Humic Substances Society) with some alterations, was applied. The sorption experiments were conducted by mixing 0,004 g of the sorbent within water solutions of phenanthrene at different concentrations of 30, 50, 100, 300 and 500 μg/l. The results show that phenanthrene sorption is higher in the humic acid samples rather than in the original lignite and peat. The original samples display higher sorption at low phenanthere concentration solutions (30 μg/l) than at the denser phenanthrene concentration solution (500 μg/l). Thus, the sorption in these samples is non-linear. In order to use these materials as sorbents, the TH4 and MT6 samples might have to be treated, because sorption is higher in the humic acid fraction than in the source material. The rest of the samples display lower variation in the sorption capacity between the humic acid samples and the original samples, thus there is no need for chemical treatment.

Made available in DSpace on 2015-04-17T14:49:12Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1477687 bytes, checksum: 499775300ecca263fde140f8d1c98bb3 (MD5) Previous issue date: 2010-09-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The aim of this work was to evaluate the PAHs contamination in muscular tissue and bile of Mugil liza fishes from Guanabara Bay. The Guanabara Bay is an estuarine ecosystem with high anthropogenic influence which receives chronic pollution from Rio de Janeiro city. It was determined 38 compounds (16 PAHs EPA + alkylated ones) in muscular tissue samples of 41 fishes captured from August 2008 to October 2008. Statistical analyzes showed that the data concentration has a normal distribution and drawn from the same population, with mean concentration of 127 ng/g and standard deviation of 18 ng/g to the 16 PAHS EPA. The mean concentration for the 38 compounds was 274 ng/g and standard deviation of 59 ng/g. It was determinated 13 metabolites of PAHs of 30 Mugil liza fishes (n=30) captured in the inner part of the Guanabara Bay. The metabolites determined were OH-Naphthalenes, OH-Biphenyl, OH-Fluorene, OH-Phenantrenes, OH-Pyrene, OH-Chrysene, OH-Benz(a)pyrene. It was observed in this study a normal distribution of concentrations for both set of data: bile PAH metabolites and PAH muscular tissue. This indicates the existence of two data populations. The mean concentration of PAH metabolites obtained was 1,039 ng/g and standard deviation of 624 ng/g. These data can be used as back ground to the inner part of Guanabara Bay. The bioindicator in this study, Mugil liza fish, has shown to be effective to evaluate the contamination and exposition of Guanabara Bay ecosystem to PAH. / Este trabalho teve como objetivo a avaliação da contaminação por HPAs em peixes provenientes da Baía de Guanabara através da identificação e quantificação desses compostos em tecido muscular e de seus metabólitos em bile. A Baía de Guanabara é um ecossistema estuarino de forte influência antropogênica que recebe poluição crônica da região metropolitana do Rio de Janeiro. Foram analisados 41 amostras de peixes da espécie Mugil liza (Tainha) coletados na Baía de Guanabara no período de agosto a outubro de 2008. Nos tecidos musculares foram quantificados 38 compostos (16 HPAs EPA e seus respectivos alquilados). A análise estatística revelou que esse grupo de dados é proveniente de uma mesma população com distribuição normal, com valor médio de concentração de 127 ng/g e desvio-padrão populacional de 18 ng/g para o Σ 16 HPAs e concentração média populacional para o Σ 38 HPAs de 274 ng/g e desvio-padrão de 59 ng/g. Em sequência, foi realizada a avaliação do nível de exposição a que os organismos aquáticos da Baía de Guanabara estão submetidos, através da análise de 30 amostras de bile de peixes da espécie Mugil Liza provenientes de currais da área de fundo da Baía de Guanabara, onde foram quantificados 13 metabólitos individuais de HPAs. Os metabólitos determinados foram 1-OH-Naftaleno, 2-OH-Naftaleno, 2-OH-Bifenila, 3-OH-Fluoreno, 1-OH-Fenantreno, 2-OH-Fenantreno, 3-OH-Fenantreno, 4-OH-Fenantreno, 9-OH-Fenantreno, 1-OH-pireno, 1-OH-criseno, 3-OH-benzo(a)pireno e 9-OH-benzo(a)pireno. O valor médio de concentração do somatório dos metabólitos foi de 1.039 ng/g e desvio-padrão populacional de 623 ng/g. Esses dados podem ser utilizados como valores característicos para a região já que apresentaram uma distribuição normal. As concentrações determinadas encontraram-se dentro da faixa de outras regiões com influência antropogênica elevada, com aporte crônico de hidrocarbonetos. O bioindicador utilizado neste estudo, o peixe da espécie Mugil liza, mostrou-se efetivo para a avaliação da contaminação por HPAs em um ecossistema como a Baía de Guanabara.

Les hydrocarbures aromatiques polycycliques (HAP) constituent une famille de polluants cancérigènes, classés comme prioritaires tant en environnement qu’en milieu professionnel avec près de 1,6 millions de travailleurs exposés en France. L’évaluation des risques sanitaires (ERS) est primordiale mais reste difficile à mettre en place car ces composés sont toujours émis sous forme de mélanges complexes de gaz et de particules dont la composition varie en fonction des sources d’émission.Les objectifs de ce travail sont de caractériser, dans les différents secteurs industriels français, les expositions professionnelles (niveaux de concentration et composition chimique des mélanges) afin d’estimer les risques de cancer liés à ces expositions. Ce travail est réalisé à partir de la base Exporisq-HAP (E-HAP) qui comprend plus de 1700 données d’exposition atmosphérique ainsi que 40 variables explicatives collectées dans 130 entreprises avec la même méthodologie et codées par le même toxicologue depuis près de 20 ans.Pour conduire l’ERS, les données ont été structurées selon deux dimensions (homogénéité et précision de description), permettant de construire des groupes homogènes d’exposition (GHE) et une analyse descriptive du paysage industriel français. En prenant le benzo[a]pyrène (BaP, HAP le plus dangereux) comme indicateur, près de 40% des activités professionnelles (niveau de codage le plus fin de la base) correspondaient à des GHE (écart-type géométrique ≤ 3) mais l’ajout d’un niveau de description supplémentaire a permis d’augmenter ce pourcentage à 87%. Des variabilités importantes des niveaux de concentration, des compositions chimiques des mélanges et des risques encourus (facteur 2 pour les bitumes à 500 pour les fonderies) lors d’une mono-exposition aux HAP (e.g., BaP, naphtalène…) existaient entre et au sein des industries, soulignant l’importance de recueillir le détail des activités effectuées par le salarié pour caractériser précisément les expositions. Dans la seconde étape, les multi-expositions aux HAP ont été analysées en termes de groupes de fonction d’exposition similaire (GFES basés sur plusieurs HAP). Ces fonctions (distributions des concentrations d’HAP) ont été utilisées pour décrire le paysage industriel français aux mélanges d’HAP, construire des marqueurs de la multi-exposition atmosphérique et réaliser l’estimation préliminaire des risques de survenue de cancers. En plus du BaP, le benzo[k]fluoranthène et le benzo[ghi]pérylène sont apparus comme des indicateurs intéressants de la multi-exposition aux HAP cancérigènes, ce qui n’était pas le cas du pyrène (gazeux ou particulaire), du naphtalène ni du phénanthrène. Les GFES étaient constitués de groupes dont l’origine des sources était la même –produits dérivés de pétrole (GFESP) ou de houille (GFESH). Les GFESH (production d’aluminium, de silicium, de produits carbonés, cokeries, fonderies) avaient des niveaux de concentration élevés et un risque important de cancer du poumon (compris entre 1/100 000 à 1/1 000 de risque d’observer un cas additionnel de cancer du poumon) ; ce qui n’était pas le cas des GFESP (émissions moteurs, huiles, combustion, bitume) pour lesquels les risques de cancers sont compris entre 1/100 000 et un sur 1 million de sujets exposés. Les mesures de prévention et de protection sont encore à améliorer dans les GFESH afin de réduire les risques de survenue de cancers. / Polycyclic aromatic hydrocarbons (PAHs) are a family of organic carcinogens substances, ranked second amongst priority targeted pollutants in the environment as well as in occupational settings where around 1.6 million workers are exposed in France. Sanitary risks assessment (SRA) is paramount but remains difficult to set up considering that PAHs are always emitted in complex mixtures of gas and particles whose composition depends on emission sources.The goals of this PhD were to characterize exposures within industries (levels and chemical composition of PAHs mixtures) in order to assess the cancer risk from occupational exposure to PAHs mixtures. This work was performed using the Exporisq-HAP database (E-HAP) that gathers more than 1,700 airborne exposure data as well as 40 independent variables collected in 130 companies with the same methodology and coded by the same toxicologist for 20 years.To conduct the SRA, data were structured following two dimensions (homogeneity and description accuracy), enabling the construction of similar exposure groups (SEGs) and the descriptive analysis of the French industrial landscape. Using the benzo[a]pyrene as indicator (BaP, the most dangerous PAH), about 40% of the occupational activities (most accurate description level in E-HAP) could be considered as SEGs (geometric standard deviation ≤ 3). Adding a new description level increased this percentage to 87%. High variabilities existed between and within industries in terms of concentrations levels, chemical mixtures composition and risk (between 2 for bitumen to 500 times within foundries) caused by mono-exposure to PAHs (e.g., BaP, naphthalene…). This underlines the importance of collecting detailed information on occupational activities performed by workers to accurately describe and characterize exposures. In the second step, multi-exposures to PAHs were analyzed in terms of similar exposure function groups (SEFG based on several PAHs). Exposure functions (PAHs concentrations distributions) were used to describe the French PAHs industrial landscape, to construct markers of the multi-exposures to airborne PAHs and to perform the preliminary assessment of the cancer risk caused by these mixtures. Besides BaP, benzo[k]fluoranthene and benzo[ghi]perylene were found to be indicators of the multi-exposures to airborne carcinogenic PAHs, which was not the case for pyrene (gaseous and particulate forms), naphthalene and phenanthrene. SEFGs were made up of groups with the same source origin –either from products derived from coal (SEFGH) or petroleum (SEGFP). SEFGH (aluminum, silicon, carbon product, coke production, and foundry) had high concentration levels and high risk of lung cancer (between 100,000 to 1 risk to 1,000 to 1 risk to observe one additional case of lung cancer). It was different for SEGFP (engine emissions, lubricating oil, combustion, bitumen) that had between 100,000 to 1 risk to a million to 1 risk of additional lung cancer. To reduce cancer risks, risk management measures still need improvements in all SEFGH.

Les sols contaminés par les polluants organiques hydrophobes tels que les Hydrocarbures Aromatiques Polycycliques (HAPs) constituent un problème majeur puisqu'ils sont difficilement éliminés et leurs impacts toxicologiques restent significatifs. Comme alternative aux procédés thermiques et physiques traditionnels, les procédés de lavages de sol in situ et ex situ apparaissent être une solution envisageable et efficace et particulièrement pour les fortes pollutions. Cependant, le traitement des solutions fortement chargées de lavages de sol est une autre barrière à surmonter. Une nouvelle approche combinée est proposée pour répondre à ce problème: les procédés de lavages de sol in situ/ex situ combinés à un Procédé Electrochimique d'Oxydation Avancée Electrochimique (PEOA) avec possibilité de recirculer l'effluent (pour réutiliser l'agent extractant) et/ou de combiner avec un post-traitement biologique (pour minimiser le coût énergétique).L'efficacité d'extraction de l'agent extractant tel que l'hydroxypropyl-beta-cyclodextrine (HPCD) est comparé au traditionnel tensioactif non-ionique dénommé Tween 80, dans les solutions synthétiques et réelles de lavages de sol. Une nouvelle méthode sensible d'analyse du Tween 80, basée sur la fluorescence, est développée pour suivre l'oxydation du Tween 80. Deux PEOAs sont comparés : l'électro-Fenton (EF) et l'oxydation anodique (OA). Les anodes de platine (Pt) (dans le procédé EF) et de diamant dopés au bore (BDD) (dans les deux procédés) sont respectivement utilisées pour étudier la recirculation des effluents et la possibilité d'une combinaison avec un post-traitement biologique. Concernant la réutilisation des agents extractants, l'évolution de la biodégradabilité des solutions et l'énergie consommée (en kWh (kg COT)-1) pendant les PEAOs testés, l'HPCD est trouvée être plus avantageuse que le Tween 80. En revanche, en terme d'efficacité d'extraction, de coût des agents extractants et d'impact sur la respirométrie du sol, le Tween 80 paraît être plus avantageux. En prenant en compte tous ces avantages et inconvénients, le Tween 80 pourrait être retenu comme la meilleure solution / Soils contaminated by hydrophobic organic pollutants like polycyclic aromatic hydrocarbons (PAHs) are a common concern since they are extremely difficult to remove and their potential toxicological impacts are significant. As an alternative to traditional thermal or physical treatments, soil washing and soil flushing processes appear to be conceivable and efficient approaches, especially for higher level of pollution. However, the treatment of highly loaded soil washing/flushing solutions is another challenge to overcome. In that way, a new integrated approach is suggested: soil washing/flushing processes combined to an electrochemical advanced oxidation process (EAOP) in a combination with a recirculation loop (to save extracting agents) and/or a biological post-treatment step (to minimize energy cost).Extraction efficiency of the extracting agent like hydroxypropyl-beta-cyclodextrin (HPCD) is compared to the traditional non-ionic surfactant Tween 80 in synthetic and real soil washing solutions. A new simple fluorescent sensitive and selective quantification method is developed to monitor Tween 80 oxidation. Two EAOPs were compared: electro-Fenton (EF) and anodic oxidation (AO). Platinum (Pt) (in EF process) and boron doped diamond (BDD) (in both treatment) anodes are the respective electrodes employed to recycle effluents and to consider a biological post-treatment, respectively. Regarding the extracting agent recovery, the biodegradability evolution of effluent and the energy consumption (in kWh (kgTOC)-1) during EAOP, HPCD is more advantageous than Tween 80. However, in terms of extraction efficiency, costs of extracting agents and impact on soil respirometry, Tween 80 is much more efficient. By considering all these advantages and drawbacks, Tween 80 could still appear to be the best option

A concentração de Fe, Ni, Cd, Mn, Zn, Cr e Pb, determinada por TXRF, foi investigada em matrizes de água, sedimento e fígados de peixes, amostrados em rios da região mineradora de carvão de Criciúma - SC/Brasil - afetadas por descargas de drenagem ácida de mina (DAM). A relação destes metais com a toxicidade para o bioindicador Daphnia magna (24 e 48 h) foi avaliada, sendo estabelecida correlação entre [Fe]solúvel e toxicidade à D. magna nas amostras de água. Para os sedimentos, há indícios de correlação dos teores de Fe e toxicidade, e nos fígados suspeita-se de níveis de Zn alterados. Efluentes da mineração, incluindo a DAM, após o tratamento por floculação e/ou decantação e/ou flotação e alcalinização mantiveram toxicidade mesmo com os metais reduzidos para concentrações não tóxicas à D. magna. Creditou-se a toxicidade remanescente a hidrocarbonetos policíclicos aromáticos (HPAs, determinada por CG/MS). Foram testados três adsorventes de baixo custo na retenção de metais (Fe, Ni, Cd, Mn, Zn, Cr e Pb) em soluções ácidas multimetais: casca de arroz (CA), carvão de casca de arroz (CCA) e turfa e carvão ativado comercial (CAC – adsorvente de confronto). As quantidades máximas adsorvidas dos metais (mg) por massa de sorbente (g) - qm, somatório dos metais, foram: CA 75,46 mg g-1; CAC 78,2 mg g-1; turfa 111,3 mg g-1 e CCA 137,49 mg g-1, (Langmuir e Freundlich - não linear). A toxicidade dos metais para D. magna destes eluatos foi reduzida. Foram preparados compósitos a partir de casca de arroz com deposição in situ de TiO2 (CCT – carbon covered with titanium), e testados como catalisador em Processos Oxidativos Avançados (POA). Os catalisadores TiO2 (P25 Degussa) e CCTs (25 e 50% de TiO2) em POA mostraram remoção dos HPAs e da toxicidade (D. magna e Scenedesmus subspicatus) nos efluentes de mineração, adequando os níveis de toxicidade à legislação ambiental vigente (Portaria FATMA 017/02) com resultados superiores do CCT. Assim, a presente tese alega que o uso de adsorventes à base de carvão de casca de arroz é capaz de reter os metais tipicamente presentes em efluentes ácidos (mineração de carvão), e que a toxicidade remanescente nestes efluentes, devida aos HPAs, pode ser reduzida pelo uso de POA, com incremento de eficiência quando o compósito CCT aqui desenvolvido é utilizado. / The concentration of Fe, Ni, Cd, Mn, Zn, Cr and Pb, determined by TXRF, was investigated in matrixes as water, sediment and fish liver, sampled at mining of coal region rivers from Criciúma - SC/Brazil – targets by acid mine drainage (ADM) discards. The relation of these metals with toxicity to Daphnia magna bioindicator (24 and 48 h) was evaluated, being established a correlation between [Fe]soluble and toxicity to D. magna in water samples. In sediments, correlation between Fe levels and toxicity was observed, and in liver Zn levels were altered. Mining effluents including AMD, after treatment by flocculation and/or decantation and/or flotation and alkalinization remain toxic even when metal concentrations had been reduced to levels which would be non toxic to D. magna. Residual toxicity was accounted to the presence of polycyclic aromatic hydrocarbons (PAHs, determined by GC/MS). Three low cost adsorbents were tested in metal retention (Fe, Ni, Cd, Mn, Zn, Cr and Pb) from multielemental acid solution: rice husk (RH), rice husk carbon (RHC), peat and commercial activated carbon (CAC – confront adsorbent). The maximum quantity of adsorbed metals (mg) by sorbent mass (g) - qm, as metals sum, were: CA 75.46 mg g-1; CAC 78.2 mg g-1; peat 111.3 mg g-1 and CCA 137.49 mg g-1, (Langmuir and Freundlich – non linear). The metal toxicity to D. magna of these eluates was reduced. Composites from rice husk with in situ deposition of TiO2 were synthesized (CCT – carbon covered with titanium), and tested as catalyst in advanced oxidative process (AOP). The catalysts TiO2 (P25 Degussa) and CCTs (25 e 50% de TiO2) in AOP showed PAHs and toxicity remotion (D. magna and Scenedesmus subspicatus) on mining effluents, adjusting toxicity levels to environmental legislation in force (FATMA 017/02), with best results to CCT. Then, the present thesis argues that rice husk carbon adsorbents is capable of retaining the metals typically presents in acid effluents (coal mining), and that remain toxicity in these effluents, from PAHs, can be reduced by AOP use, with efficient increasing when the composite here developed (CCT) is employed.

A emissão de uma grande diversidade de substâncias através dos efluentes industriais gasosos, líquidos ou sólidos acarreta que uma gama de compostos seja introduzida no ambiente atmosférico e aquático de meios urbanos. A exposição a substâncias genotóxicas no ambiente oferece freqüentemente um grande risco à saúde humana. Com essa preocupação, o presente trabalho avaliou a exposição das pessoas à qualidade do ar atmosférico e à da água para abastecimento público de duas cidades urbanas do Rio Grande do Sul (Brasil), que recebem diferentes contribuições antrópicas (cidades-alvo), comparando-as com uma cidade menos impactada - cidade referência. Os extratos orgânicos da água tratada para abastecimento público e das amostras de ar foram testados quanto a mutagenicidade através do ensaio Salmonella/microssoma (linhagens TA98 e TA100 para água e ar, com e sem fração de metabolização e, ainda para ar, YG1021 e YG1024) - marcador de mutagenicidade. As amostras de ar ainda foram analisadas por HPLC para a caracterização de HPAs e algumas amostras também por HRGC-HRMS para a composição dos PCDD/Fs. Para o biomonitoramento humano foram avaliados através do ensaio do cometa e do micronúcleo (MN), em linfócitos e células da mucosa bucal, respectivamente, as pessoas que viviam nas três cidades - biomarcador de efeito. Análises de polimorfismos genéticos (CYP1A1, GSTM1 e GSTT1) foram utilizados como biomarcadores de susceptibilidade. As duas cidades-alvo apresentaram resultados significativos quanto a mutagenicidade da água de abastecimento apresentando todos os resultados positivos, principalmente para mutação de substituição de pares de bases (TA100), indicando a presença de compostos como THMs e MX. Valores de PTS atmosféricos apresentaram-se em algumas amostragens acima dos limites da legislação brasileira (CONAMA, 1990). Os HPAs encontrados em maior quantidade foram indeno(1,2,3-c,d)pireno e benzo(ghi)perileno, sendo que em uma das amostras a análise dos PCDD/Fs, mostrou valores que superaram em dez vezes a outra amostra analisada. As duas cidades alvo apresentaram altas respostas mutagênicas nas amostras de ar tanto por mutágenos de ação direta, como indireta e também altas concentrações de nitro-HPAs. Estes resultados sinalizaram para a necessidade de uma revisão da legislação para material particulado atmosférico, já que dentro dos atuais parâmetros, grande quantidade de compostos mutagênicos foram encontrados. Para os indivíduos estudados quanto aos biomarcadores de efeito, tanto os linfócitos analisados pelo ensaio do cometa quanto às células da mucosa bucal pelo ensaio do MN não apresentaram resultados significativos, sendo que apenas uma cidade alvo apresentou quanto ao ensaio do cometa. Como a maioria dos indivíduos CYP1A1, GSTM1 e GSTT1 apresentaram genótipos prevalentes, pode estar ocorrendo uma eficiência no sistema de detoxificação garantidos pela presença desses genótipos. Este trabalho mostrou a importância de estudos ambientais que relacionem marcadores de mutagenicidade com biomarcadores de efeito e de susceptibilidade, para que haja uma maior compreensão dos efeitos da exposição humana diária à agentes genotóxicos ambientais. / The emission of a great substances amount through gaseous, liquid and solid industrial effluents have been introduced many kinds of chemical compounds in aquatic and atmospheric environments. The environmental exposure to genotoxic substances often brings great risk to human health. Therefore, the aim of this work was make an avaliation of people exposition to atmospheric air and water supply quality in two urban cities in Rio Grande do Sul State (Brazil) which were under influence of different anthropogenic sources (target cities), compared to a less intense influenced urban city (reference city). The organic extracts from supply water and airborne samples were tested to mutagenicity using the Salmonella/microsome assay (TA98 and TA100 strains for water and airborne samples, with and without metabolization fraction, and also, YG1021 and YG1024 strains for airborne) - mutagenicity marker. Moreover, the airborne samples were analysed by HPLC to PAHs composition and by HRGC-HRMS to PCDD/Fs composition. Human biomonitoring was evaluated by samples of lymphocytes and bucal mucosa cells from individuals living in this three cities using the comet and the micronuclei (MN) assays, respectively - effect biomarkers. Analysis of gene polymorphisms (CYP1A1, GSTM1 and GSTT1) was taken as susceptibility biomarkers. Both target cities showed significative results for the water mutagenicity with mutagenic responses for all samples, mainly to base-pair substitution mutation (TA100 strain), denoting the presence of THMs and MX compounds. The TSP concentrations were above the Brazilian Legislation and World Health Organization regulation limits few times. The PAHs detected in greater amout were indeno(1,2,3-c,d)pyrene and benzo(ghi)perylene and one of the samples overcame ten times the values of PCDD/Fs compared to the other analysed. The two target cities showed high mutagenicity response in all airborne samples, both by direct and indirect mutagens, besides high concentrations of nitro-PHAs. Actually, these results indicate a law revision necessity, because great amount of mutagenic compounds were assessed in smaller concentration that those present in current legal parameters. The analysed subjects for effect biomarkers, both limphocytes tested by comet assay and buccal mucosa cells tested by MN, did not show significant results, only one city show increased primary DNA damage detected through comet assay. As the majority of subjects CYP1A1, GSTM1 e GSTT1 showed prevalent genotype, it maybe occuring an efficient system detoxification warranted by these genotypes presence. This work has shown the importance of environmental studies that relate mutagenicity markers with effect and susceptibility biomarkers, thus a greater understanding about environmental genotoxic agents, which people are exposed daily, will be done carefully.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-09-06T16:08:00Z No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-08T10:48:19Z (GMT) No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / Made available in DSpace on 2016-09-08T10:48:19Z (GMT). No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / CNPq, FINEP, FAPESB e ANEEL / Os Hidrocarbonetos policíclicos aromáticos (HPA) são poluentes formados geralmente durante a combustão incompleta de petróleo e derivados, carvão mineral, biomassa e outros materiais orgânicos. São emitidos por diversas fontes naturais ou antrópicas e estão presentes na atmosfera, hidrosfera e litosfera. A atmosfera é o seu principal meio de transporte onde se encontram em fase vapor ou adsorvidos em material particulado. Em centros urbanos, sua emissão está associada principalmente aos veículos automotores, movidos a diesel e gasolina. Os HPA e seus derivados, por exemplo, os nitro-HPA e oxi-HPA, são agentes cancerígenos e/ou mutagênicos, daí a importância de estudos sobre a sua presença na atmosfera e em outras matrizes ambientais, sobre a reatividade e atividades biológicas. Neste trabalho, foram determinadas as concentrações atmosféricas para 16 HPA considerados como poluentes prioritários pela agência de proteção ambiental dos Estados Unidos da América (U. S. EPA), em amostras de material particulado atmosférico (MPA), usando o método de CG-EM com monitoramento de íons selecionados. As amostras de MPA foram coletadas em amostradores de grande volume (Hi-vol) e, em seguida, foram extraídas usando a técnica de sonicação e uma solução de acetonitrila e diclorometano (3:1) como solvente. Os extratos foram pré- concentrados (10/1) e em seguida analisados por CG-EM/SIM. Com o objetivo de assegurar uma boa separação dos 16 HPA, no menor tempo de análise, foi utilizado o planejamento multivariado para estabelecer as condições de programação de temperatura do forno (aquecimento da coluna). O processo de otimização foi realizado por meio do planejamento fatorial fracionário e através do planejamento do tipo Box-Behnken, sendo avaliados os seguintes fatores: temperatura inicial (oC), velocidade de elevação da temperatura N° 1 (°C.min-1), temperatura intermediária (oC), velocidade de elevação da temperatura N° 2 (°C.min-1) e temperatura final (oC). As condições otimizadas para a separação dos 16 HPA foram estabelecidas em: 70 °C (2 min) ? 200 °C (30 °C/min, 5 min) ? 300 °C (5 °C/min, 1,67 min). O tempo total da análise, com uma boa separação dos 16 analitos, ficou em 33 minutos. A validação da técnica de CG-EM, no modo SIM, apresentou resultados considerados satisfatórios para a repetitividade da resposta do detector, repetitividade do tempo de retenção, e linearidade das curvas de calibração. Os limites de detecção foram estabelecidos entre 0,13 e 0,34 ng mL-1 (área) e 0,18 e 0,72 ng mL-1 (altura de pico) e os limites de quantificação entre 0,38 e 1,04 ng mL-1 (área) e entre 0,61 e 2,39 ng mL-1 (altura de pico). As amostras ambientais de MPA foram coletadas em quatro diferentes locais, apresentando os seguintes resultados: i) Estação da Lapa (Salvador, BA) - Os HPA presentes em concentrações mais altas foram o criseno (CRI), pireno (PIR) e benzo[b]fluoranteno (BbF), apresentando concentrações médias de respectivamente 2,62, 1,32 e 1,30 ng m-3, e perfil compatível com emissões de veículos movidos a diesel; ii) Porto de Aratu (Candeias, BA) - Os HPA presentes em maiores concentrações foram o benzo[b]fluoranteno (BbF), benzo[g,h,i]perileno (BgP) e Indeno[1,2,3- c,d]pireno (IND), apresentando concentrações médias de respectivamente 2,53, 1,22 e 1,12 ng m-3 (AGV-PTS) e 1,74, 0,82 e 0,73 (AGV MP10); iii) Ilha de Maré, (Salvador, BA) – os valores mais altos foram observados para o benzo[b]fluoranteno (BbF), benzo[b]fluoranteno (BkF) e benzo[g,h,i]perileno (BgP), apresentando concentrações médias de respectivamente 1,62, 0,73 e 0,72 ng m-3; iv) Cidade Universitária da USP (São Paulo, SP) - Os HPA que apresentaram maiores concentrações médias foram o benzo[b]fluoranteno (BbF), criseno (CRI) e o benzo[g,h,i]perileno, com os valores de, respectivamente, 0,93, 0,50 e 0,49 ng m-3. Os resultados foram avaliados em termos de perfil das concentrações, prováveis fontes de emissões e, em alguns casos, por comparação com análises anteriores. / Polycyclic aromatic hydrocarbons (PAH) are ubiquitous pollutants that are emitted from several natural or anthropic sources and may be present in the atmosphere, hydrosphere and lithosphere. They usually originate during the incomplete combustion of petroleum and its derivatives, mineral coal, biomass and other organic materials. They are mainly transported in the atmosphere, being present either in the vapor phase or adsorbed in particulate material. In urban centers, emission is mainly associated with diesel- and gasoline-powered motor vehicles. Since PAH and derivatives, e.g. nitro-PAH and oxy-PAH, are carcinogenic and/or mutagenic agents, to study the effect of their presence in the atmosphere and in other environmental matrices on the biological activity and reactivity are of key relevance. In this study, the atmospheric concentrations of the 16 PAHs that are considered priority pollutants by the U.S. Environmental Protection Agency were evaluated in samples of atmospheric particulate material (APM), using gas chromatography / mass spectrometry with selected-ion monitoring mode (GC-MS/SIM). APM samples were collected in high-volume air samplers (Hi-vol) and then extracted under sonication with a solution of acetonitrile and dichloromethane (3:1) as a solvent. Extracts were pre-concentrated (10/1) and analyzed by GC-MS/SIM. In order to assure an adequate separation of the 16 PAHs, in the shortest analysis time, a multivariate design was used to set the conditions of the oven temperature program (column warming). The optimization process was carried out using factorial fractional design and Box-Behnken design. The following factors were evaluated: initial temperature (ºC), temperature rate N°1 (ºC.min-1), intermediate temperature (ºC), temperature rate N°2 (ºC.min-1) and final temperature (ºC). The optimized conditions for the separation of the 16 PAH were set at: 70 ºC (2 min) → 200 ºC (30 ºC/min, 5 min) → 300 ºC (5 ºC/min, 1.67 min). Total analysis time, with an adequate separation of the 16 analytes was 33 minutes. Validation of GC-MS in the SIM mode rendered satisfactory results for repeatability of detector response, repeatability of retention time, and linearity of calibration curves. Detection limits were established between 0.13 and 0.34 ng mL- 1 (area) and 0.18 and 0.72 ng mL-1 (peak height). Environmental samples of PMA were collected at four different locations, with the following results: i) Lapa Bus Station (Salvador, BA) - The PAH with the highest concentrations were crysene (CRY), pyrene (PYR) and benzo[b]fluoranthene (BbF), with mean concentrations of 2.62, 1.32, and 1.30 ng m-3, respectively, suggesting a profile compatible with diesel vehicle emissions; ii) Port of Aratu (Candeias, BA) – The PAH with the highest concentrations were benzo[b]fluoranthene (BbF), benzo[g,h,i]perylene (BgP) and indeno[1,2,3-c,d]pyrene (IND), with mean concentrations of 2.53, 1.22, and 1.12 ng m-3 (TSP) and 1.74, 0.82 e 0.73 (PM10), respectively; iii) Ilha de Maré, (Salvador, BA) – The PAH with the highest concentrations were benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF) and benzo[g,h,i]perylene (BgP), with mean concentrations of 1.62, 0.73 e 0.72 ng m-3, respectively; iv) University of São Paulo (São Paulo, SP) - The PAH with the highest mean concentrations were benzo[b]fluoranthene (BbF), chrysene (CRI) and benzo[g,h,i]perylene (BgP) with values of 0.93, 0.50 and 0.49 ng m-3, respectively. The results were evaluated with respect to concentration profile, probable emission sources and in some cases, were compared to prior analyses.

L’application de la Directive Cadre sur l’Eau et l’obligation de surveillance de la qualité de l'eau pour la consommation humaine et les activités industrielles entraînent une forte demande pour des systèmes d’évaluation et de suivi de la qualité de l’eau. Le projet de recherche MIGR'HYCAR (http://www.migrhycar.com) a donc été mis en place pour répondre à un besoin opérationnel et à un défaut d'outils d'aide à la décision adaptés face aux déversements d'hydrocarbures en eaux continentales (rivières, lacs et estuaires) qui représentent plus de 50% des déversements accidentels en France. Ce travail de thèse s'inscrit dans le cadre de ce projet et a pour but l’étude du comportement des nappes d'hydrocarbures en milieu contrôlé pour les eaux continentales. A cet effet, il propose une approche expérimentale à l’échelle laboratoire pour étudier les phénomènes agissant sur une nappe d'hydrocarbures déversée : dissolution, étalement, évaporation et volatilisation. Les données expérimentales réunis ont permis de constituer une base de données de référence, qui servira de support aux outils de modélisation mathématique de dérive de nappe d'hydrocarbures développés dans le cadre de ce projet. / The application of the European Water Framework Directive on water quality for human consumption and industrial activities creates a need for water quality assessment and monitoring systems. The MIGR'HYCAR research project (http://www.migrhycar.com) was initiated to provide decisional tools for risks connected to oil spills in continental waters (rivers, lakes and estuaries), which represent more than 50% of accidental spills in France. This work joins within the framework of this project and aims at the study of the behavior of hydrocarbons in a controlled environment for continental waters. For that purpose, the work proposes an experimental approach at laboratory scale to study the phenomena acting in oil spill: dissolution, spreading, evaporation and volatilization. The experimental data allowed establishing a reference database, which will serve as support in tools of oil spill modeling within the framework of this project.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In this study, was optimization an analytical method for identification and quantification method of Polycyclic Aromatic Hydrocarbons (PAHs) in surface water and hospital effluent samples. High Performance Liquid Chromatography with Fluorescence Detection (HPLC-FLD), assisted by Solid Phase Extraction (SPE) and Dispersive Liquid-Liquid Microextraction (DLLME), was used. For SPE, the use of organic modifiers was necessary owing to the low solubility of PAHs, and employed 20% of acetonitrile as such. Factorial design was applied and the best results were: pH 5 for the samples and washing water. The SPE method was validated in Chromabond® C18 ec cartridges and recoveries ranged from 92.0 to 100.2% (RSD 0.2 to 5. 0%). The highest concentrations of PAHs using SPE were found in surface waters from the water course crossing the UFSM Campus (5.4 to 21.5 μg L-1). Using DLLME optimized by design of experiments, the best conditions were: pH 7, 0.2 mol L-1 NaCl, 100 μL of extractor solvent (carbon tetrachloride) and 500 μL of disperser solvent (acetone). The DLLME method was validated, providing recoveries ranging from 77.2 to 100.6% (RSD 0.9 to 10.2%) for surface water and 72.7 to 100.3% (RSD 1.9 to 8.9%) for hospital effluent samples. Using DLLME, the highest concentrations of PAHs were found in surface water samples (3.2 to 19.7 μg L-1). Employing both SPE and DLLME, the concentration of anthracene and pyrene were below the limit of quantification in all sampling points. By the environmental risk assessment naphthalene, 1-methylnaphthalene and phenanthrene showed moderate environmental risk. High environmental risk was found for fluorene, anthracene and pyrene. Heterogeneous photocatalysis and ozonation was examined as remediation method. A jacketed stirred tank reactor and ultraviolet irradiation were used for photocatalysis with TiO2 supported on polydimethylsiloxane. Owing to the low solubility of PAHs, it was necessary the addition of acetonitrile to the solutions (5% in aqueous solution, and 10% in surface water and hospital effluent). A factorial design was applied and the best rates of degradation was set as pH 9 and 35 °C (aqueous solution), and pH 7 and 30 °C (surface water and hospital effluent). First order kinetics was observed for photocatalytic degradation of PAHs in aqueous solution, and, zero order, in hospital effluent and surface water. The photocatalytic degradation subproducts were identified for anthracene, phenanthrene and naphthalene by GC-MS and the fragmentation routes were proposed. Semi-batch column type reactor was used by the ozonation. The best degradation rates of the analytes, in aqueous solution and in real samples, were observed at pH 9. The ozonation kinetics showed a first-order reaction for all samples and degradation times ranging from 5 to 15 minutes. / Neste trabalho fez-se a otimização de método analítico para identificação e quantificação de Hidrocarbonetos Policíclicos Aromáticos (HPAs) em amostras de águas superficiais e efluente hospitalar. Empregou-se Cromatografia Líquida de Alta Eficiência com detecção por Fluorescência (HPLC-FLD), Extração em Fase Sólida (SPE) e Microextração Líquido-Líquido Dispersiva (DLLME). Para a SPE, investigou-se o uso de modificadores orgânicos, devido a baixa solubilidade dos HPAs, e empregou-se 20% de acetonitrila como tal. Aplicou-se planejamento fatorial e os melhores resultados foram: pH 5 para amostras e água de lavagem. O método de SPE foi validado em cartuchos Chromabond® C18 ec e as recuperações variaram de 92,0 a 100,2% (RSD 0,2 a 5,0%). As maiores concentrações de HPAs, com SPE, foram em amostras de águas superficiais do córrego do Campus da UFSM (5,4 a 21,5 μg L-1). Para a DLLME, otimizada por planejamento de experimentos, as condições ótimas foram: pH 7, 0,2 mol L-1 de NaCl, 100 μL de solvente extrator (tetracloreto de carbono) e 500 μL de solvente dispersor (acetona). O método de DLLME foi validado e as recuperações variaram 77,2 a 100,6% (RSD de 0,9 a 10,2%) para amostras de água superficiais e, de 72,7 a 100,3% (RSD de 1,9 a 8,9%), para amostras de efluente hospitalar. As maiores concentrações de HPAs, por DLLME, obtiveram-se em amostras de águas superficiais (3,2 a 19,7 μg L-1). Empregando-se SPE e DLLME, as concentrações de antraceno e pireno ficaram abaixo do limite de quantificação em todos os pontos de amostragem. Na avaliação de risco ambiental, naftaleno, 1-metilnaftaleno e fenantreno apresentaram risco ambiental moderado. Alto risco ambiental foi evidenciado para fluoreno, antraceno e pireno. Como método de remediação aplicou-se fotocatálise heterogênea e ozonização. Na fotocatálise, empregou-se reator tanque agitado termostatizado, radiação ultravioleta e TiO2 suportado em polidimetilsiloxano. Devido à baixa solubilidade fez-se necessária a adição de acetonitrila à solução de HPAs (5% em solução aquosa e 10% em água superficial e efluente hospitalar). Aplicou-se planejamento fatorial e as melhores taxas de degradação obtiveram-se com pH 9 e 35 °C (solução aquosa) e, pH 7 e 30 °C (águas superficiais e efluente hospitalar). Foi observada cinética de primeira ordem para a degradação fotocatalítica dos HPAs em solução aquosa e de ordem zero em amostras de efluente hospitalar e águas superficiais. Os subprodutos de degradação fotocatalítica de antraceno, fenantreno e naftaleno foram identificados por GC-MS e propuseram-se rotas de fragmentação. Empregou-se um reator tipo coluna de semi-batelada no processo de ozonização de HPAs. As melhores taxas de degradação dos analitos em solução aquosa e em amostras reais foram observadas em pH 9. O estudo cinético evidenciou reações de primeira ordem para todas as amostras estudadas e os tempos de degradação variaram de 5 a 15 minutos nas condições otimizadas.

Made available in DSpace on 2016-06-02T20:36:36Z (GMT). No. of bitstreams: 1 4248.pdf: 3654263 bytes, checksum: b6ca09bad78da4e11f90710ff570c7d0 (MD5) Previous issue date: 2012-02-16 / Financiadora de Estudos e Projetos / Frequent use of urban waters for public supply has been increased, due to reduction of water resources suitable for human consumption. These waters are exposed to point and non-point sources of pollution, such as, atmospheric deposition, vehicle emissions and different types of waste thrown into streets and sidewalks. With storm water events, various toxics compounds are carried by surface run-off, reaching finally, into water bodies within the city. The goal of this research was to evaluate the presence of total mercury, polycyclic aromatic hydrocarbons (PAHs), heavy metals potentially toxic and acid volatile sulfide (AVS) in the hydrographic basin of Stream Barnabé. Searching environmental impact indicators on an aquatic system located at urban area of Indaiatuba, this water is captured to supply about 40.000 persons. Three points of stream were monitored, close to source, to water intake and to outfall. Water samples were collected monthly and sediments samples quarterly, between april/2010 and junho/2011. The results showed that the highest concentrations of mercury in water were observed during periods when rain interrupted the drought, due to runoff of water containing the material deposited for non-point sources in urban areas during the dry. The point next to water intake presented the highest concentrations of total-HPAs and AVS. We found that the maximums concentrations of metals were reported in setembro/2010 and junho/2011 samples and also setembro/2011 samples it found high concentrations of low molecular weight PHAs (naphthalene, acenaphthene, acenaphthylene and _etrogen) of source _etrogenico. These values were due to superficial water s flux with material deposited by nonpoint sources, accumulated during the dry season. Even though the results have shown normal impact indicators evaluated, it was denoted a vulnerability in this type of supply option, this requires an appropriate consideration in water management, such as interruption of supply, especially in times of heavy rainfall after periods of drought. / Frente ao crescente quadro de escassez hídrica, tem sido freqüente o uso de águas do meio urbano para fins de abastecimento público. Tais águas são sujeitas às fontes localizadas de contaminações, e também a diversas fontes difusas, como deposição atmosférica de longa distância, emissões veiculares e diferentes tipos de resíduos lançados em quintais, ruas e calçadas, que acabam por ser arrastados pelo escoamento superficial até os corpos hídricos urbanos. Neste trabalho foi conduzida uma investigação acerca da presença de mercúrio total, hidrocarbonetos policíclicos aromáticos, metais potencialmente tóxicos e sulfetos volatilizáveis por acidificação na Bacia Hidrográfica do Córrego Barnabé, buscando indicadores de impactos em um corpo aquático localizado na zona urbana da cidade de Indaiatuba-SP, cujas águas são captadas para o abastecimento de cerca de 40.000 pessoas. Foram monitorados três pontos do córrego: início do contato com a zona urbana, região da captação de água e proximidades da foz. As amostras de água foram coletadas mensalmente, e as amostras de sedimento trimestralmente, no período compreendido entre Abril/2010 e Junho/2011. Os resultados mostram que as maiores concentrações de mercúrio na água foram observadas nos períodos em que as chuvas interromperam o período de estiagem, devido ao escoamento superficial das águas contendo o material depositado por fontes difusas no meio urbano durante o período seco. O ponto próximo à captação de água foi o que apresentou as maiores concentrações de SVA e HPAs total. As maiores concentrações de metais foram registradas nas amostras de setembro/10 e junho/11, também nas amostras de setembro/11 foram encontradas altas concentrações de HPAs de baixa massa molar (naftaleno, acenafteno, acenaftileno e fluoreno), de origem petrogênica. Tais valores são resultado do aporte do material trazido pelo escoamento superficial ocorrido no inicio do período chuvoso, que sucedeu a estação seca. Mesmo considerando que os resultados tenham mostrado, em geral, níveis normais nos indicadores de impacto avaliados, é denotada uma vulnerabilidade hídrica neste tipo de opção como abastecimento, sendo cabível uma consideração no gerenciamento hídrico, como a interrupção da captação principalmente em ocasiões de chuvas intensas após períodos de estiagem. xii