Made available in DSpace on 2015-04-14T13:59:01Z (GMT). No. of bitstreams: 1 451408.pdf: 2001756 bytes, checksum: 64067e77cbea30ac7596f0d09843bc92 (MD5) Previous issue date: 2013-08-09 / Due to search for different properties in polymeric materials, have increasing studies in the composites and the nanocomposites field, using inorganic fillers. Within this context one this work, which has as main objective to study experimentally the synthesis and characterization of nanocomposites of aromatic polyesters / titanium dioxide (PEA/TiO2), using raw materials trade. To do so, it was used the in situ polymerization technique to prepare the nanocomposites with PEA/TiO2 with different concentrations of the load (0%, 0.5%, 1.0%, 2.0%, 3.0% and 5.0% m/m of the polymer mass). It was used as starting materials: dimethyl terephthalate (DMT), polyethylene terephthalate (PET) and a mixture of 1,4-butanediol and 1,6-hexanediol. The nanocomposites were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Gel Permeation Chromatography (GPC). Shore D hardness, contact angle and X-ray Diffraction (DRX). The results show that there was an interaction filler/polymer evidenced by XRD and FTIR analysis. The thermal properties of nanocomposites suffered no significant changes. It was also possible to observe a change in the surface of the synthesized material indicating good compatibility btween filler and polymeric matrix and a decrease of surface hydrophilicity (measured by the contact angle) as well as an increase in hardness of the material compared to pure polymer. / Devido ? busca de propriedades diferenciadas em materiais polim?ricos, t?m-se um aumento crescente nos estudos de comp?sitos e nanocomp?sitos utilizando cargas inorg?nicas. Dentro deste contexto insere-se este trabalho, que tem como objetivo principal estudar, experimentalmente, a s?ntese e a caracteriza??o de nanocomp?sitos de poli?steres arom?ticos/di?xido de tit?nio (PEA/TiO2), utilizando-se mat?rias-primas comerciais. Para isso, utilizou-se a t?cnica de polimeriza??o in situ para preparar nanocomp?sitos de PEA/TiO2 com diferentes concentra??es da carga (0%, 0,5%, 1,0%, 2,0%, 3,0% e 5,0% m/m sobre a massa do pol?mero). Utilizou-se como reagentes iniciais: o Dimetil Tereftalato (DMT), o Politereftalato de Etileno (PET) e uma mistura de 1,4- butanodiol e 1,6- hexanodiol. Os nanocomp?sitos preparados foram caracterizados por Espectroscopia de Infravermelho por Transformada de Fourier (FTIR), Microscopia Eletr?nica de Varredura (MEV), Calorimetria Diferencial Explorat?ria (DSC), An?lise Termogravim?trica (TGA), Cromatografia em Permea??o em Gel (GPC), Dureza Shore D, ?ngulo de contato e Difra??o de Raios- X (DRX). Pelos resultados obtidos neste trabalho, pode-se ressaltar que houve intera??o carga/pol?mero comprovada pelas an?lises de DRX e FTIR onde as mesmas interferiram nas intensidades das bandas proporcionais a quantidade de carga adicionada. As propriedades t?rmicas do material analisadas por DSC e TGA n?o sofreram modifica??o significativa. Tamb?m foi poss?vel observar uma mudan?a na superf?cie do material sintetizado mostrando uma boa compatibilidade da carga com a matriz polim?rica e uma diminui??o da hidrofilicidade da superf?cie (avaliada atrav?s do ?ngulo de contato), al?m de um aumento na dureza do material quando comparado ao pol?mero puro.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-01-10T12:38:21Z No. of bitstreams: 1 BrunaMariaEmerencianoDasChagas_TESE.pdf: 6590840 bytes, checksum: f29703c72f7b97886bfe14570fa8d656 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-01-11T13:13:01Z (GMT) No. of bitstreams: 1 BrunaMariaEmerencianoDasChagas_TESE.pdf: 6590840 bytes, checksum: f29703c72f7b97886bfe14570fa8d656 (MD5) / Made available in DSpace on 2017-01-11T13:13:01Z (GMT). No. of bitstreams: 1 BrunaMariaEmerencianoDasChagas_TESE.pdf: 6590840 bytes, checksum: f29703c72f7b97886bfe14570fa8d656 (MD5) Previous issue date: 2016-06-09 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Recentemente as microalgas e cianobact?rias vem sendo muito estudadas como fonte de biocombust?veis devido a sua elevada produtividade, elevado teor de ?leo e capacidade de crescer em uma grande variedade de climas e terras sem competir com a produ??o de alimentos. A pir?lise ? um m?todo de convers?o termoqu?mica eficaz capaz de converter biomassa em bio-?leo, carv?o e gases combust?veis. O bio-?leo ? uma mistura l?quida de compostos org?nicos potencial para substituir o ?leo diesel. Tem sido demosntrado que bio-?leos de microalgas e cianobact?rias s?o mais est?veis, apresentam teor de oxig?nio mais baixo e poder calor?fico mais alto que bio-?leos de biomassa lignocelul?sica, embora contenha um alto teor de nitrog?nio devido a presen?a de prote?nas na mat?ria-prima. A Spirulina ? uma cianobact?ria que vem sendo muito estudada nos processos de degrada??o t?rmica por apresentar alto teor de prote?nas (74%) e baixo teor de lip?dios (< 1%) podendo ser totalmente convertida em biocombust?vel. Nesta tese, foi investigado o potencial de produ??o de combust?veis e qu?micos a partir da pir?lise r?pida de Spirulina. Os experimentos de pir?lise r?pida convencional em Py-GC/MS foram conduzidos para investigar a influ?ncia dos par?metros de pir?lise, tais como temperatura, taxa de aquecimento e tempo de resid?ncia nos rendimentos dos produtos. O rendimento dos produtos da pir?lise foi maximizado a 450 ?C e 30 s, independente da taxa de aquecimento. Essas condi??es foram escolhidas para o estudo da pir?lise catal?tica com 9 ze?litas diferentes para avaliar a produ??o de hidrocarbonetos espec?ficos, compostos oxigenados e nitrogenados em func?o da raz?o biomassa/catalisador. O rendimento de hidrocarbonetos arom?ticos aumentou ? medida que a propor??o de catalisador/biomassa aumentou de 1:1 para 10:1. A ze?lita H-ZSM5 (23) apresentou o rendimento m?ximo de hidrocarbonetos e a maior redu??o de f?nois quando comparada as outras ze?litas, por?m os compostos nitrogenados totais n?o foram significativamente reduzidos por nenhum catalisador testado. Posteriormente testes de pir?lise r?pida de Spirulina foram conduzidos em um reator de leito fluidizado da USDA-ARS sob diferentes atmosferas de rea??o. Foram testadas a pir?lise convencional com atmosfera inerte (N2) e um processo de pir?lise com atmosfera reativa compostas por gases reciclados da pi?lise, denominado ?Tail Gas Reactive Pyrolysis? (TGRP). O bio-?leo, carv?o e gases produzidos pelo processo TGRP tiveram suas caracter?sticas melhoradas em rela??o aos produtos obtidos na pir?lise convencional, houve um aumento na concentra??o dos hidrocarbonetos arom?ticos e predominaram compostos nitrogenados com um ?nico ?tomo de nitrog?nio (piridinas, pirroles, indoles, nitrilas e amidas). Devido a esta composi??o, esse bio-?leo apresentou um n?vel suficientemente elevado de estabilidade t?rmica para ser destilado. Al?m disso, o bio-?leo produzido pelo processo TGRP foi mais est?vel, menos ?cido e apresentou um poder calor?fico mais alto que bio-?leos de biomassa lignocelul?sica. / Recently microalgae and cyanobacteria have been widely studied as a source of biofuels due to its high yield, high oil content and ability to grow on a wide variety of climates and land without competing with food production. Pyrolysis is an effective thermochemical conversion method capable of converting biomass to fuels, including bio-oil, bio-char and gas. Bio-oil is a liquid mixture of organic compounds that can be a source of valuable chemicals and potential to replace diesel oil depending on its quality. It has been shown that bio-oil from microalgae and other proteinaceous biomass are more stable, have a low oxygen content and higher calorific value than those produced from lignocellulosic feedstock, though contains high nitrogen content due to the presence of protein in its constitution. Spirulina is a cyanobacteria that has been studied in the thermal degradation processes due to its high protein and low lipids content. In this thesis, we investigated the potential for production of fuels and chemicals from the fast pyrolysis of Spirulina. Conventional fast pyrolysis experiments in Py-GC/MS were performed to investigate the influence of pyrolysis parameters such as temperature, heating rate and residence time in distribution of products. The pyrolysis yield was maximized at 450 ?C and 30 s, regardless of heating rate. H-ZSM5 (23) showed the maximum hydrocarbon yield and the largest phenols reduction when compared to the other zeolites, but the total nitrogenated compounds were not significantly reduced by any catalyst tested although some specific nitrogenous have been reduced or eliminated. H-? (38) was also able to increase aromatics production, although its effect was less significant when compared to H-ZSM5 (23) and (50). Subsequently tests of Spirulina fast pyrolysis were conducted in USDA?s bubbling fluidized bed pyrolysis reactor under different reaction atmospheres. Conventional (N2 atmosphere) and reactive (Tail Gas Reactive Pyrolysis - TGRP) pyrolysis were tested. Biooil, bio-char and gas obtained from TGRP process had their fuel characteristics improved when compared to the products from conventional pyrolysis. TGRP Spirulina pyrolysis oil showed an increased concentration of aromatics hydrocarbon and the presence of nitrogenous compounds with single nitrogen atom (pyridines, pyrroles, indoles, nitriles and amides), low oxygen content and low acidity being thermally stable therefore a good feedstock for distillation process. Distillation successfully allowed concentrating various chemicals into distillate fractions which, in turn, could be individually isolated for processing to fuels or chemical co-products.

Made available in DSpace on 2015-04-14T14:51:13Z (GMT). No. of bitstreams: 1 434409.pdf: 489532 bytes, checksum: 6d9ad85140ac1052e70482873df7cc50 (MD5) Previous issue date: 2011-08-03 / A 2,3,7,8-tetraclorodibenzeno-p-dioxina (TCDD) ? membro de um grupo de contaminantes ambientais conhecido como hidrocarboneto arom?tico policlorinato e pode ser formada durante o processo de branqueamento com cloro, utilizado por f?brica de celulose e papel e como um subproduto da fabrica??o de determinados produtos qu?micos. Uma vez associado a ligantes como a TCDD, o receptor de hidrocarboneto arila (AHR) ? translocado para o n?cleo onde ir? formar um d?mero com o translocador nuclear do receptor hidrocarboneto arila (ARNT). O heterod?mero AHR/ARNT formado regula a express?o de uma s?rie de genes envolvidos na resposta celular a mudan?as ambientais e a condi??es de desenvolvimento. Entre os genes, est? o que codifica para NTPDase2 (previamente conhecida como ecto-ATPase). Com isso, torna-se importante avaliar a exposi??o aguda (in vivo) da TCDD sobre a hidr?lise de ectonucleotidases em membranas cerebrais de zebrafish. As ectonucleotidases s?o enzimas capazes de hidrolisar os nucleot?deos e inativar a sinaliza??o mediada pelos nucleot?deos extracelulares. Entre as ectonucleotidases, destacam-se as NTPDases e a ecto-5 -nucleotidase. A atividade de NTPDase demonstrou que n?o houve diferen?a significativa na hidr?lise de ATP e de ADP, bem como de AMP em membranas cerebrais de zebrafish. Estas descobertas parecem ser importantes para refor?ar a id?ia de que a indu??o do gene que codifica ? NTPDase2 pode n?o ser um fator geral da toxicidade de TCDD. No entanto, mais estudos utilizando doses mais elevadas de TCDD e exposi??o a longo prazo s?o necess?rias.

Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1 JulianaPSDP_DISSERT.pdf: 1777680 bytes, checksum: 11814e53360b103c7198cf617f2a583c (MD5) Previous issue date: 2010-07-06 / The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive / O presente trabalho ? dirigido ao tratamento de ?gua produzida de petr?leo usando uma tecnologia eletroqu?mica. A ?gua produzida ? um dos principais res?duos gerados durante o processo de explora??o e produ??o na ind?stria petrol?fera, onde corresponde a 98 % de todos os efluentes gerados. V?rias metodologias est?o sendo estudadas visando o tratamento desse efluente, dentre elas est?o os processos biol?gicos, os processos de oxida??o avan?ados (POAs), tratamentos eletroqu?micos como eletrooxida??o, eletrocoagula??o, eletroflota??o e eletroredu??o. Esse trabalho mostra a aplica??o da tecnologia de eletrooxida??o no tratamento da ?gua produzida, pois se trata de uma t?cnica com alta compatibilidade ambiental, onde atrav?s da a??o do pr?prio el?tron, as subst?ncias t?xicas e nocivas ao meio ambiente podem ser removidas ou transformadas atrav?s de rea??es de ?xido-redu??o em subst?ncias menos t?xicas. Para isso, foi utilizado efluente sint?tico contendo uma mistura de H2SO4 0,5M e de 16 hidrocarbonetos polic?clicos arom?ticos (HPAs), que s?o: naftaleno, acenaftileno, acenafteno, fluoreno, fenantreno, antraceno, fluoranteno, pireno, benzo(a)antraceno, criseno, benzo(b)fluoranteno, benzo(k)fluoranteno, benzo(a)pireno, indeno(1,2,3-cd)pireno, dibenzo(a,h)antraceno, benzo(g,h,i)perileno. Utilizou-se o processo de oxida??o eletroqu?mica com um reator eletroqu?mico em batelada contendo um par de eletrodos paralelos, acoplados a uma fonte de corrente cont?nua e usando um agitador magn?tico para favorecer o transporte de massa na solu??o sint?tica. Como material an?dico utilizou-se um eletrodo de ?nodo dimensionalmente est?vel (DSA), constitu?do de Ti/Pt, enquanto o material cat?dico foi o Ti. Para detec??o e quantifica??o dos HPAs utilizou ? t?cnica de cromatografia gasosa acoplada a espectrometria de massa (CG - EM), onde o efluente foi analisado antes e ap?s o tratamento eletroqu?mico. Os resultados se mostraram eficazes, obtendo-se remo??es significativas dos HPAs superiores a 80%. Como indicador da viabilidade econ?mica do tratamento eletroqu?mico foram analisados os consumos energ?ticos do processo para cada hora do tratamento eletroqu?mico com base no valor kWh cobrado pela ANEEL. Os custos dos tratamentos desta pesquisa foram bastantes atrativos

Made available in DSpace on 2014-12-17T14:08:52Z (GMT). No. of bitstreams: 1 RaoniBA_DISSERT.pdf: 2283831 bytes, checksum: 9e3bfc1213fc5b5ac439fb175ddc5631 (MD5) Previous issue date: 2012-12-14 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The retail fuel stations are partially or potentially polluters and generators of environmental accidents, potentially causing contamination of underground and surface water bodies, soil and air. Leaks in fuel retail stations? underground storage systems are often detected in Brazil and around the world. Monoaromatic hydrocarbons, BTEX (benzene, toluene, ethylbenzene and xylenes) and polycyclic aromatic hydrocarbons (PAHs) are an indication of the presence of contamination due to its high toxicity. This paper presents a case study of contamination in a Fuel Retail Station by petroleum derivative products in the city of Natal. For identification and quantification of the hydrocarbons, EPA analytical methods were used. The values of benzene quantified by EPA method 8021b CG-PID/FID, ranged from 1.164 to 4.503 mg.Kg-1 in soil samples, and from 12.10 to 27,639 &#956;g.L-1 in underground water samples. Among the PAHs, naphthalene and anthracene showed the most significant results in soil samples, 0.420 to 15.46 mg.Kg-1 and 0.110 to 0,970 mg.Kg-1, respectively. In underground water samples, the results for Naphthalene varied between 0.759 and 614.7 &#956;g.L-1. PAHs were quantified by EPA Method 8270 for GCMS. All of the results for the chemical analysis were compared with the values for the CONAMA 420/2009 resolution. The results for benzene (27,639 &#956;g.L-1) showed levels highly above the recommended by the CONAMA 420 resolution, wherein the maximum permissible for underground water is 5 &#956;g.L-1. This is a worrying factor, since underground water makes up 70% of the city of Natal?s water supply / The retail fuel stations are partially or potentially polluters and generators of environmental accidents, potentially causing contamination of underground and surface water bodies, soil and air. Leaks in fuel retail stations? underground storage systems are often detected in Brazil and around the world. Monoaromatic hydrocarbons, BTEX (benzene, toluene, ethylbenzene and xylenes) and polycyclic aromatic hydrocarbons (PAHs) are an indication of the presence of contamination due to its high toxicity. This paper presents a case study of contamination in a Fuel Retail Station by petroleum derivative products in the city of Natal. For identification and quantification of the hydrocarbons, EPA analytical methods were used. The values of benzene quantified by EPA method 8021b CG-PID/FID, ranged from 1.164 to 4.503 mg.Kg-1 in soil samples, and from 12.10 to 27,639 &#956;g.L-1 in underground water samples. Among the PAHs, naphthalene and anthracene showed the most significant results in soil samples, 0.420 to 15.46 mg.Kg-1 and 0.110 to 0,970 mg.Kg-1, respectively. In underground water samples, the results for Naphthalene varied between 0.759 and 614.7 &#956;g.L-1. PAHs were quantified by EPA Method 8270 for GCMS. All of the results for the chemical analysis were compared with the values for the CONAMA 420/2009 resolution. The results for benzene (27,639 &#956;g.L-1) showed levels highly above the recommended by the CONAMA 420 resolution, wherein the maximum permissible for underground water is 5 &#956;g.L-1. This is a worrying factor, since underground water makes up 70% of the city of Natal?s water supply

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-08-09T23:35:50Z No. of bitstreams: 1 MarcosFelipeDeOliveiraGalvao_TESE.pdf: 9830949 bytes, checksum: 3e018675f047d5354dda3fb29394cfe9 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-08-15T21:57:45Z (GMT) No. of bitstreams: 1 MarcosFelipeDeOliveiraGalvao_TESE.pdf: 9830949 bytes, checksum: 3e018675f047d5354dda3fb29394cfe9 (MD5) / Made available in DSpace on 2016-08-15T21:57:45Z (GMT). No. of bitstreams: 1 MarcosFelipeDeOliveiraGalvao_TESE.pdf: 9830949 bytes, checksum: 3e018675f047d5354dda3fb29394cfe9 (MD5) Previous issue date: 2016-04-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / O Brasil configura entre os maiores produtores de castanha de caju do mundo. Contudo a queima da castanha ainda ? realizada de forma artesanal, sobretudo no semi?rido brasileiro. Diante disto, o objetivo deste estudo foi realizar uma caracteriza??o f?sico-qu?mica do material particulado (MP) emitido pela queima artesanal da castanha de caju, assim como determinar o risco ocupacional e mecanismos moleculares associados. As caracter?sticas mais evidentes do MP foram a preval?ncia de part?culas finas, morfologias t?picas da queima de biomassa, como as "tar ball" e os elementos K, Cl, S, Ca e Fe. Al?m disso, an?lises de modelagem atmosf?rica sugerem que essas part?culas podem atingir regi?es distantes da fonte de emiss?o. Os hidrocarbonetos polic?clicos arom?ticos (HPAs) com potencial carcinog?nico, tais como: benzo(a)pireno, dibenzo(a,h)antraceno, benzo(a)antraceno, benzo(b)fluoranteno, criseno, benzo(k)fluoranteno, indeno(1,2,3,-c,d)pireno e benzo(j)fluoranteno foram os mais abundantes nas duas campanhas de monitoramento do ar. Dentre os oxi-HPAs, a benzantrona (7H-benzo(d,e)antraceno-7-ona) teve a maior concentra??o e a avalia??o do risco de c?ncer de pulm?o indicou um aumento de 12 a 37 casos de c?ncer a cada 10.000 pessoas expostas. A an?lise qu?mica da casca torrada da castanha identificou os HPAs: fenantreno, benzo(g,h,i)perileno, pireno e benzo(a)pireno, al?m do al?rgeno 3-pentadecilfenol, an?logo do urushiol, como prevalecentes. A exposi??o ocupacional aos HPAs foi confirmada pelo aumento dos n?veis urin?rios de 1-hidroxipireno, assim como a genotoxicidade foi evidenciada pelo aumento de micron?cleos e broto nuclear em c?lulas da mucosa oral, nos trabalhadores expostos. Outros biomarcadores de efeito, tais como cari?lise, cariorr?xis, picnose, e c?lulas binucleadas tamb?m tiveram a sua frequ?ncia aumentada quando comparado com um grupo controle n?o exposto. A investiga??o dos mecanismos moleculares associados ao extrato org?nico do MP mostrou citotoxicidade em c?lulas do pulm?o humano (A549) em concentra??es ? 4 nM BaPeq. Utilizando doses n?o citot?xicas o extrato foi capaz de ativar prote?nas envolvidas na via de resposta ao dano no DNA (Chk1 e p53). Al?m disso, foi verificado a contribui??o espec?fica dos quatro HPAs mais representativos na amostra de queima da castanha de caju e o benzo(a)pireno foi o HPA mais eficiente na ativa??o de Chk1 e p53. Por fim, o extrato org?nico foi capaz de aumentar de forma persistente a express?o de mRNAs envolvidos na metaboliza??o dos HPAs (CYP1A1 e CYP1B1), bem como resposta inflamat?ria (IL-8 e TNF-?) e parada no ciclo celular (CDKN1A) para reparo no DNA (DDB2). As altas concentra??es de MP e os seus efeitos biol?gicos associados alertam para os graves efeitos nocivos da queima artesanal da castanha de caju e medidas urgentes devem ser tomadas para o desenvolvimento sustent?vel da atividade. / Brazil is among the largest cashew nut producers of the world. However, the roasting process is still carried out artisanally, especially in the Brazilian semiarid region. In face of this occupational problem, the aim of this study was to perform a physical-chemical characterization of the particulate matter (PM) emitted by the roasting of cashew nuts, as well as to determine the occupational risk and molecular mechanisms associated. The most evident PM characteristics were the prevalence of fine particles, typical biomass burning morphologies such as tar ball and the presence of the elements K, Cl, S, Ca and Fe. In addition, atmospheric modeling analyses suggest that these particles can reach neighboring regions of the emission source. Polycyclic aromatic hydrocarbons (PAHs) with carcinogenic potential, such as benzo[a]pyrene, dibenz[a,h]anthracene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and benzo[j]fluoranthene were the most abundant PAHs found in the two air monitoring campaigns. Among the identified oxy-PAH the benzanthrone (7H-benz[d,e]anthracen-7-one) had the highest concentration and the evaluation of lifetime cancer risk showed an increase of 12 to 37 cases of cancer for every 10,000 exposed people. Chemical analysis of roasted cashew nuts identified the PAHs: phenanthrene, benzo[g,h,i]perylene, pyrene and benzo[a]pyrene, besides the 3-pentadecilfenol allergen (urushiol analogue) as prevalent. Occupational exposure to PAHs was confirmed by the increase of urinary 1-hydroxypyrene levels and genotoxic effects were evidenced by the increase on micronuclei and nuclear bud frequency in exfoliated buccal mucosa cells among the exposed workers. Other biomarkers of effects such as karyorrhexis, pyknotic, karyolytic, condensed chromatin and binucleated cells also have their frequencies increased when compared to an unexposed control group. The investigation of the molecular mechanisms associated with the PM organic extract showed cytotoxicity in human lung cell lines (A549) at concentrations ? 4 nM BaPeq. Using non-cytotoxic doses the extract was able to activate proteins involved in the DNA damage response pathway (Chk1 and p53). Moreover, the specific contribution of the four most representative PAHs in the cashew nut roasting sample showed that benzo[a]pyrene was the most efficient to activate Chk1 and p53. Finally, the organic extract was able to increase persistently the mRNA expression involved in the PAHs metabolism (CYP1A1 and CYP1B1), inflammatory response (IL-8 and TNF-?) and cell cycle arrest (CDKN1A) for DNA repair (DDB2). The high PM concentrations and its biological effects associated warn of the serious harmful effects of artisanal cashew nut roasting and urgent actions should be taken to the sustainable development of this activity.

Made available in DSpace on 2014-12-17T14:08:43Z (GMT). No. of bitstreams: 1 MariaSMQ_DISSERT_1-36.pdf: 5283210 bytes, checksum: e75f1aa1d6f8e40607338226667f1b0d (MD5) Previous issue date: 2011-02-07 / Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary / Os estu?rios s?o ambientes prop?cios ao aporte de poluentes qu?micos de diversas naturezas e origens, incluindo Hidrocarbonetos Polic?clicos Arom?ticos (HPA). Os HPA antr?picos s?o de duas fontes poss?veis: pirol?tica (com quatro ou mais an?is arom?ticos e baixo grau de alquila??o) e petrog?nica (com dois e tr?s an?is arom?ticos e alto grau de alquila??o). O presente trabalho teve como objetivo avaliar os n?veis, distribui??o e poss?veis fontes de Hidrocarbonetos Polic?clicos Arom?ticos no estu?rio do rio Potengi, Natal-RN. Amostras de sedimentos de fundo foram coletadas nos 12 km finais do estu?rio at? a sua foz, onde a urbaniza??o da Grande Natal ? mais concentrada. A amostragem foi realizada em 12 se??es transversais, com tr?s esta??es em cada uma, totalizando 36 amostras, identificadas de T1 a T36. Os HPA alquilados e n?o alquilados foram analisados por cromatografia gasosa acoplada a um detector seletivo de massas (CG/EM). Foram detectados HPA em todas as 36 esta??es, com concentra??o total em cada uma variando de 174 a 109407 ng g-1. Esses valores s?o compar?veis aos de v?rias regi?es estuarinas mundiais com grande influ?ncia antr?pica, o que sugere o registro de contamina??es difusas instaladas no estu?rio. O perfil de HPA foi similar para a maioria das esta??es. Em 32 das 36 esta??es predominaram HPA de baixo peso molecular (com 2 e 3 an?is: naftaleno, fenantreno e seus hom?logos alquilados), que variaram de 54% a 100% em rela??o ao total de HPA, indicando que vazamentos, derramamentos e queima de combust?veis s?o a fonte dominante de polui??o por HPA no estu?rio. O n?vel de contamina??o por HPA na maioria das esta??es sugere que h? risco potencial de ocasionais efeitos biol?gicos adversos serem observados, por?m em algumas esta??es se confirmam que impactos adversos sobre a biota ocorrem com freq??ncia. As raz?es diagn?sticas permitiram diferenciar as fontes de HPA nos sedimentos do estu?rio, que foram divididos em tr?s grupos: sedimentos com padr?es de introdu??o de hidrocarbonetos petrog?nicos, pirol?ticos e de mistura de fontes. A concentra??o urbana da Grande Natal e as atividades industriais diversas a ela associadas podem ser responsabilizadas como fontes potenciais dos HPA nos sedimentos de fundo do estu?rio estudado. Os dados apresentados evidenciam a necessidade de se controlar as causas da polui??o existente no estu?rio

Made available in DSpace on 2014-12-17T15:42:31Z (GMT). No. of bitstreams: 1 MariaFGM.pdf: 2684798 bytes, checksum: 4d672e17bab00bdd5d88eb70b9c57edf (MD5) Previous issue date: 2007-03-30 / Petr?leo Brasileiro SA - PETROBRAS / Many studies on environmental ecosystems quality related to polycyclic aromatic hydrocarbons (PAH) have been carried out routinely due to their ubiquotus presence worldwide and to their potential toxicity after its biotransformation. PAH may be introduced into the environmet by natural and anthropogenic processes from direct runoff and discharges and indirect atmospheric deposition. Sources of naturally occurring PAHs include natural fires, natural oil seepage and recent biological or diagenetic processes. Anthropogenic sources of PAHs, acute or chronic, are combustion of organic matter (petroleum, coal, wood), waste and releases/spills of petroleum and derivatives (river runoff, sewage outfalls, maritime transport, pipelines). Besides the co-existence of multiples sources of PAH in the environmental samples, these compounds are subject to many processes that lead to geochemical fates (physical-chemical transformation, biodegradation and photo-oxidation), which leads to an alteration of their composition. All these facts make the identification of the hydrocarbons sources, if petrogenic, pyrolytic or natural, a challenge. One of the objectives of this study is to establish tools to identify the origin of hydrocarbons in environmental samples. PAH diagnostic ratios and PAH principal component analysis were tested on a critical area: Guanabara Bay sediments. Guanabara Bay is located in a complex urban area of Rio de Janeiro with a high anthropogenic influence, being an endpoint of chronic pollution from the Greater Rio and it was the scenario of an acute event of oil release in January 2000. It were quantified 38 compounds, parental and alkylated PAH, in 21 sediment samples collected in two surveys: 2000 and 2003. The PAH levels varied from 400 to 58439 ng g-1. Both tested techniques for origin identification of hydrocarbons have shown their applicability, being able to discriminate the PAH sources for the majority of the samples analysed. The bay sediments were separated into two big clusters: sediments with a clear pattern of petrogenic introduction of hydrocarbons (from intertidal area) and sediments with combustion characteristics (from subtidal region). Only a minority of the samples could not display a clear contribution of petrogenic or pyrolytic input. The diagnostic ratios that have exhibited high ability to distinguish combustion- and petroleum-derived PAH inputs for Guanabara Bay sediments were Phenanthrene+Anthracene/(Phenanthrene+Anthracene+C1Phenanthrene); Fluorantene/(Fluorantene+Pyrene); &#931; (other 3-6 ring PAHs)/ &#931; (5 alkylated PAH series). The PCA results prooved to be a useful tool for PAH source identification in the environment, corroborating the diagnostic indexes. In relation to the temporal evaluation carried out in this study, it was not verified significant changes on the class of predominant source of the samples. This result indicates that the hydrocarbons present in the Guanabara Bay sediments are mainly related to the long-term anthropogenic input and not directly related to acute events such as the oil spill of January 2000. This findings were similar to various international estuarine sites. Finally, this work had a complementary objective of evaluating the level of hydrocarbons exposure of the aquatic organisms of Guanabara Bay. It was a preliminary study in which a quantification of 12 individual biliar metabolites of PAH was performed in four demersal fish representing three different families. The analysed metabolites were 1-hydroxynaphtalene, 2-hidroxinaphtalene, 1hydroxyphenanthrene, 9-hydroxyphenanthrene, 2-hydroxyphenanthrene, 1hydroxypyrene, 3-hidroxibiphenil, 3- hydroxyphenanthrene, 1-hydroxychrysene, 9hydroxyfluorene, 4-hydroxyphenanthrene, 3-hydroxybenz(a)pyrene. The metabolites concentrations were found to be high, ranging from 13 to 177 ?g g-1, however they were similar to worldwide regions under high anthropogenic input. Besides the metabolites established by the used protocol, it was possible to verified high concentrations of three other compounds not yet reported in the literature. They were related to pyrolytic PAH contribution to Guanabara Bay aquatic biota: 1-hydroxypyrine and 3-hydroxybenz(a)pyrine isomers / In?meros estudos da qualidade de ecossistemas naturais em rela??o a contamina??o de hidrocarbonetos polic?ciclos arom?ticos (HPA) t?m sido desenvolvidos continuadamente face a sua presen?a ub?quoa em todo o planeta e ao seu potencial t?xico ap?s a biotransforma??o. A introdu??o dos HPA no meio ambiente pode ocorrer atrav?s de processos naturais e antropog?nicos, atrav?s de despejos e/ou drenagens e deposi??o atmosf?rica indireta. Fontes naturais de HPA incluem queimadas naturais, exsuda??es de ?leo e processos biog?nicos recentes. Fontes antropog?nicas de HPA, advindas de eventos cr?nicos ou agudos, s?o a combust?o incompleta de ?leo combust?vel automotivo e industrial, a queima intencional de madeira e planta??es, os despejos dom?sticos e industriais, as drenagens pluviais urbanas, os efluentes da ind?stria petrol?fera, os derrames acidentais de ?leo e derivados. Al?m da coexist?ncia de m?ltiplas fontes destes hidrocarbonetos nas amostras ambientais, os HPA est?o sujeitos a v?rios processos geoqu?micos que conduzem ? altera??o de sua composi??o qu?mica ao longo do tempo, tornando a identifica??o das fontes contaminantes, se petrog?nica, pirol?tica ou natural, um verdadeiro desafio. Desta forma, um dos objetivos deste estudo foi estabelecer ferramentas que possibilitem a determina??o das fontes de hidrocarbonetos no meio ambiente. Foram utilizadas raz?es diagn?sticas e an?lise de componentes principais de HPA, tendo sido quantificados 38 compostos, incluindo os HPA parentais e alquilados, em 21 amostras de sedimento da Ba?a de Guanabara, coletadas nos anos de 2000 e 2003. A Ba?a de Guanabara ? um ecossistema estuarino com elevada influ?ncia antropog?nica, que recebe polui??o cr?nica da regi?o metropolitana do Rio de Janeiro e que foi cen?rio de um derrame de ?leo em janeiro de 2000. As concentra??es de HPA nos sedimentos estudados apresentaram-se na faixa de 400 a 58439 ng g-1. Ambas as t?cnicas de diferencia??o de fontes de HPA testadas, raz?es diagn?sticas e an?lise de componentes principais, demonstraram sua aplicabilidade, permitindo a diferencia??o das fontes de HPA para a maioria dos sedimentos da ba?a, que foram divididos em dois grandes grupos: sedimentos com padr?es de introdu??o de hidrocarbonetos predominantemente petrog?nicos e sedimentos com caracter?sticas de combust?o. Apenas uma minoria de amostras n?o apresentou com nitidez a natureza de sua contamina??o. As raz?es que apresentaram maior capacidade em diferenciar as fontes de HPA foram Fluoranteno / (Fluoranteno + Pireno), (Fenantreno + Antraceno) / (Fenantreno + Antraceno + C1Fenantreno) e o ?ndice pirol?tico, &#931; (HPA parentais de 3-6 an?is) /&#931; (5 s?ries de HPA alquilados). Na avalia??o temporal realizada neste estudo n?o foram verificadas varia??es significativas na natureza das fontes contaminantes predominantes na ba?a, revelando que os hidrocarbonetos presentes est?o correlacionados principalmente com os aportes cr?nicos e n?o diretamente com eventos agudos como o derrame de ?leo ocorrido em janeiro de 2000. Este estudo teve como segundo objetivo a avalia??o preliminar do n?vel de exposi??o a que os organismos aqu?ticos da Ba?a de Guanabara est?o submetidos, atrav?s da quantifica??o de 12 metab?litos individuais de HPA presentes em bile de peixe de quatro esp?cies demersais representativas de tr?s fam?lias diferentes. Os metab?litos analisados foram 1-hidroxinaftaleno, 1-hidroxifenantreno, 9hidroxifenantreno, 2-hidroxinaftaleno, 2-hidroxifenantreno, 1-hidroxipireno, 3hidroxibifenila, 3-hidroxifenantreno, 1-hidroxicriseno, 9-hidroxifluoreno, 4hidroxifenantreno, 3-hidroxibenzo(a)pireno. As concentra??es encontradas nas esp?cies de peixes analisadas mostraram-se elevadas, na faixa de 13 a 177 ?g g1, por?m similares ?s encontradas em algumas regi?es de grande influ?ncia antropog?nica, tanto no Brasil quanto no exterior. Al?m dos metab?litos estabelecidos pela metodologia utilizada, foi poss?vel quantificar tr?s compostos, ainda n?o reportados na literatura, em concentra??es relevantes. Estes metab?litos, relacionados a contribui??o pirol?tica de HPA aos organismos aqu?ticos da Ba?a de Guanabara, s?o is?meros de 1-hidroxipireno e de 3-hidroxibenzo(a)pireno